CN1404508A - Gel-form composition - Google Patents

Abstract

A gel-like composition comprising an associative polymer (I) with an HLB value of 16.0 to 19.5 and water, wherein the associative polymer (I) comprises two or more siloxane chains separated by hydrophilic chain portions, wherein _R1 to _R4 represent a hydrocarbon group, Y represents any one of a hydroxyl group, an epoxide, or a carbamate, ether, ester, or urea residue, A represents a portion of the hydrophilic chain composed of an epoxide, X represents one or more of a carbamate, ether, ester, or urea residue, Z represents any one of a hydrocarbon group, or a carbamate, ether, ester, or urea residue, a represents an average of 2 or more, b represents an average of 10 to 3000, and c represents an average of 1 to 500.

Description

gel composition

This application claims priority from Japanese Patent Application No. 390898, 2000, filed December 22, 2000, the contents of which are incorporated herein.

technical field

The present invention relates to gel compositions, and in particular to improvements in associative polymers having siloxane groups.

Background technique

A tackifier obtained by introducing a small amount of hydrophobic groups into a water-soluble polymer shows a strong thickening effect due to the association of hydrophobic groups caused by hydrophobic interactions in aqueous solvents. Viscosity, this is known [(Polymers in Aqueous Media, Advances in Chemistry Series) 223, 467 items, edited by J.D. Glass; (Encyclopedia of Polymer Science and Engineering), 2nd edition, 17, 772]. In recent years, people are studying how to incorporate these associative polymers into cosmetics, for example, in JP-A-5-255040, JP-11-514003, JP-11-514004, JP-11-514032, JP-2000 -63235, JP-A-2000-136228, JP-A-2000-95630, JP-A-2000-510493, etc., describe various cosmetics containing an associative polymer having a specific structure.

In order to improve association and enhance adhesion, it is necessary to extend the hydrophobic group.

However, any of the associative polymers compounded in the above-mentioned cosmetics uses a long-chain alkyl group as a hydrophobic group, and thus has the following problems. That is to say, the length of the alkyl chain purchased from the market is limited (generally use the alkyl with a carbon chain length of less than 36, usually less than 24), and the long-chain alkyl is solid at room temperature and is not easy to handle , and when the associative polymer derived from the long-chain alkyl group is blended into cosmetics, there are fatal shortcomings such as heavy use feeling and stickiness.

On the other hand, Japanese Patent No. 2682966 describes a cosmetic composition containing a polysiloxane-polyepoxide linear block copolymer.

However, the above-mentioned block copolymers are utilized as microdispersants for conditioners selected from non-volatile insoluble silicones or fluorinated oils or waxes, since the polysiloxane (hydrophobic chain moiety ) occupies a relatively large proportion in the block copolymer, so it is insoluble in water, so it does not show a thickening effect in water.

Contents of the invention

In view of the problems of the above-mentioned conventional techniques, an object of the present invention is to provide a gel-like composition containing an associative polymer which has viscosity and has a pleasant feeling of use without stickiness.

In view of the above problems, the present inventors conducted intensive studies, and found that, in an associative thickener having introduced a small amount of siloxane group as a hydrophobic group into a water-soluble polymer, by calculating the HLB value, Studies have shown that the composition containing it can obtain a non-sticky, refreshing feeling of use, and has many advantages of not being afraid of sebum and sweating when a film is formed on the skin.

That is to say, the subject of the present invention is a gel-like composition, characterized in that it contains an associative polymer and water, and that the associative polymer is a A graft polymer and/or sequence polymer of at least two siloxane chains separated by the following formula (I), the HLB value of the polymer is 16.0-19.5,

(In the above formula (I), R ₁ to R ₄ may represent hydrocarbon groups identically or differently, and Y represents one or both of hydroxyl, alkylene oxide or carbamate, ether, ester, and urea residues. More than one species, A represents the part of the hydrophilic chain composed of alkylene oxide, X represents one or two or more selected from carbamate, ether, ester, and urea residues, Z represents a hydrocarbon group, or a carbamate One or more selected from esters, ethers, esters, and urea residues, a represents an average of 2 or more, b represents an average of 10 to 3000, and c represents an average of 1 to 500).

In the above composition, the molecular weight of the associative polymer is preferably 6,000 or more.

In the above composition, the mass fraction of siloxane chains in the associative polymer is preferably 0.1 or less.

In the above composition, A of the associative polymer represented by formula (I) is preferably polyethylene oxide.

In the above composition, the associative polymer is preferably a multi-block polymer.

In the above compositions, the associative polymer is preferably a triblock polymer.

In the above composition, the multi-block polymer is preferably a block polymer whose both ends are of the siloxane type.

In the above composition, a of the associative polymer represented by formula (I) is preferably 2, b is preferably 65 or more, and c is preferably 3-105.

In the above composition, the content of the associative polymer is preferably 0.1 to 5% by mass.

Among the above compositions, an emulsion containing 0.1 to 25% by mass of oil is preferred.

Best way to practice the invention

Preferred embodiments of the present invention are described below.

The associative polymer mentioned in the present invention is a siloxane-modified epoxide sequence polymer, and it is a kind of generally containing epoxide in its chain, preferably ethylene oxide and / or non-ionic sequential copolymer (sequential copolymer) of both the hydrophilic chain part (hydrophilic sequences) of the copolymer and the like and the hydrophobic chain part (hydrophobic sequences) of the siloxane chain. It should be noted that the term "sequential copolymer" includes the meaning of block copolymer.

The aforementioned polymer can be a sequence having a triblock form as in general formula (II) or a multiblock form as in general formula (III).

B-C-A-C-B ...(II)

-A-C-B-C-A-C-B-C-A-C-B- …(III)

(A represents the hydrophilic chain part, B represents the hydrophobic chain part, and C represents the binding part)

Therefore, the hydrophobic chain part may be present at each terminal of the molecular chain (for example, a triblock copolymer having a hydrophilic chain part in its center), or may be arranged in the chain or at both ends of the chain (for example, poly sequence copolymer). The aforementioned polymers may also be graft copolymers.

The HLB value of the associative polymer in the present invention is preferably 16.0 to 19.5, particularly preferably 17.0 to 19.4. If it is less than 16.0 or exceeds 19.5, the thickening effect may not be exhibited.

The molecular weight of the associative polymer in the present invention is preferably above 6000, particularly preferably above 8000. If it is less than 6000, there is a possibility that an association network cannot be developed.

In the associative polymer mentioned in the present invention, the mass fraction of siloxane chains is preferably 0.1 or less, more preferably 0.05 or less. If it exceeds 0.1, the solubility in water will be reduced and there will be no viscosity-increasing effect. possibility.

Among the associative polymers of the present invention, a of the associative polymer represented by the above formula (I) is preferably 2, b is preferably 65 or more, c is preferably 3 to 105, particularly preferably a is 2 , b is above 75, and c is 5-70.

In the composition of the present invention, the content of the associative polymer is preferably 0.1 to 5% by mass, particularly preferably 0.5 to 2% by mass. If it is less than 0.1% by mass, the effect of the present invention may not be sufficiently exhibited, and if it exceeds 5% by mass, the viscosity may increase excessively, resulting in inconvenience in use.

The composition of this invention may contain 0.1-25 mass % of oil components further. For example, it may contain: vegetable oils such as olive oil and castor oil; waxes such as carnauba wax and candelilla wax; liquid paraffin, triodecane, vaseline, polyethylene oxide propylene oxide alkyl Hydrocarbon oils such as ethers; higher fatty acids such as lauric acid, stearic acid, isostearic acid, and 12-hydroxystearic acid; higher alcohols such as cetyl alcohol, stearyl alcohol, and behenyl alcohol; Esters of propyl ester, cetyl 2-ethylhexanoate, diethoxy succinate, etc.; esters of methylpolysiloxane, methylphenylpolysiloxane, long-chain alkylsiloxane, etc. Silicone oil etc.

The composition can be provided in the form of all drug prescriptions suitable for topical application, especially as a water-in-oil type (W/O) or an oil-in-water type (O/W) or a three-layer (triple) type (W/ Available in the form of O/W or O/W/O) dispersion or emulsion.

The viscosity of the composition of the present invention is preferably in the range of 0.1 to 100 Pa·s, more preferably in the range of 1 to 50 Pa·s, which can be measured at 25°C with a Brookfield viscometer or the like. The effect of the composition is the same whether it is an aqueous gel or an emulsion or dispersion.

According to the invention, additional or all ingredients conventionally used in the field of cosmetics and/or dermatology can also be contained in the gel-like composition. For example, it can contain: fatty acid soap, alkyl sulfate, polyoxyethylene alkyl ether sulfate, acyl-N-methyl taurate, alkyl ether phosphate, N-acyl amino acid salt, organic acid monoglyceride Anionic surfactants such as esters; cationic surfactants such as haloalkyltrimethylammonium, halodialkyldimethylammonium, benzalkonium chloride, haloalkylpyridinium, etc.; alkyldimethylaminoacetic acid beets Amphoteric surfactants such as alkali, alkylamide dimethylaminoacetic acid betaine, 2-alkyl-N-carboxy-N-hydroxyimidazolium betaine, lecithin, enzymatically decomposed lecithin, etc.; alkyl polyoxyethylene type , polyol ester type, alkyl polyglucoside type, alkyl polyglycerol type, sugar ester type, polyethylene oxide-polypropylene oxide copolymer type, sorbitan fatty acid ester, dimethicone Nonionic surfactants such as alkyl polyols; glycerin, propylene glycol, 1,3-butanediol, polyethylene glycol, sorbitol, sodium lactate, sodium 2-pyridinone-5-carboxylate, hyaluronic acid Humectants such as sodium, synthetic polymers such as carboxyvinyl polymers and polyvinylpyrrolidone; semi-synthetic polymers such as carboxymethylcellulose and hydroxypropylcellulose; xanthan gum, dextrin, hyaluronic acid , casein, collagen and other natural polymers; high molecular weight siloxane, benzophenone derivatives, p-aminobenzoic acid derivatives, methoxycinnamic acid derivatives, etc. UV absorbers; tocopherol, BHT, etc. Antioxidant; metal ion blocking agent of EDTA, citric acid, hexametaphosphoric acid, pyrophosphorous acid, etc.; microemulsion of siloxane microemulsion, high pressure emulsified microemulsion, etc., alcohol, etc.

In addition, as active ingredients, for example, whitening agents such as arbutin, ascorbic acid and its derivatives; anti-aging agents such as retinol and its derivatives; α-hydroxy acids such as lactic acid and glycolic acid; Hair growth agent; vitamins; anti-inflammatory agent, fungicide, various salts, etc.

In addition, its use form can be arbitrary, as long as it is a medicine used in the field of traditional cosmetics and/or dermatology, any form can be used, for example: lotion, cream, lotion, lotion, paste, ointment, massage, etc. Silk, and soap, in addition to: foundation cream, eye shadow, age spots, dark circles concealer, lipstick, mascara, lipstick, cosmetics for the body, etc. Make-up cosmetics; hair conditioner, shampoo, skin Sunscreen or sun cream, as well as dermatological ointments, bath preparations, etc.

Preferred embodiments of the present invention are described in more detail below. In addition, this invention is not limited to these Examples. In addition, the compounding quantity shows mass % unless otherwise specified.

Before the examples, production examples of the associative polymers mentioned in the present invention are shown.

[Manufacturing Example 1] Polyurethane Triblock Copolymer

Add 40 parts of polyethylene glycol (PEG) (molecular weight: about 20,000) and 300 parts of toluene to a 1000-ml four-necked flask equipped with a thermometer, a nitrogen inlet tube, and a stirrer, and dissolve them at 70°C. After removing water by azeotropy, 0.7 parts of hexamethylene diisocyanate, 0.03 parts of dibutyltin laurate, and polydimethylsiloxane (FM0411, manufactured by Chisso, with a molecular weight of about 1,000 ) in 4 parts were reacted at 70° C. overnight in a nitrogen stream, and then water was added thereto to stop the reaction. The solvent was removed to obtain the target polymer.

The polymer obtained according to Production Example 1 is one of the above-mentioned formula (I), R ₁ to R ₄ , Z represent -CH ₃ , A, Y represent -CH ₂ CH ₂ O-, X represents hexamethylene bis The residue of isocyanate, the polymer in which a is 2, is represented by general formula (IV) below. In addition, theoretically, b=450 and c=10.

[Manufacturing example 2] Polyurethane multi-block copolymer

Add 40 parts of polyethylene glycol (PEG) (molecular weight: about 20,000) and 300 parts of toluene to a 1000-ml four-necked flask equipped with a thermometer, a nitrogen inlet tube, and a stirrer, and dissolve them at 70°C. After water was removed by azeotropy, 1.1 parts of hexamethylene diisocyanate, 0.03 parts of dibutyltin laurate, and polydimethylsiloxane (FM4411, manufactured by Chisso) having hydroxyl groups at both ends were added thereto at 80°C. , Molecular weight about 1,000) 4 parts were reacted overnight at 70° C. in a nitrogen stream, and then water was added thereto to stop the reaction. The solvent was removed to obtain the target polymer.

The polymer obtained according to Production Example 2 is a kind of polymer in the above formula (I), R ₁ to R ₄ represent -CH ₃ , Y represents hydroxyl, Z represents -C ₃ H ₆ OC ₂ H ₄ OH or Y and Z together Represents a residue of hexamethylene diisocyanate, A represents -CH ₂ CH ₂ O-, X represents a polymer of a residue of hexamethylene diisocyanate, and is represented by general formula (V) below. It should be noted that theoretically b=450 and c=10.

[Manufacturing Example 3] Ether type triblock copolymer

Add 40 parts of polyethylene glycol (PEG) (molecular weight: about 20,000) and 300 parts of toluene to a 1000-ml four-necked flask equipped with a thermometer, a nitrogen inlet tube, and a stirrer, and dissolve them at 70°C. After removing water by azeotropy, 3 parts of dimethylsiloxane having an epoxy group terminal (FM0511, manufactured by Chicso, molecular weight about 1,000) and 0.3 parts of potassium laurate were added thereto, and reacted overnight at 70°C in a nitrogen stream. , and then ethanol was added thereto to stop the reaction. The solvent was removed to obtain the target polymer.

The polymer obtained according to Production Example 3 is a polymer in the above formula (I), R ₁ to R ₄ and Z represent -CH ₃ , A and Y represent -CH ₂ CH ₂ O-, X represents an epoxy group residue , a is a polymer of 2, represented by general formula (VI) below. In addition, theoretically, b=450 and c=10.

[Manufacturing Example 4] Ether type triblock copolymer

Add 40 parts of polyethylene glycol (PEG) (molecular weight: about 20,000) and 300 parts of toluene to a 1000-ml four-necked flask equipped with a thermometer, a nitrogen inlet tube, and a stirrer, and dissolve them at 70°C. After water was removed by azeotropy, 4 parts of dimethylsiloxane (FM0411, manufactured by Chicso, molecular weight about 1,000) having a hydroxyl end, polyethylene glycol diglycidyl ether (Denakol EX810, manufactured by Nagase Chemical Co., Ltd.) were added thereto. Industrial production) 0.7 parts, potassium hydroxide 0.07 parts, reacted overnight at 70° C. in a nitrogen stream, and then added ethanol thereto to stop the reaction. The solvent was removed to obtain the target polymer.

The polymer obtained according to Production Example 4 is a kind of polymer in the above formula (I), R ₁ to R ₄ , Z represent -CH ₃ , A, Y represent -CH ₂ CH ₂ O-, X represents polyethylene glycol di The glycidyl ether residue, a polymer in which a is 2, is represented by the general formula (VII) below. In addition, theoretically, b=450 and c=10.

[Manufacturing Example 5] Ether type multi-block copolymer

Add 20 parts of polyethylene glycol (PEG) (molecular weight: about 35,000) and 300 parts of toluene to a 1,000-ml four-necked flask equipped with a thermometer, a nitrogen inlet tube, and a stirrer, and dissolve them at 70°C. After removing water by azeotropy, 4 parts of dimethylsiloxane (FM0511, manufactured by Chicso, molecular weight about 1,000) having two-terminal epoxy groups and 0.3 parts of potassium laurate were added thereto, and reacted at 70°C in a nitrogen stream. overnight, and then ethanol was added thereto to stop the reaction. The solvent was removed to obtain the target polymer.

The polymer obtained according to Production Example 5 is one in which in the above formula (I), R ₁ to R ₄ represent -CH ₃ , Y represents a residue of a hydroxyl group or an epoxy group, A represents -CH ₂ CH ₂ O-, X represents a residue of an epoxy group, Z represents a polymer of a residue of a hydroxyl group or an epoxy group, and is represented by general formula (VIII) below. It should be noted that theoretically b=800 and c=10.

[Manufacturing Example 6] Ester Triblock Copolymer

20 parts of polyethylene glycol (PEG) (molecular weight: about 10,000) and 300 parts of toluene were added to a 1000-ml four-neck flask equipped with a thermometer, a nitrogen inlet tube and a stirrer, and dissolved at 70°C. After water was removed by azeotropy, 6 parts of 25 mol adducts of dimethylsiloxane (FM0411, manufactured by Chicso, molecular weight about 1,000) having a hydroxyl end, 0.6 parts of adipic acid, and sodium hydroxide were added thereto. 0.1 part was reacted overnight at 70°C in a nitrogen stream. The solvent was removed to obtain the target polymer.

The polymer obtained according to Production Example 6 is one in which in the above formula (I), R ₁ to R ₄ and Z represent -CH ₃ , A and Y represent -CH ₂ CH ₂ O-, and X represents adipic acid residues , a is a polymer of 2, represented by general formula (IX) below. In addition, b=230 and c=10 theoretically.

[Manufacturing Example 7] Ester-type multi-block copolymer

Add 40 parts of polyethylene glycol (PEG) (molecular weight: about 20,000) and 300 parts of toluene to a 1000-ml four-necked flask equipped with a thermometer, a nitrogen inlet tube, and a stirrer, and dissolve them at 70°C. After removing water by azeotropy, 9 parts of 25 mol adducts of dimethylsiloxane (FM4411, manufactured by Chisso, molecular weight about 1,000) having hydroxyl groups at both terminals (FM4411, manufactured by Chisso, about 1,000) and 1.2 parts of adipic acid were added thereto. 0.1 part of sodium was reacted overnight at 70°C in a nitrogen stream. The solvent was removed to obtain the target polymer.

The polymer obtained according to Production Example 7 is a kind of polymer in the above formula (I), R ₁ to R ₄ represent -CH ₃ , Y represents hydroxyl, Z represents -C ₃ H ₆ OC ₂ H ₄ OH or Y and Z together represents adipic acid residue, A represents -CH ₂ CH ₂ O-, X represents a polymer of adipic acid residue, and is represented by general formula (X) below. In addition, theoretically, b=450 and c=10.

[Manufacturing Example 8] Urea-type tri-block copolymer

Add 70 parts of polyethylene glycol (PEG) (molecular weight: about 35,000) and 300 parts of toluene to a 1,000-ml four-necked flask equipped with a thermometer, a nitrogen inlet tube, and a stirrer, and dissolve them at 70°C. After removing water by azeotropy, add 0.7 parts of hexamethylene diisocyanate, 0.03 parts of dibutyltin laurate, and 4 parts of dimethylsiloxane (molecular weight: about 1,000) having an amino terminal at 80°C in a nitrogen stream. It was reacted overnight at 70°C, and water was added thereto to stop the reaction. The solvent was removed to obtain the target polymer.

The polymer obtained according to Production Example 8 is a polymer in the above formula (I), R ₁ to R ₄ , Z represent -CH ₃ , A, Y represent -CH ₂ CH ₂ O-, X represents hexamethylene bis The isocyanate residue, the polymer in which a is 2, is represented by general formula (XI) below. In addition, theoretically, b=800 and c=10.

[Manufacturing Example 9] Urea-type multi-block copolymer

Add 70 parts of polyethylene glycol (PEG) (molecular weight: about 35,000) and 300 parts of toluene to a 1,000-ml four-necked flask equipped with a thermometer, a nitrogen inlet tube, and a stirrer, and dissolve them at 70°C. After water was removed by azeotropy, 1.1 parts of hexamethylene diisocyanate, 0.03 parts of dibutyltin laurate, and dimethylsiloxane (FM4421, manufactured by Chisso, molecular weight about 5,000)4 having amino groups at both terminals were added at 80°C. Parts were reacted overnight at 70° C. in a nitrogen stream, and water was added thereto to stop the reaction. The solvent was removed to obtain the target polymer.

The polymer obtained according to Production Example 9 is one wherein in the above formula (I), R ₁ to R ₄ represent -CH ₃ , Y represents a hydroxyl group or a residue of hexamethylene diisocyanate, and A represents -CH ₂ CH ₂ O-, X represents a residue of hexamethylene diisocyanate, Z represents -C ₃ H ₆ NH ₂ or a polymer of residues of hexamethylene diisocyanate, and is represented by general formula (XII) below. In addition, theoretically, b=800 and c=60%.

[Manufacturing Example 10] Ether type triblock copolymer

Into a four-neck flask with a capacity of 1,000 ml equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 4 parts of dimethylsiloxane (FM0411, manufactured by Chisso, molecular weight about 1,000) having a hydroxyl end and 0.8 parts of p-toluenesulfonyl chloride were added. , 300 parts of toluene, and a small amount of pyridine was added thereto. Further, 40 parts of polyethylene glycol (PEG) (molecular weight: about 20,000) metallized with potassium diphenylmethane was added in advance, and reacted at 70° C. in a nitrogen stream. The solvent was removed to obtain the target polymer.

The polymer obtained according to Production Example 10 is a residue in the above formula (I), where R ₁ to R ₄ and Z represent -CH ₃ , A and Y represent -CH ₂ CH ₂ O-, and X represents an ether bond. , a is a polymer of 2, represented by general formula (XIII) below. In addition, theoretically, b=450 and c=10.

[Manufacturing Example 11] Ether type multi-block copolymer

Into a four-neck flask with a capacity of 1000 ml equipped with a thermometer, a nitrogen gas introduction tube and a stirrer, 4 parts of dimethylsiloxane (FM4411, made by Chisso, molecular weight about 1,000) having hydroxyl groups at both terminals, 1.6 parts of p-toluenesulfonyl chloride Parts, 300 parts of toluene, and a small amount of pyridine was added thereto. Further, 40 parts of polyethylene glycol (PEG) (molecular weight: about 20,000) metallized with potassium diphenylmethane was added in advance, and reacted at 70° C. in a nitrogen stream. The solvent was removed to obtain the target polymer.

The polymer obtained according to Production Example 11 is one in which in the above formula (I), R ₁ to R ₄ represent -CH ₃ , Y represents a hydroxyl group or a residue of an ether bond, A represents -CH ₂ CH ₂ O-, X Represents a residue of an ether bond, Z represents a polymer of -C ₃ H ₆ OC ₂ H ₄ OH or a residue of an ether bond, and is represented by general formula (XIV) below. It should be noted that theoretically b=450 and c=10.

[Comparative Manufacturing Example 1]

Add 40 parts of polyethylene glycol (PEG) (molecular weight: about 20,000) and 300 parts of toluene to a 1000-ml four-necked flask equipped with a thermometer, a nitrogen inlet tube, and a stirrer, and dissolve them at 70°C. After removing the water by azeotropy, add 0.7 parts of hexamethylene diisocyanate, 0.03 parts of dibutyltin laurate, and lauryl alcohol (C12, molecular weight about 186.34) at 80°C, and react overnight at 70°C in a nitrogen stream. Water was added to quench the reaction. The solvent was removed to obtain the target polymer.

The polymer obtained according to Comparative Production Example 1 was a polymer represented by the following general formula (XV).

[Comparative Manufacturing Example 2]

Add 40 parts of polyethylene glycol (PEG) (molecular weight: about 20,000) and 300 parts of toluene to a 1000-ml four-necked flask equipped with a thermometer, a nitrogen inlet tube, and a stirrer, and dissolve them at 70°C. After removing the water by azeotropy, add 0.7 parts of hexamethylene diisocyanate, 0.03 parts of dibutyltin laurate, and myristyl alcohol (C14, molecular weight about 214.38) at 80°C, and react overnight at 70°C in a nitrogen stream. Water was added thereto to stop the reaction. The solvent was removed to obtain the target polymer.

Ethanol was added to quench the reaction. The solvent was removed to obtain the target polymer.

The polymer obtained according to Comparative Production Example 2 was a polymer represented by the following general formula (XIV).

[Comparative Manufacturing Example 3]

Add 40 parts of polyethylene glycol (PEG) (molecular weight: about 20,000) and 300 parts of toluene to a 1000-ml four-necked flask equipped with a thermometer, a nitrogen inlet tube, and a stirrer, and dissolve them at 70°C. After removing water by azeotropy, add 0.7 parts of hexamethylene diisocyanate, 0.03 parts of dibutyltin laurate, and stearyl alcohol (C18, molecular weight about 240.75) at 80 ° C, and react overnight at 70 ° C in a nitrogen stream. Water was added thereto to stop the reaction. The solvent was removed to obtain the target polymer.

Ethanol was added thereto to stop the reaction. The solvent was removed to obtain the target polymer.

The polymer obtained according to Comparative Production Example 3 was a polymer represented by the following general formula (XVII).

[Comparative Manufacturing Example 4]

Add 40 parts of polyethylene glycol (PEG) (molecular weight: about 20,000) and 300 parts of toluene to a 1000-ml four-necked flask equipped with a thermometer, a nitrogen inlet tube, and a stirrer, and dissolve them at 70°C. After removing the water by azeotropy, add 0.7 parts of hexamethylene diisocyanate, 0.03 parts of dibutyltin laurate, and behenyl alcohol (C22, molecular weight about 326.59) at 80°C, and react overnight at 70°C in a nitrogen stream. Water was added thereto to stop the reaction. The solvent was removed to obtain the target polymer.

Ethanol was added to quench the reaction. The solvent was removed to obtain the target polymer.

The polymer obtained according to Comparative Production Example 4 was a polymer represented by the following general formula (XVIII).

The polymers of Production Examples 1 to 11 were each made into a 2% aqueous solution, and then their solubility and viscosity were evaluated according to the following evaluation criteria. The results are shown in Table 1.

Evaluation benchmark

Solubility

○: Dissolved at room temperature (25°C)

△: Dissolved when heated (70°C)

×: insoluble

viscosity

○: Gelation (no fluidity)

△: Viscosification (flow)

×: no thickening

Table 1

Dissolved viscosity Manufacturing 1 ○ ○ Manufacturing Example 2 ○ ○ Manufacturing Example 3 ○ ○ Manufacturing Example 4 ○ ○ ○ ○ Manufacturing example 6 ○ ○ Manufacturing example 7 ○ ○ Manufacturing example 8 ○ ○ Manufacturing example 9 ○ ○ Manufacturing example 10 ○ ○ Manufacturing Example 11 ○ ○

As can be seen from Table 1, among the polymers of Production Examples 1 to 11, all of the polymers were excellent in solubility and viscosity.

(1) Research on HLB value

It is considered that in the above formula (I), the preferred value of c is dependent on the value of b. In other words, from the viewpoint of the balance between hydrophilicity and hydrophobicity of the molecule, it can be considered that the preferred c value is larger for a larger b value, and its numerical value is also larger for a smaller b value. smaller. These characteristics can be considered from the viewpoint of HLB (Hydrophile-Lipophile Balance).

36 parts of polyethylene glycol (PEG) (molecular weight: about 18,000) and 300 parts of toluene were added to a four-neck flask with a capacity of 1000 ml equipped with a thermometer, a nitrogen inlet tube and a stirrer, and dissolved at 70°C. After water was removed by azeotropy, hexamethylene diisocyanate, 0.03 parts of dibutyltin laurate, and polydimethylsiloxane having a hydroxyl end (corresponding to the following formula (XIX), c=0～120), react at 70° C. overnight in a nitrogen flow, and then add water therein to stop the reaction. The solvent was removed to obtain the target polymer.

The obtained polymer is a kind of in the above formula (I), A and Y represent -CH ₂ CH ₂ O-, R ₁ ~ R ₄ and Z represent -CH ₃ , X represents the residue of hexamethylene diisocyanate A compound having a=2 and b=400 is represented by the following formula (XX). In addition, by changing the molecular weight of the siloxane having a hydroxyl terminal, the values of c can be set to the values shown in Table 2, respectively. A preferable HLB value was examined by evaluating the solubility and viscosity of a 2% aqueous solution in the same manner as above.

HLB=b×20×a/total molecular weight (Griffin formula)

Table 2

C HLB dissolving viscosity test example 1-1 0 19.6 ○ × test example 1-2 1 19.6 ○ × test example 1-3 3 19.5 △ test example 1-4 5 19.4 ○ test example 1-5 10 19.2 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ Test examples 1-6 50 17.7 ○ ○ Test examples 1-7 70 17.0 ○ Test examples 1-8 105 16.0 △ △ △ test example 1-9 120 15.5 × × ×

From Table 2, it can be seen that the solubility decreases with the increase of c-layer. On the other hand, with regard to the viscosity, as the value of c increases, it shows a thickening effect, but if the value of c increases too much, the solubility will decrease instead, causing the polymer to phase separate, and as a result, it will not show a thickening effect. sticky effect. From these results, it can be seen that the preferred HLB value is 16.0 to 19.5, particularly preferably 17.0 to 19.4.

(2) Research on the average molecular weight

Next, the preferred average molecular weight of the associative polymer referred to in the present invention will be examined.

Add polyethylene glycol (PEG) of various molecular weights and 300 parts of toluene to a four-necked flask with a capacity of 1000 ml equipped with a thermometer, a nitrogen gas inlet tube and a stirrer, and dissolve them at 70° C. After removing water by azeotropy, hexamethylene diisocyanate, 0.03 parts of dibutyltin laurate, and dimethylsiloxane having a hydroxyl end (corresponding to c= 0 to 80), react overnight at 70° C. in a nitrogen stream, and then add water therein to stop the reaction. The solvent was removed to obtain the target polymer.

The obtained polymer is a kind of in the above formula (I), A and Y represent -CH ₂ CH ₂ O-, R ₁ ~ R ₄ and Z represent -CH ₃ , X represents hexamethylene diisocyanate and The reaction residue of the terminal group (-C ₃ H ₆ OC ₂ H ₄ OH) introduced by dimethylsiloxane and the terminal hydroxyl group of polyethylene glycol, a polymer of a=2, is represented by the following formula (XXI). In addition, the b and c values when the HLB value was kept constant (about 17) by changing the molecular weights of polyethylene glycol and dimethylsiloxane are the values in Table 3, respectively. A preferable average molecular weight was examined by evaluating the solubility and viscosity of a 2% aqueous solution in the same manner as above.

table 3

B C HLB Average molecular weight dissolving viscosity test example 2-1 35 0 16.6 3800 × test example 2-2 45 1 16.9 4800 × test example 2-3 60 5 16.7 6800 △ test case 2-4 75 8 16.8 8600 ○ ○ Test examples 2-5 125 18 16.9 15000 ○ Test examples 2-6 225 40 16.8 27000 ○ Test examples 2-7 400 80 16.7 48000 ○ ○ ○

As can be seen from Table 3, although the respective HLB values are approximately the same, in the case of low molecular weight, no thickening effect is seen. The reason is that, in associative polymers, when the length of the hydrophilic chain part connecting the hydrophobic associative groups is not greater than the distance between the crosslinking points, it cannot effectively act as a polymer. To make the system viscosifying and gelling. Therefore, it can be confirmed that the preferred molecular weight in the present invention is 6000 or more, particularly preferably 8000 or more.

(3) Research on the types of hydrophobic groups

Next, in the test examples, the polymers of the test examples 1-3 to 1-6 of the above (1) are used, and in the comparative examples, the polymers of the production examples 1 to 4 are used, and the polymers are used Triblock alkyl-type associative polymers prepared by replacing dimethylsiloxane with higher alcohols as the hydrophobic part, and preparing 2% aqueous solutions with the above polymers, and evaluating their viscosity and use feeling.

Evaluation benchmark

sense of use

◯: 8 or more out of 10 answered that it was not sticky.

△: More than 5 and less than 8 out of 10 answered that it was not sticky.

×: 4 or less out of 10 answered that it was not sticky.

Table 4

The trait of the hydrophobic part of the hydrophobic part CHLB viscosity test example 1-3 dioma siliconxane liquid 3 19.5 ○ test case 1-4 dioma silicone liquid 5 19.4 ○ test case 1-5 di metarisa Dimethicone Liquid 10 19.2 ○ ○ Test Example 1-6 Dimethylsiloxane Liquid 50 17.7 ○ ○

Hydrophstical Hydrophst Hydrophin HLB viscosity Avicidal Against example 1-1 laurel alcohol liquid 12 19.7 × ○ Comparison Example 1-2 Cutmemol solid state 14 19.7 △ △ Comparison Example 1-3 hard fatty glycol solid state 18 19.7 ○ ×Comparative example 1-4 Behenyl alcohol Solid state 22 19.7 ○ ×

Properties of the hydrophobic part: Appearance at 25°C

It can be seen from Table 4 that for dimethyl siloxane, even if its molecular weight increases, it still remains liquid, and the siloxanated associative polymers of Test Examples 1-3 to 1-6 formulated with it are A kind of polymer with both viscosity and non-sticky sense of use. On the contrary, for higher alcohols, as the alcohol chain increases, its properties also change from liquid to solid. When the alkylated associative polymers of 1-1 to 1-4 are in a liquid state, the alkyl groups in them have no viscosity-increasing properties; when the polymers are in a solid state, although the alkyl groups in them have viscosity-increasing properties, they feel irritating when used. stick. Therefore, it can be confirmed that the polymer of the present invention is superior in thickening performance and usability compared with conventional alkylated associative polymers.

Example 1 Cleansing Foam

Fatty Acids: Stearic Acid 15

Palm acid 20

Emollient: Coconut Oil 2

Alkali: Potassium Hydroxide 6

Moisturizer: Glycerin 15

                                                                             

Surfactant: Glyceryl Monostearate 2

           POE(20) Sorbitan Monostearic Acid 2

Associative thickener: Polymer of Production Example 1 2

Preservatives: phenoxyethanol 0.2

Chelating agent: appropriate amount

Distilled water: balance

Heat and melt fatty acids, emollients, humectants, and preservatives and keep them at 70°C. Separately, distilled water, in which base was previously dissolved, was added to the oil phase with stirring. Shortly after the addition, the neutralization reaction was terminated while maintaining 70°C. Then, melted surfactant, chelating agent, tackifier are added thereto, stirred and mixed, degassed, and cooled after filtration.

Example 2 lotion

Moisturizer: Sorbitol 4

                                             

                                                         

Surfactant: POE(20) oleyl ether 0.5

Associative thickener: The polymer of Production Example 1 0.1

Alcohol: Ethanol 10

Preservatives: Methylparaben 0.2

Spices: Appropriate amount

Chelating agent: appropriate amount

Buffer: Appropriate amount

Distilled water: balance

Take a part of distilled water to dissolve the chelating agent, mix the viscosity enhancer into it, and stir it to make a viscous liquid. A humectant and a buffer were added to the remainder of the distilled water to dissolve them at room temperature, and the above-mentioned viscous solution was added thereto to obtain a uniform aqueous solution. A preservative, a surfactant, and a fragrance are added to ethanol to make an alcohol solution, and the alcohol solution is added and mixed to the above-mentioned aqueous solution to make it soluble.

Example 3 Moisturizing Lotion

Oil: Cetyl Alcohol 1

                                                                             

Vaseline 2

                                                         

                                                                         

Alcohol: Ethanol 5

Moisturizer: Glycerin 4

                                                               

Surfactant: POE(10) monooleate 1

                                                           ,

Associative thickener: Polymer of Production Example 1 2

Preservatives: Methylparaben 0.2

Distilled water: balance

Add humectant to distilled water and heat to 70°C. Add surfactants and preservatives to the oil, and heat to 70°C. Add it to the original water phase for pre-emulsification. Thickening agent and ethanol are added therein, stirred, and after the emulsified particles are stirred evenly with a homogeneous mixer, degassing, filtering and cooling are carried out.

Example 4 Moisturizer

Oil: Cetyl Alcohol 5

                                                              

Vaseline 5

                                                                   

                                                                                                                                                                                                                                                       Tris-2-Ethylhexanoin 7

Humectant: Dipropylene Glycol 5

Glycerin 5

Sodium pyrrolidone carboxylate 1

Surfactant: Propylene Glycol Monostearate 3

POE(20) Cetyl Ether 3

Alkali: Triethanolamine 1

Associative thickener: Polymer of Production Example 1 3

Preservatives: Phenoxyethanol 0.2

Antioxidant: BHT 0.1

Spices: Appropriate amount

Distilled water: balance

Add humectant, alkali and tackifier to distilled water and heat to 70°C. After the oil is heated and melted, surfactants, preservatives, antioxidants, fragrances are added thereto, and the temperature is raised to 70°C. Add it to the original water phase for pre-emulsification. After the emulsified particles are evenly stirred by a homogeneous mixer, degassing, filtering and cooling are carried out.

Example 5 Moisturizing jelly

Humectant: Dipropylene Glycol 7

                                                                                                      

Associative thickener: Polymer of Production Example 1 1

Water-soluble polymer: Xanthan gum 0.4

                                                                                           ,

Alkali: Potassium Hydroxide 0.1

Preservatives: Methylparaben Appropriate amount

Chelating agent: appropriate amount

Spices: Appropriate amount

Distilled water: balance

An associative thickener and a water-soluble polymer were uniformly dissolved in distilled water, and then PEG1500 and a chelating agent were added thereto. In addition, a surfactant is added to dipropylene glycol, heated and dissolved at 50° C., and a preservative and fragrance are added thereto. Slowly add the previously prepared aqueous phase with stirring. Finally, add the aqueous alkali solution and stir well to complete the neutralization reaction.

Example 6 Whitening Essence

Oil: Dimethicone 2

Moisturizer: Sorbitol 8

                                                 

                                               

                                                                                                                                                                       

Alcohol: Ethanol 7

Emulsifier: carboxyvinyl polymer

(pemulen TR-2 ^™ , Goodrich Corporation) 0.15

Emollient: Olive Oil 0.2

Whitening agent: Arbutin 5

Ascorbyl Glucoside 3

Associative thickener: Polymer of Production Example 1 0.5

Preservatives: phenoxyethanol 0.2

Spices: Appropriate amount

Buffer: Appropriate amount

Distilled water: balance

Dissolve humectants, buffers, thickeners, whitening agents, and emulsifiers in distilled water at room temperature. In addition, an oil component, an emollient, a fragrance, and a preservative are dissolved in ethanol, and then added to the above-mentioned water phase to be solubilized.

Example 7 Mask

Film former: Polyvinyl alcohol 15

Associative thickener: Polymer of Production Example 1 5

Humectant: 1,3-Butanediol 5

Surfactant: POE oleyl ether 0.5

Alcohol: Ethanol 12

Preservatives: Methylparaben 0.2

Spice: Appropriate amount

Buffer: appropriate amount

Distilled water: balance

Add buffer, humectant to distilled water and heat it to 70°C. Add the tackifier and film former and stir to dissolve. In addition, fragrances, preservatives, and surfactants are added to ethanol, and after being dissolved, they are added to the above-mentioned water phase to make them solubilized.

Example 8 Liquid foundation cream

Powder: Talc 3

                                             ,

                                               

                                                                                                                                       =

Iron oxide black

Water phase: bentonite 0.5

        POE Sorbitan Monostearate 0.9

                                                  

Propylene Glycol 10

The polymer of Production Example 1 0.5

                                              

Oil Phase: Stearic Acid 2.2

                                                            

Glyceryl monostearate 2

                                                                                                                                 , 

                                                                                                 ,

        POE modified dimethyl polysiloxane 1

Preservatives: Appropriate amount

Spices: Appropriate amount

Example 9 Emulsified lipstick

Pigment: Titanium Dioxide 4.5

                                                         

2.0

Dye: Red No. 223 0.05

Solid oil: Pure ceresine 4.0

Candelilla Wax 8.0

                                                                                                                    

Liquid oil: Castor oil 30.0

                                               

Surfactant: POE(25)PPO(20)2-tetradecyl ether 1.0

Distilled water: 5.0

Moisturizer: Glycerin 2.0

Propylene Glycol 1.0

Associative thickener: Polymer of Production Example 1 2.0

UV protection agent: Appropriate amount

Antioxidant: Appropriate amount

Spices: Appropriate amount

Titanium dioxide, Red No. 201, Red No. 202 are added to a part of castor oil and processed with a roller (pigment part). Dissolve Red No. 223 in castor oil (dye section). Distilled water, glycerin, propylene glycol, and associative thickener were uniformly dissolved at 80°C (water phase). Mix the other ingredients, heat to melt, then add the pigment part and dye part to it, and disperse it evenly with a homomixer. Then add the water phase to it, emulsify and disperse it with a homomixer, and finally pour it into a mold and quench it to make it into a stick shape.

Example 10 nail polish

Resin: Polymer Emulsion 85.0

Plasticizer: diisobutyl adipate 4.0

Coalescing agent: Carbitol 4.0

Preservatives: Methylparaben 0.2

Defoamer: Appropriate amount

Pigment: Red No. 220 0.3

                                                      

Associative thickener: The polymer of Production Example 1 0.2

Ion-exchanged water: balance

The associative tackifier is heated and dissolved in ion-exchanged water, and then added to the polymer emulsion. Further, diisobutyl adipate and carbitol are gradually added, and other components are added, and after being uniformly dispersed, they are degassed.

Example 11 Shampoo

Surfactant: Sodium coconut fatty acid acyl methyl taurate 9

                                                                                        , 

Propylene glycol laurate 1

                                                  ,

                                                                                          ,

Moisturizer: Glycerin 1

Usability improver: cationized cellulose 0.5

Associative thickener: Polymer of Production Example 1 2

Salt: Chloride 1.5

Spices: Appropriate amount

Pigment: Appropriate amount

Preservatives: Appropriate amount

Metal ion blocking agent, pH regulator: Appropriate amount

Distilled water: balance

Distilled water was heated to 70°C, other ingredients were added to it and dissolved uniformly, and then cooled.

Example 12 Finishing agent

Oil content: Silicone oil 3

                                                                                                                         ,

Cetyl Alcohol 1.5

                                             

            Stearyl Trimethylammonium Chloride   0.7

Moisturizer: Glycerin 3

Associative thickener: The polymer of Production Example 1 0.5

Flavors, colorings, preservatives: Appropriate amount

Add associative tackifier, chlorinated stearyltrimethylammonium, glycerin and pigment to distilled water, keep it at 70°C (water phase), in addition, mix other ingredients, heat to melt and keep at 70°C (oil phase) Mutually). Add the oil phase to the water phase and emulsify it with a homomixer, then cool it under stirring.

Example 13 Hairspray

Associative thickener: Polymer of Production Example 1 2

Moisturizer: Glycerin 5

Alcohol: Ethanol 20

Surfactant: POE Octyl Lauryl Ether 1

Spices, chelating agents: Appropriate amount

Distilled water: balance

A part of distilled water was added to the associative thickener and glycerin, and it was heated and dissolved at 70°C. Dissolve other ingredients in remaining distilled water and add while stirring.

Example 14 Sunscreen

Oil Phase: Fatty Acid Treated Titanium Oxide 2

Dextrin Fatty Acid Treated Zinc Oxide 10

Care acid ester 3

Isopropyl myristate 2

                                                           

                                                             

Glyceryl Monostearate 2

                                                                   

                                                                                                                                                                                                                                                                               , 

    Organo-modified bentonite (organic bentonite 38, 0.5

ナショナルレツド company)

                                                                   

Aqueous phase: 1,3-butanediol 5

Polymer of Production Example 1 1

                                                                 

The oil phase part and the water phase part were each heated to 70 degreeC and dissolved. Then add the oil phase to the water phase, emulsify it with a homogenizer, and cool it with a heat exchanger.

Using the alkylated associative polymer of Comparative Production Example 1 instead of the polymer in the compositions prepared in Examples 1 to 14 and Production Example 1, as the composition of Comparative Examples 1 to 14, these combinations The sensory inspection of the sense of use is carried out.

Evaluation benchmark

sense of use

⊚: 8 or more out of 10 respondents answered favorably.

◯: 6 or more out of 10 respondents answered favorably.

△: 4 or more out of 10 respondents answered favorably.

X: 3 or less out of 10 answers were good. Evaluation results

table 5

No. Example Comparative Example

1 ◎ ◎ △

2 ○ ○ △

3 ○ ○ ×

4 ◎ ◎ △

5 ◎ ◎ △

6 ◎ ◎ ×

7 ○ ○ ×

8 ◎ ◎ △

9 ◎ ◎ △

10 ◎ ◎ ×

11 ◎ ◎ △

12 ◎ ◎ ×

13 ○ ○ △

14 ○ ○ △

As can be seen from Table 5, the composition of the example using the siliconized associative polymer has a good feeling of use. In contrast, the composition of the comparative example using the alkylated associative polymer , and its usability is poor. Therefore, it was confirmed that the present invention has an excellent feel in use as compared with a composition using a conventional alkylated associative polymer.

In addition, even if the polymer of manufacture example 2-11 was used instead of the polymer of manufacture example 1, the excellent feeling in use was obtained similarly. Example 15 Oil-in-water foundation cream

1. Microcrystalline Wax 0.7

2. Methylpolysiloxane 15

3. Decamethylcyclopentylsiloxane 1

4. 1,3-Butanediol 5

5. Candelilla Wax 3

6. Isostearic acid 1

7. Ethylene glycol fatty acid ester 0.1

8. Hydrous lanolin fatty acid octyldodecyl ester 0.5

9. Imidazolium Betaine 5

10. Titanium oxide 10

11. Iron oxide·titanium oxide sintered product 5

12. Barium sulfate 5

13. Talc 2

14. Silicic anhydride 5

15. Cross-linked silicone resin powder 0.1

16. Hydroxypropyl-β-cyclodextrin 0.001

17. Parabens in moderation

18. Iron oxide red 0.3

19. Iron oxide yellow 1

20. Iron oxide black 0.05

21. Polymer of Production Example 1 2

22. Calcium alginate 0.01

23. Sodium carboxymethylcellulose 0.2

24. Distilled water balance Example 16 Moisturizing cream

1. Liquid paraffin 10

2. Methylpolysiloxane 2

3. Glycerin 10

4.1,3-Butanediol 2

5. Erythritol 1

6. Macrogol 1500 5

7. Thiocane 15

8. Pentaerythritol tetrakis 2-ethylhexanoate 5

9. Potassium hydroxide 0.1

10. Sodium metaphosphate 0.05

11. Tocopheryl acetate 0.05

12. Parabens in moderation

13. Hydroxypropyl methylcellulose 0.3

14. Polyvinyl alcohol 0.1

15. Polymer of Production Example 1 1

16. Acrylic acid and methacrylic acid alkyl polymer 0.1

17. Polyurethane·polyether modified siloxane mixture

ョドゾ-ルPUPTM (Japan NSC) 0.5

18. Distilled water balance Example 17 Cream

1. Liquid paraffin 8

2. Vaseline 3

3. Methylpolysiloxane 2

4. Stearyl Alcohol 3

5. Behenyl alcohol 2

6. Concentrated Glycerin 5

7. Dipropylene glycol 4

8. Trehalose 1

9. Pentaerythritol tetrakis 2-ethylhexanoate 4

10. Polyoxyethylene glyceryl isostearate 2

11. Polyethylene oxide glycerol monostearate 1

12. Lipophilic monostearic acid polyethylene oxide glyceride 2

13. Citric acid 0.05

14. Sodium citrate 0.05

15. Potassium hydroxide 0.015

16. Hay flavonoids 0.1

17. Retinol Palmitate (1 million units) 0.25

18. DL-α-tocopherol acetate 0.1

19. Parabens in moderation

20. Phenoxyethanol Appropriate amount

21. Dibutylhydroxytoluene 0.1

22. Edetate 3-sodium 0.05

23.4-tert-butyl-4′-methoxydibenzoylmethane 0.01

24. 2-Ethylhexyl p-methoxycinnamate 0.1

25. β-carotene 0.01

26. The polymer of Production Example 1 0.5

27. Hydroxyethylcellulose 0.5

28. Carboxyvinyl polymer 0.05

29. Distilled water balance

30. Spices Appropriate amount

31.POE(14)POP(7)Dimethyl ether 2

32.POE(9)POP(2)Dimethyl ether 1

33. Retinol 0.1 Example 18 Whitening Essence

1. Vaseline 2

2. Methylpolysiloxane 2

3. Modified alcohol 5

4. Behenyl alcohol 0.5

5. Bakelite 0.2

6. Concentrated Glycerin 7

7. 1,3-Butanediol 5

8. Macrogol 20000 0.5

9. Jojoba oil 3

10. Thiocane 2

11. Cholesteryl Hydroxystearate 0.5

12. Pentaerythritol tetrakis 2-ethylhexanoate 1

13. Polyethylene oxide hardened castor oil 1

14. Potassium hydroxide 0.1

15. Sodium pyrophosphite 0.01

16. Sodium metaphosphate 0.05

17. Stearyl Glycyrrhizinate 0.1

18. Panthenyl ethyl ether 0.1

19. Arbutin 7

20. DL-α-tocopherol acetate 0.1

21. Sodium hyaluronate (2) 0.05

22. Parabens in moderation

23. Edetate 3-sodium 0.05

24.4-tert-butyl-4′-methoxydibenzoylmethane 0.1

25. Di-p-methoxycinnamic acid mono-2-ethylhexanoic acid glyceride 0.1

26. Iron Oxide Red Appropriate amount

27. Iron Oxide Yellow Appropriate amount

28. Xanthan gum 0.1

29. The polymer of Production Example 1 0.2

30. Distilled water balance

31.4-Cyclohexylresorcinol 2

32. Potassium 4-methoxysalicylate 1

33. L-Ascorbic acid-2-glucoside 2 Example 19 Emulsion

1. Vaseline 5

2. Methylpolysiloxane 2

3. Behenyl alcohol 0.6

4. Bakelite 0.5

5. Dipropylene glycol 2

6. 1,3-Butanediol 4

7. Xylitol 1

8. Macrogol 1500 1

9. Thiocane 5

10. Glyceryl tris-2-ethylhexanoate 2

11. Polyethylene oxide hardened castor oil 0.5

12. Dipotassium glycyrrhizinate 0.1

13. Yeast extract (3) 0.1

14. Peony extract 0.1

15. Edetate 3-sodium 0.05

16. Xanthan gum 0.1

17. The polymer of Production Example 1 0.3

18. Distilled water balance

19. Spices Appropriate amount

20. Zinc oxide coated with silicic anhydride 2

21. Tranexamic acid 0.5 Example 20 emulsion

1. Cetyl Alcohol 1

2. Glycerin 5

3. 1,3-Butanediol 5

4. Macrogol 20000 2

5. Tetrakis(2-ethylhexanoic acid p-methoxycinnamic acid) pentaerythritol 3

6. Di-2-ethylhexyl succinate 3

7. Potassium hydroxide 0.1

8. Ursodeoxycholic Acid Appropriate amount

9. Appropriate amount of phenoxyethanol

10. 3-Sodium Edetate Appropriate amount

11. Methylbis(trimethylsiloxane) trimethoxycinnamate

                                           

12.4-tert-butyl-4′-methoxydibenzoylmethane 2

13. 2-Ethylhexyl p-methoxycinnamate 2

14. Di-p-methoxycinnamic acid mono-2-ethylhexanoic acid glyceride 2

15. The polymer of Production Example 1 0.2

16. Alkyl acrylate and methacrylate copolymer 0.1

17. Distilled water balance

18. Spices Appropriate amount

19.4,5-morpholino-3-hydroxypyridazine 0.1 Example 21 sunscreen

1. Decamethylcyclosiloxane 20

2. Modified alcohol 5

3. Isostearyl Alcohol 2

4. Dipropylene glycol 3

5. Isostearic acid 2

6. Glyceryl tri-2-ethylhexanoate 5

7. Cetyl 2-ethylhexanoate 2

8. Titanium oxide (hydrophobic treatment) 2

9. Sodium Chloride 2

10. Bisresorcinol triazine 2

11. 3-Sodium Edetate Appropriate amount

12.2,4,6-tris(4-(2-ethylhexyloxycarbonyl)anilino) 1,3 1

13.4-tert-butyl-4′-methoxydibenzoylmethane 1

14. 2-Ethylhexyl p-methoxycinnamate 7.5

15. Polymer of Production Example 1 1

16. Ethyl cellulose 1

17. Spherical resin powder 5

18. Distilled water balance

19. Perfume Appropriate amount Example 22 Sunscreen

1. Methylphenyl polysiloxane 4

2. Stearyl Alcohol 2

3. Glycerin 5

4. Dipropylene Glycol 5

5. Sorbitol solution 5

6. Stearic acid 1.5

7. Palmitic acid 1

8. Pentaerythritol tetrakis 2-ethylhexanoate 4

9. Self-emulsifying glyceryl monostearate 1

10. Potassium hydroxide 0.15

11. Ursodeoxycholic Acid Appropriate amount

12. Octyl Methoxycinnamate 6

13. Oxybenzone 3

14. Iron oxide yellow 0.01

15. Vaseline 2

16.1,3-Butanediol 4

17. Thiocane 3

18. Sodium citrate 0.1

19. Sodium hyaluronate (2) 0.1

20. Polymer of Production Example 1 2

21. Bentonite 1

22. Distilled water balance

23. Spices Appropriate amount

24. Double Resorcinol Triazine 2 Example 23 Essence Gel

1. Glycerin 2

2. 1,3-Butanediol 5

3. Potassium hydroxide 0.1

4. Parabens in moderation

5. Fish collagen 20

6. 3-sodium edetate 0.05

7. Polymer of Production Example 1 1.2

8. Distilled water surplus

9. 4,5-dimorpholino-3-hydroxypyridazine 0.1 Example 24 gel

1. Polyethylene oxide·methyl polysiloxane copolymer 5

2. Dipropylene Glycol 3

3. 1,3-Butanediol 10

4. Macrogol 1500 1

5. Polyethylene oxide methyl glucoside 1

6. Polyethylene glycol diisostearate 5

7. Dipotassium glycerate 0.1

8. コラ・デ・カバロ extract 0.1

9. Parabens 0.2

10. Edetate 3-sodium 0.01

11. Polymer of Production Example 1 3.0

12. Distilled water balance Example 25 Makeup remover gel

1. Decamethylcyclopentasiloxane 18

2. Ethanol 5

3. 1,3-Butanediol 10

4. Coconut oil 0.01

5. Jojoba Oil 1

6. Cetyl 2-ethylhexanoate 3

7. L-glutamic acid 0.2

8. Hydroxypropyl-β-cyclodextrin 0.1

9. Soapberry Extract 0.1

10. Horse chestnut extract 0.1

11. Lily extract 0.1

12. Yellow tiller extract 0.1

13. Lavender oil 0.01

14. 3 sodium ethylenediamine hydroxyethyl 3 acetate 0.1

15. The polymer of Production Example 1 0.8

16. Hydroxyethylcellulose 0.1

17. Vinylpyrrolidone·methacrylic acid

N,N-Dimethylaminoethyl Acrylic Acid 0.5

18. Distilled water surplus Example 26 Treatment mask

1. Ethanol 10

2. 1,3-Butanediol 6

3. Macrogol 4000 2

4. Olive oil 1

5. Macadamia Nut Oil 1

6. Cholesterol hydroxystearate 0.005

7. Lactic acid 0.005

8. Sodium lactate solution (50%) 0.2

9. L-Ascorbyl Sulfate 2-Sodium 0.1

10. DL-α-tocopherol-2-L-ascorbyl phosphate potassium 0.1

11. Vitamin E acetate 0.1

12. Succinylinoleic Acid Bone Collagen Solution 0.1

13. Sodium chondroitin sulfate 0.1

14. Parabens 0.1

15. The polymer of Production Example 1 0.7

16. Polyvinyl alcohol 10.0

17. Distilled water balance

18. Spices Appropriate amount

It should be noted that any of the compositions of Examples 1 to 26 had a non-sticky and refreshing feeling in use. Moreover, when the polymer of manufacture example 2-11 was used instead of the polymer of manufacture example 1, the composition which has a non-sticky and refreshing feeling in use was obtained similarly.

In summary, according to the present invention, by using siloxane as the hydrophobic group of the associative polymer so that the polymer has an HLB value of 16.0 to 19.5, a gel having the following characteristics can be obtained Formed composition, said characteristics can obtain non-sticky, refreshing feeling of use, and it will not be damaged by sebum and sweat even in the case of forming a film on the skin.

Claims (10)

1. A gel-like composition, characterized in that the composition contains an associative polymer and water, and the associative polymer is a compound containing at least two silicon atoms separated by a hydrophilic chain portion. The graft polymer and/or sequence polymer of oxane chain, it is represented by following formula (I), the HLB value of this polymer is 16.0～19.5, In the above formula (I), R ₁ to R ₄ may represent hydrocarbon groups identically or differently, and Y represents one or both of hydroxyl, epoxy, or carbamate, ether, ester, and urea residues. More than one species, A represents the part of the hydrophilic chain composed of epoxide, X represents one or two or more selected from carbamate, ether, ester, and urea residues, Z represents a hydrocarbon group, or an amino group One or more selected from esters, ethers, esters, and urea residues, a represents an average of 2 or more, b represents an average of 10-3000, and c represents an average of 1-500. 2. The gel composition according to claim 1, wherein the molecular weight of the associative polymer is 6000 or more. 3. The gel composition according to claim 1 or 2, characterized in that the mass fraction of siloxane chains in the associative polymer is below 0.1. 4. The gel composition according to any one of claims 1 to 3, wherein A of the associative polymer represented by the above formula (I) is polyethylene oxide. 5. The gel composition according to any one of claims 1 to 4, wherein said associative polymer is a multi-block polymer. 6. The gel composition according to any one of claims 1 to 5, wherein said associative polymer is a triblock polymer. 7. The gel-like composition according to claim 5 or 6, wherein said multi-block polymer is a block polymer of the siloxane type at both ends. 8. The gel composition according to any one of claims 1 to 7, wherein a of the associative polymer represented by the above formula (I) is 2, b is 65 or more, and c is 3 to 105. 9. The gel composition according to any one of claims 1 to 8, wherein the content of the associative polymer is 0.1 to 5% by mass. 10. The gel composition according to any one of claims 1 to 9, which is an emulsion containing 0.1 to 25% by mass of oil.