JPWO2020162248A1 - Urethane-modified silicone and oil compositions and cosmetic compositions containing it. - Google Patents

Abstract

The present invention comprises a silicone compound (A), an oxyalkylene compound (B), a diol compound (C), a monofunctional alcohol compound (D), and a diisocyanate compound (E) having a specific structure. An oil composition containing a urethane-modified silicone and a urethane-modified silicone obtained by reacting, and a cosmetic composition containing the oil composition.

Description

The present invention relates to urethane-modified silicones capable of thickening or gelling various oily components. More specifically, a novel oil gelling agent capable of thickening or gelling various hydrocarbon oils, silicone oils, ester oils and mixtures thereof with a low addition amount, which can also be used as a gelling agent for oils. 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, etc., have the effects of softening the skin, improving the smoothness of the skin, protecting the skin, moisturizing the skin, and removing excess oil from the skin. Contains oily components such as higher alcohols, ester oils, animal and vegetable oils, and silicone oils. Oily ingredients are used in various cosmetics, such as basic cosmetics such as cleansing oils, creams and beauty liquids; makeup cosmetics such as foundations, sunscreens, mascara, eye shadows and teaks; shampoos, conditioners, conditioners and dyes. Hair cosmetics such as hair agents and styling agents; used in 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 that is a concern when the oily component is added to the cosmetics, and from the viewpoints of stability when it is added to the cosmetics, safety to the skin or hypoallergenicity, etc. Therefore, development has been carried out to thicken or gel the oily component into a preferable form by using various additives. For example, N-acylamino acid monoamide monoalkyl ester (Patent Document 1) that gives a hard wax-like form that can harden and gel a wide range of oily bases including silicone, and silicone oil can be gelled and compared. Examples thereof include a silicone compound having a polyoxyalkylene group giving a soft paste-like form and an organic group having one or more terminal hydroxyl groups (Patent Document 2). However, since these gelling agents give only a fixed form or property in the form of wax or paste, the range of use thereof has been limited in the application to cosmetics.

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

International Publication No. 2007/078013 Japanese Unexamined Patent Publication No. 2007-254538 Japanese Unexamined Patent Publication No. 2011-102256 Japanese Unexamined Patent Publication No. 2011-225729 Japanese Unexamined Patent Publication No. 2016-102156

The problem to be solved by the present invention is urethane-modified silicone and urethane-modified silicone, which can thicken or gel various kinds of oily components whether they are used alone or in a plurality of kinds. It is an object of the present invention to provide an oil composition containing an oily component and a cosmetic composition containing the oil composition.

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

(In the formula, R ¹ and R ² independently represent divalent hydrocarbon groups having 1 to 20 carbon atoms, x and y independently represent the number of 0 or 1, and l and m respectively. It independently represents a number from 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 of 0 or 1, and the average value of q is 1 to 500. The average value of r is 1 to 500. The arrangement of each structural unit may be block-shaped or random-shaped.)

(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 carbon atoms.)

(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.)

According to the present invention, an oil gel composed of urethane-modified silicone and urethane-modified silicone, which can thicken or gel various kinds of oil-based components, whether they are used alone or in a plurality of kinds. Agents can be provided. Further, according to the present invention, it is possible to provide a thickened or gelled oil composition and a cosmetic.

<Urethane modified silicone>
The urethane-modified silicone of the present invention reacts a silicone compound (A), an oxyalkylene compound (B), a diol compound (C), a monofunctional alcohol compound (D), and a diisocyanate compound (E). Can be 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 these. It is selected from the group consisting of a mixture of.

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

^{R 1} and R ² of the above general formula (a-1) independently represent divalent hydrocarbon groups having 1 to 20 carbon atoms, and examples of such groups 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, isounedecylene group, dodecylene group, isododecylene group, tridecylene group, isotridecylene group, tetradecylene group, isotetradecylene group, pentadecylene group, isopentade Silen group, hexadecylene group, isohexadecylene group, heptadecylene group, isoheptadecylene group, octadecylene group, isooctadecylene group, nonadesilene group, isononadecylene group, icosilene group, isoicocilene group and other alkylene groups; cyclopentylene group , Cycloalkylene groups such as cyclohexylene group, methylcyclohexylene group, dimethylcyclohexylene group; phenylene group, methylphenylene group, ethylphenylene group, propylphenylene group, butylphenylene group, dimethylphenylene group, diethylphenylene group, phenethylene group, etc. Divalent aromatic hydrocarbon groups of. Above all, from the viewpoint of further enhancing the thickening or gelling effect of the obtained urethane-modified silicone, ^{it is preferable that R 1} and R ² are independently alkylene groups having 1 to 20 carbon atoms, respectively, and have 1 to 5 carbon atoms. It is more preferable that it is an alkylene group of, and even more preferably it is an alkylene group having 2 to 3 carbon atoms.

The x and y of the above general formula (a-1) independently represent a number of 0 or 1, respectively. From the viewpoint of further enhancing the thickening or gelling effect of the obtained urethane-modified silicone, x and y are preferably 1 respectively.

L and m in the above general formula (a-1) independently represent numbers 0 to 10. From the viewpoint of further enhancing the thickening or gelling effect of the obtained urethane-modified silicone, it is preferable that l and m are 0 when x and y are 0, respectively. Further, when x and y are 1, respectively, l 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 1 to 500, and the average value of p is preferably 2 to 100 from the viewpoint of further enhancing the thickening or gelling effect of the obtained urethane-modified silicone. 5 to 90 is more preferable, 10 to 80 is even more preferable, and 20 to 70 is even more preferable.

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 obtained urethane-modified silicone. It is preferably 1,000 to 20,000, even more preferably 1,500 to 10,000, and even more preferably 2,000 to 5,000. When the number average molecular weight is larger than 100,000, the thickening or gelling effect of the obtained urethane-modified silicone may decrease, and when it is smaller than 500, the thickening or gelling effect of the obtained urethane-modified silicone is obtained. It may not be possible. In the present invention, the number average molecular weight can be measured by GPC and obtained 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 of 0 or 1, and the average value of q is 1 to 500. The average value of r is 1 to 500. The arrangement of each structural unit may be block-shaped or random-shaped.)

^{R 3} of the above 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 , Straight chain decylene group, isodecylene group, undecylene group, isoundesylene group, dodecylene group, isododecylene group, tridecylene group, isotridecylene group, tetradecylene group, isotetradecylene group, pentadecylene group, isopentadecylene group, hexadecylene group, iso Hexadecylene group, heptadecylene group, isoheptadecylene group, octadecylene group, isooctadecylene group, nonadesilene group, isononadecylene group, icosilene group, isoicocilene group and other alkylene groups; to cyclopentylene group, cyclohexylene group, methylcyclo Cycloalkylene groups such as xylene group and dimethylcyclohexylene group; divalent aromatic hydrocarbons such as phenylene group, methylphenylene group, ethylphenylene group, propylphenylene group, butylphenylene group, dimethylphenylene group, diethylphenylene group and phenethylene group. A hydrogen group can be mentioned. Above all, from the viewpoint of further enhancing the thickening or gelling effect of the obtained urethane-modified silicone, 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 2 carbon atoms. The alkylene group of ~ 3 is even more preferable.

In the above general formula (a-2), n represents a number from 0 to 10. From the viewpoint of further enhancing the thickening or gelling effect of the obtained urethane-modified silicone, it is preferable that n is 0 when z, which will be described later, is 0. Further, when z is 1, n is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 4.

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

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

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

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

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 obtained urethane-modified silicone. It is preferably 1,000 to 20,000, even more preferably 1,500 to 10,000, and even more preferably 2,000 to 5,000. If the number average molecular weight is greater 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 or more of the compounds represented by the general formula (a-1) may be used, and the compound represented by the general formula (a-2) may be used. One or more of them may be used, and one or more of the compounds represented by the general formula (a-1) and one or more of the compounds represented by the general formula (a-2) may be used. Two or more kinds may be used.

In the present invention, from the viewpoint of obtaining a urethane-modified silicone capable of thickening or gelling various kinds of oily components, it is preferable to use a silicone compound containing a compound represented by the general formula (a-2). From the viewpoint of the tactile sensation of the oil composition thickened or gelled by the obtained urethane-modified silicone, it is preferable to use a silicone compound containing the compound represented by the general formula (a-1), and the general formula (a) is preferable. 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) and 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 the thickening or gelling effect of the obtained urethane-modified silicone, (a-1) :( a-2) may be 0.2 to 1: 0 to 0.8 in terms of molar ratio. It is preferably 0.4 to 1: 0 to 0.6, and even more preferably 0.6 to 1: 0 to 0.4 (the total ratio is 1).

By producing the urethane-modified silicone of the present invention using such a compound as the silicone compound (A), a siloxane group, a hydrocarbon group (alkyl group, alkylene group, etc.) can be produced so as to enhance the affinity with various oily components. It is considered that a urethane-modified silicone having a structure in which an oxyalkylene group is distributed two-dimensionally or three-dimensionally in a molecule can be obtained. 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) are described in known methods (for example, JP-A-60-206834 and JP-A-4-88024). The product manufactured by the method described) may be used, or a commercially available product 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. It 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 carbon atoms.)

^{R 4} of the above 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, and 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, undesyl group, isoundesyl 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, nonadecil group, isononadecyl group, icosyl group, isoicosyl group; cycloalkyl group such as cyclopentyl group, cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group; phenyl Examples thereof include monovalent aromatic hydrocarbon groups such as a group, a methylphenyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a dimethylphenyl group, a diethylphenyl group and a phenethyl group. Among them, from the viewpoint of further enhancing the thickening or gelling effect of the obtained urethane-modified silicone, 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 8 carbon atoms. Alkyl groups of ~ 18 are even more preferable, and alkyl groups having 10 to 18 carbon atoms are even more preferable.

^{R 5} of the above 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, as the compound represented by the general formula (b-1), R ⁵ is a compound containing an oxyalkylene group which is an alkylene group having 3 carbon atoms, and R ⁵ is an oxyalkylene group which is an alkylene group having 4 carbon atoms. compounds containing, but R ⁵ may include a compound in which the oxyalkylene group is an oxyalkylene group and R ⁵ is an alkylene group having 3 carbon atoms is an alkylene group having 4 carbon atoms are arranged in a block form or random form, obtained From the viewpoint of the thickening or gelling effect of the urethane-modified silicone, R ⁵ is a compound having an alkylene group having 4 carbon atoms in the general formula (b-1), or R ⁵ is carbon in the general formula (b-1). It is preferable to contain at least one compound in which the oxyalkylene group which is the alkylene group of No. 3 and the oxyalkylene group which is the alkylene group having R ^{5 has 4 carbon atoms are arranged in a block shape or a random shape.}

The s in the above general formula (b-1) represents a number of 2 to 60. Among them, s is preferably 2 to 50, more preferably 2 to 40, still more preferably 3 to 30, and even more preferably 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} of the above 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, as the compound represented by the general formula (b-2), R ⁶ is a compound containing an oxyalkylene group which is an alkylene group having 3 carbon atoms, and R ⁶ is an oxyalkylene group which is an alkylene group having 4 carbon atoms. compounds containing, but R ⁶ can include compounds in which the oxyalkylene group oxyalkylene group and R ⁶ is an alkylene group having 3 carbon atoms is an alkylene group having 4 carbon atoms are arranged in a block form or random form, obtained From the viewpoint of the thickening or gelling effect of the urethane-modified silicone, R ⁶ is a compound having an alkylene group having 4 carbon atoms in the general formula (b-2), or R ⁶ is carbon in the general formula (b-2). It is preferable to contain at least one compound in which the oxyalkylene group, which is the alkylene group of No. 3, and the oxyalkylene group, which is the alkylene group having R ^{6 having 4 carbon atoms, are arranged in a block or random manner.}

In the general formula (b-2), t represents a number of 2 to 60. Among them, t is preferably 5 to 60, more preferably 10 to 50, still more preferably 20 to 42, from the viewpoint of further enhancing the thickening or gelling effect of the obtained urethane-modified silicone.

When the oxyalkylene compound (B) contains a compound represented by the general formula (b-1) and a compound represented by the general formula (b-2), the compound represented by the general formula (b-1). The content ratio of 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 obtained urethane-modified silicone, for example, 0.1 to 0.1 in terms of molar ratio. 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 it is ~ 0.3 (the total ratio is 1 in each case).

By producing the urethane-modified silicone of the present invention using such a compound as the oxyalkylene-based compound (B), the oxyalkylene group is two-dimensionally formed in the urethane-modified silicone molecule so as to enhance the affinity with various oily components. Alternatively, it is considered 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. As a method for producing a compound represented by the general formula (b-1) and a compound represented by the general formula (b-2), for example, one or more compounds having an active hydrogen atom are used as an initiator. Examples thereof include a method of addition polymerization of an alkylene oxide having 3 to 4 carbon atoms. At this time, if a compound having a hydrocarbon group having 1 to 20 carbon atoms and one hydroxyl group is used as the initiator, a compound represented by the general formula (b-1) can be produced, and a water molecule or a water molecule can be produced as the initiator. When a compound having two hydroxyl groups is used, a 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} of the above 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, isoheptyrene group, linear octylene group, isooctylene group, linear nonylene group, isononylene group, direct Alkylene groups such as chain decylene group and isodecylene group; cycloalkylene group such as cyclopentylene group, cyclohexylene group, methylcyclohexylene group and dimethylcyclohexylene group; phenylene group, methylphenylene group, ethylphenylene group, propylphenylene group, Examples thereof include a divalent aromatic hydrocarbon group such as a butylphenylene group, a dimethylphenylene group, a diethylphenylene group and a phenethylene 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 enhancing the thickening or gelling effect of the obtained urethane-modified silicone. 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 more specifically, the compound represented by the general formula (c) is 1,4-benzenedi. 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 since the effect of the present invention can be easily obtained, 1 It is preferable to use the seed compound as a raw material.

By producing the urethane-modified silicone of the present invention using the compound represented by the general formula (c) as the diol compound (C), hydrocarbons are contained in the urethane-modified silicone molecule so as to enhance the affinity with various oily components. It is believed that the groups (preferably alkylene groups) can have a structure that is distributed two-dimensionally or three-dimensionally. 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} of 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, 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 Alkyl group such as group; cycloalkyl group such as cyclopentyl group and cyclohexyl group; monovalent such as phenyl group, methylphenyl group, ethylphenyl group, propylphenyl group, butylphenyl group, dimethylphenyl group, diethylphenyl group, phenethyl group and the like. Aromatic hydrocarbon groups of. Among them, from the viewpoint of further enhancing the thickening or gelling effect of the obtained urethane-modified silicone, 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 having 4 carbon atoms. Alkyl groups of ~ 9 are even more preferred.

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 can be easily obtained. It is preferable to use one kind of compound as a raw material.

By producing the urethane-modified silicone of the present invention using the compound represented by the general formula (d) as the monofunctional alcohol compound (D), the urethane-modified silicone molecule is contained in the urethane-modified silicone molecule so as to enhance the affinity with various oily components. It is believed that the alkyl groups can have a two-dimensional 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} of the above 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, isounedecylene group, dodecylene group, isododecylene group, tridecylene group, isotoridesilene group. , Tetradecylene group, isotetradecylene group, pentadecylene group, isopentadecylene group, hexadecylene group, isohexadecylene group, heptadecylene group, isoheptadecylene group, octadecylene group, isooctadecylene group, nonadesilene group, isononadecylene Alkylene group such as group, icosilene group, isoicocilene group; cycloalkylene group such as cyclopentylene group, cyclohexylene group, methylcyclohexylene group, dimethylcyclohexylene group; phenylene group, methylphenylene group, ethylphenylene group, propylphenylene group , Butylphenylene group, dimethylphenylene group, diethylphenylene group, phenethylene group and other divalent aromatic hydrocarbon groups. Among them, from the viewpoint of further enhancing the thickening or gelling effect of the obtained urethane-modified silicone, 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 4 carbon atoms. An alkylene group of ~ 8 is even more preferable, and an alkylene group having 6 carbon atoms is even more preferable.

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 since the effect of the present invention can be easily obtained, 1 It is preferable to use a compound of the species.

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 a 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 considered to have. When only the compound represented by the general formula (a-1) is used as the silicone compound (A), it is considered that the urethane-modified silicone of the present invention has a molecular structure in which each structural portion 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 portion is three-dimensionally bonded. ..

The number average molecular weight of the urethane-modified silicone of the present invention is not particularly limited, but is preferably 1,000 to 500,000, preferably 2,000 to 400,000, for example, from the viewpoint of thickening or gelling effect. It is more preferably 3,000 to 300,000, still 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) react with each other, and may be produced by a known method. For example, a method may be used in which the components (A) to (E) are put into a reaction system and reacted at the same time, or a part of the components (A) to (E) is put into a reaction system and reacted, and then the rest. A method of adding ingredients and reacting may also be used. From the viewpoint of further enhancing the thickening or gelling effect of the obtained urethane-modified silicone, the components (A) to (C) and the components (E) are put into a reaction system and reacted, and then the component (D) is further enhanced. Is preferred and reacted to produce urethane-modified silicone. At this time, at each reaction stage, the entire amount of each component may be put into the reaction system at one time to react, or each component may be put into several times to react. 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 60 to 170 ° C. at a batch or in several batches for 10 minutes to 5 hours, respectively. And so on.

The compounding ratio of each of the components (A) to (E) in producing the urethane-modified silicone of the present invention is not particularly specified, but the raw material is from the viewpoint of further enhancing the thickening or gelling effect of the obtained urethane-modified silicone. 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 that of the silicone compound (A). 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. It is preferably 1: 0.5 to 2.0: 0.4 to 2.6: 0.05 to 2.0: 2.0 to 5.5, more preferably 1: 0.6. It is even more preferably set to ~ 1.5: 0.5 to 2.2: 0.1 to 1.5: 2.5 to 4.5, and 1: 0.7 to 1.1: 0.5 to. It is even more preferable to set 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 numbers of the diisocyanates and the sum of the number of isocyanate groups of the diisocyanate compound (E) is also not particularly limited, but the urethane modification obtained can be obtained. From the viewpoint of 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 blending the components (A) to (E) in the above blending ratio to produce the urethane-modified silicone of the present invention, a siloxane group and a hydrocarbon group (alkyl group, alkylene) so as to enhance compatibility with various oils are produced. It is considered that a urethane-modified silicone having a structure in which oxyalkylene groups are distributed two-dimensionally or three-dimensionally 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 contains hydroxyl groups other than the above-mentioned (for example, (A) to (D)) that can react with the components (A) to (E) within a range that does not lose the thickening or gelling ability. It may be a urethane-modified silicone obtained by using a compound having an isocyanate group other than (E), a compound having an amino group, etc.), but a siloxane group and carbonizing so as to enhance the affinity with various oils. From the viewpoint of distributing hydrogen groups (alkyl groups, alkylene groups, etc.) and oxyalkylene groups in the molecule two-dimensionally or three-dimensionally to enhance the thickening or gelling effect, only the components (A) to (E) are used. It is preferably a urethane-modified silicone obtained by reacting.

A solvent may or may not be used in 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 even in this state, but the urethane-modified silicone may be used alone by removing the solvent. Any known method may be used for removing the solvent, and examples thereof include vacuum distillation, heating and drying, spray drying, or 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; ester solvents such as ethyl acetate, butyl acetate, methyl branched butyl ketone myristate branched propyl and triglycerides. Can be mentioned. Above all, a solvent having no active hydrogen that reacts with the 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 used when using the solvent is preferably 10 to 95% by mass, more preferably 20 to 85% by mass with respect to the whole system.

It is possible to produce the urethane-modified silicone of the present invention with or without using the catalyst, but from the viewpoint of productivity, the use of the catalyst has the effect of shortening the reaction time. Therefore, it is preferable. Examples of the catalyst that can be used in the production of the urethane-modified silicone of the present invention include strong acids such as sulfuric acid and toluenesulphonic acid; titanium tetrachloride, hafnium chloride, zirconium chloride, aluminum chloride, gallium chloride, indium chloride, iron chloride and tin chloride. , Metal halides such as boron fluoride; hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, potassium acetate, sodium carbonate, alkali earth metals, alcoholates, acetic acid Salts, carbonates; metal oxides such as aluminum oxide, calcium oxide, barium oxide, sodium oxide; organic metals such as tetrabranched 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 with respect to the entire system.

The urethane-modified silicone of the present invention obtained as described above can adjust the viscosity of the oily component by adding it to the oily component, and the viscosity of the oil composition or gel can be adjusted by adjusting the amount of addition. An oil composition in the form can be obtained. Further, various kinds of oily components can be thickened or gelled regardless of whether they are used alone or in a plurality of kinds, for example, hydrocarbon oils, silicone oils, ester oils, higher alcohols and the like. It is possible to thicken or gel the oily component of.

The hydrocarbon oil is not particularly limited, and for example, liquid paraffin, squalane, pristane, zokerite, paraffin, selecin, petrolatum, polyisobutene, polyisoprene, isodecane, isododecane, isohexadecane, normalpentane, isopentane, normal hexane, isohexane, etc. Examples thereof include kerosin, decalin, tetralin, microcrystalline wax and the like.

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

The ester oil is not particularly limited, and monoester oil, diester oil, triester oil, tetraester oil and the like can be used. For example, ethyl acetate, butyl acetate, hexyl acetate, decyl acetate and propionic acid can be used. Butyl, cetyl octanate, 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 sevacinate, cetyl lactate, myristyl lactate, diisobutyl adipate, 2-hexyldecyl adipate, adipine Synthetic esters of di-2-heptylundecyl acid, cetylethylhexanoate, triethylhexanoin, polyglyceryl-2 triisostearate, neopentylglycol dioctanoate, neopentylglycol dicaprate, pentaerythrityltetraisostearate, etc. Oils; Examples include animal and vegetable ester oils such as macadamia nut oil, meadowfoam oil, red flower oil, sunflower oil, avocado oil, lanolin, mink oil, sunflower oil, and olive oil.

The higher alcohol is not particularly limited, and is, for example, a linear higher alcohol such as lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, and cetostearyl alcohol; monostearyl glycerin ether (batyl alcohol), 2. -Branch chain higher alcohols such as decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyldodecanol, isostearyl alcohol, octyldodecanol and the like can be mentioned.

Of the above oily components, those that are solid at room temperature are not used 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 kinds 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, and can be applied to, for example, lubricating oil and cosmetics. The fields of oils, pharmaceuticals, fragrances, paints, fibers and the like can be mentioned, but it is preferable to use them in cosmetics in which the form of the gelled composition and the tactile sensation of the gelled composition are important factors as a commercial 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. .. The specific hydrocarbon oil, silicone oil, and ester oil are not particularly limited, and 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 kinds of oily components depending on the purpose. From the viewpoint of easily obtaining an oil composition having desired properties, it is preferable to use an oily component containing two or more 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 types of oily components, the blending 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 mixing ratio may be 5 to 95:95 to 5 by mass ratio (total mass ratio is 100), and the mixing ratio when using three kinds of oily components is 5 to 90: 5 by mass ratio. It may be ~ 90: 5 to 90 (the total mass ratio is 100). The oil composition of the present invention can be applied to any aspect as long as it uses hydrocarbon oil, silicone oil, ester oil, for example, lubricating oil, cosmetics, pharmaceuticals, fragrances, paints, etc. Although the field of textiles and the like can be mentioned, it is preferable to use it in cosmetics in which the tactile sensation of an oil composition is an important factor as a commercial product.

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

The method for producing an oil composition by adding the urethane-modified silicone of the present invention to the oil-based 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-based component. , A method of mixing and stirring until uniform 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 about 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 an oil composition containing the above-mentioned urethane-modified silicone and an oily component. It is a cosmetic composition to be used. The specific product and form of the cosmetic composition of the present invention are not particularly limited, and include, for example, toiletry products such as shampoo and rinse, for example, lotion, cosmetic liquid, milky lotion, cream, facial cleansing foam, cleansing milk. , Cleansing lotion, hair restorer, hair liquid, set lotion, hair bleach, color rinse, permanent wave liquid, lipstick, pack, foundation, odecolon, shampoo, rinse, treatment, sunscreen, deodorant, perfume, cleansing oil and cosmetic oil, etc. Can be mentioned.

The content of the oil composition of the present invention in the cosmetic composition of the present invention is not particularly specified and may be adjusted according to the mode of use and the purpose of use. For example, with respect 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 tactile sensation of the obtained cosmetic composition. Even more preferably, it is 0.0% by mass. Further, 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 mode of use and the purpose of use. For example, it is 0 with respect to the total mass of the cosmetic composition. It 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 tactile sensation of the obtained cosmetic composition. Even more preferably, it is 0% by mass.

The cosmetic composition of the present invention has various properties (solubility, dispersibility, stability, usability, coatability, permeability, moisturizing property, safety, etc.) during storage, use, and post-use depending on the purpose of use. Other additives commonly used in cosmetic compositions can be used to improve and modify designability, optical properties, aroma, whitening properties, etc.). Other additives include, for example, powder components, waxes, higher fatty acids, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, moisturizers, water-soluble polymers, metal ion sequestering agents. , Lower alcohols, Polyhydric alcohols, Monosaccharides, Oligosaccharides, Polysaccharides, Amino acids and their derivatives, Organic amines, pH adjusters, Vitamin, UV protective ingredients, Antioxidants, Preservatives, Blood circulation promoters, Anti-inflammatory agents, Activators , Whitening agent, anti-fat leak agent, anti-inflammatory agent, various extracts, plant seaweed extract and the like, and one or more of these can be arbitrarily blended.

Examples of the powder component include inorganic powders (eg, talc, kaolin, mica, silk mica (serisite), white mica, gold mica, synthetic mica, red mica, black mica, permiculite, magnesium carbonate, calcium carbonate, silicic acid. Aluminum, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tung acid salt, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (baked sekko), calcium phosphate, fluoroapatite, hydroxyapatite, ceramic powder , Metal soap (eg, zinc myristate, calcium palmitate, aluminum stearate), titanium dioxide, 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, polytetrafluorinated ethylene powder, cellulose powder, etc.); Inorganic white pigments (eg, titanium dioxide, zinc oxide, etc.); Inorganic red pigments (eg, iron oxide (eg, iron oxide) Bengala), 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) Titanium oxide, etc.); 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, etc.) Navy blue, etc.); Pearl pigments (eg, 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 pigments (eg, aluminum powder, etc.) Copper powder, etc.); Organic pigments such as zirconium, barium or aluminum lake (eg, Red 201, Red 202, Red 204, Red 205, Red 220, Red 226, Red 228, Red 405, Organic pigments such as orange 203, orange 204, yellow 205, yellow 401, and blue 404, red 3, red 104, red 106, red 227, red 230, red 401, red. 505, orange 205, yellow 4, yellow 5, yellow 202, yellow 203, green 3 and blue 1 etc.); natural pigments (eg, chlorophyll, β-carotene, etc.) and the like.

Examples of waxes include honey wax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibotarou, whale wax, monttan wax, nukarou, lanolin, capoc wax, lanolin acetate, liquid lanolin, sugar cane, reduced lanolin, jojo lanolin, hard lanolin, and cerac wax. Examples thereof include POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether and the like.

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), and docosahexaenoic acid. (DHA) and the like.

Examples of the anionic surfactant include fatty acid sequent (eg, sodium laurate, sodium palmitate, etc.); higher alkyl sulfate ester salts (eg, sodium lauryl sulfate, potassium lauryl sulfate, etc.); alkyl ether sulfate ester salts (eg, eg, sodium lauryl sulfate). POE-sodium lauryl sulfate triethanolamine, POE-sodium lauryl sulfate, etc.); N-acylsarcosic acid (eg, sodium lauroyl sulcosin, etc.); higher fatty acid amide sulfonate (eg, N-myristoyl-N-methyltaurine sodium, palm). Oil fatty acid methyl taurine sodium, lauryl methyl taurine sodium, etc.); Phosphate ester salts (POE-oleyl ether phosphate sodium, POE-stearyl ether phosphoric acid, etc.); Monolauroyl monoethanolamide polyoxyethylene sulfosuccinate sodium, lauryl polypropylene glycol sulfosuccinate sodium, etc.); ); Higher fatty acid ester sulfate ester salt (eg, hardened coconut oil fatty acid sodium glycerin sulfate, etc.); N-acylglutamate (eg, N-sodium 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-alkylallyl ether sulfonate; α-olefin sulfonate; Higher fatty acid ester sulfonate; Secondary alcohol sulfate Examples thereof include ester salt; higher fatty acid alkyrrole amide sulfate ester salt; sodium lauroyl monoethanolamide succinate; N-palmitoyl aspartate ditriethanolamine; sodium caseinate and the like.

Examples of the cationic surfactant include alkyltrimethylammonium salts (eg, stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, etc.); alkylpyridinium salts (eg, cetylpyridinium chloride, etc.); disstearyldimethylammonium chloride dialkyldimethylammonium salts; Polychloride (N, N'-dimethyl-3,5-methylenepiperidinium); alkyl quaternary ammonium salt; alkyldimethylbenzylammonium salt; alkylisoquinolinium salt; dialkylmoriphonium salt; POE-alkylamine; Examples thereof include an alkylamine salt; a polyamine fatty acid derivative; an ammonium alcohol fatty acid derivative; a benzalconium chloride; and a benzethonium chloride.

Examples of the amphoteric surfactant include imidazoline-based amphoteric surfactants (eg, 2-undesyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroki. Side-1-carboxyethyroxy 2-sodium salt, etc.); Betaine-based surfactants (eg, 2-heptadecyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkylbetaine, amide betaine) , 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 triole). Ate, penta-2-ethylhexylate diglycerol sorbitan, tetra-2-ethylhexylate diglycerol sorbitan, etc.); , Α, α'-Glycerin pyroglutamate oleate, Glycerin apple acid monostearate, etc.); Propropylene glycol fatty acid esters (eg, propylene glycol monostearate, etc.); Hardened 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-Sorbitan monolaurate, etc.) POE-Solbit monooleate, POE-Solbit pentaoleate, POE-Solbit monostearate, etc.); POE-glycerin fatty acid esters (eg, POE-glycerin monostearate, POE-glycerin monoisostearate, POE-glycerin) POE-monooleate such as triisostearate); POE-fatty acid esters (eg, POE-distearate, POE-monodiolate, 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 types (eg, pluronic, etc.); POE / POP-alkyl ethers (eg, POE) / POP-cetyl ether, POE / POP-2-decyltetradecyl ether, POE / POP-monobutyl ether, POE / POP-hydrogenated lanolin, POE / POP-glycerin ether, etc.); Tetra POE / Tetra POP-ethylene diamine condensate Kind (for example, Tetronic ); POE-cured bean oil hardened bean oil derivative (for example, POE-hidashi oil, POE-hardened bean oil, POE-hardened bean oil monoisostearate, POE-hardened bean oil triisostearate, POE-hardened bean paste Oil monopyroglutamic acid monoisostearic acid diester, POE-hardened castor oil maleic acid, etc.); POE-mitsurou lanolin derivative (eg, POE-Sorbit honeyrow, etc.); alkanolamide (eg, coconut oil fatty acid diethanolamide, lauric acid monoethanol) Amid, fatty acid isopropanolamide, etc.); POE-propylene glycol fatty acid ester; POE-alkylamine; POE-fatty acid amide; sucrose fatty acid ester; alkylethoxydimethylamine oxide; trioleyl phosphate and the like.

Examples of the moisturizing agent include polyethylene glycol, xylitol, sorbitol, martitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate, bile salt, and dl-pyrrolidone carboxylic acid. Examples thereof include acid salts, short-chain soluble collagen, diglycerin (EO) PO adducts, Izayoibara extract, Seiyo-no-kogirisou extract, Merirot extract and the like.

Natural water-soluble polymers include, for example, plant-based polymers (eg, Arabic gum, tragacanto gum, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, canten, quince seed (malmero), algae colloid (cassow extract), starch. (Rice, corn, potato, wheat), glycyrrhizinic acid); Micromolecular macromolecules (eg, xanthan gum, dextran, succinoglucan, burran, gellan gum, etc.); Animal macromolecules (eg, collagen, casein, albumin, gelatin, etc.) ) Etc. can be mentioned.

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

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

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

Examples of the polyvalent alcohol include trivalent alcohols (eg, glycerin, trimethylolpropane, etc.); tetravalent alcohols (eg, pentaerythritol such as 1,2,6-hexanetriol, etc.); pentavalent alcohols (eg, pentaerythritol, etc.); Xylitol, etc.); Hexoic alcohols (eg, sorbitol, mannitol, etc.); Polyhydric alcohol polymers (eg, diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, etc.) 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 mono Butyl ether, propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, etc.; dihydric alcohol ether esters (eg, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono). Butyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diazibate, ethylene glyco Ludisuccinate, 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 (eg, Kimi) Lu alcohol, ceracyl alcohol, bacil alcohol, etc.); Sugar alcohols (eg, sorbitol, martitol, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, starch-degrading sugar, maltose, xylitos, starch-degrading sugar-reducing alcohol) Etc.); Glysolid; Tetrahydroflufuryl alcohol; POE-Tetrahydrofurfuryl alcohol; POP-butyl ether; POP / POE-butyl ether; Tripolyoxypropylene glycerin ether; POP-glycerin ether; POP-glycerin ether phosphate; POP / POE-pentane erythritol ether, polyglycerin and the like can be mentioned.

Examples of the monosaccharide include tricarbose (eg, D-glycerylaldehyde, dihydroxyacetone, etc.); tetracarbose (eg, D-erythrose, D-erythrose, D-treose, erythritol, etc.); , L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-librose, D-xylrose, L-xylrose, etc.); -Bushicose, D-galactose, D-fluctose, L-galactose, L-mannose, D-tagatose, etc.); Seven-carbon sugar (eg, aldoheptose, heprose, etc.); For example, 2-deoxy-D-ribose, 6-deoxy-L-galactose, 6-deoxy-L-mannose, etc.; amino sugars (eg, D-glucosamine, D-galactosamine, sialic acid, aminouronic acid, muramic acid, etc.) ); Uronic acid (for example, D-glucuronic acid, D-mannuronic acid, L-gluuronic acid, D-galacturonic acid, L-isulonic acid, etc.) and the like.

Examples of oligosaccharides include sucrose, umbelliferose, lactose, planteose, isolikunoses, α, α-trehalose, raffinose, lycnoses, umbilicin, stachyose velva course and the like.

Examples of polysaccharides include cellulose, quince seed, chondroitin sulfate, starch, galactan, dermatan sulfate, glycogen, Arabic gum, heparan sulfate, hyaluronic acid, tragant gum, keratan sulfate, chondroitin, xanthan gum, mucoitin sulfate, guagam, dextran, and kerato sulfate. , Locust bin gum, 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 acyl sarcosine sodium (lauroyl sarcosine sodium), acyl glutamate, acyl β-alanine sodium, glutathione, pyrrolidone carboxylic acid and the like.

Examples of the organic amine include monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol and the like. Can be mentioned.
Examples of the pH adjuster include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinate-sodium succinate.

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

As the ultraviolet protective component, an inorganic ultraviolet protective component such as a powder pigment or a metal powder pigment, a surface-treated product thereof, or an organic ultraviolet protective component can be used, for example, titanium oxide, zinc oxide, or oxidation. Metal oxides such as cerium, low-order titanium oxide, iron-doped titanium oxide, metal hydroxides such as iron hydroxide, metal flakes such as plate-shaped iron oxide and 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 treatment, N-acylated lysine treatment, polyacrylic acid treatment, metal soap treatment, acrylic resin treatment , Metal oxide-treated products, salicylic acid-based, paraaminobenzoic acid-based, benzophenone-based, silicic acid-based, benzoylmethane-based, 2-cyano-3,3-diphenylprop-2-enoic acid 2-ethylhexyl ester, dimethoxy 2-Ethylhexyl benzilidendioxoimidazolidinepropionate, 1- (3,4-dimethoxyphenyl) -4,4-dimethyl-1,3-pentandione, cinoxate, methyl-O-aminobenzoate, 2-ethylhexyl- 2-Cyano-3,3-diphenylacrylate, 3- (4-methylbenzylidene) camphor, octyltriazone, 4- (3,4-dimethoxyphenylmethylene) -2,5-dioxo-1-imidazolidinepropionic acid 2 -Ethylhexyl, these polymer derivatives and the like can be mentioned.

Other compoundable components include, for example, preservatives (methylparaben, ethylparaben, butylparaben, phenoxyethanol, etc.); anti-inflammatory agents (eg, glycyrrhizinic acid derivative, glycyrrhetinic acid derivative, salicylic acid derivative, hinokithiol, zinc oxide, allantin, etc.); Whitening agents (eg, yukinoshita extract, albutin, etc.); various extracts (eg, sardine, auren, shikon, shakuyaku, senburi, birch, sage, biwa, carrot, aloe, zeniaoi, iris, grape, yokunin, hechima, lily) , Saffron, Senkyu, Shokyu, Otogirisou, Ononis, Garlic, Togarashi, Chimpi, Touki, Seaweed, etc.), Activators (eg, Royal Jelly, Photosensitizer, Cholesterol Derivatives, etc.); Niacinic acid β-butoxyethyl ester, capsaicin, zingeron, cantalistinki, ictamol, tannic acid, α-borneol, tocopherol nicotinate, inositol hexanicotinate, cyclanderlate, cinnaridine, trazoline, acetylcholine, verapamil, cepharanthin, γ- Orizanol, etc.); Anti-lipid leaking agents (eg, sulfur, thiantoll, 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 and purpose of use, for example, 0.01 to 0.01. 10.0% by mass may be added respectively.

Hereinafter, the present invention will be specifically described with reference to 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 in the production of urethane-modified silicone are shown below.

<Silicone compound (A)>
-Silicone compound 1
In the general formula (a-1), R ¹ and R ² are independently ethylene groups, x and y are 1 respectively, l and m are 3 respectively, and the average value of p is 39. , Compound / Silicone compound 2 having a number average molecular weight of 3200 g / mol
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 the number. Compounds with 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). System 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 3 carbon atoms, and R ⁵ is an oxyalkylene group having 4 carbon atoms. And oxyalkylene compound 3 in a random manner with a molar ratio of 8: 7 and s of 12 to 18 (average value is 15).
In the general formula (b-2), R ⁶ is an alkylene group having 4 carbon atoms, and t is 30 to 42 (average value is 36).

<Glycol compound (C)>
-Glycol compound 1
1,4-Benzene dimethanol / 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
In the general formula (e), R ⁹ is a compound having a hexamethylene group.

[Manufacturing 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 diol compound in a four-necked flask equipped with a thermometer, nitrogen introduction tube, reflux cooling tube and stirrer. 1.48 g (10.7 mmol) of 1 was added, the inside of the system was replaced with nitrogen, the temperature was raised to 140 ° C., 7.07 g (42.0 mmol) of diisocyanate compound 1 was added, and the temperature was 140 ° C. for 4 hours. It was reacted. After completion of the reaction, 2.49 g (19.1 mmol) of monofunctional alcohol compound 1 was added and further reacted at 140 ° C. for 30 minutes, and the infrared spectroscope (IR) did not absorb isocyanate (all isocyanate groups reacted). The reaction was terminated after confirming that the reaction was completed, and urethane-modified silicone 1 was obtained.

[Manufacturing of urethane-modified silicones 2 to 13]
Urethane-modified silicones 2 to 13 were obtained by reacting each raw material by the same method as 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 (mmol) of the raw material used in the production of each polymer.

[Thickening / gelling test]
Urethane-modified silicones 1 to 13 (urethane-modified silicones 1 to 6 are examples, urethane-modified silicones 7 to 13 are comparative examples) are placed in a 50 ml glass bottle, and urethane-modified silicone is 5.0% by mass based on the total mass of the oil composition. An oil composition was prepared by adding to the following nine kinds of oily components so as to be uniform, heating at 120 to 130 ° C. and shaking to homogenize. 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.

<Oil component used>
Oil component 1: Isododecan Oil component 2: Diphenylsiloxyphenyltrimethicone Oil component 3: Cyclopentasiloxane Oil component 4: Ethylhexyl palmitate Oil component 5: Neopentyl glycol dicaprate Oil component 6: Triethylhexanoin Oil component 7: Triethylhexa Mixed oil of noin and isododecane (mass ratio 5:90)
Oil component 8: Mixed oil of triethylhexanoin and cyclopentasiloxane (mass ratio 5:90)
Oil component 9: Mixed oil of triethylhexanoin and diphenylsiloxane phenyltrimethicone (mass ratio 5:90)

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

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 with respect to various hydrocarbon oils, silicone oils, ester oils and mixed oils thereof. rice field. On the other hand, the urethane-modified silicones 7 to 13 of the comparative example exhibit thickening or gelling ability only for a specific oily component, or do not exhibit thickening or gelling ability for any of the oily components. rice field.

The urethane-modified silicone of the present invention can thicken or gel various kinds of oily components such as hydrocarbon oils, silicone oils, and ester oils, whether they are used alone or in a plurality of kinds. , A new polymer. The urethane-modified silicone of the present invention can thicken or gel more kinds of oily components and combinations thereof so as to have a desired tactile sensation 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 aspects that could not be used so far.

Claims (12)

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

(In the formula, R ¹ and R ² independently represent divalent hydrocarbon groups having 1 to 20 carbon atoms, x and y independently represent the number of 0 or 1, and l and m respectively. It independently represents a number from 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 of 0 or 1, and the average value of q is 1 to 500. The average value of r is 1 to 500. The arrangement of each structural unit may be block-shaped or random-shaped.)

(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 carbon atoms.)

(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.) 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 an 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 shape or a random shape, a compound in which R ⁶ is an alkylene group having 4 carbon atoms in the general formula (b-2), and from a compound R ⁶ in general formula (b-2) is an oxyalkylene group and R ⁶ is an alkylene group of 3 carbon atoms and the oxyalkylene groups is an alkylene group having 4 carbon atoms are arranged in a block form or random form The urethane-modified silicone according to claim 1, which comprises at least one selected from the group. The urethane-modified silicone according to claim 1 or 2, wherein the diol compound (C) contains 1,4-benzenedimethanol. The urethane-modified silicone according to any one of claims 1 to 3, wherein the diisocyanate compound (E) contains a compound in which R ^{9 is an alkylene group having 4 to 8 carbon atoms in the general formula (e).} The urethane-modified silicone according to any one of claims 1 to 4, wherein the silicone compound (A) comprises a compound represented by the general formula (a-1) having a number average molecular weight of 500 to 100,000. A gelling agent for oil, which comprises the urethane-modified silicone according to any one of claims 1 to 5. 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. The oil composition according to claim 7, wherein the content of the urethane-modified silicone is 0.1% by mass to 20% by mass with respect to the total mass of the oil composition. A cosmetic composition containing the oil composition according to claim 7 or 8. The silicone compound (A) selected from the group consisting of the compound represented by the following general formula (a-1), the compound represented by the following general formula (a-2), and a mixture thereof, and the following general 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, and the following general formula. The diol compound (C) represented by (c), the monofunctional alcohol compound (D) represented by the following general formula (d), and the diisocyanate compound (E) represented by the following general formula (e). A method for producing a urethane-modified silicone, which comprises reacting with and.

(In the formula, R ¹ and R ² independently represent divalent hydrocarbon groups having 1 to 20 carbon atoms, x and y independently represent the number of 0 or 1, and l and m respectively. It independently represents a number from 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 of 0 or 1, and the average value of q is 1 to 500. The average value of r is 1 to 500. The arrangement of each structural unit may be block-shaped or random-shaped.)

(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 carbon atoms.)

(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.) Use of the urethane-modified silicone according to any one of claims 1 to 5 for thickening or gelling an oily component. 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.