Review

1. Introduction

In a circular-economy perspective, wastes are deemed precious feedstock usable in the production of fertilisers, fuels, chemicals and a variety of materials for packaging, housing, transport and clothing [1,2]. A considerable fraction of the waste currently produced by our society is due to plastics, which is a major problem [3,4]. Plastics are usually synthetic polymers recalcitrant to decomposition, and hence liable to accumulate in landfills or the environment when discarded [5,6]. Not all plastics can be reused, and thus having limited economic value [7,8]. Plastics may release toxic compounds dangerous to human health and the habitat [9,10]. Plastic materials are ubiquitous in our everyday life, which accounts for a global production of plastics of around 360 million tons in [11], of which more than 60% are disposed [12,13]. As a consequence, pollution from plastics is impressive, resulting in the diffusion of microplastics into soil [14,15], oceans [16,17], crustaceans [18] and rain [19].

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Valorisation of plastic waste, via chemical conversion into reusable building blocks, may contribute to solving these problems while representing a strategy to reduce the carbon footprint of the chemical industry [20,21]. The approach deepens the concept of plastic recycling [22,23], first of all requiring a careful design of efficient and controlled depolymerisation processes. Despite of this hurdle, the implementation of effective plastics value chains through recovery, reprocessing and upgrade would be a tangible mean to turn a challenge into an opportunity [24,25]. The waste-to-products strategy is already in place for both animal [26,27] and plant biomass polymeric waste [28,29], for which mature technologies are operative [30].

When referring to polymers in general, there is often a lack of univocal definitions, which may lead to confusion between terminologies used as synonyms, though they are not [31,32]. The IUPAC recommendations provide a useful reference to this aim [33]. Thus, “degradation” is a broad term describing the “progressive loss of the performance or of the characteristics of a substance" due to the action of chemical (acids, air, halogens, solvents) or physical agents (heat, light). For polymers, the properties involved are, for instance, tensile strength, colour or shape, the change of which is usually associated with a modification of the chemical composition (e.g., as a consequence of oxidation, cross-linkage, bond cleavage). The term “biodegradation” indicates a “degradation caused by enzymatic processes resulting from the action of cells”. Although commonly used, also for artificial polymers, the term “biodegradable” specifically refers to biorelated polymers (i.e., proteins, nucleic acids, polysaccharides), which are "susceptible to degradation by biological activity by lowering of the molar masses of macromolecules". Therefore, in this situation, “chain cleavage” and “degradation” are used interchangeably. To avoid confusion, instead of “(bio)degradation”, in the present review, we will use the term “depolymerisation” to identify the “process of converting a macromolecule into (recoverable) monomers or a mixture of monomers". Another relevant definition is that of “bioplastic”, meaning “biobased polymer derived from the biomass or issued from monomers derived from the biomass”, wherein “biobased” indicates “composed or derived in whole or in part of biological products issued from the biomass”. Also, there is no universally accepted definition for “compostable”, as it differs between diverse issuers [34]. The criteria indicated by the European Commission through the standard EN “Packaging–Requirements for packaging recoverable through composting and biodegradation” include disintegration (i.e., breakdown of material to particles of a defined size), biodegradability, absence of negative effects on the composting process and amount of heavy metals below given maximum values [35,36].

“Recycling” itself is a general term for which multiple definitions exist, depending on the year and the author [37]. Plastics manufacturers have also delivered their own guidelines under the name “Design for Recycling” [38,39]. A generally accepted definition for plastic recycling is “the process of recovering scrap or waste plastics and reprocessing the material into useful products, sometimes completely different in form from their original state” [40,41]. A possible classification of reported plastic recycling techniques is schematically shown in Figure 1 [42], wherein breakdown by the recycled polymer, the final product or the process involved further differentiates between methods, which may lead to occasional overlaps and inconsistencies [43,44].

“Reuse” is considered a zero-order recycling option, meaning “any operation by which products or components that are not waste are used again for the same purpose for which they were conceived” [45]. A typical example are plastic containers that are washed and reused as they are [46]. True recycling includes “any recovery operation by which waste materials are reprocessed into products, materials or substances whether for the original or other purposes. It includes the reprocessing of organic material but does not include energy recovery and the reprocessing into materials that are to be used as fuels” [45]. Therein, three options can be distinguished. “Reextrusion” (also known as closed-loop recycling) refers to the recycling of clean, uncontaminated single-polymer materials to give products with analogous performance and applications [47]. For example, polyethylene bottles are recycled into new bottles. Similarly, in “physical recycling”, the polymeric structure of the original material is maintained, although purification steps, the addition of additives or blending with fresh polymers may be included [48]. For this reason, both reextrusion and physical recycling are also referred to as “mechanical recycling”, primary and secondary, respectively [49,50]. However, materials of lower quality and economic value can be obtained [51,52]. By contrast, the term “chemical recycling” (or feedstock recycling) refers to those processes involving an alteration of the polymeric chain due to breakage of chemical bonds [53,54]. This definition may be confusing since chain scission may actually occur using either physical (heat) or chemical agents. Indeed, chemical recycling processes can be divided into two main categories: thermochemical and chemolytic routes. All of these processes may result in a variety of valuable products and the mixture thereof, including C1 molecules (CO, CO2, CH4), H2O and H2 due to complete decomposition of the polymeric chain, monomers or oligomers, depending on the waste polymer and the process. The as-obtained compounds can be reused as raw materials for the process industry (hence the term feedstock) to produce chemicals, fuels or other polymers. Thermochemical processes include pyrolysis [55], catalytic cracking [56] and gasification [57]. These are usually unselective, high-temperature treatments (300– °C) that may efficiently provide light hydrocarbons or small molecules [58,59]. Chemolytic processes, wherein a chemical reagent is used to achieve depolymerisation, mainly involve solvolysis (a solvent is the reagent and solvolyses include hydrolysis, glycolysis, alcoholysis and aminolysis) and hydrogenolysis reactions (H2 as reagent). Hydrolysis (sometimes called hydrocracking) is in between thermochemical and chemolytic processing, basically consisting of depolymerisation by the combined action of heat and dihydrogen [60]. Chemolytic processes may or may not be catalytic. They will be discussed in detail in the following section. A fourth option is “energy recovery”. Strictly speaking, this cannot be considered as recycling, consisting in the recovery of the energy contained in a material rather than the material itself, and it is usually achieved by combustion or incineration [61,62]. This method is generally used for plastics that cannot be economically recycled by other means [63,64]. However, it often entails the emission of toxic volatile compounds (furans, dioxins) [65]. The tar obtained may be used for road construction [66].

The present paper shortly reviews the most significant contributions that appeared in the literature, from January to January , in the field of metal-catalysed selective depolymerisation of plastics to reusable monomers, oligomers or added-value chemicals (see Figure 1). Scientific achievements will be described according to the plastic substrate, irrespective of the metal catalyst. Uncatalysed depolymerisations, full chain-cracking or unselective processes, acid–base treatments, as well as the production of fuels from plastics, will not be covered. Conversion of plastic waste to fuels [67,68] and biocatalytic depolymerisation methods [69,70] have been extensively and recently reviewed elsewhere, hence they will not be considered herein.

2. Depolymerisation of plastics

As outlined above, depolymerisation of plastic waste to reusable building blocks is an attractive option for effective recycling and valorisation. This is most conveniently achieved through chemolytic processes because of the higher selectivity and lower energy inputs compared to thermochemical approaches [71]. This is a “hot” research topic, mainly due to the few industrial applications developed in the field so far, despite the urgent need for innovative technologies that overcome the high costs of recycling, the legal constraints for dumping, the accumulation of plastic scraps and the dependence on nonrenewable (fossil) sources [72,73]. A reason for this underdevelopment is that chemolysis of plastics is still challenging due to multiple critical factors: i) the achievement of selective depolymerisation is only possible by carefully controlled reaction conditions, ii) the related processes must be “green” and economically viable and, iii) tailored solutions are required to overcome the chemical inertness for, and the thermodynamic limitations of the reversal of each polymer. Indeed, the ease (and outcome) of chain scission does not depend on the origin of the polymer but on its chemical structure [74,75]. For instance, plastics derived from biomass are not necessarily biodegradable, particularly if similar to those obtained from petroleum sources [76,77]. For depolymerisation to be effective at reasonable operating temperature and selective, the plastic substrate should in principle originate from low-exergonic polymerisation reactions [78]. This justifies for the easier depolymerisation of polyesters and polycarbonates compared to polyolefins [79,80]. By contrast, poor selectivity and slow kinetics of depolymerisation can be circumvented using a catalyst.

2.1 Chemolysis

Several catalytic depolymerisation processes of plastics have been developed, using a solvent or molecular hydrogen as cleaving agents [81]. The main solvolytic process include:

Advantages of catalytic processes are obvious and can be witnessed in the hydrolysis and the glycolysis reactions of poly(ethylene terephthalate) (PET) [82,83]. Representative data are reported in graphical format in Figure 2 for the glycolysis reaction of PET, using titanium(IV) n-butoxide as the catalyst. Compared to the uncatalysed process, benefits include milder reaction conditions, higher selectivity and productivity and reduced generation of waste; in short, improved sustainability [84,85]. However, solvolytic methods are usually not cost-competitive and energy-intensive [86], while they may involve the management of large amounts of noxious solvents and a variety of (decomposition) byproducts [87,88]. Depolymerisation products of course depend on the polymer, the solvent and the reaction conditions. For instance, for polyesters, alcoholysis may provide mixed monomers formally derived from transesterification reactions [89,90], while aminolysis provides amides and alcohols [91,92].

In the search of “greener” technologies for plastic recycling, catalytic hydrogenolysis processes have been developed that benefit from the use of H2 as clean reagent and that usually result in a limited number of secondary products [93,94]. The excess of H2 reagent can also be easily removed from the reaction mixture. The approach, referred to as hydrodeoxygenation [95,96], is already in use for the valorisation of naturally-occurring polymeric waste, i.e., lignocellulosic biomass [97,98], particularly lignin [99,100] and cellulose [101], to monomers or added-value platform molecules [102,103]. Here the main drawbacks concern safety hazards, supply, transport and storage costs of hydrogen. Catalytic transfer hydrogenation (CTH) methods from safer reagents have thus been developed and successfully applied to lignocellulose polymers [104,105].

2.2 Catalysts

Catalysts of various types, including homogeneous and heterogeneous, have been reported for the above-mentioned depolymerisation processes of plastics. Heterogeneous systems are preferred by industry due to the easier separation from the reaction mixture, reuse and integration into existing reactor equipment [106,107]. Metal-based catalysts have been used for both solvolytic and hydrogenolytic methods, wherein the latter are usually achieved by supported metal species (Ru, Ir), due to the ability to activate molecular hydrogen, functioning as redox centres. The mechanisms of the metal-catalysed solvolytic reactions of plastics are all very similar and typical of conventional organic processes: a metal ion acts as Lewis acid centre for the activation of the chain-linking group of the polymer (either an ester, carbonate, ketone or amide) toward the nucleophilic attack of the various solvents. Specific examples, broken down according to the nature of the polymer and the process, will be reported in the next sections, in which metal catalysts are described in detail. Solvolytic depolymerisations can also be promoted by metal-free soluble acid or base catalysts. However, concentrated solutions, quasistoichiometric amounts or strong mineral acids (HNO3, H2SO4, H3PO4) or bases (NaOH, KOH, potassium butoxide) are often required, particularly for hydrolysis reactions [108,109], which may result in corrosion problems, troublesome neutralisation and purification procedures as well as a considerable generation of waste, which makes these process economically and environmentally unappealing [110,111]. These systems are not considered in the present review.

Biological catalysts for the deconstruction of plastics were extensively studied in the past years, and several hydrolytic-enzymes-containing microorganisms have been shown to be usable for this purpose [112,113]. However, enzymatic depolymerisation is hampered by high molecular weight and crystallinity, reduced chain mobility and hydrophobicity of polymers [114,115], which makes biodegradation often ineffective and time-consuming, particularly for polyolefins, such as polyethylene, polyvinyl chloride (PVC), polystyrene or PET [116,117]. Thus, abiotic pretreatments may be required, including UV irradiation [118], oxidation [119] or acidic degradation [120].

It is worth mentioning that organocatalytic depolymerisation methods have also been reported [121,122]. Despite these systems represent promising “greener” options, they still are in an early development stage. Uses are mainly limited to nitrogen-based catalysts, ionic liquids [123,124] and alcoholysis of oxygen-containing polymers, such as polyesters, polycarbonates and polyamides, i.e., glycolysis of PET, wherein high temperatures and nearly stoichiometric amounts of catalysts are often required to achieve moderate yields of monomers [125,126].

3. Selective depolymerisation of plastics via metal catalysis

Research in depolymerisation of plastics by artificial metal catalysts is relatively recent as most of the earliest studies are related to biocatalytic systems. Metal salts are the conventional catalysts for these processes, wherein acetates, phosphates and chlorides of heavy metals (Ti, Zn, Mg, Co, Fe) or lead oxide are commonly used in the alcoholysis and glycolysis of polyesters [127,128]. Despite that these systems ensure high conversions and selectivity, shortcomings relate to the harsh reaction conditions, slow kinetics, cost of metals, toxicity, difficulty in catalyst reusing and need of downstream processing. Significant efforts have thus been made to develop greener and sustainable catalytic systems featuring high efficiency under mild conditions. The use of sodium carbonate or bicarbonate as ecofriendly catalyst replacements for zinc acetate in the glycolysis of PET are examples of this direction [129,130]. Recent studies focused on molecular complexes as homogeneous catalysts, whereas heterogeneous systems based on solid-supported metal nanoparticles (NPs) have been scarcely investigated.

3.1 Polyolefins

Due to the intrinsic chemical resistance of the hydrocarbon skeleton devoid of functional groups, polyolefins are neither prone to chemical recycling nor biodegradable [131,132]. Hence, they are more commonly repurposed via mechanical recycling, burned or just discarded [133,134]. Depolymerisation of polyolefins usually requires thermal treatments at high temperature [54,135].

3.1.1 Polyethylene (PE): PE is the most used thermoplastic material today, having a variety of uses in several fields. Applications of PE depend on the mechanical and physical properties (particularly the tensile strength, hardness and melting point Tm), which are, in turn, ruled by the molecular weight and degree of branching [136,137]. Various types of PE exist, which are classified according to the density, the most common being high-density polyethylene (HDPE) and low-density polyethylene (LDPE). HDPE (0.94–0.97 g⋅cm−3, Tm 130 °C) is a highly crystalline material with a low degree of short chain branching. Owing to the high stiffness, tensile strength, resistance to moisture and gas permeability, it is mainly used in the manufacture of water pipes, toys, beverage bottles, outdoor furniture, housewares and electrical cables [138,139]. LDPE (0.91–0.94 g⋅cm−3, Tm 120 °C) is a poorly crystalline material having a high degree of short chain and long chain branching. It is featured by a good flexibility, transparency and high impact strength, which make it suitable for short-term applications, such as films, food packaging, squeezable bottles, plastic bags and medical devices [140]. PEs (except cross-linked samples) are partially soluble in (hot) aromatic hydrocarbons or in chlorinated solvents [141].

Depolymerisation of PE by catalytic pyrolysis or cracking into liquid fuels was recently reviewed [67,142]. Most of these processes are promoted by heterogeneous acid catalysts (e.g., zeolites, alumina, silica) and are usually unselective, resulting in a broad distribution of gas (C3 and C4 hydrocarbons), liquids (cycloparaffins, oligomers, aromatics) and solid products (char, coke) as a consequence of the random scission of C–C bonds into radicals, which leads to a complex mixture of olefinic and cross-linked compounds [143].

In a few cases, good selectivity to a liquid fraction was achieved. For instance, nanostructured BaTiO3 doped with Pb provided a mixture of liquid products, which includes alkanes (73.4%), olefins (22.5%) and naphthalene (4.1%) at total HDPE conversion at 350 °C [144]. In another example, hydrocracking of PE was performed over Pt NPs supported on SrTiO3 perovskite nanocuboids [145]. Virgin PE (Mw = – g⋅mol−1) or PE from single-use plastic bags (Mw = g⋅mol−1) was converted in >97% yield into liquid hydrocarbon (alkane) products having a narrow distribution of the molecular weight (960– g⋅mol−1) under 11.7 bar H2 at 300 °C and solvent-free conditions [146]. The pyrolysis oils produced may be used as lubricants, waxes or further processed into detergents and cosmetics [147]. The catalyst could be recycled, however, with reduced performance due to Pt nanoparticle oxidation.

3.1.2 Polybutadiene (PBD): Partial depolymerisation of 1,4-PBD (cis, trans, Mw – g⋅mol−1) was achieved by an unconventional tandem ring-opening–ring-closing metathesis route mediated by commercially available Ru homogeneous catalysts [148]. The process afforded C16 to C44 mixtures of macrocyclic oligobutadienes with up to 98% selectivity at moderate conversions (59–88%) using first-generation Ru complexes bearing a tricyclohexylphosphine (PCy3) ligand, mild reaction temperature (35 °C) but toxic CH2Cl2 solvent (Scheme 1). The reaction using second-generation N-heterocyclic carbene ligands was faster and preferably yielded cyclododecatriene. Larger cyclic butadienes may be used in the production of flame retardants, lubricants and specialty polymers [149,150].

3.1.3 Polystyrene (PS): PS is a low-cost, hard and brittle plastic used both as a solid or foam in protective packaging, containers and trays [151]. It is a nonbiodegradable material accounting for about 10% of municipal solid waste [135]. It is soluble in benzene, carbon disulfide, chlorinated hydrocarbons, lower ethers and N-methyl-2-pyrrolidone (NMP) and has a melting point around 240 °C [152]. Most methods for PS recycling are not economically advantageous [153]. Mechanical recycling, based on pelletizing and moulding, produces low-grade plastics with poor mechanical strength and low market value. Solid PS products, such as coffee cups or take-away containers, can be recycled into videocassette cases or office equipment. Incineration at a temperature below °C and insufficient air is believed to produce a mixture of volatile compounds, including hazardous polycyclic aromatic hydrocarbons, alkylbenzenes and benzoperylene [154,155]. As for other polymers, pyrolytic methods end up to be poorly selective.

In some cases, metal-catalysed depolymerisation processes of PS were described, showing significant selectivity. In an earlier example, thermal treatment of PS waste over a Fe–K@Al2O3 catalyst at 400 °C provided a hydrocarbon oil in 92% yield, 71.4% of which were attributable to styrene monomer [156]. A decrease of 56 kJ mol−1 for the activation energy of PS depolymerisation was calculated in the presence of the catalysts. More recently, high-porosity montmorillonite (Mt) was used to prepare Mg-, Zn-, Al-, Cu- or Fe-decorated heterogeneous catalysts [157,158]. An oil yield around 89% was obtained at 450 °C over 20% Fe@Mt, composed by 51%, 10% and 6% (wt) styrene, toluene and ethylbenzene, respectively, and additional oligomers.

3.2 Polyesters

3.2.1 PET: PET is one of the most widely used thermoplastic polyesters, particularly in the textile and food packaging industry (e.g., soft-drink and water bottles, food container, films) due to the excellent thermal and mechanical properties, durability, inertness and transparency. The global production of PET exceeds 50 million tons pear year, while PET accounts for around 8% by weight and 12% by volume of the world's solid waste [159,160]. PET is a copolymer of terephthalic acid (TPA) and EG [161]. It is best soluble in chlorophenol, tetrachloroethane, m-cresol, NMP, nitrobenzene and 1,1,1,3,3,3-hexafluoro-2-propanol, insoluble in common alcohols and water and has a melting point of 250 °C and a glass transition temperature Tg of 76 °C [162,163]. It was suggested that under certain circumstances, PET may leach phthalates [164], which are known for potentially adverse health effects and subject to ECHA regulation restrictions [165,166]. Coupled with the fact that TPA is produced from petrochemical sources, bioderived 2,5-furandicarboxylic acid has been proposed as TPA replacement in the production of plastic bottles, representing one of the rare examples of industrial manufacture of biobased polymers [167,168].

From the chemical recycling point of view, PET is one of the most studied plastics, so as to represent a case study in the field [169,170]. A variety of added-value, reusable chemicals and monomers can be recovered from PET via chemolytic depolymerisation, including 1,4-benzenedimethanol (BDM), TPA, dimethylterephthalate (DMT), bis(2-hydroxyethyl)terephthalate (BHET), terephthalamides (TPM [171]) and EG (Figure 3). Catalytic hydrogenolysis, hydrolysis, methanolysis and glycolysis reactions of (postconsumer) PET have been reviewed, each showing their own advantages and disadvantages [172,173]. For instance, glycolysis usually requires more problematic purifications than methanolysis, which, on the other hand, is generally more energy-intensive. Some solvolytic processes of PET are already in operation at the industrial or pilot scale [174,175]. However, they often rely on the use of considerable amounts of strong alkali bases and chlorinated solvents [176,177], which makes them neither economically competitive nor environmentally friendly [178,179]. A survey of patents related to the chemical recycling of PET up to can be found in the literature [180].

Hydrogenolysis. In the recent years, hydrogenolysis reactions of PET were developed mostly using Ru metal-based catalysts, due to their higher affinity for C=O bond (ester) hydrogenation compared to other metals (Scheme 2) [181,182]. Thus, a 73% BDM yield was obtained using a soluble Ru(II)–PNN complex at 110 °C in THF/anisole solvent, 50 bar of hydrogen and a 20:1 excess of strong base potassium tert-butoxide as cocatalyst (Table 1, entry 1) [183]. Although the reaction mechanism was not investigated in detail, it was suggested that cleavage of the ester linkage may occur in a concerted manner through the reported heterolytic route [184,185]. The role of butoxide was postulated to be the activation of the heterogeneous splitting of dihydrogen. BDM is an important building block for the production of resins and polyesters other than PET [186,187]. Analogously, a similar Milstein-type ruthenium–PNN complex, generated in situ by treatment of the chloride catalyst precursor with potassium butoxide in a 2:1 molar ratio, resulted in a nearly quantitative yield of BDM and EG at a slightly higher reaction temperature (160 °C, 54 bar H2, Table 1, entry 2). Interestingly, PET flakes from postconsumer bottles could be used, showing the catalytic system to be resistant to the presence of contaminants and impurities (e.g., additives, pigments) [188]. More recently, effective PET depolymerisation was accomplished by a ruthenium molecular catalysts bearing the well-known tripodal phosphorous ligand 1,1,1-tri(diphenylphosphinomethyl)ethane (triphos) [189,190]. Thus, use of Ru(triphos)tmm (tmm = trimethylenemethane) and acidic bis(trifluoromethane)sulfonimide (HNTf2) cocatalyst (1:1) in noxious 1,4-dioxane solvent resulted in 41% PET conversion and 64% BDM selectivity at 140 °C and 100 bar H2 due to the formation of ether byproducts (Table 1, entry 3) [191]. No hypotheses for the reaction mechanism were formulated. Higher conversion (64%) and selectivity (99%) were observed using the bulkier xylyl derivative Ru(triphos-xyl)tmm (Table 1, entry 4), which was attributed to reduced catalyst degradation [192]. The catalyst could be employed for the depolymerisation of PET flakes from various sources (water bottles, dyed soda bottles, pillow filling, yoghurt pots). However, the role of HNTf2 was unclear.

In a different approach, hydrogenolysis-like depolymerisation was achieved through a hydrosilylation strategy, using the pincer Ir(III) complex [Ir(POCOP)H(THF)][B(C6F5)4] (POCOP = 1,3-(t-Bu2PO)2C6H3) as catalyst and an excess of Et3SiH as reagent (chlorobenzene solvent, 70 °C) [193]. BDM could be obtained in an overall 58% yield from PET from fibres or bottles, after hydrolysis of the intermediate silyl ether using Bu4NF·3H2O in THF (Scheme 3).

Hydrolysis. Methods for the metal-catalysed hydrolysis of PET were developed, allowing for the recovery of costly TPA monomer (Scheme 4, top). TPA was obtained in 97.1% yield at full PET conversion, using 70 wt % aqueous ZnCl2 as catalyst at 180 °C and no organic solvent [194]. However, a high ZnCl2/PET weight ratio of 35 was required. The catalyst could be reused, showing significant activity decrease starting from the fourth cycle due to biochar formation. A mechanism was hypothesised in which Zn2+ ions act as a Lewis acid activator for the carbonyl ester bond. In a previous work, complete depolymerisation of PET was achieved using zinc acetate as catalyst in hot compressed water [195]. A TPA yield of 90.5% was obtained at 240 °C after 30 min reaction time, using a ZnAc2/PET weight ratio as low as 0.015. For this, a mechanism was speculated in which proton ions act as activators.

Methanolysis. To the best of our knowledge, only one example of a depolymerisation reaction of PET through alcoholysis was recently reported, which is however devoid of any catalysts [196]. Therein, a 97.3% yield of DMT was obtained at full PET conversion, by treatment of PET with methanol at 200 °C for 3.5 h (Scheme 4, bottom). No details of byproducts were provided. Ethanol and butanol were much less reactive under identical reaction conditions. The as-prepared DMT could be used for the production of hydrocarbon jet fuels by catalytic hydrogenation. Metal-catalysed methanolysis of PET was described in previous years [109,197].

Glycolysis. Glycolysis is a convenient process for PET chemical recycling, owing to the low cost, relatively mild reaction conditions and the potential for the production of useful monomers and oligomers. These compounds can be used in the synthesis of recycled polyesters, polyurethanes, polyisocyanurates and resins [43]. Among the various glycols, EG is the most popular, resulting in the formation of BHET, formally through a (reversible) transesterification reaction (Scheme 5) [198]. Drawbacks of this method are the difficulty of purification of BHET, the need of an excess of EG and the possible product contamination by homogeneous catalysts [199]. The conventional catalysts for this reaction are EG-soluble metal acetates, the activity of which showed a decrease in the order Zn2+ > Mn2+ > Co2+, which was attributed to the diverse interaction between the metal cation promoter and the carbonyl group of polyester [200]. Indeed, several studies showed Zn-based catalysts to provide the best performances. A summary of recent findings and reaction conditions is reported in Table 2. In an earlier study, a 85.6% BHET yield was obtained at 196 °C, using an EG/PET ratio of 5:1 (w/w) and 1 wt % Zn(OAc)2 loading (Table 2, entry 1) [201]. The system resulted in partial selectivity to BHET due to the formation of significant amounts of oligomers, mainly BHET dimers, which increased upon standing. The kinetic of the zinc acetate-promoted process was studied over a range of reaction conditions, showing the best combination to be 196 °C, an EG/PET ratio of 2.45:1 (w/w) and a catalyst loading of 0.3 wt % (Table 2, entry 2) [129]. Under these conditions, an equilibrium yield of BHET around 65% was achieved within short reaction times (1 h), much faster than in the absence of catalysts or using alkali salt promoters (Na2CO3, NaHCO3, Na2SO4 or K2SO4, Figure 4). PET wastes, including highly coloured and multilayered PET, could be used as substrate. More recently, it was demonstrated that the addition of a cosolvent for PET, such as dimethyl sulfoxide (DMSO), NMP, nitrobenzene or aniline to the conventional PET-insoluble EG system, greatly enhanced the depolymerisation kinetics, resulting in improved conversions (the solubility of PET at T > 130 °C was aniline > NMP > nitrobenzene > DMSO) [202]. For instance, the use of a DMSO/EG 2:1, w/w solvent mixture resulted in an increase of PET conversion from 43.0% to 83.9% compared to pure EG (190 °C, 5 wt % catalyst loading, 5 min reaction time, Table 2, entry 4 vs entry 3). Using the same reaction conditions and solvent mixture, Mn, Co, Cu and Ni acetate catalysts were less active than Zn (Table 2, entries 5 and 6). In a further study, glycolysis of PET was performed under microwave heating in the presence of Zn(OAc)2, yielding BHET with an 80% selectivity at 97% conversion due to formation of dimers (Table 2, entry 7) [203,204]. Soluble metal chlorides (zinc, magnesium, iron, zirconium, cobalt, nickel) were also explored as catalysts in the glycolytic depolymerisation of PET [128,205]. The highest BHET yield (74.7%) was achieved using zinc chloride (0.5% w/w), an EG/PET ratio of 14:1 and reflux conditions (Table 2, entry 8). The use of preformed soluble Co(II) complexes bearing bidentate phosphorus ligands (e.g., 1,2-bis(dicyclophosphino)ethane) showed minimal improvements compared to the chloride salt catalyst [205]. The use of transition metal-substituted polyoxometallates (POMs), of the general formula K6SiW11MO39(H2O) (M = Zn2+, Mn2+, Co2+, Cu2+, Ni2+) [206,207], was also investigated [208]. The catalytic activity was found to decrease in the order Zn > Mn > Co > Cu > Ni, consistent with previous reports [209]. The best catalyst afforded BHET in 84.1% yield (Table 2, entry 9), which was rather constant over eight catalyst reuses [210]. A stepwise depolymerisation mechanism was proposed, via intermediate oligomers, in which Zn ions act as Lewis acid activators for the C=O ester bonds toward nucleophilic attack by EG.

In addition to soluble catalysts, metal-containing insoluble materials, namely solid acid catalysts, were developed for the glycolytic depolymerisation of PET by EG. Representative data are summarised in Table 3, wherein the catalyst productivity is reported for comparison as molBHET⋅gcat.−1⋅h−1. Despite that both catalyst and PET were insoluble in EG at the reaction temperature, most systems displayed substantial activity. Thus, sulfated titania, zinc oxide and mixed oxides (SO42−/TiO2, SO42−/ZnO and SO42−/ZnO–TiO2) were prepared, showing the amount of Lewis acid sites and the high surface area of the solid material to be critical in affecting the catalytic efficiency [211]. Best results were obtained for the binary oxide SO42−/ZnO–TiO2 calcined at 200–300 °C (surface area 192 m2⋅g−1, density of acidic sites 4.34 mmol⋅g−1), which provided BHET in 73% selectivity at full PET conversion at 180 °C reaction temperature and a moderate excess of EG (5.5:1, w/w, Table 3, entry 1). The formation of a significant amount of oligomers was detected. The catalyst could be recovered by centrifugation and reused over four cycles with no efficiency decay. Similar effects were reported for Zn-substituted titanate nanotube (TiNT) catalysts [212,213]. Therein, a positive role of Zn2+ Lewis acid sites was demonstrated by the higher efficiency compared to the Na+ catalyst counterpart (Table 3, entry 2 vs entry 3), whilst a high surface area around 150 m2⋅g−1 was proposed to increase the number of exposed sites [214]. Zn@TiNT afforded BHET in 87% yield at 196 °C reaction temperature. TiNT have received significant general interest in heterogeneous catalysis because of the better active-site-accessibility compared to 2D materials, thanks to a typical 8–16 nm outer diameter tubular morphology [215,216] and the potential for facile metal doping via ion-exchange of the solid support [217,218]. Lewis acid-type catalytic activity was also postulated for γ-Fe2O3 NPs, which provided BHET in 90% yield at 300 °C (Table 3, entry 4) [219]. Therein, thanks to the superparamagnetic properties, easy recovery of the highly dispersed solid catalyst (11 nm size) was possible by application of a magnetic field. The catalyst could be reused over ten cycles without significant activity loss. Other solid-supported nanostructured metal oxides were tested as catalysts for PET glycolysis. Thus, a graphene oxide (GO)–Mn3O4 nanocomposite (Table 3, entry 5) [220] and silica NPs-supported Mn3O4 [221] resulted in a good yield of BHET (>90%), however, at a high reaction temperature. A zinc manganite spinel ZnMn2O4 gave BHET in 92% yield at 260 °C and 5 atm pressure (Table 3, entry 6) [222]. On the other hand, amphoteric solid catalysts have also shown usability in EG depolymerisation of PET. For instance, a BHET yield of 75% was achieved over (Mg–Zn)–Al-layered double hydroxides (LDH) catalysts at 196 °C (Table 2, entry 7) [223]. A cooperative mechanism was proposed in which Lewis acid sites (Mg2+, Al3+, Zn2+) activate the C=O ester bond, while the basic sites (OH−) deprotonate EG, enhancing the nucleophilic cleavage of the ester unit [224].

Notably, the depolymerisation of PET by EG was also reported using metal-containing catalysts in the form of ionic liquids (ILs) [209]. Advantages of metallated ILs include low flammability, high thermal stability and versatility. However, their “greenness” and toxicity are still debated [225,226]. Thus, amim[ZnCl3] (amin = 1-allyl-3-methylimidazolium, Table 4, entry 1) [227] and amim[ZnCl3] (bmim = 1-butyl-3-methylimidazolium, Table 4, entry 2) [228] were recently studied, showing higher catalytic activity compared to metal-free ionic liquids (i.e., bmim chloride), the conventional catalysts (i.e., ZnCl2, Zn(OAc)2) or the analogous Mn, Co and Cu ionic liquids. Typically, 80–85% BHET yields were observed for metallated ILs, while under the same experimental conditions, ZnCl2 gave BHET in ≈70% yield (Table 4, entry 5). Similar results were reported for the bmim2[MCl4] (M = Cr, Fe, Co, Zn, Ni, Cu) catalysts, wherein the cobalt derivative resulted in the best performance (Table 4, entry 3) [229]. Based on infrared studies, the higher catalytic activities of the metallated ILs was attributed to their higher Lewis acidity compared to both the metal-free catalysts and the metal salts. A mechanism was therefore proposed in which a synergistic effect of the metallated ILs takes place, based on the activation of the C=O bond by the IL Lewis acid cation and of the hydroxy group in EG by the IL anion (Scheme 6). The IL catalysts could be easily separated by distillation and reused up to six times with no significant efficiency drop. Catalytic glycolysis by heterogenised, metallated ionic liquids was also investigated [230], however, showing a lower performance compared to the soluble systems. Thus, PET pellets were fully converted by a bmim[Fe(OAc)3] catalyst immobilised onto bentonite, affording BHET in 44% yield (Table 4, entry 4) [231]. The solid catalyst could be recovered by filtration and reused.

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As an alternative to ILs, metal-based deep eutectic solvent (DES) systems were also explored as catalysts for the glycolysis reaction of PET using EG. DES have similar properties to metallated ILs, but they are cheaper and less toxic [232,233]. Because of this, they have found application in many fields [234,235], though they cannot be considered inherently “green” [236]. In a recent work, the DES combination zinc acetate and 1,3-dimethylurea (1:4) showed the highest catalytic activity among a series of transition metal acetates (Zn, Mn, Co, Ni, Cu), affording BHET with 82% yield and noticeable productivity (TOF = 129 h−1, based on the moles of Zn) at 190°C, EG/PET 4:1, w/w and 5 wt % catalyst [237]. A mechanism was proposed analogous to that depicted in Scheme 6, but in which Zn2+ acts as Lewis acid and dimethylurea acts as base promoter for EG hydroxy deprotonation [238]. The remarkable activity was attributed to the dual effect of base and acid catalysis, in addition to the solubility of the catalyst in EG.

It is worth mentioning that, in addition to the recovery of chemicals via chemolytic processes, repurposing techniques of PET were developed based on one-pot, two-step glycolysis-reprocessing strategies, wherein the depolymerisation products are directly used in a polymerisation reaction, without intermediate purifications. In order to avoid the presence of free glycols in the polymerisation mixture, most of these processes were performed using (sub)stoichiometric amounts of diol cleaving agents, other than EG (for instance, PD [239], DEG [240,241]). As a consequence, the depolymerisation step usually results in complex mixtures of oligomers. Moreover, reacting diols may be unstable under the reaction conditions adopted. Hence, if used in excess, a significant formation of decomposition byproducts may be observed (i.e., dioxane and acetaldehyde for DEG [242]). Because of that, these metal-catalysed depolymerisations cannot be strictly considered as selective, although the overall processes are interesting from a practical and sustainability point of view. Some recent examples are cited herein. Postconsumer PET was depolymerised in the melt (at 250 °C) using DEG and Ca/Zn stearate as catalyst, and the product mixture was used in situ in conjunction with bis(2-ethylhexyl)phthalate and the same metal promoter for the production of flexible poly(vinyl chloride) compounds [243]. One-pot depolymerisation–polycondensation reactions were developed to produce random copolyesters poly(ethylene terephthalate-co-adipate) from PET in the presence of EG and adipic acid [244]. The depolymerisation step was carried out using a zinc acetate catalyst (1 wt %), with no need of excess of chemicals. Polymerisation was then achieved by raising the reaction temperature, without purification of the intermediate oligomers being required. An interesting one-pot process was developed that combines the use of bioderived chemicals, isosorbide and succinic acid, with PET chemical recycling to produce novel polyesters [245]. In this process, isosorbide was used as depolymerising diol to give a mixture of differently composed oligomers, whereas succinic acid was added in the second step as polymerising comonomer (Scheme 7). Both steps were efficiently catalysed by monobutyltin oxide, using substoichiometric amounts of isosorbide and succinic acid and no solvent at 230 °C reaction temperature. Isosorbide is a safe chemical [246] that is obtainable on the large scale from renewable glucose [247,248]. Because of this and due to the inherent rigid structure, conferring the resulting polymers with excellent mechanical properties (e.g., stiffness, toughness, hardness), isosorbide is used as monomer in the production of a variety of plastics [249,250]. By contrast, the rigidity results in a poor reactivity as depolymerising agent [251].

3.2.2 Polylactic acid (PLA): PLA is a bioderived plastic [252] that is manufactured on a 190 kton scale directly from lactic acid by condensation or from lactide by ring-opening polymerisation (Scheme 8) [253,254]. The main renewable raw material for lactic acid is starch, e.g., from corn, cassava, sugarcane or beet pulp [255]. Owing to the chirality of lactic acid, three forms of PLA (ʟ, PLLA; ᴅ, PDLA; ᴅʟ, PDLLA) with slightly different properties (crystallinity, Tg 60–65 °C, Tm 130–180 °C) exist [256]. PLA is soluble in benzene, tetrahydrofuran, ethyl acetate, propylene carbonate and dioxane [257], and it is biodegradable [258,259]. Because of these features, PLA is largely employed in several applications: microelectronics, biomedicine and food packaging [260].

Although chemical recycling of PLA is possible by thermal methods over metal catalysts [261,262], these often result in a poor selectivity and in a variety of volatile compounds, with the notable exception of calcium oxide, which gave ʟ,ʟ-lactide from PLLA in ≈98% yield at 250 °C [263].

Alcoholysis. The solvolytic depolymerisation of PLA was mostly reported using zinc-based catalysts, ethanol or methanol agents, wherein a higher reactivity of the latter was ascribed to the better nucleophilicity. Indeed, a methyl lactate (Me-La) and ethyl lactate yield of 70% and 21% was obtained, respectively, using soluble zinc acetate at reflux temperature [264]. Interestingly, under the same reaction conditions, PET was unreactive, thus enabling the selectively recycle of mixed PET/PLA plastic waste. It was suggested that the different reactivity between PLA and PET is attributable to the amorphous, less rigid structure of PLA and to the potential of forming five-membered chetate ring intermediates between Zn(II) ions and lactate units, which favour the transesterification process. More recently, the use of soluble Zn(II) molecular catalysts was investigated. An in-depth study of the methanolysis reaction of PLA was carried out via design of experiments technique, using a series of imino monophenolate–Zn complexes and THF solvent. Different commercial samples of PLA were examined, showing the critical operational parameters to be temperature and catalyst concentration, whereas the process was not significantly affected by particle size or stirring speed. Thus, up to 100% Me-La yield was obtained using the six-coordinated Zn(ligand)2 complex sketched in Scheme 9a, either at 90 °C and 16 wt % catalyst or 130 °C and 8 wt % catalyst [265]. Higher efficiency was provided by the tetrahedral complex ZnA2 bearing a similar ligand, as shown in (Scheme 9b), which resulted in 81% Me-La selectivity at full PLA conversion at under 50 °C and 4 wt % catalyst loading [266]. However, in the absence of THF solvent, the latter catalysts gave a 98% Me-La yield at 130 °C. The comparable complexes ZnL12, ZnL22 and ZnL32 shown in Scheme 9c resulted in a lower catalytic efficiency (Me-La yield 41–88%, 50 °C, 8 wt % catalyst loading, 18 h), and thus indicating a significant steric and electronic effect of the ligand [267]. A reaction mechanism for PLA depolymerisation was proposed, consisting of two consecutive first-order steps, in which Me-La production follows the formation of chain-end groups intermediates [265]. A zinc–N-heterocyclic carbene complex was used as catalysts for the methanolysis reaction of PLLA via a two-step, one-pot procedure using CH2Cl2 solvent and an excess of methanol at room temperature (Scheme 10) [268]. At full substrate conversion, a Me-La/oligomers ratio around 10:1 was detected by GPC analysis. Notably, mutatis mutandis, almost all of the above described zinc complexes could be used as catalysts, both in PLA alcoholysis and in PLA synthesis via lactide polymerisation.

Metal species other than zinc were reported as effective catalysts for PLA methanolysis. Group 4 metal complexes with salalen ligands of the formula M(ligand)(OiPr)2 (M = Ti, Zr, Hf) were used in the methanolysis reaction of PLA at room temperature with an excess of methanol and CH2Cl2 cosolvent (Scheme 11) [269,270]. A 75% yield of Me-La and residual oligomers with Mn 500 g⋅mol−1 were obtained by conversion of Mn g⋅mol−1 PLA using the hafnium derivative. As an alternative to expensive metal (complex) catalysts, methanolysis of PLA was recently described using alkali metal halides [271]. In an optimised experiment, PLA from various goods (cups, fork, spoons, containers, Mw – g⋅mol−1) was converted into Me-La in up to 97% yield using 2.5 mol % KF, 180 °C microwave heating and 23.1 equiv CH3OH. The potassium fluoride catalyst could be reused in up to three runs with no change in performance, while a 50% drop of the yield was observed afterwards.

Me-La is a low-toxic chemical used as substitute for hydrocarbon solvents, with applications in the field of paints, lacquers and cleaning agents [272,273]. It should be finally mentioned that during the alcoholysis reaction of PLA using alkoxide catalysts, alkaline earth metal adducts (typically of Ca2+) were isolated, and thus suggesting a potential involvement of the metal centre in the depolymerisation mechanism [274,275].

Hydrogenolysis. The Ru(triphos)tmm/HNTf2 catalytic system described above for the hydrogenolysis reaction of PET was also successfully applied in PLA hydrogenative depolymerisation (Scheme 12) [191]. PLA was directly converted to 1,2-propanediol in 99% yield using 1 mol % catalyst (with respect to lactic acid units) and 1,4-dioxane solvent at 140 °C and 100 bar H2. A TOF of 6.19 molPD⋅molRu−1⋅h−1 can be calculated based on this. Scale-up using PLA granulates and beverage cups was also possible using a lower catalyst loading. In addition, the method allowed for the selective recycle of equimolar mixtures of PET and PLA using the [Ru(triphos-xyl)methylallyl]NTf2 catalyst congener at 45 °C reaction temperature, wherein insoluble PET was filtered out, while PLA was fully converted to PD. Similarly to PET, the ruthenium(II)–PNN complex sketched in Table 1, entry 2 was also used in PLA hydrogenolysis to give PD in 99% yield at 160 °C, 54 bar H2 and in anisole/THF solvent [182,188]. PD is a safe chemical that is mainly produced from propylene oxide or catalytically from lactic acid intermediate, and it serves in the polymer and food industry or as antifreezing agent [276,277].

Under milder reaction conditions, PLA could be converted to the corresponding silyl ether in 92% yield, propane and silicon byproducts (8%) using the above mentioned Brookhart pincer complex [Ir(POCOP)H(THF)][B(C6F5)4] shown in Scheme 3, an excess of Et3SiH and chlorobenzene solvent at 90 °C (Scheme 13) [193]. The use of 6 equiv of 1,1,3,3-tetramethyldisiloxane (TMDS) led to the total conversion to propane and polydimethylsiloxane (PDMS), a silicon oil with several applications (lubricants, food-additives, breast implants).

3.2.3 Other polyesters: The hydrogenolysis reaction of esters other than PET and PLA was carried out using the above described soluble Ru(triphos)tmm/HNTf2 catalytic system [191]. Thus, poly(butylene terephthalate) (PBT) and polycaprolactone (PCL) were depolymerised into the corresponding (co)monomeric diols at 140 °C and 100 bar H2 in 1,4-dioxane solvent (Scheme 14). A 99% selectivity to 1,6-hexanediol was observed at full PCL conversion, whereas the selectivity to diols was only 22% for PBT (due to the formation of ethers byproducts), which could be raised to 99% by using the bulkier Ru(triphos-xyl)tmm catalyst derivative.

PCL could be converted to 1,6-hexanediol in 68% yield also through a two-step procedure involving hydrosilylation by the above mentioned cationic Ir catalyst complex [Ir(POCOP)H(THF)][B(C6F5)4] and TMDS reagent (chlorobenzene solvent, 90 °C), followed by alkaline hydrolysis (10% NaOH in CH3OH/H2O) [193]. PCL is a biodegradable polymer with a low melting point (≈60 °C) and glass transition temperature (−60 °C). It is commonly used in the manufacture of polyurethanes, to which it imparts improved solvent resistance, flexibility and toughness [278].

The glycolysis of poly(1,4-cyclohexylenedimethylene terephthalate) (PCT) was reported using DEG as reagent and zinc acetate as catalyst (0.12 mol %, Scheme 15) [279]. A 56% yield of bis(2-hydroxydiethylene terephthalate) (BHDET) was obtained at 196 °C and a DEG/PCT 15:1, w/w ratio, which was five times lower than that using PET under the same reaction conditions. This finding was attributed to the steric hindrance of the 1,4-cyclohexanedimethanol (CHDM)-based chain that hampers the transesterification process. A 90% BHDET yield was achieved using Zn(OCH3)2 catalysts under the same conditions.

Recently, a quantitatively and selectively depolymerisable novel polyester was developed based on a trans-fused six-membered γ-butyrolactone ring, 3,4-T6GBL (Scheme 16) [280]. This material joins the advantages of the ease of depolymerisation (97% monomer yield, 180 °C, toluene, 2 mol % ZnCl2 catalyst), rigid structure of the monomer (which provides the polymer with good thermal and mechanical properties) and facile synthesis (ring-opening polymerisation, solvent-free, room temperature, La, Y or Zn catalyst), significantly contributing to a closed-loop concept of plastics recycle. The approach enabled to perform the polymerisation–depolymerisation cycle over three times and on a multigram scale, using both linear and cyclic polymers. These advantages are not provided, for example, by more conventional poly(γ-butyrolactone) plastics, which require high depolymerisation temperatures (260–300 °C) and undesirable synthetic conditions (−40 °C) [281].

Following the same approach to purposely designed, chemically recyclable polymers, it was reported that poly(2-(2-hydroxyethoxybenzoate) (P2HEB) is reversibly depolymerised to 2,3-dihydro-5H-1,4-benzodioxepin-5-one (2,3-DHB) in 94% yield by an aluminium–salen catalyst at room temperature (Scheme 17) [282]. Thus, a polymerisation–depolymerisation cycle could be established using the same metal catalyst, simply by adjusting the initial monomer concentration in a one-pot process.

3.3 Polycarbonates

3.3.1 Poly(bisphenol A carbonate) (PBPAC): Bisphenol A (BPA) is a monomer for a variety of polymers widespread in our everyday life, namely polycarbonates, polyesters, polyethers, polysulphones and epoxy resins [249,283]. Particularly, PBPAC is used in the manufacture of plastics for food and beverage containers, safety helmets, optical lenses, electronic and medical equipment, phones, automotive components and toys [284,285]. This justifies for BPA to be one of the highest-volume chemicals produced worldwide, with a global market of around 6 million tons in , 68% of which account for the manufacture of polycarbonates [286,287]. However, BPA is considered a hazardous substance [288,289] and an endocrine disrupting agent [290,291]. BPA can leach from the corresponding polymers, including water- and temperature-sensitive polycarbonates [292,293]. BPA is industrially obtained by the condensation reaction of phenol with acetone, using an excess of phenol [294]. All byproducts of the process, including unreacted phenol, are toxic [295,296], whereas a purity greater than 98% is required for most BPA applications [297,298]. PBPAC is then produced by the condensation of BPA and a carbonyl source, usually phosgene or diphenyl carbonate [299,300]. Commercial PBPAC is a tough material with an average Mw of g⋅mol−1 and Tg around 150 °C. It is soluble in THF, hazardous NMP and chlorinated solvents and insoluble in alcohols and water [301]. A number of chemolytic processes have been developed in the recent years for the selective depolymerisation of PBPAC, including hydrogenolysis, hydrolysis, alcoholysis and aminolysis, some of which are metal-catalysed [302,303].

Hydrogenolysis. The hydrogenative depolymerisation of PBPAC was accomplished through the Ru–triphos molecular catalyst described above for PET, PLA, PBT and PCL polyesters [191]. Thus, use of the soluble Ru(triphos)tmm complex, in conjunction with acid HNTf2 cocatalyst (1:1) in 1,4-dioxane, resulted in complete conversion and selectivity to BPA and methanol under the moderate conditions of using 100 bar H2 at 140 °C (Scheme 18 and Table 5, entry 1). The protocol could be successfully extended to the depolymerisation of consumer goods, such as compact discs and beverage cups. Notably, pure BPA could be recovered in >70% yield after simple CH2Cl2 extraction. A similar approach was recently reported using commercially available Ru(II) catalysts, namely the Milstein [304] and the Ru–MACHO–BH [305] complexes bearing tridentate PN ligands, as shown in Table 5, entries 2 and 3, which are known as efficient hydrogenation catalysts of organic carbonates [306,307]. High BPA yields were obtained in those experiments as well, though with lower hydrogen pressure and catalyst productivity in terms of turnover frequency (molBPA⋅molRu cat.−1⋅h−1). Potassium tert-butoxide was used as cocatalyst, the role of which was speculated to activate the carbonate group of the polymer [308]. The depolymerisation of a digital versatile disc (DVD) using the latter catalyst afforded BPA in an estimated 97% yield after THF pretreatment.

Hydrolysis. The hydrolytic depolymerisation of PBPAC in hot compressed water was achieved via manganese acetate catalyst (Scheme 19, top) [309]. Under optimal conditions (280 °C, catalyst loading 2 wt %), the reaction resulted in 55% selectivity to BPA and 19% to phenol at full polymer conversion. A higher selectivity to BPA was obtained by simple Lewis acid treatment using rare earth metal triflate catalysts [310]. The process occurred in the homogeneous phase using a THF/H2O solvent mixture and a H2O/PBPAC weight ratio of ≤1. The highest BPA yield (97% at 160 °C) was observed for La(CF3SO3)3 due to the reduced decomposition of BPA to phenol, 4-isopropenylphenol and 4-isopropylphenol. A comparison with triflic acid catalyst ruled out the possibility of a proton-catalysed depolymerisation process.

Alcoholysis. A variety of metal-based catalytic systems was recently described for the alcoholysis reaction of PBPAC using diverse alcohols (Scheme 19, middle). Thus, a Lewis acid catalyst consisting of a soluble FeCl3–ionic liquid adduct, namely BmimCl·2FeCl3, was reported for the methanolysis of PBPAC, providing BPA in 97% yield at 120 °C [311]. Higher alcohols resulted in lower BPA yields. A mechanism was hypothesised in which the iron centre activates the carbonyl group of the polymer toward nucleophilic attack of methanol. The catalyst could be efficiently recovered and reused over six runs, after ethyl acetate/water extraction. On the other hand, CeO2–CaO particles onto hollow ZrO2 nanospheres were used as heterogeneous catalyst for the methanolysis of PBPAC, yielding around 95% BPA at 100 °C in a THF/methanol mixture [312]. The basic sites, due to lattice O2− of CeO2, were attributed to be responsible for the deprotonation of methanol, and thus initiating the solvolytic process in that reaction. Depolymerisation of PBPAC was reported using various alcohols (methanol, phenol, benzyl alcohol, 1-naphthol, PD, glycerol), a mechanical mixture of zinc oxide NPs and tetrabutylammonium chloride as catalyst as well as THF cosolvent to give BPA and the corresponding carbonates in >98% yield at 100 °C reaction temperature (Scheme 19) [313]. The insoluble Lewis acid ZnO catalyst could be removed from the reaction mixture by centrifugation and reused five times with a minor loss of activity. However, Bu4NCl was only partially recovered and had to be integrated with fresh cocatalyst after each run. Remarkably, the reaction with glycerol enabled the recycling of two industrial wastes (PBPAC and glycerol) into the valuable chemicals BPA and glycerol carbonate in one process only, with the latter compound being industrially used as synthetic intermediate, solvent and in the formulation of cosmetics [314].

Aminolysis. The ZnO–Bu4NCl Lewis acid catalytic mixture was also successfully used in the aminolytic depolymerisation of PBPAC by different amines (cyclohexylamine, aniline, imidazole, 1,2-diaminopropane, 1,3-diaminopropane) to give the corresponding substituted (cyclic) ureas in >97% yield (Scheme 19, bottom) [313]. The reaction with 2-amino-1-propanol gave 4-methyloxazolidin-2-one. Despite the complications due to separation from BPA, the process provides ureas of industrial relevance as anticancer or antiviral agents [315,316].

3.3.2 Poly(propylene carbonate) (PPC) and poly(ethylene carbonate) (PEC): PPC is a thermoplastic material obtained by the copolymerisation of CO2 with propylene oxide or propylenediol, which is mainly used as a packing material and in binder applications [317]. It has a low thermal stability, with a decomposition temperature around 200 °C and a Tg around 40 °C, depending on the molecular weight. PPC may be readily dissolved in many solvents (e.g., chlorinated hydrocarbons, THF, benzene, ethyl acetate and lower ketones), but it is insoluble in longer-chain alkanes, alcohols and water [318].

Hydrogenative depolymerisation of PPC and PEC to methanol and the respective glycols (PD and EG, respectively) was achieved using the soluble Milstein ruthenium catalysts described above for the hydrogenolysis of PET (Scheme 20) [188]. Thus, more than 91% glycol yield was obtained using a 1:2 Ru catalyst/butoxide molar ratio, 160 °C reaction temperature, 55 bar H2 pressure and an anisole/THF 1:1 solvent mixture (Table 6, entries 1 and 2). The same approach was adopted using a Ru(II)–PNP pincer complex, showing higher catalytic activity (TOF 41.3 h−1) under similar reaction conditions (Table 6, entry 3) [319]. The role of butoxide was proposed to be the conversion of the staring molecular complex in the catalytically active species by elimination of HCl. Similarly, a nonprecious PNN–manganese carbonyl complex was reported to afford PD from PPC in 91% yield (Table 6, entry 4) [320]. By contrast, use of a comparable Mn complex and KH as activator resulted in a much lower selectivity to PD (68%) at full PPC conversion (110 °C, 50 bar H2, in toluene), resulting in the formation of a propylene carbonate byproduct [321].

In the search of safer and “greener” alternatives, a slightly different approach to controlled PPC depolymerisation was recently proposed, based on catalytic hydrogen transfer rather than hydrogenation reaction, and thus to avoid involvement of high H2 pressures [322]. Thus, hydrogen transfer from isopropanol to PPC using a soluble iron pincer-type catalyst resulted in a 65% PD yield at 140 °C (Table 6, entry 5). However, a relatively high amount of catalyst was required. Potassium butoxide and THF were used as precatalyst activator and cosolvent, respectively.

3.3.3 Other carbonates: A polycarbonate suitable for smooth chemical recycle was engineered based on 1-benzyloxycarbonyl-3,4-epoxypyrrolidine (BEP) units [323]. In fact, a one-pot copolymerisation–depolymerisation cycle was enabled using a dinuclear salen–chromium complex in the presence of a bis(triphenylphosphine)iminium cocatalyst (Scheme 21). Therein, the BEP monomer was fully converted to the polycarbonate at 60 °C reaction temperature, while complete and selective depolymerisation back to BEP was achieved at 100 °C. The process could be repeated several times with no changes in either the monomer or the copolymer structure. After removing the catalyst, the polymer was stable at 200 °C for 10 h.

3.4 Polyamides (PA)

Polyamides may be natural (e.g., silk, wool) or synthetic polymers (e.g., nylons, aramids, polyaspartates) that are largely used in the manufacture of fibres and automotive components as well as in biomedicine, due to their excellent mechanical and thermal properties [324,325]. The widespread use of polyamides and the high price of the starting monomers, such as ε-caprolactam, have led to the development of several methods for their chemical recycling. Most of these are based on mineral acid [326], organic base (e.g., 4-dimethylaminopyridine, triethylenetetramine) [327,328] or organic acid (e.g., glycolic, lactic, benzoic acid) [329] catalysis, using supercritical methanol or ionic liquids as solvent [330]. Few literature reports exist on the depolymerisation of polyamides using metal catalysts. In an earlier paper, the hydrolysis of nylon-6 was achieved by a combination of zinc chloride (40 wt %) and phosphoric acid (20 wt %) under microwave irradiation, however, resulting in a mixture of linear and cyclic oligomers at 89% polymer conversion [121,331]. While drafting the present review, the first example of catalytic hydrogenative depolymerisation of polyamides and polyurethanes was described, using soluble Milstein-type Ru–pincer complexes (2 mol %), DMSO solvent and Kt-BuO cocatalyst at 150 °C and 70 bar H2 [332]. Typically, a selectivity to the corresponding diols/diamines/amino alcohols in the range of 20–80% was observed at 60–99% conversion, depending on the polymeric substrate. For instance, 6-amino-hexan-1-ol and BDM were obtained in 24% and 80% yield, respectively, from nylon-6 and the polyamide shown in Scheme 22.

3.5 Other plastics

3.5.1 Epoxy resins (EP): EP are thermosetting polymers featuring high thermal and chemical resistance. They are widely used in the manufacture of paints, metal coatings, electronic components and adhesives [333]. EP are usually reinforced with fibres to give composite materials for the aeronautical, automotive and sport industries. Actually, recycling efforts of EP were mainly focused on the recovery of valuable (expensive) carbon fibres rather than the polymers themselves. Recently, a metal-catalysed route was reported for the degradation of the epoxy resin of bisphenol A diglycidyl ether (BADGE)–carbon fibres composites [334]. Therein, low-coordinated aquo ions of zinc enabled the selective cleavage of the R2CH–N bond while keeping intact RCH2–N, C–C and C–O bonds (Scheme 23). The method was previously adopted for the conversion of cellulose to hydroxymethylfurfural and required the use of highly soluble zinc chloride to obtain a concentrated aqueous solution of metal (60 wt % ZnCl2) [335]. On this basis, the small, incompletely coordinated Zn2+ ions were proposed to activate the selective cleavage of C–N bonds, acting as Lewis acid centres. The process carried out at 220 °C led to carbon fibres, a dimer of DGEBA reused for the synthesis of new EP, and 4,4'-methylenebis(2-methylcyclohexanol). The concentrated ZnCl2 solution showed good reusability, and thus adding some advantages to common highly energy-consuming methods.

3.5.2 Polyethers: Polyethers are polymers with a solubility that depends heavily on the solvent used, including water, and they find applications in the cosmetic, pharmacy or paint industries [336]. Thermal decomposition or disposal into landfills are consolidated management systems of “end-of-life” polyethers [337,338], whereas very few studies cope with the catalytic depolymerisation through selective C–O bond cleavage into specific low-molecular-weight chemicals.

The group of Enthaler reported a number of research with a common strategy for polyethers depolymerisation [339-341]: Basically, the solvent-free reaction of a polyether with an acyl chloride in the presence of a catalytic amount (5 mol %) of zinc or iron salts as Lewis acid catalysts results in monomeric chloroesters, which are valuable chemicals reprocessable into other polymers (Scheme 24). A deep study was carried out investigating the effect of key reaction parameters: metal salt, catalyst loading, temperature, depolymerisation agent and the applicability to a variety of polyethers. Successful examples include depolymerisation of polyethylene glycol (PEG) and polytetrahydrofuran (polyTHF) to chloroesters in 70–78% and 92% yield, respectively, using ZnCl2 at 130 °C or Zn(OTf)2 catalyst when acetic anhydride was used as depolymerising agent [339,340]. Chloroester yields in the range 89–95% were obtained for PEG depolymerisation at 100 °C using FeCl2 as catalyst [341]. A mechanism was postulated in which the ether bond is cleaved via formation of an iron alkoxide intermediate (Scheme 25). Sustainability issues relate to the hazardous properties of low-molecular-weight acyl chlorides, which could be partially circumvented by the use of bioderived fatty acid chlorides [340].

USA1 - Composition for straightening keratin fibres, comprising a urea and/or a urea derivative and a nonionic, cationic, amphoteric or anionic associative polymeric thickener, process and use thereof - Google Patents

Composition for straightening keratin fibres, comprising a urea and/or a urea derivative and a nonionic, cationic, amphoteric or anionic associative polymeric thickener, process and use thereof Download PDF

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USA1

USA1 US14/786,608 USA USA1 US A1 US A1 US A1 US A US A US A US A1 US A1 US A1

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chosen

urea

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-04-25

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Grégory Plos

Patrice Lerda

Anne Bouchara

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LOreal SA

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-04-25 Priority claimed from FRA external-priority patent/FRB1/en

-04-25 Priority claimed from FRA external-priority patent/FRB1/en

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-07-14 Publication of USA1 publication Critical patent/USA1/en

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• 0 [1*]N([2*])C(=O)N([3*])[4*].[5*]N1*N([6*])C1=O Chemical compound [1*]N([2*])C(=O)N([3*])[4*].[5*]N1*N([6*])C1=O 0.000 description 24
• VIYHCYJLAWALFL-UHFFFAOYSA-M C.C.C=C(NC(=O)C(C)(C)C)C(=O)NC(C)(C)C.S.[H]C(CSSCC([H])(NC(=O)C(C)(C)C)C(=O)NC(C)(C)C)(NC(=O)C(C)(C)C)C(=O)NC(C)(C)C.[H]C(C[S-])(NC(=O)C(C)(C)C)C(=O)NC(C)(C)C.[OH-] Chemical compound C.C.C=C(NC(=O)C(C)(C)C)C(=O)NC(C)(C)C.S.[H]C(CSSCC([H])(NC(=O)C(C)(C)C)C(=O)NC(C)(C)C)(NC(=O)C(C)(C)C)C(=O)NC(C)(C)C.[H]C(C[S-])(NC(=O)C(C)(C)C)C(=O)NC(C)(C)C.[OH-] VIYHCYJLAWALFL-UHFFFAOYSA-M 0.000 description 1
• QQQQJNGKTNJMGO-UHFFFAOYSA-M C.C=C(NC(=O)C(C)(C)C)C(=O)NC(C)(C)C.[H]C(CSCC([H])(NC(=O)C(C)(C)C)C(=O)NC(C)(C)C)(NC(=O)C(C)(C)C)C(=O)NC(C)(C)C.[H]C(C[S-])(NC(=O)C(C)(C)C)C(=O)NC(C)(C)C Chemical compound C.C=C(NC(=O)C(C)(C)C)C(=O)NC(C)(C)C.[H]C(CSCC([H])(NC(=O)C(C)(C)C)C(=O)NC(C)(C)C)(NC(=O)C(C)(C)C)C(=O)NC(C)(C)C.[H]C(C[S-])(NC(=O)C(C)(C)C)C(=O)NC(C)(C)C QQQQJNGKTNJMGO-UHFFFAOYSA-M 0.000 description 1
• VQTUBCCKSQIDNK-UHFFFAOYSA-N C=C(C)C Chemical compound C=C(C)C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
• AMWKIVUSFMONDI-UHFFFAOYSA-N CCC(C)C(=O)NC(C)(C)CS(=O)(=O)[O-]C Chemical compound CCC(C)C(=O)NC(C)(C)CS(=O)(=O)[O-]C AMWKIVUSFMONDI-UHFFFAOYSA-N 0.000 description 1
• AVQQQNCBBIEMEU-UHFFFAOYSA-N CN(C)C(=O)N(C)C Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1

Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/87—Polyurethanes
• • A—HUMAN NECESSITIES
  • A45—HAND OR TRAVELLING ARTICLES
  • A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
  • A45D2/00—Hair-curling or hair-waving appliances ; Appliances for hair dressing treatment not otherwise provided for
  • A45D2/001—Hair straightening appliances
• • A—HUMAN NECESSITIES
  • A45—HAND OR TRAVELLING ARTICLES
  • A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
  • A45D7/00—Processes of waving, straightening or curling hair
  • A45D7/06—Processes of waving, straightening or curling hair combined chemical and thermal
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
  • A61K8/42—Amides
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/73—Polysaccharides
  • A61K8/731—Cellulose; Quaternized cellulose derivatives
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • A61K8/—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/86—Polyethers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/04—Preparations for permanent waving or straightening the hair
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K/48—Thickener, Thickening system
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K/49—Solubiliser, Solubilising system
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K/54—Polymers characterized by specific structures/properties
  • A61K/542—Polymers characterized by specific structures/properties characterized by the charge
  • A61K/—Polymers characterized by specific structures/properties characterized by the charge anionic
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K/54—Polymers characterized by specific structures/properties
  • A61K/548—Associative polymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K/59—Mixtures
  • A61K/592—Mixtures of compounds complementing their respective functions
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/12—Preparations containing hair conditioners

Definitions

• the present invention relates to a composition for the long-lasting straightening of keratin fibres, in particular of human keratin fibres such as the hair, comprising one or more compounds chosen from urea and derivatives thereof and one or more nonionic, cationic, amphoteric or anionic associative polymeric thickeners comprising one or more acrylic and/or methacrylic units.
• the present invention also relates to the use of the composition according to the invention for straightening keratin fibres, in particular human keratin fibres such as the hair.
• a subject of the present invention is a process for straightening keratin fibres, in particular human keratin fibres such as the hair, comprising a step of applying the composition according to the invention to the keratin fibres, and then a step of raising the temperature of the keratin fibres, using a heating means, to a temperature ranging from 25 to 250° C.
• the first of the techniques usually used for permanently reshaping the hair consists, in a first step, in opening the —S—S-disulfide bonds of keratin (keratocystine) using a composition containing a suitable reducing agent (reduction step), and then, after having rinsed the head of hair thus treated, generally with water, in reconstituting said disulfide bonds, in a second step, by applying to the hair, which has been placed under tension beforehand (with, for example, rollers), an oxidizing composition (oxidation step, also known as the fixing step) so as finally to give the hair the desired shape.
• This technique thus makes it possible to straighten (relax) the hair.
• the new shape given to the hair by a chemical treatment such as that above is permanent and in particular withstands washing with water or with shampoos, as opposed to the simple conventional techniques of temporary straightening, such as hairsetting.
• the reducing compositions that may be used for the first step of a permanent straightening operation generally contain sulfites, bisulfites, alkylphosphines or, preferably, thiols as reducing agents.
• sulfites bisulfites, alkylphosphines or, preferably, thiols as reducing agents.
• those commonly used are cysteine and various derivatives thereof, cysteamine and derivatives thereof, thiolactic acid or thioglycolic acid, and salts thereof and also esters thereof, especially glyceryl thioglycolate.
• the oxidizing compositions required for performing the fixing step are usually compositions based on aqueous hydrogen peroxide solution.
• this permanent straightening operation is generally performed on curly or voluminous hair so as to obtain more or less pronounced straightening and a reduction of the volume and apparent mass of the hair.
• This technique can thus induce, in the long-term, impairment of the quality of the hair, leading to a decrease in its cosmetic properties, such as its sheen, and degradation of its mechanical properties, more particularly of its mechanical strength, due to swelling of the hairs during the rinsing between the reduction step and the oxidation step, which can also be reflected by an increase in the porosity of the hairs.
• These drawbacks are especially observed with thioglycolic acid, which is generally used in basic medium at pH values ranging from 8.5 to 9.5.
• the colour obtained is very different from the colour normally obtained on non-permanent-waved natural hair.
• the second technique usually used for obtaining hair straightening or relaxing consists in performing an operation known as lanthionization, using a composition containing a base belonging to the hydroxide family. It leads to replacement of the disulfide bonds (—CH 2 —S—S—CH 2 —) with lanthionine bonds (—CH 2 —S—CH 2 —).
• This lanthionization operation involves two consecutive chemical reactions:
• the first reaction consists of a beta-elimination on the cystine caused by a hydroxide ion, resulting in the breaking of this bond and in the formation of dehydroalanine, as shown in the following reaction scheme.
• the second reaction is a reaction of the dehydroalanine with a thiol group.
• the double bond of the dehydroalanine formed is a reactive double bond. It can react with the thiol group of the cysteine residue that was released to form a new bond known as a lanthionine bridge or bond or residue. This second reaction is illustrated by the following reaction scheme.
• this lanthionization technique does not require a fixing step since the formation of the lanthionine bridges is irreversible. It is therefore performed in a single step and makes it possible without distinction either to wave the hair, or to shape or relax or straighten the hair. This technique is mainly used for shaping naturally frizzy hair.
• hydroxides employed during this process have the major drawback of being caustic. This causticity affects the scalp by causing irritation which is sometimes severe, and can also affect the condition of the hair by making it, on the one hand, rough to the touch and, on the other hand, much more brittle. The use of hydroxides can also in certain cases cause bleaching of the natural colour of the hair.
• compositions should have good working qualities, especially in terms of texture and viscosity and more particularly in terms of ease of spreading on the head of hair, of ease of blow-drying and of ease of passage of a heating device, for example flat tongs.
• a keratin fibre straightening composition comprising (a) one or more compounds chosen from urea and/or urea derivatives, (b) one or more nonionic, cationic, amphoteric polymeric associative thickeners or anionic polymeric associative thickeners comprising one or more acrylic and/or methacrylic units makes it possible to achieve the desired long-lasting straightening properties, in particular when it is combined with the use of a heating means.
• One subject of the present invention is thus a cosmetic composition
• a cosmetic composition comprising:
• nonionic, cationic, amphoteric or anionic polymeric thickeners chosen from nonionic, cationic, amphoteric or anionic associative thickening polymers, the said anionic polymeric thickener(s) comprising one or more acrylic and/or methacrylic units.
• composition according to the invention has very good cosmetic qualities and very good working qualities.
• composition according to the invention comprises:
• nonionic, cationic, amphoteric or anionic polymeric thickeners chosen from nonionic, cationic, amphoteric or anionic associative thickening polymers, the said anionic polymeric thickener(s) comprising one or more acrylic and/or methacrylic units.
• urea derivative means any compound other than urea CO(NH 2 ) 2 itself, comprising in its chemical formula a carbonyl group simply bonded to two nitrogen atoms, i.e. a unit
• the said compound(s) (a) are chosen from the compounds of formula (I) or (II), salts thereof or hydrates thereof:
• (ii) a linear or branched, cyclic or acyclic C 1 -C 5 lower alkyl or alkenyl radical, a C 1 -C 5 alkoxy radical, a C 6 -C 18 aryl radical, a 5- to 8-membered heterocyclic radical; these radicals being optionally substituted with a radical chosen from the following radicals: hydroxyl, (di)(C 1 -C 4 )(alkyl)amino such as dimethylamino, carboxyl, halogen, C 6 -C 18 aryl, carboxamide and N-methylcarboxamide;
• the said compound(s) (a) are chosen from urea and hydroxyethylurea.
• the said compound(s) (a) preferably represent from 2% to 50% by weight, more preferentially from 2% to 20% by weight, better still from 2% to 12% by weight and even better still from 2% to 10% by weight, relative to the total weight of the composition.
• composition according to the invention also comprises one or more nonionic, cationic, amphoteric associative polymeric thickeners or anionic associative polymeric thickeners comprising one or more acrylic and/or methacrylic units (b).
• thickener means compounds which, by their presence, increase the viscosity of the aqueous phase into which they are introduced by at least 20 cps and preferably by at least 50 cps, at 25° C. and at a shear rate of 1 s ⁇ 1 (the viscosity may be measured using a cone/plate viscometer, a Haake R600 rheometer or the like).
• nonionic, cationic, amphoteric associative polymeric thickeners or anionic associative polymeric thickeners comprising one or more acrylic and/or methacrylic units are preferably water-soluble or water-dispersible at a pH of 7 and at room temperature (25° C.).
• water-soluble and water-dispersible refer to a polymer which forms in water at a weight concentration of 0.1% at pH 7 and at room temperature (25° C.) a visually homogeneous (one-phase) medium.
• sociative polymer refers to polymers that are capable, in an aqueous medium, of reversibly combining with each other or with other molecules.
• Associative polymers more particularly comprise at least one hydrophilic part and at least one hydrophobic part.
• associative polymers comprise at least one hydrophobic group.
• hydrophobic group means a radical or polymer with a saturated or unsaturated, linear or branched hydrocarbon-based chain, comprising at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 18 to 30 carbon atoms.
• the hydrocarbon-based group is derived from a monofunctional compound.
• the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also denote a hydrocarbon-based polymer, for instance polybutadiene.
• the associative thickening polymers that are used according to the invention are especially chosen from:
• nonionic amphiphilic polymers comprising at least one fatty chain and at least one hydrophilic unit
• amphoteric amphiphilic polymers comprising at least one hydrophilic unit and at least one fatty-chain unit, the fatty chains containing from 10 to 30 carbon atoms.
• the nonionic associative polymers are preferably chosen from:
• the polyurethane polyethers comprise at least two hydrocarbon-based lipophilic chains containing from 8 to 30 carbon atoms, separated by a hydrophilic block, the hydrocarbon-based chains possibly being pendent chains or chains at the end of the hydrophilic block.
• the polymer may comprise a hydrocarbon-based chain at one end or at both ends of a hydrophilic block.
• the polyurethane polyethers may be multiblock, in particular in triblock form.
• the hydrophobic blocks may be at each end of the chain (for example: triblock copolymer containing a hydrophilic central block) or distributed both at the ends and in the chain (for example multiblock copolymer).
• These same polymers may also be graft polymers or star polymers.
• the nonionic fatty-chain polyurethane polyethers may be triblock copolymers in which the hydrophilic block is a polyoxyethylenated chain comprising from 50 to oxyethylene groups.
• the nonionic polyurethane polyethers comprise a urethane bond between the hydrophilic blocks, whence arises the name.
• nonionic fatty-chain polyurethane polyethers include those in which the hydrophilic blocks are linked to the lipophilic blocks via other chemical bonds.
• fatty-chain nonionic polyurethane polyethers use may also be made of Rheolate 205 containing a urea function, sold by the company Rheox, or Rheolate 208, 204 or 212, and also Acrysol RM 184, Aculyn 44 and Aculyn 46 from the company Röhm & Haas [Aculyn 46 is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of stearyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%) and water (81%); Aculyn 44 is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of decyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 35% by weight in a mixture of propylene glycol (
• the product DW B from Röhm & Haas containing a C 20 alkyl chain and a urethane bond, sold at a solids content of 20% in water, may also be used.
• Use may also be made of solutions or dispersions of these polymers, especially in water or in aqueous-alcoholic medium.
• examples of such polymers that may be mentioned are Rheolate 255, Rheolate 278 and Rheolate 244 sold by the company Rheox.
• Use may also be made of the products DW F and DW J sold by the company Röhm & Haas.
• polyurethane polyethers that may be used according to the invention are in particular those described in the article by G. Fonnum, J. Bakke and Fk. Hansen—Colloid Polym. Sci 271, 380.389 ().
• the cationic associative polymers are preferably chosen from:
• the molecule containing at least one protonated or quaternized amine function and at least one hydrophobic group.
• the only hydrophobic groups are the groups R and R′ at the chain ends.
• R and R′ both independently represent a hydrophobic group
• X and X′ both independently represent a group comprising a quaternary amine
• n and p are zero
• L, L′, Y and m have the meaning given above.
• the number-average molecular mass of the cationic associative polyurethanes is preferably between 400 and 500 000 inclusive, in particular between and 400 000 inclusive and ideally between and 300 000 inclusive.
• hydrophobic group means a radical or polymer containing a saturated or unsaturated, linear or branched hydrocarbon-based chain, which may contain one or more heteroatoms such as P, O, N or S, or a radical containing a perfluoro or silicone chain.
• hydrophobic group denotes a hydrocarbon-based radical, it comprises at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 18 to 30 carbon atoms.
• the hydrocarbon-based group is derived from a monofunctional compound.
• the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also denote a hydrocarbon-based polymer, for instance polybutadiene.
• X and/or X′ denote(s) a group comprising a tertiary or quaternary amine
• X and/or X′ may represent one of the following formulae:
• R 2 represents a linear or branched alkylene radical containing from 1 to 20 carbon atoms, optionally comprising a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, O and P;
• R 1 and R 3 which may be identical or different, denote a linear or branched C 1 -C 30 alkyl or alkenyl radical or an aryl radical, at least one of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, O and P;
• a ⁇ is a physiologically acceptable anionic counterion such as a halide, for instance chloride or bromide, or mesylate.
• the groups L, L′ and L′′ represent a group of formula:
• Z represents —O—, —S— or —NH—
• R 4 represents a linear or branched alkylene radical containing from 1 to 20 carbon atoms, optionally comprising a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, O and P.
• the groups P and P′ comprising an amine function may represent at least one of the following formulae:
• R 5 and R 7 have the same meanings as R 2 defined above;
• R 6 , R 8 and R 9 have the same meanings as R 1 and R 3 defined above;
• R 10 represents a linear or branched, optionally unsaturated alkylene group possibly containing one or more heteroatoms chosen from N, O, S and P;
• a ⁇ is a physiologically acceptable anionic counterion such as a halide, for instance chloride or bromide, or mesylate.
• hydrophilic group means a polymeric or non-polymeric water-soluble group.
• hydrophilic polymer when it is a hydrophilic polymer, in accordance with one preferred embodiment, mention may be made, for example, of polyethers, sulfonated polyesters, sulfonated polyamides or a mixture of these polymers.
• the hydrophilic compound is preferentially a polyether and especially a poly(ethylene oxide) or poly(propylene oxide).
• the cationic associative polyurethanes of formula (Ia) according to the invention are formed from diisocyanates and from various compounds bearing functions containing a labile hydrogen.
• the functions containing a labile hydrogen may be alcohol, primary or secondary amine or thiol functions, giving, after reaction with the diisocyanate functions, polyurethanes, polyureas and polythioureas, respectively.
• the term “polyurethanes” encompasses these three types of polymer, namely polyurethanes per se, polyureas and polythioureas, and also copolymers thereof.
• a first type of compound involved in the preparation of the polyurethane of formula (Ia) is a compound comprising at least one unit bearing an amine function.
• This compound may be multifunctional, but the compound is preferentially difunctional, that is to say that, according to one preferential embodiment, this compound comprises two labile hydrogen atoms borne, for example, by a hydroxyl, primary amine, secondary amine or thiol function.
• a mixture of multifunctional and difunctional compounds in which the percentage of multifunctional compounds is low may also be used.
• this compound may comprise more than one unit containing an amine function.
• it is a polymer bearing a repetition of the unit containing an amine function.
• Examples of compounds containing an amine function that may be mentioned include N-methyldiethanolamine, N-tert-butyldiethanolamine and N-sulfoethyldiethanolamine.
• the second compound included in the preparation of the polyurethane of formula (Ia) is a diisocyanate corresponding to the formula:
• methylenediphenyl diisocyanate By way of example, mention may be made of methylenediphenyl diisocyanate, methylenecyclohexane diisocyanate, isophorone diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, butane diisocyanate and hexane diisocyanate.
• a third compound involved in the preparation of the polyurethane of formula (Ia) is a hydrophobic compound intended to form the terminal hydrophobic groups of the polymer of formula (Ia).
• This compound is formed from a hydrophobic group and a function containing a labile hydrogen, for example a hydroxyl, primary or secondary amine, or thiol function.
• this compound may be a fatty alcohol such as, in particular, stearyl alcohol, dodecyl alcohol or decyl alcohol.
• this compound may be, for example, ⁇ -hydroxylated hydrogenated polybutadiene.
• the hydrophobic group of the polyurethane of formula (Ia) may also result from the quaternization reaction of the tertiary amine of the compound comprising at least one tertiary amine unit.
• the hydrophobic group is introduced via the quaternizing agent.
• This quaternizing agent is a compound of the type RQ or R′Q, in which R and R′ are as defined above and Q denotes a leaving group such as a halide, a sulfate, etc.
• the cationic associative polyurethane may also comprise a hydrophilic block.
• This block is provided by a fourth type of compound involved in the preparation of the polymer.
• This compound may be multifunctional. It is preferably difunctional. It is also possible to have a mixture in which the percentage of multifunctional compound is low.
• the functions containing a labile hydrogen are alcohol, primary or secondary amine or thiol functions. This compound may be a polymer terminated at the chain ends with one of these functions containing a labile hydrogen.
• hydrophilic polymer When it is a hydrophilic polymer, mention may be made, for example, of polyethers, sulfonated polyesters and sulfonated polyamides, or a mixture of these polymers.
• the hydrophilic compound is preferentially a polyether and especially a poly(ethylene oxide) or poly(propylene oxide).
• the hydrophilic group termed Y in formula (Ia) is optional. Specifically, the units containing a quaternary amine or protonated function may suffice to provide the solubility or water-dispersibility required for this type of polymer in an aqueous solution.
• hydrophilic group Y is optional, cationic associative polyurethanes comprising such a group are, however, preferred.
• the quaternized cellulose derivatives are, in particular:
• R and R′ which may be identical or different, represent an ammonium group such as RaRbRcN + , Q ⁇ in which Ra, Rb and Rc, which may be identical or different, represent a hydrogen atom or a linear or branched C 1 -C 30 and preferentially C 1 -C 20 alkyl group, such as methyl or dodecyl; and
• Q ⁇ represents an anionic counterion such as a halide, for instance a chloride or bromide
• n, x and y which may be identical or different, represent an integer between 1 and 10 000.
• the alkyl radicals borne by the above quaternized celluloses i) or hydroxyethylcelluloses ii) preferably comprise from 8 to 30 carbon atoms.
• the aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups.
• Examples of quaternized alkylhydroxyethylcelluloses containing C 8 -C 30 fatty chains that may be indicated include the products Quatrisoft LM 200®, Quatrisoft LM-X 529-18-A®, Quatrisoft LM-X 529-18B® (C 12 alkyl) and Quatrisoft LM-X 529-8® (C 18 alkyl) sold by the company Amerchol, and the products Crodacel QM®, Crodacel QL® (C 12 alkyl) and Crodacel QS® (C 18 alkyl) sold by the company Croda.
• R represents a trimethylammonium halide and R′ represents a dimethyldodecylammonium halide
• R′ represents a dimethyldodecylammonium halide
• R′ represents dimethyldodecylammonium chloride (CH 3 ) 2 (C 12 H 25 )N + Cl ⁇
• Polymers of this type are known under the trade name Softcat Polymer SL®, such as SL-100 and SL-60.
• the polymers of formula (Ib) are those whose viscosity is between and cPs inclusive. Preferentially, the viscosity is between and cPs inclusive.
• the said polymers comprise:
• X denotes an oxygen atom or a radical NR 6 ,
• R 1 and R 6 denote, independently of each other, a hydrogen atom or a linear or branched C 1 -C 5 alkyl radical
• R 2 denotes a linear or branched C 1 -C 4 alkyl radical
• R 3 , R 4 and R 5 denote, independently of each other, a hydrogen atom, a linear or branched C 1 -C 30 alkyl radical or a radical of formula (IIIc):
• p, q and r denote, independently of each other, either the value 0 or the value 1,
• n and n denote, independently of each other, an integer ranging from 0 to 100 inclusive
• x denotes an integer ranging from 1 to 100 inclusive
• Z denotes an anionic counterion of an organic or mineral acid, such as a halide, for instance chloride or bromide, or mesylate;
• the cationic poly(vinyllactam) polymers which may be used according to the invention may be crosslinked or noncrosslinked and may also be block polymers.
• the counterion Z ⁇ of the monomers of formula (Ic) is chosen from halide ions, phosphate ions, the methosulfate ion and the tosylate ion.
• R 3 , R 4 and R 5 denote, independently of each other, a hydrogen atom or a linear or branched C 1 -C 30 alkyl radical.
• the monomer b) is a monomer of formula (Ic) for which, even more preferentially, m and n are equal to 0.
• the vinyllactam or alkylvinyllactam monomer is preferably a compound of structure (IVc):
• s denotes an integer ranging from 3 to 6
• R 9 denotes a hydrogen atom or a linear or branched C 1 -C 5 alkyl radical
• R 10 denotes a hydrogen atom or a linear or branched C 1 -C 5 alkyl radical
• radicals R 9 and R 10 denotes a hydrogen atom.
• the monomer (IVc) is vinylpyrrolidone.
• the cationic poly(vinyllactam) polymers which may be used according to the invention may also contain one or more additional monomers, preferably cationic or nonionic monomers.
• R 3 and R 4 denote, independently of each other, a hydrogen atom or a linear or branched C 1 -C 5 alkyl radical.
• terpolymers comprising, by weight, 40% to 95% of monomer a), 0.1% to 55% of monomer c) and 0.25% to 50% of monomer b) will be used.
• cationic poly(vinyllactam) polymers which may be used according to the invention, vinylpyrrolidone/dimethylaminopropylmethacrylamide/dodecyldimethylmethacrylamidopropylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/cocoyldimethyl methacrylamidopropylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethyl methacrylamidopropylammonium tosylate or chloride terpolymers are used in particular.
• the weight-average molecular mass of the cationic poly(vinyllactam) polymers which may be used according to the present invention is preferably between 500 and 20 000 000. It is more particularly between 200 000 and 2 000 000 and even more preferentially between 400 000 and 800 000.
• amphoteric associative polymers are preferably chosen from those comprising at least one non-cyclic cationic unit. Even more particularly, the ones that are preferred are those prepared from or comprising 1 mol % to 20 mol %, preferably 1.5 mol % to 15 mol % and even more particularly 1.5 mol % to 6 mol % of fatty-chain monomer relative to the total number of moles of monomers.
• amphoteric associative polymers according to the invention comprise those that are prepared by copolymerizing:
• R 1 and R 2 which may be identical or different, represent a hydrogen atom or a methyl radical
• R 3 , R 4 and R 5 which may be identical or different, represent a linear or branched alkyl radical containing from 1 to 30 carbon atoms
• Z represents an NH group or an oxygen atom
• n is an integer from 2 to 5
• a ⁇ is an anion derived from an organic or mineral acid, such as a methosulfate anion or a halide such as chloride or bromide;
• R 6 and R 7 which may be identical or different, represent a hydrogen atom or a methyl radical
• R 6 and R 7 which may be identical or different, represent a hydrogen atom or a methyl radical
• X denotes an oxygen or nitrogen atom
• R 8 denotes a linear or branched alkyl radical containing from 1 to 30 carbon atoms
• the monomers of formulae (Va) and (Vb) of the present invention are preferably chosen from the group formed by:
• these monomers optionally being quaternized, for example with a C 1 -C 4 alkyl halide or a C 1 -C 4 dialkyl sulfate.
• the monomer of formula (Va) is chosen from acrylamidopropyltrimethylammonium chloride and methacrylamidopropyltrimethylammonium chloride.
• the monomers of formula (VI) of the present invention are preferably chosen from the group formed by acrylic acid, methacrylic acid, crotonic acid and 2-methylcrotonic acid. More particularly, the monomer of formula (VI) is acrylic acid.
• the monomers of formula (VII) of the present invention are preferably chosen from the group formed by C 12 -C 22 and more particularly C 16 -C 18 alkyl acrylates or methacrylates.
• the monomers constituting the fatty-chain amphoteric polymers of the invention are preferably already neutralized and/or quaternized.
• the ratio of the number of cationic charges/anionic charges is preferably equal to about 1.
• amphoteric associative polymers according to the invention preferably comprise from 1 mol % to 10 mol % of the monomer comprising a fatty chain (monomer of formula (Va), (Vb) or (VII)), and preferably from 1.5 mol % to 6 mol %.
• amphoteric associative polymers according to the invention may also contain other monomers such as nonionic monomers and in particular such as C 1 -C 4 alkyl acrylates or methacrylates.
• Amphoteric associative polymers according to the invention are described and prepared, for example, in patent application WO 98/.
• amphoteric associative polymers the ones that are preferred are acrylic acid/(meth)acrylamidopropyltrimethylammonium chloride/stearyl methacrylate terpolymers.
• the preferred associative polymers are chosen from nonionic and cationic polymers.
• the associative polymers of the invention are celluloses or polyurethanes, and preferably celluloses.
• the polymeric thickeners (b) that are used according to the invention may also be chosen from anionic associative polymeric thickeners containing acrylic and/or methacrylic units.
• the (meth)acrylic anionic associative thickeners that may be used according to the invention may be chosen from those comprising at least one hydrophilic unit of unsaturated olefinic carboxylic acid type, and at least one hydrophobic unit of the type such as a (C 10 -C 30 )alkyl ester of an unsaturated carboxylic acid.
• these (meth)acrylic associative thickeners are preferably chosen from those in which the hydrophilic unit of unsaturated olefinic carboxylic acid type corresponds to the monomer of formula (VIII) below:
• R 1 denotes H or CH 3 , i.e. acrylic acid or methacrylic acid units
• hydrophobic unit of (C 10 -C 30 )alkyl ester of unsaturated carboxylic acid type corresponds to the monomer of formula (IX) below:
• R 1 denotes H or CH 3 (i.e. acrylate or methacrylate units)
• R 2 denoting a C 10 -C 30 and preferably C 12 -C 22 alkyl radical.
• (C 10 -C 30 )alkyl esters of unsaturated carboxylic acids according to formula (IX) mention may be made more particularly of lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate.
• the (meth)acrylic associative thickeners that may be used according to the invention may more particularly denote polymers formed from a mixture of monomers comprising:
• R 3 denotes H or CH 3
• R 4 denoting an alkyl radical having from 12 to 22 carbon atoms
• a crosslinking agent for instance those consisting of from 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of C 10 -C 30 alkyl acrylate (hydrophobic unit), and 0 to 6% by weight of crosslinking polymerizable monomer, or 98% to 96% by weight of acrylic acid (hydrophilic unit), 1% to 4% by weight of C 10 -C 30 alkyl acrylate (hydrophobic unit) and 0.1% to 0.6% by weight of crosslinking polymerizable monomer; or
• crosslinking agent means a monomer containing a group
• crosslinking agent that may be used according to the invention, mention may be made especially of polyallyl ethers especially such as polyallyl sucrose and polyallylpentaerythritol.
• the ones most particularly preferred according to the present invention are the products sold by the company Goodrich under the trade names Pemulen TR1, Pemulen TR2, Carbopol , and more preferably still Pemulen TR1, and the product sold by the company S.E.P.C. under the name Coatex SX.
• (meth)acrylic associative thickeners mention may also be made of the copolymer of methacrylic acid/methyl acrylate/dimethyl-meta-isopropenylbenzyl isocyanate of ethoxylated alcohol sold under the name Viscophobe DB by the company Amerchol.
• (meth)acrylic associative thickeners may also be sulfonic polymers comprising at least one (meth)acrylic monomer bearing sulfonic group(s), in free form or partially or totally neutralized form and comprising at least one hydrophobic portion.
• the said hydrophobic portion present in the said sulfonic polymers that may be used according to the invention preferably comprises from 8 to 22 carbon atoms, more preferably still from 8 to 18 carbon atoms and more particularly from 12 to 18 carbon atoms.
• these sulfonic polymers that may be used according to the invention are partially or totally neutralized with a mineral base (sodium hydroxide, potassium hydroxide or aqueous ammonia) or an organic base such as mono-, di- or triethanolamine, an aminomethylpropanediol, N-methylglucamine, basic amino acids, for instance arginine and lysine, and mixtures of these compounds.
• a mineral base sodium hydroxide, potassium hydroxide or aqueous ammonia
• organic base such as mono-, di- or triethanolamine, an aminomethylpropanediol, N-methylglucamine, basic amino acids, for instance arginine and lysine, and mixtures of these compounds.
• These said sulfonic polymers generally have a number-average molecular weight ranging from to 20 000 000 g/mol, preferably ranging from 20 000 to 5 000 000 and even more preferably from 100 000 to 1 500 000 g/mol.
• the sulfonic polymers that may be used according to the invention may or may not be crosslinked.
• Crosslinked polymers are preferably chosen.
• the crosslinking agents may be selected from polyolefinically unsaturated compounds commonly used for the crosslinking of polymers obtained by free-radical polymerization. Mention may be made, for example, of divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, ethylene glycol diacrylatedi(meth)acrylate or tetraethylene glycol diacrylatedi(meth)acrylate, trimethylolpropane triacrylate, methylenebisacrylamide, methylenebismethacrylamide, triallylamine, triallyl cyanurate, diallyl maleate, tetraallylethylenediamine, tetraallyloxyethane, trimethylolpropane diallyl ether, allyl (meth)acrylate, allyl ethers of alcohols of the sugar series, or other allyl or
• Methylenebisacrylamide, allyl methacrylate or trimethylolpropane triacrylate (TMPTA) will be used more particularly.
• the degree of crosslinking will generally range from 0.01 mol % to 10 mol % and more particularly from 0.2 mol % to 2 mol % relative to the polymer.
• the (meth)acrylic monomers bearing sulfonic group(s) of the sulfonic polymers that may be used according to the invention are chosen especially from (meth)acrylamido(C 1 -C 22 )alkylsulfonic acids and N—(C 1 -C 22 )alkyl(meth)acrylamido(C 1 -C 22 )alkylsulfonic acids, for instance undecylacrylamidomethanesulfonic acid, and also partially or totally neutralized forms thereof.
• (Meth)acrylamido(C 1 -C 22 )alkylsulfonic acids for instance acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid or 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and also partially or totally neutralized forms thereof, will more preferentially be used.
• APMS 2-Acrylamido-2-methylpropanesulfonic acid
• the (meth)acrylic associative thickeners that may be used according to the invention may be chosen especially from random amphiphilic AMPS polymers modified by reaction with a C 6 -C 22 n-monoalkylamine or C 6 -C 22 di-n-alkylamine, and such as those described in patent application WO 00/ (which forms an integral part of the content of the description).
• These polymers may also contain other ethylenically unsaturated hydrophilic monomers selected, for example, from (meth)acrylic acids, ⁇ -substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.
• the (meth)acrylic associative thickeners bearing sulfonic group(s) that may particularly preferably be used according to the invention are preferably chosen from amphiphilic copolymers of AMPS and of at least one ethylenically unsaturated hydrophobic monomer comprising at least one hydrophobic portion containing from 8 to 50 carbon atoms, more preferably from 8 to 22 carbon atoms, more preferably still from 8 to 18 carbon atoms and more particularly 12 to 18 carbon atoms.
• copolymers may also contain one or more ethylenically unsaturated monomers not comprising a fatty chain, such as (meth)acrylic acids, ⁇ -substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.
• monomers not comprising a fatty chain such as (meth)acrylic acids, ⁇ -substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.
• the ethylenically unsaturated hydrophobic monomers of these particular copolymers are preferably selected from the acrylates or acrylamides of formula (XI) below:
• R 5 and R 7 which may be identical or different, denote a hydrogen atom or a linear or branched C 1 -C 6 alkyl radical (preferably methyl); Y denotes O or NH; R 6 denotes a hydrophobic hydrocarbon-based radical containing at least 8 to 50 carbon atoms, more preferentially from 8 to 22 carbon atoms, even more preferentially from 6 to 18 carbon atoms and more particularly from 12 to 18 carbon atoms; x denotes a number of moles of alkylene oxide and ranges from 0 to 100.
• the radical R 6 is preferably chosen from linear C 6 -C 18 alkyl radicals (for example n-hexyl, n-octyl, n-decyl, n-hexadecyl, n-dodecyl), or branched or cyclic C 6 -C 18 alkyl radicals (for example cyclododecane (C 12 ) or adamantane (C 10 )); C 6 -C 18 perfluoroalkyl radicals (for example the group of formula —(CH 2 ) 2 —(CF 2 ) 9 —CF 3 ); the cholesteryl radical (C 27 ) or a cholesterol ester residue, for instance the cholesteryl oxyhexanoate group; aromatic polycyclic groups such as naphthalene or pyrene.
• these radicals the ones that are more particularly preferred are linear alkyl radicals and more particularly the n-dodecyl radical.
• the monomer of formula (XI) comprises at least one alkylene oxide unit (x ⁇ 1) and preferably a polyoxyalkylene chain.
• the polyoxyalkylene chain preferentially consists of ethylene oxide units and/or propylene oxide units and even more particularly consists of ethylene oxide units.
• the number of oxyalkylene units generally ranges from 3 to 100, more preferably from 3 to 50 and more preferably still from 7 to 25.
• copolymers of totally neutralized AMPS and of dodecyl methacrylate and also crosslinked and non-crosslinked copolymers of AMPS and of n-dodecylmethacrylamide, such as those described in the Morishima articles mentioned above.
• X + is a proton, an alkali metal cation, an alkaline-earth metal cation or an ammonium ion
• x denotes an integer ranging from 3 to 100, preferably from 5 to 80 and more preferentially from 7 to 25;
• R 5 has the same meaning as that indicated above in formula (XI) and R 8 denotes a linear or branched C 6 -C 22 and more preferentially C 10 -C 22 alkyl.
• the polymers for which X + denotes sodium or ammonium are more particularly preferred.
• the nonionic, cationic, amphoteric or anionic associative polymeric thickening polymer(s) (b) may be present in the composition according to the invention in a content ranging from 0.01% to 30% by weight, preferably from 0.1% to 20% by weight and better still from 0.2% to 10% by weight relative to the total weight of the composition.
• composition according to the invention may also comprise one or more thickeners other than the associative polymeric thickeners already mentioned.
• composition according to the invention may also comprise one or more surfactants, more particularly nonionic, anionic, cationic or amphoteric surfactants.
• nonionic surfactant(s) that may be used in the cosmetic composition according to the invention are described, for example, in the Handbook of Surfactants by M. R. Porter, published by Blackie & Son (Glasgow and London), , pp. 116-178.
• They are especially chosen from alcohols, ⁇ -diols and (C 1 -C 20 )alkylphenols, these compounds being polyethoxylated, polypropoxylated and/or polyglycerolated, and containing at least one fatty chain comprising, for example, from 8 to 18 carbon atoms, it being possible for the number of ethylene oxide and/or propylene oxide groups to especially range from 2 to 50, and for the number of glycerol groups to especially range from 2 to 30.
• fatty compound for example a fatty acid
• fatty acid denotes for these surfactants a compound comprising, in its main chain, at least one saturated or unsaturated alkyl chain containing at least 6 carbon atoms, preferably from 8 to 30 carbon atoms, and better still from 10 to 22 carbon atoms.
• anionic surfactant means a surfactant comprising, as ionic or ionizable groups, only anionic groups. These anionic groups are chosen preferably from the groups CO 2 H, CO 2 ⁇ , SO 3 H, SO 3 ⁇ , OSO 3 H, OSO 3 ⁇ , O 2 PO 2 H, O 2 PO 2 H ⁇ and O 2 PO 2 2 ⁇ .
• the anionic surfactant(s) that may be used in the composition of the invention are especially chosen from alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamide sulfonates, alkylarylsulfonates, ⁇ -olefin sulfonates, paraffin sulfonates, alkylsulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfoacetates, acylsarcosinates, acylglutamates, alkylsulfosuccinamates, acylisethionates and N-acyltaurates, salts of alkyl monoesters and polyglycoside-polycarbox
• Some of these compounds may be oxyethylenated and then preferably comprise from 1 to 50 ethylene oxide units.
• the salts of C 6 -C 24 alkyl monoesters of polyglycoside-polycarboxylic acids may be chosen from C 6 -C 24 alkyl polyglycoside-citrates, C 6 -C 24 alkyl polyglycoside-tartrates and C 6 -C 24 alkyl polyglycoside-sulfo succinates.
• anionic surfactant(s) are in salt form, they are not in the form of zinc salts, and they may be chosen from alkali metal salts, such as the sodium or potassium salt, and preferably the sodium salt, ammonium salts, amine salts, and in particular amino alcohol salts, and alkaline-earth metal salts such as the magnesium salt.
• amino alcohol salts examples include monoethanolamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2-amino-2-methyl-1-propanol salts, 2-amino-2-methyl-1,3-propanediol salts and tris(hydroxymethyl)aminomethane salts.
• Alkali metal or alkaline-earth metal salts and in particular the sodium or magnesium salts are preferably used.
• Use is preferably made of (C 6 -C 24 )alkyl sulfates, (C 6 -C 24 )alkyl ether sulfates, which are optionally ethoxylated, comprising from 2 to 50 ethylene oxide units, and mixtures thereof, in particular in the form of alkali metal salts or alkaline-earth metal salts, ammonium salts or amino alcohol salts. More preferentially, the anionic surfactant(s) are chosen from (C 10 -C 20 )alkyl ether sulfates, and in particular sodium lauryl ether sulfate containing 2.2 mol of ethylene oxide.
• cationic surfactant means a surfactant that is positively charged when it is contained in the composition according to the invention. This surfactant may bear one or more positive permanent charges or may contain one or more functions that are cationizable in the composition according to the invention.
• the cationic surfactant(s) are preferably selected from primary, secondary or tertiary fatty amines, optionally polyoxyalkylenated, or salts thereof, and quaternary ammonium salts, and mixtures thereof.
• the fatty amines generally comprise at least one C 8 -C 30 hydrocarbon-based chain.
• examples that may be mentioned include stearylamidopropyldimethylamine and distearylamine.
• quaternary ammonium salts examples include:
• the groups R 8 to R 11 which may be identical or different, represent a linear or branched aliphatic group containing from 1 to 30 carbon atoms, or an aromatic group such as aryl or alkylaryl, at least one of the groups R 8 to R 11 denoting a group containing from 8 to 30 carbon atoms, preferably from 12 to 24 carbon atoms.
• the aliphatic groups may comprise heteroatoms especially such as oxygen, nitrogen, sulfur and halogens.
• the aliphatic groups are chosen, for example, from C 1 -C 30 alkyl, C 2 -C 30 alkenyl, C 1 -C 30 alkoxy, polyoxy(C 2 -C 6 )alkylene, C 1 -C 30 alkylamide, (C 12 -C 22 )alkylamido(C 2 -C 6 )alkyl, (C 12 -C 22 )alkyl acetate and C 1 -C 30 hydroxyalkyl groups;
• X ⁇ is an anion chosen from the group of halides, phosphates, acetates, lactates, (C 1 -C 4 )alkyl sulfates, and (C 1 -C 4 )alkyl- or (C 1 -C 4 )alkylarylsulfonates.
• quaternary ammonium salts of formula (XIV) those that are preferred are, on the one hand, tetraalkylammonium salts, for instance dialkyldimethylammonium or alkyltrimethylammonium salts in which the alkyl group contains approximately from 12 to 22 carbon atoms, in particular behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium or benzyldimethylstearylammonium salts, or, on the other hand, palmitylamidopropyltrimethylammonium salts, stearamidopropyltrimethylammonium salts and stearamidopropyldimethylcetearylammonium salts. It is particularly preferred to use the chloride salts of these compounds.
• R 12 represents an alkenyl or alkyl group comprising from 8 to 30 carbon atoms, derived for example from tallow fatty acids
• R 13 represents a hydrogen atom, a C 1 -C 4 alkyl group or an alkyl or alkenyl group comprising from 8 to 30 carbon atoms
• R 14 represents a C 1 -C 4 alkyl group
• R 15 represents a hydrogen atom or a C 1 -C 4 alkyl group
• X ⁇ is an anion chosen from the group of halides, phosphates, acetates, lactates, alkyl sulfates, alkyl- or alkylaryl-sulfonates in which the alkyl and aryl groups preferably comprise, respectively, from 1 to 20 carbon atoms and from 6 to 30 carbon atoms.
• R 12 and R 13 preferably denote a mixture of alkenyl or alkyl groups containing from 12 to 21 carbon atoms, derived for example from tallow fatty acids, R 14 preferably denotes a methyl group, and R 15 preferably denotes a hydrogen atom.
• R 12 and R 13 preferably denote a mixture of alkenyl or alkyl groups containing from 12 to 21 carbon atoms, derived for example from tallow fatty acids
• R 14 preferably denotes a methyl group
• R 15 preferably denotes a hydrogen atom.
• Such a product is sold, for example, under the name Rewoquat® W 75 by the company Rewo;
• R 16 denotes an alkyl radical comprising approximately from 16 to 30 carbon atoms, which is optionally hydroxylated and/or interrupted with one or more oxygen atoms
• R 17 is chosen from hydrogen or an alkyl radical comprising from 1 to 4 carbon atoms or a group (R 16a )(R 17a )(R 18a )N—(CH 2 ) 3 ;
• R 16a , R 17a , R 18a , R 18 , R 19 , R 20 and R 21 which may be identical or different, are chosen from hydrogen and an alkyl radical comprising from 1 to 4 carbon atoms, and X ⁇ is an anion chosen from the group of halides, acetates, phosphates, nitrates and methyl sulfates.
• Such compounds are, for example, Finquat CT-P, sold by the company Finetex (Quaternium 89), and Finquat CT, sold by the company Finetex (Quaternium 75),
• R 22 is chosen from C 1 -C 6 alkyl groups and C 1 -C 6 hydroxyalkyl or dihydroxyalkyl groups;
• R 23 is chosen from:
• R 25 is chosen from:
• R 24 , R 26 and R 28 which may be identical or different, are chosen from linear or branched, saturated or unsaturated C 7 -C 21 hydrocarbon-based groups;
• r, s and t which may be identical or different, are integers ranging from 2 to 6;
• y is an integer ranging from 1 to 10;
• x and z which may be identical or different, are integers ranging from 0 to 10;
• X— is a simple or complex, organic or mineral anion
• the alkyl groups R 22 may be linear or branched, and more particularly linear.
• R 22 denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl group, and more particularly a methyl or ethyl group.
• the sum x+y+z is from 1 to 10.
• R 23 is a hydrocarbon-based group R 27 , it may be long and contain from 12 to 22 carbon atoms, or may be short and contain from 1 to 3 carbon atoms.
• R 25 is an R 29 hydrocarbon-based group, it preferably contains 1 to 3 carbon atoms.
• R 24 , R 26 and R 28 which may be identical or different, are chosen from linear or branched, saturated or unsaturated C 11 -C 21 hydrocarbon-based groups, and more particularly from linear or branched, saturated or unsaturated C 11 -C 21 alkyl and alkenyl groups.
• x and z which may be identical or different, are equal to 0 or 1.
• y is equal to 1.
• r, s and t which may be identical or different, are equal to 2 or 3, and even more particularly are equal to 2.
• the anion X ⁇ is preferably a halide (chloride, bromide or iodide) or an alkyl sulfate, more particularly methyl sulfate.
• halide chloride, bromide or iodide
• alkyl sulfate more particularly methyl sulfate.
• methanesulfonate, phosphate, nitrate, tosylate an anion derived from an organic acid, such as acetate or lactate, or any other anion compatible with the ammonium containing an ester function.
• the anion X ⁇ is even more particularly chloride or methyl sulfate.
• R 22 denotes a methyl or ethyl group
• x and y are equal to 1;
• z is equal to 0 or 1;
• r, s and t are equal to 2;
• R 23 is chosen from:
• R 25 is chosen from:
• R 24 , R 26 and R 28 which may be identical or different, are chosen from linear or branched, saturated or unsaturated C 13 -C 17 hydrocarbon-based groups, and preferably from linear or branched, saturated or unsaturated C 13 -C 17 alkyl and alkenyl groups.
• hydrocarbon-based groups are advantageously linear.
• acyl groups preferably contain 14 to 18 carbon atoms and are obtained more particularly from a plant oil, such as palm oil or sunflower oil. When the compound contains several acyl groups, these groups may be identical or different.
• These products are obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, an alkyldiethanolamine or an alkyldiisopropanolamine, which are optionally oxyalkylenated, with C 10 -C 30 fatty acids or with mixtures of C 10 -C 30 fatty acids of plant or animal origin, or by transesterification of the methyl esters thereof.
• This esterification is followed by quaternization using an alkylating agent such as an alkyl (preferably methyl or ethyl) halide, a dialkyl (preferably methyl or ethyl) sulfate, methyl methanesulfonate, methyl para-toluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.
• an alkylating agent such as an alkyl (preferably methyl or ethyl) halide, a dialkyl (preferably methyl or ethyl) sulfate, methyl methanesulfonate, methyl para-toluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.
• Such compounds are, for example, sold under the names Dehyquart® by the company Henkel, Stepanquat® by the company Stepan, Noxamium® by the company Ceca or Rewoquat® WE 18 by the company Rewo-Witco.
• composition according to the invention may contain, for example, a mixture of quaternary ammonium monoester, diester and triester salts with a weight majority of diester salts.
• ammonium salts containing at least one ester function that are described in U.S. Pat. No. 4,874,554 and U.S. Pat. No. 4,137,180.
• Use may be made of behenoylhydroxypropyltrimethylammonium chloride, provided by Kao under the name Quatarmin BTC 131.
• the ammonium salts containing at least one ester function contain two ester functions.
• quaternary ammonium salts containing at least one ester function which may be used according to the invention, it is preferred to use dipalmitoylethylhydroxyethylmethylammonium salts.
• amphoteric or zwitterionic surfactant(s) that may be used in the present invention may especially be secondary or tertiary aliphatic amine derivatives, optionally quaternized, in which the aliphatic group is a linear or branched chain containing from 8 to 22 carbon atoms, the said amine derivatives containing at least one anionic group, for instance a carboxylate, sulfonate, sulfate, phosphate or phosphonate group.
• Ra represents a C 10 -C 30 alkyl or alkenyl group derived from an acid RaCOOH preferably present in hydrolysed coconut oil, or a heptyl, nonyl or undecyl group;
• Rb represents a beta-hydroxyethyl group
• Rc represents a carboxymethyl group
• M + represents a cationic counterion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine;
• X ⁇ represents an organic or mineral anionic counterion, preferably chosen from halides, acetates, phosphates, nitrates, (C 1 -C 4 )alkyl sulfates, (C 1 -C 4 )alkyl or (C 1 -C 4 )alkylaryl sulfonates, in particular methyl sulfate and ethyl sulfate;
• n 0, 1 or 2;
• Z represents a hydrogen atom or a hydroxyethyl or carboxymethyl group
• B represents the group —CH 2 —CH 2 —O—X′
• X′ represents the group —CH 2 —C(O)OH, —CH 2 —C(O)OZ′, —CH 2 —CH 2 —C(O)OH, —CH 2 —CH 2 —C(O)OZ′, or a hydrogen atom;
• Y′ represents the group —C(O)OH, —C(O)OZ′, —CH 2 —CH(OH)—SO 3 H or the group —CH 2 —CH(OH)—SO 3 —Z′;
• Z′ represents a cationic counterion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine;
• Ra′ represents a C 10 -C 30 alkyl or C 10 -C 30 alkenyl group of an acid Ra′—COOH, which is preferably present in coconut oil or in hydrolysed linseed oil, or an alkyl group, especially a C 17 alkyl group and its iso form, or an unsaturated C 17 group.
• n′ is equal to 0, 1 or 2
• Z represents a hydrogen atom or a hydroxyethyl or carboxymethyl group.
• the compounds of this type are classified in the CTFA dictionary, 5th edition, , under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate, disodium capryloamphodipropionate, lauroamphodipropionic acid, cocoamphodipropionic acid and hydro xyethylcarbo xymethylcocamidopropylamine.
• Examples that may be mentioned include the cocoamphodiacetate sold by the company Rhodia under the trade name Miranol® C2M Concentrate or under the trade name Miranol Ultra C 32 and the product sold by the company Chimex under the trade name Chimexane HA.
• Y′′ represents the group —C(O)OH, —C(O)OZ′′, —CH 2 —CH(OH)—SO 3 H or the group CH 2 —CH(OH)—SO 3 —Z′′;
• Rd and Re independently of each other, represent a C 1 -C 4 alkyl or hydroxyalkyl radical
• Z′′ represents a cationic counterion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine;
• Ra′′ represents a C 10 -C 30 alkyl or alkenyl group of an acid Ra′′—C(O)OH which is preferably present in coconut oil or in hydrolysed linseed oil;
• n and n′ denote, independently of each other, an integer ranging from 1 to 3.
• amphoteric or zwitterionic surfactants it is preferred to use (C 8 -C 20 alkyl)betaines such as cocoylbetaine, (C 8 -C 20 alkyl)amido(C 2 -C 8 alkyl)betaines such as cocoylamidopropylbetaine, and mixtures thereof.
• amphoteric or zwitterionic surfactant(s) are chosen from cocoylamidopropylbetaine and cocoylbetaine.
• the surfactants used in the composition according to the invention are preferably nonionic or cationic.
• the surfactant(s) may be present in an amount ranging from 0.01% to 30% by weight, preferably from 0.1% to 10% by weight and better still from 1% to 5% by weight relative to the total weight of the composition.
• composition according to the invention advantageously comprises water, which advantageously represents from 1% to 95%, preferably from 20% to 80% and better still from 40% to 70% by weight relative to the total weight of the composition.
• composition according to the invention may also comprise one or more fatty substances.
• fatty substance means an organic compound that is insoluble in water at ordinary room temperature (25° C.) and at atmospheric pressure (760 mmHg), with a solubility in water of less than 5%, preferably less than 1% and even more preferentially less than 0.1%.
• the fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance chloroform, ethanol, benzene, liquid petroleum jelly or decamethylcyclopentasiloxane.
• the said fatty substance(s) that may be used in the composition according to the invention are preferably chosen from hydrocarbons, fatty alcohols, fatty acid and/or fatty alcohol esters, non-salified fatty acids, silicones and mixtures thereof.
• the fatty substance(s) may be liquid or non-liquid at room temperature and at atmospheric pressure.
• the said fatty substance(s) may represent from 0.001% to 90% by weight, better still from 0.1% to 50% by weight, preferably from 0.5% to 30% by weight and better still from 1% to 20% by weight, relative to the total weight of the composition.
• composition may also comprise one or more water-soluble organic solvents (solubility of greater than or equal to 5% in water at 25° C. and at atmospheric pressure).
• water-soluble organic solvents examples include linear or branched and preferably saturated monoalcohols or diols, comprising 2 to 10 carbon atoms, such as ethyl alcohol, isopropyl alcohol, hexylene glycol (2-methyl-2,4-pentanediol), neopentyl glycol and 3-methyl-1,5-pentanediol, butylene glycol, dipropylene glycol and propylene glycol; aromatic alcohols such as phenylethyl alcohol; polyols containing more than two hydroxyl functions, such as glycerol; polyol ethers, for instance ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol or ethers thereof, for instance propylene glycol monomethyl ether; and also diethylene glycol alkyl ethers, especially C 1 -C 4 alkyl ethers, for instance diethylene glycol monoethyl ether
• the water-soluble organic solvents when they are present, generally represent between 1% and 20% by weight relative to the total weight of the composition according to the invention, and preferably between 5% and 10% by weight relative to the total weight of the composition.
• composition according to the invention may also contain one or more additives chosen from the active principles and cosmetic adjuvants commonly used in the field of haircare.
• additives are chosen, for example, from fixing polymers other than the thickening polymers already mentioned, conditioning agents and especially cationic polymers, silicones, chitosans and derivatives, hydrophobic solvents, hair dyes such as direct dyes, in particular cationic or natural dyes, oxidation dyes and pigments; UV-screening agents, fillers such as nacres, titanium dioxide, resins and clays; fragrances, peptizers, vitamins, preserving agents, acidic agents, alkaline agents, reducing agents, oxidizing agents, amino acids, oligopeptides, peptides, hydrolysed or non-hydrolysed, modified or unmodified proteins, enzymes, organic acids, antioxidants and free-radical scavengers, chelating agents, antidandruff agents, seborrhoea regulators, calmatives, plasticizers,
• the above additives may be present in an amount ranging from 0.01% to 20% by weight relative to the total weight of the composition according to the invention.
• composition according to the invention may be in the form of a wax, a paste, a cream, a gel, a foam, a spray or a lotion.
• a subject of the present invention is also the use of the composition as defined according to the invention for straightening keratin fibres, preferably the hair.
• a subject of the invention is also a process for straightening keratin fibres, preferably the hair, comprising:
• the temperature is raised by means of the said heating means to a temperature ranging from 100 to 250° C. and better still from 150 to 230° C.
• the composition according to the invention is applied to a wet or dry head of hair, preferably wet hair, with or without a leave-on time.
• the bath ratio of the applied formulation may range from 0.1 to 10 and more particularly from 0.2 to 5.
• the keratin fibres are then optionally rubbed dry, preferably rubbed dry.
• One or more heating means are applied once or in succession to the keratin fibres at a temperature ranging from 25 to 250° C., preferably from 100 to 250° C. and better still from 150 to 230° C. for a time ranging from 5 seconds to 1 hour and preferably from 5 seconds to 1 minute.
• the hair then optionally undergoes one or more of the following operations: rinsing, shampooing and treatment with a rinse-out hair conditioner, drying, preferably using a hood or a hairdryer.
• the said leave-on time is preferably from 5 minutes to 1 hour.
• bath ratio means the ratio between the total weight of the applied composition and the total weight of keratin fibres to be treated.
• Heating means that may especially be used include a straightening iron, a curling iron, a crimping iron, a waving iron, a hood, a hairdryer, an infrared heating system or a heating roller (of the digital perm type).
• the heating means is preferably an iron.
• compositions 1 to 2 for straightening keratin fibres according to the invention are prepared, along with a control composition not containing any thickener according to the invention.
• the formulations are indicated in Table I (the amounts are expressed as weight percentages relative to the total weight of the composition).
• compositions 1 and 2 and the control composition are applied to locks of moderately curly hair (curliness level 3 according to the article Shape variability and classification of human hair , Roland De La Mettrie et al., Human Biology, , vol. 79, No. 3, pages 265-281) according to the following protocol:
• the keratin fibres are prewashed with a shampoo.
• compositions are applied to a separate wet lock. The excess product is then removed by rubbing dry.
• the locks are then predried with a hairdryer.
• a straightening iron is then applied slowly along the locks twice in succession at a temperature of 210° C. (for about 1 minute).
• the locks are then shampooed and are finally dried using a hairdryer.
• the Applicant finds that the straightening of the hair for the two compositions according to the invention and the control composition is persistent.
• the Applicant finds that the working qualities in terms of ease of distribution onto the head of hair, the ease of blow-drying and the ease of passage of flat tongs are greater in the case of compositions 1 and 2 according to the invention relative to the control composition.
• compositions 1 and 2 according to the invention afford the hair greater sheen and cosmeticity than the control composition.
• Composition 3 for straightening keratin fibres according to the invention is prepared, along with a control composition not containing any thickener according to the invention.
• the formulations are indicated in Table II (the amounts are expressed as weight percentages relative to the total weight of the composition).
• Composition 3 and the control composition are applied to locks of moderately curly hair (curliness level 3 according to the article Shape variability and classification of human hair , Roland De La Mettrie et al., Human Biology, , vol. 79, No. 3, pages 265-281) according to the following protocol:
• the keratin fibres are prewashed with a shampoo.
• compositions are applied to a separate wet lock. The excess product is then removed by rubbing dry.
• the locks are then predried with a hairdryer.
• a straightening iron is then applied slowly along the locks twice in succession at a temperature of 210° C. (for about 1 minute).
• the locks are then shampooed and are finally dried using a hairdryer.
• the Applicant finds that the straightening of the hair for composition 3 according to the invention and the control composition is persistent.
• the Applicant finds that the working qualities in terms of ease of distribution onto the head of hair, the ease of blow-drying and the ease of passage of flat tongs are greater in the case of composition 3 according to the invention relative to the control composition.
• composition 3 according to the invention affords the hair greater sheen and cosmeticity than the control composition.

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Abstract

The invention relates to a cosmetic composition comprising: (a) at least 2% by weight, relative to the total weight of the composition, of one or more compounds chosen from urea and/or urea derivatives, (b) one or more polymeric thickeners chosen from nonionic, cationic, amphoteric polymeric associative thickeners or anionic polymeric associative thickeners comprising one or more acrylic and/or methacrylic units. The invention also relates to the use of this composition for straightening keratin fibres. Finally, the invention relates to a process for straightening keratin fibres.

Description

• The present invention relates to a composition for the long-lasting straightening of keratin fibres, in particular of human keratin fibres such as the hair, comprising one or more compounds chosen from urea and derivatives thereof and one or more nonionic, cationic, amphoteric or anionic associative polymeric thickeners comprising one or more acrylic and/or methacrylic units.
• The present invention also relates to the use of the composition according to the invention for straightening keratin fibres, in particular human keratin fibres such as the hair.
• Finally, a subject of the present invention is a process for straightening keratin fibres, in particular human keratin fibres such as the hair, comprising a step of applying the composition according to the invention to the keratin fibres, and then a step of raising the temperature of the keratin fibres, using a heating means, to a temperature ranging from 25 to 250° C.
• Many people are dissatisfied with the appearance of their hair; in particular, people who have curly hair usually wish to obtain straight hair, and, conversely, people who have curl-free hair wish to have curly hair.
• The first of the techniques usually used for permanently reshaping the hair consists, in a first step, in opening the —S—S-disulfide bonds of keratin (keratocystine) using a composition containing a suitable reducing agent (reduction step), and then, after having rinsed the head of hair thus treated, generally with water, in reconstituting said disulfide bonds, in a second step, by applying to the hair, which has been placed under tension beforehand (with, for example, rollers), an oxidizing composition (oxidation step, also known as the fixing step) so as finally to give the hair the desired shape. This technique thus makes it possible to straighten (relax) the hair. The new shape given to the hair by a chemical treatment such as that above is permanent and in particular withstands washing with water or with shampoos, as opposed to the simple conventional techniques of temporary straightening, such as hairsetting.
• The reducing compositions that may be used for the first step of a permanent straightening operation generally contain sulfites, bisulfites, alkylphosphines or, preferably, thiols as reducing agents. Among the latter, those commonly used are cysteine and various derivatives thereof, cysteamine and derivatives thereof, thiolactic acid or thioglycolic acid, and salts thereof and also esters thereof, especially glyceryl thioglycolate.
• The oxidizing compositions required for performing the fixing step are usually compositions based on aqueous hydrogen peroxide solution.
• In the context of hair straightening techniques, this permanent straightening operation is generally performed on curly or voluminous hair so as to obtain more or less pronounced straightening and a reduction of the volume and apparent mass of the hair.
• However, such a technique is not entirely satisfactory. This is because, although this technique proves to be very effective for modifying the shape of the hair, it still degrades the hair fibres, which is mainly due to the high contents of reducing agents used in the reducing compositions and also to the various more or less long leave-on times that may be involved in such a process.
• This technique can thus induce, in the long-term, impairment of the quality of the hair, leading to a decrease in its cosmetic properties, such as its sheen, and degradation of its mechanical properties, more particularly of its mechanical strength, due to swelling of the hairs during the rinsing between the reduction step and the oxidation step, which can also be reflected by an increase in the porosity of the hairs. These drawbacks are especially observed with thioglycolic acid, which is generally used in basic medium at pH values ranging from 8.5 to 9.5.
• Moreover, if the technique of permanent straightening of the hair described previously is applied to hair that has undergone prior artificial coloration, it usually leads to degradation or stripping of this artificial coloration.
• Similarly, if a coloration is applied to permanent-waved hair according to the technique described previously, the colour obtained is very different from the colour normally obtained on non-permanent-waved natural hair.
• It has also been observed that the use of reducing agents results in an unsatisfactory durability for the straightening of the hair, in particular for the relaxing or defrizzing of the hair.
• Moreover, it has also been found that the use of these reducing agents leads to scalp discomfort (irritation, itching, etc.).
• Finally, it is very common to have to deal with problems of odours, both with the reducing compositions used, and in particular those containing thiols, and with the hair reduced.
• The second technique usually used for obtaining hair straightening or relaxing consists in performing an operation known as lanthionization, using a composition containing a base belonging to the hydroxide family. It leads to replacement of the disulfide bonds (—CH2—S—S—CH2—) with lanthionine bonds (—CH2—S—CH2—). This lanthionization operation involves two consecutive chemical reactions:
• The first reaction consists of a beta-elimination on the cystine caused by a hydroxide ion, resulting in the breaking of this bond and in the formation of dehydroalanine, as shown in the following reaction scheme.
• The second reaction is a reaction of the dehydroalanine with a thiol group. Specifically, the double bond of the dehydroalanine formed is a reactive double bond. It can react with the thiol group of the cysteine residue that was released to form a new bond known as a lanthionine bridge or bond or residue. This second reaction is illustrated by the following reaction scheme.
• Compared with the first technique previously described, using a reducing agent, this lanthionization technique does not require a fixing step since the formation of the lanthionine bridges is irreversible. It is therefore performed in a single step and makes it possible without distinction either to wave the hair, or to shape or relax or straighten the hair. This technique is mainly used for shaping naturally frizzy hair.
• However, the hydroxides employed during this process have the major drawback of being caustic. This causticity affects the scalp by causing irritation which is sometimes severe, and can also affect the condition of the hair by making it, on the one hand, rough to the touch and, on the other hand, much more brittle. The use of hydroxides can also in certain cases cause bleaching of the natural colour of the hair.
• There is thus a real need to find novel compositions and to implement processes for the long-lasting straightening of keratin fibres, in particular human keratin fibres such as the hair, which do not have the set of drawbacks described above, i.e. which do not involve the use of alkaline active agents or reducing agents, and which afford long-lasting straightening of keratin fibres, while at the same time giving satisfactory capillary properties especially in terms of sheen and cosmeticity.
• Furthermore, such compositions should have good working qualities, especially in terms of texture and viscosity and more particularly in terms of ease of spreading on the head of hair, of ease of blow-drying and of ease of passage of a heating device, for example flat tongs.
• The Applicant has now found that the use of a keratin fibre straightening composition comprising (a) one or more compounds chosen from urea and/or urea derivatives, (b) one or more nonionic, cationic, amphoteric polymeric associative thickeners or anionic polymeric associative thickeners comprising one or more acrylic and/or methacrylic units makes it possible to achieve the desired long-lasting straightening properties, in particular when it is combined with the use of a heating means.
• One subject of the present invention is thus a cosmetic composition comprising:
• (a) at least 2% by weight, relative to the total weight of the composition, of one or more compounds chosen from urea and/or urea derivatives,
• (b) one or more nonionic, cationic, amphoteric or anionic polymeric thickeners chosen from nonionic, cationic, amphoteric or anionic associative thickening polymers, the said anionic polymeric thickener(s) comprising one or more acrylic and/or methacrylic units.
• The application to keratin fibres of this composition according to the present invention followed by the use of a heating means, at a temperature ranging from 25 to 250° C. in particular affords long-lasting straightening of keratin fibres without, however, having the drawbacks of straightening using strong alkaline agents or reducing agents.
• Furthermore, the composition according to the invention has very good cosmetic qualities and very good working qualities.
• Other characteristics and advantages of the invention will emerge more clearly on reading the description and the examples that follow.
• As indicated previously, the composition according to the invention comprises:
• (a) at least 2% by weight, relative to the total weight of the composition, of one or more compounds chosen from urea and/or urea derivatives,
• (b) one or more nonionic, cationic, amphoteric or anionic polymeric thickeners chosen from nonionic, cationic, amphoteric or anionic associative thickening polymers, the said anionic polymeric thickener(s) comprising one or more acrylic and/or methacrylic units.
• The term “urea derivative” means any compound other than urea CO(NH2)2 itself, comprising in its chemical formula a carbonyl group simply bonded to two nitrogen atoms, i.e. a unit
• Preferably, the said compound(s) (a) are chosen from the compounds of formula (I) or (II), salts thereof or hydrates thereof:
• in which:
• • R1, R2, R3 and R4 represent, independently:
• (i) a hydrogen atom or
• (ii), a linear or branched, cyclic or acyclic C1-C5 lower alkyl or alkenyl radical, a C1-C5 alkoxy radical, a C6-C18 aryl radical, a 5- to 8-membered heterocyclic radical; these radicals being optionally substituted with a radical chosen from the following radicals: hydroxyl, (di)(C1-C4)(alkyl)amino such as dimethylamino, carboxyl, halogen, C6-C18 aryl, carboxamide and N-methylcarboxamide;
• it being understood that:
• • when R1, R2 and R3 represent a hydrogen atom, R4 may denote a carboxamide, methoxy, ethoxy, 1,2,4-triazolyl, cyclopentyl, (C1-C6)alkylcarbonyl such as acetyl, or (C1-C6)alkoxycarbonyl radical such as methoxycarbonyl or ethoxycarbonyl, —CO—CH═CH—COOH, phenyl optionally substituted with a chlorine atom or a hydroxyl, benzyl or 2,5-dioxo-4-imidazolidinyl radical;
  • when R1 and R3 represent a hydrogen atom, R2 may represent a hydrogen atom or a methyl or ethyl radical and R4 may represent an acetyl radical;
  • when R1=R2=H, R3 and R4 can form, with the nitrogen atom that bears them, a piperidine, 3-methylpyrazole, 3,5-dimethylpyrazole or maleimide ring;
  • R1 and R2 and also R3 and R4 can form, with the nitrogen atom that bears them, an imidazole ring;
  • R5 and R6 represent, independently of each other:
• (iii) a hydrogen atom or
• (iv) a linear or branched, cyclic or acyclic C1-C5 lower alkyl, acyl or alkenyl radical, a C1-C5 alkoxy radical, a C6-C18 aryl radical, a 5- to 8-membered heterocyclic radical; these radicals being optionally substituted with a radical chosen from the following radicals: hydroxyl, amino, dimethylamino, carboxyl, halogen, C6-C18 aryl, carboxamide and N-methylcarboxamide;
• • A is a radical chosen from the following radicals: CH2—CH2, CH═CH, CH2—CO, CO—NH, CH═N, CO—CO, CHOH—CHOH, (HOOC)CH—CH, CHOH—CO, CH2—CH2—CH2, CH2—NH—CO, CH═C(CH3)—CO, NH—CO—NH, CH2—CH2—CO, CH2—N(CH3)—CH2, NH—CH2—NH, CO—CH(CH3)—CH2, CO—CH2—CO, CO—NH—CO, CO—CH(COOH)—CH2, CO—CH═C(COOH), CO—CH═C(CH3), CO—C(NH2)═CH, CO—C(CH3)═N, CO—CH═CH, CO—CH═N and CO—N═CH.
• Among the compounds of formula (I) that are particularly preferred according to the invention, mention may be made of:
• urea
• methylurea
• ethylurea
• propylurea
• n-butylurea
• sec-butylurea
• isobutylurea
• tert-butylurea
• cyclopentylurea
• ethoxyurea
• hydroxyethylurea
• N-(2-hydroxypropyl)urea
• N-(3-hydroxypropyl)urea
• N-(2-dimethylaminopropyl)urea
• N-(3-dimethylaminopropyl)urea
• 1-(3-hydroxyphenyl)urea
• benzylurea
• N-carbamoylmaleamide
• N-carbamoylmaleamic acid
• piperidinecarboxamide
• 1,2,4-triazol-4-ylurea
• hydantoic acid
• methyl allophanate
• ethyl allophanate
• acetylurea
• hydroxyethyleneurea
• 2-(hydroxyethyl)ethyleneurea
• diallylurea
• chloroethylurea
• N,N-dimethylurea
• N,N-diethylurea
• N,N-dipropylurea
• cyclopentyl-1-methylurea
• 1,3-dimethylurea
• 1,3-diethylurea
• 1,3-bis(2-hydroxyethyl)urea
• 1,3-bis(2-hydroxypropyl)urea
• 1,3-bis(3-hydroxypropyl)urea
• 1,3-dipropylurea
• ethyl-3-propylurea
• sec-butyl-3-methylurea
• isobutyl-3-methylurea
• cyclopentyl-3-methylurea
• N-acetyl-N′-methylurea
• trimethylurea
• butyl-3,3-dimethylurea
• tetramethylurea and
• benzylurea.
• Among the compounds of formula (II) that are particularly preferred according to the invention, mention may be made of:
• parabanic acid
• 1,2-dihydro-3H-1,2,4-triazol-2-one
• barbituric acid
• uracil
• 1-methyluracil
• 3-methyluracil
• 5-methyluracil
• 1,3-dimethyluracil
• 5-azauracil
• 6-azauracil
• 5-fluorouracil
• 6-fluorouracil
• 1,3-dimethyl-5-fluorouracil
• 5-aminouracil
• 6-aminouracil
• 6-amino-1-methyluracil
• 6-amino-1,3-dimethyluracil
• 4-chlorouracil
• 5-chlorouracil
• 5,6-dihydrouracil
• 5,6-dihydro-5-methyluracil
• 2-imidazolidone
• 1-methyl-2-imidazolidinone
• 1,3-dimethyl-2-imidazolidinone
• 4,5-dihydroxy-imidazolidin-2-one
• 1-(2-hydroxyethyl)-2-imidazolidinone
• 1-(2-hydroxypropyl)-2-imidazolidinone
• 1-(3-hydroxypropyl)-2-imidazolidinone
• 4,5-dihydroxy-1,3-dimethyl-imidazolidin-2-one
• 1,3-bis(2-hydroxyethyl)-2-imidazolidinone
• 2-imidazolidone-4-carboxylic acid
• 1-(2-aminoethyl)-2-imidazole
• 4-methyl-1,2,4-triazoline-3,5-dione
• 2,4-dihydroxy-6-methylpyrimidine
• 1-amino-4,5-dihydro-1H-tetrazol-5-one
• hydantoin
• 1-methylhydantoin
• 5-methylhydantoin
• 5,5-dimethylhydantoin
• 5-ethylhydantoin
• 5-n-propylhydantoin
• 5-ethyl-5-methylhydantoin
• 5-hydroxy-5-methylhydantoin
• 5-hydroxymethylhydantoin
• 1-allylhydantoin
• 1-aminohydantoin
• hydantoin-5-acetic acid
• 4-amino-1,2,4-triazolone-3,5-dione
• hexahydro-1,2,4,5-tetrazine-3,6-dione
• 5-methyl-1,3,5-triazinon-2-one
• 1-methyltetrahydropyrimidin-2-one
• 2,4-dioxohexahydro-1,3,5-triazine
• urazole
• 4-methylurazole
• orotic acid
• dihydroxyorotic acid
• 2,4,5-trihydroxypyrimidine
• 2-hydroxy-4-methylpyrimidine
• 4,5-diamino-2,6-dihydroxypyrimidine
• barbituric acid
• 1,3-dimethylbarbituric acid
• cyanuric acid
• 1-methyl-hexahydropyrimidine-2,4-dione
• 1,3-dimethyl-3,4,5,6-tetrahydro-2-1H-pyrimidinone
• 5-(hydroxymethyl-2,4-(1H,3H)-pyrimidinedione
• 2,4-dihydroxypyrimidine-5-carboxylic acid
• 6-azathymine
• 5-methyl-1,3,5-triazinan-2-one
• N-carbamoylmaleamic acid and
• alloxan monohydrate.
• Preferentially, the said compound(s) (a) are chosen from urea and hydroxyethylurea.
• The said compound(s) (a) preferably represent from 2% to 50% by weight, more preferentially from 2% to 20% by weight, better still from 2% to 12% by weight and even better still from 2% to 10% by weight, relative to the total weight of the composition.
• The composition according to the invention also comprises one or more nonionic, cationic, amphoteric associative polymeric thickeners or anionic associative polymeric thickeners comprising one or more acrylic and/or methacrylic units (b).
• According to the present invention, the term “thickener” means compounds which, by their presence, increase the viscosity of the aqueous phase into which they are introduced by at least 20 cps and preferably by at least 50 cps, at 25° C. and at a shear rate of 1 s−1 (the viscosity may be measured using a cone/plate viscometer, a Haake R600 rheometer or the like).
• These nonionic, cationic, amphoteric associative polymeric thickeners or anionic associative polymeric thickeners comprising one or more acrylic and/or methacrylic units are preferably water-soluble or water-dispersible at a pH of 7 and at room temperature (25° C.).
• The terms “water-soluble” and “water-dispersible” refer to a polymer which forms in water at a weight concentration of 0.1% at pH 7 and at room temperature (25° C.) a visually homogeneous (one-phase) medium.
• The term “associative polymer” refers to polymers that are capable, in an aqueous medium, of reversibly combining with each other or with other molecules.
• Associative polymers more particularly comprise at least one hydrophilic part and at least one hydrophobic part.
• Thus, in particular, associative polymers comprise at least one hydrophobic group.
• The term “hydrophobic group” means a radical or polymer with a saturated or unsaturated, linear or branched hydrocarbon-based chain, comprising at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 18 to 30 carbon atoms.
• Preferentially, the hydrocarbon-based group is derived from a monofunctional compound.
• By way of example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also denote a hydrocarbon-based polymer, for instance polybutadiene.
• The associative thickening polymers that are used according to the invention are especially chosen from:
• (i) nonionic amphiphilic polymers comprising at least one fatty chain and at least one hydrophilic unit;
• (ii) cationic amphiphilic polymers comprising at least one hydrophilic unit and at least one fatty-chain unit;
• (iii) amphoteric amphiphilic polymers comprising at least one hydrophilic unit and at least one fatty-chain unit, the fatty chains containing from 10 to 30 carbon atoms.
• The nonionic associative polymers are preferably chosen from:
• • (1) celluloses modified with groups comprising at least one fatty chain; examples that may be mentioned include:
    • hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as alkyl, arylalkyl or alkylaryl groups, or mixtures thereof, and in which the alkyl groups are preferably C8-C22, for instance the product Natrosol Plus Grade 330 CS (C16 alkyls) sold by the company Aqualon, or the product Bermocoll EHM 100 sold by the company Berol Nobel,
    • hydroxyethylcellulo ses modified with alkylphenyl polyalkylene glycol ether groups, such as the product Amercell Polymer HM (nonylphenyl polyethylene glycol (15) ether) sold by the company Amerchol,
  • (2) hydroxypropyl guars modified with groups comprising at least one fatty chain, such as the product Esaflor HM 22 (C22 alkyl chain) sold by the company Lamberti, and the products RE210-18 (C14 alkyl chain) and RE205-1 (C20 alkyl chain) sold by the company Rhodia,
  • (3) copolymers of C1-C6 alkyl methacrylates or acrylates and of amphiphilic monomers comprising at least one fatty chain, for instance the oxyethylenated methyl acrylate/stearyl acrylate copolymer sold by the company Goldschmidt under the name Antil 208,
  • (4) copolymers of hydrophilic methacrylates or acrylates and of hydrophobic monomers comprising at least one fatty chain, for instance the polyethylene glycol methacrylate/lauryl methacrylate copolymer,
  • (5) polyurethane polyethers comprising in their chain both hydrophilic blocks usually of polyoxyethylenated nature and hydrophobic blocks, which may be aliphatic sequences alone and/or cycloaliphatic and/or aromatic sequences,
  • (6) polymers with an aminoplast ether backbone bearing at least one fatty chain, such as the Pure Thix compounds sold by the company Sud-Chemie,
  • (7) copolymers of vinylpyrrolidone and of fatty-chain hydrophobic monomers; examples that may be mentioned include:
    • the products Antaron V216 or Ganex V216 (vinylpyrrolidone/hexadecene copolymer) sold by the company ISP,
    • the products Antaron V220 or Ganex V220 (vinylpyrrolidone/eicosene copolymer) sold by the company ISP.
• Preferably, the polyurethane polyethers comprise at least two hydrocarbon-based lipophilic chains containing from 8 to 30 carbon atoms, separated by a hydrophilic block, the hydrocarbon-based chains possibly being pendent chains or chains at the end of the hydrophilic block. In particular, it is possible for one or more pendent chains to be envisaged. In addition, the polymer may comprise a hydrocarbon-based chain at one end or at both ends of a hydrophilic block.
• The polyurethane polyethers may be multiblock, in particular in triblock form. The hydrophobic blocks may be at each end of the chain (for example: triblock copolymer containing a hydrophilic central block) or distributed both at the ends and in the chain (for example multiblock copolymer). These same polymers may also be graft polymers or star polymers.
• The nonionic fatty-chain polyurethane polyethers may be triblock copolymers in which the hydrophilic block is a polyoxyethylenated chain comprising from 50 to oxyethylene groups. The nonionic polyurethane polyethers comprise a urethane bond between the hydrophilic blocks, whence arises the name.
• By extension, also included among the nonionic fatty-chain polyurethane polyethers are those in which the hydrophilic blocks are linked to the lipophilic blocks via other chemical bonds.
• As examples of fatty-chain nonionic polyurethane polyethers, use may also be made of Rheolate 205 containing a urea function, sold by the company Rheox, or Rheolate 208, 204 or 212, and also Acrysol RM 184, Aculyn 44 and Aculyn 46 from the company Röhm & Haas [Aculyn 46 is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of stearyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%) and water (81%); Aculyn 44 is a polycondensate of polyethylene glycol containing 150 or 180 mol of ethylene oxide, of decyl alcohol and of methylenebis(4-cyclohexyl isocyanate) (SMDI), at 35% by weight in a mixture of propylene glycol (39%) and water (26%)].
• Mention may also be made of the product Elfacos T210 containing a C12-C14 alkyl chain, and the product Elfacos T212 containing a C18 alkyl chain, from Akzo.
• The product DW B from Röhm & Haas containing a C20 alkyl chain and a urethane bond, sold at a solids content of 20% in water, may also be used.
• Use may also be made of solutions or dispersions of these polymers, especially in water or in aqueous-alcoholic medium. Examples of such polymers that may be mentioned are Rheolate 255, Rheolate 278 and Rheolate 244 sold by the company Rheox. Use may also be made of the products DW F and DW J sold by the company Röhm & Haas.
• The polyurethane polyethers that may be used according to the invention are in particular those described in the article by G. Fonnum, J. Bakke and Fk. Hansen—Colloid Polym. Sci 271, 380.389 ().
• The cationic associative polymers are preferably chosen from:
• • (A′) cationic associative polyurethanes, the family of which has been described by the Applicant in French patent application No. 00/; it may be represented by the general formula (Ia) below:
• 
  R—X—(P)n-[L-(Y)m]r-L′-(P′)p—X′—R′  (Ia)
• in which:
• • R and R′, which may be identical or different, represent a hydrophobic group or a hydrogen atom;
  • X and X′, which may be identical or different, represent a group comprising an amine function optionally bearing a hydrophobic group, or alternatively a group L″;
  • L, L′ and L″, which may be identical or different, represent a group derived from a diisocyanate;
  • P and P′, which may be identical or different, represent a group comprising an amine function optionally bearing a hydrophobic group;
  • Y represents a hydrophilic group;
  • r is an integer between 1 and 100 inclusive, preferably between 1 and 50 inclusive and in particular between 1 and 25 inclusive;
  • n, m and p are each, independently of each other, between 0 and inclusive;
• the molecule containing at least one protonated or quaternized amine function and at least one hydrophobic group.
• In one preferred embodiment of these polyurethanes, the only hydrophobic groups are the groups R and R′ at the chain ends.
• One preferred family of cationic associative polyurethanes is the one corresponding to formula (Ia) described above and in which:
• • R and R′ both independently represent a hydrophobic group,
  • X and X′ each represent a group L″,
  • n and p are integers that are between 1 and inclusive, and
  • L, L′, L″, P, P′, Y and m have the meaning given above.
• Another preferred family of cationic associative polyurethanes is the one corresponding to formula (Ia) above in which:
• • the fact that n and p are 0 means that these polymers do not comprise units derived from a monomer containing an amine function, incorporated into the polymer during the polycondensation.
  • the protonated amine functions of these polyurethanes result from the hydrolysis of excess isocyanate functions, at the chain end, followed by alkylation of the primary amine functions formed with alkylating agents containing a hydrophobic group, i.e. compounds of the type RQ or R′Q, in which R and R′ are as defined above and Q denotes a leaving group such as a halide, a sulfate, etc.
• Yet another preferred family of cationic associative polyurethanes is the one corresponding to formula (Ia) above in which:
• R and R′ both independently represent a hydrophobic group,
• X and X′ both independently represent a group comprising a quaternary amine,
• n and p are zero, and
• L, L′, Y and m have the meaning given above.
• The number-average molecular mass of the cationic associative polyurethanes is preferably between 400 and 500 000 inclusive, in particular between and 400 000 inclusive and ideally between and 300 000 inclusive.
• The expression “hydrophobic group” means a radical or polymer containing a saturated or unsaturated, linear or branched hydrocarbon-based chain, which may contain one or more heteroatoms such as P, O, N or S, or a radical containing a perfluoro or silicone chain. When the hydrophobic group denotes a hydrocarbon-based radical, it comprises at least 10 carbon atoms, preferably from 10 to 30 carbon atoms, in particular from 12 to 30 carbon atoms and more preferentially from 18 to 30 carbon atoms.
• Preferentially, the hydrocarbon-based group is derived from a monofunctional compound.
• By way of example, the hydrophobic group may be derived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol or decyl alcohol. It may also denote a hydrocarbon-based polymer, for instance polybutadiene.
• When X and/or X′ denote(s) a group comprising a tertiary or quaternary amine, X and/or X′ may represent one of the following formulae:
• in which:
• R2 represents a linear or branched alkylene radical containing from 1 to 20 carbon atoms, optionally comprising a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, O and P;
• R1 and R3, which may be identical or different, denote a linear or branched C1-C30 alkyl or alkenyl radical or an aryl radical, at least one of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, O and P;
• A− is a physiologically acceptable anionic counterion such as a halide, for instance chloride or bromide, or mesylate.
• The groups L, L′ and L″ represent a group of formula:
• in which:
• Z represents —O—, —S— or —NH—; and
• R4 represents a linear or branched alkylene radical containing from 1 to 20 carbon atoms, optionally comprising a saturated or unsaturated ring, or an arylene radical, one or more of the carbon atoms possibly being replaced with a heteroatom chosen from N, S, O and P.
• The groups P and P′ comprising an amine function may represent at least one of the following formulae:
• in which:
• R5 and R7 have the same meanings as R2 defined above;
• R6, R8 and R9 have the same meanings as R1 and R3 defined above;
• R10 represents a linear or branched, optionally unsaturated alkylene group possibly containing one or more heteroatoms chosen from N, O, S and P; and
• A− is a physiologically acceptable anionic counterion such as a halide, for instance chloride or bromide, or mesylate.
• As regards the meaning of Y, the term “hydrophilic group” means a polymeric or non-polymeric water-soluble group.
• By way of example, when it is not a polymer, mention may be made of ethylene glycol, diethylene glycol and propylene glycol.
• When it is a hydrophilic polymer, in accordance with one preferred embodiment, mention may be made, for example, of polyethers, sulfonated polyesters, sulfonated polyamides or a mixture of these polymers. The hydrophilic compound is preferentially a polyether and especially a poly(ethylene oxide) or poly(propylene oxide).
• The cationic associative polyurethanes of formula (Ia) according to the invention are formed from diisocyanates and from various compounds bearing functions containing a labile hydrogen. The functions containing a labile hydrogen may be alcohol, primary or secondary amine or thiol functions, giving, after reaction with the diisocyanate functions, polyurethanes, polyureas and polythioureas, respectively. In the present invention, the term “polyurethanes” encompasses these three types of polymer, namely polyurethanes per se, polyureas and polythioureas, and also copolymers thereof.
• A first type of compound involved in the preparation of the polyurethane of formula (Ia) is a compound comprising at least one unit bearing an amine function. This compound may be multifunctional, but the compound is preferentially difunctional, that is to say that, according to one preferential embodiment, this compound comprises two labile hydrogen atoms borne, for example, by a hydroxyl, primary amine, secondary amine or thiol function. A mixture of multifunctional and difunctional compounds in which the percentage of multifunctional compounds is low may also be used.
• As mentioned above, this compound may comprise more than one unit containing an amine function. In this case, it is a polymer bearing a repetition of the unit containing an amine function.
• Compounds of this type may be represented by one of the following formulae:
• 
  HZ—(P)n-ZH
• 
  or
• 
  HZ—(P′)p-ZH
• in which Z, P, P′, n and p are as defined above.
• Examples of compounds containing an amine function that may be mentioned include N-methyldiethanolamine, N-tert-butyldiethanolamine and N-sulfoethyldiethanolamine.
• The second compound included in the preparation of the polyurethane of formula (Ia) is a diisocyanate corresponding to the formula:
• 
  O═C═N—R4—N═C═O
• in which R4 is defined above.
• By way of example, mention may be made of methylenediphenyl diisocyanate, methylenecyclohexane diisocyanate, isophorone diisocyanate, tolylene diisocyanate, naphthalene diisocyanate, butane diisocyanate and hexane diisocyanate.
• A third compound involved in the preparation of the polyurethane of formula (Ia) is a hydrophobic compound intended to form the terminal hydrophobic groups of the polymer of formula (Ia).
• This compound is formed from a hydrophobic group and a function containing a labile hydrogen, for example a hydroxyl, primary or secondary amine, or thiol function.
• By way of example, this compound may be a fatty alcohol such as, in particular, stearyl alcohol, dodecyl alcohol or decyl alcohol. When this compound comprises a polymer chain, it may be, for example, α-hydroxylated hydrogenated polybutadiene.
• The hydrophobic group of the polyurethane of formula (Ia) may also result from the quaternization reaction of the tertiary amine of the compound comprising at least one tertiary amine unit. Thus, the hydrophobic group is introduced via the quaternizing agent. This quaternizing agent is a compound of the type RQ or R′Q, in which R and R′ are as defined above and Q denotes a leaving group such as a halide, a sulfate, etc.
• The cationic associative polyurethane may also comprise a hydrophilic block. This block is provided by a fourth type of compound involved in the preparation of the polymer. This compound may be multifunctional. It is preferably difunctional. It is also possible to have a mixture in which the percentage of multifunctional compound is low.
• The functions containing a labile hydrogen are alcohol, primary or secondary amine or thiol functions. This compound may be a polymer terminated at the chain ends with one of these functions containing a labile hydrogen.
• By way of example, when it is not a polymer, mention may be made of ethylene glycol, diethylene glycol and propylene glycol.
• When it is a hydrophilic polymer, mention may be made, for example, of polyethers, sulfonated polyesters and sulfonated polyamides, or a mixture of these polymers. The hydrophilic compound is preferentially a polyether and especially a poly(ethylene oxide) or poly(propylene oxide).
• The hydrophilic group termed Y in formula (Ia) is optional. Specifically, the units containing a quaternary amine or protonated function may suffice to provide the solubility or water-dispersibility required for this type of polymer in an aqueous solution.
• Although the presence of a hydrophilic group Y is optional, cationic associative polyurethanes comprising such a group are, however, preferred.
• • (B′) quaternized cellulose derivatives.
• The quaternized cellulose derivatives are, in particular:
• • i) quaternized celluloses modified with groups comprising at least one fatty chain, such as linear or branched alkyl, linear or branched arylalkyl or linear or branched alkylaryl groups comprising at least 8 carbon atoms, or mixtures thereof;
  • ii) quaternized hydroxyethylcelluloses modified with groups comprising at least one fatty chain, such as linear or branched alkyl, linear or branched arylalkyl or linear or branched alkylaryl groups comprising at least 8 carbon atoms, or mixtures thereof;
  • iii) the hydroxyethylcelluloses of formula (Ib):
• in which formula (Ib):
• R and R′, which may be identical or different, represent an ammonium group such as RaRbRcN+, Q− in which Ra, Rb and Rc, which may be identical or different, represent a hydrogen atom or a linear or branched C1-C30 and preferentially C1-C20 alkyl group, such as methyl or dodecyl; and
• Q− represents an anionic counterion such as a halide, for instance a chloride or bromide;
• n, x and y, which may be identical or different, represent an integer between 1 and 10 000.
• The alkyl radicals borne by the above quaternized celluloses i) or hydroxyethylcelluloses ii) preferably comprise from 8 to 30 carbon atoms. The aryl radicals preferably denote phenyl, benzyl, naphthyl or anthryl groups.
• Examples of quaternized alkylhydroxyethylcelluloses containing C8-C30 fatty chains that may be indicated include the products Quatrisoft LM 200®, Quatrisoft LM-X 529-18-A®, Quatrisoft LM-X 529-18B® (C12 alkyl) and Quatrisoft LM-X 529-8® (C18 alkyl) sold by the company Amerchol, and the products Crodacel QM®, Crodacel QL® (C12 alkyl) and Crodacel QS® (C18 alkyl) sold by the company Croda.
• Mention may also be made of the hydroxyethylcelluloses of formula (Ib) in which R represents a trimethylammonium halide and R′ represents a dimethyldodecylammonium halide, more preferentially R represents trimethylammonium chloride (CH3)3N+Cl− and R′ represents dimethyldodecylammonium chloride (CH3)2(C12H25)N+Cl−. Polymers of this type are known under the trade name Softcat Polymer SL®, such as SL-100 and SL-60.
• More particularly, the polymers of formula (Ib) are those whose viscosity is between and cPs inclusive. Preferentially, the viscosity is between and cPs inclusive.
• • (C′) Cationic polyvinyllactams, the family of which has been described by the Applicant in French patent application No. 01/.
• The said polymers comprise:
• • a) at least one monomer of vinyllactam or alkylvinyllactam type;
  • b) at least one monomer of structure (Ic) or (IIc) below:
• in which formulae (Ic) and (IIc):
• X denotes an oxygen atom or a radical NR6,
• R1 and R6 denote, independently of each other, a hydrogen atom or a linear or branched C1-C5 alkyl radical,
• R2 denotes a linear or branched C1-C4 alkyl radical,
• R3, R4 and R5 denote, independently of each other, a hydrogen atom, a linear or branched C1-C30 alkyl radical or a radical of formula (IIIc):
• 
  —(Y2)r—(CH2—CH(R7)—O)x—R8  (IIIc)
• • Y, Y1 and Y2 denote, independently of each other, a linear or branched C2-C16 alkylene radical,
  • R7 denotes a hydrogen atom or a linear or branched C1-C4 alkyl radical or a linear or branched C1-C4 hydroxyalkyl radical,
  • R8 denotes a hydrogen atom or a linear or branched C1-C30 alkyl radical,
• p, q and r denote, independently of each other, either the value 0 or the value 1,
• m and n denote, independently of each other, an integer ranging from 0 to 100 inclusive,
• x denotes an integer ranging from 1 to 100 inclusive,
• Z denotes an anionic counterion of an organic or mineral acid, such as a halide, for instance chloride or bromide, or mesylate;
• with the proviso that:
• • at least one of the substituents R3, R4, R5 or R8 denotes a linear or branched C9-C30 alkyl radical,
  • if m or n is other than zero, then q is equal to 1,
  • if m or n is equal to zero, then p or q is equal to 0.
• The cationic poly(vinyllactam) polymers which may be used according to the invention may be crosslinked or noncrosslinked and may also be block polymers.
• Preferably, the counterion Z− of the monomers of formula (Ic) is chosen from halide ions, phosphate ions, the methosulfate ion and the tosylate ion.
• Preferably, R3, R4 and R5 denote, independently of each other, a hydrogen atom or a linear or branched C1-C30 alkyl radical.
• More preferentially, the monomer b) is a monomer of formula (Ic) for which, even more preferentially, m and n are equal to 0.
• The vinyllactam or alkylvinyllactam monomer is preferably a compound of structure (IVc):
• in which:
• s denotes an integer ranging from 3 to 6,
• R9 denotes a hydrogen atom or a linear or branched C1-C5 alkyl radical,
• R10 denotes a hydrogen atom or a linear or branched C1-C5 alkyl radical,
• with the proviso that at least one of the radicals R9 and R10 denotes a hydrogen atom.
• Even more preferentially, the monomer (IVc) is vinylpyrrolidone.
• The cationic poly(vinyllactam) polymers which may be used according to the invention may also contain one or more additional monomers, preferably cationic or nonionic monomers.
• As compounds that are more particularly preferred according to the invention, mention may be made of the following terpolymers comprising at least:
• a) one monomer of formula (IVc),
• b) one monomer of formula (Ic) in which p=1, q=0, R3 and R4 denote, independently of each other, a hydrogen atom or a C1-C5 alkyl radical and R5 denotes a linear or branched C9-C24 alkyl radical, and
• c) one monomer of formula (IIc) in which R3 and R4 denote, independently of each other, a hydrogen atom or a linear or branched C1-C5 alkyl radical.
• Even more preferentially, terpolymers comprising, by weight, 40% to 95% of monomer a), 0.1% to 55% of monomer c) and 0.25% to 50% of monomer b) will be used.
• Such polymers are described in patent application WO 00/, the content of which forms an integral part of the invention.
• As cationic poly(vinyllactam) polymers which may be used according to the invention, vinylpyrrolidone/dimethylaminopropylmethacrylamide/dodecyldimethylmethacrylamidopropylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/cocoyldimethyl methacrylamidopropylammonium tosylate terpolymers, vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethyl methacrylamidopropylammonium tosylate or chloride terpolymers are used in particular.
• The weight-average molecular mass of the cationic poly(vinyllactam) polymers which may be used according to the present invention is preferably between 500 and 20 000 000. It is more particularly between 200 000 and 2 000 000 and even more preferentially between 400 000 and 800 000.
• The amphoteric associative polymers are preferably chosen from those comprising at least one non-cyclic cationic unit. Even more particularly, the ones that are preferred are those prepared from or comprising 1 mol % to 20 mol %, preferably 1.5 mol % to 15 mol % and even more particularly 1.5 mol % to 6 mol % of fatty-chain monomer relative to the total number of moles of monomers.
• The amphoteric associative polymers according to the invention comprise those that are prepared by copolymerizing:
• 1) at least one monomer of formula (Va) or (Vb):
• in which R1 and R2, which may be identical or different, represent a hydrogen atom or a methyl radical, R3, R4 and R5, which may be identical or different, represent a linear or branched alkyl radical containing from 1 to 30 carbon atoms,
• Z represents an NH group or an oxygen atom,
• n is an integer from 2 to 5,
• A− is an anion derived from an organic or mineral acid, such as a methosulfate anion or a halide such as chloride or bromide;
• 2) at least one monomer of formula (VI):
• 
  R6—CH═CR7—COOH  (VI)
• in which R6 and R7, which may be identical or different, represent a hydrogen atom or a methyl radical; and
• 3) at least one monomer of formula (VII):
• 
  R6—CH═CR7—COXR8  (VII)
• in which R6 and R7, which may be identical or different, represent a hydrogen atom or a methyl radical, X denotes an oxygen or nitrogen atom and R8 denotes a linear or branched alkyl radical containing from 1 to 30 carbon atoms;
• at least one of the monomers of formula (Va), (Vb) or (VII) comprising at least one fatty chain.
• The monomers of formulae (Va) and (Vb) of the present invention are preferably chosen from the group formed by:
• • dimethylaminoethyl methacrylate, dimethylaminoethyl acrylate,
  • diethylaminoethyl methacrylate, diethylaminoethyl acrylate,
  • dimethylaminopropyl methacrylate, dimethylaminopropyl acrylate,
  • dimethylaminopropylmethacrylamide, dimethylaminopropylacrylamide,
• these monomers optionally being quaternized, for example with a C1-C4 alkyl halide or a C1-C4 dialkyl sulfate.
• More particularly, the monomer of formula (Va) is chosen from acrylamidopropyltrimethylammonium chloride and methacrylamidopropyltrimethylammonium chloride.
• The monomers of formula (VI) of the present invention are preferably chosen from the group formed by acrylic acid, methacrylic acid, crotonic acid and 2-methylcrotonic acid. More particularly, the monomer of formula (VI) is acrylic acid.
• The monomers of formula (VII) of the present invention are preferably chosen from the group formed by C12-C22 and more particularly C16-C18 alkyl acrylates or methacrylates.
• The monomers constituting the fatty-chain amphoteric polymers of the invention are preferably already neutralized and/or quaternized.
• The ratio of the number of cationic charges/anionic charges is preferably equal to about 1.
• The amphoteric associative polymers according to the invention preferably comprise from 1 mol % to 10 mol % of the monomer comprising a fatty chain (monomer of formula (Va), (Vb) or (VII)), and preferably from 1.5 mol % to 6 mol %.
• The amphoteric associative polymers according to the invention may also contain other monomers such as nonionic monomers and in particular such as C1-C4 alkyl acrylates or methacrylates.
• Amphoteric associative polymers according to the invention are described and prepared, for example, in patent application WO 98/.
• Among the amphoteric associative polymers according to the invention, the ones that are preferred are acrylic acid/(meth)acrylamidopropyltrimethylammonium chloride/stearyl methacrylate terpolymers.
• The preferred associative polymers are chosen from nonionic and cationic polymers.
• Preferably, the associative polymers of the invention are celluloses or polyurethanes, and preferably celluloses.
• The polymeric thickeners (b) that are used according to the invention may also be chosen from anionic associative polymeric thickeners containing acrylic and/or methacrylic units.
• The (meth)acrylic anionic associative thickeners that may be used according to the invention may be chosen from those comprising at least one hydrophilic unit of unsaturated olefinic carboxylic acid type, and at least one hydrophobic unit of the type such as a (C10-C30)alkyl ester of an unsaturated carboxylic acid.
• More particularly, these (meth)acrylic associative thickeners are preferably chosen from those in which the hydrophilic unit of unsaturated olefinic carboxylic acid type corresponds to the monomer of formula (VIII) below:
• in which formula R1 denotes H or CH3, i.e. acrylic acid or methacrylic acid units, and in which the hydrophobic unit of (C10-C30)alkyl ester of unsaturated carboxylic acid type corresponds to the monomer of formula (IX) below:
• in which formula R1 denotes H or CH3 (i.e. acrylate or methacrylate units), R2 denoting a C10-C30 and preferably C12-C22 alkyl radical.
• As (C10-C30)alkyl esters of unsaturated carboxylic acids according to formula (IX), mention may be made more particularly of lauryl acrylate, stearyl acrylate, decyl acrylate, isodecyl acrylate and dodecyl acrylate, and the corresponding methacrylates, lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate.
• (Meth)acrylic associative thickeners of this type are described and prepared, for example, according to U.S. Pat. No. 3,915,921 and U.S. Pat. No. 4,509,949.
• The (meth)acrylic associative thickeners that may be used according to the invention may more particularly denote polymers formed from a mixture of monomers comprising:
• (i) acrylic acid and one or more esters of formula (X) below:
• in which R3 denotes H or CH3, R4 denoting an alkyl radical having from 12 to 22 carbon atoms, and optionally a crosslinking agent, for instance those consisting of from 95% to 60% by weight of acrylic acid (hydrophilic unit), 4% to 40% by weight of C10-C30 alkyl acrylate (hydrophobic unit), and 0 to 6% by weight of crosslinking polymerizable monomer, or 98% to 96% by weight of acrylic acid (hydrophilic unit), 1% to 4% by weight of C10-C30 alkyl acrylate (hydrophobic unit) and 0.1% to 0.6% by weight of crosslinking polymerizable monomer; or
• (ii) essentially acrylic acid and lauryl methacrylate, such as the product formed from 66% by weight of acrylic acid and 34% by weight of lauryl methacrylate.
• For the purposes of the invention, the term “crosslinking agent” means a monomer containing a group
• and at least one other polymerizable group, the unsaturated bonds of the monomer being unconjugated relative to each other.
• As crosslinking agent that may be used according to the invention, mention may be made especially of polyallyl ethers especially such as polyallyl sucrose and polyallylpentaerythritol.
• Among the said (meth)acrylic associative thickeners above, the ones most particularly preferred according to the present invention are the products sold by the company Goodrich under the trade names Pemulen TR1, Pemulen TR2, Carbopol , and more preferably still Pemulen TR1, and the product sold by the company S.E.P.C. under the name Coatex SX.
• As (meth)acrylic associative thickeners, mention may also be made of the copolymer of methacrylic acid/methyl acrylate/dimethyl-meta-isopropenylbenzyl isocyanate of ethoxylated alcohol sold under the name Viscophobe DB by the company Amerchol.
• Other (meth)acrylic associative thickeners that may be used according to the invention may also be sulfonic polymers comprising at least one (meth)acrylic monomer bearing sulfonic group(s), in free form or partially or totally neutralized form and comprising at least one hydrophobic portion.
• The said hydrophobic portion present in the said sulfonic polymers that may be used according to the invention preferably comprises from 8 to 22 carbon atoms, more preferably still from 8 to 18 carbon atoms and more particularly from 12 to 18 carbon atoms.
• Preferentially, these sulfonic polymers that may be used according to the invention are partially or totally neutralized with a mineral base (sodium hydroxide, potassium hydroxide or aqueous ammonia) or an organic base such as mono-, di- or triethanolamine, an aminomethylpropanediol, N-methylglucamine, basic amino acids, for instance arginine and lysine, and mixtures of these compounds.
• These said sulfonic polymers generally have a number-average molecular weight ranging from to 20 000 000 g/mol, preferably ranging from 20 000 to 5 000 000 and even more preferably from 100 000 to 1 500 000 g/mol.
• The sulfonic polymers that may be used according to the invention may or may not be crosslinked. Crosslinked polymers are preferably chosen.
• When they are crosslinked, the crosslinking agents may be selected from polyolefinically unsaturated compounds commonly used for the crosslinking of polymers obtained by free-radical polymerization. Mention may be made, for example, of divinylbenzene, diallyl ether, dipropylene glycol diallyl ether, polyglycol diallyl ethers, triethylene glycol divinyl ether, hydroquinone diallyl ether, ethylene glycol diacrylatedi(meth)acrylate or tetraethylene glycol diacrylatedi(meth)acrylate, trimethylolpropane triacrylate, methylenebisacrylamide, methylenebismethacrylamide, triallylamine, triallyl cyanurate, diallyl maleate, tetraallylethylenediamine, tetraallyloxyethane, trimethylolpropane diallyl ether, allyl (meth)acrylate, allyl ethers of alcohols of the sugar series, or other allyl or vinyl ethers of polyfunctional alcohols, and also allyl esters of phosphoric and/or vinylphosphonic acid derivatives, or mixtures of these compounds.
• Methylenebisacrylamide, allyl methacrylate or trimethylolpropane triacrylate (TMPTA) will be used more particularly.
• The degree of crosslinking will generally range from 0.01 mol % to 10 mol % and more particularly from 0.2 mol % to 2 mol % relative to the polymer.
• The (meth)acrylic monomers bearing sulfonic group(s) of the sulfonic polymers that may be used according to the invention are chosen especially from (meth)acrylamido(C1-C22)alkylsulfonic acids and N—(C1-C22)alkyl(meth)acrylamido(C1-C22)alkylsulfonic acids, for instance undecylacrylamidomethanesulfonic acid, and also partially or totally neutralized forms thereof.
• (Meth)acrylamido(C1-C22)alkylsulfonic acids, for instance acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid, acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, methacrylamido-2-methylpropanesulfonic acid, 2-acrylamido-n-butanesulfonic acid, 2-acrylamido-2,4,4-trimethylpentanesulfonic acid, 2-methacrylamidododecylsulfonic acid or 2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and also partially or totally neutralized forms thereof, will more preferentially be used.
• 2-Acrylamido-2-methylpropanesulfonic acid (AMPS), and also partially or totally neutralized forms thereof, will even more particularly be used.
• The (meth)acrylic associative thickeners that may be used according to the invention may be chosen especially from random amphiphilic AMPS polymers modified by reaction with a C6-C22 n-monoalkylamine or C6-C22 di-n-alkylamine, and such as those described in patent application WO 00/ (which forms an integral part of the content of the description). These polymers may also contain other ethylenically unsaturated hydrophilic monomers selected, for example, from (meth)acrylic acids, β-substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.
• The (meth)acrylic associative thickeners bearing sulfonic group(s) that may particularly preferably be used according to the invention are preferably chosen from amphiphilic copolymers of AMPS and of at least one ethylenically unsaturated hydrophobic monomer comprising at least one hydrophobic portion containing from 8 to 50 carbon atoms, more preferably from 8 to 22 carbon atoms, more preferably still from 8 to 18 carbon atoms and more particularly 12 to 18 carbon atoms.
• These same copolymers may also contain one or more ethylenically unsaturated monomers not comprising a fatty chain, such as (meth)acrylic acids, β-substituted alkyl derivatives thereof or esters thereof obtained with monoalcohols or mono- or polyalkylene glycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid or maleic acid, or mixtures of these compounds.
• These copolymers are described especially in patent application EP-A-750 899, U.S. Pat. No. 5,089,578 and in the following Yotaro Morishima publications:
• • Self-assembling amphiphilic polyelectrolytes and their nanostructures, Chinese Journal of Polymer Science, Vol. 18, No. 40, (), 323-336;
  • Micelle formation of random copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and a nonionic surfactant macromonomer in water as studied by fluorescence and dynamic light scattering, Macromolecules, , Vol. 33, No. 10--;
  • Solution properties of micelle networks formed by nonionic moieties covalently bound to a polyelectrolyte: salt effects on rheological behavior—Langmuir, , Vol. 16, No. 12, -;
  • Stimuli responsive amphiphilic copolymers of sodium 2-(acrylamido)-2-methylpropanesulfonate and associative macromonomers, Polym. Preprint, Div. Polym. Chem. , 40(2), 220-221.
• The ethylenically unsaturated hydrophobic monomers of these particular copolymers are preferably selected from the acrylates or acrylamides of formula (XI) below:
• in which R5 and R7, which may be identical or different, denote a hydrogen atom or a linear or branched C1-C6 alkyl radical (preferably methyl); Y denotes O or NH; R6 denotes a hydrophobic hydrocarbon-based radical containing at least 8 to 50 carbon atoms, more preferentially from 8 to 22 carbon atoms, even more preferentially from 6 to 18 carbon atoms and more particularly from 12 to 18 carbon atoms; x denotes a number of moles of alkylene oxide and ranges from 0 to 100.
• The radical R6 is preferably chosen from linear C6-C18 alkyl radicals (for example n-hexyl, n-octyl, n-decyl, n-hexadecyl, n-dodecyl), or branched or cyclic C6-C18 alkyl radicals (for example cyclododecane (C12) or adamantane (C10)); C6-C18 perfluoroalkyl radicals (for example the group of formula —(CH2)2—(CF2)9—CF3); the cholesteryl radical (C27) or a cholesterol ester residue, for instance the cholesteryl oxyhexanoate group; aromatic polycyclic groups such as naphthalene or pyrene. Among these radicals, the ones that are more particularly preferred are linear alkyl radicals and more particularly the n-dodecyl radical.
• According to a particularly preferred form of the invention, the monomer of formula (XI) comprises at least one alkylene oxide unit (x≧1) and preferably a polyoxyalkylene chain. The polyoxyalkylene chain preferentially consists of ethylene oxide units and/or propylene oxide units and even more particularly consists of ethylene oxide units. The number of oxyalkylene units generally ranges from 3 to 100, more preferably from 3 to 50 and more preferably still from 7 to 25.
• Among these polymers, mention may be made of:
• • copolymers, which may or may not be crosslinked and which may or may not be neutralized, comprising from 15% to 60% by weight of AMPS units and from 40% to 85% by weight of (C8-C16)alkyl(meth)acrylamide units or of (C8-C16)alkyl (meth)acrylate units, relative to the polymer, such as those described in patent application EP-A-750 899;
  • terpolymers comprising from 10 mol % to 90 mol % of acrylamide units, from 0.1 mol % to 10 mol % of AMPS units and from 5 mol % to 80 mol % of n-(C6-C18)alkylacrylamide units, such as those described in U.S. Pat. No. 5,089,578.
• Mention may also be made of copolymers of totally neutralized AMPS and of dodecyl methacrylate, and also crosslinked and non-crosslinked copolymers of AMPS and of n-dodecylmethacrylamide, such as those described in the Morishima articles mentioned above.
• Mention will be made more particularly of the copolymers constituted of 2-acrylamido-2-methylpropanesulfonic acid (AMPS) units of formula (XII) below:
• in which X+ is a proton, an alkali metal cation, an alkaline-earth metal cation or an ammonium ion;
• and units of formula (XIII) below:
• in which x denotes an integer ranging from 3 to 100, preferably from 5 to 80 and more preferentially from 7 to 25; R5 has the same meaning as that indicated above in formula (XI) and R8 denotes a linear or branched C6-C22 and more preferentially C10-C22 alkyl.
• The polymers that are particularly preferred are those for which x=25, R5 denotes methyl and R8 represents n-dodecyl; they are described in the Morishima articles mentioned above.
• The polymers for which X+ denotes sodium or ammonium are more particularly preferred.
• The nonionic, cationic, amphoteric or anionic associative polymeric thickening polymer(s) (b) may be present in the composition according to the invention in a content ranging from 0.01% to 30% by weight, preferably from 0.1% to 20% by weight and better still from 0.2% to 10% by weight relative to the total weight of the composition.
• The composition according to the invention may also comprise one or more thickeners other than the associative polymeric thickeners already mentioned.
• The composition according to the invention may also comprise one or more surfactants, more particularly nonionic, anionic, cationic or amphoteric surfactants.
• The nonionic surfactant(s) that may be used in the cosmetic composition according to the invention are described, for example, in the Handbook of Surfactants by M. R. Porter, published by Blackie & Son (Glasgow and London), , pp. 116-178. They are especially chosen from alcohols, α-diols and (C1-C20)alkylphenols, these compounds being polyethoxylated, polypropoxylated and/or polyglycerolated, and containing at least one fatty chain comprising, for example, from 8 to 18 carbon atoms, it being possible for the number of ethylene oxide and/or propylene oxide groups to especially range from 2 to 50, and for the number of glycerol groups to especially range from 2 to 30.
• Mention may also be made of copolymers of ethylene oxide and propylene oxide, polyoxyalkylenated fatty acid esters, optionally oxyalkylenated alkylpolyglycosides, alkyl glucoside esters, N-alkylglucamine and N-acyl-methylglucamine derivatives, aldobionamides, oxyethylenated oils and amine oxides.
• Unless otherwise mentioned, the term “fatty” compound (for example a fatty acid) denotes for these surfactants a compound comprising, in its main chain, at least one saturated or unsaturated alkyl chain containing at least 6 carbon atoms, preferably from 8 to 30 carbon atoms, and better still from 10 to 22 carbon atoms.
• As regards the “anionic surfactants”, the term “anionic surfactant” means a surfactant comprising, as ionic or ionizable groups, only anionic groups. These anionic groups are chosen preferably from the groups CO2H, CO2 −, SO3H, SO3 −, OSO3H, OSO3 −, O2PO2H, O2PO2H− and O2PO2 2−.
• The anionic surfactant(s) that may be used in the composition of the invention are especially chosen from alkyl sulfates, alkyl ether sulfates, alkylamido ether sulfates, alkylaryl polyether sulfates, monoglyceride sulfates, alkylsulfonates, alkylamide sulfonates, alkylarylsulfonates, α-olefin sulfonates, paraffin sulfonates, alkylsulfosuccinates, alkyl ether sulfosuccinates, alkylamide sulfosuccinates, alkyl sulfoacetates, acylsarcosinates, acylglutamates, alkylsulfosuccinamates, acylisethionates and N-acyltaurates, salts of alkyl monoesters and polyglycoside-polycarboxylic acids, acyllactylates, salts of D-galactoside uronic acids, salts of alkyl ether carboxylic acids, salts of alkyl aryl ether carboxylic acids, and salts of alkylamido ether carboxylic acids; or the non-salified forms of all of these compounds, the alkyl and acyl groups of all of these compounds containing from 6 to 24 carbon atoms and the aryl group denoting a phenyl group.
• Some of these compounds may be oxyethylenated and then preferably comprise from 1 to 50 ethylene oxide units.
• The salts of C6-C24 alkyl monoesters of polyglycoside-polycarboxylic acids may be chosen from C6-C24 alkyl polyglycoside-citrates, C6-C24 alkyl polyglycoside-tartrates and C6-C24 alkyl polyglycoside-sulfo succinates.
• When the anionic surfactant(s) are in salt form, they are not in the form of zinc salts, and they may be chosen from alkali metal salts, such as the sodium or potassium salt, and preferably the sodium salt, ammonium salts, amine salts, and in particular amino alcohol salts, and alkaline-earth metal salts such as the magnesium salt.
• Examples of amino alcohol salts that may especially be mentioned include monoethanolamine, diethanolamine and triethanolamine salts, monoisopropanolamine, diisopropanolamine or triisopropanolamine salts, 2-amino-2-methyl-1-propanol salts, 2-amino-2-methyl-1,3-propanediol salts and tris(hydroxymethyl)aminomethane salts.
• Alkali metal or alkaline-earth metal salts and in particular the sodium or magnesium salts are preferably used.
• Use is preferably made of (C6-C24)alkyl sulfates, (C6-C24)alkyl ether sulfates, which are optionally ethoxylated, comprising from 2 to 50 ethylene oxide units, and mixtures thereof, in particular in the form of alkali metal salts or alkaline-earth metal salts, ammonium salts or amino alcohol salts. More preferentially, the anionic surfactant(s) are chosen from (C10-C20)alkyl ether sulfates, and in particular sodium lauryl ether sulfate containing 2.2 mol of ethylene oxide.
• The term “cationic surfactant” means a surfactant that is positively charged when it is contained in the composition according to the invention. This surfactant may bear one or more positive permanent charges or may contain one or more functions that are cationizable in the composition according to the invention.
• The cationic surfactant(s) are preferably selected from primary, secondary or tertiary fatty amines, optionally polyoxyalkylenated, or salts thereof, and quaternary ammonium salts, and mixtures thereof.
• The fatty amines generally comprise at least one C8-C30 hydrocarbon-based chain. Among the fatty amines that may be used according to the invention, examples that may be mentioned include stearylamidopropyldimethylamine and distearylamine.
• Examples of quaternary ammonium salts that may especially be mentioned include:
• • those corresponding to the general formula (XIV) below:
• in which the groups R8 to R11, which may be identical or different, represent a linear or branched aliphatic group containing from 1 to 30 carbon atoms, or an aromatic group such as aryl or alkylaryl, at least one of the groups R8 to R11 denoting a group containing from 8 to 30 carbon atoms, preferably from 12 to 24 carbon atoms. The aliphatic groups may comprise heteroatoms especially such as oxygen, nitrogen, sulfur and halogens. The aliphatic groups are chosen, for example, from C1-C30 alkyl, C2-C30 alkenyl, C1-C30 alkoxy, polyoxy(C2-C6)alkylene, C1-C30 alkylamide, (C12-C22)alkylamido(C2-C6)alkyl, (C12-C22)alkyl acetate and C1-C30 hydroxyalkyl groups; X− is an anion chosen from the group of halides, phosphates, acetates, lactates, (C1-C4)alkyl sulfates, and (C1-C4)alkyl- or (C1-C4)alkylarylsulfonates.
• Among the quaternary ammonium salts of formula (XIV), those that are preferred are, on the one hand, tetraalkylammonium salts, for instance dialkyldimethylammonium or alkyltrimethylammonium salts in which the alkyl group contains approximately from 12 to 22 carbon atoms, in particular behenyltrimethylammonium, distearyldimethylammonium, cetyltrimethylammonium or benzyldimethylstearylammonium salts, or, on the other hand, palmitylamidopropyltrimethylammonium salts, stearamidopropyltrimethylammonium salts and stearamidopropyldimethylcetearylammonium salts. It is particularly preferred to use the chloride salts of these compounds.
• • quaternary ammonium salts of imidazoline, for instance those of formula (XV) below:
• in which R12 represents an alkenyl or alkyl group comprising from 8 to 30 carbon atoms, derived for example from tallow fatty acids, R13 represents a hydrogen atom, a C1-C4 alkyl group or an alkyl or alkenyl group comprising from 8 to 30 carbon atoms, R14 represents a C1-C4 alkyl group, R15 represents a hydrogen atom or a C1-C4 alkyl group, X− is an anion chosen from the group of halides, phosphates, acetates, lactates, alkyl sulfates, alkyl- or alkylaryl-sulfonates in which the alkyl and aryl groups preferably comprise, respectively, from 1 to 20 carbon atoms and from 6 to 30 carbon atoms. R12 and R13 preferably denote a mixture of alkenyl or alkyl groups containing from 12 to 21 carbon atoms, derived for example from tallow fatty acids, R14 preferably denotes a methyl group, and R15 preferably denotes a hydrogen atom. Such a product is sold, for example, under the name Rewoquat® W 75 by the company Rewo;
• • quaternary diammonium or triammonium salts, in particular of formula (XVI):
• in which R16 denotes an alkyl radical comprising approximately from 16 to 30 carbon atoms, which is optionally hydroxylated and/or interrupted with one or more oxygen atoms, R17 is chosen from hydrogen or an alkyl radical comprising from 1 to 4 carbon atoms or a group (R16a)(R17a)(R18a)N—(CH2)3;
• R16a, R17a, R18a, R18, R19, R20 and R21, which may be identical or different, are chosen from hydrogen and an alkyl radical comprising from 1 to 4 carbon atoms, and X− is an anion chosen from the group of halides, acetates, phosphates, nitrates and methyl sulfates. Such compounds are, for example, Finquat CT-P, sold by the company Finetex (Quaternium 89), and Finquat CT, sold by the company Finetex (Quaternium 75),
• • quaternary ammonium salts containing at least one ester function, such as those of formula (XVII) below:
• in which:
• R22 is chosen from C1-C6 alkyl groups and C1-C6 hydroxyalkyl or dihydroxyalkyl groups;
• R23 is chosen from:
• • the group
• • groups R27, which are linear or branched, saturated or unsaturated C1-C22 hydrocarbon-based groups,
  • a hydrogen atom,
• R25 is chosen from:
• • the group
• • groups R29, which are linear or branched, saturated or unsaturated C1-C6 hydrocarbon-based groups,
  • a hydrogen atom,
• R24, R26 and R28, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C7-C21 hydrocarbon-based groups;
• r, s and t, which may be identical or different, are integers ranging from 2 to 6;
• y is an integer ranging from 1 to 10;
• x and z, which may be identical or different, are integers ranging from 0 to 10;
• X— is a simple or complex, organic or mineral anion;
• • with the proviso that the sum x+y+z is from 1 to 15, that when x is 0 then R23 denotes R27, and that when z is 0 then R25 denotes R29.
• The alkyl groups R22 may be linear or branched, and more particularly linear.
• Preferably, R22 denotes a methyl, ethyl, hydroxyethyl or dihydroxypropyl group, and more particularly a methyl or ethyl group.
• Advantageously, the sum x+y+z is from 1 to 10.
• When R23 is a hydrocarbon-based group R27, it may be long and contain from 12 to 22 carbon atoms, or may be short and contain from 1 to 3 carbon atoms.
• When R25 is an R29 hydrocarbon-based group, it preferably contains 1 to 3 carbon atoms.
• Advantageously, R24, R26 and R28, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C11-C21 hydrocarbon-based groups, and more particularly from linear or branched, saturated or unsaturated C11-C21 alkyl and alkenyl groups.
• Preferably, x and z, which may be identical or different, are equal to 0 or 1.
• Advantageously, y is equal to 1.
• Preferably, r, s and t, which may be identical or different, are equal to 2 or 3, and even more particularly are equal to 2.
• The anion X− is preferably a halide (chloride, bromide or iodide) or an alkyl sulfate, more particularly methyl sulfate. However, use may be made of methanesulfonate, phosphate, nitrate, tosylate, an anion derived from an organic acid, such as acetate or lactate, or any other anion compatible with the ammonium containing an ester function.
• The anion X− is even more particularly chloride or methyl sulfate.
• Use is made more particularly, in the composition according to the invention, of the ammonium salts of formula (XVII) in which:
• R22 denotes a methyl or ethyl group,
• x and y are equal to 1;
• z is equal to 0 or 1;
• r, s and t are equal to 2;
• R23 is chosen from:
• • the group
• • methyl, ethyl or C14-C22 hydrocarbon-based groups,
  • a hydrogen atom;
• R25 is chosen from:
• • the group
• • a hydrogen atom;
• R24, R26 and R28, which may be identical or different, are chosen from linear or branched, saturated or unsaturated C13-C17 hydrocarbon-based groups, and preferably from linear or branched, saturated or unsaturated C13-C17 alkyl and alkenyl groups.
• The hydrocarbon-based groups are advantageously linear.
• Mention may be made, for example, of the compounds of formula (XVII) such as the diacyloxyethyldimethylammonium, diacyloxyethylhydroxyethylmethylammonium, monoacyloxyethyldihydroxyethylmethylammonium, triacyloxyethylmethylammonium and monoacyloxyethylhydroxyethyldimethylammonium salts (chloride or methyl sulfate in particular), and mixtures thereof. The acyl groups preferably contain 14 to 18 carbon atoms and are obtained more particularly from a plant oil, such as palm oil or sunflower oil. When the compound contains several acyl groups, these groups may be identical or different.
• These products are obtained, for example, by direct esterification of triethanolamine, triisopropanolamine, an alkyldiethanolamine or an alkyldiisopropanolamine, which are optionally oxyalkylenated, with C10-C30 fatty acids or with mixtures of C10-C30 fatty acids of plant or animal origin, or by transesterification of the methyl esters thereof. This esterification is followed by quaternization using an alkylating agent such as an alkyl (preferably methyl or ethyl) halide, a dialkyl (preferably methyl or ethyl) sulfate, methyl methanesulfonate, methyl para-toluenesulfonate, glycol chlorohydrin or glycerol chlorohydrin.
• Such compounds are, for example, sold under the names Dehyquart® by the company Henkel, Stepanquat® by the company Stepan, Noxamium® by the company Ceca or Rewoquat® WE 18 by the company Rewo-Witco.
• The composition according to the invention may contain, for example, a mixture of quaternary ammonium monoester, diester and triester salts with a weight majority of diester salts.
• Use may also be made of the ammonium salts containing at least one ester function that are described in U.S. Pat. No. 4,874,554 and U.S. Pat. No. 4,137,180.
• Use may be made of behenoylhydroxypropyltrimethylammonium chloride, provided by Kao under the name Quatarmin BTC 131.
• Preferably, the ammonium salts containing at least one ester function contain two ester functions.
• Among the quaternary ammonium salts containing at least one ester function, which may be used according to the invention, it is preferred to use dipalmitoylethylhydroxyethylmethylammonium salts.
• The amphoteric or zwitterionic surfactant(s) that may be used in the present invention may especially be secondary or tertiary aliphatic amine derivatives, optionally quaternized, in which the aliphatic group is a linear or branched chain containing from 8 to 22 carbon atoms, the said amine derivatives containing at least one anionic group, for instance a carboxylate, sulfonate, sulfate, phosphate or phosphonate group. Mention may be made in particular of (C8-C20)alkylbetaines, sulfobetaines, (C8-C20alkyl)amido(C3-C8alkyl)betaines or (C8-C20alkyl)amido(C6-C8alkyl)sulfobetaines.
• Among the secondary or tertiary aliphatic amine derivatives, optionally quaternized, that may be used, as defined above, mention may also be made of the compounds of respective structures (B1) and (B2) below:
• 
  Ra—C(O)—N(Z)CH2(CH2)mN+(Rb)(Rc)-CH2C(O)O−,M+,X−  (B1)
• in which formula (B1):
• Ra represents a C10-C30 alkyl or alkenyl group derived from an acid RaCOOH preferably present in hydrolysed coconut oil, or a heptyl, nonyl or undecyl group;
• Rb represents a beta-hydroxyethyl group; and
• Rc represents a carboxymethyl group;
• M+ represents a cationic counterion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine; and
• X− represents an organic or mineral anionic counterion, preferably chosen from halides, acetates, phosphates, nitrates, (C1-C4)alkyl sulfates, (C1-C4)alkyl or (C1-C4)alkylaryl sulfonates, in particular methyl sulfate and ethyl sulfate;
• m is equal to 0, 1 or 2;
• Z represents a hydrogen atom or a hydroxyethyl or carboxymethyl group;
• or alternatively M+ and X− are absent;
• 
  Ra′—C(O)—N(Z)—CH2—(CH2)m′-N(B)(B′)  (B2)
• in which formula:
• B represents the group —CH2—CH2—O—X′;
• B′ represents the group —(CH2)zY′, with z=1 or 2;
• X′ represents the group —CH2—C(O)OH, —CH2—C(O)OZ′, —CH2—CH2—C(O)OH, —CH2—CH2—C(O)OZ′, or a hydrogen atom;
• Y′ represents the group —C(O)OH, —C(O)OZ′, —CH2—CH(OH)—SO3H or the group —CH2—CH(OH)—SO3—Z′;
• Z′ represents a cationic counterion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine;
• Ra′ represents a C10-C30 alkyl or C10-C30 alkenyl group of an acid Ra′—COOH, which is preferably present in coconut oil or in hydrolysed linseed oil, or an alkyl group, especially a C17 alkyl group and its iso form, or an unsaturated C17 group.
• m′ is equal to 0, 1 or 2,
• Z represents a hydrogen atom or a hydroxyethyl or carboxymethyl group.
• The compounds of this type are classified in the CTFA dictionary, 5th edition, , under the names disodium cocoamphodiacetate, disodium lauroamphodiacetate, disodium caprylamphodiacetate, disodium capryloamphodiacetate, disodium cocoamphodipropionate, disodium lauroamphodipropionate, disodium caprylamphodipropionate, disodium capryloamphodipropionate, lauroamphodipropionic acid, cocoamphodipropionic acid and hydro xyethylcarbo xymethylcocamidopropylamine.
• Examples that may be mentioned include the cocoamphodiacetate sold by the company Rhodia under the trade name Miranol® C2M Concentrate or under the trade name Miranol Ultra C 32 and the product sold by the company Chimex under the trade name Chimexane HA.
• Use may also be made of compounds of formula (B′2):
• 
  Ra″—NH—CH(Y″)—(CH2)n—C(O)NH(CH2)n′—N(Rd)(Re)  (B′2)
• in which formula:
• Y″ represents the group —C(O)OH, —C(O)OZ″, —CH2—CH(OH)—SO3H or the group CH2—CH(OH)—SO3—Z″;
• Rd and Re, independently of each other, represent a C1-C4 alkyl or hydroxyalkyl radical;
• Z″ represents a cationic counterion derived from an alkali metal or alkaline-earth metal, such as sodium, an ammonium ion or an ion derived from an organic amine;
• Ra″ represents a C10-C30 alkyl or alkenyl group of an acid Ra″—C(O)OH which is preferably present in coconut oil or in hydrolysed linseed oil;
• n and n′ denote, independently of each other, an integer ranging from 1 to 3.
• Among the compounds of formula (B′2), mention may be made of the compound classified in the CTFA dictionary under the name sodium diethylaminopropyl cocoaspartamide and sold by the company Chimex under the name Chimexane HB.
• Among the abovementioned amphoteric or zwitterionic surfactants, it is preferred to use (C8-C20 alkyl)betaines such as cocoylbetaine, (C8-C20 alkyl)amido(C2-C8 alkyl)betaines such as cocoylamidopropylbetaine, and mixtures thereof.
• More preferentially, the amphoteric or zwitterionic surfactant(s) are chosen from cocoylamidopropylbetaine and cocoylbetaine.
• The surfactants used in the composition according to the invention are preferably nonionic or cationic.
• The surfactant(s) may be present in an amount ranging from 0.01% to 30% by weight, preferably from 0.1% to 10% by weight and better still from 1% to 5% by weight relative to the total weight of the composition.
• The composition according to the invention advantageously comprises water, which advantageously represents from 1% to 95%, preferably from 20% to 80% and better still from 40% to 70% by weight relative to the total weight of the composition.
• The composition according to the invention may also comprise one or more fatty substances.
• The term “fatty substance” means an organic compound that is insoluble in water at ordinary room temperature (25° C.) and at atmospheric pressure (760 mmHg), with a solubility in water of less than 5%, preferably less than 1% and even more preferentially less than 0.1%.
• In addition, the fatty substances are generally soluble in organic solvents under the same temperature and pressure conditions, for instance chloroform, ethanol, benzene, liquid petroleum jelly or decamethylcyclopentasiloxane.
• The said fatty substance(s) that may be used in the composition according to the invention are preferably chosen from hydrocarbons, fatty alcohols, fatty acid and/or fatty alcohol esters, non-salified fatty acids, silicones and mixtures thereof.
• The fatty substance(s) may be liquid or non-liquid at room temperature and at atmospheric pressure.
• The said fatty substance(s) may represent from 0.001% to 90% by weight, better still from 0.1% to 50% by weight, preferably from 0.5% to 30% by weight and better still from 1% to 20% by weight, relative to the total weight of the composition.
• The composition may also comprise one or more water-soluble organic solvents (solubility of greater than or equal to 5% in water at 25° C. and at atmospheric pressure).
• Examples of water-soluble organic solvents that may be mentioned include linear or branched and preferably saturated monoalcohols or diols, comprising 2 to 10 carbon atoms, such as ethyl alcohol, isopropyl alcohol, hexylene glycol (2-methyl-2,4-pentanediol), neopentyl glycol and 3-methyl-1,5-pentanediol, butylene glycol, dipropylene glycol and propylene glycol; aromatic alcohols such as phenylethyl alcohol; polyols containing more than two hydroxyl functions, such as glycerol; polyol ethers, for instance ethylene glycol monomethyl, monoethyl and monobutyl ethers, propylene glycol or ethers thereof, for instance propylene glycol monomethyl ether; and also diethylene glycol alkyl ethers, especially C1-C4 alkyl ethers, for instance diethylene glycol monoethyl ether or monobutyl ether, alone or as a mixture.
• The water-soluble organic solvents, when they are present, generally represent between 1% and 20% by weight relative to the total weight of the composition according to the invention, and preferably between 5% and 10% by weight relative to the total weight of the composition.
• The composition according to the invention may also contain one or more additives chosen from the active principles and cosmetic adjuvants commonly used in the field of haircare. These additives are chosen, for example, from fixing polymers other than the thickening polymers already mentioned, conditioning agents and especially cationic polymers, silicones, chitosans and derivatives, hydrophobic solvents, hair dyes such as direct dyes, in particular cationic or natural dyes, oxidation dyes and pigments; UV-screening agents, fillers such as nacres, titanium dioxide, resins and clays; fragrances, peptizers, vitamins, preserving agents, acidic agents, alkaline agents, reducing agents, oxidizing agents, amino acids, oligopeptides, peptides, hydrolysed or non-hydrolysed, modified or unmodified proteins, enzymes, organic acids, antioxidants and free-radical scavengers, chelating agents, antidandruff agents, seborrhoea regulators, calmatives, plasticizers, glitter flakes and propellent gases.
• The above additives may be present in an amount ranging from 0.01% to 20% by weight relative to the total weight of the composition according to the invention.
• The composition according to the invention may be in the form of a wax, a paste, a cream, a gel, a foam, a spray or a lotion.
• A subject of the present invention is also the use of the composition as defined according to the invention for straightening keratin fibres, preferably the hair.
• Finally, a subject of the invention is also a process for straightening keratin fibres, preferably the hair, comprising:
• (i) a step of applying to the keratin fibres the composition according to the invention, followed by;
• (ii) a step of raising the temperature of the keratin fibres via a heating means, to a temperature ranging from 25 to 250° C.
• Preferably, the temperature is raised by means of the said heating means to a temperature ranging from 100 to 250° C. and better still from 150 to 230° C.
• In a first embodiment, the composition according to the invention is applied to a wet or dry head of hair, preferably wet hair, with or without a leave-on time. The bath ratio of the applied formulation may range from 0.1 to 10 and more particularly from 0.2 to 5. The keratin fibres are then optionally rubbed dry, preferably rubbed dry. One or more heating means are applied once or in succession to the keratin fibres at a temperature ranging from 25 to 250° C., preferably from 100 to 250° C. and better still from 150 to 230° C. for a time ranging from 5 seconds to 1 hour and preferably from 5 seconds to 1 minute. The hair then optionally undergoes one or more of the following operations: rinsing, shampooing and treatment with a rinse-out hair conditioner, drying, preferably using a hood or a hairdryer.
• Preferably, when a leave-on time is observed, the said leave-on time is preferably from 5 minutes to 1 hour.
• The term “bath ratio” means the ratio between the total weight of the applied composition and the total weight of keratin fibres to be treated.
• Heating means that may especially be used include a straightening iron, a curling iron, a crimping iron, a waving iron, a hood, a hairdryer, an infrared heating system or a heating roller (of the digital perm type).
• In a second embodiment, the sequence formed by the steps: (i) application of the composition according to the invention to keratin fibres, followed by (ii) raising the temperature of the keratin fibres, via a heating means, to a temperature ranging from 25 to 250° C., is performed one or more times, optionally separated by one or more cosmetic treatments, preferably shampooing, until the desired shape or shape intensity is obtained.
• In these two embodiments, the heating means is preferably an iron.
• The examples that follow serve to illustrate the invention without, however, being limiting in nature.
EXAMPLE 1
• Compositions 1 to 2 for straightening keratin fibres according to the invention are prepared, along with a control composition not containing any thickener according to the invention. The formulations are indicated in Table I (the amounts are expressed as weight percentages relative to the total weight of the composition).
• TABLE I Weight % of Composition Compound active material Control Urea 10% Water qs 100% 1 Urea 10% Cetylhydroxyethylcellulose(a) 1% Water qs 100% 2 Urea 10% SMDI/polyethylene glycol 8.5% polymer bearing decyl end groups, as a water-glycol solution(b) Water qs 100% (a)The cetylhydroxyethylcellulose used is sold under the name Polysurf 67CS by the company Ashland. (b)the SMDI/polyethylene glycol polymer bearing decyl end groups, as a water-glycol solution, used is sold under the name Aculyn 44 by the company Röhm & Haas.
• Compositions 1 and 2 and the control composition are applied to locks of moderately curly hair (curliness level 3 according to the article Shape variability and classification of human hair, Roland De La Mettrie et al., Human Biology, , vol. 79, No. 3, pages 265-281) according to the following protocol:
• The keratin fibres are prewashed with a shampoo.
• Each composition is applied to a separate wet lock. The excess product is then removed by rubbing dry.
• The locks are then predried with a hairdryer. A straightening iron is then applied slowly along the locks twice in succession at a temperature of 210° C. (for about 1 minute). The locks are then shampooed and are finally dried using a hairdryer.
• The Applicant finds that the straightening of the hair for the two compositions according to the invention and the control composition is persistent.
• On the other hand, the Applicant finds that the working qualities in terms of ease of distribution onto the head of hair, the ease of blow-drying and the ease of passage of flat tongs are greater in the case of compositions 1 and 2 according to the invention relative to the control composition.
• Furthermore, the Applicant finds that compositions 1 and 2 according to the invention afford the hair greater sheen and cosmeticity than the control composition.
EXAMPLE 2
• Composition 3 for straightening keratin fibres according to the invention is prepared, along with a control composition not containing any thickener according to the invention. The formulations are indicated in Table II (the amounts are expressed as weight percentages relative to the total weight of the composition).
• TABLE II Weight % of Composition Compound active material Control Urea 5% Water qs 100% 3 Urea 5% Crosslinked acrylic acid/alkyl 1% acrylate polymer(a) Water qs 100% (a)The crosslinked acrylic acid/alkyl acrylate polymer used is sold under the name Pemulen TR-2 Polymer by the company Lubrizol.
• Composition 3 and the control composition are applied to locks of moderately curly hair (curliness level 3 according to the article Shape variability and classification of human hair, Roland De La Mettrie et al., Human Biology, , vol. 79, No. 3, pages 265-281) according to the following protocol:
• The keratin fibres are prewashed with a shampoo.
• Each composition is applied to a separate wet lock. The excess product is then removed by rubbing dry.
• The locks are then predried with a hairdryer. A straightening iron is then applied slowly along the locks twice in succession at a temperature of 210° C. (for about 1 minute). The locks are then shampooed and are finally dried using a hairdryer. The Applicant finds that the straightening of the hair for composition 3 according to the invention and the control composition is persistent.
• On the other hand, the Applicant finds that the working qualities in terms of ease of distribution onto the head of hair, the ease of blow-drying and the ease of passage of flat tongs are greater in the case of composition 3 according to the invention relative to the control composition.
• Furthermore, the Applicant finds that composition 3 according to the invention affords the hair greater sheen and cosmeticity than the control composition.

Claims (21)

1.-20. (canceled) 21. A cosmetic composition comprising: (a) at least one compound chosen from urea or urea derivatives, present in at least 2% by weight, relative to the total weight of the composition; and (b) at least one polymeric thickener chosen from nonionic, cationic, amphoteric or anionic polymeric associative thickeners wherein the anionic polymeric associative thickener comprises at least one acrylic or methacrylic unit. 22. The composition according to claim 21, wherein the at least one compound is chosen from the compounds represented by formula (I) or (II) below, or their salts or hydrates thereof: wherein: R1, R2, R3 and R4, independently of each other, are chosen from: (i) a hydrogen atom or (ii) a linear or branched, cyclic or acyclic, C1-C5 lower alkyl or alkenyl radical, a C1-C5 alkoxy radical, a C6-C18 aryl radical, or a 5- to 8-membered heterocyclic radical; optionally substituted with at least one radical chosen from hydroxyl, (di)(C1-C4)(alkyl)amino, dimethylamino, carboxyl, halogen, C6-C18 aryl, carboxamide, or N-methylcarboxamide; with the proviso that when R1, R2 and R3 are each a hydrogen atom, R4 may be a radical chosen from carboxamide, methoxy, ethoxy, 1,2,4-triazolyl, cyclopentyl, (C1-C6)alkylcarbonyl,acetyl, (C1-C6)alkoxycarbonyl, methoxycarbonyl, ethoxycarbonyl, —CO—CH═CH—COOH, phenyl optionally substituted with a chlorine atom or a hydroxyl, benzyl, or 2,5-dioxo-4-imidazolidinyl; with the proviso that when R1 and R3 are each a hydrogen atom, R2 may be chosen from a hydrogen atom or methyl or ethyl radical, and R4 may be an acetyl radical; with the proviso that when R1 and R2 are each a hydrogen atom, R3 and R4 can form, with the nitrogen atom that bears them, a piperidine, 3-methylpyrazole, 3,5-dimethylpyrazole, or maleimide ring; R1 and R2 and also R3 and R4 can form, with the nitrogen atom that bears them, an imidazole ring; R5 and R6, independently of each other, are chosen from: (iii) a hydrogen atom or (iv) a linear or branched, cyclic or acyclic, C1-C5 lower alkyl, acyl or alkenyl radical, a C1-C5 alkoxy radical, a C6-C18 aryl radical, or a 5- to 8-membered heterocyclic radical; optionally substituted with at least one radical chosen from hydroxyl, amino, dimethylamino, carboxyl, halogen, C6-C18 aryl, carboxamide, or N-methylcarboxamide; and A is chosen from CH2—CH2, CH═CH, CH2—CO, CO—NH, CH═N, CO—CO, CHOH—CHOH, (HOOC)CH—CH, CHOH—CO, CH2—CH2—CH2, CH2—NH—CO, CH═C(CH3)—CO, NH—CO—NH, CH2—CH2—CO, CH2—N(CH3)—CH2, NH—CH2—NH, CO—CH(CH3)—CH2, CO—CH2—CO, CO—NH—CO, CO—CH(COOH)—CH2, CO—CH═C(COOH), CO—CH═C(CH3), CO—C(NH2)═CH, CO—C(CH3)═N, CO—CH═CH, CO—CH═N, or CO—N═CH. 23. The composition according to claim 22, wherein the at least one compound represented by formula (I) is chosen from: urea, methylurea, ethylurea, propylurea, n-butylurea, sec-butylurea, isobutylurea, tert-butylurea, cyclopentylurea, ethoxyurea, hydroxyethylurea, N-(2-hydroxypropyl)urea, N-(3-hydroxypropyl)urea, N-(2-dimethylaminopropyl)urea, N-(3-dimethylaminopropyl)urea, 1-(3-hydroxyphenyl)urea, benzylurea, N-carbamoylmaleamide, N-carbamoylmaleamic acid, piperidinecarboxamide, 1,2,4-triazol-4-ylurea, hydantoic acid, methyl allophanate, ethyl allophanate, acetylurea, hydroxyethyleneurea, 2-(hydroxyethyl)ethyleneurea, diallylurea, chloroethylurea, N,N-dimethylurea, N,N-diethylurea, N,N-dipropylurea, cyclopentyl-1-methylurea, 1,3-dimethylurea, 1,3-diethylurea, 1,3-bis(2-hydroxyethyl)urea, 1,3-bis(2-hydroxypropyl)urea, 1,3-bis(3-hydroxypropyl)urea, 1,3-dipropylurea, ethyl-3-propylurea, sec-butyl-3-methylurea, isobutyl-3-methylurea, cyclopentyl-3-methylurea, N-acetyl-N′-methylurea, trimethylurea, butyl-3,3-dimethylurea, tetramethylurea, or benzylurea. 24. The composition according to claim 22, wherein the at least one compound represented by formula (II) is chosen from: parabanic acid, 1,2-dihydro-3H-1,2,4-triazol-2-one, barbituric acid, uracil, 1-methyluracil, 3-methyluracil, 5-methyluracil, 1,3-dimethyluracil, 5-azauracil, 6-azauracil, 5-fluorouracil, 6-fluorouracil, 1,3-dimethyl-5-fluorouracil, 5-am inouracil, 6-am inouracil, 6-amino-1-methyluracil, 6-amino-1,3-dimethyluracil, 4-chlorouracil, 5-chlorouracil, 5,6-dihydrouracil, 5,6-dihydro-5-methyluracil, 2-imidazolidone, 1-methyl-2-imidazolidinone, 1,3-dimethyl-2-imidazolidinone, 4,5-dihydroxy-imidazolidin-2-one, 1-(2-hydroxyethyl)-2-imidazolidinone, 1-(2-hydroxypropyl)-2-imidazolidinone, 1-(3-hydroxypropyl)-2-imidazolidinone, 4,5-dihydroxy-1,3-dimethyl-imidazolidin-2-one, 1,3-bis(2-hydroxyethyl)-2-imidazolidinone, 2-imidazolidone-4-carboxylic acid, 1-(2-aminoethyl)-2-imidazole, 4-methyl-1,2,4-triazoline-3,5-dione, 2,4-dihydroxy-6-methylpyrimidine, 1-amino-4,5-dihydro-1H-tetrazol-5-one, hydantoin, 1-methylhydantoin, 5-methylhydantoin, 5,5-dimethylhydantoin, 5-ethylhydantoin, 5-n-propylhydantoin, 5-ethyl-5-methylhydantoin, 5-hydroxy-5-methylhydantoin, 5-hydroxymethylhydantoin, 1-allylhydantoin, 1-aminohydantoin, hydantoin-5-acetic acid, 4-amino-1,2,4-triazolone-3,5-dione, hexahydro-1,2,4,5-tetrazine-3,6-dione, 5-methyl-1,3,5-triazinon-2-one, 1-methyltetrahydropyrimidin-2-one, 2,4-dioxohexahydro-1,3,5-triazine, urazole, 4-methylurazole, orotic acid, dihydroxyorotic acid, 2,4,5-trihydroxypyrimidine, 2-hydroxy-4-methylpyrimidine, 4,5-diamino-2,6-dihydroxypyrimidine, barbituric acid, 1,3-dimethylbarbituric acid, cyanuric acid, 1-methyl-hexahydropyrimidine-2,4-dione, 1,3-dimethyl-3,4,5,6-tetrahydro-2-1H-pyrimidinone, 5-(hydroxymethyl-2,4-(1H,3H)-pyrimidinedione, 2,4-dihydroxypyrimidine-5-carboxylic acid, 6-azathymine, 5-methyl-1,3,5-triazinan-2-one, N-carbamoylmaleamic acid, and alloxan monohydrate. 25. The composition according to claim 21, wherein the at least one compound is chosen from urea or hydroxyethylurea. 26. The composition according to claim 21, wherein the at least one compound is present in an amount ranging from about 2% to about 50% by weight, relative to the total weight of the composition. 27. The composition according to claim 21, wherein the at least one compound is present in an amount ranging from about 2% to about 10% by weight, relative to the total weight of the composition. 28. The composition according to claim 21, wherein the at least one polymeric thickener is water-soluble or water-dispersible at a pH of 7 and at room temperature (25° C.). 29. The composition according to claim 21, wherein the at least one polymeric thickener is chosen from: (i) nonionic amphiphilic polymers comprising at least one fatty chain and at least one hydrophilic unit; (ii) cationic amphiphilic polymers comprising at least one hydrophilic unit and at least one fatty-chain unit; or (iii) amphoteric amphiphilic polymers comprising at least one hydrophilic unit and at least one fatty-chain unit containing from 10 to 30 carbon atoms. 30. The composition according to claim 21, wherein the at least one polymeric thickener is chosen from nonionic or cationic associative thickening polymers, celluloses, and polyurethanes. 31. The composition according to claim 21, wherein the at least one polymeric thickener is chosen from anionic polymeric associative thickeners comprising at least one acrylic or methacrylic unit. 32. The composition according to claim 31, wherein the at least one polymeric thickener chosen from anionic polymeric associative thickeners comprises at least one hydrophilic unit of unsaturated olefinic carboxylic acid type and at least one hydrophobic unit of (C10-C30)alkyl ester of unsaturated carboxylic acid type. 33. The composition according to claim 32, wherein the at least one polymeric thickener chosen from anionic polymeric associative thickener comprises: at least one hydrophilic unit of unsaturated olefinic carboxylic acid type represented by formula (VIII): wherein R1 is chosen from H or CH3; and at least one hydrophobic unit of (C10-C30)alkyl ester of unsaturated carboxylic acid type represented by formula (IX): wherein R1 is chosen from H or CH3 and R2 is a C10-C30 and alkyl radical. 34. The composition according to claim 31, wherein the at least one polymeric thickener is chosen from those comprising at least one (meth)acrylic monomer bearing at least one sulfonic group, in free form or partially or totally neutralized form, and comprising at least one hydrophobic part. 35. The composition according to claim 21, wherein the at least one polymeric thickener is present in an amount ranging from about 0.01% to about 30% by weight, relative to the total weight of the composition. 36. The composition according to claim 21, further comprising at least one additional polymeric thickener. 37. The composition according to claim 21, further comprising at least one surfactant. 38. The composition according to claim 21, further comprising at least one fatty substance. 39. A process for straightening keratin fibers, comprising: (i) applying to the keratin fibers a cosmetic composition comprising: (a) at least one compound chosen from urea or urea derivatives, present in at least 2% by weight, relative to the total weight of the composition; and (b) at least one polymeric thickener chosen from nonionic, cationic, amphoteric or anionic polymeric associative thickeners wherein the anionic polymeric associative thickener comprises at least one acrylic or methacrylic unit; and (ii) raising the temperature of the keratin fibers via a heating tool, to a temperature ranging from about 25 to about 250° C. 40. The process according to claim 39, wherein the heating tool is an iron. US14/786,608 -04-25 -04-25 Composition for straightening keratin fibres, comprising a urea and/or a urea derivative and a nonionic, cationic, amphoteric or anionic associative polymeric thickener, process and use thereof Abandoned USA1 (en)

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Application Number Priority Date Filing Date Title FR -04-25 FRA FRB1 (en) -04-25 -04-25 COMPOSITION FOR SMOOTHING KERATIN FIBERS COMPRISING A UREA AND / OR A UREA DERIVATIVE AND A NONIONIC, CATIONIC OR AMPHOTERIC POLYMERIC THICKENER, METHOD AND USE FRA FRB1 (en) -04-25 -04-25 COMPOSITION FOR SMOOTHING KERATIN FIBERS COMPRISING UREA AND / OR UREA DERIVATIVE AND ANIONIC (METH) ACRYLIC POLYMERIC THICKENER, METHOD AND USE FR -04-25 PCT/EP/ WOA2 (en) -04-25 -04-25 Composition for straightening keratin fibres, comprising a urea and/or a urea derivative and a nonionic, cationic, amphoteric or anionic associative polymeric thickener, process and use thereof

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KGaA Cosmetic and dermatological compositions comprising (2-hydroxyethyl)urea JPB2 (en) * -09-30 -02-08 アクゾノーベル株式会社 Hair cosmetics FRB1 (en) * -11-09 -03-02 Oreal COSMETIC AND / OR DERMATOLOGICAL COMPOSITION CONTAINING A UREA COMPOUND WOA1 (en) * -11-24 -06-01 The Procter & Gamble Company Method for the permanent shaping of hair using a cationic cellulose derivative FRB1 (en) * -11-26 -04-03 Oreal METHOD FOR DETERMINING KERATIN FIBERS WITH A HEATING MEANS AND A DENATURING AGENT FRB1 (en) * -12-20 -02-23 Oreal SOLAR COMPOSITION COMPRISING AT LEAST MINERAL PIGMENTS OF METAL OXIDE AND AT LEAST ONE HYDROXYALKYLUREE FRB1 (en) * -12-20 -02-23 Oreal SOLAR COMPOSITION COMPRISING AT LEAST ONE INSOLUBLE ORGANIC UV FILTER AND AT LEAST ONE HYDROXYALKYLUREE FRB1 (en) * -12-20 -02-23 Oreal SOLAR COMPOSITION COMPRISING AT LEAST ONE HYDROPHILIC UV FILTER AND AT LEAST ONE HYDROXYALKYLUREE FRB1 (en) * -03-17 -05-11 Oreal COSMETIC CLEANING COMPOSITION CONTAINING A UREA COMPOUND AND A POLYMER FRB1 (en) * -03-17 -05-11 Oreal COSMETIC CLEANING COMPOSITION CONTAINING A UREA COMPOUND AND AN ALKYL GLYCOL CARBOXYLATE COMPOUND JPA (en) * -09-27 -04-12 Shiseido Co Ltd Hair internal damage-improving agent and hair cosmetic FRB1 (en) * -05-24 -08-13 Oreal PROCESS FOR DETERMINING KERATIN FIBERS WITH A HEATING MEANS AND DENATURING AGENTS EPA1 (en) * -07-21 -01-23 Wella Aktiengesellschaft Method and composition for permanently shaping hair EPA1 (en) * -07-21 -01-23 Wella Aktiengesellschaft Method and composition for permanently shaping hair EPA1 (en) * -07-21 -01-23 Wella Aktiengesellschaft Method and composition for permanently shaping hair DEA1 (en) * -07-24 -01-31 Beiersdorf Ag Cosmetic preparation, useful e.g. for hair restructuring, for topical application on skin and/or hair and to prepare shampoo, comprises hydroxyalkyl-urea derivative and cationic caring agent such as cationic- surfactant and/or polymer DEA1 (en) -07-24 -01-31 Beiersdorf Ag Cosmetic preparation, useful e.g. as repellents to protect against mosquitoes, as protective skin cream and to protect against UV-induced skin aging, comprises (2-hydroxyethyl)urea and myristylmyristate DEA1 (en) -12-27 -07-03 Henkel Kgaa Cosmetic or dermatological composition, useful e.g. in the topical treatment of the skin, comprises an aporphine-alkaloids and a further active agent of e.g. purine, natural betaine compounds, monomer, oligomer or polymer of aminoacid USB2 (en) * -06-19 -02-25 Cognis Ip Management Gmbh Shampoo composition with improved care performance WOA2 (en) * -03-19 -09-24 L'oreal Use of a composition and process involving the use of a non-hydroxide base and a protein denaturant with heat for relaxing or straightening hair JPB2 (en) * -03-27 -12-11 株式会社 資生堂 Hair cosmetics BRPIB1 (en) * -05-06 -04-12 Basf Se cosmetic preparation WOA2 (en) * -10-29 -05-06 L'oreal Process for relaxing or straightening hair, using weak dicarboxylic acids with heat JPB2 (en) * -01-14 -07-20 株式会社 資生堂 Hair cosmetics BRPIA2 (en) * -02-04 -03-08 Unilever Nv hair styling method and hair treatment composition USB2 (en) * -12-21 -06-05 Robert Saute Composition and method for hair straightening

• • -04-25 US US14/786,608 patent/USA1/en not_active Abandoned
  • -04-25 BR BRA patent/BRA2/en not_active Application Discontinuation
  • -04-25 ES EST patent/EST3/en active Active
  • -04-25 EP EP.6A patent/EPB1/en active Active
  • -04-25 WO PCT/EP/ patent/WOA2/en active Application Filing
  • -04-25 JP JPA patent/JPB2/en not_active Expired - Fee Related
• • -12-21 US US16/230,323 patent/USB2/en active Active

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Also Published As

Publication number Publication date JPA (en) -06-23 BRA2 (en) -07-25 EPA2 (en) -03-02 JPB2 (en) -11-20 WOA3 (en) -03-19 USB2 (en) -08-17 WOA2 (en) -10-30 EST3 (en) -11-12 EPB1 (en) -03-17 USA1 (en) -04-25

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