WO2007145399A1

WO2007145399A1 - Associative polymeric thickener and surfactant

Info

Publication number: WO2007145399A1
Application number: PCT/KR2006/004470
Authority: WO
Inventors: Do Hoon Kim; Yong Jin Kim; Chang Man Park; Jin Woong Kim; Jun Oh Kim; Chae Wook Kim
Original assignee: Amorepacific Corporation
Priority date: 2006-06-12
Filing date: 2006-10-31
Publication date: 2007-12-21
Also published as: KR100715613B1

Abstract

Disclosed herein are the use as a thickener and surfactant of an associative polymer represented by formula 1, and a cosmetic composition containing the polymer as an active ingredient. More specifically, disclosed are the use as a thickener and surfactant of the associative polymer (formula 1), which is obtained by allowing a polyisocyanate compound represented by R2- (NCO) 2 to react with polyethylene glycol HO(CH2CH2O)nCH2CH2OH (n= 100-3000), and then allowing the reaction product to react with a monoalcohol represented by R1-OH, as well as the use of the associative polymer as a surfactant, and a cosmetic composition containing the associative polymer as an active ingredient. Because the associative polymer represented by formula 1 has hydrophilic and lipophilic groups, it can be used alone to prepare an emulsion. In addition, because the associative polymer can maintain viscosity even in conditions of various pHs and salts, the use of the associative polymer as an active ingredient makes it possible to prepare an excellent cosmetic composition, which is stable and shows no decrease in viscosity.

Description

[DESCRIPTION]

[invention Title]

ASSOCIATIVE POLYMERIC THICKENER AND SURFACTANT [Technical Field] The present invention relates to a thickener composed of an associative polymer represented by formula 1 below, the use of the associative polymer as a surfactant, and a cosmetic composition containing the associative polymer as an active ingredient. More particularly, the present invention relates to a thickener composed of an associative polymer (formula 1) , which is obtained by allowing a polyisocyanate compound represented by R₂- (NCO) ₂ to react with polyethylene glycol HO(CH₂CH₂O)_nCH₂CH₂OH (n= 100-3000), and then allowing the reaction product to react with a monoalcohol represented by Ri-OH, as well as the use of the associative polymer as a surfactant, and an excellent cosmetic composition containing the associative polymer as an active ingredient.

Because the inventive associative polymer represented by formula 1 has hydrophilic and lipophilic groups, it can be used alone to prepare an emulsion. In addition, because the associative polymer can maintain viscosity even in conditions of various pHs and salts, the use of the associative polymer as an active ingredient makes it possible to prepare a cosmetic composition, which is stable and shows no decrease in viscosity. [Formula 1]

wherein Ri represents a branched, secondary monovalent hydrocarbon group or primary hydrocarbon group having 8-36 carbon atoms, R₂ represents a hydrocarbon group, which may have an urethane bond, n is an integer ranging from 100 to 3000, and m is an integer ranging from 1 to 5. [Background Art]

In the prior art, many kinds of polymers have been frequently used as viscosity adjusters in personal care products. Such water-soluble polymers have anionic groups and cationic groups and are thickened by ionic repulsion. The most frequently used anionic polymer is a carboxyvinyl polymer, which is very excellent with respect to thickening ability and emulsion stabilization. However, the water- soluble polymers exhibit thickening ability by electrostatic repulsive forces, and thus, in conditions of various salts or pHs, the electrostatic repulsive forces are offset to greatly reduce the thickening ability. Accordingly, in such conditions, the water-soluble polymers cannot show normal emulsion stability and thickening ability.

Recently, there have been efforts to develop products, which contain various active ingredients or are used at various pHs . However, in the case of such various active ingredients and pHs, viscosity is rapidly reduced, making it difficult to develop products. This is because such active ingredients contain various salts, which reduce the thickening ability of the above-described polymers. The reduction in viscosity leads to the reduction in the stability of an emulsion and also makes it difficult to develop normal cosmetic products . [Disclosure] [Technical Problem]

Accordingly, the present inventors have conducted studies on a polymer, which is stable in conditions of various salts and pHs and can show thickening ability, and as a result, found that, when a nonionic associative polymer (formula 1) prepared according to the present invention is applied in an emulsion-type cosmetic composition, the preparation of an emulsion-type cosmetic composition, which shows a low decrease in viscosity even under conditions of various pHs and salts and is very stable, becomes easy, and ultimately, the associative polymer can be used as a thickener and a surfactant, thereby completing the present invention. Accordingly, it is an object of the present invention to provide the use as a thickener and surfactant of a nonionic associative polymer, represented by formula 1 and having excellent thickening ability, and an emulsion-type cosmetic composition containing the polymer as an active ingredient .

[Technical Solution]

To achieve the above object, in one aspect, the present invention provides an associative polymeric thickener represented by formula 1 below: [Formula 1]

wherein Ri represents a branched, secondary monovalent hydrocarbon group or primary hydrocarbon group having 8-36 carbon atoms, R₂ represents a hydrocarbon group, which may have an urethane bond, n is an integer ranging from 100 to 3000, and m is an integer ranging from 1 to 5.

In another aspect, the present invention provides an associative polymeric surfactant represented by formula 1 above .

In still another aspect, the present invention provides a cosmetic composition containing the associative polymer represented by formula 1. Hereinafter, the present invention will be described in further detail.

The associative polymer (formula 1) according to the present invention can be obtained by allowing a polyisocyanate compound represented by R₂- (NCO) ₂ to react with polyethylene glycol HO(CH₂CH₂O)_nCH₂CH₂OH (n= 100-3000) and then allowing the reaction product to react with a monoalcohol represented by Ri-OH. In this case, Ri and R₂ in formula 1 are determined by R₂-(NCO)₂ and Ri-OH.

The polyisocyanate compound represented by R₂-(NCO)₂, which can preferably be used in the present invention, has two isocyanates in the molecule, and the carbon atom number thereof have no great effect on the physical properties thereof. Accordingly, as the polyisocyanate compound, any diisocyanate compound can be used without a particular limitation in the present invention as long as it has two isocyanates, and the kind thereof or the carbon atoms of R₂ are not specifically limited. Examples of the diisocyanate compounds include aliphatic diisocyanates, aromatic diisocyanates, alicyclic diisocyanates, biphenyl diisocyanates and phenylmethane diisocyanates. Examples of aliphatic diisocyanates include methylene diisocyanate, dimethylene diisocyanate, triethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dipropylether diisocyanate, 2, 2-dimethylpentane diisocyanate, 3- methoxyhexane diisocyanate, octamethylene diisocyanate, 2,2, 4 -trimethylpentane diisocyanate , nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxygexane diisocyanate, 1, 4-butyleneglycolpropylether diisocyanate, thiodihexyl diisocyanate, meta-xylylene diisocyanate, para- xylylene diisocyanate, tetramethylxylene diisocyanate and the like.

Examples of aromatic diisocynates include meta- phenylene diisocyanate, para-phenylene diisocyanate, 2,4- tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, tolidine diisocyanate, 1,4- naphthalene diisocyanate, 1, 5-naphthalene diisocyanate, 2, 6-naphthalene diisocyanate and 2, 7-naphthalene diisocyanate.

Examples of alicyclic diisocyanates include hydrogenated xylylene diisocyanate and isophorone diisocyanate.

Examples of biphenyl diisocyanates include biphenyl diisocyanate, 3, 3 ' -dimethylbiphenyl diisocyanate and 3,3'- dimethoxybiphenyl diisocyanate.

Examples of phenylmethane diisocyanates include diphenylmethane-4 , 4 ' -diisocyanate, 2,2'- dimethyldiphenylmethane4 , 4 ' -diisocyanate, diphenyldimethylmethane-4, 4' -diisocyanate, 2, 5, 2', 5'- tetramethyldipheny1-methane-4,4'-diisocyanate , cyclohexylbis (4-isocyonthophenyl) methane, 3 , 3' -dimethoxy- diphenylmethane-4 , 4 ' -diisocyanate, 4,4'- dimethoxydiphenylethane-3 , 3 ' -diisocyanate, 4,4'- diethoxydiphenylmethane-3 , 3 ' -diisocyanate, 2,2' -dimethyl- 5,5' -dimethoxydiphenylmethane-4,4' -diisocyanate, 3,3'- dichlorodiphenyldimethylmethane-4 , 4 ' -diisocyanate, benzophenone-3 , 3 ' -diisocyanate and the like.

The monoalcohols represented by Ri-OH, which can preferably be used in the present invention, is branched alcohol (formula 2) , secondary monoalcohol (formula 3) and primary alcohol (formula 4) , and the kind thereof is not specifically limited.

Among the monoalcohols, the branched alcohol is represented by formula 2 below. [Formula 2]

wherein R₃, R₄ and R₅, which may be the same or different from each other, represent hydrocarbon groups, including alkyl, alkenyl, alkylaryl, cycloalkyl and cycloalkenyl groups, and particularly R₅ is preferably a - CH₂- group. Preferably, each of R₃, R₄ and R₅ has more than 4 carbon atoms .

Among the monoalcohols, the secondary monovalent alcohol is represented by formula 3 below. [Formula 3] k_/n Un 6

wherein R₆ and R₇, which may be the same or different from each other, represent hydrocarbon groups, including alkyl, alkenyl, alkylaryl, cycloalkyl and cycloalkenyl groups. Preferably, each of R₆ and R₇ has more than 4 carbon atoms .

Among the monoalcohols, the primary alcohol is represented by formula 4 below. [Formula 4]

R-OH a wherein R₈ is a hydrocarbon group such as an alkyl, alkenyl, alkylaryl, cycloalkyl or cycloalkenyl group and preferably has more than 8 carbon atoms .

Accordingly, R₁ is a group excluding a hydroxyl group in the above formulas 2, 3 and 4.

In the above formulas 2, 3 and 4, R₃ to R₈ are hydrocarbon groups, for example, alkyl, alkenyl, alkylaryl, cycloalkyl and cycloalkenyl groups.

Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, myristyl, palmityl, stearyl, isostearyl, icosyl, docosyl, tetracosyl, thoriacontyl , 2-octyldodecyl, 2-dodecylhexadecyl, 2-tetradecyl-octadecyl and monomethyl branched isostearyl groups .

Examples of the alkenyl group include vinyl, allyl, propenyl, isopropenyl, butenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl and oleyl groups.

Examples of the alkylaryl group include phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl , butylphenyl , pentylphenyl , hexylphenyl , heptylphenyl , octylphenyl, nonylphenyl, α-naphthyl and β-naphthyl groups.

Examples of the cycloalkyl and cycloalkenyl groups include cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, and methylcycloheptenyl groups. R₃, R₄, R₅, R₆ and R₇ and R₈ preferably represent an alkyl group, and the sum of carbon atoms in Ri is preferably 8-36, and more preferably 12-24. Particularly, in order to show good thickening effects, R₃, R₄, R₅, R₆ and R₇ in the above formulas 2 and 3 preferably have more than 4 carbon atoms, and R₆ preferably has more than 8 carbon atoms. In this case, a good thickening effect is obtained.

The molecular weight of the polyethylene glycol

HO(CH₂CH₂O)_nCH₂CH₂OH is preferably 500-135000, and more preferably 2000-35000. In this case, a good thickening effect can be obtained.

The inventive thickener consisting of the associative polymer represented by formula 1 is nonionic, and shows a good thickening effect when it is added to an aqueous system. Also, it shows an excellent thickening effect under conditions of various salts and pH values . According to the present invention, it is possible to prepare an emulsion-type cosmetic composition, which is stable and has a given viscosity, because the polymer of formula 1 maintains a given range of viscosity in conditions of various salts and pH values and has hydrophilic and lipophilic properties, unlike prior thickeners. This is the characteristic effect of the present invention, which results from the use of the polymer of formula 1, which has both a nonionic nature and the thickening ability of associative polymers.

The associative polymer of the present invention can be dissolved or dispersed in water and be used as a thickener and an emulsifier. It is generally added to a cosmetic composition in an amount of 0.001-10 wt%, and preferably 0.001-5 wt%, based on the total weight of the cosmetic composition. If the polymer is used in an amount of less than 0.001%, the resulting cosmetic composition will not be thickened and the high-temperature stability thereof will be reduced, and if it is used in an amount of more than 10 wt%, the resulting cosmetic composition will not give a satisfactory feeling of use, because it will show hardness and stickiness when it is applied to the skin.

The associative polymer can be compounded directly into a cosmetic composition. Alternatively, it may also be compounded after it is diluted in water or a solvent to a suitable viscosity.

No particular limitation is imposed on the formulation of the cosmetic composition containing the inventive associative polymer represented by formula 1. For example, the cosmetic composition may be a formulation such as skin lotion, milk lotion, massage cream, nourishing cream, pack, gel or a skin adhesive type cosmetic composition. Also, it may be a transdermal formulation such as lotion, an ointment, gel, cream, a patch or a spray. [Description of Drawings]

FIG. 1 shows the results of measurement of the change in viscosity according to the concentration of the inventive associative polymer (formula 1) in an aqueous solution. FIG. 2 shows measurement results indicating that the inventive associative polymer (formula 1) functions as a surfactant .

FIG. 3 is a photograph of an emulsion prepared using the inventive associative polymer (formula 1) . [Mode for Invention]

Hereinafter, the present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited only to these examples . Example 1: Synthesis of associative polymer of formula 1

In a 1000-ml four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer, 1 mole of polyethylene glycol HO(CH₂CH₂O) nCH₂CH₂OH (n=794) , dewatered under reduced pressure and having a molecular weight of about 35000, and 2 moles of isophorone diisocyanate, a polyisocyanate compound (R₂-(NCO)₂) having two isocyanates, were placed, and allowed to react at 80 ^°C for 3 hours under a nitrogen stream. Then, 2 moles of palmityl monoalcohol (Ri-OH) was added and allowed to react with the reaction product at 80 ^°C for 3 hours, thus obtaining a white solid reaction product as an associative polymer (formula 1) determined to have an isocyanate content of 0%.

Test Example 1: Viscosity measurement test The associative polymer (palmityl monoalcohol Ri-OH, isophorone diisocyanate R₂-(NCO)₂ and polyethylene glycol HO (CH₂CH₂O) nCH₂CH₂OH (molecular weight: 35000) obtained in Example 1 was completely dissolved in water at concentrations of 0.5, 1, 1.2, 1.5 and 2 wt%, and then the viscosities of the aqueous solutions were measured with a viscometer at 30 ^°C . The measurement results are shown in FIG. 1.

FIG. 1 shows the results of measurement of the change in viscosity according to the concentration of the associative polymer (prepared in Example 1) in the aqueous solution. As shown in FIG. 1, the increase in the concentration of the associative polymer led to the increase in the viscosity of the aqueous solution. These results suggest that the inventive polymer of formula 1 has excellent thickening ability (see FIG. 1) .

Test Example 2 : Measurement of change in viscosity at varying contents of salt (NaCl)

The polymer synthesized in Example 1 was dissolved in water at a concentration of 1%, and then NaCl was added thereto in concentrations of 0.02, 0.04, 0.08, 0.12 and 0.5 wt%. Then, the viscosities of the aqueous solutions were measured at 30 'C, In Comparative Example 1, Carbomer

(Neveon, USA) , which has been frequently used in cosmetic compositions, was used as an active ingredient, it was dissolved in water at a concentration of 0.2 wt% and then neutralized with 0.2% triethanolamine, NaCl was added thereto at concentrations of 0.02, 0.04, 0.08, 0.12 and 0.5 wt%, and the viscosities of the aqueous solutions were measured at 30 ^°C . The measurement results are shown in Table 1 below.

As can be seen in Table 1, Example 1 did not show a reduction in viscosity caused by NaCl, unlike Comparative Example 1. This is because the polymer of Example 1, which is nonionic in nature, was not particularly influenced by the salt in the aqueous solutions .

[Table 1]

Test Example 3 : Comparison of viscosity at various pHs

The polymer synthesized in Example 1 was dissolved in water at a concentration of 1%, and the aqueous solution was adjusted to pHs of 2.5, 4.5, 6.5 and 9 with lactic acid and sodium lactate, and then measured for viscosity at 30 ^°C . In Comparative Example 2, Carbomer (Neveon, USA), which has been frequently used in cosmetic compositions, was used as an active ingredient, it was dissolved in water at a concentration of 0.2 wt% and then neutralized with 0.2% triethanolamine, and the aqueous solution was adjusted to pHs of 2.5, 4.5, 6.5 and 9 with lactic acid and sodium lactate and then measured for viscosity at 30 °C . The measurement results are shown in Table 2 below.

As can be seen in Table 2 , Example 1 did not show a reduction in viscosity in the entire pH range, unlike Comparative Example 2. On the other hand, Comparative Example 2 showed a great reduction in viscosity at a pH of less than 5, and this is because the ionic polymers of Comparative Example 2 were influenced by other ions in the aqueous solution to reduce viscosity. However, it can be seen that the polymer of Example 1 shows little or no reduction in viscosity, because it is nonionic in nature, and thus is not particularly influenced by other ions in the aqueous solution. [Table 2]

Test Example 4 : Examination of surfactant function of Example 1

The polymer of Example 1 was dissolved in an aqueous solution at concentrations of 0.0025, 0.0057, 0.0096, 0.0145, 0.0206, 0.0282, 0.0375 and 0.0491 wt%, and the surface tensions of the aqueous solutions were measured with a surface tensiometer. The measurement results are shown in FIG. 2. As shown in FIG. 2, the polymer of Example 1 lowered the surface tensions of the aqueous solutions to 38 mN/m and showed a critical micelle concentration of 0.025 wt%. This suggests that, because the polymer of Example 1 has a hydrophilic group and a lipophilic group, it functions to lower surface tension by adsorption onto a surface or an interface, and also because it forms micelles, like a surfactant, it is a compound having a surfactant function (see FIG. 2) .

Test Example 5: Preparation of emulsion using polymer of Example 1

The polymer of Example 1 alone was dissolved in an aqueous solution at a concentration of 1 wt%, and then 2 wt% of squalane was added thereto. The mixture solution was emulsified at 7000 rpm for 3 minutes, thus preparing a non-transparent viscous emulsion containing emulsified particles having a size of 2-5 μm. Accordingly, it was confirmed that, even when the polymer of Example 1 was used alone, an oil-in-water emulsion could be obtained (see FIG. 3) . Test Example 6 : Test I for comparison of viscosity between formulations and comparative formulations

In order to confirm the function of the polymer of Example 1 in formulations, transparent gel-type solubilized formulations having compositions shown in Table 3 below were prepared. Formulation 1 and formulation 2 contained the polymer of Example 1 and were adjusted to a pH of 4 using 0.5 wt% of NaCl and a suitable amount of sodium lactate/lactic acid, respectively. Comparative formulations 1, 2 and 3 contained Carbomer (Noveon, USA), which has been frequently used in cosmetic compositions, and comparative formulations 1 and 2 were adjusted to a pH of 4 using 0.5 wt% of NaCl and a suitable amount of sodium lactate/lactic acid, respectively. The viscosities of the formulations were measured with a Brookfield (LVDVII+) viscometer at 30 ^°C and 12 rpm for 2 minutes. [Table 3] Solubilized formulations

The above-prepared samples were stored in an oven at 30 "C , and after a given period of time, the viscosities thereof were measured with a viscometer. The measurement results are shown in Table 4 below.

As can be seen in Table 4 , the formulations 1 and 2 containing the polymer of Example 1 showed a thickening effect even under conditions of salts or low pH. [Table 4] Viscosities of formulations

Test Example 7 : Test II for comparison of viscosity between formulations and comparative formulations

To examine the function of the polymer of Example 1 in emulsified formulations, lotions having the compositions shown in Table 5 below were prepared. In each of the compositions of Table 5, an oil phase and an aqueous phase were separately completely dissolved at 70 ^°C , and then the oil phase was added to the aqueous phase. Then, the mixtures were emulsified at 7000 rpm for 5 minutes, thus obtaining non-transparent viscous emulsified lotion formulations . Formulation 3 and formulation 4 contained the polymer of Example 1 and adjusted to a pH of 4 using 0.5 wt% of NaCl and a suitable amount of sodium lactate/lactic acid, respectively. Comparative formulations 4, 5 and 6 contained Carbomer (Noveon, USA) , which has been frequently used in cosmetic compositions, and comparative formulations 4 and 5 were adjusted to a pH of 4 using 0.5 wt% of NaCl and a suitable amount, of sodium lactate/lactic acid, respectively. The viscosities of the formulations were measured with a Brookfield (LVDVII+) viscometer at 30^°C and 12 rpm for 2 minutes. [Table 5]

The above-prepared samples were stored in an oven at 30 ^°C , and after a given period of time, the viscosities thereof were measured with a viscometer. The measurement results are shown in Table 6 below.

[Table 6] Viscosities of formulations

[industrial Applicability]

As described in detail above, the polymer

(associative polymer of Example 1 shows a very excellent thickening effect in salts and various pH conditions, and particularly, shows an excellent ability to prepare an emulsion, because it functions as a surfactant. Till now, it was not easy to prepare cosmetic compositions, because the thickening effects of polymers were reduced in conditions of excess salts and various pHs . However, when the inventive polymer (formula 1) is used, the preparation of cosmetic compositions becomes easy due to the thickening effect of the inventive polymer in conditions of excess salts and various pHs . Also, because the inventive polymer has an ability to function as a surfactant, the applicability thereof in the cosmetic field is considered to be unlimited. The application of the associative polymer suggested in the present invention is not limited only to the cosmetic field. This approach can be used in various fields, including medical drugs, health supplements, foods, etc., which require emulsifying and thickening effects .

Claims

[CLAIMS]

[Claim l]

A thickener composed of an associative polymer represented by formula 1 : [Formula 1]

0 O

wherein Ri represents a branched, secondary monovalent hydrocarbon group or primary hydrocarbon group having 8-36 carbon atoms, R₂ represents a hydrocarbon group, which may have an urethane bond, n is an integer ranging from 100 to 3000, and m is an integer ranging from 1 to 5. [Claim 2]

The thickener of Claim 1, wherein the associative polymer of formula 1 is obtained by allowing a polyisocyanate compound represented by R₂-(NCO)₂ to react with polyethylene glycol HO(CH₂CH₂OnCH₂CH₂OH (n= 100-3000), and then allowing the reaction product to react with a monoalcohol represented by Ri-OH.

[Claim 3] The thickener of Claim 2, wherein the polyisocyanate compound represented by R₂- (NCO) ₂ is selected from the group consisting of aliphatic diisocyanate, aromatic diisocyanate, alicyclic diisocyanate, biphenyl diisocyanate and phenylmethane diisocyanate. [Claim 4]

The thickener of Claim 3, wherein the aliphatic diisocyanate is selected from the group consisting of methylene diisocyanate, dimethylene diisocyanate, triethylene diisocyanate/ tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dipropylether diisocyanate, 2 , 2-dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, octamethylene diisocyanate, 2, 2,4-trimethylpentane diisocyanate, nonatnethylene diisocyanate, decamethylene diisocyanate, 3- butoxygexane diisocyanate, 1, 4-butyleneglycolpropylether diisocyanate, thiodihexyl diisocyanate, meta-xylylene diisocyanate, para-xylylene diisocyanate and tetramethylxylene diisocyanate. [Claim 5]

The thickener of Claim 3, wherein the aromatic diisocyanate is selected from the group consisting of meta- phenylene diisocyanate, para-phenylene diisocyanate, 2,4- tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, tolidine diisocyanate, 1,4- naphthalene diisocyanate, 1, 5-naphthalene diisocyanate, 2 , 6-naphthalene diisocyanate and 2, 7-naphthalene diisocyanate .

[Claim 6]

The thickener of Claim 3, wherein the alicyclic diisocyanate is selected from the group consisting of hydrogenated xylylene diisocyanate and isophorone diisocyanate . [Claim 7]

The thickener of Claim 3 , wherein the biphenyl diisocyanate is selected from the group consisting of biphenyl diisocyanate, 3 , 3' -dimethylbiphenyl diisocyanate and 3, 3' -dimethoxybiphenyl diisocyanate. [Claim 8]

The thickener of Claim 3 , wherein the phenylmethane diisocyanate is selected from the group consisting of diphenylmethane-4, 4' -diisocyanate, 2,2'- dimethyldiphenylmethane4 , 4 ' -diisocyanate , diphenyldimethylmethane-4,4' -diisocyanate, 2, 5, 2' , 5' - tetramethyldiphenyl-methane-4 , 4 ' -diisocyanate, cyclohexylbis (4-isocyonthophenyl) methane, 3 , 3 ' -dimethoxy- diphenylmethane-4, 4' -diisocyanate, 4,4'- dimethoxydiphenylethane-3 , 3 ' -diisocyanate, 4,4'- diethoxydiphenylmethane-3 , 3 ' -diisocyanate, 2,2' -dimethyl- 5,5' -dimethoxydiphenylmethane-4,4' -diisocyanate, 3,3'- dichlorodiphenyldimethylmethane-4 , 4 ' -diisocyanate and benzophenone-3 , 3 ' -diisocyanate . [Claim 9]

The thickener of Claim 2, wherein the monoalcohol represented by R_1-OH is selected from the group consisting of a branched-chain alcohol represented by formula 2, a secondary monovalent alcohol represented by formula 3 , and a primary alcohol represented by formula 4 : [Formula 2]

^R< wherein R₃, R₄ and R₅, which may be the same or different from each other, are selected from the group consisting of alkyl, alkenyl, alkylaryl, cycloalkyl and cycloalkenyl groups; [Formula 3] Un Un 6 ^'

wherein R₆ and R₇, which may be the same or different from each other, are selected from the group consisting of alkyl, alkenyl, alkylaryl, cycloalkyl and cycloalkenyl groups ; and [Formula 4]

wherein R₈ is selected from the group consisting of alkyl, alkenyl, alkylaryl, cycloalkyl and cycloalkenyl groups.

[Claim 10]

The thickener of Claim 9, wherein R₃, R₄, R₅, R₅, R₇ and R₈, which may be the same or different from each other, represent an alkyl group selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl, isopentyl, neopentyl, tertiary pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotridecyl, myristyl, palmityl, stearyl, isostearyl, icosyl, docosyl, tetracosyl, thoriacontyl, 2-octyldodecyl, 2-dodecylhexadecyl, 2- tetradecyl-octadecyl and monomethyl branched isostearyl groups . [Claim ll]

The thickener of Claim 9, wherein R₃, R₄, R₅, R₆, R₇ and R₈, which may be the same or different from each other, represent an alkenyl group selected from the group consisting of vinyl, allyl, propenyl, isopropenyl, butenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl and oleyl groups .

[Claim 12] The thickener of Claim 9, wherein R₃, R₄, R₅, R₆, R₇ and R₈, which may be the same or different from each other, represent an alkylaryl group selected from the group phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, α-naphthyl, and β-naphthyl groups. [Claim 13]

The thickener of Claim 9, wherein R₃, R₄, R₅, R₆, R₇ and R₈, which may be the same or different from each other, represent a cycloalkyl or cycloalkenyl group selected from cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, and methylcycloheptenyl groups. [Claim 14]

A surfactant composed of an associative polymer represented by formula 1 : [Formula r]

0 O

wherein Ri represents a branched, secondary monovalent hydrocarbon or primary hydrocarbon group having 8-36 carbon atoms, R₂ represents a hydrocarbon group, which may have an urethane bond, n is an integer ranging from 100 to 3000, and m is an integer ranging from 1 to 5. [Claim 15]

A cosmetic composition containing, as an active ingredient, an associative polymer represented by formula 1: [Formula 1]

wherein R₁ represents a branched, secondary monovalent hydrocarbon group or primary hydrocarbon group having 8-36 carbon atoms, R₂ represents a hydrocarbon group, which may have an urethane bond, n is an integer ranging from 100 to 3000, and m is an integer ranging from 1 to 5. [Claim 16]

The cosmetic composition of Claim 15, wherein the associative polymer of formula 1 is contained in an amount of 0.001-10 wt% based on the total weight of the cosmetic composition.