WO2020162248A1 - Urethane-modified silicone, and oil composition and cosmetic composition containing same - Google Patents

Abstract

The present invention relates to: a urethane-modified silicone which has a specific structure and is obtained by reacting a silicone compound (A), an oxyalkylene compound (B), a diol compound (C), a monofunctional alcohol compound (D) and a diisocyanate compound (E); an oil composition containing the urethane- modified silicone; and a cosmetic compound containing the oil composition.

Description

Urethane-modified silicone, oil composition containing the same, and cosmetic composition

The present invention relates to a urethane-modified silicone capable of thickening or gelating various oily components. More specifically, a novel hydrocarbon oil, silicone oil, ester oil and a mixture thereof which can be thickened or gelled with a low addition amount and can be used as a gelling agent for oil The present invention relates to a urethane-modified silicone, an oil composition containing the same, and a cosmetic composition containing the oil composition.

In cosmetics, hydrocarbons, in order to impart the effect of giving the skin softness, the effect of improving the smoothness of the skin, the effect of protecting the skin, the effect of moisturizing the skin, the effect of removing excess oil from the skin, etc. Oily ingredients such as higher alcohols, ester oils, animal and vegetable oils, and silicone oils are blended. Oily ingredients are used in various cosmetics, for example, basic cosmetics such as cleansing oils, creams, serums; makeup cosmetics such as foundations, sunscreens, mascaras, eye shadows, and cheeks; shampoos, conditioners, dyes. Used in hair cosmetics such as hair agents and styling agents; lip cosmetics such as lipsticks and lip glosses.

On the other hand, from the viewpoint of improving the tactile sensation such as suppressing the sticky feeling which is a concern when blending an oily component into cosmetics, the stability when blended into cosmetics, the safety to skin or the hypoallergenicity. Therefore, various additives have been developed to thicken or gel the oily component into a preferable form. For example, N-acyl amino acid monoamide monoalkyl ester (Patent Document 1), which gives a hard waxy form capable of solidifying and gelling a wide range of oily bases containing silicone, and silicone oil can be gelled. A silicone compound (Patent Document 2) having a polyoxyalkylene group that gives a relatively soft paste-like form and an organic group having one or more terminal hydroxyl groups can be mentioned. However, since these gelling agents give only a waxy or paste-like fixed form or property, their application range is limited in the application to cosmetics.

Therefore, polyurethane compounds (Patent Documents 3 to 5) and the like, which are capable of more elastic thickening or gelation and give good feel and spread to the skin, have been developed, but they are used in cosmetics. There was still concern that the thickening or gelling effect could not be achieved depending on the type and amount of the oily component. Specifically, various types of oily components such as hydrocarbon oils, cyclic or chain silicone oils, low-polarity or high-polarity ester oils that are generally blended in cosmetics, even when used alone, There is a demand for the development of additives capable of thickening or gelling, without any limitation even when a plurality of types are used.

International Publication No. 2007/078013 JP, 2007-254538, A JP, 2011-102256, A JP, 2011-225729, A JP, 2016-102156, A

The problem to be solved by the present invention is a urethane-modified silicone capable of thickening or gelling various types of oily components both when used alone and when used in a plurality of types, and a urethane-modified silicone. An object of the present invention is to provide an oil composition containing the oily component and an oily component, and a cosmetic composition containing the oil composition.

Therefore, the present inventors diligently studied, and found various kinds of oily components, and found a novel urethane-modified silicone capable of thickening or gelling both when used alone and when used in plural types, The present invention has been completed. That is, the present invention provides a silicone compound (A which is selected from the group consisting of a compound represented by the following general formula (a-1), a compound represented by the following general formula (a-2) or a mixture thereof. ) And a compound represented by the following general formula (b-1), a compound represented by the following general formula (b-2), or a mixture thereof, and an oxyalkylene compound (B). And a diol compound (C) represented by the following general formula (c), a monofunctional alcohol compound (D) represented by the following general formula (d), and a general formula (e) below. Is a urethane-modified silicone obtained by reacting with a diisocyanate compound (E).

(In the formula, R ¹ and R ² each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms, x and y each independently represent a number of 0 or 1, and l and m are respectively (Independently, it represents a number of 0 to 10, and the average value of p is 1 to 500.)

(In the formula, R ³ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, n represents a number from 0 to 10, z represents a number from 0 or 1, and an average value of q ranges from 1 to 500. And the average value of r is 1 to 500. The arrangement of each structural unit may be block or random.)

(In the formula, R ⁴ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, R ⁵ represents an alkylene group having 3 to 4 carbon atoms, and s represents a number of 2 to 60.)

(In the formula, R ⁶ represents an alkylene group having 3 to 4 carbon atoms, and t represents a number of 2 to 60.)

(In the formula, R ⁷ represents a divalent hydrocarbon group having 1 to 10 carbon atoms.)

(In the formula, R ⁸ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 9 carbon atoms.)

(In the formula, R ⁹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms.)

ADVANTAGE OF THE INVENTION According to this invention, the oil type|mold gel which consists of urethane modified silicone and urethane modified silicone which can thicken or gelate various types of oily components, even when it is used individually and when it uses two or more types. An agent can be provided. Moreover, according to this invention, the thickened or gelled oil composition and cosmetics can be provided.

<Urethane modified silicone>
The urethane-modified silicone of the present invention is obtained by reacting a silicone compound (A), an oxyalkylene compound (B), a diol compound (C), a monofunctional alcohol compound (D), and a diisocyanate compound (E). Obtained.

The silicone compound (A) used as a raw material for the urethane-modified silicone of the present invention is a compound represented by the following general formula (a-1), a compound represented by the following general formula (a-2), or a compound thereof. Is selected from the group consisting of mixtures of

(In the formula, R ¹ and R ² each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms, x and y each independently represent a number of 0 or 1, and l and m are respectively (Independently, it represents a number of 0 to 10, and the average value of p is 1 to 500.)

R ¹ and R ^{2 in the} above general formula (a-1) each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms, and examples of such a group include a methylene group, an ethylene group and a direct group. Chain propylene group, isopropylene group, linear butylene group, isobutylene group, linear pentylene group, isopentylene group, linear hexylene group, isohexylene group, linear heptylene group, isoheptylene group, linear octylene group, isooctylene group, Linear nonylene group, isononylene group, linear decylene group, isodecylene group, undecylene group, isoundecylene group, dodecylene group, isododecylene group, tridecylene group, isotridecylene group, tetradecylene group, isotetradecylene group, pentadecylene group, isopentadecene group Alkylene groups such as silene group, hexadecylene group, isohexadecylene group, heptadecylene group, isoheptadecylene group, octadecylene group, isooctadecylene group, nonadecylene group, isononadecylene group, icosylene group, isoicosylene group; cyclopentylene group , Cyclohexylene group, methylcyclohexylene group, dimethylcyclohexylene group, and other cycloalkylene groups; phenylene group, methylphenylene group, ethylphenylene group, propylphenylene group, butylphenylene group, dimethylphenylene group, diethylphenylene group, phenethylene group, etc. And a divalent aromatic hydrocarbon group. Among them, R ¹ and R ² are preferably each independently an alkylene group having 1 to 20 carbon atoms, and 1 to 5 carbon atoms, from the viewpoint of further enhancing the thickening or gelling effect of the resulting urethane-modified silicone. Is more preferable, and an alkylene group having 2 to 3 carbon atoms is even more preferable.

X and y in the general formula (a-1) each independently represent a number of 0 or 1. From the viewpoint of further increasing the thickening or gelling effect of the urethane-modified silicone obtained, x and y are preferably 1.

L and m in the general formula (a-1) each independently represent a number from 0 to 10. From the viewpoint that the thickening or gelling effect of the urethane-modified silicone obtained is further enhanced, when x and y are 0 respectively, 1 and m are preferably 0 respectively. When x and y are each 1, 1 and m are preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 4.

The average value of p in the general formula (a-1) is from 1 to 500, and the average value of p is preferably from 2 to 100, from the viewpoint of further enhancing the thickening or gelling effect of the urethane-modified silicone obtained. 5 to 90 are more preferred, 10 to 80 are even more preferred, and 20 to 70 are even more preferred.

The number average molecular weight of the silicone compound represented by the general formula (a-1) is not particularly limited, but is 500 to 100,000 from the viewpoint of further enhancing the thickening or gelling effect of the urethane-modified silicone obtained. It is preferably 1,000 to 20,000, more preferably 1,500 to 10,000, still more preferably 2,000 to 5,000. When the number average molecular weight is more than 100,000, the thickening or gelling effect of the urethane-modified silicone obtained may be reduced, and when it is less than 500, the thickening or gelling effect of the urethane-modified silicone obtained may be obtained. You may not be able to. In the present invention, the number average molecular weight can be measured by GPC and calculated in terms of styrene.

(In the formula, R ³ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, n represents a number from 0 to 10, z represents a number from 0 or 1, and an average value of q ranges from 1 to 500. And the average value of r is 1 to 500. The arrangement of each structural unit may be block or random.)

R ^{3 in the} general formula (a-2) represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and examples of such a group include a methylene group, an ethylene group, a linear propylene group, and an isopropylene group. , Linear butylene group, isobutylene group, linear pentylene group, isopentylene group, linear hexylene group, isohexylene group, linear heptylene group, isoheptylene group, linear octylene group, isooctylene group, linear nonylene group, isononylene group , Linear decylene group, isodecylene group, undecylene group, isoundecylene group, dodecylene group, isododecylene group, tridecylene group, isotridecylene group, tetradecylene group, isotetradecylene group, pentadecylene group, isopentadecylene group, hexadecylene group, iso Alkylene groups such as hexadecylene group, heptadecylene group, isoheptadecylene group, octadecylene group, isooctadecylene group, nonadecylene group, isononadecylene group, icosylene group, isoicosylene group; cyclopentylene group, cyclohexylene group, methylcyclo Cycloalkylene groups such as xylene groups and dimethylcyclohexylene groups; divalent aromatic carbons such as phenylene groups, methylphenylene groups, ethylphenylene groups, propylphenylene groups, butylphenylene groups, dimethylphenylene groups, diethylphenylene groups, phenetylene groups A hydrogen group is mentioned. Of these, R ³ is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and more preferably 2 carbon atoms from the viewpoint of further enhancing the thickening or gelling effect of the urethane-modified silicone obtained. Even more preferred are alkylene groups of ˜3.

“N” in the general formula (a-2) represents a number from 0 to 10. From the viewpoint of further increasing the thickening or gelling effect of the obtained urethane-modified silicone, when z described later is 0, n is preferably 0. When z is 1, n is preferably 1-10, more preferably 1-5, even more preferably 2-4.

Z in the above general formula (a-2) represents a number of 0 or 1. From the viewpoint of further increasing the thickening or gelling effect of the urethane-modified silicone obtained, z is preferably 1.

The average value of q in the general formula (a-2) is 1 to 500. Among them, the average value of q is preferably from 2 to 100, more preferably from 5 to 90, even more preferably from 10 to 80, and further preferably from 20 to 70, from the viewpoint of further increasing the thickening or gelling effect of the urethane-modified silicone obtained. Is even more preferable.

The average value of r in the general formula (a-2) is 1 to 500. Among them, the average value of r is preferably from 1.5 to 100, more preferably from 2 to 20, and even more preferably from 2 to 10, from the viewpoint of further enhancing the thickening or gelling effect of the urethane-modified silicone obtained. -5 are even more preferred.

The ratio of the values of q and r in the general formula (a-2) is not particularly limited, but from the viewpoint of further enhancing the thickening or gelling effect of the urethane-modified silicone obtained, the ratio q of the average value of q and r. :R is preferably 0.1 to 200:1, more preferably 1 to 100:1, still more preferably 2 to 70:1, and still more preferably 5 to 50:1, when r is 1. .. The arrangement of each structural unit may be block or random.

The number average molecular weight of the silicone compound represented by the general formula (a-2) is not particularly limited, but is 500 to 100,000 from the viewpoint of further enhancing the thickening or gelling effect of the urethane-modified silicone obtained. It is preferably 1,000 to 20,000, more preferably 1,500 to 10,000, still more preferably 2,000 to 5,000. If the number average molecular weight is more than 100,000 or less than 500, the thickening or gelling effect may be reduced.

In the present invention, as the silicone compound (A), one type or two or more types of the compound represented by the general formula (a-1) may be used, and the compound represented by the general formula (a-2) may be used. One kind or two or more kinds may be used, and one kind or two kinds or more of the compound represented by the general formula (a-1) and one kind or two kinds of the compound represented by the general formula (a-2) or You may use 2 or more types.

In the present invention, it is preferable to use a silicone compound containing a compound represented by the general formula (a-2) from the viewpoint of obtaining a urethane-modified silicone capable of thickening or gelating various kinds of oily components, and From the viewpoint of the feel of the resulting oil composition thickened or gelled with the urethane-modified silicone, it is preferable to use a silicone compound containing a compound represented by the general formula (a-1), It is more preferable to use only the compound represented by -1) as the silicone compound (A).

In the present invention, the content ratio (a-1):(a-2) of the compound represented by the general formula (a-1) to the compound represented by the general formula (a-2) in the silicone compound (A) is It is not particularly limited and can be appropriately adjusted according to the purpose. For example, from the viewpoint of thickening or gelling effect of the resulting urethane-modified silicone, the molar ratio of (a-1):(a-2) is 0.2 to 1:0 to 0.8. The ratio is more preferably 0.4 to 1:0 to 0.6, and even more preferably 0.6 to 1:0 to 0.4 (the sum of the ratios is 1 in each case).

By producing the urethane-modified silicone of the present invention by using such a compound as the silicone compound (A), a siloxane group, a hydrocarbon group (alkyl group, alkylene group, etc.) so as to enhance the affinity with various oily components. It is considered possible to obtain a urethane-modified silicone having a structure in which oxyalkylene groups are two-dimensionally or three-dimensionally distributed in the molecule. Therefore, the thickening or gelling effect of the urethane-modified silicone can be enhanced.

The compound represented by the general formula (a-1) and the compound represented by the general formula (a-2) can be prepared by known methods (for example, JP-A-60-206834 and JP-A-4-88024). What was manufactured by the described method) may be used, and a commercial item may be used.

The oxyalkylene compound (B) used as a raw material for the urethane-modified silicone of the present invention is a compound represented by the general formula (b-1), a compound represented by the general formula (b-2), or a mixture thereof. Is selected from the group consisting of.

(In the formula, R ⁴ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, R ⁵ represents an alkylene group having 3 to 4 carbon atoms, and s represents a number of 2 to 60.)

R ^{4 in the} general formula (b-1) represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and examples of such a group include a methyl group, an ethyl group, a linear propyl group, an isopropyl group, Linear butyl group, isobutyl group, linear pentyl group, isopentyl group, linear hexyl group, isohexyl group, linear heptyl group, isoheptyl group, linear octyl group, isooctyl group, linear nonyl group, isononyl group, Linear decyl group, isodecyl group, undecyl group, isoundecyl group, dodecyl group, isododecyl group, tridecyl group, isotridecyl group, tetradecyl group, isotetradecyl group, pentadecyl group, isopentadecyl group, hexadecyl group, isohexadecyl group, Alkyl groups such as heptadecyl group, isoheptadecyl group, octadecyl group, isooctadecyl group, nonadecyl group, isononadecyl group, icosyl group, isoicosyl group, etc.; cycloalkyl groups such as cyclopentyl group, cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group; phenyl Examples thereof include monovalent aromatic hydrocarbon groups such as groups, methylphenyl group, ethylphenyl group, propylphenyl group, butylphenyl group, dimethylphenyl group, diethylphenyl group and phenethyl group. Of these, R ⁴ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 4 to 20 carbon atoms, and more preferably 8 carbon atoms from the viewpoint of further enhancing the thickening or gelling effect of the resulting urethane-modified silicone. Alkyl groups of -18 are even more preferred, and alkyl groups of 10-18 are even more preferred.

R ^{5 in the} general formula (b-1) represents an alkylene group having 3 to 4 carbon atoms, and examples of such a group include an alkylene group having 3 carbon atoms and an alkylene group having 4 carbon atoms. At this time, the compound represented by the general formula (b-1) includes a compound containing an oxyalkylene group in which R ⁵ is an alkylene group having 3 carbon atoms, and an oxyalkylene group in which R ⁵ is an alkylene group having 4 carbon atoms. And a compound in which R ⁵ is an oxyalkylene group in which R ⁵ is an alkylene group having 3 carbon atoms and an oxyalkylene group in which R ⁵ is an alkylene group having 4 carbon atoms are arranged in a block or random manner. From the viewpoint of the thickening or gelling effect of the urethane-modified silicone obtained, a compound in which R ⁵ is an alkylene group having 4 carbon atoms in the general formula (b-1), or R ⁵ in the general formula (b-1) is a carbon atom It is preferable to include at least one compound in which an oxyalkylene group which is an alkylene group of the number 3 and an oxyalkylene group which R ⁵ is an alkylene group having a carbon number of 4 are arranged in a block or random manner.

S in the above general formula (b-1) represents a number from 2 to 60. Among them, s is preferably from 2 to 50, more preferably from 2 to 40, even more preferably from 3 to 30, and even more preferably from 3 to 20 from the viewpoint of further enhancing the thickening or gelling effect of the obtained urethane-modified silicone. preferable.

(In the formula, R ⁶ represents an alkylene group having 3 to 4 carbon atoms, and t represents a number of 2 to 60.)

R ^{6 in the} general formula (b-2) represents an alkylene group having 3 to 4 carbon atoms. Examples of such a group include an alkylene group having 3 carbon atoms and an alkylene group having 4 carbon atoms. At this time, the compound represented by the general formula (b-2) is a compound containing an oxyalkylene group in which R ⁶ is an alkylene group having 3 carbon atoms, and an oxyalkylene group in which R ⁶ is an alkylene group having 4 carbon atoms. And a compound in which R ⁶ is an oxyalkylene group in which R ⁶ is an alkylene group having 3 carbon atoms and an oxyalkylene group in which R ⁶ is an alkylene group having 4 carbon atoms are arranged in a block or random manner. From the viewpoint of the thickening or gelling effect of the urethane-modified silicone, a compound in which R ⁶ is an alkylene group having 4 carbon atoms in the general formula (b-2) or R ⁶ in the general formula (b-2) is a carbon atom It is preferable to include at least one compound in which an oxyalkylene group which is an alkylene group of the formula 3 and an oxyalkylene group which is an alkylene group of which R ⁶ is a carbon number 4 are arranged in a block or random manner.

“T” in the general formula (b-2) represents a number of 2 to 60. Above all, t is preferably from 5 to 60, more preferably from 10 to 50, and even more preferably from 20 to 42, from the viewpoint of further enhancing the thickening or gelling effect of the urethane-modified silicone obtained.

A compound represented by the general formula (b-1), which includes the compound represented by the general formula (b-1) and the compound represented by the general formula (b-2) as the oxyalkylene compound (B). The content ratio of the compound represented by the formula (b-2) and the compound represented by the general formula (b-2) is not particularly limited, but from the viewpoint of further enhancing the thickening or gelling effect of the urethane-modified silicone obtained, for example, a molar ratio of 0.1 to It is preferably 0.9:0.9 to 0.1, more preferably 0.2 to 0.8:0.8 to 0.2, and 0.3 to 0.7:0.7. It is even more preferable that the ratio is ˜0.3 (the sum of the ratios in each case is 1).

When the urethane-modified silicone of the present invention is produced by using such a compound as the oxyalkylene compound (B), the urethane-modified silicone molecule has two-dimensional oxyalkylene groups so as to enhance the affinity with various oily components. Alternatively, it may be possible to have a three-dimensionally distributed structure. Therefore, the thickening or gelling effect of the urethane-modified silicone can be enhanced.

As the compound represented by the general formula (b-1) and the compound represented by the general formula (b-2), those produced by a known method may be used, or commercially available products may be used. The method for producing the compound represented by the general formula (b-1) and the compound represented by the general formula (b-2) is, for example, one or more compounds having an active hydrogen atom as an initiator. Examples of the method include a method of addition-polymerizing an alkylene oxide having 3 to 4 carbon atoms. At this time, when a compound having a hydrocarbon group having 1 to 20 carbon atoms and one hydroxyl group is used as an initiator, the compound represented by the general formula (b-1) can be produced, and a water molecule or an initiator is used. By using a compound having two hydroxyl groups, the compound represented by the general formula (b-2) can be produced.

The diol compound (C) used as a raw material for the urethane-modified silicone of the present invention is represented by the following general formula (c).

(In the formula, R ⁷ represents a divalent hydrocarbon group having 1 to 10 carbon atoms.)

R ^{7 in the} general formula (c) represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and examples of such a group include a methylene group, an ethylene group, a linear propylene group, an isopropylene group, and a direct group. Chain butylene group, isobutylene group, linear pentylene group, isopentylene group, linear hexylene group, isohexylene group, linear heptylene group, isoheptylene group, linear octylene group, isooctylene group, linear nonylene group, isononylene group, direct Alkylene groups such as chain decylene group and isodecylene group; cycloalkylene groups such as cyclopentylene group, cyclohexylene group, methylcyclohexylene group, dimethylcyclohexylene group; phenylene group, methylphenylene group, ethylphenylene group, propylphenylene group, Examples thereof include divalent aromatic hydrocarbon groups such as a butylphenylene group, a dimethylphenylene group, a diethylphenylene group, and a phenetylene group. Among them, R ⁷ is preferably an alkylene group having 1 to 10 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, from the viewpoint of further increasing the thickening or gelling effect of the urethane-modified silicone obtained. An alkylene group having 4 to 10 carbon atoms or a divalent aromatic hydrocarbon group having 7 to 9 carbon atoms is more preferable, and specifically, the compound represented by the general formula (c) is 1,4-benzenediene. Even more preferably it is methanol.

As the diol compound (C), one kind of compound represented by the general formula (c) may be used, or two or more kinds of compounds may be used, but it is easy to obtain the effect of the present invention. It is preferred to use seed compounds as raw materials.

By producing the urethane-modified silicone of the present invention by using the compound represented by the general formula (c) as the diol compound (C), the hydrocarbon in the urethane-modified silicone molecule is enhanced so as to enhance the affinity with various oily components. It is considered that the group (preferably an alkylene group) can have a two-dimensionally or three-dimensionally distributed structure. Therefore, the thickening or gelling effect of the urethane-modified silicone can be enhanced.

The monofunctional alcohol compound (D) used as a raw material for the urethane-modified silicone of the present invention is represented by the following general formula (d).

(In the formula, R ⁸ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 9 carbon atoms.)

R ^{8 in the} general formula (d) represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 9 carbon atoms, and examples of such a hydrocarbon group include a methyl group, an ethyl group, a linear propyl group and isopropyl group. Group, linear butyl group, isobutyl group, linear pentyl group, isopentyl group, linear hexyl group, isohexyl group, linear heptyl group, isoheptyl group, linear octyl group, isooctyl group, linear nonyl group, isononyl Groups such as alkyl groups; cyclopentyl groups, cyclohexyl groups, and other cycloalkyl groups; phenyl groups, methylphenyl groups, ethylphenyl groups, propylphenyl groups, butylphenyl groups, dimethylphenyl groups, diethylphenyl groups, phenethyl groups, etc. The aromatic hydrocarbon group of Of these, R ⁸ is preferably an alkyl group having 1 to 9 carbon atoms, more preferably an alkyl group having 2 to 9 carbon atoms, and more preferably 4 carbon atoms from the viewpoint of further increasing the thickening or gelling effect of the urethane-modified silicone obtained. Even more preferred are alkyl groups from -9.

As the monofunctional alcohol compound (D), one kind of compound represented by the general formula (d) may be used, or two or more kinds of compounds may be used, but the effect of the present invention is easily obtained. It is preferable to use one of these compounds as a raw material.

By producing the urethane-modified silicone of the present invention by using the compound represented by the general formula (d) as the monofunctional alcohol compound (D), the urethane-modified silicone molecule can be incorporated into the molecule so as to enhance the affinity with various oily components. It is believed that the alkyl groups can have a two-dimensionally or three-dimensionally distributed structure. Therefore, the thickening or gelling effect of the urethane-modified silicone can be enhanced.

The diisocyanate compound (E) used as a raw material for the urethane-modified silicone of the present invention is represented by the following general formula (e).

(In the formula, R ⁹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms.)

R ^{9 in the} general formula (e) represents a divalent hydrocarbon group having 1 to 20 carbon atoms. Examples of such a group include a methylene group, an ethylene group, a linear propylene group, an isopropylene group, a linear butylene group, an isobutylene group, a linear pentylene group, an isopentylene group, a linear hexylene group, and an isohexylene group, Linear heptylene group, isoheptylene group, linear octylene group, isooctylene group, linear nonylene group, isononylene group, linear decylene group, isodecylene group, undecylene group, isoundecylene group, dodecylene group, isododecylene group, tridecylene group, isotridecylene group , Tetradecylene group, isotetradecylene group, pentadecylene group, isopentadecylene group, hexadecylene group, isohexadecylene group, heptadecylene group, isoheptadecylene group, octadecylene group, isooctadecylene group, nonadecylene group, isononadecylene group Group, alkylene group such as icosylene group, isoicosylene group; cycloalkylene group such as cyclopentylene group, cyclohexylene group, methylcyclohexylene group, dimethylcyclohexylene group; phenylene group, methylphenylene group, ethylphenylene group, propylphenylene group And a divalent aromatic hydrocarbon group such as a butylphenylene group, a dimethylphenylene group, a diethylphenylene group and a phenethylene group. Of these, R ⁹ is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 2 to 10 carbon atoms, and more preferably 4 carbon atoms from the viewpoint of further enhancing the thickening or gelling effect of the urethane-modified silicone obtained. More preferably, it is an alkylene group having 8 to 8 carbon atoms, and even more preferably an alkylene group having 6 carbon atoms.

As the diisocyanate compound (E), one kind of compound represented by the general formula (e) may be used, or two or more kinds of compounds may be used, but it is easy to obtain the effect of the present invention. Preference is given to using certain compounds.

The urethane-modified silicone of the present invention can be obtained by reacting the above components (A) to (E). This reaction is caused by the reaction between each hydroxyl group contained in the components (A) to (D) and the isocyanate group contained in the component (E). On the other hand, since the isocyanate compound (E) and the component having a hydroxyl group react arbitrarily, it is impossible to uniquely describe the structure of the urethane-modified silicone of the present invention by the general formula.

The urethane-modified silicone of the present invention has a siloxane group, a hydrocarbon group (alkyl group, alkylene group, etc.), and an oxyalkylene group in the molecule, and these groups are two-dimensionally or three-dimensionally bonded by a urethane bond. Is believed to have. When only the compound represented by the general formula (a-1) is used as the silicone compound (A), the urethane-modified silicone of the present invention is considered to have a molecular structure in which each structural part is two-dimensionally bonded. When the compound represented by the general formula (a-2) is used as the silicone compound (A), the urethane-modified silicone of the present invention is considered to have a molecular structure in which each structural part is three-dimensionally bonded. ..

The number average molecular weight of the urethane-modified silicone of the present invention is not particularly limited, but from the viewpoint of thickening or gelling effect, it is preferably 1,000 to 500,000, and preferably 2,000 to 400,000. More preferably, it is more preferably 3,000 to 300,000, and even more preferably 5,000 to 200,000.

The method for producing the urethane-modified silicone of the present invention is not particularly limited as long as the compounds (A) to (E) are reacted, and a known method may be used. For example, a method may be used in which the components (A) to (E) are placed in the reaction system and reacted at the same time, or a part of the components (A) to (E) is placed in the reaction system and reacted, and then the remaining A method of adding components and reacting may be used. From the viewpoint of further enhancing the thickening or gelling effect of the urethane-modified silicone obtained, after the components (A) to (C) and the component (E) are put into the reaction system and reacted, the component (D) is further added. The method of producing a urethane-modified silicone by adding and reacting is preferable. At this time, in each reaction stage, the whole amount of each component may be put into the reaction system at one time for the reaction, or each component may be put in several times and reacted. Further, the specific production method for reacting each component is not particularly limited, and a known method can be used. For example, a method of reacting at a temperature of 60 to 170° C. or in several batches for 10 minutes to 5 hours, respectively. Etc.

The respective compounding ratios of the components (A) to (E) at the time of producing the urethane-modified silicone of the present invention are not particularly specified, but from the viewpoint of further enhancing the thickening or gelling effect of the obtained urethane-modified silicone, the raw materials The sum of the number of hydroxyl groups of the silicone compound (A), the sum of the number of hydroxyl groups of the oxyalkylene compound (B), the sum of the number of hydroxyl groups of the diol compound (C), and the monofunctional alcohol compound (D) The ratio (A):(B):(C):(D):(E) of the sum of the number of hydroxyl groups of the diisocyanate compound (E) to the sum of the number of isocyanate groups of the diisocyanate compound (E) is When the sum of the number of hydroxyl groups is 1, the compounding ratio is 1:0.4 to 2.5:0.3 to 3.0:0.01 to 2.5:1.8 to 8.0. The ratio is preferably 1:0.5 to 2.0:0.4 to 2.6:0.05 to 2.0:2.0 to 5.5, and more preferably 1:0.6. ˜1.5:0.5 to 2.2:0.1 to 1.5:2.5 to 4.5 is even more preferred, and 1:0.7 to 1.1:0.5 to It is even more preferable to be 2.0:0.2 to 1.1:2.8 to 4.2.

Further, in the components (A) to (E) used in the reaction, the hydroxyl group of the silicone compound (A), the hydroxyl group of the oxyalkylene compound (B), the hydroxyl group of the diol compound (C) and the hydroxyl group of the monofunctional alcohol compound (D). The ratio (A)+(B)+(C)+(D):(E) of the sum of the number of the above and the number of the isocyanate groups of the diisocyanate compound (E) is not particularly limited, but the obtained urethane-modified From the viewpoint of the thickening or gelling ability of silicone, safety and stability, it is preferably 1:0.5 to 1.4, more preferably 1:0.6 to 1.2, It is even more preferably 1:0.7 to 1.1, and even more preferably 1:0.8 to 1.05.

By mixing the components (A) to (E) in the above mixing ratio to produce the urethane-modified silicone of the present invention, a siloxane group, a hydrocarbon group (an alkyl group, an alkylene group) is added so as to enhance the affinity with various oils. It is believed that a urethane-modified silicone having a structure in which oxyalkylene groups are two-dimensionally or three-dimensionally distributed in the molecule can be obtained. Therefore, the thickening or gelling effect of the urethane-modified silicone can be enhanced.

The urethane-modified silicone of the present invention is capable of reacting with other components (for example, hydroxyl groups other than the above-mentioned (A) to (D)) that can react with the components (A) to (E) as long as the thickening or gelling ability is not lost. Compound, a compound having an isocyanate group other than (E), a compound having an amino group, and the like) may be used, but a siloxane group or a carbonized group may be used so as to enhance the affinity with various oils. From the viewpoint of distributing hydrogen groups (alkyl groups, alkylene groups, etc.) and oxyalkylene groups two-dimensionally or three-dimensionally in the molecule and enhancing the thickening or gelling effect, only (A) to (E) components are used. It is preferably a urethane-modified silicone obtained by reaction.

A solvent may or may not be used when producing the urethane-modified silicone of the present invention. When a solvent is used, the urethane-modified silicone of the present invention can be obtained in a state of being dissolved or dispersed in the solvent, and the product can be obtained in this state. However, the solvent may be removed to use the urethane-modified silicone as a simple substance. Any known method may be used for removing the solvent, and examples thereof include vacuum distillation, drying by heating, spray drying, and a combination of these methods.

Examples of the solvent that can be used in the above reaction include hydrocarbon solvents such as hexane, cyclohexane, toluene, and xylene; ethyl acetate, butyl acetate, methyl branched butyl ketone, branched propyl myristate, ester solvents such as triglycerides, and the like. Can be mentioned. Among them, a solvent having no active hydrogen that reacts with an isocyanate compound in the molecule is preferable because it does not adversely affect the production of the urethane-modified silicone of the present invention. The amount of the solvent used is preferably 10 to 95% by mass, and more preferably 20 to 85% by mass, based on the whole system.

Although it is possible to produce the urethane-modified silicone of the present invention with or without a catalyst, from the viewpoint of productivity, the use of a catalyst has the effect of shortening the reaction time. Therefore, it is preferable. Examples of catalysts that can be used during the production of the urethane-modified silicone of the present invention include strong acids such as sulfuric acid and toluenesulfonic acid; titanium tetrachloride, hafnium chloride, zirconium chloride, aluminum chloride, gallium chloride, indium chloride, iron chloride, tin chloride. , Metal halides such as boron fluoride; hydroxides, alcoholates and acetic acid of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, potassium acetate and sodium carbonate. Salts, carbonates; metal oxides such as aluminum oxide, calcium oxide, barium oxide and sodium oxide; organic metals such as tetra-branched propyl titanate, dibutyltin dichloride, dibutyltin oxide, dibutyltin bis(2-ethylhexylthioglycolate) Compounds: Soaps such as sodium octylate, potassium octylate, sodium laurate, potassium laurate and the like can be mentioned. The amount of the catalyst used is about 0.01 to 1% by mass based on the whole system.

The urethane-modified silicone of the present invention obtained as above can be added to an oily component to adjust the viscosity of the oily component, and the viscosity of the oil composition or gel can be adjusted by adjusting the addition amount. It is possible to obtain an oil composition in the form of oil. In addition, various types of oily components can be thickened or gelled when used alone or when used in plural types. For example, hydrocarbon oil, silicone oil, ester oil, higher alcohol, etc. It is possible to thicken or gel the oily component of.

The hydrocarbon oil is not particularly limited, for example, liquid paraffin, squalane, pristane, ozokerite, paraffin, ceresin, vaseline, polyisobutene, polyisoprene, isodecane, isododecane, isohexadecane, normal pentane, isopentane, normal hexane, isohexane, Kerosene, decalin, tetralin, microcrystalline wax and the like can be mentioned.

The silicone oil is not particularly limited, for example, dimethylpolysiloxane, diphenylpolysiloxane, diphenylsiloxyphenyltrimethicone, chain silicone oil such as octamethyltrisiloxane, decamethylcyclotetrasiloxane, dodecamethylcyclotetrasiloxane, Cyclic silicone oil such as octamethylcyclotetrasiloxane, cyclopentasiloxane, dodecamethylcyclopentasiloxane, octamethylcyclopentasiloxane, decamethylcyclohexasiloxane, dodecamethylcyclohexasiloxane, octamethylcyclohexasiloxane, alkyl-modified dimethylpolysiloxane And modified silicone oils such as polyether-modified dimethylpolysiloxane, fatty acid-modified polysiloxane, higher alcohol-modified polysiloxane, amino-modified polysiloxane, and fluorine-modified polysiloxane.

The ester oil is not particularly limited and may be a monoester oil, a diester oil, a triester oil, a tetraester oil or the like, for example, ethyl acetate, butyl acetate, hexyl acetate, decyl acetate, propionic acid. Butyl, cetyl octanoate, hexyldecyl dimethyloctanoate, isononyl isononanoate, isononyl isononanoate, isotridecyl isononanoate, ethyl laurate, hexyl laurate, myristyl myristate, branched propyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate , 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, decyl oleate, oleyl oleate, octyldodecyl oleate, isocetyl stearate, glycerin stearate, butyl stearate, ethylhexyl hydroxystearate, ethylene glycol stearate. Octyl oxystearate, diethyl phthalate, triethyl citrate, 2-ethylhexyl succinate, diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, myristyl lactate, diisobutyl adipate, 2-hexyldecyl adipate, adipine Acid di-2-heptylundecyl, cetylethylhexanoate, triethylhexanoin, polyglyceryl-2 triisostearate, neopentyl glycol dioctanoate, neopentyl glycol dicaprate, pentaerythrityl tetraisostearate, etc. Oils; animal and vegetable ester oils such as macadamia nut oil, meadowfoam oil, safflower oil, sunflower oil, avocado oil, lanolin, mink oil, castor oil and olive oil.

The higher alcohol is not particularly limited, and examples thereof include linear higher alcohols such as lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, and cetostearyl alcohol; monostearyl glycerin ether (batyl alcohol), 2 -Branched chain higher alcohols such as decyl tetradecynol, lanolin alcohol, cholesterol, phytosterol, hexyldodecanol, isostearyl alcohol, octyldodecanol and the like.

Note that, of the above oily components, those that are solid at room temperature are to be used not as a single oily component but as a mixed oil with other liquid oils.

The urethane-modified silicone of the present invention can be used as a gelling agent for oils because it can thicken or gel various types of oily components so as to have elasticity and fluidity. When the urethane-modified silicone of the present invention is used as a gelling agent for oil, it can be applied to any aspect as long as it uses a hydrocarbon oil, a silicone oil, or an ester oil. Examples of the fields include cosmetics, pharmaceuticals, fragrances, paints, fibers, and the like, and it is preferably used for cosmetics in which the form of the gelled composition and the feel of the gelled composition are important factors as a product.

<Oil composition>
The oil composition of the present invention is an oil composition containing the urethane-modified silicone of the present invention and an oily component containing at least one selected from the group consisting of hydrocarbon oils, silicone oils and ester oils. .. Specific hydrocarbon oils, silicone oils and ester oils are not particularly limited, but for example, one or more selected from the hydrocarbon oils, silicone oils and ester oils exemplified above can be used. The oil composition of the present invention may use a single oily component or a plurality of oily components depending on the purpose. From the viewpoint of easily obtaining an oil composition having desired characteristics, it is preferable to use an oily component containing two or more kinds selected from hydrocarbon oils, silicone oils and ester oils. For example, ester oils and hydrocarbon oils It is preferable to use an oily component containing, an oily component containing ester oil and silicone oil, and an oily component containing ester oil, hydrocarbon oil and silicone oil. Further, when the oil composition of the present invention contains a plurality of oily components, the mixing ratio of each oily component is not particularly limited and may be adjusted according to the purpose. For example, when two types of oily components are used. The compounding ratio may be 5 to 95:95 to 5 by mass ratio (the total mass ratio is 100), and the compounding ratio when using three kinds of oily components is 5 to 90:5 by mass ratio. ˜90:5 to 90 (total mass ratio is 100). The oil composition of the present invention can be applied to any embodiment as long as it uses a hydrocarbon oil, a silicone oil, an ester oil, for example, a lubricating oil, a cosmetic, a pharmaceutical, a fragrance, a paint, Although the field of fibers and the like can be mentioned, it is preferably used for cosmetics in which the feel of the oil composition is an important factor as a product.

The content of the urethane-modified silicone in the oil composition of the present invention is not particularly limited, but is preferably 0.1 to 20.0 mass% with respect to the total mass of the oil composition, and 0.3 to 15 0.0 mass% is more preferable, and 0.5 to 10.0 mass% is even more preferable. When the content of the urethane-modified silicone in the oil composition is less than 0.1% by mass, the gelling or thickening effect may not be exhibited, and when it exceeds 20.0% by mass, the effect commensurate with the added amount may be obtained. You may not get it.

The method of producing the oil composition by adding the urethane-modified silicone of the present invention to an oil component is not particularly limited, and a known method can be used. For example, the urethane-modified silicone of the present invention is added to the oil component. Alternatively, a method of mixing and stirring until uniform, or the like can be used. At this time, the temperature at the time of mixing is not particularly limited, and for example, it may be heated to room temperature to about 200° C. and mixed until uniform.

<Cosmetic composition>
The cosmetic composition of the present invention is a cosmetic composition containing the oil composition of the present invention, and specifically contains the oil composition containing the urethane-modified silicone described above and an oil component. It is a cosmetic composition. The specific product and form of the cosmetic composition of the present invention are not particularly limited, and for example, toiletry products such as shampoo and conditioner are also included, and examples thereof include lotion, lotion, emulsion, cream, face-wash foam, and cleansing milk. , Cleansing lotion, hair nourishing agent, hair liquid, set lotion, hair bleach, color rinse, permanent wave liquid, lipstick, pack, foundation, cologne, shampoo, rinse, treatment, sunscreen, deodorant, perfume, cleansing oil and cosmetic oil, etc. Are listed.

The content of the oil composition of the present invention in the cosmetic composition of the present invention is not particularly limited, and may be adjusted according to the usage mode and purpose of use, for example, relative to the total mass of the cosmetic composition. It may be 0.1 to 80.0% by mass, more preferably 0.5 to 50.0% by mass, and 1.0 to 30 from the viewpoint of the feel of the resulting cosmetic composition. It is even more preferably 0.0% by mass. Moreover, the content of the urethane-modified silicone in the cosmetic composition of the present invention is not particularly limited and may be adjusted according to the usage mode and purpose of use. For example, it is 0 with respect to the total mass of the cosmetic composition. The amount may be 0.01 to 16.0% by mass, more preferably 0.02 to 10.0% by mass, and 0.03 to 5% from the viewpoint of the feel of the resulting cosmetic composition. Even more preferably, it is 0% by mass.

The cosmetic composition of the present invention has various properties (solubility, dispersibility, stability, feeling of use, applicability, penetrability, moisturizing property, safety, during storage, during use, and after use depending on the purpose of use. Other additives commonly used in cosmetic compositions can be used to improve and improve design properties, optical properties, aromatic properties, whitening properties, etc.). Other additives include, for example, powder components, waxes, higher fatty acids, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, humectants, water-soluble polymers, sequestering agents. , Lower alcohols, polyhydric alcohols, monosaccharides, oligosaccharides, polysaccharides, amino acids and their derivatives, organic amines, pH regulators, vitamins, UV protection components, antioxidants, preservatives, blood circulation promoters, anti-inflammatory agents, activators , Whitening agents, antiseborrheic agents, anti-inflammatory agents, various extracts, plant seaweed extracts, and the like, and one or more of these may be arbitrarily blended.

Examples of powder components include inorganic powders (eg, talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, phlogopite, biotite, permiculite, magnesium carbonate, calcium carbonate, silicic acid). Aluminum, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (calculated gypsum), calcium phosphate, fluoroapatite, hydroxyapatite, ceramic powder , Metal soap (eg, zinc myristate, calcium palmitate, aluminum stearate), boron nitride, etc.; organic powder (eg, polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, polystyrene powder, styrene) And acrylic acid copolymer resin powder, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, etc.); inorganic white pigments (eg, titanium dioxide, zinc oxide, etc.); inorganic red pigments (eg, iron oxide ( Red iron oxide), iron titanate, etc.; inorganic brown pigments (eg, γ-iron oxide, etc.); inorganic yellow pigments (eg, yellow iron oxide, ocher, etc.); inorganic black pigments (eg, black iron oxide, low) Inorganic purple pigments (eg manganese violet, cobalt violet etc.); Inorganic green pigments (eg chromium oxide, chromium hydroxide, cobalt titanate etc.); Inorganic blue pigments (eg ultramarine blue, etc.) Navy blue or the like); Pearl pigment (for example, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored titanium oxide coated mica, bismuth oxychloride, fish scale foil, etc.); Metal powder pigment (for example, aluminum powder, Copper powder and the like); organic pigments such as zirconium, barium or aluminum lake (for example, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 228, Red No. 405, Organic pigments such as Orange No. 203, Orange No. 204, Yellow No. 205, Yellow No. 401, and Blue No. 404, Red No. 3, Red No. 104, Red No. 106, Red No. 227, Red No. 230, Red No. 401, Red No. 505, orange No. 205, yellow No. 4, yellow No. 5, yellow No. 202, yellow No. 203, green No. 3, blue No. 1, etc.); natural pigments (eg chlorophyll, β-carotene etc.) and the like.

As the wax, for example, beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ivota wax, whale wax, montan wax, nukarou, lanolin, capock wax, lanolin acetate, liquid lanolin, sugarcane wax, reduced lanolin, jojoba wax, hard lanolin, shellac wax, Examples thereof include POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, and POE hydrogenated lanolin alcohol ether.

Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, tall oil fatty acid, isostearic acid, linoleic acid, linoleic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid. (DHA) and the like.

Examples of the anionic surfactant include fatty acid soap (eg, sodium laurate, sodium palmitate, etc.); higher alkyl sulfate ester salt (eg, sodium lauryl sulfate, potassium lauryl sulfate); alkyl ether sulfate salt (eg, POE-triethanolamine lauryl sulfate, POE-sodium lauryl sulfate, etc.; N-acyl sarcosinic acid (eg, sodium lauroyl sarcosinate); higher fatty acid amide sulfonate (eg, sodium N-myristoyl-N-methyl taurine, coconut) Oil fatty acid sodium methyl taurine, sodium lauryl methyl taurine, etc.; Phosphate ester salts (sodium POE-oleyl ether phosphate, POE-stearyl ether phosphoric acid, etc.); Sulfosuccinates (eg sodium di-2-ethylhexyl sulfosuccinate, Monolauroyl monoethanolamide sodium polyoxyethylene sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc.; alkylbenzene sulfonates (eg sodium linear dodecylbenzene sulfonate, triethanolamine linear dodecylbenzene sulfonate, linear dodecyl benzene sulfonate, etc.) ); higher fatty acid ester sulfate ester salt (for example, hydrogenated coconut oil fatty acid glycerin sodium sulfate, etc.); N-acyl glutamate (for example, monosodium N-lauroyl glutamate, disodium N-stearoyl glutamate, N-myristoyl-L-glutamic acid) Monosodium etc.); Sulfated oil (eg, funnel oil etc.); POE-alkyl ether carboxylic acid; POE-alkyl allyl ether carboxylate; α-olefin sulfonate; higher fatty acid ester sulfonate; secondary alcohol sulfate Ester salts; higher fatty acid alkylolamide sulfate ester salts; sodium lauroyl monoethanolamide succinate; ditriethanolamine N-palmitoyl aspartate; sodium caseinate and the like.

Examples of the cationic surfactant include alkyl trimethyl ammonium salts (eg stearyl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride etc.); alkyl pyridinium salts (eg cetyl pyridinium chloride etc.); distearyl dimethyl ammonium dialkyl dimethyl ammonium salts; Poly(N,N'-dimethyl-3,5-methylenepiperidinium) chloride; Alkyl quaternary ammonium salt; Alkyl dimethyl benzyl ammonium salt; Alkyl isoquinolinium salt; Dialkyl morphonium salt; POE-Alkyl amine; Examples thereof include alkylamine salts, polyamine fatty acid derivatives, amyl alcohol fatty acid derivatives, benzalkonium chloride, and benzethonium chloride.

Examples of the amphoteric surfactant include imidazoline-based amphoteric surfactants (for example, 2-undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide). Side-1-carboxyethyloxy disodium salt and the like); betaine-based surfactants (eg, 2-heptadecyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, lauryl dimethylaminoacetic acid betaine, alkyl betaine, amidobetaine , Sulfobetaine, etc.) and the like.

Examples of the nonionic surfactant include sorbitan fatty acid esters (eg, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate). Ate, penta-2-ethylhexyl acid diglycerol sorbitan, tetra-2-ethylhexyl acid diglycerol sorbitan, etc.); glycerin polyglycerin fatty acid (eg, monocottonseed oil fatty acid glycerin, monoerucic acid glycerin, sesquioleate glycerin, monostearic acid glycerin) , Α,α'-glyceryl pyroglutamate oleate, glyceryl monostearate malic acid, etc.); propylene glycol fatty acid esters (eg, propylene glycol monostearate); hydrogenated castor oil derivative; glycerin alkyl ether; POE-sorbitan fatty acid Esters (eg, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate, etc.); POE sorbit fatty acid esters (eg, POE-sorbit monolaurate, POE-sorbit monooleate, POE-sorbit pentaoleate, POE-sorbit monostearate, etc.; POE-glycerin fatty acid esters (eg, POE-glycerin monostearate, POE-glycerin monoisostearate, POE-glycerin) POE-monooleates such as triisostearate); POE-fatty acid esters (eg POE-distearate, POE-monodioleate, ethylene glycol distearate etc.); POE-alkyl ethers (eg POE-lauryl ether, POE-) Oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, POE-cholestanol ether, etc.); pluronic type (eg, pluronic); POE/POP-alkyl ethers (eg, POE) /POP-cetyl ether, POE/POP-2-decyl tetradecyl ether, POE/POP-monobutyl ether, POE/POP-hydrogenated lanolin, POE/POP-glycerin ether, etc.); tetra-POE/tetra-POP-ethylenediamine condensate Class (eg Tetroni POE-castor oil hydrogenated castor oil derivative (eg, POE-castor oil, POE-hardened castor oil, POE-hardened castor oil monoisostearate, POE-hardened castor oil triisostearate, POE-hardened Castor oil monopyroglutamic acid monoisostearate diester, POE-hardened castor oil maleic acid, etc.); POE-beeswax lanolin derivative (eg, POE-sorbit beeswax, etc.); alkanolamide (eg, coconut oil fatty acid diethanolamide, lauric acid monoester) Ethanolamide, fatty acid isopropanolamide and the like); POE-propylene glycol fatty acid ester; POE-alkylamine; POE-fatty acid amide; sucrose fatty acid ester; alkylethoxydimethylamine oxide; trioleylphosphoric acid and the like.

Examples of the moisturizers include polyethylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate, bile salt, dl-pyrrolidone carboxylic acid. Examples thereof include acid salts, short-chain soluble collagen, diglycerin (EO)PO adducts, Iris yezoensis extract, yarrow extract, and melilot extract.

Examples of natural water-soluble polymers include plant-based polymers (for example, gum arabic, tragacanth, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seed (quince), algecoloid (cassius extract), starch. (Rice, corn, potato, wheat), glycyrrhizic acid); microbial macromolecules (eg xanthan gum, dextran, succinoglucan, bullan, gellan gum etc.); animal macromolecules (eg collagen, casein, albumin, gelatin etc.) ) And the like.

Examples of the water-soluble polymer include starch-based polymers (eg, carboxymethyl starch, methyl hydroxypropyl starch, etc.); cellulose-based polymers (methyl cellulose, ethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, hydroxypropyl). Cellulose, carboxymethyl cellulose, sodium carboxymethyl cellulose, crystalline cellulose, cellulose powder, etc.; Alginic acid-based polymer (eg, sodium alginate, propylene glycol alginate, etc.); Vinyl-based polymer (eg, polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone) , Carboxyvinyl polymer, etc.); polyoxyethylene-based polymer (eg, polyethylene glycol 20,000, 40,000, 60,000 polyoxyethylene-polyoxypropylene copolymer etc.); acrylic-based polymer (eg, poly Sodium acrylate, polyethyl acrylate, polyacrylamide, etc.); polyethyleneimine; cationic polymers and the like.

Examples of the sequestering agent include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, edetate disodium, edetate trisodium, and edetate tetrasodium salt. , Sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, trisodium ethylenediamine hydroxyethyl triacetate and the like.

Examples of the lower alcohol include ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol and the like.

Examples of polyhydric alcohols include trihydric alcohols (eg, glycerin, trimethylolpropane, etc.); tetrahydric alcohols (eg, pentaerythritol, such as 1,2,6-hexanetriol); pentahydric alcohols (eg, Xylitol etc.); hexahydric alcohol (eg sorbitol, mannitol etc.); polyhydric alcohol polymer (eg diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, Tetraglycerin, polyglycerin, etc.); divalent alcohol alkyl ethers (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2) -Methylhexyl ether, ethylene glycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, etc.); Dihydric alcohol alkyl ethers (eg, diethylene glycol monomethyl ether, diethylene glycol) Monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether Butyl ether, propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, etc.); dihydric alcohol ether ester (eg, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono) Butyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diabate, ethylene glycol Diol disuccinate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, etc.); glycerin monoalkyl ether ( For example, chymyl alcohol, ceracyl alcohol, batyl alcohol, etc.; sugar alcohols (for example, sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, amylolytic sugar, maltose, xylitolose, starch degradation Glysolid; Tetrahydrofurfuryl alcohol; POE-Tetrahydrofurfuryl alcohol; POP-butyl ether; POP/POE-butyl ether; Tripolyoxypropylene glycerin ether; POP-glycerin ether; POP-glycerin ether phosphate POP/POE-pentaneerythritol ether, polyglycerin and the like.

Examples of monosaccharides include tricarbon sugars (eg D-glyceryl aldehyde, dihydroxyacetone etc.); tetracarbon sugars (eg D-erythrose, D-erythrulose, D-threose, erythritol etc.); pentacarbon sugars (eg , L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose and the like); hexose (eg D-glucose, D-talose, D -Bucicose, D-galactose, D-fructose, L-galactose, L-mannose, D-tagatose, etc.); heptacarbon sugar (eg, aldoheptose, heprose, etc.); octose sugar (eg, octulose, etc.); deoxy sugar ( For example, 2-deoxy-D-ribose, 6-deoxy-L-galactose, 6-deoxy-L-mannose, etc.; Amino sugar (eg, D-glucosamine, D-galactosamine, sialic acid, aminouronic acid, muramic acid, etc.) ); uronic acid (eg, D-glucuronic acid, D-mannuronic acid, L-guluronic acid, D-galacturonic acid, L-iduronic acid, etc.) and the like.

Examples of oligosaccharides include sucrose, umbelliferose, lactose, planteose, isoliknoses, α,α-trehalose, raffinose, lycnose, umbilicin, stachyose verbascose.

Examples of the polysaccharide include cellulose, quince seed, chondroitin sulfate, starch, galactan, dermatan sulfate, glycogen, gum arabic, heparan sulfate, hyaluronic acid, tragacanth gum, keratan sulfate, chondroitin, xanthan gum, mucoitin sulfate, guar gum, dextran, and keratosulfate. , Locust Bingham, succinoglucan, caronic acid and the like.

Examples of amino acids include neutral amino acids (eg, threonine, cysteine, etc.); basic amino acids (eg, hydroxylysine, etc.) and the like. Examples of the amino acid derivative include sodium acylsarcosine (sodium lauroylsarcosine), acylglutamate, sodium β-alanine acyl, glutathione, and pyrrolidonecarboxylic acid.

Examples of organic amines include monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, etc. Are listed.
Examples of the pH adjusting agent include buffering agents such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.

Examples of vitamins include vitamins A, B1, B2, B6, C, E and derivatives thereof, pantothenic acid and derivatives thereof, biotin and the like.
Examples of the antioxidant include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters and the like.

As the UV protection component, inorganic UV protection components such as powder pigments and metal powder pigments and surface-treated products thereof, and organic UV protection components can be used, and examples thereof include titanium oxide, zinc oxide, and oxidation. Cerium, low-order titanium oxide, metal oxides such as iron-doped titanium oxide, metal hydroxides such as iron hydroxide, plate-shaped iron oxide, metal flakes such as aluminum flakes, ceramics such as silicon carbide, and fluorine thereof. Compound treatment, silicone treatment, silicone resin treatment, pendant treatment, silane coupling agent treatment, titanium coupling agent treatment, silane treatment, oil agent treatment, N-acylated lysine treatment, polyacrylic acid treatment, metal soap treatment, acrylic resin treatment , Metal oxide treated products, salicylic acid-based, para-aminobenzoic acid-based, benzophenone-based, cinnamic acid-based, benzoylmethane-based, 2-cyano-3,3-diphenylprop-2-enoic acid 2-ethylhexyl ester, dimethoxy Benzylidenedioxoimidazolidine 2-ethylhexyl propionate, 1-(3,4-dimethoxyphenyl)-4,4-dimethyl-1,3-pentanedione, sinoxate, methyl-O-aminobenzoate, 2-ethylhexyl- 2-cyano-3,3-diphenyl acrylate, 3-(4-methylbenzylidene)camphor, octyltriazone, 4-(3,4-dimethoxyphenylmethylene)-2,5-dioxo-1-imidazolidinepropionic acid 2 -Ethylhexyl, high molecular weight derivatives thereof, and the like.

Other components that can be compounded include, for example, preservatives (methylparaben, ethylparaben, butylparaben, phenoxyethanol, etc.); antiphlogistics (eg, glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, etc.); Whitening agents (for example, Yukinoshita extract, arbutin, etc.); Various extracts (for example, pearl oyster, laurel, shikon, peony, senburi, birch, sage, loquat, carrot, aloe, mallow, iris, grape, yokuinin, loofah, lily) , Saffron, senkyu, ginger, capsicum, ononis, garlic, capsicum, chimpi, touki, seaweed, etc., activator (eg, royal jelly, photosensitizer, cholesterol derivative, etc.); blood circulation promoter (eg, nicotinic acid benzyl ester, Nicotinic acid β-butoxyethyl ester, capsaicin, zingerone, cantharisin tincture, ictamol, tannic acid, α-borneol, nicotinic acid tocopherol, inositol hexanicotinate, cyclanderate, cinnarizine, tolazoline, acetylcholine, verapamil, cepharanthin, γ- Oryzanols); antiseborrheic agents (eg sulfur, thiantol etc.); anti-inflammatory agents (eg tranexamic acid, thiotaurine, hypotaurine etc.) and the like.

The content of each of these other additives in the cosmetic composition of the present invention is not particularly limited, and may be adjusted according to the embodiment or the purpose of use. You may add 10.0 mass% each.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples and may be changed without departing from the scope of the present invention. In the following examples and the like,% is based on mass unless otherwise specified.

The raw materials used to manufacture the urethane-modified silicone are shown below.

<Silicone compound (A)>
・Silicone compound 1
In the general formula (a-1), R ¹ and R ² are each independently an ethylene group, x and y are 1, l and m are 3, and the average value of p is 39. , A compound having a number average molecular weight of 3200 g/mol/silicone compound 2
In the general formula (a-2), R ³ is a propylene group, n is 3, z is 1, the average value of q is 48, the average value of r is 3.5, and A compound having an average molecular weight of 4200 g/mol

<Oxyalkylene compound (B)>
・Oxyalkylene compound 1
In the general formula (b-1), R ⁴ is an alkyl group having 12 carbon atoms, R ⁵ is an alkylene group having 4 carbon atoms, and s is 10 to 14 (average value is 12). Compound 2
In the general formula (b-1), R ⁴ is an alkyl group having 12 carbon atoms, R ⁵ is an oxyalkylene group having an alkylene group having 3 carbon atoms, and R ⁵ is an oxyalkylene group having an alkylene group having 4 carbon atoms. And oxyalkylene compound 3 in which and are randomly included in a molar ratio of 8:7, and s is 12 to 18 (average value is 15)
A compound represented by the formula (b-2), wherein R ⁶ is an alkylene group having 4 carbon atoms, and t is 30 to 42 (average value is 36).

<diol compound (C)>
・Diol compound 1
1,4-benzenedimethanol/diol compound 2
1,6-hexanediol/diol compound 3
1,4-Cyclohexanedimethanol/diol compound 4 (comparative compound)
Diethylene glycol

<Monofunctional alcohol compound (D)>
・Monofunctional alcohol compound 1
2-Ethyl-1-hexanol/monofunctional alcohol compound 2
Benzyl alcohol/monofunctional alcohol compound 3
1-hexanol

<Diisocyanate compound (E)>
・Diisocyanate compound 1
A compound in which R ⁹ is a hexamethylene group in the general formula (e)

[Production of urethane-modified silicone 1]
40 g (12.5 mmol) of silicone compound 1, 20.6 g (18.7 mmol) of oxyalkylene compound 1, and a diol compound were placed in a four-necked flask equipped with a thermometer, a nitrogen introduction tube, a reflux condenser and a stirrer. 1.48 g (10.7 mmol) of 1 was charged, the system was replaced with nitrogen, and the temperature was raised to 140°C. Then, 7.07 g (42.0 mmol) of diisocyanate compound 1 was added, and the mixture was heated at 140°C for 4 hours. It was made to react. After completion of the reaction, 2.49 g (19.1 mmol) of monofunctional alcohol compound 1 was added, and the mixture was further reacted at 140° C. for 30 minutes, and there was no absorption of isocyanate by infrared spectroscopy (IR) (all isocyanate groups reacted. The reaction was terminated and the urethane-modified silicone 1 was obtained.

[Production of urethane modified silicones 2 to 13]
Urethane-modified silicones 2 to 13 were obtained by reacting each raw material in the same manner as in the method for producing urethane-modified silicone 1 except that the raw materials used and the blending amount were changed as shown in Table 1. The numerical values in Table 1 indicate the number of moles (millimol) of the raw materials used in the production of each polymer.

[Thickening/gelation test]
In a 50 ml glass bottle, urethane-modified silicones 1 to 13 (urethane-modified silicones 1 to 6 are examples, urethane-modified silicones 7 to 13 are comparative examples), and urethane-modified silicone is 5.0 mass% with respect to the total mass of the oil composition. Was added to the following 9 types of oily components so as to be uniform and heated at 120 to 130° C. and shaken to prepare an oil composition. The obtained oil composition was allowed to stand in a constant temperature bath at 25° C. for 8 hours, and then the state of the oil composition was evaluated according to the following evaluation criteria for thickening or gelling ability. The results are shown in Table 2.

<Used oily ingredients>
Oily component 1: isododecane oily component 2: diphenylsiloxyphenyltrimethicone oily component 3: cyclopentasiloxane oily component 4: ethylhexyl palmitate oily component 5: neopentyl glycol dicaprate oily component 6: triethylhexanoin oily component 7: triethylhexa Mixed oil of noin and isododecane (mass ratio 5:90)
Oily component 8: mixed oil of triethylhexanoin and cyclopentasiloxane (mass ratio 5:90)
Oily component 9: mixed oil of triethylhexanoin and diphenylsiloxane phenyltrimethicone (mass ratio 5:90)

<Evaluation criteria for thickening/gelling ability>
⊚: Resilient gel-like ○: Flowable thickened state or gel-like ×: Not thickened or urethane-modified silicone was not dissolved

As a result, it was shown that the urethane-modified silicones 1 to 6 which are the urethane-modified silicones of the present invention exhibit thickening or gelling ability for various hydrocarbon oils, silicone oils, ester oils and mixed oils thereof. It was On the other hand, the urethane-modified silicones 7 to 13 of Comparative Examples exert a thickening or gelling ability only on a specific oily component, or do not exert a thickening or gelling ability on any oily component. It was

The urethane-modified silicone of the present invention can thicken or gel various types of oily components such as hydrocarbon oils, silicone oils, and ester oils both when used alone and when used in plural types. , A new polymer. The urethane-modified silicone of the present invention is capable of thickening or gelling more types of oily components and combinations thereof so as to have a desired feel and viscosity, as compared with conventional thickeners or gelling agents. Therefore, it is very useful because it can be expected to be used in all modes that could not be used until now.

Claims (12)

1. A silicone compound (A) selected from the group consisting of a compound represented by the following general formula (a-1), a compound represented by the following general formula (a-2) and a mixture thereof; An oxyalkylene compound (B) selected from the group consisting of a compound represented by the formula (b-1), a compound represented by the following general formula (b-2) and a mixture thereof; A diol compound (C) represented by (c), a monofunctional alcohol compound (D) represented by the following general formula (d), and a diisocyanate compound (E) represented by the following general formula (e). A urethane-modified silicone obtained by reacting with.
   

   

   (In the formula, R ¹ and R ² each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms, x and y each independently represent a number of 0 or 1, and l and m are respectively (Independently, it represents a number of 0 to 10, and the average value of p is 1 to 500.)
   

   

   (In the formula, R ³ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, n represents a number from 0 to 10, z represents a number from 0 or 1, and an average value of q ranges from 1 to 500. And the average value of r is 1 to 500. The arrangement of each structural unit may be block or random.)
   

   

   (In the formula, R ⁴ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, R ⁵ represents an alkylene group having 3 to 4 carbon atoms, and s represents a number of 2 to 60.)
   

   

   (In the formula, R ⁶ represents an alkylene group having 3 to 4 carbon atoms, and t represents a number of 2 to 60.)
   

   

   (In the formula, R ⁷ represents a divalent hydrocarbon group having 1 to 10 carbon atoms.)
   

   

   
   (In the formula, R ⁸ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 9 carbon atoms.)
   

   

   (In the formula, R ⁹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms.)
2. The oxyalkylene compound (B) is a compound in which R ⁵ is an alkylene group having 4 carbon atoms in the general formula (b-1), and oxy in which R ⁵ is an alkylene group having 3 carbon atoms in the general formula (b-1). A compound in which an alkylene group and an oxyalkylene group in which R ⁵ is an alkylene group having 4 carbon atoms are arranged in a block or random manner, a compound in which R ⁶ is an alkylene group having 4 carbon atoms in the general formula (b-2), And a compound of the general formula (b-2) in which R ⁶ is an alkylene group having 3 carbon atoms and R ⁶ is an oxyalkylene group having 4 carbon atoms are arranged in a block or random manner. The urethane-modified silicone according to claim 1, comprising at least one selected from the group consisting of:
3. The urethane-modified silicone according to claim 1 or 2, wherein the diol compound (C) contains 1,4-benzenedimethanol.
4. The urethane-modified silicone according to any one of claims 1 to 3, wherein the diisocyanate compound (E) includes a compound in which R ⁹ is an alkylene group having 4 to 8 carbon atoms in the general formula (e).
5. The urethane-modified silicone according to any one of claims 1 to 4, wherein the silicone compound (A) contains a compound represented by the general formula (a-1) having a number average molecular weight of 500 to 100,000.
6. A gelling agent for oil, comprising the urethane-modified silicone according to any one of claims 1 to 5.
7. An oil composition comprising the urethane-modified silicone according to any one of claims 1 to 5 and at least one oily component selected from the group consisting of hydrocarbon oils, silicone oils and ester oils.
8. The oil composition according to claim 7, wherein the content of the urethane-modified silicone is 0.1% by mass to 20% by mass based on the total mass of the oil composition.
9. A cosmetic composition containing the oil composition according to claim 7.
10. A silicone compound (A) selected from the group consisting of a compound represented by the following general formula (a-1), a compound represented by the following general formula (a-2) and a mixture thereof; An oxyalkylene compound (B) selected from the group consisting of a compound represented by the formula (b-1), a compound represented by the following general formula (b-2) and a mixture thereof; A diol compound (C) represented by (c), a monofunctional alcohol compound (D) represented by the following general formula (d), and a diisocyanate compound (E) represented by the following general formula (e). And a method for producing a urethane-modified silicone, comprising:
    

    

    (In the formula, R ¹ and R ² each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms, x and y each independently represent a number of 0 or 1, and l and m are respectively (Independently, it represents a number of 0 to 10, and the average value of p is 1 to 500.)
    

    

    (In the formula, R ³ represents a divalent hydrocarbon group having 1 to 20 carbon atoms, n represents a number from 0 to 10, z represents a number from 0 or 1, and an average value of q ranges from 1 to 500. And the average value of r is 1 to 500. The arrangement of each structural unit may be block or random.)
    

    

    (In the formula, R ⁴ represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, R ⁵ represents an alkylene group having 3 to 4 carbon atoms, and s represents a number of 2 to 60.)
    

    

    (In the formula, R ⁶ represents an alkylene group having 3 to 4 carbon atoms, and t represents a number of 2 to 60.)
    

    

    (In the formula, R ⁷ represents a divalent hydrocarbon group having 1 to 10 carbon atoms.)
    

    

    (In the formula, R ⁸ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 9 carbon atoms.)
    

    

    (In the formula, R ⁹ represents a divalent hydrocarbon group having 1 to 20 carbon atoms.)
11. Use of the urethane-modified silicone according to any one of claims 1 to 5 for thickening or gelling an oily component.
12. A method for thickening or gelling an oily component, which comprises adding the urethane-modified silicone according to any one of claims 1 to 5 to the oily component.