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1 Patentamt JEuropaisches European Patent Office 1 1 Office europeen des brevets (11) EP B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention (51) int. CI.6: C08F 290/06, C08F 246/00 of the grant of the patent: Bulletin 1997/07 (21) Application number: (22) Date of filing: (54) Alkyl and/or alkylphenyl poly(oxyalkylene)sorbate copolymers and the use thereof as thickening agents Alkylierte und/oder alkylphenylierte Poly(oxyalkylen)sorbatcopolymere und deren Verwendung als Verdickungsmittel Copolymeres a base de sorbate de poly(oxyalkylene) alkyle et/ou alkylphenyle et leur usage comme agents d'epaississement (84) Designated Contracting States: BE DE ES FR GB (30) Priority: IT MI (43) Date of publication of application: Bulletin 1995/25 (73) Proprietor: 3V SIGMA S.p.A Milano(IT) (72) Inventor: Berte', Ferruccio Bergamo (IT) (74) Representative: Bianchetti, Giuseppe Studio Consulenza Brevettuale, Via Rossini, Milano(IT) (56) References cited: EP-A US-A CO 10 CO 10 CO o Q_ LU Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention). Printed by Rank Xerox (UK) Business Services /3.4

2 Description The present invention relates to thickening agents and the use thereof in cosmetics and textiles. In particular, the present invention relates to alkyl and/or alkylphenyl poly(oxyalkylene)sorbate copolymers and the salts thereof. 5 The major part of synthetic thickening agents consist of polymers and copolymers capable of acting as thickening agents following a partial or total neutralization. In these cases, the low solubility or the insolubility in water of the non-neutralized polymer are made use of, thus allowing to obtain solutions or dispersions of the polymer in relatively high concentrations and of sufficiently low viscosities. This permits the use and the dosage of the thickening agent until the time of the neutralization thereof. 10 Polymer systems behaving like this have been known for a long time and they are in various physical forms which are more or less easy to use. Thickening agents in aqueous solutions are known, e. g. some non cross-linked poly(meth)acrylic acids which, however, are rather difficult to use due to the high viscosity thereof, and moreover are not very effective. Powdered thickening agents are also known, for example, cross-linked poly(meth)acrylic acids described in USA 15 Patent 2,798,053. These products are very effective, but they are used more and more seldom as they cannot meet the current technological requirements since, to use them it is necessary to prepare an aqueous dispersion of the acidic form to use in the thickening process. The step of dispersion of the acidic form is very laborious and lengthy, moreover the obtained thickening agents are not resistant to salts. 20 Effective and easy to use polymer thickening agents are the copolymers in aqueous emulsion or polymer latexes, as those described in the UK Patent 870,994. They are copolymers of methacrylic acid with alkyl (C1-C4) acrylates, optionally cross-linked, obtained with emulsion polymerization techniques. According to these methods, poorly viscous latexes can be obtained, the active content of which ranges from 25 to 50 % by weight. Nevertheless, the salt resistance of these products is still insufficient. 25 Polymer systems, preferably in the form of latex, which are a further advance in terms of effectiveness and salt resistance while being easy to handle are those described in EP-A- 0,013,836 and European Patents 0,01 1,806 and 0,109,820. These publications claim copolymers obtained from monomeric mixtures similar to those described in the already cited UK Patent 870,994 in which, however, novel comonomers are present having a particular structure, such as (meth)acrylates or itaconates of non-ionic surfactants, such as ethoxylated fatty alcohols or ethoxylated alkylphe- 30 nols. These thickening agents are widely used in the textile, detergent and cosmetic fields. Particularly important is the use of the latter thickening agents in latex form as additives to adjust, increasing it, the final viscosity of pastes for pigment printing of textiles. A technological problem in printing textiles, in particular mixed synthetic fiber/cotton textiles, such as polyester/cot- 35 ton, arises from the colour rendering of the paste and the dye fastness and contour sharpness of the printed design ("bleeding" effect). Surprisingly it has been found that, using the copolymers according to the present invention in these systems, not only an increase in viscosity takes place, but also the yield of the printing process improves also compared with the copolymers according to the above cited literature. Particularly, the copolymers of the present invention are character- 40 ized by a better colour rendering index and the excellent contour sharpness in the pigment printing on cotton and mixed polyester/cotton. An object of the present invention are alkyl and/or alkylphenyl poly(oxyalkylene)sorbate copolymers and the salts thereof with alkali metals, ammonia or amines obtained by copolymerization of: 45 (1) at least 10% by weight of one or more monomers selected from: methacrylic acid, acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, citraconic acid and sorbic acid; (2) from 0.5 to 30% by weight of at least one monomer of formula: 50 wherein: CH3-CH=CH-CH=CH-C(0)-0-[(CH2CH20)x(CHR'CH20)y] - R x and y can be the same or different and can have values from 0 to 60 and 55 x + y can range from 1 to 60 R' is CrC2 alkyl R is C6-C30 alkyl or C6-C30 alkylcycloalkyl or C6-C30 aralkyl and the expression (CH2CH20)x(CHR'CH20)y means that the (CH2CH20)x and (CHR'CH20)y groups can be present in any order, from random to block and, optionally, also reversed. 2

3 Preferably, the copolymers of the present invention contain a further component (3) consisting of vinyl compounds or mixtures thereof selected from esters and amides of the acrylic, methacrylic and itaconic acids, acrylonitrile, methacrylonitrile, styrene, a-methylstyrene, vinyltoluene, vinyl and vinylidene halides, butadiene and isopropene, vinyl ethers and vinyl esters. 5 If desired, the copolymers of the present invention can have various cross-linking degrees. In this case, the copolymerization also comprises from 0 to 2% by weight of one or more polyunsaturated monomers, such as ethylene glycol dimethacrylate, divinylbenzene, allyl methacrylate and pentaerythritol polyallyl ethers. Preferably the component (1) is methacrylic acid and/or acrylic acid; the component (3) is an alkyl (meth)acrylate, for example, ethyl acrylate. 10 Another object of the present invention is a process for the preparation of the above copolymers, by means of radical polymerization. Preferably, the polymerization is carried out in aqueous emulsion, so as to obtain polymeric latexes, with a polymeric solid content up to 50% on the total weight. Sodium lauryl sulfate and sulfates of ethoxylated long chain alcohols are used as emulsifying agents, in amounts ranging from 0,2 to 6% by weight related to the monomers. 15 Among the radical polymerization initiators, ammonium or alkali metal persulfates are used, in amounts of % by weight related to the monomers. Temperatures can range from 40 to 1 00 C. Moreover, it is possible to use chain-transfer agents as molecular weight modifiers, such as mercaptoethanol and alkylmercaptanes, or also polyunsaturated monomers as cross-linking or branching agents, such as divinylbenzene 20 and ethylene glycol dimethylacrylate. The molecular weight modifiers and the cross-linkers can optionally be used to modify the thickening properties of the copolymers according to the present invention. In particular, the molecular weight modifiers serve to decrease the thickening action, but they can lead to products having a rheology more suitable to some uses, on the contrary crosslinkers can give polymers with a higher thickening action. 25 In a preferred embodiment, the invention provides a polymeric latex obtained by polymerization in aqueous emulsion of a monomeric system consisting of: (1) from 20 to 50% by weight of methacrylic and/or acrylic acid, (2) from 1 to 20% by weight of ester of sorbic acid with a Ci0-C22 alkyl poly(oxyethylene)ethanol in which the 30 number of oxyethylene units is at least 10, (3) from 40 to 60% by weight of ethyl acrylate, (4) from 0 to 1% by weight of one or more polyunsaturated monomers. Though the copolymers of the present invention are easier to use when in the form of latex, for particular purposes, 35 it would be preferable to use them in other physical forms, for example as powders. In these cases, a satisfactory product can be obtained drying the polymeric latex in a spray-dryer. Another object of the present invention is the use of the copolymers described herein as thickening agents. Generally speaking, said copolymers are useful in thickening and suspending gelatin-like mucilaginous or colloidal aqueous systems, in particular cosmetic or personal care compositions, such as shampoos, tooth pastes, creams, oint- 40 ments. In a second preferred embodiment, the copolymers of the invention, provided in various forms, latexes or powders, are used to thicken pastes for pigment printing. The present invention also relates to a process for thickening the above aqueous systems. Said process is carried out preferably adding the copolymers according to the present invention to the system to 45 thicken and thickening the mixture by means of neutralization with bases, for example alkali metal hydroxides, ammonium hydroxide, ammonia and amines. In the case of pastes for pigment printing already neutralized and ready-to-use, the adjustment of the viscosity is obtained by simple addition and admixing of the latex of the copolymers according to the present invention in sufficiently low amounts not to appreciably change the final ph. so In any case, it is possible to thicken the same aqueous systems adding the copolymers in an already partially or completely neutralized form. It has surprisingly been found that the copolymers of the present invention interact in aqueous solutions with a number of water-soluble surfactants, preferably the anionic and/or non-ionic ones. The effect on the viscosity of the system is, in these cases, synergistic, leading to viscosity values much higher than those expected, and it can be made 55 use of to thicken aqueous systems based on surfactants, for example shampoos. Further embodiments of the invention can be seen from the dependant claims. In the following, examples illustrative of the invention are reported. Parts and percent values are by weight and temperatures are in degrees centigrade. 3

4 Example A Preparation of the monomer (component 2). A mixture of 150 g of cetyl stearyl ethoxylated alcohol with 25 moles of ethylene oxide, 0.50 g of hydroquinone mon- 5 omethyl ether and 100 g of toluene is heated to C until a homogeneous solution. After that, under an air stream, g of sorbic acid and 2.0 g of concentrated sulfuric acid are added. The mixture is refluxed removing the reaction water. When no more water develops, air bubbling is stopped and toluene is distilled off at atmospheric pressure, then under vacuum to reach 100 C and 30 mmhg of vacuum residue. 158 g of a brown liquid product are obtained, which solidifies below 40 C. 10 Example B Preparation of the copolymer. An aqueous emulsion of the monomers is prepared, consisting of: g of demineralized water, 6.6 g of 28% 15 aqueous sodium lauryl sulfate, g of ethyl acrylate, 92.7 g of methacrylic acid, 24.3 g of monomer of the example A. This emulsion is deoxygenated by nitrogen bubbling. A solution of g of demineralized water and 6.6 g of 28% aqueous sodium lauryl sulfate, deoxygenated and heated to 85 C, is quickly added, under a nitrogen stream, with 18.9 g of emulsion of the monomers prepared above and 37.7 g of a 0.70% ammonium persulfate aqueous solution. The mixture is reacted for 15 min., then the remaining g of monomeric emulsion and 18.3 g of 0.70% ammonium persulfate aqueous solution are fed continuously for a time of about 90 minutes. At the end of feeding, after about 30 minutes, a further 28.5 g of 0.35% ammonium persulfate aqueous solution are added and the polymerization is completed in 60 minutes at 85 C. Finally, the resulting latex is cooled and discharged. In Table I, the Brookfield (RVT-20 rpm) viscosity values of 0.50% by weight polymer aqueous solutions neutralized 25 with sodium hydroxide are reported. The values after addition of 0.20% by weight of sodium lauryl sulfate (SLS) are also given. For comparison, the data relating to two latexes obtained following the procedures of other patents cited above are reported. 30 Table I Polymeric latex Brookfield RVT viscosity 25 C - 20 rpm -mpa.s % SLS 35 A 800 9, B 1,800 8,000 C 860 7,000 Wherein: A = Polymeric latex obtained according to the present example B = Comparison polymeric latex obtained according to example Bl of EP 0,109,820 C = Comparison polymeric latex obtained according to example 4 - Tab. IV - Polymer BL of EP-A- 0,013, Example C A paste for pigment printing is prepared mixing by means of a Silverson stirrer the following products: 3.80 g DEFOPRINT 3.40 g 25% AMMONIA g NOVAPRINT NS g LEGOPRINT EPC g FIXOL ST g HARD WATER (hardness 25 F) g BLUE RT PIGMENT 4

5 The viscosity of this paste is of mpa.s (RVT-25 C-20 rpm) g of latex are added to 500 g of paste. After homogenization with a Silverson stirrer, the same final viscosity of mpa.s (RV2-20 rpm) is obtained, respectively with each of the three latexes A, B, C described. Printing tests on cotton textile and mixed 65:35 polyester/cotton textile are then carried out. 5 The printing process is effected on a mini laboratory machine type MDF R376 by the firm J. Zimmer. The prints are subsequently fixed by heat treatment at 160 C for 3 min. In Table II the obtained results are reported, the evaluation being visual. Table II 10 LATEX COLOUR YIELD CONTOUR SHARPNESS 15 wherein 20 0 = Low 1 = Average 2 = High COTTON PES/COT 65:35 COTTON PES/COT 65: A B C Claims 1. Copolymers obtained by copolymerization of: (1) at least 10% by weight of a caboxylic acid selected from: methacrylic acid, acrylic acid, itaconic acid, maleic 30 acid, fumaric acid, crotonic acid, citraconic acid and sorbic acid and mixtures thereof, (2) from 0.5 to 30% by weight of at least one monomer of formula: 35 wherein: CH3-CH=CH-CH=CH-C(0)-0-[(CH2CH20)x(CHR'CH20)y] - R x and y can be the same or different and can have values from 0 to 60 and x + y can range from 1 to 60 R' is CrC2 alkyl 40 R is C6-C30 alkyl or C6-C30 alkylcycloalkyl or C6-C30 aralkyl and the expression (CH2CH20)x(CHR'CH20)y means that the (CH2CH20)x and (CHR'CH20)y groups can be present in any order, from random to block and, optionally, also reversed, and the salts thereof with alkali metals, ammonia and amines Copolymers according to claim 1 copolymeryzed with a further component 3 selected from esters and amides of acrylic, methacrylic, itaconic acids, acrylonitrile, methacrylonitrile, -methylstyrene, vinyltoluenes, vinyl and vinylidene halides, butadiene and isoprene, vinyl esters and vinyl ethers or mixtures thereof Copolymers according to claims 1-2, cross-linked with at least one polyunsaturated monomer. 4. Copolymers according to claims 1-3, wherein the component (2) is present in an amount ranging from 1 to 20% by weight. 5. Copolymers according to claims 1-4, wherein the component 1 is present in an amount ranging from 20 to 50% by 55 weight. 6. Copolymers according to claims 1-5, wherein the component (1) is acrylic acid, methacrylic acid, itaconic acid or mixtures thereof. 5

6 7. Copolymers according to claims 1-6, wherein the component (2) is an ester of sorbic acid with an ethoxylated C10- C22 alcohol. 8. Copolymers according to claims 2-7, wherein the component (3) comprises one or more C1-C4 alkyl acrylates 5 and/or methacrylates. 9. A process for the preparation of copolymers of the claims 1-8, the process comprising of: 10 a) the radical copolymerization of: (1) at least 10% by weight of a carboxylic acid selected from: methacrylic acid, acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, citraconic acid and sorbic acid and mixtures thereof; (2) from 0.5 to 30% by weight of at least one monomer of formula: 15 CH3-CH=CH-CH=CH-C(0)-0-[(CH2CH20)x(CHR'CH20)y] - R wherein: x and y can be the same or different and can have values from 0 to 60, 20 and x + y can range from 1 to 60 R' is CrC2 alkyl R is C6-C30 alkyl or C6-C30 alkylcycloalkyl or C6-C30 aralkyl and the expression (CH2CH20)x(CHR'CH20)y means that the (CH2CH20)x and (CHR'CH20)y groups can be present in any order, from random to block and, optionally, also reversed; 25 (3) optionally one monomer or mixtures of monomers selected from esters and amides of acrylic, methacrylic, itaconic acids, acrylonitrile, methacrylonitrile, -methylstyrene, vinyltoluenes, vinyl and vinylidene halides, butadiene and isoprene, vinyl esters and vinyl ethers and/or one or more polyunsaturated monomers as cross-linking agents, and/or a molecular weight modifier; 30 b) possible neutralization of the resulting copolymer with a base selected from alkali metal hydroxides, ammonium hydroxide or an amine. 10. A process according to claim 9, comprising the emulsion polymerization in the presence of an emulsifying agent to 35 give a polymeric latex A process according to claim 1 0, comprising drying said latex to give a polymeric powder Polymeric latexes obtainable with the process of claim Polymeric powders obtainable with the process of claim Use of the copolymers of claims 1-8 as thickening agents Use of the polymeric latexes of claim 1 2 as thickening agents. 16. Use of the polymeric powders of claim 13 as thickening agents A process for thickening gelatin-like mucilaginous aqueous or colloidal systems comprising: a) addition of a thickening agent of claims 14-16; b) neutralization of the mixture with bases. 18. A process according to claim 17, comprising the addition of said thickening agent, partially or totally neutralized, 55 without said subsequent step b) of neutralization. 19. A process according to claims 17 or 18, wherein said aqueous system contains one or more water-soluble surfactants, preferably anionic and/or non-ionic ones. 6

7 20. Gelatin-like mucilaginous or colloidal aqueous systems obtainable by the processes of claims Aqueous systems according to claim 20 in the form of cosmetic compositions, preferably shampoos, toothpastes, creams, ointments. 22. Aqueous systems according to claim 20 in the form of pastes for pigment printing of textiles. 23. A process for printing textiles, preferably polyester/cotton, wherein the printing is carried out with a pigment paste of claim Printed textiles, preferably polyester/cotton, obtainable by the process of claim 23. Patentanspruche Copolymere, erhalten durch Copolymerisation von (1) mindestens 10 Gew% einer der Carbonsauren ausgewahlt aus: Methacrylsaure, Acrylsaure, Itaconsaure, Maleinsaure, Fumarsaure, Crotonsaure, Citrakonsaure und Sorbinsaure und deren Mischungen, 20 (2) von 0,5 bis 30 Gew% mindestens eines Monomeren der Formel: CH3-CH=CH-CH=CH-C(0)-0-[(CH2CH20)x(CHR'CH20)y]-R, worin 25 x und y gleich oder unterschiedlich sind und Werte von 0 bis 60 aufweisen und x + y einen Wert von 1 bis 60 hat, R' fur CrC2-Alkyl steht, R C6-C30-Alkyl, C6-C30-Alkylcycloalkyl oder C6-C30-Aralkyl darstellt, 30 und wobei der Ausdruck (CH2CH20)x(CHR'CH20)y bedeutet, dab die Gruppen (CH2CH20)x und (CHR'CH20)y in beliebiger Reihenfolge vorliegen konnen, von statistischer Ordnung bis zu blockweiser Ordnung und gegebenenfalls auch umgekehrt, und deren Salze mit Alkalimetallen, Ammoniak und Aminen Copolymere nach Anspruch 1, copolymerisiert mit einer weiteren Komponente 3, ausgewahlt aus Estern und Amiden von Acrylsaure, Metacrylsaure, Itaconsauren, Acrylnitril, Methacrylnitril, a-methylstyrol, Vinyltoluolen, Vinylund Vinylidenhalogeniden, Butadien und Isopren, Vinylestern und Vinylethern oder deren Mischungen Copolymere nach den Anspriichen 1-2, die mit mindestens einem polyungesattigten Monomer vernetzt sind. 4. Copolymere nach den Anspriichen 1-3, worin Komponente (2) in einer Menge von 1 bis 20 Gew% vorliegt. 5. Copolymere nach den Anspriichen 1-4, worin Komponente (1) in einer Menge von 20 bis 50 Gew% vorliegt Copolymere nach den Anspriichen 1-5, worin Komponente (1) Acrylsaure, Methacrylsaure, Itaconsaure oder eine Mischung daraus ist Copolymere nach den Anspriichen 1-6, worin Komponente (2) ein Ester der Sorbinsaure mit einem ethoxylierten Ci0-C22-Alkohol ist. 8. Copolymere nach den Anspriichen 2-7, worin Komponente (3) ein oder mehrere C1-C4-Alkylacrylate und/oder Methacrylate umfabt. 9. Verfahren zur Herstellung von Copolymeren nach den Anspriichen 1-8, umfassend: (a) die radikalische Copolymerisation von (1) mindestens 10 Gew% einer der Carbonsauren ausgewahlt aus: Methacrylsaure, Acrylsaure, Itaconsaure, Maleinsaure, Fumarsaure, Crotonsaure, Citraconsaure und 7

8 Sorbinsaure und deren Mischungen, (2) von 0,5 bis 30 Gew% mindestens eines Monomeren der Formel: worin CH3-CH=CH-CH=CH-C(0)-0-[(CH2CH20)x(CHR'CH20)y]-R, x und y gleich oder unterschiedlich sind und Werte von 0 bis 60 aufweisen und x + y einen Wert von 1 bis 60 haben kann, R' fur CrC2-Alkyl steht, R C6-C30-Alkyl, C6-C30-Alkylcycloalkyl oder C6-C30-Aralkyl darstellt, und wobei der Ausdruck (CH2CH20)x(CHR'CH20)y bedeutet, dab die Gruppen (CH2CH20)x und (CHR'CH20)y in beliebiger Reihenfolge vorliegen konnen, von statistischer bis zu blockweiser Ordnung und gegebenenfalls auch umgekehrt; (3) gegebenenfalls einem Monomer oder Mischungen von Monomeren ausgewahlt aus Estern und Amiden von Acrylsaure, Methacrylsaure, Itaconsaure, Acrylnitril, Methacrylnitril, a-methylstyrol, Vinyltoluolen, Vinyl- und Vinylidenhalogeniden, Butadien und Isopren, Vinylestern und Vinylethern und/oder einem oder mehreren polyungesattigten Monomeren als Vernetzungsmitteln und/oder eine das Molekulargewicht modifizierende Substanz; (b) mogliche Neutralisierung des resultierenden Copolymers mit einer Base, ausgewahlt aus Alkalimetallhydroxiden, Ammoniumhydroxid oder einem Amin. 10. Verfahren nach Anspruch 9, welches die Emulsionspolymerisation in Anwesenheit eines Emulgators unter Erhalt eines polymeren Latex umfabt. 11. Verfahren nach Anspruch 10, umfassend das Trocknen der Latex unter Erhalt eines Polymerpulvers. 12. Polymere Latizes, erhaltlich nach dem Verfahren nach Anspruch Polymere Pulver, erhaltlich nach dem Verfahren nach Anspruch Verwendung der Copolymere der Anspriiche 1-8 als Verdickungsmittel. 15. Verwendung der polymeren Latizes nach Anspruch 12 als Verdickungsmittel. 16. Verwendung der polymeren Pulver nach Anspruch 13 als Verdickungsmittel. 17. Verfahren zur Eindickung Gelatine-ahnlicher, mucilager wabriger oder kolloidaler Systeme, umfassend: a) die Zugabe eines Verdickungsmittels nach den Anspriichen 14-16; b) Neutralisation der Mischung mit Basen. 18. Verfahren nach Anspruch 17, umfassend die Zugabe teilweise oder vollstandig neutralisierten Verdickungsmittels, ohne den anschliebenden Neutralisationsschritt b) Verfahren nach den Anspriichen 1 7 oder 1 8, wobei die genannten wabrigen Systeme einen oder mehrere wasserlosliche oberflachenaktive Substanzen, vorzugsweise anionische und/oder nichtionische oberflachenaktive Substanzen, enthalten. 20. Gelatine-ahnliche, mucilage oder kolloidale wabrige Systeme, erhaltlich nach den Verfahren gemab den Anspriichen WaBrige Systeme nach Anspruch 20, in Form von kosmetischen Praparaten, bevorzugterweise Shampoos, Zahnpasten, Cremes und Salben. 22. WaBrige Systeme nach Anspruch 20, in Form von Pasten zum Pigmentdruck von Textilien. 8

9 23. Verfahren zum Bedrucken von Textilien, vorzugsweise Polyester/Baumwolle, wobei man das Bedrucken mit einer Pigmentpaste nach Anspruch 22 durchfuhrt. 24. Bedruckte Textilien, vorzugsweise Polyester/Baumwolle, erhaltlich nach dem in Anspruch 23 genannten Verfahren. Revendications 1. Copolymeres obtenus par la copolymerisation de: (1) au moins 10% en poids d'un acide carboxylique choisi parmi: I'acide methacrylique, I'acide acrylique, I'acide itaconique, I'acide maleique, I'acide fumarique, I'acide crotonique, I'acide citraconique et I'acide sorbique et des melanges de ceux-ci, (2) de 0,5 a 30% en poids d'au moins un monomere de formule: dans laquelle: CH3-CH=CH-CH=CH-C(0)-0-[(CH2CH20)x(CHR'CH20)y] - R x et y peuvent etre identiques ou differents et peuvent avoir des valeurs de 0 a 60 et x + y peut varier de 1 a 60 R' est un alkyle en C1-C2 R est un alkyle en C6-C30 ou un alkylcycloalkyle en C6-C30 ou un aralkyle en C6-C30 et I'expression (CH2CH20)x(CHR'CH20)y signifie que les groupes (CH2CH20)x et (CHR'CH20)y peuvent etre presents dans un ordre quelconque, de statistique a bloc et, eventuellement, egalement inverse, et des sels de ceux-ci avec des metaux alcalins, I'ammoniac et des amines. 2. Copolymeres selon la revendication 1, copolymerises avec un composant supplemental 3 choisi parmi des esters et des amides des acides acrylique, methacrylique et itaconique, I'acrylonitrile, le methacrylonitrile, I'amethylstyrene, des vinyltoluenes, des halogenures de vinyle et de vinylidene, le butadiene et I'isoprene, des esters vinyliques et des ethers vinyliques ou des melanges de ceux-ci. 3. Copolymeres selon les revendications 1-2, reticules avec au moins un monomere polyinsature. 4. Copolymeres selon les revendications 1-3, dans lesquels le composant (2) est present en une quantite variant de 1 a 20% en poids. 5. Copolymeres selon les revendications 1-4, dans lesquels le composant (1) est present en une quantite variant de 20 a 50% en poids. 6. Copolymeres selon les revendications 1-5, dans lesquels le composant (1) est I'acide acrylique, I'acide methacrylique, I'acide itaconique ou des melanges de ceux-ci. 7. Copolymeres selon les revendications 1-6, dans lesquels le composant (2) est un ester de I'acide sorbique avec un alcool en C10-C22 ethoxyle. 8. Copolymeres selon les revendications 2-7, dans lesquels le composant (3) comprend un ou plusieurs acrylates et/ou methacrylates d'alkyle en Ci -C4. 9. Procede de preparation de copolymeres des revendications 1-8, le procede comprenant: a) la copolymerisation radicalaire de: (1) au moins 10% en poids d'un acide carboxylique choisi parmi: I'acide methacrylique, I'acide acrylique, I'acide itaconique, I'acide maleique, I'acide fumarique, I'acide crotonique, I'acide citraconique et I'acide sorbique et des melanges de ceux-ci, (2) de 0,5 a 30% en poids d'au moins un monomere de formule: CH3-CH=CH-CH=CH-C(0)-0-[(CH2CH20)x(CHR'CH20)y] - R

10 dans laquelle: x et y peuvent etre identiques ou differents et peuvent avoir des valeurs de 0 a 60 et x + y peut varier de 1 a 60 R' est un alkyle en Ci-C2 R est un alkyle en C6-C30 ou un alkylcycloalkyle en C6-C30 ou un aralkyle en C6-C30 et I'expression (CH2CH20)x(CHR'CH20)y signifie que les groupes (CH2CH20)x et (CHR'CH20)y peuvent etre presents dans un ordre quelconque, de statistique a bloc et, eventuellement, egalement inverse, (3) eventuellement un monomere ou des melanges de monomeres choisis parmi des esters et des amides des acides acrylique, methacrylique et itaconique, I'acrylonitrile, le methacrylonitrile, I'a-methylstyrene, des vinyltoluenes, des halogenures de vinyle et de vinylidene, le butadiene et I'isoprene, des esters vinyliques et des ethers vinyliques et/ou un ou plusieurs monomeres polyinsatures en tant qu'agents de reticulation, et/ou un modificateur de poids moleculaire; b) une neutralisation possible du copolymere resultant avec une base choisie parmi des hydroxydes de metaux alcalins, I'hydroxyde d'ammonium ou une amine. 10. Procede selon la revendication 9, comprenant la polymerisation en emulsion en presence d'un agent emulsifiant pour donner un latex polymere. 11. Procede selon la revendication 10, comprenant le sechage dudit latex pour donner une poudre polymere. 12. Latex polymeres pouvant etre obtenus avec le procede de la revendication Poudres polymeres pouvant etre obtenues avec le procede de la revendication Utilisation des copolymeres des revendications 1-8 en tant qu'agents d'epaississement Utilisation des latex polymeres de la revendication 1 2 en tant qu'agents d'epaississement Utilisation des poudres polymeres de la revendication 1 3 en tant qu'agents d'epaississement. 17. Procede d'epaississement de systemes gelatineux colloi'daux ou mucilagineux aqueux comprenant: a) I'addition d'un agent epaississant des revendications 14-16; b) la neutralisation du melange avec des bases. 18. Procede selon la revendication 17, comprenant I'addition dudit agent epaississant, partiellement ou totalement neutralise, sans ladite etape subsequente b) de neutralisation Procede selon les revendications 1 7 ou 1 8, dans lequel ledit systeme aqueux contient un ou plusieurs agents tensio-actifs hydrosolubles, de preference anioniques et/ou non ioniques. 20. Systemes gelatineux mucilagineux ou colloi'daux aqueux pouvant etre obtenus par les procedes des revendications Systemes aqueux selon la revendication 20, sous la forme de compositions cosmetiques, de preference des shampooings, des dentifrices, des cremes, des pommades. 22. Systemes aqueux selon la revendication 20, sous la forme de pates pour la teinture pigmentaire de textiles. 23. Procede d'impression de textiles, de preference de polyester/coton, dans lequel I'impression est effectuee avec une pate pigmentaire de la revendication Textiles imprimes, de preference de polyester/coton, pouvant etre obtenus par le procede de la revendication 23.