JP2020045438A - Modified silicone and modified silicone production method - Google Patents

Abstract

To provide a modified silicone that can be used as a thickening-gelating agent capable of thickening and gelating, with a small amount of addition, various oily components, particularly silicone oil, ester oil, hydrocarbon oil or the like.SOLUTION: The present invention provides a modified silicone that is obtained by the reaction between a specific silicone derivative raw material having a hydroxy group or an amino group and a mono isocyanate compound raw material.SELECTED DRAWING: None

Description

  The present invention relates to a modified silicone that can be used as a thickener / gelling agent for various oily components. More specifically, the present invention relates to a novel modified silicone capable of thickening and gelling various oil components such as silicone oil, ester oil, and hydrocarbon oil so as to have good feel and elasticity at a low addition amount, and a method for producing the same. .

  In the fields of cosmetics, foods, fuel oils, lubricating oils and the like, various oils (oils) such as mineral oils, animal and vegetable oils, and synthetic oils are often thickened and solidified, and various gelling agents are used. -Thickeners have been proposed. Among these, in cosmetics, for example, by thickening oil components such as hydrocarbon oils, ester oils, animal and vegetable oils, silicone oils, polyhydric alcohols, etc., the effect of giving softness to the skin, skin slipping It can be expected to improve the skin, keep the skin moist, and remove excess oil from the skin. Accordingly, gelling agents and thickeners are basic cosmetics such as cleansing oils, creams, and serums; makeup cosmetics such as foundations, sunscreens, mascaras, eye shadows, and teaks; shampoos, rinses, conditioners, and hair dyes Hair cosmetics as styling agents; used as raw materials for lip cosmetics such as lipstick and lip gloss.

  Generally, the oily component is often concerned with the sticky feeling, safety and irritation to the skin, and the stability when blended in cosmetics, which are characteristic of the oily component. Among the above oily components, ester oils and silicone oils are known to have high safety, have a relatively low stickiness and low irritation. Therefore, it is widely used as an oily component to be blended in cosmetics, and various gelling agents and thickeners have been proposed so far.

  Examples of the thickening / gelling agent developed so far include, for example, N-acylamino acid monoamide monoalkyl ester which gives a hard wax-like form, capable of solidifying and gelling a wide range of oily bases including silicone. (Patent Document 1) and a silicone compound having a polyoxyalkylene group capable of gelling silicone oil and giving a relatively soft paste-like form and an organic group having at least one terminal hydroxyl group (Patent Document 2). No. However, since they only give a fixed form or property such as a wax or paste, the range of use in cosmetic applications is limited. Accordingly, polyurethane compounds (Patent Documents 3 and 4), which have a more elastic form and provide a gel-like or jelly-like form that can be used in a wide range of cosmetics that give a good feel and spread to the skin, have also been developed. Have been. However, since it is practically essential to use a heavy metal-containing catalyst such as a tin-based metal compound at the time of synthesis, and the amount thereof is extremely large to obtain a thickening / gelling effect, these It was not sufficient as an additive to be added to the mixture.

  Thickening and gelling of various oily components, especially thickening and gelling of silicone oil, ester oil and hydrocarbon oil, for example, lead to diversification of cosmetics, that is, development of various forms of oil products. This is a remarkable technology for. Therefore, the market demands the development of a thickening / gelling agent having a higher oil thickening effect, and can be industrially manufactured without using a heavy metal-containing catalyst, and has a good effect at a low addition amount. There is a need for the development of additives capable of thickening and gelling various oily components so as to have feel and elasticity.

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

  Therefore, the problem to be solved by the present invention is to use various oily components, especially silicone oil, ester oil, hydrocarbon oil and the like, as a thickening / gelling agent capable of thickening / gelling with a small amount of addition. It is to provide a modified silicone which is possible.

  Therefore, the present inventors have studied diligently, and have found a novel modified silicone capable of thickening and gelling various oily components such as silicone oil, ester oil, and hydrocarbon oil with a small addition amount, and have reached the present invention. . That is, it is a modified silicone having a structure represented by the following general formula (I-i) or the following general formula (II-i).

(Wherein, R ¹ and R ² each independently represent a hydrocarbon chain having 1 to 8 carbon atoms, and X ¹ and X ² each independently represent a hydrogen atom, a hydroxyl group, an amino group, or a compound represented by the following general formula: A group represented by the following general formula (Ii-1), a group represented by the following general formula (Ii-2), or a group represented by the following general formula (Ii-2) Ii-3) represents any of the groups represented by the following formula (wherein at least one of X ¹ and X ² is a group represented by the general formula (I-i-1), a group represented by the general formula (I-i) 2) or a group represented by the general formula (Ii-3)), and the value of a represents a number from 0 to 2000.)

(In the formula, R ¹¹ represents a hydrocarbon chain having 1 to 10 carbon atoms.)

(In the formula, R ²¹ represents a residue of a monoisocyanate compound.)

(In the formula, R ²² represents a residue of a monoisocyanate compound.)

(In the formula, R ²³ represents a residue of a monoisocyanate compound, and R ¹² represents a hydrocarbon chain having 1 to 10 carbon atoms.)

(Wherein, R ⁵ and R ⁶ each independently represent a hydrocarbon chain having 1 to 20 carbon atoms, X ⁵ represents a hydroxyl group, an amino group, or a group represented by the general formula (b-1); ⁶ is a group represented by the following general formula (II-i-1), a group represented by the following general formula (II-i-2), or a group represented by the following general formula (II-i-3) The value of c represents the number of 1 to 2000, the value of d represents the number of 0 to 1000, the value of e represents the number of 1 to 1000, and the average of c, d and e The ratio c: d: e is 200 to 0.1: 0.99 to 0: 1 to 0.01 (the sum of the ratios of d and e is 1), provided that the unit units are arranged in a block or random arrangement. Any of them may be used, and a combination of a block-shaped portion and a random-shaped portion may be used.)

(In the formula, R ¹⁵ represents a hydrocarbon chain having 1 to 10 carbon atoms.)

(In the formula, R ²⁴ represents a residue of a monoisocyanate compound.)

(In the formula, R ²⁵ represents a residue of a monoisocyanate compound.)

(In the formula, R ²⁶ represents a residue of a monoisocyanate compound, and R ¹⁶ represents a hydrocarbon chain having 1 to 10 carbon atoms.)

  An effect of the present invention is to provide a novel modified silicone capable of thickening and gelling various oil components such as silicone oil, ester oil, and hydrocarbon oil with a small amount of addition, and a method for producing the same. .

  The modified silicone of the present invention is a gel-like or jelly-like oil having good feel and elasticity by thickening and gelling various oily components such as silicone oil, ester oil and hydrocarbon oil in a small amount. A novel compound capable of forming a similar composition, specifically, a modified silicone having a structure represented by the following general formula (I-i) or the following general formula (II-i).

(Wherein, R ¹ and R ² each independently represent a hydrocarbon chain having 1 to 8 carbon atoms, and X ¹ and X ² each independently represent a hydrogen atom, a hydroxyl group, an amino group, or a compound represented by the following general formula: A group represented by the following general formula (Ii-1), a group represented by the following general formula (Ii-2), or a group represented by the following general formula (Ii-2) Ii-3) represents any of the groups represented by the following formula (wherein at least one of X ¹ and X ² is a group represented by the general formula (I-i-1), a group represented by the general formula (I-i) 2) or a group represented by the general formula (Ii-3)), and the value of a represents a number from 0 to 2000.)

(In the formula, R ¹¹ represents a hydrocarbon chain having 1 to 10 carbon atoms.)

(In the formula, R ²¹ represents a residue of a monoisocyanate compound.)

(In the formula, R ²² represents a residue of a monoisocyanate compound.)

(In the formula, R ²³ represents a residue of a monoisocyanate compound, and R ¹² represents a hydrocarbon chain having 1 to 10 carbon atoms.)

R ¹ and R ^{2 in the} general formula (Ii) each independently represent a hydrocarbon chain having 1 to 8 carbon atoms. Examples of such a hydrocarbon chain include straight-chain saturated hydrocarbons having 1 to 8 carbon atoms. , Straight-chain unsaturated hydrocarbons having 1 to 8 carbon atoms, branched saturated hydrocarbons having 2 to 8 carbon atoms, branched unsaturated hydrocarbons having 2 to 8 carbon atoms and the like, and ranges that do not impair the effects of the present invention. And may have a functional group such as an ether group, a carbonyl group, and an ester group. Among them, R ¹ and R ² are each preferably a straight-chain saturated hydrocarbon having 1 to 8 carbon atoms or a branched saturated hydrocarbon having 2 to 8 carbon atoms, from the viewpoint of the thickening and gelling effects of the modified silicone. More preferably a straight-chain saturated hydrocarbon having 1 to 8 carbon atoms, even more preferably a straight-chain saturated hydrocarbon having 1 to 6 carbon atoms, such as a methylene group, an ethylene group, a propylene group, and a trimethylene group. Particularly preferred are straight-chain saturated hydrocarbons having the formulas 1 to 3.

  The value of a represents a number from 0 to 2000. Among them, from the viewpoint of enhancing the thickening / gelling effect of the modified silicone, 0 to 1000 is preferable, 0 to 500 is more preferable, 1 to 200 is more preferable, and 1 to 100 is particularly preferable. In addition, the average value of a is preferably 2 to 500, more preferably 3 to 200, and still more preferably 5 to 100, from the viewpoint of enhancing the thickening and gelling effects of the modified silicone.

R ^{11 in the} general formula (a-1) represents a hydrocarbon chain having 1 to 10 carbon atoms. Examples of such a hydrocarbon chain include a linear saturated hydrocarbon chain having 1 to 10 carbon atoms, and a hydrocarbon chain having 1 to 10 carbon atoms. Straight-chain unsaturated hydrocarbon chain, a branched saturated hydrocarbon chain having 2 to 10 carbon atoms, a branched unsaturated hydrocarbon chain having 2 to 10 carbon atoms and the like, and within a range that does not impair the effects of the present invention. It may have a functional group such as an ether group, a carbonyl group and an ester group. Among them, R ¹¹ is preferably a straight-chain saturated hydrocarbon having 1 to 10 carbon atoms or a branched saturated hydrocarbon chain having 2 to 10 carbon atoms, from the viewpoint of the thickening / gelling effect of the modified silicone. It is more preferably a straight-chain saturated hydrocarbon having 1 to 10 carbon atoms, and further preferably a straight-chain saturated hydrocarbon having 2 to 8 carbon atoms.

R ²¹ in the general formula (I-i-1) represents a residue of a monoisocyanate compound, and is, for example, a total of a hydrocarbon group containing a linear alkyl group having 1 to 30 carbon atoms, a main chain, and a side chain. A hydrocarbon group containing a branched alkyl group having 3 to 30 carbon atoms, a hydrocarbon group containing a cycloalkyl group having 3 to 8 carbon atoms, and an aromatic hydrocarbon having 1 to 4 aromatic rings having 4 to 12 carbon atoms. And a hydrogen group. Among them, a hydrocarbon group containing a straight-chain alkyl group having 1 to 30 carbon atoms or an aromatic ring having 4 to 12 carbon atoms from the viewpoint of enhancing the thickening / gelling ability so as to have a good feel and elasticity. Is preferably an aromatic hydrocarbon group having from 1 to 4 aromatic hydrocarbon groups. Among them, the aromatic hydrocarbon group having 1 to 4 aromatic rings having 4 to 12 carbon atoms has 1 to 2 aromatic rings having 4 to 8 carbon atoms from the viewpoint of increasing the viscosity and gelling ability. It is more preferably an aromatic hydrocarbon group, more preferably an aromatic hydrocarbon group having 1 to 2 aromatic rings having 6 carbon atoms, and more preferably an aromatic hydrocarbon group having 1 aromatic ring having 6 carbon atoms. Particularly preferred is a group.

R ²² in the general formula (I-i-2) represents the residue of a monoisocyanate compound, for example, hydrocarbon groups having a carbon number containing a linear alkyl group of 1 to 30, the sum of the main chain and the side chain A hydrocarbon group containing a branched alkyl group having 3 to 30 carbon atoms, a hydrocarbon group containing a cycloalkyl group having 3 to 8 carbon atoms, and an aromatic hydrocarbon having 1 to 4 aromatic rings having 4 to 12 carbon atoms. And a hydrogen group. Among them, a hydrocarbon group containing a straight-chain alkyl group having 1 to 30 carbon atoms or an aromatic ring having 4 to 12 carbon atoms from the viewpoint of enhancing the thickening / gelling ability so as to have a good feel and elasticity. Is preferably an aromatic hydrocarbon group having from 1 to 4 aromatic hydrocarbon groups. Among them, the aromatic hydrocarbon group having 1 to 4 aromatic rings having 4 to 12 carbon atoms has 1 to 2 aromatic rings having 4 to 8 carbon atoms from the viewpoint of increasing the viscosity and gelling ability. It is more preferably an aromatic hydrocarbon group, more preferably an aromatic hydrocarbon group having 1 to 2 aromatic rings having 6 carbon atoms, and more preferably an aromatic hydrocarbon group having 1 aromatic ring having 6 carbon atoms. Particularly preferred is a group.

R ²³ in the general formula (I-i-3) represents the residue of a monoisocyanate compound, for example, hydrocarbon groups having a carbon number containing a linear alkyl group of 1 to 30, the sum of the main chain and the side chain A hydrocarbon group containing a branched alkyl group having 3 to 30 carbon atoms, a hydrocarbon group containing a cycloalkyl group having 3 to 8 carbon atoms, and an aromatic hydrocarbon having 1 to 4 aromatic rings having 4 to 12 carbon atoms. And a hydrogen group. Among them, a hydrocarbon group containing a straight-chain alkyl group having 1 to 30 carbon atoms or an aromatic ring having 4 to 12 carbon atoms from the viewpoint of enhancing the thickening / gelling ability so as to have a good feel and elasticity. Is preferably an aromatic hydrocarbon group having from 1 to 4 aromatic hydrocarbon groups. Among them, the aromatic hydrocarbon group having 1 to 4 aromatic rings having 4 to 12 carbon atoms has 1 to 2 aromatic rings having 4 to 8 carbon atoms from the viewpoint of increasing the viscosity and gelling ability. It is more preferably an aromatic hydrocarbon group, more preferably an aromatic hydrocarbon group having 1 to 2 aromatic rings having 6 carbon atoms, and more preferably an aromatic hydrocarbon group having 1 aromatic ring having 6 carbon atoms. Particularly preferred is a group.

R ¹² represents a hydrocarbon chain having 1 to 10 carbon atoms. Examples of such a hydrocarbon chain include a linear saturated hydrocarbon chain having 1 to 10 carbon atoms and a linear unsaturated hydrocarbon chain having 1 to 10 carbon atoms. And a branched saturated hydrocarbon chain having 2 to 10 carbon atoms, a branched unsaturated hydrocarbon chain having 2 to 10 carbon atoms, and an ether group, a carbonyl group, and an ester group as long as the effects of the present invention are not impaired. And the like. Among them, R ¹² is preferably a straight-chain saturated hydrocarbon having 1 to 10 carbon atoms or a branched saturated hydrocarbon chain having 2 to 10 carbon atoms, from the viewpoint of the thickening and gelling effects of the modified silicone. It is more preferably a straight-chain saturated hydrocarbon chain having 1 to 8 carbon atoms, further preferably a straight-chain saturated hydrocarbon chain having 2 to 6 carbon atoms, and a straight-chain saturated hydrocarbon chain having 2 carbon atoms. Is particularly preferred.

The modified silicone represented by the general formula (I-i) can exhibit a thickening / gelling ability to various oily components by having the above-mentioned structure, but has a more thickening / gelling effect. from the viewpoint of enhancing, preferably ^{X 1} and ^{X 2} is a group represented by the general formula (I-i-1) or general formula (I-i-2), X 1 and ^{X 2} are the general formula More preferably, it is a group represented by (I-i-2).

  The weight average molecular weight of the modified silicone represented by the general formula (I-i) is preferably 500 to 100,000, and 2,000 to 40,000, since a thickening / gelling effect is easily obtained. Is more preferable, and it is still more preferable that it is 3,000 to 10,000. When the weight average molecular weight is larger than 100,000 or smaller than 500, the thickening / gelling effect may be reduced. In the present invention, all weight average molecular weights can be measured by gel permeation chromatography (GPC) and calculated in terms of styrene.

  Among the modified silicones represented by the general formula (Ii), from the viewpoint of further increasing the thickening / gelling ability to various oily components so as to have good feel and elasticity at a low addition amount, the following general formula: Modified silicone having the structure represented by (I-ii) is preferred.

(Wherein, R ³ and R ⁴ each independently represent a hydrocarbon chain having 1 to 8 carbon atoms, and X ³ and X ⁴ each independently represent a hydrogen atom, a hydroxyl group, an amino group, or a compound represented by the following general formula ( a′-1), a group represented by the following general formula (I-ii-1), a group represented by the following general formula (I-ii-2), or a group represented by the following general formula (I-ii-2) Represents any of the groups represented by I-ii-3) (provided that at least one of X ³ and X ⁴ is a group represented by the general formula (I-ii-1), a group represented by the general formula (I-ii) -2) or a group represented by general formula (I-ii-3)), and the value of b represents a number from 0 to 2000.)

(In the formula, R ¹³ represents a hydrocarbon chain having 1 to 10 carbon atoms.)

(Where p represents a number from 0 to 29)

(Where q represents a number from 0 to 29)

(Wherein, R ¹⁴ represents a hydrocarbon chain having 1 to 10 carbon atoms, and r represents a number of 0 to 29)

R ³ and R ^{4 in the} general formula (I-ii) each independently represent a hydrocarbon chain having 1 to 8 carbon atoms. Examples of such a hydrocarbon chain include straight-chain saturated hydrocarbons having 1 to 8 carbon atoms. , Straight-chain unsaturated hydrocarbons having 1 to 8 carbon atoms, branched saturated hydrocarbons having 2 to 8 carbon atoms, branched unsaturated hydrocarbons having 2 to 8 carbon atoms, and the like, and ranges that do not impair the effects of the present invention. Among them, it may have a functional group such as an ether group, a carbonyl group and an ester group. Above all, from the viewpoint of the thickening and gelling effects of the modified silicone, R ³ and R ⁴ may each be a straight-chain saturated hydrocarbon having 1 to 8 carbon atoms or a branched saturated hydrocarbon having 2 to 8 carbon atoms. Preferably, it is a straight-chain saturated hydrocarbon having 1 to 8 carbon atoms, more preferably a straight-chain saturated hydrocarbon having 1 to 6 carbon atoms, such as a methylene group, an ethylene group, a propylene group, and a trimethylene group. Particularly preferred is a straight-chain saturated hydrocarbon having 1 to 3 carbon atoms.

  The value of b represents a number from 0 to 2000. Among them, from the viewpoint of enhancing the thickening / gelling effect of the modified silicone, 0 to 1000 is preferable, 0 to 500 is more preferable, 1 to 200 is more preferable, and 1 to 100 is particularly preferable. In addition, the average value of b is preferably from 2 to 500, more preferably from 3 to 200, and still more preferably from 5 to 100, from the viewpoint of enhancing the thickening / gelling effect of the modified silicone.

R ^{13 in the} general formula (a′-1) represents a hydrocarbon chain having 1 to 10 carbon atoms. Examples of such a hydrocarbon chain include a linear saturated hydrocarbon chain having 1 to 10 carbon atoms and a carbon chain having 1 to 10 carbon atoms. 10 straight-chain unsaturated hydrocarbon chains, branched saturated hydrocarbon chains having 2 to 10 carbon atoms, branched unsaturated hydrocarbon chains having 2 to 10 carbon atoms, and the like, provided that the effects of the present invention are not impaired. , An ether group, a carbonyl group, an ester group and the like. Among them, R ¹³ is preferably a straight-chain saturated hydrocarbon having 1 to 10 carbon atoms or a branched saturated hydrocarbon chain having 2 to 10 carbon atoms, from the viewpoint of the thickening / gelling effect of the modified silicone. It is more preferably a straight-chain saturated hydrocarbon chain having 1 to 8 carbon atoms, further preferably a straight-chain saturated hydrocarbon chain having 2 to 6 carbon atoms, and a straight-chain saturated hydrocarbon chain having 2 carbon atoms. Is particularly preferred.

  P in the general formula (I-ii-1) represents a number from 0 to 29. Above all, p is preferably 2 to 25, more preferably 9 to 23, and more preferably 13 to 21 from the viewpoint of enhancing the thickening / gelling ability so as to have good feel and elasticity. More preferably, it is particularly preferably 15 to 19.

  Q in the general formula (I-ii-2) represents a number of 0 to 29. Among them, q is preferably 2 to 25, more preferably 9 to 23, and more preferably 13 to 21, from the viewpoint of enhancing the thickening / gelling ability so as to have a good feel and elasticity. More preferably, it is particularly preferably 15 to 19.

  R in the general formula (I-ii-3) represents a number from 0 to 29. Among them, r is preferably 2 to 25, more preferably 9 to 23, and more preferably 13 to 21, from the viewpoint of enhancing the thickening / gelling ability so as to have good feel and elasticity. More preferably, it is particularly preferably 15 to 19.

R ¹⁴ represents a hydrocarbon chain having 1 to 10 carbon atoms, such as a linear saturated hydrocarbon having 1 to 10 carbon atoms, a linear unsaturated hydrocarbon having 1 to 10 carbon atoms, Examples include a branched saturated hydrocarbon having 2 to 10 carbon atoms and a branched unsaturated hydrocarbon having 2 to 10 carbon atoms, and a functional group such as an ether group, a carbonyl group, or an ester group within a range that does not impair the effects of the present invention. May be provided. Among them, R ¹⁴ is preferably a straight-chain saturated hydrocarbon having 1 to 10 carbon atoms or a branched saturated hydrocarbon chain having 2 to 10 carbon atoms, from the viewpoint of the thickening / gelling effect of the modified silicone. It is more preferably a straight-chain saturated hydrocarbon chain having 1 to 8 carbon atoms, further preferably a straight-chain saturated hydrocarbon chain having 2 to 6 carbon atoms, and a straight-chain saturated hydrocarbon chain having 2 carbon atoms. Is particularly preferred.

  The weight average molecular weight of the modified silicone represented by the general formula (I-ii) is preferably 500 to 100,000, and 2,000 to 40,000, since a thickening / gelling effect is easily obtained. Is more preferable, and it is still more preferable that it is 3,000 to 10,000. When the weight average molecular weight is larger than 100,000 or smaller than 500, the thickening / gelling effect may be reduced.

Among the modified silicones represented by the general formula (I-ii), from the viewpoint of enhancing the thickening / gelling ability to various oily components so as to have good feel and elasticity at a low addition amount, X ³ And X ⁴ is preferably a group represented by formula (I-ii-1) or (I-ii-2), and X ³ and X ⁴ are represented by formula (I-ii-2). More preferably, the group is

  Next, the modified silicone of the present invention having a structure represented by the following general formula (II-i) will be described.

(Wherein, R ⁵ and R ⁶ each independently represent a hydrocarbon chain having 1 to 20 carbon atoms, X ⁵ represents a hydroxyl group, an amino group, or a group represented by the general formula (b-1); ⁶ is a group represented by the following general formula (II-i-1), a group represented by the following general formula (II-i-2), or a group represented by the following general formula (II-i-3) The value of c represents the number of 1 to 2000, the value of d represents the number of 0 to 1000, the value of e represents the number of 1 to 1000, and the average of c, d and e The ratio c: d: e is 200 to 0.1: 0.99 to 0: 1 to 0.01 (the sum of the ratios of d and e is 1), provided that the unit units are arranged in a block or random arrangement. Any of them may be used, and a combination of a block-shaped portion and a random-shaped portion may be used.)

(In the formula, R ¹⁵ represents a hydrocarbon chain having 1 to 10 carbon atoms.)

(In the formula, R ²⁴ represents a residue of a monoisocyanate compound.)

(In the formula, R ²⁵ represents a residue of a monoisocyanate compound.)

(In the formula, R ²⁶ represents a residue of a monoisocyanate compound, and R ¹⁶ represents a hydrocarbon chain having 1 to 10 carbon atoms.)

R ⁵ and R ^{6 in the} general formula (II-i) each independently represent a hydrocarbon chain having 1 to 20 carbon atoms, and an ether group, a carbonyl group, and an ester group as long as the effects of the present invention are not impaired. And the like. Such hydrocarbon chains include, for example, straight-chain saturated hydrocarbons having 1 to 20 carbon atoms, straight-chain unsaturated hydrocarbons having 1 to 20 carbon atoms, branched saturated hydrocarbons having 2 to 20 carbon atoms, and 2 to 20 carbon atoms. And branched unsaturated hydrocarbons. Among them, from the viewpoint of the thickening and gelling effects of the modified silicone, R ⁵ and R ⁶ are each independently a straight-chain saturated hydrocarbon having 1 to 20 carbon atoms or a branched saturated hydrocarbon having 2 to 20 carbon atoms. Preferably, it is a straight-chain saturated hydrocarbon having 1 to 10 carbon atoms, more preferably a straight-chain saturated hydrocarbon having 1 to 6 carbon atoms.

  In the general formula (II-i), the value of c represents a number of 1 to 2,000, the value of d represents a number of 0 to 1,000, and the value of e represents a number of 1 to 1,000. Among them, the value of c is preferably from 1 to 1,000, more preferably from 1 to 500, still more preferably from 2 to 200, from the viewpoint of enhancing the thickening / gelling ability so as to have good feel and elasticity at a low addition amount. The value of d is preferably from 0 to 500, more preferably from 0 to 200, still more preferably from 0 to 100, and the value of e is preferably from 1 to 500, more preferably from 1 to 300, and still more preferably from 1 to 200. The average value of c, d, and e is not particularly limited as long as the above value is satisfied. For example, the average value of c may be 2 to 1000, and the average value of d may be 0 to 300. The average value of e may be 2 to 500. The ratio c: d: e of the average values of c, d, and e is 200 to 0.1: 0.99 to 0: 1 to 0.01 (the sum of the ratios of d and e is 1). Above all, c: d: e is 200 to 1: 0.9 to 0: 1 to 0 from the viewpoint of enhancing the thickening / gelling ability to various oily components so as to have good feel and elasticity at a low addition amount. .1 (the sum of the ratios of d and e is preferably 1), and more preferably 200 to 1: 0.5 to 0: 1 to 0.5 (the sum of the ratios of d and e is 1). More preferably, the ratio is 200 to 1: 0.2 to 0 to 1 to 0.8 (the sum of the ratios of d and e is 1).

R ^{15 in the} general formula (b-1) represents a hydrocarbon chain having 1 to 10 carbon atoms. Examples of such a hydrocarbon chain include a linear saturated hydrocarbon chain having 1 to 10 carbon atoms and a carbon chain having 1 to 10 carbon atoms. Straight-chain unsaturated hydrocarbon chain, a branched saturated hydrocarbon chain having 2 to 10 carbon atoms, a branched unsaturated hydrocarbon chain having 2 to 10 carbon atoms and the like, and within a range that does not impair the effects of the present invention. It may have a functional group such as an ether group, a carbonyl group and an ester group. Among them, R ¹⁵ is preferably a straight-chain saturated hydrocarbon having 1 to 10 carbon atoms or a branched saturated hydrocarbon chain having 2 to 10 carbon atoms, from the viewpoint of the thickening / gelling effect of the modified silicone. It is more preferably a straight-chain saturated hydrocarbon chain having 1 to 8 carbon atoms, further preferably a straight-chain saturated hydrocarbon chain having 2 to 6 carbon atoms, and a straight-chain saturated hydrocarbon chain having 2 carbon atoms. Is particularly preferred.

R ²⁴ in the general formula (II-i-1) represents a residue of a monoisocyanate compound, and is, for example, a total of a hydrocarbon group containing a linear alkyl group having 1 to 30 carbon atoms, a main chain, and a side chain. A hydrocarbon group containing a branched alkyl group having 3 to 30 carbon atoms, a hydrocarbon group containing a cycloalkyl group having 3 to 8 carbon atoms, and an aromatic hydrocarbon having 1 to 4 aromatic rings having 4 to 12 carbon atoms. And a hydrogen group. Among them, from the viewpoint of enhancing the thickening / gelling ability so as to have a good feel and elasticity at a low addition amount, a hydrocarbon group having a straight-chain alkyl group having 1 to 30 carbon atoms or a carbon group having 4 to 12 carbon atoms. It is preferably an aromatic hydrocarbon group having 1 to 4 aromatic rings. Among them, the aromatic hydrocarbon group having 1 to 4 aromatic rings having 4 to 12 carbon atoms has 1 to 2 aromatic rings having 4 to 8 carbon atoms from the viewpoint of increasing the viscosity and gelling ability. It is more preferably an aromatic hydrocarbon group, further preferably an aromatic hydrocarbon group having 1 to 2 aromatic rings having 6 carbon atoms, and more preferably an aromatic hydrocarbon group having one aromatic ring having 6 carbon atoms. Is particularly preferred.

R ²⁵ in the general formula (II-i-2) represents a residue of a monoisocyanate compound, and is, for example, a total of a hydrocarbon group containing a linear alkyl group having 1 to 30 carbon atoms, a main chain, and a side chain. A hydrocarbon group containing a branched alkyl group having 3 to 30 carbon atoms, a hydrocarbon group containing a cycloalkyl group having 3 to 8 carbon atoms, and an aromatic hydrocarbon having 1 to 4 aromatic rings having 4 to 12 carbon atoms. And a hydrogen group. Among them, from the viewpoint of enhancing the thickening / gelling ability so as to have a good feel and elasticity at a low addition amount, a hydrocarbon group having a straight-chain alkyl group having 1 to 30 carbon atoms or a carbon group having 4 to 12 carbon atoms. It is preferably an aromatic hydrocarbon group having 1 to 4 aromatic rings. Among them, the aromatic hydrocarbon group having 1 to 4 aromatic rings having 4 to 12 carbon atoms has 1 to 2 aromatic rings having 4 to 8 carbon atoms from the viewpoint of increasing the viscosity and gelling ability. It is more preferably an aromatic hydrocarbon group, further preferably an aromatic hydrocarbon group having 1 to 2 aromatic rings having 6 carbon atoms, and more preferably an aromatic hydrocarbon group having one aromatic ring having 6 carbon atoms. Is particularly preferred.

R ²⁶ in the general formula (II-i-3) represents a residue of a monoisocyanate compound, and is, for example, a total of a hydrocarbon group containing a linear alkyl group having 1 to 30 carbon atoms, a main chain, and a side chain. A hydrocarbon group containing a branched alkyl group having 3 to 30 carbon atoms, a hydrocarbon group containing a cycloalkyl group having 3 to 8 carbon atoms, and an aromatic hydrocarbon having 1 to 4 aromatic rings having 4 to 12 carbon atoms. And a hydrogen group. Among them, from the viewpoint of enhancing the thickening / gelling ability so as to have a good feel and elasticity at a low addition amount, a hydrocarbon group having a straight-chain alkyl group having 1 to 30 carbon atoms or a carbon group having 4 to 12 carbon atoms. It is preferably an aromatic hydrocarbon group having 1 to 4 aromatic rings. Among them, the aromatic hydrocarbon group having 1 to 4 aromatic rings having 4 to 12 carbon atoms has 1 to 2 aromatic rings having 4 to 8 carbon atoms from the viewpoint of increasing the viscosity and gelling ability. It is more preferably an aromatic hydrocarbon group, further preferably an aromatic hydrocarbon group having 1 to 2 aromatic rings having 6 carbon atoms, and more preferably an aromatic hydrocarbon group having one aromatic ring having 6 carbon atoms. Is particularly preferred.

R ¹⁶ represents a hydrocarbon chain having 1 to 10 carbon atoms. Examples of such a hydrocarbon chain include a linear saturated hydrocarbon having 1 to 10 carbon atoms, a linear unsaturated hydrocarbon having 1 to 10 carbon atoms, and a carbon chain having 1 to 10 carbon atoms. Examples include a branched saturated hydrocarbon having 2 to 10 carbon atoms and a branched unsaturated hydrocarbon having 2 to 10 carbon atoms, and a functional group such as an ether group, a carbonyl group, or an ester group within a range that does not impair the effects of the present invention. May be provided. Among them, R ¹⁶ is preferably a straight-chain saturated hydrocarbon having 1 to 10 carbon atoms or a branched saturated hydrocarbon having 2 to 10 carbon atoms, from the viewpoint of the thickening / gelling effect of the modified silicone. It is more preferably a linear saturated hydrocarbon having 1 to 10 carbon atoms, and further preferably a linear saturated hydrocarbon having 2 to 8 carbon atoms.

  The weight-average molecular weight of the modified silicone represented by the general formula (II-i) is preferably 500 to 100,000, and 2,000 to 40,000, since a thickening / gelling effect is easily obtained. Is more preferable, and it is still more preferable that it is 3,000 to 10,000. When the weight average molecular weight is larger than 100,000 or smaller than 500, the thickening / gelling effect may be reduced.

The modified silicone represented by the general formula (II-i) can exhibit a thickening / gelling ability with respect to various oily components by having the above-described structure. X ⁶ is preferably a group represented by the general formula (II-i-2) or (II-i-3) from the viewpoint of further increasing the thickening / gelling ability so as to have elasticity. More preferably, it is a group represented by (II-i-3).

  Further, among the modified silicones represented by the general formula (II-i), from the viewpoint of the thickening and gelling effects of the modified silicone, the modified silicones represented by the following general formula (II-ii) Is preferred.

(Wherein, R ⁷ and R ⁸ each independently represent a hydrocarbon chain having 1 to 20 carbon atoms; X ⁷ represents a hydroxyl group, an amino group or a group represented by the general formula (b′-1); Table in X ⁸ is the following general formula (II-ii-1) group, or the general formula represented by (II-ii-2) a group or the general formula represented (II-ii-3) The value of f represents the number of 1 to 2000, the value of g represents the number of 0 to 1000, the value of h represents the number of 1 to 1000, and the average value of f, g, and h The ratio f: g: h is 200 to 0.1: 0.99 to 0: 1 to 0.01 (the sum of the ratios of g and h is 1), provided that the unit units are arranged in a block shape or a random shape. And a combination of a block-shaped portion and a random-shaped portion may be used.)

(In the formula, R ¹⁷ represents a hydrocarbon chain having 1 to 10 carbon atoms.)

(Where s represents a number from 0 to 29)

(Where t represents a number from 0 to 29)

(Wherein, R ¹⁸ represents a hydrocarbon chain having 1 to 10 carbon atoms, and u represents a number of 0 to 29)

R ⁷ and R ^{8 in the} general formula (II-ii) each independently represent a hydrocarbon chain having 1 to 20 carbon atoms, and an ether group, a carbonyl group, and an ester group as long as the effects of the present invention are not impaired. And the like. Such hydrocarbon chains include, for example, straight-chain saturated hydrocarbons having 1 to 20 carbon atoms, straight-chain unsaturated hydrocarbons having 1 to 20 carbon atoms, branched saturated hydrocarbons having 2 to 20 carbon atoms, and 2 to 20 carbon atoms. And branched unsaturated hydrocarbons. Among them, from the viewpoint of the thickening and gelling effects of the modified silicone, R ⁷ and R ⁸ are each independently a straight-chain saturated hydrocarbon having 1 to 20 carbon atoms or a branched saturated hydrocarbon having 2 to 20 carbon atoms. Preferably, it is a straight-chain saturated hydrocarbon having 1 to 10 carbon atoms, more preferably a straight-chain saturated hydrocarbon having 1 to 6 carbon atoms.

  In the general formula (II-ii), the value of f represents a number of 1 to 2,000, the value of g represents a number of 0 to 1,000, and the value of h represents a number of 1 to 1000. Among them, the value of f is preferably from 1 to 1000, more preferably from 1 to 500, still more preferably from 2 to 200, from the viewpoint of enhancing the thickening / gelling ability so as to have a good feel and elasticity at a low addition amount. The value of g is preferably from 0 to 500, more preferably from 0 to 200, still more preferably from 0 to 100, and the value of h is preferably from 1 to 500, more preferably from 1 to 300, and still more preferably from 1 to 200. The average value of f, g, and h is not particularly limited as long as the above value is satisfied. For example, the average value of f may be 2 to 1000, and the average value of g may be 0 to 300. The average value of h may be 2 to 500. The ratio f: g: h of the average value of f, g, and h is 200 to 0.1: 0.99 to 0: 1 to 0.01 (the total value of the ratio of g and h is 1). Among them, f: g: h is 200 to 1: 0.9 to 0: 1 to 0 from the viewpoint of enhancing the thickening / gelling ability to various oily components so as to have good feel and elasticity at a low addition amount. .1 (the sum of the ratios of g and h is 1), and more preferably 200-1: 0.5-0: 1-0.5 (the sum of the ratios of g and h is 1). More preferably, the ratio is 200 to 1: 0.2 to 0 to 1 to 0.8 (the sum of the ratios of g and h is 1).

R ^{17 in the} general formula (b′-1) represents a hydrocarbon chain having 1 to 10 carbon atoms, such as a straight-chain saturated hydrocarbon chain having 1 to 10 carbon atoms or 1 to 10 carbon atoms. 10 straight-chain unsaturated hydrocarbon chains, branched saturated hydrocarbon chains having 2 to 10 carbon atoms, branched unsaturated hydrocarbon chains having 2 to 10 carbon atoms, and the like, provided that the effects of the present invention are not impaired. , An ether group, a carbonyl group, an ester group and the like. Among them, R ¹⁷ is preferably a straight-chain saturated hydrocarbon having 1 to 10 carbon atoms or a branched saturated hydrocarbon chain having 2 to 10 carbon atoms, from the viewpoint of the thickening / gelling effect of the modified silicone. It is more preferably a straight-chain saturated hydrocarbon chain having 1 to 8 carbon atoms, further preferably a straight-chain saturated hydrocarbon chain having 2 to 6 carbon atoms, and a straight-chain saturated hydrocarbon chain having 2 carbon atoms. Is particularly preferred.

  S in the general formula (II-ii-1) represents a number from 0 to 29. Above all, s is preferably from 2 to 25, more preferably from 9 to 23, and even more preferably from 13 to 21, from the viewpoint of enhancing the thickening / gelling ability so as to have good feel and elasticity. More preferably, it is particularly preferably 15 to 19.

  T in the general formula (II-ii-2) represents a number from 0 to 29. Among them, t is preferably 2 to 25, more preferably 9 to 23, and more preferably 13 to 21 from the viewpoint of enhancing the thickening / gelling ability so as to have a good feel and elasticity. More preferably, it is particularly preferably 15 to 19.

R ^{18 in the} general formula (II-ii-3) represents a hydrocarbon chain having 1 to 10 carbon atoms. Examples of such a hydrocarbon chain include a linear saturated hydrocarbon having 1 to 10 carbon atoms, and a hydrocarbon chain having 1 to 10 carbon atoms. And straight-chain unsaturated hydrocarbons having 10 to 10 carbon atoms, branched saturated hydrocarbons having 2 to 10 carbon atoms, branched unsaturated hydrocarbons having 2 to 10 carbon atoms, and ether groups within a range not to impair the effects of the present invention. , A carbonyl group, an ester group or the like. Among them, R ¹⁸ is preferably a straight-chain saturated hydrocarbon having 1 to 10 carbon atoms or a branched saturated hydrocarbon having 2 to 10 carbon atoms, from the viewpoint of the thickening / gelling effect of the modified silicone. It is more preferably a linear saturated hydrocarbon having 1 to 10 carbon atoms, and further preferably a linear saturated hydrocarbon having 2 to 8 carbon atoms.

  u represents the number of 0-29. Among them, u is preferably 2 to 25, more preferably 9 to 23, and more preferably 13 to 21 from the viewpoint of enhancing the thickening / gelling ability so as to have good feel and elasticity at a low addition amount. Is more preferable, and 15 to 19 is particularly preferable.

  The weight average molecular weight of the modified silicone represented by the general formula (II-ii) is preferably from 500 to 100,000, and preferably from 2,000 to 40,000, since a thickening / gelling effect is easily obtained. Is more preferable, and it is still more preferable that it is 3,000 to 10,000. When the weight average molecular weight is larger than 100,000 or smaller than 500, the thickening / gelling effect may be reduced.

Among the modified silicone represented by the general formula (II-ii), from the viewpoint of thickening-gelation effect of the modified silicone, ^{X 8} is the general formula (II-ii-2) or (II-ii -3), and more preferably a group represented by the general formula (II-ii-3).

  The modified silicone of the present invention comprises a raw material of one or more silicone derivatives represented by the following general formula (A) or (B), and a raw material of a monoisocyanate compound composed of one or more kinds More specifically, when the silicone derivative raw material represented by the general formula (A) is used as the silicone derivative raw material, the modified compound represented by the general formula (Ii) described above is used. Silicone is obtained, and when the silicone derivative raw material represented by the general formula (B) is used, the modified silicone represented by the general formula (II-i) is obtained.

(Wherein, R ³¹ and R ³² each independently represent a hydrocarbon chain having 1 to 8 carbon atoms, and Y ¹ and Y ² each independently represent a hydrogen atom, a hydroxyl group, an amino group, or a compound represented by the following general formula (c) -1) (wherein at least one of Y ¹ and Y ² is not a hydrogen atom), and the value of i represents a number from 0 to 2000.)

(In the formula, R ⁴¹ represents a hydrocarbon chain having 1 to 10 carbon atoms.)

(Wherein, R ³³ represents a hydrocarbon chain having 1 to 20 carbon atoms, Y ³ represents a hydroxyl group, an amino group or a group represented by the general formula (d-1), and the value of j is 1 to 2,000. Represents the number, the value of k represents the number of 1 to 1000, and the ratio j: k of the average value of j and k is 200: 1 to 1: 1, provided that the arrangement of the unit units is block-like or random-like. Any of them may be used, and a combination of a block-shaped portion and a random-shaped portion may be used.)

(In the formula, R ⁴² represents a hydrocarbon chain having 1 to 10 carbon atoms.)

The silicone derivative represented by the general formula (A) used as a raw material for producing the modified silicone of the present invention will be described in detail. R ³¹ and R ^{32 in the} general formula (A) each independently represent a hydrocarbon chain having 1 to 8 carbon atoms. Examples of such a hydrocarbon chain include linear saturated hydrocarbons having 1 to 8 carbon atoms. , Straight-chain unsaturated hydrocarbons having 1 to 8 carbon atoms, branched saturated hydrocarbons having 2 to 8 carbon atoms, branched unsaturated hydrocarbons having 2 to 8 carbon atoms and the like, and ranges that do not impair the effects of the present invention. Among them, it may have a functional group such as an ether group, a carbonyl group and an ester group. Above all, from the viewpoint of good reactivity with the monoisocyanate compound and enhancing the thickening and gelling effects of the resulting modified silicone, R ³¹ and R ³² are each a straight-chain saturated carbon having 1 to 8 carbon atoms. It is preferably hydrogen or a branched saturated hydrocarbon having 2 to 8 carbon atoms, more preferably a straight-chain saturated hydrocarbon having 1 to 8 carbon atoms, and more preferably a straight-chain saturated hydrocarbon having 1 to 6 carbon atoms. And further preferably a straight-chain saturated hydrocarbon having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group, and a trimethylene group.

^Y 1, ^{Y 2} in the general formula (A) are each independently a hydrogen atom, a hydroxyl group, a group represented by the amino group or the following formula (c-1), in this case ^Y 1, ^{Y 2} At least one must be a group other than a hydrogen atom. From the viewpoint of the thickening and gelling effects of the modified silicone obtained, it is preferable that Y ¹ and Y ² are the same group. Above all, from the viewpoint of the thickening / gelling effect of the obtained modified silicone and the feel and elasticity of the oil composition, whether Y ¹ and Y ² are both amino groups or both are hydroxyl groups, It is preferably a group represented by the general formula (c-1), particularly preferably an amino group, and particularly preferably a group represented by the general formula (c-1).

  The value of i in the general formula (A) represents a number from 0 to 2000. Among them, the value of i is preferably from 0 to 1000, more preferably from 0 to 500, more preferably from 0 to 1000, from the viewpoint of good reactivity with the monoisocyanate compound and enhancing the thickening / gelling effect of the resulting modified silicone. -200 is more preferable, and 1-100 is particularly preferable. At this time, from the viewpoint of enhancing the thickening / gelling effect of the modified silicone, the average value of i is preferably from 2 to 500, more preferably from 3 to 200, and still more preferably from 5 to 100.

R ^{41 in the} general formula (c-1) represents a hydrocarbon chain having 1 to 10 carbon atoms. Examples of such a hydrocarbon chain include a straight-chain saturated hydrocarbon having 1 to 10 carbon atoms and a hydrocarbon chain having 1 to 10 carbon atoms. Examples thereof include a linear unsaturated hydrocarbon, a branched saturated hydrocarbon having 2 to 10 carbon atoms, a branched unsaturated hydrocarbon having 2 to 10 carbon atoms, and the like. It may have a functional group such as a group or an ester group. Above all, from the viewpoint of good reactivity with monoisocyanate compounds and reaction controllability, and from the viewpoint of enhancing the thickening / gelling effect of the resulting modified silicone, R ⁴¹ is a linear saturated carbon having 1 to 10 carbon atoms. It is preferably hydrogen or a branched saturated hydrocarbon having 2 to 10 carbon atoms, more preferably a straight-chain saturated hydrocarbon having 1 to 10 carbon atoms, and more preferably a straight-chain saturated hydrocarbon having 2 to 8 carbon atoms. Is more preferred.

  The weight average molecular weight of the silicone derivative represented by the general formula (A) is preferably from 450 to 95,000, and more preferably from 1,900 to 9, since the thickening and gelling effects of the obtained modified silicone are easily obtained. It is more preferably 35,000, and further preferably 2,900 to 9,500. If the weight average molecular weight is more than 95,000, the thickening / gelling effect may be reduced, and if it is less than 450, the resulting modified silicone may not have the thickening / gelling effect.

  The functional group equivalent of the silicone derivative represented by the general formula (A) is not particularly limited as long as it can react with the monoisocyanate compound. For example, in the case of a hydroxyl-containing silicone derivative, the functional group equivalent is 100 It is preferably from 10 to 10,000 g / mol, more preferably from 200 to 5,000 g / mol, even more preferably from 300 to 3,000 g / mol. The functional group equivalent of the silicone derivative containing a hydroxyl group can be calculated based on the hydroxyl value [mgKOH / g] measured by the method described in JIS K0070. Further, in the case of a silicone derivative containing an amino group, for example, the functional group equivalent is preferably 100 to 10,000 g / mol, more preferably 200 to 5,000 g / mol, and 300 to 3, More preferably, it is 000 g / mol. Further, for example, in the case of a silicone derivative containing a group represented by the general formula (c-1), the functional group equivalent is preferably 100 to 10,000 g / mol, and 200 to 5,000 g / mol. More preferably, it is more preferably 300 to 3,000 g / mol. The functional group equivalent of the silicone derivative containing an amino group or a group represented by the general formula (c-1) can be calculated based on the total amine value measured according to the method described in JIS K 7237. . When the functional group equivalents are in these ranges, respectively, they have a sufficient bonding point with the monoisocyanate compound, and can also sufficiently show affinity with various oily components, and thus increase the viscosity of the obtained modified silicone. -The property as a gelling agent can be enhanced.

  As the silicone derivative represented by the general formula (A), one kind of silicone derivative may be used as a raw material, or two or more kinds of silicone derivatives may be used. It is preferable to use one kind of silicone derivative as a raw material.

  As the silicone derivative represented by the general formula (A), those obtained by synthesizing by a known method (for example, methods described in JP-A-4-88024 and JP-A-11-323661) may be used. Alternatively, commercially available products may be used. Examples of such commercially available products include modified silicone oil manufactured by Shin-Etsu Chemical Co., Ltd., side-chain monoamine-modified reactive silicone oil (product names: KF-868, KF-865, and KF-864). Chain-type diamine-modified type reactive silicone oil (product name: KF-393, KF-859, KF-860, KF-861, KF-8002, KF-8004, KF-8005, KF-8022), side chain type monoamino -Polyether-modified type reactive silicone oil (product name: X-22-3939A) and the like.

Next, the silicone derivative represented by the general formula (B) used as a raw material of the modified silicone of the present invention will be described in detail. R ^{33 in the} general formula (B) represents a hydrocarbon chain having 1 to 20 carbon atoms, and examples of such a hydrocarbon chain include a linear saturated hydrocarbon having 1 to 20 carbon atoms and a linear chain having 1 to 20 carbon atoms. Unsaturated hydrocarbons, branched saturated hydrocarbons having 2 to 20 carbon atoms, branched unsaturated hydrocarbons having 2 to 20 carbon atoms, and the like, and within a range that does not impair the effects of the present invention, an ether group, a carbonyl group, It may have a functional group such as an ester group. Among them, a reactivity and reaction control with the monoisocyanate compound is good, also from the viewpoint of enhancing the thickening-gelation effect of the obtained modified silicone, R ³³ represents hydrocarbon linear saturated C1-20 It is preferably hydrogen or a branched saturated hydrocarbon having 2 to 20 carbon atoms, more preferably a straight-chain saturated hydrocarbon having 1 to 10 carbon atoms, and more preferably a straight-chain saturated hydrocarbon having 1 to 6 carbon atoms. Is more preferred.

Y ^{3 in the} general formula (B) represents a hydroxyl group, an amino group, or a group represented by the general formula (d-1). Among them, an amino group or a group represented by the general formula (d-1) is preferable, and a group represented by the general formula (d-1) is preferable from the viewpoint of the thickening / gelling ability of the obtained modified silicone. Is particularly preferred.

  In the general formula (B), the value of j represents a number from 1 to 2,000, and the value of k represents a number from 1 to 1,000. Among them, the value of j is preferably from 1 to 1000, more preferably from 1 to 500, still more preferably from 2 to 300, from the viewpoint of enhancing the thickening / gelling ability so as to have good feel and elasticity at a low addition amount. The value of k is particularly preferably 3 to 200, and the value of k is preferably 1 to 500, more preferably 1 to 300, and still more preferably 1 to 200. The average value of j and k is not particularly limited as long as the above value is satisfied. For example, the average value of j may be 2 to 1000, and the average value of k may be 2 to 500. .

  The ratio j: k of the average value of j and k in the general formula (B) is 200: 1 to 1: 1. When the ratio of the average value of j and k is within this range, the thickening and gelling effects of the resulting modified silicone can be enhanced. Above all, the ratio j: k of the average value of j and k is from 150: 1 to 1.5: 1 from the viewpoint of enhancing the thickening / gelling ability so as to have good feel and elasticity at a low addition amount. Is preferably 100: 1 to 2: 1, more preferably 20: 1 to 2: 1, and particularly preferably 10: 1 to 2: 1. The arrangement of the unit units may be either a block shape or a random shape, or a combination of a block portion and a random portion.

^{R 42} in Formula (d-1) represents a hydrocarbon chain having 1 to 10 carbon atoms, examples of such hydrocarbon chains, for example, straight-chain saturated hydrocarbon having 1 to 10 carbon atoms, having 1 to 10 carbon atoms Examples thereof include a linear unsaturated hydrocarbon, a branched saturated hydrocarbon having 2 to 10 carbon atoms, a branched unsaturated hydrocarbon having 2 to 10 carbon atoms, and the like. It may have a functional group such as a group or an ester group. Among them, a reactivity and reaction control with the monoisocyanate compound is good, also from the viewpoint of enhancing the thickening-gelation effect of the obtained modified silicone, R ⁴² is carbonized linear saturated C1-10 It is preferably hydrogen or a branched saturated hydrocarbon having 2 to 10 carbon atoms, more preferably a straight-chain saturated hydrocarbon having 1 to 8 carbon atoms, and a straight-chain saturated hydrocarbon having 2 to 6 carbon atoms. Is more preferable, and a linear saturated hydrocarbon having 2 carbon atoms is particularly preferable.

  The weight-average molecular weight of the silicone derivative represented by the general formula (B) is preferably 450 to 95,000, and 1,900 to 1,900, since the resulting modified silicone can easily obtain a thickening / gelling effect. It is more preferably 35,000, and further preferably 2,900 to 9,500. If the weight average molecular weight is more than 95,000, the thickening / gelling effect may be reduced, and if it is less than 450, the thickening / gelling effect may not be obtained.

  The functional group equivalent of the silicone derivative represented by the general formula (B) is not particularly limited as long as it can react with the monoisocyanate compound. For example, in the case of a hydroxyl-containing silicone derivative, the functional group equivalent is It is preferably from 100 to 30,000 g / mol, more preferably from 300 to 20,000 g / mol, even more preferably from 500 to 10,000 g / mol, and from 900 to 5,000 g / mol. Is more preferable. In the case of a silicone derivative containing an amino group, for example, the functional group equivalent is preferably from 100 to 30,000 g / mol, more preferably from 300 to 20,000 g / mol, and more preferably from 500 to 20,000 g / mol. 2,000 g / mol, more preferably 2,000 to 6,000 g / mol. Further, for example, in the case of a silicone derivative containing a group represented by the general formula (d-1), the functional group equivalent is preferably 100 to 60,000 g / mol, and 150 to 20,000 g / mol. Is more preferably 200 to 12,000 g / mol, and further preferably 250 to 6,000 g / mol. The functional group equivalent of the silicone derivative can be measured by the method described above. When the functional group equivalents are in these ranges, respectively, they have a sufficient bonding point with the monoisocyanate compound, and can also sufficiently show affinity with various oily components, and thus increase the viscosity of the obtained modified silicone. -The property as a gelling agent can be enhanced.

  As the silicone derivative represented by the general formula (B), one obtained by synthesizing by a known method (for example, a method described in JP-A-5-194969 or JP-A-11-323661) may be used. Alternatively, commercially available products may be used. Examples of such commercially available products include a modified silicone oil manufactured by Shin-Etsu Chemical Co., Ltd. and a double-ended amino-modified reactive silicone oil (product names: PAM-E, KF-8010, X-22-161A, X -22-161B, KF-8012, KF-8008, X-22-9409), both ends type carbinol-modified type reactive silicone (product names: KF-6000, KF-6001, KF-6002, KF-6003) And the like.

  As the silicone derivative raw material represented by the general formula (A) or (B) used in the present invention, even if a silicone derivative raw material composed of one or more kinds represented by the general formula (A) is used, Even if one or more silicone derivative raw materials represented by the general formula (B) are used, one or more silicone derivative raw materials represented by the general formula (A) may be used together with the general formula ( It is also possible to use one or more silicone derivative raw materials represented by B). Among these, from the viewpoint of imparting a thickening / gelling ability so that the obtained modified silicone has a good feel and elasticity with a low addition amount, one or more kinds represented by the general formula (B) are used. It is preferable to use a silicone derivative raw material.

  Next, the monoisocyanate compound used as a raw material of the modified silicone of the present invention will be described in detail. The monoisocyanate compound is not particularly limited as long as it is a compound having an isocyanate group capable of reacting with the silicone derivative raw material represented by the general formula (A) or (B). Or a monoisocyanate compound containing a cyclic alkyl group and an isocyanate group, a monoisocyanate compound containing a linear or branched unsaturated hydrocarbon group and an isocyanate group in the molecule, and containing an aromatic hydrocarbon group and an isocyanate group in the molecule Monoisocyanate compounds and the like may be mentioned. At this time, the compound may have a functional group such as a carbonyl group, a methoxy group, a silyl group, and a tosyl group. Among such compounds, from the viewpoint of the thickening / gelling ability of the obtained modified silicone, the monoisocyanate compound containing a linear alkyl group having 1 to 30 carbon atoms and an isocyanate group, the total of the main chain and the side chain A monoisocyanate compound having a branched alkyl group having 3 to 30 carbon atoms and an isocyanate group; a monoisocyanate compound having at least one cycloalkyl group having 3 to 8 carbon atoms and an isocyanate group; an aromatic ring having 4 to 12 carbon atoms Is preferably at least one selected from the group consisting of a monoisocyanate compound containing an aromatic hydrocarbon group having 1 to 4 and an isocyanate group. Among them, examples of the monoisocyanate compound containing a branched alkyl group having 3 to 30 carbon atoms in the main chain and the side chain and an isocyanate group include, for example, t-butyl isocyanate, 2-methylpropyl isocyanate, and 2-methylhexyl isocyanate. And 2-ethylhexyl isocyanate. Of these, 2-ethylhexyl isocyanate is preferred from the viewpoint of improving the viscosity and gelling ability of the modified silicone by crystallization of the alkyl group. Examples of the monoisocyanate compound containing at least one cycloalkyl group having 3 to 8 carbon atoms and an isocyanate group include, for example, cyclopropyl isocyanate, cyclobutyl isocyanate, cyclopentyl isocyanate, cyclohexyl isocyanate, dimethylcyclohexyl isocyanate, diethylenecyclohexyl isocyanate, Examples thereof include cycloheptyl isocyanate and cyclooctyl isocyanate. Among these, cyclohexyl isocyanate is preferable from the viewpoint of improving the viscosity and gelling ability of the modified silicone by crystallization of the alkyl group. Examples of the monoisocyanate compound containing an aromatic hydrocarbon group having 1 to 4 aromatic rings having 4 to 12 carbon atoms and an isocyanate group include phenyl isocyanate, benzyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate, diisopropylphenylisocyanate, Naphthyl isocyanate, biphenyl isocyanate and the like, among these, phenyl isocyanate or benzyl isocyanate is preferred, and phenyl isocyanate is preferred from the viewpoint of improving the thickening and gelling ability of the modified silicone by π-π interaction derived from the aromatic ring. More preferred.

  By using such a monoisocyanate compound as a raw material, it is possible to obtain a modified silicone capable of thickening and gelling various oily components such as silicone oil, ester oil and hydrocarbon oil with a small amount of addition. If a compound having two or more isocyanate groups in the molecule is used as the isocyanate compound, it is difficult to control the reaction system so that the resulting modified silicone is suitable for thickening and gelling, so that by-products are formed. It is not suitable for obtaining a modified silicone having a thickening / gelling ability as in the present invention, for example, due to the inclusion of substances and the problem of non-uniformity of the thickening / gelling ability.

  The monoisocyanate compound raw material is composed of a linear alkyl group having 1 to 30 carbon atoms and an isocyanate group represented by the following general formula (C) from the viewpoint of enhancing the thickening and gelling effects of the resulting modified silicone. It is preferable to use a raw material containing a monoisocyanate compound.

  M in the general formula (C) represents a number from 0 to 29. From the viewpoint of the thickening / gelling ability of the resulting modified silicone, m is preferably from 2 to 25, more preferably from 9 to 23, still more preferably from 13 to 21, and preferably from 15 to 19. It is particularly preferred that there is. As such a monoisocyanate compound, a compound synthesized by a known method may be used, or a commercially available product may be used. In the present invention, by using a raw material containing the monoisocyanate compound represented by the general formula (C) as the monoisocyanate compound raw material, the monoisocyanate compound represented by the general formula (I-ii) or the general formula (II-ii) described above is used. Thus, a modified silicone can be obtained.

  As the monoisocyanate compound raw material, one kind of monoisocyanate compound or two or more kinds of monoisocyanate compounds may be used. It is preferable to use one type of monoisocyanate compound from the viewpoint of homogenizing the silicone resin, and from the viewpoint of enhancing the thickening / gelling ability of the modified silicone so as to have good feel and elasticity at a low addition amount, use two types of monoisocyanate compounds. It is preferable to use the above monoisocyanate compounds. When two or more monoisocyanate compounds are used, it is preferable to use two types of monoisocyanate compounds from the viewpoint of controlling the reaction system and further increasing the thickening / gelling ability. A monoisocyanate compound containing 30 linear alkyl groups and an isocyanate group; a monoisocyanate compound containing a branched alkyl group and an isocyanate group having a total of 3 to 30 carbon atoms in a main chain and a side chain; It is more preferable to use a monoisocyanate compound having a cycloalkyl group of 1 to 8 and an isocyanate group.

  When two or more monoisocyanate compounds are used, the ratio of the charged amount of each monoisocyanate compound is not particularly limited, but from the viewpoint of further increasing the viscosity and gelling ability, for example, a linear alkyl having 1 to 30 carbon atoms. Compound containing a group and an isocyanate group, a monoisocyanate compound containing a branched alkyl group and an isocyanate group having a total of 3 to 30 carbon atoms in a main chain and a side chain, or at least one cycloalkyl having 3 to 8 carbon atoms When using two types of monoisocyanate compounds of a monoisocyanate group and a monoisocyanate compound containing an isocyanate group, the number of isocyanate groups derived from the monoisocyanate compound containing a linear alkyl group having 1 to 30 carbon atoms and an isocyanate group , Branched alkyl having a total of 3 to 30 carbon atoms in the main chain and side chains And the ratio of the isocyanate group-containing monoisocyanate compound or at least one cycloalkyl group having 3 to 8 carbon atoms to the number of isocyanate groups derived from the isocyanate group-containing monoisocyanate compound is 1: 0.01 to 1: 1. : 1, preferably 1: 0.1 to 1: 0.8, more preferably 1: 0.2 to 1: 0.5.

  The modified silicone of the present invention is obtained by reacting one or more kinds of silicone derivative materials represented by the above general formula (A) or (B) with one or more kinds of monoisocyanate compound raw materials. As a method for producing a compound, for example, a silicone derivative raw material and a monoisocyanate compound raw material may be reacted under a known mixing method and a known reaction temperature and reaction atmosphere. As a specific production method, for example, a silicone derivative raw material and a monoisocyanate compound and, if necessary, other raw materials are charged into a reaction system, and are reacted at a time at 40 to 120 ° C. for 0.1 to 10 hours, A modified silicone may be obtained. At this time, the silicone derivative raw material and the monoisocyanate compound raw material may all be mixed and reacted simultaneously, or may be divided and mixed according to the progress of the reaction to react. Similarly, even when two or more types of silicone derivative raw materials or two or more types of monoisocyanate compound raw materials are used, all of them may be mixed and reacted at the same time, or may be divided and mixed according to the progress of the reaction. May be. When reacting the silicone derivative raw material with the monoisocyanate compound raw material, the reaction may be carried out in the presence of another reactive compound, a catalyst, or the like, depending on the purpose.

  The amount of each raw material charged when producing the modified silicone of the present invention is not particularly limited, but the silicone derivative raw material and the monoisocyanate compound are converted into a hydroxyl group and an amino group calculated from the functional group equivalent derived from the silicone derivative raw material. Preferably, the charge amount is such that the ratio between the number and the number of isocyanate groups derived from the monoisocyanate compound is 10: 1 to 1:10, and the charge amount is 3: 1 to 1: 3. More preferably, it is more preferable that the charged amount is 1.5: 1 to 1: 1.5. By controlling the number of hydroxyl groups and amino groups derived from the silicone derivative material and the number of isocyanate groups derived from the monoisocyanate compound in such a ratio, the reaction system is controlled to be suitable for thickening and gelling. It is preferable because the resulting modified silicone can be increased in viscosity and gelling ability so as to have good feel and elasticity with a small amount of addition.

  Although the solvent can be used to produce the modified silicone of the present invention with or without use, it is preferable to use a solvent from the viewpoint of reducing the viscosity of the entire system and uniformly proceeding the reaction. Is preferred from the viewpoint that the viscosity of the final product decreases and handling becomes easy. When the solvent is used, the modified silicone of the present invention can be obtained in a state of being dissolved in the solvent. In this state, the modified silicone of the present invention can be used as a thickener / gelling agent. It may be in a state of a substance. The solvent may be removed by any known method, for example, distillation under reduced pressure, drying by heating, 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, and propyl triglycerides; And silicone oil. Among them, a solvent having no active hydrogen that reacts with the isocyanate group in the molecule is preferable because it does not adversely affect the production of the modified silicone of the present invention. When a solvent is used, the amount used is preferably from 95 to 30% by mass, more preferably from 85 to 50% by mass, based on the entire system. When silicone oil or some ester oils are used as a solvent, the obtained silicone oil composition or ester oil composition can be used as it is for cosmetics.

  The catalyst may or may not be used to produce the modified silicone of the present invention, for example, a strong acid such as sulfuric acid or toluenesulfonic acid; titanium tetrachloride, hafnium chloride, zirconium chloride, aluminum chloride, Metal halides such as gallium chloride, indium chloride, iron chloride, tin chloride and boron fluoride; hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide, sodium methylate and sodium carbonate , Alcoholates, carbonates; metal oxides such as aluminum oxide, calcium oxide, barium oxide, and sodium oxide; tetrabranched propyl titanate, dibutyltin dichloride, dibutyltin oxide, dibutyltin bis (2-ethylhexylthioglycolate) and the like Organic metal compounds; sodium octylate, octyl Potassium, sodium laurate, and soaps such as potassium laurate.

  Since the modified silicone of the present invention can exhibit a thickening / gelling ability with respect to various oil components, it can be used as a thickening / gelling agent for various oil components. Such oily components are not particularly limited, and include, for example, silicone oils, ester oils, hydrocarbon oils, animal and vegetable oils, liquid higher fatty acids, and liquid higher alcohols. Among them, it can be particularly suitably used as a thickening / gelling agent for silicone oil, ester oil and hydrocarbon oil.

The silicone oil capable of thickening and gelling the modified silicone of the present invention is not particularly limited as long as it has a siloxane skeleton and is a liquid at ordinary temperature (however, general formula (Ii) or general formula (II-i) Dimethylpolysiloxane, methylphenylpolysiloxane, decamethyltetracyclosiloxane, octamethyltrisiloxane, alkyl-modified dimethylpolysiloxane, polyether-modified dimethylpolysiloxane, fatty acid-modified polysiloxane And higher alcohol-modified polysiloxanes and amino-modified polysiloxanes. Among them, dimethylpolysiloxane and cyclic dimethylpolysiloxane are preferable from the viewpoint of suitably exhibiting the thickening / gelling effect. Restrictions on the molecular weight and viscosity of these silicone oils are not, but the kinematic viscosity of silicone oils are preferably 1 to 500 mm ² / s at 25 ° C., more preferably ^{1~100mm 2 / s, 1~50mm 2 /} s is further And more preferably 1 to ²⁰ mm ² / s.

  Although the addition amount of the modified silicone of the present invention to the silicone oil is not particularly limited, it is preferably added to the silicone oil in an amount of 0.10 to 20.0% by mass, more preferably 0.50 to 15.0% by mass, and Even more preferred is 5 to 10.0% by weight. If the amount of the modified silicone is less than 0.10% by mass, the effect of gelation may not be exhibited. If the amount exceeds 20.0% by mass, the effect corresponding to the added amount cannot be obtained. May not completely dissolve in silicone oil. When the modified silicone of the present invention is added to silicone oil to produce a silicone oil composition, the modified silicone of the present invention may be added to the silicone oil and mixed until uniform. 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.

  The ester oil which the modified silicone of the present invention can thicken and gel is not particularly limited, and examples thereof include ethyl acetate, butyl acetate, hexyl acetate, decyl acetate, butyl propionate, hydrogenated polybutene myristate myristyl, and hexyl laurate. Decyl oleate, branched propyl myristate, hexyldecyl dimethyloctanoate, glyceryl monostearate, diethyl phthalate, ethylene glycol monostearate, octyl oxystearate, cetyl ethyl hexanoate, triethylhexanoin, polyglyceryl-2tri Synthetic ester oils such as isostearate and pentaerythrityl tetraisostearate; triglycerides such as lanolin, mink oil, cocoa butter, coconut oil, palm kernel oil, camellia oil, sesame oil, castor oil, olive oil, etc. Ester oil), and the like.

  The amount of the modified silicone of the present invention to be added to the ester oil is not particularly limited, but it is preferable to add 0.10 to 20.0% by mass to the ester oil, more preferably 0.50 to 15.0% by mass. Even more preferred is 5 to 10.0% by weight. If the amount of the modified silicone is less than 0.1% by mass, the gelling effect may not be exhibited. If the amount exceeds 20.0% by mass, the effect corresponding to the added amount cannot be obtained. It may not completely dissolve in ester oil. When the modified silicone of the present invention is added to an ester oil to produce an ester oil composition, the modified silicone of the present invention may be added to the ester oil and mixed until uniform. 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. The modified silicone of the present invention exerts a gelling effect even when added to an oil in which silicone oil and ester oil are mixed in advance.

  Examples of the hydrocarbon oil capable of thickening and gelling the modified silicone of the present invention include liquid paraffin, squalane, pristane, ozokerite, paraffin, ceresin, vaseline, isodecane, isododecane, isohexadecane, normal pentane, isopentane, normal hexane, Isohexane, kerosene, decalin, tetralin, microcrystalline wax and the like.

  Although the addition amount of the modified silicone of the present invention to the hydrocarbon oil is not particularly limited, it is preferably added to the hydrocarbon oil in an amount of 0.10 to 20.0% by mass, more preferably 0.50 to 15.0% by mass, 1.5 to 10.0% by mass is even more preferred. If the amount of the modified silicone is less than 0.1% by mass, the gelling effect may not be exhibited. If the amount exceeds 20.0% by mass, the effect corresponding to the added amount cannot be obtained. May not completely dissolve in hydrocarbon oils. When the modified silicone of the present invention is added to a hydrocarbon oil to produce a hydrocarbon oil composition, the modified silicone of the present invention may be added to the hydrocarbon oil and mixed until uniform. 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.

  The use of the oil composition obtained by thickening and gelling various oily components with the modified silicone of the present invention is not particularly limited, and can be used, for example, in the fields of lubricating oils, cosmetics, pharmaceuticals, fragrances, paints, and the like. Among them, the oil composition of the present invention is particularly preferably used for cosmetics because it is particularly excellent in the form and feel of the thickened and gelled composition. At this time, the content of the modified silicone in the oil composition is not particularly limited, and may be adjusted according to the properties required.For example, when the oil composition is used as a thickened and gelled oil composition, the total amount of the oil composition is reduced. On the other hand, the modified silicone is preferably contained in an amount of 0.10 to 20.0% by mass, more preferably 0.50 to 15.0% by mass, and even more preferably 1.5 to 10.0% by mass. preferable. Among various oil compositions, a silicone oil composition containing a modified silicone in a silicone oil and an ester oil composition containing a modified silicone in an ester oil are particularly excellent in feel. It can be used particularly suitably as a product. When such a silicone oil composition or an ester oil composition is used as a cosmetic composition, the stability as an oily component, the ease of application to the skin, and the ease of placing on the skin are improved. It can be expected to contribute to expansion of use and improvement of functionality. Further, according to the purpose, the silicone oil composition and the ester oil composition of the present invention can be used by mixing them, and oils other than the silicone oil composition and the ester oil composition can be used. It is also possible to mix and use similar compositions.

  The oil composition containing the modified silicone of the present invention is a polymer having excellent heat resistance, water resistance, corrosion resistance, and chemical resistance. It can be diverted to fuel oil and new solvents.

  The cosmetic composition of the present invention contains at least one selected from the group consisting of a silicone oil composition, an ester oil composition, and a hydrocarbon oil composition thickened and gelled by the modified silicone of the present invention. It is a cosmetic composition. In the cosmetic composition of the present invention, from the viewpoint of avoiding adverse effects on human health and from the viewpoint of quality stability, etc., the silicone derivative raw material is reacted with the monoisocyanate compound substantially without using heavy metals. It is preferable to contain the modified silicone obtained. At this time, specifically, the heavy metal content measured by the heavy metal test method described in the general test method section of the Quasi-drug raw material standard (2006) is preferably 20 ppm or less in terms of lead, preferably 10 ppm or less. More preferably, it is more preferably 5 ppm or less.

  Specific products as cosmetic compositions include, for example, sunscreens, foundations, W / O-based emulsions, creams, cleansing oils, hair waxes, hair creams, perfumes, etc., containing various UV inhibitors. Can be. In addition, in order to produce these cosmetic compositions, qualitative or quantitative ranges that do not impair the effects of the present invention are generally used in cosmetic compositions for the purpose of imparting various properties as appropriate. Other additives can be used. For example, powder components, liquid fats and oils, solid fats and oils, waxes, higher fatty acids, higher alcohols, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, humectants, polymer compounds, sequestering Agents, lower alcohols, polyhydric alcohols, sugars, amino acids and their derivatives, organic amines, pH adjusters, 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 can be arbitrarily blended.

  Examples of the powder component include inorganic powders (eg, talc, kaolin, mica, sericite (sericite), muscovite, phlogopite, synthetic mica, biotite, biotite, permiculite, magnesium carbonate, calcium carbonate, silicate) Aluminum, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (baked gypsum), calcium phosphate, fluorine apatite, hydroxyapatite, ceramic powder , Metal soaps (eg, zinc myristate, calcium palmitate, aluminum stearate), boron nitride, etc.); organic powders (eg, polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, Styrene powder, copolymer resin powder of styrene and acrylic acid, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, etc.); inorganic white pigments (eg, titanium dioxide, zinc oxide, etc.); inorganic red pigments (eg, Inorganic brown pigments (eg, γ-iron oxide); inorganic yellow pigments (eg, yellow iron oxide, loess); inorganic black pigments (eg, black) Inorganic purple pigments (eg, manganese violet, cobalt violet, etc.); inorganic green pigments (eg, chromium oxide, chromium hydroxide, cobalt titanate, etc.); inorganic blue pigments (eg, iron oxide, lower titanium oxide, etc.); Pearl pigments (for example, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated pigment) Luk, colored titanium oxide coated mica, bismuth oxychloride, fish scale foil, etc .; metal powder pigments (eg, aluminum powder, copper powder, etc.); organic pigments such as zirconium, barium or aluminum lake (eg, Red No. 201, Red 202) No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 228, Red No. 405, Orange No. 203, Orange No. 204, Yellow No. 205, Yellow No. 401 and Blue No. 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 No. 3 and Blue No. 1); natural pigments (eg, chlorophyll, β-carotene, etc.).

  Examples of liquid fats and oils include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, southern oil, castor oil, linseed oil , Safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, teaseed oil, kaya oil, rice bran oil, sinagiri oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin and the like.

Examples of solid fats and oils include cocoa butter, coconut oil, hydrogenated coconut oil, palm oil, palm kernel oil, molle kernel oil, hydrogenated oil, molle, and hydrogenated castor oil.
Examples of the wax include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, whale wax, montan wax, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, hexyl laurate, reduced lanolin, Jojoba wax, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, and the like.

  As higher fatty acids, for example, 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 higher alcohol include straight-chain alcohols (eg, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol, and the like); and branched-chain alcohols (eg, monostearyl glycerin ether (bacyl alcohol)). ), 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyldecanol, isostearyl alcohol, octyldodecanol, etc.).

  Examples of the anionic surfactant include fatty acid soaps (eg, sodium laurate, sodium palmitate, etc.); higher alkyl sulfates (eg, sodium lauryl sulfate, potassium lauryl sulfate, etc.); alkyl ether sulfates (eg, POE-triethanolamine lauryl sulfate, POE-sodium lauryl sulfate, etc.); N-acyl sarcosine acids (eg, sodium lauroyl sarcosine); higher fatty acid amide sulfonates (eg, sodium N-myristoyl-N-methyltaurine, coconut) Oil fatty acid sodium methyltaurine, sodium laurylmethyltaurine, etc.); phosphoric acid ester salts (POE-sodium oleyl ether phosphate, POE-stearyl ether phosphoric acid, etc.); sulfosuccinates (eg, Sodium di-2-ethylhexyl sulfosuccinate, monolauroyl monoethanolamide polyoxyethylene sodium sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc .; alkylbenzene sulfonates (for example, sodium linear dodecylbenzene sulfonate, linear dodecylbenzene sulfonate) Ethanolamine, linear dodecylbenzenesulfonic acid, etc.); higher fatty acid ester sulfates (eg, hydrogenated coconut oil fatty acid sodium glycerin sulfate); N-acyl glutamates (eg, monosodium N-lauroyl glutamate, N-stearoyl glutamate) Sodium, N-myristoyl-L-glutamate monosodium, etc.); sulfated oil (eg, funnel oil, etc.); POE-A Kill ether carboxylic acid; POE-alkyl allyl ether carboxylate; α-olefin sulfonate; higher fatty acid ester sulfonate; secondary alcohol sulfate; higher fatty acid alkylolamide sulfate; lauroyl monoethanolamide succinic acid Sodium; N-palmitoyl aspartate ditriethanolamine; sodium caseinate;

  Examples of the cationic surfactant include alkyltrimethylammonium salts (eg, stearyltrimethylammonium chloride, lauryltrimethylammonium chloride); alkylpyridinium salts (eg, cetylpyridinium chloride); distearyldimethylammonium dialkyldimethylammonium salt; Poly (N, N'-dimethyl-3,5-methylenepiperidinium) chloride; alkyl quaternary ammonium salt; alkyldimethylbenzylammonium salt; alkylisoquinolinium salt; dialkylmorphonium salt; POE-alkylamine; Alkylamine salts; polyamine fatty acid derivatives; amyl alcohol fatty acid derivatives; benzalkonium chloride; benzethonium chloride and the like.

  Examples of the amphoteric surfactant include imidazoline-based amphoteric surfactants (eg, 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxy). Betaine-based surfactants (eg, 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryl dimethylaminoacetic acid betaine, alkyl betaine, amido betaine) , Sulfobetaine and the like).

  Examples of the nonionic surfactant include sorbitan fatty acid esters (for example, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate) Ethates, diglycerol sorbitan penta-2-ethylhexylate, diglycerol sorbitan tetra-2-ethylhexylate and the like; glycerin polyglycerin fatty acids (for example, mono-cottonseed oil fatty acid glycerin, glycerin monoerucate, glycerin sesquioleate, glycerin monostearate) , Α, α'-glycolic acid pyroglutamate oleate, glyceryl monostearate malic acid, etc.); propylene glycol fatty acid esters (eg, monos Hydrogenated castor oil derivatives; glycerin alkyl ethers; POE-sorbitan fatty acid esters (eg, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate) 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-monooleate such as POE-glycerin monostearate, POE-glycerin monoisostearate, POE-glycerin triisostearate, etc.); POE-fatty acid ester (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 (for example, Pluronic); POE.POP-alkyl ethers (for example, 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-ethylenediamine condensates (for example, Tetronic, etc.) A POE-castor oil-hardened castor oil derivative (for example, POE-castor oil, POE-hardened castor oil, POE-hardened castor oil monoisostearate, POE-hardened castor oil triisostearate, POE-hardened castor oil monopyro; Glutamic acid monoisostearic acid diester, POE-hardened castor oil maleic acid, etc.); POE- beeswax lanolin derivative (eg, POE-sorbitol beeswax, etc.); alkanolamides (eg, coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid) POE-propylene glycol fatty acid ester; POE-alkylamine; POE-fatty acid amide; sucrose fatty acid ester; alkylethoxydimethylamine oxide; trioleyl phosphoric acid and the like.

  As the humectant, for example, polyethylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate, bile salt, dl-pyrrolidone carboxylate Acid salt, short-chain soluble collagen, adduct of diglycerin (EO) PO, extract of Isola radiata, extract of Achillea millefolium, extract of melilot and the like.

  Examples of natural water-soluble polymers include, for example, vegetable polymers (eg, gum arabic, tragacanth gum, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, agar, quince seed (quince), alge colloid (cassow extract), starch (Rice, corn, potato, wheat), glycyrrhizic acid); a microbial polymer (eg, xanthan gum, dextran, succinoglucan, burlan, gellan gum, etc.); an animal polymer (eg, collagen, casein, albumin, gelatin, etc.) ) And the like.

  Examples of the water-soluble polymer include starch-based polymers (eg, carboxymethyl starch, methylhydroxypropyl starch, etc.); cellulose-based polymers (methylcellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate, hydroxypropyl Cellulose, carboxymethylcellulose, sodium carboxymethylcellulose, crystalline cellulose, cellulose powder, etc.); alginic acid-based polymers (eg, sodium alginate, propylene glycol alginate, etc.); vinyl-based polymers (eg, polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone) , Carboxyvinyl polymers, etc.); polyoxyethylene polymers (eg, polyethylene glycol) 20,000, 40,000, 60,000 polyoxyethylene polyoxypropylene copolymers); acrylic polymers (for example, sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.); polyethylene imines; And cationic polymers.

Examples of the sequestering agent include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, edetate disodium, edetate trisodium, edetate tetrasodium , Sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, trisodium ethylenediaminehydroxyethyl 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, Hexahydric alcohols (eg, sorbitol, mannitol, etc.); polyhydric alcohol polymers (eg, diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, Divalent alcohol alkyl ethers (eg, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono) Tyl 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 di Butyl 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) Tyl ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, Dihydric alcohol ether esters (eg, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diazibate, ethylene glycol) 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 (for example, Kimi) Sugar alcohols (eg, sorbitol, maltitol, maltotriose, mannitol, erythritol, amylolytic sugar, maltose, xylitolose, amylolytic sugar reducing alcohol, etc.); glysolid; tetra Hydrofurfuryl alcohol; POE-tetraha Mud furfuryl alcohol; POP-butyl ether; POP · POE- ether; Tripoli polyoxypropylene glycerol ether; POP-glycerin ether; POP-glycerol ether phosphoric acid; POP · POE- pentane erythritol ether, polyglycerol and the like.

  Monosaccharides include, for example, tricarbonates (eg, D-glyceryl aldehyde, dihydroxyacetone, etc.); tetracarbon sugars (eg, D-erythrose, D-erythrulose, D-threose, erythritol, etc.); 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 -Bucose, D-galactose, D-fructose, L-galactose, L-mannose, D-tagatose and the like); heptose (for example, aldheptose, heptrose and the like); octose (for example, octulose and the like); deoxysaccharide ( For example, 2-deoxy-D-ribose, 6-deoxy-L-galactose, 6-deoxy-L Amino sugars (eg, D-glucosamine, D-galactosamine, sialic acid, aminouronic acid, muramic acid, etc.); uronic acids (eg, D-glucuronic acid, D-mannuronic acid, L-guluronic acid, D- Galacturonic acid, L-iduronic acid, etc.).

  Oligosaccharides include, for example, sucrose, umbelliferose, lactose, planteose, isorikunoses, α, α-trehalose, raffinose, ricknoses, umbilicin, stachyose verbascoses and the like.

Polysaccharides include, for example, 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, kerato sulfate 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.). Examples of amino acid derivatives include acyl sarcosine sodium (sodium lauroyl sarcosine), acyl glutamate, sodium acyl β-alanine, glutathione, and pyrrolidone carboxylic acid.

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. Is mentioned.
Examples of the pH adjusting agent include buffers 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, and biotin.
Examples of the antioxidant include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, and gallic esters.

  Other compoundable ingredients include, for example, preservatives (eg, methyl paraben, ethyl paraben, butyl paraben, phenoxyethanol); anti-inflammatory agents (eg, glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin) Whitening agents (for example, Sakinoshita extract, arbutin, etc.); various extracts (for example, oak, oak, sicon, peony, assembly, birch, sage, loquat, carrot, aloe, mallow, iris, grape, yoquinin, loofah, lily , Saffron, senkyu, ginger, hypericum, ononis, garlic, capsicum, chimpanzee, touki, seaweed, etc.), activators (eg, royal jelly, photosensitizer, cholesterol derivatives, etc.); blood circulation promoters (eg, nicotinic acid) Undil ester, nicotinic acid β-butoxyethyl ester, capsaicin, gingerone, canthari tincture, itctamol, tannic acid, α-borneol, tocopherol nicotinate, inositol hexanicotinate, cyclandate, cinnarizine, trazoline, acetylcholine, verapamil, cepharanthin, γ-oryzanol, etc.); antiseborrheic agents (eg, sulfur, thiantol, etc.); anti-inflammatory agents (eg, tranexamic acid, thiotaurine, hypotaurine, etc.).

  The method for producing a modified silicone of the present invention comprises a method of preparing a silicone derivative material comprising one or more of the general formula (A) or the general formula (B) without using a heavy metal-containing catalyst. Alternatively, it is a method of reacting with two or more monoisocyanate compound raw materials. It should be noted that the silicone derivative raw material represented by the general formula (A) or (B) used in the method for producing the modified silicone of the present invention, the monoisocyanate compound, the solvent and the amount of each raw material, reaction temperature, reaction atmosphere and the like. As for the conditions and the like, the compounds and conditions described above can be used.

  In the method for producing the modified silicone of the present invention, substantially without using a heavy metal-containing catalyst, and excluding compounds that are inevitably contained in the raw materials used, derived from a heavy metal-containing catalyst such as a tin-based catalyst Indicates that a catalyst containing a heavy metal element is not used intentionally.Specifically, a modified silicone is used without using a catalyst or using a catalyst containing only an alkali metal element or an alkaline earth metal element as a metal element. Indicates the manufacturing method. ADVANTAGE OF THE INVENTION According to the manufacturing method of the modified silicone of this invention, the modified silicone in which the heavy metal element derived from a heavy metal containing catalyst is 20 ppm or less in terms of lead, for example, can be obtained, and therefore, the cosmetic in which the heavy metal element is not preferred is contained. It is possible to obtain a modified silicone that can be suitably used as a material for fields and the like. Further, an oil composition containing no heavy metal element derived from the heavy metal-containing catalyst and a cosmetic composition containing the oil composition can be produced. In the method for producing a modified silicone using a polyfunctional isocyanate compound such as a diisocyanate compound, there is a problem that a by-product such as isocyanurate is further included in a target product. Since monoisocyanate is used, such a problem does not occur, and homogenization of the properties of the product and material deterioration due to the presence of impurities can be prevented. In the method for producing a modified silicone of the present invention, from the viewpoint of controlling the reaction system and reducing the generation of by-products, it is preferable to react the silicone derivative raw material with the monoisocyanate compound substantially without using a catalyst.

  In the method for producing a modified silicone of the present invention, a hydroxyl group or an amino group (a compound represented by the general formula (a-)) present at the terminal or side chain of the silicone main chain of the silicone derivative raw material represented by the general formula (A) or (B) is used. (Including the amino group contained in the group represented by 1) and the general formula (b-1)) and the isocyanate group of the monoisocyanate compound are considered to react with each other, for example, when the silicone derivative has a hydroxyl group, Is considered to react with an isocyanate group to form a urethane bond, and when the silicone derivative has an amino group, it is thought to react with an isocyanate group to form a urea bond.

  The modified silicone of the present invention may be one in which the above-mentioned urethane bond is formed, one in which a urea bond is formed, one in which a urethane bond and a urea bond are formed, and a wide variety of types. It is preferable that urethane bonds are formed from the viewpoint of expression of thickening / gelling ability to the oily component, and that various oily components are added so as to have good feel and elasticity at a low addition amount. From the viewpoint of viscous / gelling, it is preferable that the urea bond is formed.

  Hereinafter, the present invention will be described in detail with reference to examples. However, 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,% is based on mass unless otherwise specified.

  The silicone derivative raw materials used in producing the modified silicone of the present invention are shown below.

<Silicone derivative represented by general formula (A)>
Silicone derivative 1:
In the general formula (A), R ³¹ and R ³² are propylene groups, Y ¹ and Y ² are amino groups, the value of i is 1 to 50, the average value of i is 8.5, Silicone derivative having a functional group equivalent of 400 g / mol Silicone derivative 2:
In the general formula (A), R ³¹ and R ³² are propylene groups, Y ¹ and Y ² are amino groups, the value of i is 5 to 100, the average value of i is 56, and the functional group is Silicone derivative having an equivalent weight of 2,200 g / mol Silicone derivative 3:
In the general formula (A), R ³¹ and R ³² are methylene groups, Y ¹ and Y ² are hydroxyl groups, the value of i is 1 to 100, the average value of i is 22, and the functional group equivalent is Is 900g / mol silicone derivative

<Silicone derivative represented by general formula (B)>
Silicone derivative 4:
In the general formula (B), R ³³ is a propylene group, Y ³ is an amino group, the value of j is 10 to 1000, the value of k is 1 to 100, and the average value of j and k A silicone derivative having a ratio j: k of 50: 1 and a functional group equivalent of 3,800 g / mol.
In Formula (B), R ³³ is a propylene group, Y ³ is a group represented by Formula (d-1) in which R ⁴² is an ethylene group, and the value of j is 3 to 200. , K is from 1 to 200, the ratio j: k of the average value of j and k is 2.5: 1, and the functional group equivalent is 350 g / mol.
In Formula (B), R ³³ is a propylene group, Y ³ is a group represented by Formula (d-1) in which R ⁴² is an ethylene group, and the value of j is 3 to 500. , K is 1 to 50, the ratio j: k of the average value of j and k is 18: 1, and the functional group equivalent is 1,500 g / mol.
In Formula (B), R ³³ is a propylene group, Y ³ is a group represented by Formula (d-1) in which R ⁴² is an ethylene group, and the value of j is 10 to 2,000. , K is from 1 to 50, the ratio j: k of the average value of j and k is 146: 1, and the functional group equivalent is 11,000 g / mol.
In the general formula (B), R ³³ is a methylene group, Y ³ is a hydroxyl group, the value of j is 10 to 1000, the value of k is 1 to 100, and the ratio of the average value of j and k A silicone derivative in which j: k is 12: 1 and the functional group equivalent is 1,000 g / mol.

<Monoisocyanate compound>
Compound 1:
Octadecyl isocyanate (compound of formula (C) wherein m = 17)
Compound 2:
Phenyl isocyanate compound 3:
2-ethylhexyl isocyanate compound 4:
Cyclohexyl isocyanate

<Example 1: Production of modified silicone 1>
25.00 g of silicone derivative 1 and 100 g of butyl acetate as a solvent were charged into a four-necked flask equipped with a thermometer, a nitrogen inlet tube and a stirrer, and after the atmosphere in the system was replaced with nitrogen, the temperature was raised to 75 ° C. 17.18 g of Compound 1 was added, and reacted at 70 to 80 ° C. for 2 hours. After confirming that there was no absorption of isocyanate (all isocyanates were reacted) with an infrared spectroscope (IR), the reaction was terminated. did. In this reaction system, the ratio of the number of hydroxyl groups and amino groups derived from the silicone derivative raw material to the number of isocyanate groups derived from the monoisocyanate compound was 1: 1. After the reaction, butyl acetate as a solvent was removed from the obtained reaction product by an evaporator to obtain a modified silicone 1 (polymer 1). In the production of the modified silicone 1, no catalyst was used.

<Examples 2 to 13: Production of modified silicones 2 to 13>
According to the blending amount (g) shown in Table 1, each raw material was reacted in the same manner as in Example 1 to obtain modified silicones 2 to 13 (polymers 2 to 13). In each case, the ratio of the number of hydroxyl groups and amino groups derived from the silicone derivative raw material to the number of isocyanate groups derived from the monoisocyanate compound was 1: 1. In each of the examples, in the examples using a silicone derivative having a hydroxyl group (silicone derivative 3 and silicone derivative 8) as the silicone derivative, 0.50 g of potassium laurate was added as a catalyst to cause a reaction. Was manufactured.

<Measurement of weight average molecular weight Mw>
The obtained modified silicones 1 to 13 (excluding the modified silicones 2, 4, 5, and 13) were measured by gel permeation chromatography (GPC), and the weight average molecular weight Mw was calculated in terms of styrene. Table 1 shows the results.

<Comparative Example 1>
Comparative compound 1 was 12-hydroxystearic acid, which is generally used as a thickening / gelling agent for oil.

Evaluation of Thickening / Gelling Ability The modified silicones 1 to 13 (polymers 1 to 13) and comparative compound 1 of the examples were respectively 2.0% by mass, 5.0% by mass, and 10.0% by mass with respect to the following three types of oils. 0% by mass was added, and the mixture was stirred for 1 hour while heating at 80 to 90 ° C. to homogenize. 50 ml of each of the obtained solutions was put into a 100 ml glass bottle, left in a constant temperature bath at 25 ° C. for 24 hours, and the state and appearance of the oil after standing were observed and evaluated according to the following evaluation criteria. Table 2 shows the results.

<Oil used>
Oil 1: Triethylhexanoin oil 2: Liquid paraffin oil 3: Diphenylsiloxyphenyl trimethicone (Kinematic viscosity at 25 ° C. 15 mm ² / s)
<Evaluation criteria for oil condition>
：: elastic gel state ○: thickened oil state showing uniform fluidity △: thickened but non-uniform state ×: waxy solid without elasticity

  As a result, Polymers 1 to 13, which are modified silicones of the present invention, exhibited a thickening / gelling effect at a low addition amount to any of Oil 1, Oil 2 and Oil 3. In addition, the oil compositions obtained by thickening and gelling these ester oils, hydrocarbon oils, and silicone oils use modified silicones synthesized without substantially using heavy metal-containing catalysts as thickening and gelling agents. Since it is an oil composition having excellent feel and elasticity, it can be suitably used particularly for cosmetic compositions.

  The modified silicone of the present invention is a novel polymer capable of thickening and gelling various oily components such as silicone oil, ester oil and hydrocarbon oil with a low addition amount. The modified silicone of the present invention can be synthesized without using a heavy metal-containing catalyst. It is expected to have excellent chemical resistance and can be expected to be used in all applications that could not be used until now, so it is very useful.

Claims (8)

A modified silicone having a structure represented by the following general formula (I-i) or the following general formula (II-i).

(Wherein, R ¹ and R ² each independently represent a hydrocarbon chain having 1 to 8 carbon atoms, and X ¹ and X ² each independently represent a hydrogen atom, a hydroxyl group, an amino group, or a compound represented by the following general formula: A group represented by the following general formula (Ii-1), a group represented by the following general formula (Ii-2), or a group represented by the following general formula (Ii-2) Ii-3) represents any of the groups represented by the following formula (wherein at least one of X ¹ and X ² is a group represented by the general formula (I-i-1), a group represented by the general formula (I-i) 2) or a group represented by the general formula (Ii-3)), and the value of a represents a number from 0 to 2000.)

(In the formula, R ¹¹ represents a hydrocarbon chain having 1 to 10 carbon atoms.)

(In the formula, R ²¹ represents a residue of a monoisocyanate compound.)

(In the formula, R ²² represents a residue of a monoisocyanate compound.)

(In the formula, R ²³ represents a residue of a monoisocyanate compound, and R ¹² represents a hydrocarbon chain having 1 to 10 carbon atoms.)

(Wherein, R ⁵ and R ⁶ each independently represent a hydrocarbon chain having 1 to 20 carbon atoms, X ⁵ represents a hydroxyl group, an amino group, or a group represented by the general formula (b-1); ⁶ is a group represented by the following general formula (II-i-1), a group represented by the following general formula (II-i-2) or a group represented by the following general formula (II-i-3) The value of c represents the number of 1 to 2000, the value of d represents the number of 0 to 1000, the value of e represents the number of 1 to 1000, and the average of c, d and e The ratio c: d: e is 200 to 0.1: 0.99 to 0: 1 to 0.01 (the sum of the ratios of d and e is 1), provided that the unit units are arranged in a block or random arrangement. Any of them may be used, and a combination of a block-shaped portion and a random-shaped portion may be used.)

(In the formula, R ¹⁵ represents a hydrocarbon chain having 1 to 10 carbon atoms.)

(In the formula, R ²⁴ represents a residue of a monoisocyanate compound.)

(In the formula, R ²⁵ represents a residue of a monoisocyanate compound.)

(In the formula, R ²⁶ represents a residue of a monoisocyanate compound, and R ¹⁶ represents a hydrocarbon chain having 1 to 10 carbon atoms.)   An oil composition containing the modified silicone according to claim 1 in an amount of 1 to 20 parts by mass based on 100 parts by mass of an oily component containing at least one selected from the group consisting of silicone oil, ester oil, and hydrocarbon oil.   A cosmetic composition containing the oil composition according to claim 2. A material containing one or more silicone derivatives represented by the following general formula (A) or (B) and a material containing one or more monoisocyanate compounds substantially containing a heavy metal A method for producing a modified silicone, wherein the reaction is performed without using a catalyst.

(Wherein, R ³¹ and R ³² each independently represent a hydrocarbon chain having 1 to 8 carbon atoms, and Y ¹ and Y ² each independently represent a hydrogen atom, a hydroxyl group, an amino group, or a compound represented by the following general formula (c) -1) (wherein at least one of Y ¹ and Y ² is not a hydrogen atom), and the value of i represents a number from 0 to 2000.)

(In the formula, R ⁴¹ represents a hydrocarbon chain having 1 to 10 carbon atoms.)

(Wherein, R ³³ represents a hydrocarbon chain having 1 to 20 carbon atoms, Y ³ represents a hydroxyl group, an amino group or a group represented by the general formula (d-1), and the value of j is 1 to 2,000. Represents the number, the value of k represents the number of 1 to 1000, and the ratio j: k of the average value of j and k is 200: 1 to 1: 1, provided that the arrangement of the unit units is block-like or random-like. Any of them may be used, and a combination of a block-shaped portion and a random-shaped portion may be used.)

(In the formula, R ⁴² represents a hydrocarbon chain having 1 to 10 carbon atoms.)   The method for producing a modified silicone according to claim 4, wherein the functional equivalent of the silicone derivative raw material is 100 to 10,000 g / mol. The method for producing a modified silicone according to claim 4 or 5, wherein the monoisocyanate compound raw material contains one or more monoisocyanate compounds represented by the following general formula (C).

(In the formula, m represents a number from 0 to 29.)   The method for producing a modified silicone according to any one of claims 4 to 6, wherein the monoisocyanate compound raw material comprises two kinds of monoisocyanate compounds.   A modified silicone obtained by the production method according to claim 4.