JP2009024012A - Gel-form composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gel-form composition containing an associative polymer, giving fresh feeling in use without sticking and resistant to sebum and sweat when coating is formed on the skin, in an associative thickener introduced with a small amount of silicone groups as hydrophobic groups in a water-soluble polymer. <P>SOLUTION: The gel-form composition comprises following (I), (II) and (III): (I) a triblock polymer having a structure B-C-A-C-B in 0.1-5 mass% [wherein A represents a polyethylene glycol residue having 10,000-35,000 average molecular weight; B represents a silicone residue having a dimethyl chain expressed by chemical formula (1) (c=5-70); C represents a reactive residue which the silicone residue B had and/or a hexamethylene diisocyanate residue, an ethylene glycol glycidyl ether residue or an adipic acid residue as a binding agent], (II) an oil in 0.1-25 mass% and (III) water. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an improvement in a gel composition, particularly an associative polymer having a silicone group.

Thickeners with a small amount of hydrophobic groups introduced into water-soluble polymers are known to show a significant thickening effect in aqueous solvents due to the association of hydrophobic groups due to hydrophobic interactions (Polymers in Aqueous Media, Advances in Chemistry Series 223, 467, JD Glass, Encyclopedia of Polymer Science and Engineering, 2nd edition, 17, 772). In recent years, it has been studied to incorporate these associative polymers into cosmetics, and various cosmetics containing associative polymers having a specific structure have been described (Patent Documents 1 to 8).
In order to improve the associability and enhance the thickening action, it is necessary to extend the hydrophobic group.
However, all of the associative polymers blended in the cosmetics have the following problems because they use long-chain alkyl as a hydrophobic group. In other words, the alkyl chain length obtained at a commercial level is limited (generally, an alkyl chain having a carbon chain length of 36 or less, usually 24 or less is used). Further, when the associative polymer derived from a long-chain alkyl group is added to a cosmetic product, the feeling of use is heavy, and fatal defects such as stickiness are caused.

On the other hand, a cosmetic composition containing a polysiloxane-polyoxyalkylene linear block copolymer has been described (Patent Document 9).
However, the above-mentioned block copolymer is used as a fine dispersing agent for a conditioning agent selected from nonvolatile insoluble silicones or fluorinated oils or waxes. Since the ratio of the sex-linked portion) is large, it is insoluble in water and does not exhibit a thickening action in water.
JP 5-255040 A 11-514003 Special table 11-514004 Special table hei 11-514032 JP 2000-63235 A JP 2000-136228 A JP 2000-95630 A Special table 2000-510493 Japanese Patent No. 2682966

  The present invention has been made in view of the above-described problems of the prior art, and an object thereof is to provide a gel-like composition containing an associative polymer having a viscosity and having a non-sticky and fresh feeling.

In view of the above problems, the present inventors have studied intensively, to a water soluble polymer Te small amount of associative thickener odor introduced silicone group as a hydrophobic group, the composition comprising Re This, greasy and refreshing It has been found that when a feeling of use is obtained and a film is formed on the skin, there are many advantages such as resistance to sebum and sweat.

（ｃ＝５〜７０）
であるジメチル鎖を有するシリコーン残基、
Ｃは前記シリコーン残基Ｂが有していた反応性残基及び／又は結合剤としてのヘキサメチレンジイソシアネート残基、エチレングリコールグリシジルエーテル残基、アジピン酸残基を示す。）
（ＩＩ）油を０．１〜２５質量％
（ＩＩＩ）水 The subject of the present invention is thus a gel composition comprising the following (I), (II), (III).
(I) 0.1 to 5% by mass of a triblock polymer having a B—C—A—C—B structure;
(A is a polyethylene glycol residue having an average molecular weight of 10,000 to 35,000,
B is

(C = 5-70)
A silicone residue having a dimethyl chain,
C represents a reactive residue and / or a hexamethylene diisocyanate residue, an ethylene glycol glycidyl ether residue, or an adipic acid residue as a binder that the silicone residue B had. )
(II) 0.1-25 mass% of oil
(III) Water

In the composition, it is preferable that the associative polymer has a molecular weight of 6000 or more.
In the composition, it is preferable that the mass fraction of the silicone chain in the associative polymer is 0.1 or less.
In the composition, an emulsion containing 0.1 to 25% by mass of oil is preferable.

According to the present invention, the water-soluble polymer Te small amount of associative thickener odor introduced silicone group as a hydrophobic group, the composition comprising Re This, greasy, obtained using sense of refreshing, and the skin When a film is formed with, it is resistant to sebum and sweat.

Hereinafter, preferred embodiments of the present invention will be described.
The associative polymer according to the present invention is a silicone-modified alkylene oxide sequential polymer and generally has hydrophilic chains such as alkylene oxide, preferably ethylene oxide and / or copolymers thereof, in the chain. And a nonionic sequential copolymer containing both the hydrophobic chains of the silicone chain. The sequential copolymer includes the meaning of a block copolymer.

The polymer can be sequential in the form of a tri-block like the general formula (I).
B-C-A-C-B (I)
(A is hydrophilic chain part, B is hydrophobic chain part, C is binding part)
The molecular weight of the associative polymer according to the present invention is preferably 6000 or more, and particularly preferably 8000 or more. If it is less than 6000, there is a possibility that the network by the meeting cannot be developed.

In the associative polymer according to the present invention, the mass fraction of the silicone chain is preferably 0.1 or less, more preferably 0.05 or less. If it exceeds 0.1, the solubility in water may be reduced and the thickening action may not be exhibited.
In the associative polymer according to the present invention, it is preferable that a of the associative polymer represented by the formula (I) is 2, b is 65 or more, and c is 3 to 105.
It is preferable that a is 2, b is 65 or more, and c is 3 to 105, and it is particularly preferable that a is 2, b is 75 or more, and c is 5 to 70.

  In the composition of the present invention, the content of the associative polymer is preferably 0.1 to 5% by mass, and 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 sufficient, and if it exceeds 5% by mass, the viscosity may be excessively increased and the usability may be unfavorable.

  The composition of the present invention may further contain 0.1 to 25% by mass of oil. For example, vegetable oils such as olive oil and castor oil, waxes such as carnauba wax and candelilla wax, hydrocarbon oils such as liquid paraffin, squalane, petrolatum, polyethylene oxide propylene oxide alkyl ether, lauric acid, stearic acid, isostearic acid, Higher fatty acids such as 12-hydroxystearic acid, higher alcohols such as cetyl alcohol, stearyl alcohol and behenyl alcohol, isopropyl myristate, cetyl 2-ethylhexanoate, succinic acid diethoxy ester, methylpolysiloxane, methylphenylpoly Silicone oils such as siloxane and long chain alkylsiloxane can be included.

This composition can be in any pharmaceutical formulation suitable for topical application, in particular water-in-oil (W / O) or oil-in-water (O / W) or triple (W / O). O / W or O / W / O) dispersions or emulsions can be provided.
The composition of the present invention preferably has a viscosity range of 0.1 to 100 Pa · s, more preferably 1 to 50 Pa · s, and the viscosity is measured at 25 ° C. using a Brookfield viscometer or the like. Is done. This is the same whether it is an aqueous gel or an emulsion or dispersion.

  In the present invention, the gel composition may further comprise any additional ingredients conventionally used in cosmetic and / or dermatological fields. For example, anionic surfactants such as fatty acid soap, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate salt, acyl-N-methyl taurate salt, alkyl ether phosphate ester salt, N-acyl amino acid salt, organic acid monoglyceride, Cationic surfactants such as alkyltrimethylammonium chloride, dialkyldimethylammonium chloride, benzalkonium chloride, alkylpyridinium chloride, alkyldimethylaminoacetic acid betaine, alkylamidodimethylaminoacetic acid betaine, 2-alkyl-N-carboxy-N-hydroxy Amphoteric surfactants such as imidazolinium betaine, lecithin, and enzymolytic lecithin, alkylpolyoxyethylene type, polyhydric alcohol ester type, alkylpolyglucoside type, alkylpolyglycerin type, Nuger ester type, polyethylene oxide / polypropylene oxide copolymer type, nonionic surfactants such as sorbitan fatty acid ester, dimethicone copolyol, glycerin, propylene glycol, 1,3-butylene glycol, polyethylene glycol, sorbitol, sodium lactate, 2- Moisturizers such as sodium pyrrolidone-5-carboxylate and sodium hyaluronate, synthetic polymers such as carboxyvinyl polymer and polyvinylpyrrolidone, semi-synthetic polymers such as carboxymethylcellulose and hydroxypropylcellulose, xanthan gum, dextran, hyaluronic acid, casein, Ultraviolet rays such as natural polymers such as collagen, high molecular weight silicone, benzophenone derivatives, paraaminobenzoic acid derivatives, methoxycinnamic acid derivatives It can contain anti-collecting agents, tocopherols, antioxidants such as BHT, sequestering agents such as EDTA, citric acid, hexametaphosphoric acid, pyrosulfurous acid, fine emulsions such as silicone microemulsions, high-pressure emulsified microemulsions, alcohol, etc. .

  Further active ingredients include, for example, whitening agents such as arbutin, ascorbic acid and derivatives thereof, anti-aging agents such as retinol and derivatives thereof, α-hydroxy acids such as lactic acid and glycolic acid, hair restorers, vitamins and anti-inflammatory agents. , Fungicides, various salts and the like.

  Moreover, the usage form is also arbitrary, for example, lotion, cream, emulsion, lotion, pack, ointment, mousse, soap, foundation, eye shadow, blotch / glaze cover, lip balm, mascara, lipstick, body Makeup products such as makeup products, hair rinses, shampoos, skin sunscreen creams or sun creams, dermatological ointments, bath preparations, etc., which are conventionally used in cosmetics and / or dermatological fields Any form can be used.

EXAMPLES Hereinafter, examples suitable for the present invention will be described in more detail. In addition, this invention is not limited by this. Unless otherwise specified, the blending amount is expressed in mass%.
Prior to the examples, production examples of the associative polymer according to the present invention will be described.

<Production Example 1> Urethane type triblock copolymer 40 parts of polyethylene glycol (PEG) (molecular weight of about 20,000) and 300 parts of toluene are placed in a 1000 mL four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer. And dissolved at 70 ° C. After removing water azeotropically, 0.7 parts of hexamethylene diisocyanate, 0.03 parts of dibutyltin lauric acid, 4 parts of dimethyl silicone having a hydroxyl terminal (FM0411, manufactured by Chisso, molecular weight of about 1,000) at 80 ° C. The mixture was reacted at 70 ° C. overnight under a nitrogen stream, and water was added to stop the reaction. The solvent was removed to obtain the desired polymer.

（ｃ＝５〜７０）
であるジメチル鎖を有するシリコーン残基、Ｃは結合剤としてのヘキサメチレンジイソシアネート残基を示し、下記式（ＩＩ）で表される。

The triblock polymer obtained by Production Example 1 has a B-C-A-C-B structure,
A is a polyethylene glycol residue having an average molecular weight of 20,000, and B is

(C = 5-70)
A silicone residue having a dimethyl chain and C represents a hexamethylene diisocyanate residue as a binder and is represented by the following formula (II).

<Production Example 2> Ether type triblock copolymer 40 parts of polyethylene glycol (PEG) (molecular weight of about 20,000) and 300 parts of toluene are placed in a 1000 mL four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer. And dissolved at 70 ° C. After removing water azeotropically, 3 parts of dimethylsilicone having an epoxy group terminal (FM0511, manufactured by Chisso, molecular weight of about 1,000) and 0.3 part of potassium laurate were added and reacted overnight at 70 ° C. under a nitrogen stream. The reaction was stopped by adding ethanol. The solvent was removed to obtain the desired polymer.

（ｃ＝５〜７０）
であるジメチル鎖を有するシリコーン残基、Ｃは前記シリコーン残基Ｂが有していた反応性残基を示し、下記式（ＩＩＩ）で表される。

The triblock polymer obtained by Production Example 2 has a B-C-A-C-B structure,
A is a polyethylene glycol residue having an average molecular weight of 20,000, and B is

(C = 5-70)
A silicone residue having a dimethyl chain and C represents a reactive residue that the silicone residue B had, and is represented by the following formula (III).

<Production Example 3> Ether type triblock copolymer 40 parts of polyethylene glycol (PEG) (molecular weight of about 20,000) and 300 parts of toluene are placed in a 1000 mL four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer. And dissolved at 70 ° C. After removing water azeotropically, 4 parts of dimethyl silicone having a hydroxyl end (FM0411, manufactured by Chisso, molecular weight of about 1,000), 0.7 parts of ethylene glycol diglycidyl ether (Denacol EX810, manufactured by Nagase Chemical Industries), 0.07 parts of potassium hydroxide was added and reacted overnight at 70 ° C. under a nitrogen stream, and ethanol was added to stop the reaction. The solvent was removed to obtain the desired polymer.

（ｃ＝５〜７０）
であるジメチル鎖を有するシリコーン残基、Ｃはエチレングリコールグリシジルエーテル残基を示し、下記式（ＩＶ）で表される。

The triblock polymer obtained by Production Example 3 has a B-C-A-C-B structure,
A is a polyethylene glycol residue having an average molecular weight of 20,000, and B is

(C = 5-70)
A silicone residue having a dimethyl chain and C represents an ethylene glycol glycidyl ether residue, which is represented by the following formula (IV).

<Production Example 4> Ester-type triblock copolymer 20 parts of polyethylene glycol (PEG) (molecular weight of about 10,000) and 300 parts of toluene are placed in a 1000 mL four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer. And dissolved at 70 ° C. After removing water azeotropically, dimethyl silicone having a hydroxyl terminal (FM0411, manufactured by Chisso, molecular weight of about 1,000) ethylene oxide 25 mol adduct, 6 parts of adipic acid, 0.6 parts of sodium hydroxide, 0.1% of sodium hydroxide The mixture was added and reacted overnight at 70 ° C. under a nitrogen stream. The solvent was removed to obtain the desired polymer.

（ｃ＝５〜７０）
であるジメチル鎖を有するシリコーン残基、Ｃはアジピン酸残基を示し、下記式（Ｖ）で表される。

The triblock polymer obtained by Production Example 4 has a B-C-A-C-B structure,
A is a polyethylene glycol residue having an average molecular weight of 10,000, and B is

(C = 5-70)
A silicone residue having a dimethyl chain, C represents an adipic acid residue, and is represented by the following formula (V).

<Production Example 5> Urea-type triblock copolymer 70 parts of polyethylene glycol (PEG) (molecular weight of about 35,000) and 300 parts of toluene are placed in a 1000 mL four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer. And dissolved at 70 ° C. After removing water azeotropically, 0.7 parts of hexamethylene diisocyanate, 0.03 parts of dibutyltin lauric acid and 4 parts of dimethyl silicone having an amino group terminal (molecular weight of about 1,000) were added at 80 ° C., and nitrogen was added. The reaction was carried out overnight at 70 ° C. under an air stream, and the reaction was stopped by adding water. The solvent was removed to obtain the desired polymer.

（ｃ＝５〜７０）
であるジメチル鎖を有するシリコーン残基、Ｃは結合剤としてのヘキサメチレンジイソシアネート残基を示し、下記式（ＶＩ）で表される。

The triblock polymer obtained by Production Example 5 has a B-C-A-C-B structure,
A is a polyethylene glycol residue with an average molecular weight of 35,000, B is

(C = 5-70)
A silicone residue having a dimethyl chain and C represents a hexamethylene diisocyanate residue as a binder and is represented by the following formula (VI).

<Production Example 6> Ether type triblock copolymer 4 parts of dimethyl silicone (FM0411, manufactured by Chisso, molecular weight of about 1,000) having a hydroxyl terminal in a 1000 mL four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer, A small amount of pyridine was added to 0.8 parts of p-toluenesulfonyl chloride and 300 parts of toluene. Forty parts of polyethylene glycol (PEG) (molecular weight of about 20,000) previously metallated with potassium diphenylmethane was added and reacted at 70 ° C. under a nitrogen stream. The solvent was removed to obtain the desired polymer.

（ｃ＝５〜７０）
であるジメチル鎖を有するシリコーン残基、Ｃは前記シリコーン残基Ｂが有していた反応性残基を示し、下記式（ＶＩＩ）で表される。

The triblock polymer obtained by Production Example 6 has a B-C-A-C-B structure,
A is a polyethylene glycol residue having an average molecular weight of 20,000, and B is

(C = 5-70)
A silicone residue having a dimethyl chain and C represents a reactive residue that the silicone residue B had, and is represented by the following formula (VII).

<Comparative Production Example 1>
40 parts of polyethylene glycol (PEG) (molecular weight of about 20,000) and 300 parts of toluene were placed in a 1000 mL four-necked flask equipped with a thermometer, a nitrogen introduction tube and a stirrer, and dissolved at 70 ° C. After removing water azeotropically, 0.7 parts of hexamethylene diisocyanate, 0.03 parts of dibutyltin lauric acid and lauryl alcohol (C12, molecular weight of about 186.34) were added at 80 ° C., and at 70 ° C. under a nitrogen stream. The reaction was allowed to proceed overnight, and water was added to stop the reaction. The solvent was removed to obtain the desired polymer. Ethanol was added to stop the reaction. The solvent was removed to obtain the desired polymer.

The polymer obtained by Comparative Production Example 1 is a polymer represented by the following formula (XIII) .

<Comparative Production Example 2>
40 parts of polyethylene glycol (PEG) (molecular weight of about 20,000) and 300 parts of toluene were placed in a 1000 mL four-necked flask equipped with a thermometer, a nitrogen introduction tube and a stirrer, and dissolved at 70 ° C. After removing water azeotropically, 0.7 parts of hexamethylene diisocyanate, 0.03 parts of dibutyltin lauric acid and myristyl alcohol (C14, molecular weight of about 214.38) were added at 80 ° C. The reaction was allowed to proceed overnight, and water was added to stop the reaction. The solvent was removed to obtain the desired polymer.

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

The polymer obtained by Comparative Production Example 2 is a polymer represented by the following formula (IX) .

<Comparative Production Example 3>
40 parts of polyethylene glycol (PEG) (molecular weight of about 20,000) and 300 parts of toluene were placed in a 1000 mL four-necked flask equipped with a thermometer, a nitrogen introduction tube and a stirrer, and dissolved at 70 ° C. After removing water azeotropically, 0.7 parts of hexamethylene diisocyanate, 0.03 parts of dibutyltin lauric acid and stearyl alcohol (C18, molecular weight of about 270.50) were added at 80 ° C., and at 70 ° C. under a nitrogen stream. The reaction was allowed to proceed overnight, and water was added to stop the reaction. The solvent was removed to obtain the desired polymer.
Ethanol was added to stop the reaction. The solvent was removed to obtain the desired polymer.

The polymer obtained by Comparative Production Example 3 is a polymer represented by the following formula (X) .

<Comparative Production Example 4>
40 parts of polyethylene glycol (PEG) (molecular weight of about 20,000) and 300 parts of toluene were placed in a 1000 mL four-necked flask equipped with a thermometer, a nitrogen introduction tube and a stirrer, and dissolved at 70 ° C. After water was removed azeotropically, 0.7 parts of hexamethylene diisocyanate, 0.03 parts of dibutyltin lauric acid and behenyl alcohol (C22, molecular weight of about 326.59) were added at 80 ° C., and overnight at 70 ° C. under a nitrogen stream. The reaction was stopped by adding water. The solvent was removed to obtain the desired polymer. Ethanol was added to stop the reaction. The solvent was removed to obtain the desired polymer.

The polymer obtained by Comparative Production Example 4 is a polymer represented by the following formula (XI) .

The solubility and viscosity in 2% aqueous solution of Preparation Example 1 to 11 polymer was evaluated based on the following evaluation criteria. The results are shown in Table 1.

Evaluation criteria
Solubility ○: Soluble at normal temperature (25 ° C) Δ: Soluble at heating (70 ° C) x: Insoluble

Viscosity : Gelled (does not flow)
Δ: Thicken (flow)
×: Does not thicken

(Table 1)
Solubility Viscosity
Production Example 1 ○ ○
Production Example 2 ○ ○
Production Example 3 ○ ○
Production Example 4 ○ ○
Production Example 5 ○ ○
Production Example 6 ○ ○

As is clear from Table 1, the polymers of Production Examples 1 to 11 were both excellent in solubility and viscosity.
(1) Examination of c Value In the above formula (I), it is considered that a suitable value of c depends on the value of b. That is, from the balance between the hydrophilicity and the hydrophobicity of the molecule, the preferable value of c is considered to increase for larger b and decrease for smaller b.

36 parts of polyethylene glycol (PEG) (molecular weight of about 18,000) and 300 parts of toluene were placed in a 1000 mL four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer, and dissolved at 70 ° C. After removing water azeotropically, at 80 ° C., hexamethylene diisocyanate, 0.03 part of dibutyltin lauric acid, and dimethyl silicone having a hydroxyl terminal (corresponding to c = 0 to 120 in the following formula (XII)) were added, The reaction was carried out overnight at 70 ° C. under a nitrogen stream, and water was added to stop the reaction. The solvent was removed to obtain a polymer.

（ｃ＝５〜７０）であるジメチル鎖を有するシリコーン残基、Ｃは結合剤としてのヘキサメチレンジイソシアネート残基を示し、下記式（ＸＩＩＩ）で表される。また、水酸基末端を有するシリコーンの分子量を変えてｃがそれぞれ表２の値となるようにした。 The obtained polymer has a B-C-A-C-B structure, A is a polyethylene glycol residue having an average molecular weight of 20,000, and B is

(C = 5 to 70) A silicone residue having a dimethyl chain, C represents a hexamethylene diisocyanate residue as a binder, and is represented by the following formula (XIII). In addition, the molecular weight of the silicone having a hydroxyl terminal was changed so that c had the value shown in Table 2.

(Table 2)
c Solubility Viscosity
Test Example 1-1 0 ○ ×
Test Example 1-2 1 ○ ×
Test Example 1-3 3 ○ △
Test Example 1-4 5 ○ ○
Test Example 1-5 10 ○ ○
Test Example 1-6 50 ○ ○
Test Example 1-7 70 ○ ○
Test Example 1-8 105 △ △
Test Example 1-9 120 × ×

As is apparent from Table 2, the solubility decreases as the value of c increases. On the other hand, the viscosity increases as the value of c increases. On the other hand, if the value of c increases too much, the solubility decreases and the polymer undergoes phase separation, resulting in increased viscosity. Not shown .

(2) Examination of type of hydrophobic group Next, as a polymer of Test Examples 1-3 to 1-6 in (1) above and a comparative example, a triblock alkyl type using a higher alcohol instead of dimethylsiloxane as a hydrophobic part A 2% aqueous solution was prepared using the polymers of Comparative Production Examples 1 to 4, which are the associative polymers, and the viscosity and usability were evaluated.

Evaluation criteria
Feeling ○: 8 or more people in 10 people is not sticky and answers △: say less than 10 people in five more than 8 people is not sticky ×: 10 is not sticky 4 people following in people and answers

(Table 3)
Hydrophobic part Properties of hydrophobic part c Viscosity Feeling of use
Test Example 1-3 Dimethylsiloxane Liquid 3 ○ ○
Test Example 1-4 Dimethylsiloxane liquid 5 ○ ○
Test Example 1-5 Dimethylsiloxane Liquid 10 ○ ○
Test Example 1-6 Dimethylsiloxane Liquid 50 ○ ○
Hydrophobic part Properties and carbon number of hydrophobic part Viscosity Feeling of use
Comparative Example 1-1 Lauryl alcohol liquid 12 × ○
Comparative Example 1-2 Myristyl alcohol solid 14 △ △
Comparative Example 1-3 Stearyl alcohol Solid 18 ○ ×
Comparative Example 1-4 Behenyl alcohol Solid 22 ○ ×
Properties of hydrophobic part: Appearance at 25 ° C

As is clear from Table 3 , dimethylsiloxane remains liquid even when the molecular weight is increased, and the silicone-associated associative polymers of Test Examples 1-3 to 1-6 prepared using this have viscosity. In contrast to the non-sticky feeling of use, higher alcohols change from liquid to solid as the alkyl chain increases, and the alkylated associations of Comparative Examples 1-1 to 1-4 prepared using this alcohol The functional polymer has no thickening property when the alkyl group is in a liquid state, and has a thickening property when the alkyl group is in a solid state. Therefore, it was confirmed that the polymer of the present invention is superior in terms of thickening and usability when compared to conventional alkylated associative polymers.

Example 1 Cleansing foam Fatty acid: Stearic acid 15
Palmitic acid 20
Emollient: palm oil 2
Alkali: Potassium hydroxide 6
Moisturizer: Glycerin 15
PEG 1500 10
Surfactant: Glycerol monostearate 2
POE (20) sorbitan monostearic acid 2
Associative thickener: Polymer of Production Example 1 2
Preservative: Phenoxyethanol 0.2
Chelating agent: appropriate amount Purified water: remaining amount Fatty acid, emollient, moisturizing agent and preservative are dissolved by heating and kept at 70 ° C. Purified water, in which the alkali was previously dissolved, was added to the stirring oil phase. After the addition, the temperature was kept at 70 ° C. for a while to complete the neutralization reaction. Next, the melt | dissolved surfactant, chelating agent, and the thickener were added, and it cooled after stirring mixing, deaeration, and filtration.

Example 2 lotion moisturizer: Sorbit 4
Dipropylene glycol 6
PEG 1500 5
Surfactant: POE (20) oleyl alcohol ether 0.5
Associative thickener: Polymer of Production Example 1 0.1
Alcohol: ethanol 10
Preservative: Methylparaben 0.2
Fragrance: Appropriate amount of chelating agent: Appropriate amount of buffering agent: Appropriate amount of purified water: remaining amount A portion of purified water was taken to dissolve the chelating agent, and a thickener was mixed and stirred to prepare a viscous liquid. A moisturizing agent and a buffering agent were added to the remainder of the purified water and dissolved at room temperature, and the above-mentioned viscous liquid was added thereto to obtain a uniform aqueous solution. Preservatives, surfactants, and fragrances were added to ethanol to make an alcohol solution, which was added to and mixed with the above aqueous solution for solubilization.

Example 3 Emollient lotion Oil: Cetyl alcohol 1
Beeslow 0.5
Vaseline 2
Squalane 6
Dimethylpolysiloxane 2
Alcohol: Ethanol 5
Moisturizer: Glycerin 4
1.3-Butylene glycol 4
Surfactant: POE (10) monooleate 1
Glycerol monostearate 1
Associative thickener: Polymer of Production Example 1 2
Preservative: Methylparaben 0.2
Purified water: remaining amount A humectant was added to purified water and heated to 70 ° C. A surfactant and preservative were added to the oil and heated to 70 ° C. This was added to the previous aqueous phase and pre-emulsified. A thickener and ethanol were added and stirred, and the emulsified particles were made uniform with a homomixer, followed by deaeration, filtration and cooling.

Example 4 Emollient cream Oil: Cetyl alcohol 5
Stearic acid 3
Vaseline 5
Squalane 10
Glycerol tri-2-ethylhexanoate 7
Moisturizer: Dipropylene glycol 5
Glycerin 5
Sodium pyrrolidonecarboxylate 1
Surfactant: Propylene glycol monostearate 3
POE (20) cetyl alcohol ether 3
Alkali Triethanolamine 1
Associative thickener: Polymer of Production Example 1 3
Preservative: Phenoxyethanol 0.2
Antioxidant: BHT 0.1
Fragrance: Appropriate amount of purified water: remaining amount A moisturizer, alkali, and thickener were added to purified water and heated to 70 ° C. After heating and dissolving the oil, a surfactant, preservative, antioxidant, and fragrance were added and heated to 70 ° C. This was added to the previous aqueous phase and pre-emulsified. After homogenizing the emulsified particles with a homomixer, deaeration, filtration, and cooling were performed.

Example 5 Moisture gel Moisturizer: Dipropylene glycol 7
PEG 1500 8
Associative thickener: Polymer of Production Example 1 1
Water-soluble polymer: xanthan gum 0.4
Methylcellulose 0.2
Alkali: Potassium hydroxide 0.1
Preservative: Methyl paraben Appropriate amount Chelating agent: Appropriate perfume: Appropriate amount Purified water: Remaining amount
After associative thickener and water-soluble polymer were uniformly dissolved in purified water, PEG1500 and a chelating agent were added. Preservatives and fragrances were added to dipropylene glycol. The previously prepared aqueous phase was gradually added with stirring. Finally, an aqueous alkali solution was added and stirred well for neutralization.

Example 6 whitening essence <br/> oil: dimethylsiloxane 2
Moisturizer: Sorbitol 8
1,3-butylene glycol 5
PEG 1500 7
Hyaluronic acid 0.1
Alcohol: Ethanol 7
Emulsifier: carboxyl vinyl polymer 0.15
(Pemulen TR-2 ^TM , Goodrich)
Emollient: Olive oil 0.2
Whitening Agent: Arbutin 5
Ascorbic acid glucoside 3
Associative thickener: Polymer of Production Example 1 0.5
Preservative: Phenoxyethanol 0.2
Fragrance Appropriate amount of buffer: Appropriate amount of purified water: remaining amount Moisturizer, buffer, thickener, whitening agent and emulsifier were dissolved in purified water at room temperature. Oil, emollient, fragrance, and preservative were dissolved in ethanol and then solubilized in the aqueous phase.

Example 7 Pack Filming agent: Polyvinyl alcohol 15
Associative thickener: Polymer of Production Example 1 5
Moisturizer: 1,3-butylene glycol 5
Surfactant: POE oleyl alcohol ether 0.5
Alcohol: ethanol 12
Preservative: Methylparaben 0.2
Fragrance: Appropriate amount of buffer: Appropriate amount of purified water: remaining amount A buffer and a humectant were heated to 70 ° C in purified water. A thickener and a film agent were added here and dissolved while stirring. A fragrance, a preservative, and a surfactant were added to ethanol and dissolved, and then added to the aqueous phase and solubilized.

Example 8 Liquid foundation Powder: Talc 3
Titanium dioxide 5
Bengala 0.5
Yellow iron oxide 1.4
Black iron oxide 0.1
Aqueous phase: Bentonite 0.5
POE sorbitan monostearate 0.9
Triethanolamine 1
Propylene glycol 10
Polymer of Production Example 1 0.5
Purified water Residual oil phase: Stearic acid 2.2
Cyclic dimethylpolysiloxane 7
Glycerol monostearate 2
Liquid lanolin 2
Liquid paraffin 8
POE-modified dimethylpolysiloxane 1
Preservative: appropriate amount Fragrance: appropriate amount

Example 9 Emulsification type lipstick Pigment: Titanium dioxide 4.5
Red No. 201 0.5
Red 202 No. 2.0
Dye: Red 223 0.05
Solid oil content: Ceresin 4.0
Candelilla Row 8.0
Carnavalo 2.0
Liquid oil: castor oil 30.0
Isostearic acid diglyceride 40.0
Surfactant: POE (25) PPO (20) 2-tetradecyl ether 1.0
Purified water: 5.0
Moisturizer: Glycerin 2.0
Propylene glycol 1.0
Associative thickener: Polymer of Production Example 1 2.0
Ultraviolet ray inhibitor: Appropriate amount Antioxidant: Appropriate amount Fragrance: Appropriate amount Add titanium dioxide, red No. 201 and red No. 202 to a part of castor oil and treat with a roller (pigment part) Red No. 223 is dissolved in castor oil (dye part). Purified water, glycerin, propylene glycol and associative thickener are uniformly dissolved at 80 ° C. (aqueous phase). Other ingredients are mixed, heated and melted, and then the pigment part and dye part are added and dispersed uniformly with a homomixer. Thereafter, the aqueous phase was added and emulsified and dispersed with a homomixer, then poured into a mold and rapidly cooled to form a stick.

Example 10 Nail enamel Resin: Polymer emulsion 85.0
Plasticizer: Diisobutyl adipate 4.0
Film forming aid: Carbitol 4.0
Preservative: Methylparaben 0.2
Defoaming agent Appropriate amount of pigment: Red No. 220 0.3
Titanium oxide 0.2
Associative thickener: polymer of Production Example 1 0.2
Residual amount of ion-exchanged water The associative thickener was dissolved in ion-exchanged water by heating and added to the polymer emulsion. Further, diisobutyl adipate and carbitol were gradually added, and other components were added and dispersed uniformly, followed by deaeration.

Example 11 Shampoo Surfactant: Palm Fatty Acid Acylmethyl Taurine Sodium 9
Palm fatty acid acid propyl betaine 3
Propylene glycol laurate 1
Palm oil fatty acid diethanolamide 1
Sodium dodecane-1,2-diol acetate 2
Moisturizer: Glycerin 1
Usability improver: Cationized cellulose 0.5
Associative thickener: Polymer of Production Example 1 2
Salt: Sodium chloride 1.5
Fragrance: Appropriate amount Dye: Appropriate amount Preservative: Appropriate amount sequestering agent, pH adjuster Appropriate amount purified water: remaining amount Purified water was heated to 70 ° C., and other components were added and dissolved uniformly, and then cooled.

Example 12 Rinse Oil content: Silicone oil 3
Liquid paraffin 1
Cetyl alcohol 1.5
Stearyl alcohol 1
Stearyltrimethylammonium chloride 0.7
Moisturizer: Glycerin 3
Associative thickener: Polymer of Production Example 1 0.5
Fragrance, coloring matter, preservative: appropriate amount Add associative thickener, stearyltrimethylammonium chloride, glycerin, coloring matter to purified water and keep at 70 ° C (aqueous phase), mix other ingredients, heat and melt and keep at 70 ° C (Oil phase). The oil phase was added to the aqueous phase, emulsified with a homomixer, and then cooled with stirring.

Example 13 Hair gel Associative thickener: Polymer of Production Example 1 2
Moisturizer: Glycerin 5
Alcohol: ethanol 20
Surfactant: POE octyldodecyl ether 1
Fragrance, chelating agent Appropriate amount of purified water: remainder A part of purified water was added to the associative thickener and glycerin, and the mixture was dissolved by heating at 70 ° C. The other ingredients were dissolved in the remaining purified water and added with stirring.

Example 14 Sunscreen Oil phase: Fatty acid treated titanium oxide 2
Dextrin fatty acid-treated zinc oxide 10
Octyl paramethoxycinnamate 3
Isopropyl myristate 2
Cyclic dimethylpolysiloxane 10
Dimethylpolysiloxane 6CS 3
Glyceryl monostearate 2
Vitamin E acetate 0.05
PEO-modified dimethylsiloxane 2
Organically modified bentonite 0.5
(Benton 38, National Red)
Preservative, fragrance Appropriate amount Water phase: 1,3-butylene glycol 5
Polymer 1 of Production Example 1
Purified water remainder The oil phase and the aqueous phase were heated to 70 ° C. and dissolved. The oil phase was added to the aqueous phase, emulsified using a homogenizer, and cooled using a heat exchanger.

  For the compositions prepared in Examples 1 to 14 and the compositions of Comparative Examples 1 to 14 using the alkylated associative polymer of Comparative Production Example 1 instead of the polymer of Production Example 1, a sensory test for feeling of use was conducted. went.

Evaluation criteria
Feeling ◎: 10 persons 8 or more people in the answered good ○: more than 10 people in six answered that good △: × 10 people in four or more people answered that good: that of 10 people three below Answered good

Evaluation results
(Table 4)
――――――――――――――――――――――――
No. Examples Comparative Examples ------------
1 ◎ △
2 ○ △
3 ○ ×
4 ◎ △
5 ◎ △
6 ◎ ×
7 ○ ×
8 ◎ △
9 ◎ △
10 ◎ ×
11 ◎ △
12 ◎ ×
13 ○ △
14 ○ △
――――――――――――――――――――――

As is clear from Table 4, the composition of the example using the silicone-associated associative polymer has a good feeling on use, whereas the composition of the comparative example using the alkylated associative polymer has a feeling of use Is inferior. Therefore, it was confirmed that the composition of the present invention is superior in usability compared to a composition using a conventional alkylated associative polymer.
In addition, even if it used the polymer of manufacture example 2-11 instead of the polymer of manufacture example 1, the usability | use_condition was excellent similarly.

Example 15 O / W type solid foundation Micro-Crystan wax 0.7
2. Methyl polysiloxane 15
3. Decamethylcyclopentasiloxane 1
4.1,3-Butylene glycol 5
5). Candelilla Row 3
6). Isostearic acid 1
7). Ethylene glycol fatty acid ester 0.1
8). Lanolin fatty acid octyldodecyl 0.5
9. Imidazolinium betaine 5
Ten. Titanium oxide 10
11． Sintered iron oxide and titanium oxide 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． P-Hydroxybenzoate ester
18． Bengala 0.3
19. Yellow iron oxide 1
20． Black iron oxide 0.05
twenty one. Polymer 1 of Production Example 1
twenty two. Calcium alginate 0.01
twenty three. Sodium carboxymethylcellulose 0.2
twenty four. Purified water balance

Example 16 Moisturizing cream Liquid paraffin 10
2. Methyl polysiloxane 2
3. Glycerin 10
4.1,3-Butylene glycol 2
5). Erythritol 1
6). Polyethylene glycol 1500 5
7). Squalane 15
8). Tetra-2-ethylhexanoic acid pentaerythrit 5
9. Potassium hydroxide 0.1
Ten. Sodium metaphosphate 0.05
11． Tocophenol acetate 0.05
12． P-Hydroxybenzoate ester
13. Hydroxypropyl methylcellulose 0.3
14. Polyvinyl alcohol 0.1
15． Polymer 1 of Production Example 1
16． Acrylic acid / alkyl methacrylate polymer 0.1
17． Polyurethane / polyether modified silicone mixture 0.5
Yodosol PUP ^TM (Japan NSC)
18． Purified water balance

Example 17 Cream Liquid paraffin 8
2. Vaseline 3
3. Methyl polysiloxane 2
4). Stearyl alcohol 3
5). Behenyl alcohol 2
6). Concentrated glycerin 5
7). Dipropylene glycol 4
8). Trehalose 1
9. Tetra-2-ethylhexanoic acid pentaerythrit 4
Ten. Polyoxyethylene glyceryl isostearate 2
11． Polyoxyethylene glyceryl monostearate 1
12． Lipophilic polyoxyethylene glyceryl monostearate 2
13. Citric acid 0.05
14. Sodium citrate 0.05
15． Potassium hydroxide 0.015
16． Licorice flavonoid 0.1
17． Retinol palmitate (1 million units) 0.25
18． DL-α-tocopherol acetate 0.1
19. P-Hydroxybenzoate ester
20． Appropriate amount of phenoxyethanol
twenty one. Dibutylhydroxytoluene 0.1
twenty two. Edetic acid 3-sodium 0.05
23. 4-tert-butyl-4'-methoxydibenzoylmethane 0.01
twenty four. 2-Ethylhexyl paramethoxycinnamate 0.1
twenty five. β-carotene 0.01
26. Polymer of Production Example 1 0.5
27. Hydroxyethyl cellulose 0.5
28. Carboxyvinyl polymer 0.05
29. Purified water balance
30. Perfume
31. POE (14) POP (7) Dimethyl ether 2
32. POE (9) POP (2) Dimethyl ether 1
33. Retinol 0.1

Example 18 Whitening Essence Vaseline 2
2. Methyl polysiloxane 2
3. Denatured alcohol 5
4). Behenyl alcohol 0.5
5). Batyl alcohol 0.2
6). Concentrated glycerin 7
7.1,3-Butylene glycol 5
8). Polyethylene glycol 20000 0.5
9. Jojoba oil 3
Ten. Squalane 2
11． Cholesteryl hydroxystearate 0.5
12． Tetra-2-ethylhexanoic acid pentaerythrit 1
13. Polyoxyethylene hydrogenated castor oil 1
14. Potassium hydroxide 0.1
15． Sodium pyrosulfite 0.01
16． Sodium metaphosphate 0.05
17． Stearyl glycyrrhetinate 0.1
18． Pantothenyl ethyl ether 0.1
19. Arbutin 7
20． DL-α-tocopherol acetate 0.1
twenty one. Sodium hyaluronate (2) 0.05
twenty two. P-Hydroxybenzoate ester
twenty three. Edetic acid 3-sodium 0.05
24.4-tert-butyl-4′-methoxydibenzoylmethane 0.1
twenty five. Diparamethoxycinnamic acid mono-2-ethylhexanoate glyceryl 0.1
26. Bengala appropriate amount
27. Yellow iron oxide
28. Xanthan gum 0.1
29. Polymer of Production Example 1 0.2
30. Purified water balance
31.4-Cyclohexylresorcinol 2
32.4 Potassium 4-methoxysalicylate 1
33. L-ascorbic acid-2-glucoside 2

Example 19 Emulsion Vaseline 5
2. Methyl polysiloxane 2
3. Behenyl alcohol 0.6
4). Batyl alcohol 0.5
5). Dipropylene glycol 2
6.1,3-Butylene glycol 4
7). Xylit 1
8). Polyethylene glycol 1500 1
9. Squalane 5
Ten. Glyceryl tri-2-ethylhexanoate 2
11． Polyoxyethylene hydrogenated castor oil 0.5
12． Dipotassium glycyrrhizinate 0.1
13. Yeast extract (3) 0.1
14. Peonies extract 0.1
15． Edetate trisodium 0.05
16． Xanthan gum 0.1
17． Polymer of Production Example 1 0.3
18． Purified water balance
19. Perfume
20． Silica-coated zinc oxide 2
twenty one. Tranexamic acid 0.5

Example 20 Emulsion Cetanol 1
2. Glycerin 5
3. 1,3-butylene glycol 5
4). Polyethylene glycol 20000 2
5). Tetra (2-ethylhexanoic acid paramethoxycinnamic acid)
Penta Eli Slit 3
6). Di-2-ethylhexyl succinate 3
7). Potassium hydroxide 0.1
8). Paraben appropriate amount 9. Appropriate amount of phenoxyethanol
Ten. Edetate 3-sodium
11． Methyl bis (trimethylsiloxy) silylisopentyl trimethoxycinnamate 2
12. 4-tert-butyl-4′-methoxydibenzoylmethane 2
13. Paramethoxycinnamic acid-2-ethylhexyl 2
14. Diparamethoxycinnamate mono-2-ethylhexanoate glyceryl 2
15． Polymer of Production Example 1 0.2
16． Acrylic acid / alkyl methacrylate copolymer 0.1
17． Purified water balance
18． Perfume
19.4,5-Dimorpholino-3-hydroxypyridazine 0.1

Example 21 Sunscreen Cream Decamethylcyclosiloxane 20
2. Denatured 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 (hydrophobized product) 2
9. Sodium chloride 2
Ten. Bisresorcinol triazine 2
11． Edetate 3-sodium
12． 2,4,6-tris (4- (2-ethylhexyloxycarbonyl) anilino)
1,3,5-triazine 1
13. 4-tert-butyl-4′-methoxydibenzoylmethane 1
14. 2-methoxyhexyl paramethoxycinnamate 7.5
15． Polymer 1 of Production Example 1
16． Ethyl cellulose 1
17． Spherical resin powder 5
18． Purified water balance
19. Perfume

Example 22 Sunscreen Cream Methylphenylpolysiloxane 4
2. Stearyl alcohol 2
3. Glycerin 5
4). Dipropylene glycol 5
5). Sorbit liquid 5
6). Stearic acid 1.5
7). Palmitic acid 1
8). Tetra-2-ethylhexanoic acid pentaerythrit 4
9. Self-emulsifying glyceryl monostearate 1
Ten. Potassium hydroxide 0.15
11． Paraben appropriate amount
12． Octyl methoxycinnamate 6
13. Oxybenzone 3
14. Yellow iron oxide 0.01
15． Vaseline 2
16.1,3-Butylene glycol 4
17． Squalane 3
18． Sodium citrate 0.1
19. Sodium hyaluronate (2) 0.1
20． Polymer 1 of Production Example 1
twenty one. Bentonite 1
twenty two. Purified water residue
twenty three. Perfume
twenty four. Bisresorcinol triazine 2

Example 23 Essence Gel Glycerin 2
2. 1,3-butylene glycol 5
3. Potassium hydroxide 0.1
4). Paraoxybenzoic acid ester 5 Fish collagen 20
6). Edetic acid 3-sodium 0.05
7). Polymer of Production Example 1 1.2
8). Purified water balance 9.4,5-dimorpholino-3-hydroxypyridazine 0.1

Example 24 Gel Polyoxyethylene / methylpolysiloxane copolymer 5
2. Dipropylene glycol 3
3. 1,3-butylene glycol 10
4). Polyethylene glycol 1500 1
5). Polyoxyethylene methyl glucoside 1
6). Polyethylene glycol diisostearate 5
7). Dipotassium glycyrrhizinate 0.1
8). Cola de Cavallo extract 0.1
9. P-Hydroxybenzoate ester 0.2
Ten. Edetic acid 3-sodium 0.01
11． Polymer of Production Example 1 3.0
12． Purified water balance

Example 25 Makeup Gel 1. Decamethylcyclopentasiloxane 18
2. Ethanol 5
3. 1,3-butylene glycol 10
4). Sage 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. Mukuroji extract 0.1
Ten. Maronier extract 0.1
11． Lily extract 0.1
12． Oat extract 0.1
13. Lavender oil 0.01
14. Ethylenediamine hydroxyethyl triacetic acid trisodium 0.1
15． Polymer of Production Example 1 0.8
16． Hydroxyethyl cellulose 0.1
17． Vinylpyrrolidone / methacrylic acid,
N-dimethylaminoethyl acrylic acid 0.5
18． Purified water balance

Example 26 Treatment Mask Ethanol 10
2. 1,3-butylene glycol 6
3. Polyethylene glycol 4000 2
4). Olive oil 1
5). Macadamia nut oil 1
6). Cholesteryl hydroxystearate 0.005
7). Lactic acid 0.005
8). Sodium lactate solution (50%) 0.2
9. L-ascorbic acid sulfate 2-sodium 0.1
Ten. DL-α-tocopherol-2-L-ascorbic acid potassium phosphate diester 0.1
11． Vitamin E acetate 0.1
12． Succinyl atelocollagen solution 0.1
13. Sodium chondroitin sulfate 0.1
14. Paraoxybenzoic acid ester 0.1
15． Polymer of Production Example 1 0.7
16． Polyvinyl alcohol 10.0
17． Purified water balance
18． Perfume

In addition, all the compositions of Examples 1-26 had a refreshing feeling without being sticky. Moreover, even if it used the polymer of the manufacture examples 2-6 instead of the polymer of the manufacture example 1, the composition which was similarly sticky and had the refreshing feeling was obtained.
According to the present invention described above, by using the silicone hydrophobic groups of the associative polymer, greasy, it obtained using sense of refreshing, if further forming a film on the skin, sebum, strong sweat A gel-like composition having such characteristics can be obtained.

Claims (4)

A gel composition containing the following (I), (II) and (III).
(I) 0.1 to 5% by mass of a triblock polymer having a B—C—A—C—B structure;
(A is a polyethylene glycol residue having an average molecular weight of 10,000 to 35,000,
B is

(C = 5-70)
A silicone residue having a dimethyl chain,
C represents a reactive residue and / or a hexamethylene diisocyanate residue, an ethylene glycol glycidyl ether residue, or an adipic acid residue as a binder that the silicone residue B had. )
(II) 0.1-25 mass% of oil
(III) Water   The gel composition according to claim 1, wherein the associative polymer has a molecular weight of 6000 or more.   The gel composition according to claim 1 or 2, wherein the mass fraction of the silicone chain in the associative polymer is 0.1 or less. The gel composition according to any one of claims 1 to 3 , which is an emulsion containing 0.1 to 25% by mass of oil.