JP2007291026A - Thickening composition and cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thickening composition capable of exhibiting a very high thickening effect even when the blending quantity of a thickener is decreased; to provide a thickening composition capable of maintaining thickening effect even in a wide pH range or even in an aqueous composition containing a salt-type compound; and to provide a thickening composition which has a novel feeling and is excellent in use feeling at the time of coating and especially preferably usable for a cosmetic. <P>SOLUTION: Both of the thickening composition and the cosmetic contain (A) 0.01-10 mass% thickening agent consisting of a microgel which is obtained by dissolving a water-soluble ethylenic unsaturated monomer in a dispersion phase and radical-polymerizing in the dispersion phase, (B) 0.1-10 mass% thickening agent consisting of an associative polymer, and (C) 0.1-99.89 mass% water. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a thickening composition and a cosmetic. More specifically, the present invention relates to a thickening composition in which the thickening effect by the microgel and the thickening effect by the associative polymer increase synergistically and has a novel feel, and a cosmetic containing the same.

  In technical fields such as pharmaceuticals and cosmetics, various aqueous thickeners are blended to maintain the dosage form. Examples of organic thickeners include natural polymers such as polysaccharides, casein, and xanthan gum; synthetic polymers such as acrylic acid polymers and carboxyvinyl polymers, polyethylene oxide, and the like, and montmorillonite as inorganic thickeners. Various clay minerals such as silica and silica are appropriately selected and used according to the purpose and effect.

  Among these thickeners, carboxyvinyl polymer is frequently used because it is inexpensive and has a high thickening effect and gels in a small amount. However, the carboxyvinyl polymer has a limited pH range in which thickening is possible, a markedly reduced thickening effect when a salt-type effective drug is blended, and a blending amount of polymer to obtain a thickening effect There was a problem that when the amount was increased, it was easy to feel stickiness when applied to the skin.

  On the other hand, as a water-soluble thickener having an excellent thickening effect, a water-swellable polymer microgel which is the component (A) of the present invention has been developed by the present inventors and used in cosmetics (patent) Reference 1). In addition, a thickener made of hydrophobic polyether urethane has been developed as an associative polymer as component (B) of the present invention (Patent Document 2), cosmetics (Patent Document 3), hair cosmetics and cleaning materials ( Patent Document 4).

  Since these thickeners function as excellent thickeners alone, there is no need to mix them together, and they are thickeners that are blended separately in cosmetics as separate thickeners. .

JP 2004-43785 A JP-A-9-71766 JP 2000-239120 A WO02 / 00179

  As a result of intensive research on various thickeners, the present inventors have surprisingly increased the synergistic thickening effect dramatically when the microgel and the associative polymer are combined in water. It was found that it can be obtained. In addition, it has a stable thickening effect even when blended with a wide pH range and salt-type compound. Furthermore, it has a new feel (elasticity), and a cosmetic composition with excellent feel when applied is prepared. The present inventors have found that this can be done and have completed the present invention.

  An object of the present invention is to provide a thickening composition capable of exhibiting an extremely high thickening effect even if the blending amount of the thickener is reduced. Another object of the present invention is to provide a thickening composition capable of maintaining the thickening effect even in an aqueous composition containing a salt-type compound in a wide pH range. Furthermore, it is to provide a thickening composition which has a new feel, is excellent in use feeling at the time of application, and can be particularly preferably used for cosmetics.

  That is, the present invention comprises (A) a thickener 0.01 to 10% by mass comprising a microgel obtained by dissolving a water-soluble ethylenically unsaturated monomer in a dispersed phase and radical polymerization in the dispersed phase; The present invention provides a thickening composition comprising 0.1) to 10% by weight of a thickening agent comprising an associative polymer and (C) 0.1 to 99.89% by weight of water. is there.

  In the present invention, the associative polymer (B) has a hydrophobic group composed of at least two linear or branched alkyl, aromatic, fluorocarbon, and alkylsilicone groups separated by a hydrophilic chain moiety. The above thickening composition is characterized by being a graft or sequential polymer.

Furthermore, the present invention provides the above thickening composition, wherein the associative polymer is a hydrophobically modified polyether urethane represented by the following general formula (1).
[Chemical 1]
R ¹ − {(O—R ² ) _k —OCONH—R ³ [—NHCOO— (R ⁴ —O) _n —R ⁵ ] _h } _m (1)
[Wherein R ¹ , R ² and R ⁴ represent a hydrocarbon group which may be the same or different from each other, R ³ represents a hydrocarbon group which may have a urethane bond, and R ⁵ represents a straight chain Represents a branched or secondary hydrocarbon group, a fluorocarbon group, an alkylsilicone group and / or an aromatic hydrocarbon group, m is a number of 2 or more, h is a number of 1 or more, k and n is independently a number in the range of 0 to 1000]

Further, the present invention provides the hydrophobic modified polyether urethane of the general formula (1), wherein R ² and / or R ⁴ may be the same as or different from each other, an alkylene group having 2 to 4 carbon atoms, or a phenylethylene group. The above thickening composition is provided.

Furthermore, the present invention provides the above-described increase characterized in that in the hydrophobically modified polyether urethane of the general formula (1), R ³ is a polyisocyanate residue represented by R ^3- (NCO) _{h + 1.} A viscous composition is provided.

In the present invention, the polyisocyanate residue represented by R ^3- (NCO) _{h + 1} is a polyisocyanate obtained by reacting a 2 to 8 valent polyol with a 2 to 4 valent polyisocyanate. The thickening composition described above is characterized by being a residue.

Further, the present invention provides the above thickening composition, wherein in the hydrophobically modified polyether urethane of the general formula (1), R ¹ is a residue of a polyol represented by R ^1- (OH) _m. It provides things.

In the hydrophobic modified polyether urethane of the general formula (1), R ⁵ is a linear, branched or secondary hydrocarbon group having 8 to 36 carbon atoms or a linear chain having 4 to 24 carbon atoms. The thickening composition is a branched or secondary fluorocarbon.

Furthermore, the present invention provides the above thickening composition which is an aromatic carbon group having 10 or more carbon atoms of R ⁵ in the hydrophobic polyether urethane of the general formula (1).

The present invention also provides the above thickening composition wherein R ⁵ is an alkyl silicone having a molecular weight of 200 or more in the hydrophobic polyether urethane of the general formula (1).

Furthermore, in the present invention, the polyether urethane represented by the general formula (1) is a polyether polyol represented by R ¹ -[(O—R ² ) _k OH] _m , and R ³ — (NCO) _h. Provided is the above thickening composition, which is a reaction product of a polyisocyanate represented by ₊₁ and a polyether monoalcohol represented by HO- (R ⁴ -O) _n -R ⁵ Is.

  Moreover, this invention provides said thickening composition whose ethylenically unsaturated monomer which comprises the said microgel is dimethylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid.

  Furthermore, the present invention relates to (A) a thickener 0.01 to 10% by mass comprising a microgel obtained by dissolving a water-soluble ethylenically unsaturated monomer in a dispersed phase and radical polymerization in the dispersed phase; It provides a cosmetic comprising 0.1 to 10% by weight of a thickening agent comprising an associative polymer and (C) 0.1 to 99.89% by weight of water.

1. The thickening composition of the present invention is synergistic rather than an additive thickening effect due to the thickening effect of the microgel of component (A) and the thickening effect of the associative polymer of component (B). It exhibits a greatly increased thickening effect. Therefore, it is possible to provide a thickening composition having a target viscosity with a small blending amount without blending a thickener in a large amount.
2. The thickening composition of the present invention exhibits a stable thickening effect over a wide pH range, and is excellent in the salt resistance of the thickening effect when a salt-type drug is blended.
3. Has a new feel. The new feel is the elasticity of the thickening composition. That is, the thickening composition of the present invention feels elastic when pressed with a finger to apply a load. And although it does not collapse until it reaches a certain load, it feels like it collapses at once when it exceeds a certain limit load. As a result, it is easy to take out a certain amount from the container into the skin, and when it is stretched on the skin (a load is applied with a finger), the thickening composition tends to collapse and stretch, and when it collapses, the water will shed Gives a fresh feeling of application.
4). Although the mechanism of action of the remarkable effect described above is not necessarily clear, the microgel of component (A) and the associative polymer of component (B) form a huge network structure that is preferable for the thickening effect in an aqueous solution. As a result, it is considered that the thickening effect is remarkably increased and the elasticity of the gel of the thickening composition is increased. Since this network structure is dynamic, it is considered to have a property of being immediately reconfigured although it is temporarily destroyed when a load (impact) is applied.
5). Since the thickener / thickener of the present invention has the above-mentioned excellent effects, it can be preferably used particularly for cosmetics.

  Hereinafter, the configuration of the present invention will be described in detail.

“(A) A thickener comprising a microgel obtained by dissolving a water-soluble ethylenically unsaturated monomer in a dispersed phase and radical polymerization in the dispersed phase”
The thickener composed of a microgel used in the present invention is a composition having an organic solvent or oil as a dispersion medium and water as a dispersed phase, in which a water-soluble ethylenically unsaturated monomer is dissolved in the dispersed phase and radicals are formed in the dispersed phase. It is a thickener composed of a synthetic polymer microgel obtained by polymerization, and is a thickener described in Patent Document 1 (Japanese Patent Application Laid-Open No. 2004-43785).

  That is, a polymer microgel produced by a polymerization method generally referred to as a reverse emulsion polymerization method is used for the use of a thickener, and uniform polymerization as disclosed in JP-A-2001-114641. The polymerization method and mechanical properties are different from those of a thickener made of a synthetic polymer obtained by the system. A microgel is fine particles of a synthetic polymer electrolyte produced by a reverse phase microemulsion polymerization method or the like. This microgel swells in water, ethanol, or a water-ethanol mixed solution, and can provide a high-viscosity solution that is visually uniform in appearance. On the other hand, the synthetic polymer based on the homogeneous polymerization system disclosed in Japanese Patent Application Laid-Open No. 2001-114641 is not a microgel, and must be pulverized into a powder state in order to blend the synthetic polymer into cosmetics. I must. In addition, a synthetic polymer gel is noticeable and may cause problems in appearance. The microgel used in the present invention is polymerized in a heterogeneous polymerization system. The resulting synthetic polymer becomes a fine polymer gel, that is, a microgel, and when blended into cosmetics, it does not need to be pulverized and powdered, exhibits an excellent thickening effect and excellent usability. Furthermore, the appearance of the cosmetic is also preferable.

The thickener comprising a microgel used in the present invention is preferably produced by a reverse phase emulsion polymerization method. That is, in a composition having an organic solvent or an oil as a dispersion medium and water as a dispersed phase, it is produced by dissolving a water-soluble ethylenically unsaturated monomer in the dispersed phase and radical polymerization in the dispersed phase. The polymerized microgel is washed and dried, but need not be crushed.
In particular, by using a surfactant adjusted to an appropriately selected hydrophilic / hydrophobic balance (HLB), the microgel under the condition that the polymerization system in the inverse emulsion polymerization forms a one-phase microemulsion or a fine W / O emulsion. It is preferred that a thickener consisting of

  A single-phase microemulsion is a state in which the oil phase and the water phase coexist thermodynamically and the interfacial tension between the oil and water is minimized. The fine W / O emulsion is thermodynamically unstable, but oil and water are present as fine W / O emulsions stably in kinetics. Generally, the particle diameter of the inner aqueous phase of the fine W / O emulsion is about several tens to 100 nm. These states are determined only by the composition and temperature of the system and do not depend on mechanical stirring conditions.

The composition constituting the polymerization system is composed of an organic solvent or oil that does not mix with water (dispersing medium constituting the outer phase) and a dispersed phase consisting of water (constituting the inner phase).
Preferable organic solvents include alkanes such as pentane, hexane, heptane, octane, nonane, decane, undecane; cycloalkanes such as cyclopentane, cyclohexane, cycloheptane, cyclooctane; benzene, toluene, xylene, decalin, naphthalene, etc. And aromatic and cyclic hydrocarbons.
Preferred oils include nonpolar oils such as paraffin oil.
The water-soluble ethylenically unsaturated monomer is dissolved in water as a dispersed phase, then mixed with an organic solvent or oil as a dispersion medium, heated to a desired temperature, and then a polymerization initiator is added to the aqueous phase for polymerization. .

  In general, in the heterogeneous polymerization method, it is known that the properties of the polymer produced vary depending on the stirring conditions during the polymerization. The reason is that since the emulsification system is not thermodynamically stable, the shape and size of the emulsified particles change depending on the stirring conditions. In the present invention, it has been found that these problems can be avoided by performing polymerization in a thermodynamically stable one-phase microemulsion region or a fine W / O emulsion region that exists in the vicinity of a metastable one-phase region. It was. Specifically, the composition of the polymerization system (type of organic solvent, so that the above-mentioned one-phase microemulsion or fine W / O emulsion region appears in the vicinity of the optimum polymerization temperature of the polymerization initiator for normal thermal polymerization or redox polymerization. By adjusting the surfactant (HLB), it became possible to obtain a microgel with a high thickening effect by polymerizing the polymer in a fine aqueous phase (water droplets).

A phase diagram example is shown in FIG. FIG. 1 is a three-component phase diagram of hexane (indicated by O) / surfactant / water-soluble ethylene monomer aqueous solution (indicated by W) when hexane is used as an organic solvent. The region A shown in the figure is a one-phase microemulsion region to a fine W / O emulsion region, and by performing polymerization in this region, preferable microgel polymerization is possible.
In contrast, conventional polymer thickeners based on suspension polymerization (for example, the method described in JP-A-2001-114641) are difficult to control the particle diameter of water droplets during polymerization, and thus a high-quality microgel is obtained. It is difficult.

（Ｒ₆はＨまたはメチル基、Ｒ₇及びＲ₈はそれぞれ独立にメチル基、エチル基、プロピル基、イソプロピル基を表わす。） The water-soluble ethylenically unsaturated monomer is preferably a combination of a nonionic monomer and an ionic monomer (anionic monomer or cationic monomer).
The nonionic monomer is preferably a dialkylacrylamide represented by the general formula (2).
General formula (2)

(R ₆ represents H or a methyl group, and R ₇ and R ₈ each independently represents a methyl group, an ethyl group, a propyl group, or an isopropyl group.)

（Ｒ₉及びＲ₁₀はそれぞれ独立にＨ又はメチル基、Ｒ₁₁は炭素原子数１〜６の直鎖若しくは分岐のアルキル基、Ｘは金属イオン若しくはＮＨ₃を表わす。）

一般式（４）

（Ｒ₁₂はＨ又はメチル基、Ｒ₁₃はＨまたは炭素原子数１〜６の直鎖若しくは分岐のアルキル基、Ｒ₁₄は炭素原子数１〜６の直鎖若しくは分岐のアルキル基、Ｒ₁₅、Ｒ₁₆、Ｒ₁₇はメチル基またはエチル基、Ｙは金属イオンを表わす。） The ionic monomer is preferably an anionic acrylamide derivative represented by the general formula (3) or a cationic acrylamide derivative represented by the general formula (4).
General formula (3)

(R ₉ and R ₁₀ are each independently H or a methyl group, R ₁₁ is a linear or branched alkyl group having 1 to 6 carbon atoms, and X is a metal ion or NH _3. )

General formula (4)

(R ₁₂ is H or a methyl group, R ₁₃ is H or a linear or branched alkyl group having 1 to 6 carbon atoms, R ₁₄ is a linear or branched alkyl group having 1 to 6 carbon atoms, R ₁₅ , R ₁₆ and R ₁₇ represent a methyl group or an ethyl group, and Y represents a metal ion.)

Particularly preferred dialkylacrylamides are dimethylacrylamide and diethylacrylamide.
Particularly preferred ionic acrylamide derivatives are 2-acrylamide 2-methylpropanesulfonic acid and its salts.
A particularly preferred cationic acrylamide derivative is N, N, -dimethylaminopropylacrylamide methyl chloride.

  The monomer composition ratio in the polymerization system of the nonionic monomer and the ionic monomer (the charge ratio of the polymerization system) is arbitrarily determined arbitrarily according to the monomer composition ratio of the target microgel. The monomer composition ratio of the microgel and the charging ratio to the polymerization system are almost the same. The charging ratio (molar ratio) of the polymerization system of the nonionic monomer and the ionic monomer is usually nonionic monomer: ionic monomer = 0.5: 9.5 to 9.5: 0.5, preferably 1. : 9 to 9: 1, more preferably 7: 3 to 9: 1. The optimum ratio is nonionic monomer: ionic monomer = 8: 2.

  The above-mentioned water-soluble ethylenically unsaturated monomer is arbitrarily selected, and the thickener of component (A) used in the present invention is polymerized. A preferred thickener is a microgel of a binary copolymer using dimethylacrylamide and 2-acrylamido-2-methylpropanesulfonic acid as water-soluble ethylenically unsaturated monomers and copolymerized from these monomers. In this case, there is no need for a crosslinking monomer, and a thickener that exhibits an excellent thickening effect and a feeling of use due to self-crosslinking can be obtained. In addition, a crosslinking monomer can also be used, and in that case, the crosslinking monomer represented by the general formula (5) is preferable. In particular, methylenebisacrylamide is preferable, and a microgel of a copolymer composed of dimethylacrylamide, 2-acrylamido-2-methylpropanesulfonic acid and methylenebisacrylamide is also preferably used in the present invention.

  In order to dissolve the water-soluble ethylenically unsaturated monomer in the dispersed phase and polymerize the preferred microgel for the present invention, it is necessary to select the optimum outer phase oil or organic solvent and surfactant. . That is, as described in Patent Document 1, by creating a phase diagram of the hydrophilic-hydrophobic balance (HLB) of the nonionic surfactant in the composition of the polymerization system, the cloud point at a temperature suitable for thermal radical polymerization By preparing so as to show a state that forms a one-phase microemulsion or a fine W / O emulsion at a normal thermal radical polymerization temperature, a microgel having a rheological property preferable as a thickener can be obtained.

Preferred surfactants are polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene hexyl decyl ether, polyoxyethylene isostearyl ether , Polyoxyethylene octyldodecyl ether, polyoxyethylene behenyl ether, polyoxyethylene cholesteryl ether, polyoxyethylene hydrogenated castor oil, sorbitan fatty acid ester, mono fatty acid glycerin, tri fatty acid glycerin, polyglycerin fatty acid ester, isostearic acid polyoxyethylene glycerin, Polyoxyethylene glycerin triisostearate, polyoxymonostearate Ji Ren glycerin distearate, polyoxyethylene glyceryl, and the like tristearate polyoxyethylene glyceryl.
These surfactants can be appropriately combined to adjust to a desired HLB and added to the polymerization system.

  As described above, in the microgel obtained by copolymerizing dialkylacrylamide and acrylamide-based ionic monomer, the spontaneous crosslinking reaction proceeds. In particular, even if the polyfunctional crosslinking monomer is not copolymerized as the third component, A self-crosslinked microgel is obtained and is a preferred thickener. The third component polyfunctional cross-linking monomer is not necessary, but the microgel preferably used in the present invention can be synthesized even if it is added and copolymerized.

The multifunctional crosslinking monomer is preferably a monomer represented by the general formula (5), and can be crosslinked using one or more kinds of crosslinking monomers represented by the general formula (5). It is essential that these crosslinkable monomers can take a crosslinked structure efficiently in a polymerization system of dialkylacrylamide and an ionic acrylamide derivative.



General formula (5)

  Preferred crosslinkable monomers include, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyoxyethylene diacrylate, polyoxyethylene dimethacrylate, diethylene glycol dimethacrylate, trimethylolpropane triacrylate, N, N′-methylenebisacrylamide, N, N′-ethylenebisacrylamide, triallyl isocyanurate, pentaerythritol dimethacrylate, and the like can be used, and one or more selected from these can be used. In the present invention, N, N'-methylenebisacrylamide is particularly preferably used.

  The molar ratio of the content of 2-acrylamido-2-methylpropanesulfonic acid unit and dialkylacrylamide unit in the copolymer is usually 2-acrylamido-2-methylpropanesulfonic acid unit: dialkylacrylamide unit = 0.5: 9.5 to 9.5: 0.5, preferably 1: 9 to 9: 1, and more preferably = 3: 7 to 1: 9. The optimum ratio is 2-acrylamido-2-methylpropanesulfonic acid unit: dialkylacrylamide unit = 2: 8.

  The viscosity of the thickener is due to the extension of the molecular chain by electrostatic repulsion based on the sulfonyl group, which is a strong dissociation group, and from the spontaneous crosslinking reaction of dialkylacrylamide or the crosslinking structure with a crosslinking monomer. If the content of the 2-methylpropanesulfonic acid unit or a salt thereof is less than 5 mol% with respect to the dialkylacrylamide unit, the molecular chain is not sufficiently stretched, so that sufficient viscosity may not be obtained.

  The use amount of the crosslinkable monomer is preferably in the range of 0.0001 to 2.0 mol% with respect to the total number of moles of 2-acrylamido-2-methylpropanesulfonic acid or a salt thereof and dialkylacrylamide. Thickeners prepared at less than 0.0001 mol% may not have a crosslinking effect. Moreover, when it exceeds 2 mol%, since a crosslinking density is too high and a microgel cannot fully swell, it may not exhibit sufficient thickening effect.

  The molecular weight of the thickener that is a microgel used in the present invention is about a weight average molecular weight of 100,000 to 5,000,000 (PEG conversion: measured by GPC), and is adjusted by the viscosity required as the thickener.

The microgel obtained by the above polymerization method has all the rheological properties of the following (1) to (3). The thickener composed of the microgel is obtained by the production method by the polymerization method described above, and is preferably used as a thickener.
(1) The apparent viscosity of an aqueous dispersion of 0.5% (mass percentage) of the microgel is 10,000 mPa · s or more at a shear rate of 1.0 s ⁻¹ .
(2) The apparent viscosity of the 0.5% (percentage by mass) ethanol dispersion of the microgel is 5000 mPa · s or more at a shear rate of 1.0 s ⁻¹ .
(3) The dynamic elastic modulus in a 0.5% (mass percentage) aqueous dispersion or ethanol dispersion of the microgel is G ′> G ″ within a strain of 1% or less and a frequency of 0.01 to 10 Hz.
The apparent viscosity of microgel water or ethanol dispersion is a viscosity at a measurement temperature of 25 ° C. and a shear rate of 1 s ⁻¹ using a cone plate rheometer (MCR-300 manufactured by Paar Rhysica).
The dynamic elastic modulus is a value of storage elastic modulus (G ') and loss elastic modulus (G ") measured at a measuring temperature of 25 ° C and a strain of 1% or less in a frequency range of 0.1 to 10 Hz using the same measuring apparatus. Means.

The microgel used as a thickener in the present invention can be separated in a powder state through a simple precipitation purification step after polymerization. The microgel separated into a powder form easily disperses in water or ethanol or a mixed solvent of water / ethanol, swells quickly, and functions as a thickener.
In addition, by selecting a strongly acidic monomer (for example, a monomer containing a sulfonic acid residue) as an ionic monomer to be copolymerized with the microgel, an acidic preparation that cannot be thickened with a conventional carboxyvinyl polymer can be obtained. Thickening is also possible.

“(B) Thickener made of associative polymer”
On the other hand, the thickener comprising the associative polymer used in the present invention comprises at least two linear or branched alkyl, aromatic, fluorocarbon, and alkylsilicone hydrophobic groups separated by a hydrophilic chain moiety. A graft or sequential polymer is preferred.
And the thickener which consists of hydrophobic modified polyether urethane represented by following General formula (1) is preferable. The thickener made of this hydrophobically modified polyether urethane is described in Patent Documents 2 to 4.

General formula (1)
[Chemical 6]
R ¹ − {(O—R ² ) _k —OCONH—R ³ [—NHCOO— (R ⁴ —O) _n —R ⁵ ] _h } _m (1)
[Wherein R ¹ , R ² and R ⁴ represent a hydrocarbon group which may be the same or different from each other, R ³ represents a hydrocarbon group which may have a urethane bond, and R ⁵ represents a straight chain Represents a branched or secondary hydrocarbon group, a fluorocarbon group, an alkylsilicone group and / or an aromatic hydrocarbon group, m is a number of 2 or more, h is a number of 1 or more, k and n is independently a number in the range of 0 to 1000]

In the present invention, R ² and / or R ⁴ are preferably an alkylene group having 2 to 4 carbon atoms which may be the same or different from each other, or a phenylethylene group.
Furthermore, R ³ is R ³ - is preferably a residue of a polyisocyanate, further, R ³ represented by _{(NCO) h + 1 - (} NCO) polyisocyanate residue represented by _{h + 1} is It is preferably a polyisocyanate residue obtained by reacting a divalent to octavalent polyol with a divalent to tetravalent polyisocyanate.
R ¹ is preferably a polyol residue represented by R ^1- (OH) _m .
Further, R ⁵ is a linear, branched or secondary hydrocarbon group having 8 to 36 carbon atoms or a linear, branched or secondary fluorocarbon group having 4 to 24 carbon atoms. preferable.
R ⁵ is preferably an aromatic carbon group having 10 or more carbon atoms.
Further, R ⁵ is preferably an alkyl silicone having a molecular weight of 200 or more.
The hydrophobically modified polyether urethane of the general formula (1) is represented by a polyether polyol represented by R ¹ -[(O—R ² ) _k —OH] _m and R ³ — (NCO) _{h + 1} . It is preferable that the reaction product is a reaction product of a polyisocyanate represented by HO— (R ⁴ —O) _n —R ⁵ .

The hydrophobically modified polyether urethane of the general formula (1) is preferably one or two or more polyether polyols represented by R ¹ -[(O—R ² ) _k —OH] _m , R ³ — (NCO) Reaction of one or more polyisocyanates represented by _{h + 1} with one or more polymonoalcohols represented by HO— (R ⁴ —O) _n —R ⁵ Can be obtained.
In this case, R ^{1 to} R ⁵ in the general formula (1) are R ¹ — [(O—R ² ) _k —OH] _m , R ³ — (NCO) _{h + 1} , HO— (R ⁴ — O) is determined by _n -R ^5. The charging ratio of the three members is not particularly limited, but the ratio of the hydroxyl group derived from polyether polyol and polyether monoalcohol to the isocyanate group derived from polyisocyanate is NCO / OH = 0.8: 1 to 1.4: 1. Is preferred.

The polyether polyol represented by R ¹ — [(O—R ² ) _k —OH] _m that is preferably used to obtain the hydrophobically modified polyether urethane of the general formula (1) is an methylene polyol and an ethylene oxide. , Propylene oxide, butylene oxide, epichlorohydrin and other alkylene oxides, styrene oxide, and the like.

  Here, the m-valent polyol is preferably a divalent to octavalent polyol, for example, a dihydric alcohol such as ethylene glycol, propylene glycol, butylene glycol, hexamethylene glycol, neopentyl glycol; glycerin, trioxyisobutane, 1, 2,3-butanetriol, 1,2,3-pentatriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2, 3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol , Pentamethylglycerin, pentaglycerin, 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylol Trihydric alcohols such as tan and trimethylolpropane; pentaerythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, Tetravalent alcohols such as 1,3,4,5-hexanetetrol; pentavalent alcohols such as adnit, arabit and xylit; hexavalent alcohols such as dipentaerythritol, sorbit, mannitol and exit; 8 such as sucrose And monohydric alcohols.

In addition, R ² is determined depending on the alkylene oxide, styrene oxide or the like to be added, and is particularly easily available. In order to exhibit excellent effects, alkylene oxide or styrene oxide having 2 to 4 carbon atoms is preferable. The alkylene oxide and styrene oxide to be added may be homopolymerization, two or more types of random polymerization, or block polymerization. The adding method may be a normal method.

The degree of polymerization k is 0 to 1000, preferably 1 to 500, and more preferably 10 to 250.
Furthermore, the proportion of ethylene group occupying the R ² is preferably When it is 50 to 100 wt% of the total R ^2, preferred associative thickeners in the invention can be obtained.
Further, the molecular weight of R ¹ -[(O—R ² ) _k —OH] _m is preferably 500 to 100,000, particularly preferably 1,000 to 50,000.

The polyisocyanate represented by R ³ — (NCO) _{h + 1} that is preferably used for obtaining the hydrophobically modified polyether urethane of the general formula (1) is one having two or more isocyanate groups in the molecule. There is no particular limitation. For example, aliphatic diisocyanate, aromatic diisocyanate, alicyclic diisocyanate, biphenyl diisocyanate, diisocyanate of phenylmethane, triisocyanate, tetraisocyanate and the like can be mentioned.

  Examples of the aliphatic diisocyanate include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dipropyl ether diisocyanate, 2,2-dimethylpentane diisocyanate, 3-methoxyhexane diisocyanate, Octamethylene diisocyanate, 2,2,4-trimethylpentane diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, 3-butoxyhexane diisocyanate, 1,4-butylene glycol dipropyl ether diisocyanate, thiodihexyl diisocyanate, metaxylylene diisocyanate, paraxylylene Range isocyanate, Examples include tetramethylxylylene diisocyanate.

  Examples of the aromatic diisocyanate include metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, tolidine diisocyanate, and 1,4- Naphthalene diisocyanate, 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 2,7-naphthalene diisocyanate and the like can be mentioned.

  Examples of the alicyclic diisocyanate include hydrogenated xylylene diisocyanate and isophorone diisocyanate. Examples of biphenyl diisocyanate include biphenyl diisocyanate, 3,3′-dimethylbiphenyl diisocyanate, 3,3′-dimethoxybiphenyl diisocyanate, and the like.

  Examples of the diisocyanate of phenylmethane include diphenylmethane-4,4′-diisocyanate, 2,2′-dimethyldiphenylmethane-4,4′-diisocyanate, diphenyldimethylmethane-4,4′-diisocyanate, 2,5,2 ′. , 5′-tetramethyldiphenylmethane-4,4′-diisocyanate, cyclohexylbis (4-isothiontphenyl) methane, 3,3′-dimethoxydiphenylmethane-4,4′-diisocyanate, 4,4′-dimethoxydiphenylmethane 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.

  Examples of the triisocyanate include 1-methylbenzene-2,4,6-triisocyanate, 1,3,5-trimethylbenzene-2,4,6-triisocyanate, 1,3,7-naphthalene triisocyanate, and biphenyl. -2,4,4'-triisocyanate, diphenylmethane-2,4,4'-triisocyanate, 3-methyldiphenylmethane-4,6,4'-triisocyanate, triphenylmethane-4,4 ', 4' ' -Triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanatephenyl) thiophosphate, etc. Is mentioned.

Moreover, you may use with the dimer and trimer (isocyanurate coupling | bonding) of these polyisocyanate compounds, and you may make it react with an amine and use it as a biuret. Further, polyisocyanates having urethane bonds obtained by reacting these polyisocyanate compounds with polyols can also be used. As a polyol, the thing of 2-8 valence is preferable, and the above-mentioned polyol is preferable. Incidentally, R ³ - (NCO) if the _{h + 1} using trivalent or more polyisocyanates, polyisocyanate preferably has the urethane bond.

The polyether monoalcohol represented by HO— (R ⁴ —O) _n —R ⁵ that is preferably used to obtain the hydrophobic modified polyether urethane of the general formula (1) is finally in the associative polymer structure. It is not particularly limited as long as it is a polyether of a linear and branched chain or secondary monohydric alcohol and corresponds to at least two hydrophobic groups separated by a hydrophilic chain portion.

Such a compound can be obtained by, for example, addition polymerization of alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, or styrene oxide to a linear, branched, or secondary monohydric alcohol. Here, the linear alcohol is represented by the following general formula (6).
General formula (6)
[Chemical 7]
R ²³ —OH

The branched chain alcohol is represented by the following general formula (7).
General formula (7)

The secondary alcohol is represented by the following general formula (8).
General formula (8)

Accordingly, R ²³ is a group obtained by removing the hydroxyl group in the above general formulas (6) to (8). In the above general formulas (6) to (8), R ²³ , R ²⁴ , R ²⁵ , R ²⁷ and R ²⁸ are a hydrocarbon group or a fluorocarbon group, for example, an alkyl group, an alkenyl group, an alkylaryl group, a cyclo An alkyl group, a cycloalkenyl group, and the like; 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, triacontyl, 2-octyldodecyl, 2-dodecylhexadecyl, 2-tetradecyloctadecyl, monomethyl branched-isostearyl and the like. Examples of the alkenyl group include vinyl, allyl, propenyl, isopropenyl, butenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl and the like. The alkylaryl group includes phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonyl Examples include phenyl, α-naphthyl, β-naphthyl group and the like. Examples of the cycloalkyl group and cycloalkenyl group include a cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, methylcycloheptenyl group. Etc.

In the general formula (7), R ²⁶ is a hydrocarbon group or a fluorocarbon group. For example, an alkylene group, an alkenylene group, an alkylarylene group, a cycloalkylene group, a cycloalkenylene group, and the like, and an alkylene group is particularly preferable. R ⁷ and R ⁸ are preferably methyl groups.

In the general formulas (6), (7), and (8), the total number of carbon atoms in the chemical formula is preferably 8 to 36, more preferably 12 to 30, and most preferably 18 to 24. It is. That is, the total number of carbon atoms of R ⁵ .

R ⁵ is not particularly limited as long as it is a group that acts as a hydrophobic group in the final associative polymer structure, and examples thereof include hydrocarbons, fluorocarbon groups, alkylsilicone groups, and aromatic hydrocarbon groups.

A preferable alkyl silicone group is represented by the following general formula (9).
General formula (9)

  Here, R29 represents a linear, branched and aromatic hydrocarbon or fluorocarbon group which may be the same or different from each other, and R30 represents a hydrocarbon or fluorocarbon residue which may contain an oxygen or nitrogen atom. . In the general formula (9), a structure having a hydroxyl group at the terminal is shown, but the position of the hydroxyl group may be at any position in the alkylsiloxane structure. Examples of the compound having such a structure include Silaplane FM0411, FM0421, FM0425 manufactured by Chisso Corporation. The alkyl silicone preferably has a molecular weight of 200 or more, more preferably a molecular weight of 500 or more.

Aromatic hydrocarbons are suitable as an associative polymer material because they have the property of very strongly associating not only with hydrophobic interactions but also with π-π interactions in aqueous solvents. As the aromatic hydrocarbon having a hydroxyl group, cholesterol, cholestanol, phytosterol, phytostanol and derivatives thereof are preferable.
Further, the alkylene oxide and styrene oxide to be added may be homopolymerization, two or more kinds of random polymerization, or block polymerization. The adding method may be a normal method. The degree of polymerization n is 0 to 1000, preferably 1 to 200, more preferably 10 to 50. The ratio of ethylene to total R ⁴ is preferably 50 to 100 wt% of the total R ^4, more preferably, if it is 65 to 100 mass%, the purpose preferred associative thickeners are obtained of the present invention It is done.

As a method for producing the hydrophobically modified polyether urethane represented by the above general formula (1), the reaction is carried out, for example, by heating at 80 to 90 ° C. for 1 to 3 hours in the same manner as in the reaction of a normal polyether and isocyanate. You can get it at least.
Further, a polyether polyol (a) represented by R ¹ — [(O—R ² ) _k —OH] _m , a polyisocyanate (b) represented by R ³ — (NCO) _{h + 1} , and HO When the polyether monoalcohol (c) represented by — (R ⁴ —O) _n —R ⁵ is reacted, other than the compound having the structure of the general formula (1) may be by-produced. For example, when diisocyanate is used, the main product is a c-b-a-b-c type compound represented by the general formula (1). Compounds such as the b- (ab) _x -abc type may be by-produced. In this case, the compound of the general formula (1) can be used in the present invention in the form of a mixture containing the compound of the general formula (1) without separating the compound.

  The associative polymer used in the present invention is preferably a hydrophobically modified polyether urethane. However, since the essence is hydrophobic association in water, the bond between the hydrophilic chain and the hydrophobic chain in the polymer is in urethane. It is not limited, and urea, ether, ester, amide bond or the like may be formed in the polymer depending on the starting material used.

"Thickening and thickening agent of the present invention"
The thickening composition of the present invention comprises 0.01 to 10% by mass of the microgel of the above component (A), 0.1 to 10% by mass of (B) associative polymer, and water as component (C). Manufactured by mixing. The contents of the (A) component and the (B) component in the thickening composition are arbitrary within the above ranges, respectively, but the blending amounts are less than 0.01% by mass and 0.1% by mass, respectively. May not have a synergistic effect of thickening. In addition, when the amount is more than 10% by mass, the viscosity becomes too high, resulting in inconvenience in handling during production, work efficiency is reduced, inconvenience in taking out from the container during actual use, Elongation when applied to the skin may worsen.

  In addition, since the maximum effect of this invention is synergistically increasing each thickening effect by mixing, in order to obtain the target viscosity, the component (A) or (B) is added conventionally. It is not necessary to add a large amount of each thickener as compared with the case of adding them alone. The upper limit of the combined amount is 10% by mass, and even if the upper limit is 1% by mass or even 0.5% by mass, a sufficient synergistic thickening effect is exhibited, and the technical significance of the present invention Is even larger.

  (C) The water of a component is contained 0.1-99.89 mass% in a thickening composition. In the thickening composition of the present invention, optional components can be blended in addition to the essential components as long as the effects of the present invention are not impaired. The water content in that case is the remainder of the essential components (A) and (B) and the optional compounding components. In the present invention, even when a salt-type compound (such as an effective drug) is contained in the thickening composition, the thickening effect is not significantly reduced. It is also preferable to contain a salt-type compound such as an effective drug as a component.

"Cosmetics of the present invention"
The cosmetic of the present invention is an optional cosmetic component, for example, a powder component, liquid fat, solid fat, wax, hydrocarbon oil, higher fatty acid, higher alcohol, as long as the effect of the present invention is not impaired in the above thickening composition. , Ester oil, silicone oil, anionic surfactant, cationic surfactant, amphoteric surfactant, nonionic surfactant, moisturizer, water-soluble polymer, film agent, UV absorber, sequestering agent, lower alcohol , Polyhydric alcohols, sugars, amino acids, organic amines, polymer emulsions, pH adjusters, skin nutrients, vitamins, antioxidants, antioxidant auxiliaries, and perfumes as appropriate Accordingly, it can be produced by a conventional method.

  EXAMPLES Next, an Example is given and this invention is demonstrated in more detail. The present invention is not limited by these examples. In addition, about a compounding quantity, unless otherwise indicated, the mass% is shown.

"(A) Production of thickener consisting of microgel"
Synthesis example 1
40 g of dimethylacrylamide (manufactured by Kojin) and 9 g of 2-acrylamido-2-methylpropanesulfonic acid (manufactured by Sigma) are dissolved in 250 g of ion-exchanged water and adjusted to pH = 7.0 with sodium hydroxide. To a 1000 ml three-necked flask equipped with a reflux apparatus, 250 g of n-hexane, 8.2 g of polyoxyethylene (3) oleyl ether (Emalex 503, manufactured by Nippon Emulsion) and polyoxyethylene (6) oleyl ether (Emalex 506, 16.4g (made in Japan Emulsion) is mixed and dissolved to replace N ₂ An aqueous monomer solution is added to the three-necked flask and heated to 65 ° C. to 70 ° C. in an oil bath while stirring in an N ₂ atmosphere. After confirming that the system is in a translucent microemulsion state when the temperature of the system reaches 65 ° C. to 70 ° C., 2 g of ammonium persulfate is added to the polymerization system to start the polymerization. A microgel is produced by maintaining the polymerization system at 65 ° C. to 70 ° C. with stirring for 3 hours. After the polymerization is completed, acetone is added to the microgel suspension to precipitate the microgel, followed by washing with acetone three times to remove residual monomer and surfactant. The precipitate is filtered and dried under reduced pressure to obtain a dried white powdered microgel.

Synthesis example 2
35 g of dimethylacrylamide (manufactured by Kojin) and 17.5 g of 2-acrylamido-2-methylpropanesulfonic acid (manufactured by Sigma) are dissolved in 260 g of ion-exchanged water and adjusted to pH = 7.0 with sodium hydroxide. In a 1000 ml three-necked flask equipped with a reflux apparatus, 260 g of n-hexane, polyoxyethylene (3) oleyl ether (Emalex 503, manufactured by Nippon Emulsion) 8.7 g and polyoxyethylene (6) oleyl ether (Emalex 506, Japanese-made emulsion) 17.6g were mixed and dissolved into the N ₂ to replace. An aqueous monomer solution is added to the three-necked flask and heated to 65 ° C. to 70 ° C. in an oil bath while stirring in an N ₂ atmosphere. After confirming that the system is in a translucent microemulsion state when the temperature of the system reaches 65 ° C. to 70 ° C., 2 g of ammonium persulfate is added to the polymerization system to start the polymerization. A microgel is produced by maintaining the polymerization system at 65 ° C. to 70 ° C. with stirring for 3 hours. After the polymerization is completed, acetone is added to the microgel suspension to precipitate the microgel, followed by washing with acetone three times to remove residual monomer and surfactant. The precipitate is filtered and dried under reduced pressure to obtain a dried white powdered microgel.

Synthesis example 3
30 g of dimethylacrylamide (manufactured by Kojin) and 26.7 g of 2-acrylamido-2-methylpropanesulfonic acid (manufactured by Sigma) are dissolved in 280 g of ion-exchanged water and adjusted to pH = 7.0 with sodium hydroxide. To a 1000 ml three-necked flask equipped with a reflux apparatus, 280 g of n-hexane, 9.4 g of polyoxyethylene (3) oleyl ether (Emalex 503, manufactured by Nippon Emulsion) and polyoxyethylene (6) oleyl ether (Emalex 506, Japanese-made emulsion) 19g were mixed and dissolved into the N ₂ to replace. An aqueous monomer solution is added to the three-necked flask and heated to 65 ° C. to 70 ° C. in an oil bath while stirring in an N ₂ atmosphere. After confirming that the system is in a translucent microemulsion state when the temperature of the system reaches 65 ° C. to 70 ° C., 2 g of ammonium persulfate is added to the polymerization system to start the polymerization. A microgel is produced by maintaining the polymerization system at 65 ° C. to 70 ° C. with stirring for 3 hours. After the polymerization is completed, acetone is added to the microgel suspension to precipitate the microgel, followed by washing with acetone three times to remove residual monomer and surfactant. The precipitate is filtered and dried under reduced pressure to obtain a dried white powdered microgel.

Synthesis example 4
Dissolve 35 g of dimethylacrylamide (manufactured by Kojin), 17.5 g of 2-acrylamide-2-methylpropanesulfonic acid (manufactured by Sigma) and 7 mg of methylenebisacrylamide in 260 g of ion-exchanged water, and adjust the pH to 7.0 with sodium hydroxide. In a 1000 ml three-necked flask equipped with a reflux apparatus, 260 g of n-hexane, polyoxyethylene (3) oleyl ether (Emalex 503, manufactured by Nippon Emulsion) 8.7 g and epolyoxyethylene (6) oleyl ether (Emalex 506) , manufactured by Nippon emulsion) 17.6g were mixed and dissolved into the N ₂ to replace. An aqueous monomer solution is added to the three-necked flask and heated to 65 ° C. to 70 ° C. in an oil bath while stirring in an N ₂ atmosphere. After confirming that the system is in a translucent microemulsion state when the temperature of the system reaches 65 ° C. to 70 ° C., 2 g of ammonium persulfate is added to the polymerization system to start the polymerization. A microgel is produced by maintaining the polymerization system at 65 ° C. to 70 ° C. with stirring for 3 hours. After the polymerization is completed, acetone is added to the microgel suspension to precipitate the microgel, followed by washing with acetone three times to remove residual monomer and surfactant. The precipitate is filtered and dried under reduced pressure to obtain a dried white powdered microgel.

Synthesis example 5
Dissolve 35 g of dimethylacrylamide (manufactured by Kojin), 17.5 g of 2-acrylamide-2-methylpropanesulfonic acid (manufactured by Sigma) and 70 mg of methylenebisacrylamide in 260 g of ion-exchanged water, and adjust the pH to 7.0 with sodium hydroxide. In a 1000 ml three-necked flask equipped with a reflux apparatus, 260 g of n-hexane, polyoxyethylene (3) oleyl ether (Emalex 503, manufactured by Nippon Emulsion) 8.7 g and polyoxyethylene (6) oleyl ether (Emalex 506, Japanese-made emulsion) 17.6g were mixed and dissolved into the N ₂ to replace. An aqueous monomer solution is added to the three-necked flask and heated to 65 ° C. to 70 ° C. in an oil bath while stirring in an N ₂ atmosphere. After confirming that the system is in a translucent microemulsion state when the temperature of the system reaches 65 ° C. to 70 ° C., 2 g of ammonium persulfate is added to the polymerization system to start the polymerization. A microgel is produced by maintaining the polymerization system at 65 ° C. to 70 ° C. with stirring for 3 hours. After the polymerization is completed, acetone is added to the microgel suspension to precipitate the microgel, followed by washing with acetone three times to remove residual monomer and surfactant. The precipitate is filtered and dried under reduced pressure to obtain a dried white powdered microgel.

Synthesis Example 6
Dissolve 35 g of dimethylacrylamide (manufactured by Kojin) and 17.5 g of N, N-dimethylaminopropylacrylamide methyl chloride (manufactured by Kojin) in 260 g of ion-exchanged water. In a 1000 ml three-necked flask equipped with a reflux apparatus, 260 g of n-hexane, polyoxyethylene (3) oleyl ether (Emalex 503, manufactured by Nippon Emulsion) 8.7 g and polyoxyethylene (6) oleyl ether (Emalex 506, Japanese-made emulsion) 17.6g were mixed and dissolved into the N ₂ to replace. An aqueous monomer solution is added to the three-necked flask and heated to 65 ° C. to 70 ° C. in an oil bath while stirring in an N ₂ atmosphere. After confirming that the system is in a translucent microemulsion state when the temperature of the system reaches 65 ° C. to 70 ° C., 2 g of ammonium persulfate is added to the polymerization system to start the polymerization. A microgel is produced by maintaining the polymerization system at 65 ° C. to 70 ° C. with stirring for 3 hours. After the polymerization is completed, acetone is added to the microgel suspension to precipitate the microgel, followed by washing with acetone three times to remove residual monomer and surfactant. The precipitate is filtered and dried under reduced pressure to obtain a dried white powdered microgel.

Synthesis example 7
Dissolve 35 g of dimethylacrylamide (manufactured by Kojin), 17.5 g of N, N-dimethylaminopropylacrylamide methyl chloride (manufactured by Kojin) and 7 mg of methylenebisacrylamide in 260 g of ion-exchanged water. In a 1000 ml three-necked flask equipped with a reflux apparatus, 260 g of n-hexane, polyoxyethylene (3) oleyl ether (Emalex 503, manufactured by Nippon Emulsion) 8.7 g and polyoxyethylene (6) oleyl ether (Emalex 506, Japanese-made emulsion) 17.6g were mixed and dissolved into the N ₂ to replace. An aqueous monomer solution is added to the three-necked flask and heated to 65 ° C. to 70 ° C. in an oil bath while stirring in an N ₂ atmosphere. After confirming that the system is in a translucent microemulsion state when the temperature of the system reaches 65 ° C. to 70 ° C., 2 g of ammonium persulfate is added to the polymerization system to start the polymerization. A microgel is produced by maintaining the polymerization system at 65 ° C. to 70 ° C. with stirring for 3 hours. After the polymerization is completed, acetone is added to the microgel suspension to precipitate the microgel, followed by washing with acetone three times to remove residual monomer and surfactant. The precipitate is filtered and dried under reduced pressure to obtain a dried white powdered microgel.

“(B) Manufacture of thickeners composed of associative polymers”
Synthesis example 8
550 ml of polyethylene glycol (PEG) (molecular weight of about 11000) (corresponding to R ¹ -[(O—R ² ) _k —OH] _m ) in a 1000 mL four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer Part, the following general formula (10)
[Chemical 11]
_{C 12 H 25 -CH (C 10} H 21) -CH 2 -O- (CH 2 CH 2 O) 20 -H (10)
198 parts of a branched alcohol ethylene oxide (EO) adduct (corresponding to HO— (R ⁴ —O) _n —R ⁵ ) was charged, and then cooled to 80 ° C. and hexamethylene diisocyanate (HMDI) (R ^3- (NCO) _{h + 1} ) (29.6 parts) is added and reacted at 80 to 100 ° C. for 2 hours under a nitrogen stream to confirm that the isocyanate is 0%. I got a thing.

＊１：サイラプレーンFM0411（チッソ社）
＊２：サイラプレーンFM0421（チッソ社） Various hydrophobic modified polyether urethanes can be prepared in the same manner as in Synthesis Example 8. For example, hydrophobically modified polyether urethanes according to Synthesis Examples 8 to 14 shown in “Table 1” can be preferably used in the present invention.

* 1: Silaplane FM0411 (Chisso Corporation)
* 2: Silaplane FM0421 (Chisso)

  In addition to the above synthesis examples, commercially available associative polymers such as hydrophobically modified polyether urethane include Adecanol UH140S, UH-420, UH-438, UH-750, GT-700, Serad- manufactured by HULS, manufactured by Asahi Denka Kogyo. FX1100, FX1010, 1035, Rheox Rheolate 205, 208, 204, 225, 278, 244, Rohm & Haas DW1206F, 1206J, 1206G, Akzo Dapral-T212, Borchers Borchigel-LW44, L75Ac 44 46 and the like. Also, as other associative polymers, Crothix manufactured by Croda, PEG-4000 manufactured by Kessco, Witcon L32 manufactured by Witco, Natrosol Plus Grade 330 CS by Aqualon, and Nanosol Plus Grade 430 CS are also suitable for use in the present invention. Yes.

"Example 1: Synergistic thickening effect by thickener made of microgel and thickener made of associative polymer"
Below, the data regarding the viscosity behavior of the thickening composition which mix-blended the thickener of (A) and (B) component are shown.
In the thickening composition shown in the table, the remainder other than the thickener is water. The viscosity of the thickening composition is a viscosity measured at a measurement temperature of 25 ° C. and a shear rate of 10 s ⁻¹ using a cone plate viscometer (Parr Physica MCR300).

The results of “Table 2” are shown in FIG. The horizontal axis of the graph in FIG. 2 represents the blending ratio of Synthesis Example 8.
That is, it can be seen that the compositions 2, 3, and 4 are dramatically increased compared to the viscosities of the compositions 1 and 5 (composition 2 is approximately 1. 5 times, composition 3 is increased by about 2.5 times, and composition 3 is increased by about 1.7 times).
From the above results, in the thickening composition of the present invention, the viscosity due to the mixing of the thickener made of microgel and the thickener made of an associative polymer is not an additive of the respective viscosities but synergistically. It increases and exhibits a dramatic increase effect.

"Example 2: Salt resistance of thickening composition"
The data regarding the viscosity behavior of the thickening composition which mix | blended salt below is shown.
The remainder other than the components shown in the table is water. The viscosity of the thickening composition is a viscosity measured at a measurement temperature of 25 ° C. and a shear rate of 10 s ⁻¹ using a cone plate viscometer (Parr Physica MCR300).

  From the above results, although the thickening composition of the present invention is reduced in viscosity by the addition of sodium chloride, the thickening effect remains sufficiently even after the reduction in viscosity, and salt resistance is higher than that of a general ionic thickener. High nature. Moreover, since a high thickening effect is exhibited with a small blending amount, the target viscosity can be stably maintained by blending an appropriate amount of the thickening agent in consideration of the reduced viscosity.

"Example 3: New feel (new elasticity)"
Ten expert panelists evaluated whether the thickening composition shown in Table 6 (aqueous solution) felt a new feeling of elasticity when applied to the skin. The evaluation criteria are as follows.
<Evaluation criteria>
◎: Eight or more panelists recognized that they could feel a new elasticity.
○: It was recognized that 6 or more panelists and less than 8 panelists can feel a new elasticity.
Δ: 3 or more panelists and less than 6 panelists recognized that they could feel a new elasticity.
X: Less than 3 panelists recognized that they could feel a new elasticity.

＊ブルックスフィールド（ＢＬ）がた粘度計（ＤＩＧＩＴＡＬ ＶＩＳＭＥＴＲＯＮ ＶＤＨ：芝浦システム社製）により４番のスピンドルを用い、回転数１２ｒｐｍの条件で、３０℃において測定した

* Measured at 30 ° C. using a No. 4 spindle with a Brooksfield (BL) viscometer (DIGITAL VISMETRON VDH: manufactured by Shibaura System Co., Ltd.) at a rotation speed of 12 rpm.

From the above results, a thickener composition containing carboxyvinyl polymer, alkyl-modified carboxyvinyl polymer, hydroxyethyl cellulose, which is a conventional general thickener component, and a thickener alone compounded with components (A) and (B). The thickening composition could not make the user feel a new elasticity.
On the other hand, in the case of the thickening composition of the present invention, it was revealed that the user can feel a new elasticity and a base having a new feeling of use can be obtained. Therefore, when the thickening composition of the present invention is used as a cosmetic, a cosmetic that exhibits a novel feeling of use can be provided. That is, the cosmetic of the present invention can be prepared so as to feel elasticity. And although it does not collapse until it reaches a certain load, it feels like it collapses at once when it exceeds a certain limit load. As a result, when a certain amount is taken out from the container into the skin and stretched on the skin (a load is applied with a finger), the thickening composition breaks down and becomes easy to stretch. Gives a fresh application feeling.

  Below, the formulation example of the cosmetics which use the thickening composition of this invention is shown. Both are thickening compositions that exhibit an excellent thickening effect

Example 4 Latex (1) Dimethylpolysiloxane 2
(2) Behenyl alcohol 1
(3) Batyl alcohol 0.5
(4) Glycerin 5
(5) 1,3-butylene glycol 7
(6) Erythritol 2
(7) Hardened oil 3
(8) Squalane 6
(9) Tetra-2-ethylhexanoic acid pentaerythlit 2
(10) Polyoxyethylene glyceryl isostearate 1
(11) Polystearic acid polyoxyethylene glycerol 1
(12) Sodium hexametaphosphate 0.05
(13) Appropriate amount of phenoxyethanol (14) Thickener obtained in Synthesis Example 1 0.5
(15) Thickener obtained in Synthesis Example 8 0.5
(16) Purified water residue

Example 5 Protector (1) Cetanol 1
(2) Glycerin 5
(3) 1,3-butylene glycol 5
(4) Polyethylene glycol 20000 2
(5) Tetra (2-ethylhexanoic acid / paramethoxycinnamic acid) pentaerythritol
Three
(6) Di-2-ethylhexyl succinate 3
(7) Potassium hydroxide appropriate amount (8) Trisodium edetate 0.1
(9) Methylbis (trimethylsiloxy) silylisopentyl trimethoxycinnamate
2
(10) 4-t-butyl-4′-methoxydibenzoylmethane 2
(11) 2-ethylhexyl paramethoxycinnamate 2
(12) Diparamethoxycinnamate mono-2-ethylhexanoate glyceryl
2
(13) Thickener obtained in Synthesis Example 1 0.1
(14) Thickener obtained in Synthesis Example 8 0.1
(15) Acrylic acid / alkyl methacrylate copolymer (Pemulene TR-1)
0.1
(16) Paraben appropriate amount (17) Phenoxyethanol appropriate amount (18) Purified water Residual (19) Fragrance appropriate amount

Example 6 Emulsion (1) Petrolatum 5
(2) Behenyl alcohol 0.5
(3) Batyl alcohol 0.5
(4) Glycerin 7
(5) 1,3-butylene glycol 7
(6) 1,2-pentanediol 1
(7) Xylit 3
(8) Polyethylene glycol 20000 2
(9) Hardened oil 2
(10) Jojoba oil 2
(11) Squalane 5
(12) Isostearic acid 0.5
(13) Tetra-2-ethylhexanoic acid pentaerythrit slit 2
(14) Polyoxyethylene hydrogenated castor oil 0.5
(15) Lauryldimethylaminoacetic acid betaine 0.4
(16) Sodium pyrosulfite 0.01
(17) Sodium hexametaphosphate 0.05
(18) Dipotassium glycyrrhizinate 0.05
(19) Trimethylglycine 3
(20) Arbutin 3
(21) Yeast extract 0.1
(22) Tocopherol acetate 0.1
(23) Thiotaurine 0.1
(24) Clara extract 0.1
(25) Bengala appropriate amount (26) quince seed extract 0.1
(27) Thickener obtained in Synthesis Example 3 0.2
(28) Thickener obtained in Synthesis Example 11 0.3
(29) Appropriate amount of phenoxyethanol (30) Purified water remaining

Example 7 Acne Gel (1) Ethanol 50
(2) Lactic acid 0.3
(3) β-glycyrrhetinic acid 0.05
(4) Arginine hydrochloride 0.1
(5) Peonies extract 0.1
(6) Sulfur 0.2
(7) POE (20) sorbitan monooleate 1
(8) Thickener obtained in Synthesis Example 2 0.8
(9) Thickener obtained in Synthesis Example 8 0.2
(10) Purified water residue

Example 8 Whitening emulsion (1) Petrolatum 5
(2) Behenyl alcohol 0.5
(3) Batyl alcohol 0.5
(4) Glycerin 7
(5) 1,3-butylene glycol 7
(6) 1,2-pentanediol 1
(7) Xylit 3
(8) Polyethylene glycol 20000 2
(9) Hardened oil 2
(10) Jojoba oil 2
(11) Squalane 5
(12) Isostearic acid 0.5
(13) Tetra-2-ethylhexanoic acid pentaerythrit slit 2
(14) Polyoxyethylene hydrogenated castor oil 0.5
(15) Lauryldimethylaminoacetic acid betaine 0.4
(16) Sodium pyrosulfite 0.01
(17) Sodium hexametaphosphate 0.05
(18) Dipotassium glycyrrhizinate 0.05
(19) Trimethylglycine 3
(20) Arbutin 3
(21) Tocopherol acetate 0.1
(22) Thiotaurine 0.1
(23) Bengala appropriate amount (24) quince seed extract 0.1
(25) Thickener obtained in Synthesis Example 3 0.25
(26) Thickener obtained in Synthesis Example 9 0.25
(27) Appropriate amount of phenoxyethanol (28) Purified water residue

Example 9 Protector (1) Decamethylcyclopentasiloxane 3
(2) Methylphenylpolysiloxane 3
(3) Behenyl alcohol 1
(4) 1,3-butylene glycol 5
(5) Polyoxyethylene glyceryl isostearate 1.5
(6) Polyoxyethylene glyceryl monostearate 1
(7) Dipotassium glycyrrhizinate 0.05
(8) Trimethylglycine 1
(9) L-ascorbic acid 2-glucoside 2
(10) Trisodium edetate 0.1
(11) 2-ethylhexyl paramethoxycinnamate 7
(12) Xanthan gum 0.1
(13) Thickener obtained in Synthesis Example 4 0.1
(14) Thickener obtained in Synthesis Example 8 0.4
(15) Phenoxyethanol appropriate amount (16) Purified water Residue (17) Fragrance appropriate amount

Example 10 Cream (1) Liquid Paraffin 3
(2) Vaseline 1
(3) Dimethylpolysiloxane 1
(4) Stearyl alcohol 1.8
(5) Behenyl alcohol 1.6
(6) Glycerin 8
(7) Dipropylene glycol 5
(8) Macadamia nut oil 2
(9) Hardened oil 3
(10) Squalane 6
(11) Stearic acid 2
(12) Cholesteryl hydroxystearate 0.5
(13) Cetyl 2-ethylhexanoate 4
(14) Polyoxyethylene hydrogenated castor oil 0.5
(15) Self-emulsifying glyceryl monostearate 3
(16) Sodium hexametaphosphate 0.05
(17) Trimethylglycine 2
(18) α-tocopherol 2-L-ascorbic acid phosphate diester potassium
1
(19) Tocopherol acetate 0.1
(20) Green tea extract 0.1
(21) Paraben appropriate amount (22) Trisodium edetate 0.05
(23) 4-t-butyl-4′-methoxydibenzoylmethane 0.05
(24) Diparamethoxycinnamate mono-2-ethylhexanoate glyceryl
0.05
(25) Colorant appropriate amount (26) Thickener obtained in Synthesis Example 3 0.4
(27) Thickener obtained in Synthesis Example 9 0.4
(28) Purified water residue

Example 11 Moisturizing pack (1) Ethanol 3
(2) Glycerin 5
(3) 1,3-butylene glycol 6
(4) Polyethylene glycol 1500 5
(5) Polyoxyethylene methyl glucoside 2
(6) Glyceryl tri-2-ethylhexanoate 1
(7) Sodium hexametaphosphate 0.05
(8) Hydroxypropyl-β-cyclodextrin 0.1
(9) Dipotassium glycyrrhizinate 0.1
(10) Loquat leaf extract 0.1
(11) Sodium L-glutamate 0.1
(12) Fennel extract 0.1
(13) Hamelis extract 0.1
(14) Oat extract 0.1
(15) Giant extract 0.1
(16) Eucalyptus oil 0.05
(17) Dimorpholinopyridazinone 0.1
(18) Xanthan gum 0.05
(19) Thickener obtained in Synthesis Example 5 0.5
(20) Thickener obtained in Synthesis Example 12 0.5
(21) Acrylic acid / alkyl methacrylate copolymer (Pemulene TR-1)
0.05
(22) Potassium hydroxide appropriate amount (23) Phenoxyethanol appropriate amount (24) Purified water remainder

Example 12 Hairist (1) Dimethylpolysiloxane 1
(2) Ethanol 5
(3) Stearyl alcohol 0.1
(4) Behenyl alcohol 0.2
(5) Glycerin 2
(6) Dipropylene glycol 1
(7) 1,3-butylene glycol 1
(8) Alkyltrimethylammonium chloride (77%) 0.5
(9) Thickener obtained in Synthesis Example 6 0.1
(10) Thickener obtained in Synthesis Example 10 0.1
(11) Paraoxybenzoic acid ester appropriate amount (12) Purified water Residue (13) Fragrance appropriate amount

Example 13 Hair Treatment (1) Dimethylpolysiloxane 0.5
(2) Benzyl alcohol 5
(3) cetostearyl alcohol 7
(4) Behenyl alcohol 3
(5) Self-emulsifying glyceryl monostearate 1
(6) N-stearoyl-N-methyltaurine sodium 1
(7) Thickener obtained in Synthesis Example 2 0.5
(8) Thickener obtained in Synthesis Example 10 0.5
(9) Citric acid 0.2
(10) Phenoxyethanol appropriate amount (11) Purified water Residue (12) Fragrance appropriate amount

Example 14 Shampoo (1) Dimethylpolysiloxane 1.5
(2) Dipropylene glycol 3
(3) Ethylene glycol distearate 2
(4) Palm oil fatty acid monoethanolamide 2
(5) Lauroylmethyl taurine sodium 0.1
(6) Sodium polyoxyethylene lauryl ether sulfate 7.5
(7) Polyoxyethylene lauryl ether sulfate triethanolamine
3.5
(8) Palm oil fatty acid amidopropyl betaine 3.5
(9) Thickener obtained in Synthesis Example 1 0.3
(10) Thickener obtained in Synthesis Example 8 0.3
(11) Citric acid 0.01
(12) L-glutamic acid 0.2
(13) Sodium chloride 1
(14) Sodium benzoate appropriate amount (15) Disodium edetate appropriate amount (16) Sodium hydroxide 0.01
(17) Purified water Residual (18) Perfume appropriate amount

Example 15 Body Soap (1) Propylene Glycol 5
(2) Polyoxypropylene glyceryl ether 0.5
(3) Isostearic acid 1
(4) Lauric acid 10
(5) Palm fatty acid 9
(6) Myristic acid 1
(7) Ethylene glycol distearate 2
(8) Palm oil fatty acid diethanolamide 1
(9) Sodium polyoxyethylene lauryl ether sulfate 1.5
(10) Palm oil fatty acid methyl taurine sodium 0.3
(11) Taurine sodium laurate 0.3
(12) 2-alkyl-N-carboxymethyl-N-
Hydroxyethyl imidazolinium betaine 2
(13) Thickener obtained in Synthesis Example 1 0.4
(14) Thickener obtained in Synthesis Example 8 0.1
(15) Potassium hydroxide 5
(16) Hydroxypropyl methylcellulose 0.4
(17) loquat leaf extract appropriate amount (18) edetate disodium appropriate amount (19) purified water residue (20) perfume appropriate amount

Example 16 Face Wash (1) Glycerin 6
(2) 1,3-butylene glycol 4
(3) Polyethylene glycol 400 13
(4) White beeswax 0.5
(5) Stearic acid 20
(6) Lauric acid 5
(7) Myristic acid 10
(8) Polyoxyethylene (25) Polyoxypropylene glycol (30)
0.5
(9) Self-emulsifying glyceryl monostearate 2
(10) Titanium oxide 0.2
(11) Sodium citrate 0.05
(12) Potassium hydroxide 6.5
(13) Thickener obtained in Synthesis Example 3 0.3
(14) Thickener obtained in Synthesis Example 10 0.2
(15) Chamomile extract 0.1
(16) Trisodium edetate appropriate amount (17) Purified water Residual (18) Fragrance Appropriate amount

Example 17 Eye Shadow (1) Decamethylcyclopentasiloxane 16
(2) Methylphenylpolysiloxane 1
(3) Batyl alcohol 1
(4) 1,3-butylene glycol 5
(5) Macadamia nut oil 0.1
(6) Stearic acid 1
(7) Palmitic acid 1
(8) Self-emulsifying glyceryl monostearate 1
(9) Self-emulsifying propylene glycol stearate 1
(10) Bengala-coated mica titanium (pearl agent) 13
(11) Synthetic phlogopite 0.1
(12) Silicic anhydride 2
(13) Triethanolamine 1
(14) DL-α-tocopherol acetate 0.1
(15) Paraoxybenzoic acid ester appropriate amount (16) Phenoxyethanol appropriate amount (17) Thickener obtained in Synthesis Example 7 0.1
(18) Thickener 0.2 obtained in Synthesis Example 13
(19) Bentonite 1
(20) Trimethylsiloxysilicate 5
(21) Purified water Residual (22) Stearyl alcohol 0.5
(23) Behenyl alcohol 0.5

Example 18 Foundation (1) Behenyl alcohol 0.5
(2) Dipropylene glycol 6
(3) Stearic acid 1
(4) Glycerol monostearate 1
(5) Potassium hydroxide 0.2
(6) Triethanolamine 0.8
(7) DL-α-tocopherol acetate 0.1
(8) Paraoxybenzoic acid ester appropriate amount (9) Yellow iron oxide 1
(10) α-olefin oligomer 3
(11) Dimethylpolysiloxane (6 mPa.s) 2
(12) Dimethylpolysiloxane (100 mPa.s) 5
(13) Batyl alcohol 0.5
(14) Isostearic acid 1
(15) Behenic acid 0.5
(16) Cetyl 2-ethylhexanoate 10
(17) Polyoxyethylene glycerol monostearate 1
(18) Titanium oxide 3
(19) Mica titanium / polyalkyl acrylate composite powder 0.5
(20) Surface-treated titanium oxide (MT-062) 10
(21) Polyalkyl acrylate coated mica titanium 0.5
(22) Black iron oxide coated mica titanium 0.5
(23) Silicic anhydride 6
(24) 2-Ethylhexyl paramethoxycinnamate 2
(25) Bengala appropriate amount (26) ultramarine blue appropriate amount (27) black iron oxide appropriate amount (28) legal dye appropriate amount (29) thickener obtained in Synthesis Example 3 0.1
(30) Thickener obtained in Synthesis Example 14 0.1
(31) Bentonite 1
(32) Sodium carboxymethyl cellulose 0.1
(33) Purified water Residual (34) Perfume appropriate amount

Example 19 Makeup Base (1) Methylpolysiloxane 2
(2) Decamethylcyclopentasiloxane 5
(3) Ethanol 3
(4) Behenyl alcohol 0.1
(5) Batyl alcohol 0.1
(6) Dipropylene glycol 5
(7) 1,3-butylene glycol 3
(8) Polyethylene glycol 1500 4
(9) Plant squalane 0.1
(10) Polyoxyethylene glyceryl isostearate 0.3
(11) Titanium oxide Bengala-coated mica 0.3
(12) Mica titanium 0.3
(13) Sodium hexametaphosphate 0.05
(14) Tocopherol acetate 0.1
(15) Paraoxybenzoic acid ester appropriate amount (16) Lithium cobalt titanate appropriate amount (17) Porous spherical cellulose powder 0.5
(18) Polyethylene glycol (MW = 1 million) 0.2
(19) Thickener obtained in Synthesis Example 1 0.5
(20) Thickener obtained in Synthesis Example 8 0.5
(21) Purified water residue

  ADVANTAGE OF THE INVENTION According to this invention, even if it reduces the compounding quantity of a thickener, the thickening composition which exhibits a very high thickening effect can be provided. The thickening composition of the present invention exhibits a stable thickening effect even when blended with a wide pH range and a salt-type drug. Furthermore, since it has a novel feel, it can be used particularly preferably in cosmetics.

(A) It is an example of the phase diagram of hexane / surfactant / water-soluble ethylene monomer aqueous solution at the time of superposing | polymerizing the microgel of a component. It is a graph which shows that a thickening effect increases synergistically when (A) and (B) component are mixed.

Claims (13)

  (A) A thickener 0.01 to 10% by mass comprising a microgel obtained by dissolving a water-soluble ethylenically unsaturated monomer in a dispersed phase and radical polymerization in the dispersed phase, and (B) an associative polymer. The thickening composition characterized by containing 0.1-10 mass% of thickener which becomes and (C) 0.1-99.89 mass% of water.   (B) The associative polymer is a graft or sequential polymer containing a hydrophobic group composed of at least two linear or branched alkyl, aromatic, fluorocarbon, and alkylsilicone groups separated by a hydrophilic chain moiety. The thickening composition according to claim 1, wherein The thickening composition according to claim 1 or 2, wherein the associative polymer is a hydrophobically modified polyether urethane represented by the following general formula (1).
[Chemical 1]
R ¹ − {(O—R ² ) _k —OCONH—R ³ [—NHCOO— (R ⁴ —O) _n —R ⁵ ] _h } _m (1)
[Wherein R ¹ , R ² and R ⁴ represent a hydrocarbon group which may be the same or different from each other, R ³ represents a hydrocarbon group which may have a urethane bond, and R ⁵ represents a straight chain Represents a branched or secondary hydrocarbon group, a fluorocarbon group, an alkylsilicone group and / or an aromatic hydrocarbon group, m is a number of 2 or more, h is a number of 1 or more, k and n is independently a number in the range of 0 to 1000] 4. The hydrophobic modified polyether urethane of the general formula (1), wherein R ² and / or R ⁴ are an alkylene group having 2 to 4 carbon atoms which may be the same or different from each other, or a phenylethylene group. Thickening composition. The thickening agent according to claim 3 or 4, wherein in the hydrophobically modified polyether urethane of the general formula (1), R ³ is a polyisocyanate residue represented by R ^3- (NCO) _{h + 1.} Composition. The polyisocyanate residue represented by R ^3- (NCO) _{h + 1} is a residue of a polyisocyanate obtained by reacting a 2 to 8 valent polyol with a 2 to 4 valent polyisocyanate. The thickening composition according to claim 5, wherein The hydrophobic modified polyether urethane of the general formula (1), wherein R ¹ is a polyol residue represented by R ^1- (OH) _m . Thickening composition. In the hydrophobically modified polyether urethane of the general formula (1), R ⁵ is a linear, branched or secondary hydrocarbon group having 8 to 36 carbon atoms or a linear, branched or secondary hydrocarbon group having 4 to 24 carbon atoms. The thickening composition according to claim 3, 4, 5, 6, or 7, which is fluorocarbon. The thickening composition according to claim 3, 4, 5, 6 or 7, wherein in the hydrophobic polyether urethane of the general formula (1), R ⁵ is an aromatic carbon group having 10 or more carbon atoms. The thickening composition according to claim 3, 4, 5, 6, 7, 8, or 9, wherein in the hydrophobic polyether urethane of the general formula (1), R ⁵ is an alkyl silicone having a molecular weight of 200 or more. The polyether urethane described in the general formula (1) is represented by a polyether polyol represented by R ¹ — [(O—R ² ) _k OH] _m and R ³ — (NCO) _{h + 1.} a polyisocyanate, HO- (R ⁴ -O) according to claim 3 thickening composition, wherein it is a reaction product of a polyether monoalcohol represented by _n -R ^5.   The ethylenically unsaturated monomer constituting the microgel is dimethylacrylamide and 2-acrylamido-2-methylpropane sulfonic acid, 2, 1, 2, 4, 4, 6, 7, 8, 9, 10 or 11 The thickening composition as described. (A) A thickener 0.01 to 10% by mass comprising a microgel obtained by dissolving a water-soluble ethylenically unsaturated monomer in a dispersed phase and radical polymerization in the dispersed phase, and (B) an associative polymer. A cosmetic comprising 0.1 to 10% by mass of a thickener and (C) 0.1 to 99.89% by mass of water.

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