JP5004514B2 - Gelling agent, gel-like composition and cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a gelling agent capable of easily gelling a silicone oil, an organic compound having low polarity and a nonpolar organic compound, especially an organic oil having high alkyl group content, and provide a gelatinous composition and cosmetics. <P>SOLUTION: The gelling agent is composed of an organopolysiloxane having an organic group (-Y) bonded to a silicon atom and expressed by general formula (1) and a &ge;9C substituted or unsubstituted univalent hydrocarbon group (-Z) bonded to a silicon atom. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

The present invention relates to a silicone oil, a gelling agent of a low polar organic compound and a nonpolar organic compound, and a gel composition comprising the gelling agent and silicone oil, a low polar organic compound or a nonpolar organic compound, More specifically, the present invention relates to a gel composition used in the fields of paints, inks, lubricating oils, agricultural products, marine products, cosmetics, pharmaceuticals, fibers, resins, polymers, rubbers, metals, and the like. Excellent stability over time, moisture retention, feel, gloss, and curl retention by blending a gel-like composition consisting of a silicone oil or a nonpolar liquid organic compound and the same gelling agent or gel-like composition Related to cosmetics.

Examples of gelling agents having the function of gelling organic liquids include alkali metal salts and alkaline earth metal salts of higher fatty acids, 1,2-hydroxystearic acid, dibenzylidene sorbitol, amino acid derivatives, amide compounds, urea compounds, etc. It has been known. However, such a gelling agent has low compatibility with silicone oil, and silicone cannot be gelled with the gelling agent. In addition, gelling agents that stably and simultaneously gel both silicone oil and fats and oils have been limited.

On the other hand, silicone oils, particularly low-viscosity silicone oils, are generally used in various applications because of their excellent progress, refreshing feeling, lubricity, water repellency, safety, and the like, and are particularly blended in cosmetics. However, silicone oils generally have low compatibility with other oils, and it has been difficult to prepare products with excellent stability. For example, in order to obtain a gel-like product based on a low-viscosity silicone oil, there is a problem that a stable product cannot be obtained even if a wax is blended, and the appearance becomes cloudy. Further, when cross-linked silicone is used instead of wax, there is a drawback that the sticky feeling remains and the original refreshing feeling of the silicone oil is lost. Patent Document 1 proposes a polyether-grafted organopolysiloxane as a gelling agent for silicone oil, but this gelling agent needs to be used in combination with an appropriate amount of water. In addition, the stability over time was not satisfactory.

US Pat. No. 6,057,049 describes the use of carboxamide polysiloxanes in cosmetic preparations and skin care and hair care compositions in the form of an aqueous emulsion of carboxamide polysiloxane. However, this document does not describe or suggest that such a carboxamide group-containing organopolysiloxane can be used as a gelling agent for silicone oil, nonpolar organic compounds or low polar organic compounds. Patent Document 3 proposes a carboxylic acid polyvalent metal salt-modified organopolysiloxane as a gelling agent for silicone oil and a cosmetic containing the same. However, when the gelling agent is used, there is a problem that a gel having sufficient viscosity and elastic modulus cannot be obtained unless a large amount of the gelling agent is used.

In order to solve such a problem, Patent Document 4 proposes a gelling agent composed of an organopolysiloxane having an amino alcohol salt structure of an amide carboxylic acid. However, the gel composition formed using the gelling agent is not satisfactory in its thermal stability and stability over time. Further, Patent Document 4 discloses only that the main chain structure is composed only of dimethylpolysiloxane, and this gelling agent is used for gelling organic oil having a high alkyl group content such as heavy paraffin. When used in the above, there is an unsolved problem that the gelling agent has insufficient compatibility with the organic oil, the gel cannot be easily formed, and the cosmetic formulation is limited.

JP 7-215817 A JP-A-10-158150 JP-A-8-109263 WO2005 / 063856

The present invention is a gelling agent capable of easily gelling an oil agent comprising a silicone oil, a nonpolar organic compound and a low polarity organic compound, particularly an organic oil having a high alkyl group content, without using water together, It is an object of the present invention to provide a gel composition having excellent thermal stability and stability over time and having thixotropic rheological properties, and further a cosmetic containing the gelling agent or the gel composition.

［式中、Ｒ^１は−COO⁻（M^ｎ＋）_１／ｎで表されるカルボン酸の金属塩（Mは一価以上の金属、ｎはMの原子価を示す）、Ｘは同種もしくは異種の炭素原子数2〜14の二価の炭化水素基、ｐは０〜１０の整数である。］が、シリコーンオイル、低極性有機化合物または非極性有機化合物のゲル化剤として有用であり、
（Ａ）該ゲル化剤 １〜99重量％および
（Ｂ）シリコーンオイル、非極性有機化合物または低極性有機化合物 99〜１重量％
からなるゲル状組成物、
さらに、該ゲル化剤またはゲル状組成物を配合した化粧料が前記課題を解決する上で有用であることを見出し、本発明に到達した。 As a result of intensive studies, the present inventors have found that the organic group (—Y) represented by the general formula (1) bonded to the silicon atom and the substituted or unsubstituted monovalent carbonization having 9 or more carbon atoms bonded to the silicon atom. Gelling agent general formula (1) comprising an organopolysiloxane having a hydrogen group (-Z) in the molecule:

[In the formula, R ^{1 -COO - (M n +) 1} / n represented by metal salts of carboxylic acids (M is a monovalent or more metals, n represents represents an atomic valence of M), X is identical or different A divalent hydrocarbon group having 2 to 14 carbon atoms, p is an integer of 0 to 10. Is useful as a gelling agent for silicone oil, low-polar organic compounds or non-polar organic compounds,
(A) 1 to 99% by weight of the gelling agent and (B) silicone oil, nonpolar organic compound or low polar organic compound 99 to 1% by weight
A gel composition comprising:
Furthermore, the present inventors have found that a cosmetic containing the gelling agent or gel-like composition is useful in solving the above-mentioned problems and has reached the present invention.

［式中、Ｒ^１は−COO⁻（M^ｎ＋）_１／ｎで表されるカルボン酸の金属塩（Mは一価以上の金属、ｎはMの原子価を示す）、Ｘは同種もしくは異種の炭素原子数2〜14の二価炭化水素基、ｐは０〜１０の整数である。］
〔２〕一般式（１）において、Mがアルカリ金属であり、二価炭化水素基Ｘがアルキレン基である〔１〕に記載のゲル化剤。
〔３〕一価炭化水素基（−Ｚ）が炭素原子数１０〜４５のアルキル基である〔１〕に記載のゲル化剤。
〔４〕オルガノポリシロキサンが下記一般式（２）で表される直鎖状オルガノポリシロキサンである〔１〕に記載のゲル化剤

［式中、Ｒは炭素原子数１〜８の非置換もしくは置換の一価炭化水素基（ただし、一般式（１）で表される有機基を除く）、Ｙは上記一般式（１）で表される有機基、Ｚは炭素原子数９以上の置換もしくは非置換の一価炭化水素基、BはR、Ｙ、Ｚから選ばれ、ｔ＝０のとき、Bのうち少なくとも一つはＹであり、u＝０のとき、Ｂのうち少なくとも一つはＺであり、ｔ＝０かつｕ＝０であるとき、Ｂのうち一方はＹであり、他方はＺである。ｓは１０〜１０００００の整数であり、ｔは０〜５０の整数であり、uは０〜１０００である。］
〔５〕一般式（２）において、Rが炭素原子数1〜8のアルキル基であり、(ｓ＋ｔ＋ｕ)が２０〜５０００の整数であり、ｔ／(ｓ＋ｔ＋ｕ)が０．００１〜０．０５であり、ｕ／(ｓ＋ｔ＋ｕ)が０．００１〜０．３０である〔４〕に記載のゲル化剤。
〔６〕シリコーンオイル用、非極性有機化合物用または低極性有機化合物用である〔１〕〜〔５〕のいずれか1項に記載のゲル化剤。
〔７〕（Ａ）〔１〕〜〔６〕のいずれか１項に記載のゲル化剤 １〜99重量％
および
（Ｂ）シリコーンオイル、非極性有機化合物または低極性有機化合物 99〜１重量％
からなることを特徴とするゲル状組成物。
〔８〕シリコーンオイルが２５℃における粘度が０．６５〜１００，０００ｍｍ^２／ｓの疎水性シリコーンオイルであるである〔７〕に記載のゲル状組成物。
〔９〕非極性有機化合物または低極性有機化合物が５〜１００℃で液状である〔７〕に記載のゲル状組成物。
〔１０〕ゲル状組成物の屈折率が１．２０〜１．６０の範囲にあることを特徴とする〔７〕〜〔９〕のいずれか１項に記載のゲル状組成物。
〔１１〕〔１〕〜〔６〕のいずれか１項に記載のゲル化剤を配合した化粧料。
〔１２〕〔７〕〜〔１０〕のいずれか１項に記載のゲル状組成物を配合した化粧料。
〔１３〕更に（ｃ）アニオン性界面活性剤、カチオン性界面活性剤、ノニオン性界面活性剤、両性界面活性剤、半極性界面活性剤からなる群より選ばれる１種又は２種類以上を含有する〔１１〕または〔１２〕に記載の化粧料。
〔１４〕更に（ｄ）粉体及び／又は着色剤を含有する〔１１〕〜〔１３〕のいずれか１項に記載の化粧料。
〔１５〕（ｄ）成分が平均粒子径が1ｎｍ〜２０μｍの範囲にある無機顔料粉体、有機顔料粉体、樹脂粉体よりなる群より選ばれる１種又は２種類以上の粉体及び／または着色剤である〔１４〕に記載の化粧料。
〔１６〕（ｄ）成分の一部または全部が撥水化処理された粉体及び／または着色剤である〔１４〕または〔１５〕に記載の化粧料。
〔１７〕更に（ｅ）水溶性高分子を含有する〔１１〕〜〔１６〕のいずれか１項に記載の化粧料。
〔１８〕更に（ｆ）シリコーン樹脂を含有する〔１１〕〜〔１７〕のいずれか１項に記載の化粧料。
〔１９〕更に（ｇ）シリコーンエラストマーを含有する〔１１〕〜〔１８〕のいずれか１項に記載の化粧料。
〔２０〕更に（ｈ）紫外線防御成分を含有する〔１１〕〜〔１９〕のいずれか１項に記載の化粧料。
〔２１〕〔１１〕〜〔２０〕のいずれか１項に記載された化粧料からなる皮膚洗浄剤製品。
〔２２〕〔１１〕〜〔２０〕のいずれか１項に記載された化粧料からなるクレンジング化粧品。」に関する。 That is, the present invention provides “[1] an organic group (—Y) represented by the general formula (1) bonded to a silicon atom and a substituted or unsubstituted monovalent carbon atom having 9 or more carbon atoms bonded to the silicon atom. A gelling agent comprising an organopolysiloxane having a hydrogen group (-Z) in the molecule.
General formula (1):

[In the formula, R ^{1 -COO - (M n +) 1} / n represented by metal salts of carboxylic acids (M is a monovalent or more metals, n represents represents an atomic valence of M), X is identical or different Divalent hydrocarbon group having 2 to 14 carbon atoms, p is an integer of 0 to 10. ]
[2] The gelling agent according to [1], wherein, in the general formula (1), M is an alkali metal and the divalent hydrocarbon group X is an alkylene group.
[3] The gelling agent according to [1], wherein the monovalent hydrocarbon group (—Z) is an alkyl group having 10 to 45 carbon atoms.
[4] The gelling agent according to [1], wherein the organopolysiloxane is a linear organopolysiloxane represented by the following general formula (2):

[Wherein, R represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms (excluding the organic group represented by the general formula (1)), and Y represents the above general formula (1). An organic group represented, Z is a substituted or unsubstituted monovalent hydrocarbon group having 9 or more carbon atoms, B is selected from R, Y, and Z, and when t = 0, at least one of B is Y And when u = 0, at least one of B is Z, and when t = 0 and u = 0, one of B is Y and the other is Z. s is an integer of 10 to 100,000, t is an integer of 0 to 50, and u is 0 to 1000. ]
[5] In the general formula (2), R is an alkyl group having 1 to 8 carbon atoms, (s + t + u) is an integer of 20 to 5000, and t / (s + t + u) is 0.001 to 0.05. The gelling agent according to [4], wherein u / (s + t + u) is 0.001 to 0.30.
[6] The gelling agent according to any one of [1] to [5], which is for silicone oil, nonpolar organic compound, or low polarity organic compound.
[7] (A) 1 to 99% by weight of a gelling agent according to any one of [1] to [6]
And (B) 99 to 1% by weight of silicone oil, non-polar organic compound or low-polar organic compound
A gel-like composition comprising:
[8] The gel composition according to [7], wherein the silicone oil is a hydrophobic silicone oil having a viscosity of 0.65 to 100,000 mm ² / s at 25 ° C.
[9] The gel composition according to [7], wherein the nonpolar organic compound or the low polarity organic compound is liquid at 5 to 100 ° C.
[10] The gel composition according to any one of [7] to [9], wherein the refractive index of the gel composition is in the range of 1.20 to 1.60.
[11] A cosmetic comprising the gelling agent according to any one of [1] to [6].
[12] A cosmetic comprising the gel composition according to any one of [7] to [10].
[13] Further, (c) contains one or more selected from the group consisting of an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and a semipolar surfactant. [11] or the cosmetic according to [12].
[14] The cosmetic according to any one of [11] to [13], further comprising (d) a powder and / or a colorant.
[15] The component (d) has one or more powders selected from the group consisting of inorganic pigment powder, organic pigment powder, and resin powder having an average particle diameter in the range of 1 nm to 20 μm and / or The cosmetic according to [14], which is a colorant.
[16] The cosmetic according to [14] or [15], wherein part or all of the component (d) is a water-repellent-treated powder and / or colorant.
[17] The cosmetic according to any one of [11] to [16], further comprising (e) a water-soluble polymer.
[18] The cosmetic according to any one of [11] to [17], further comprising (f) a silicone resin.
[19] The cosmetic according to any one of [11] to [18], further comprising (g) a silicone elastomer.
[20] The cosmetic according to any one of [11] to [19], further comprising (h) an ultraviolet protection component.
[21] A skin cleanser product comprising the cosmetic according to any one of [11] to [20].
[22] A cleansing cosmetic comprising the cosmetic according to any one of [11] to [20]. ".

According to the present invention, a gelling agent that can easily gel silicone oil, non-polar organic compounds and low-polar organic compounds, particularly organic oils having a high alkyl group content, without using water together, and heat stability In addition, it is possible to provide a gel composition having excellent stability with time and thixotropic rheological properties, and further a gelling agent or a cosmetic blended with the gel composition.

一般式（１）において、Ｒ^１は−COO⁻（M^ｎ＋）_１／ｎで表されるカルボン酸の金属塩（Mは一価以上の金属、ｎはMの原子価を示す）であり、Ｘは同種もしくは異種の炭素原子数2〜14の二価炭化水素基、ｐは０〜１０の整数を表す。二価炭化水素基Ｘはアルキレン基が一般的であり、中でも炭素原子数２〜６のアルキレン基が好ましく、エチレン基またはプロピレン基が特に好ましい。ｐは０と１が好ましい。一般式（１）で表される有機基としては、下式で表される有機基が例示される。式中、Mは一価以上の金属であり、ｎはMの原子価を表す。

The gelling agent of the present invention includes an organic group (—Y) represented by the general formula (1) bonded to a silicon atom and a substituted or unsubstituted monovalent hydrocarbon group having 9 or more carbon atoms bonded to the silicon atom. It is an organopolysiloxane having (-Z).

In the general formula (1), R ¹ is a metal salt of a carboxylic acid represented by —COO ⁻ (M ^{n +} ) _{1 / n} (M is a monovalent or higher metal, and n is a valence of M), X represents the same or different divalent hydrocarbon group having 2 to 14 carbon atoms, and p represents an integer of 0 to 10. The divalent hydrocarbon group X is generally an alkylene group, among which an alkylene group having 2 to 6 carbon atoms is preferable, and an ethylene group or a propylene group is particularly preferable. p is preferably 0 or 1. Examples of the organic group represented by the general formula (1) include organic groups represented by the following formula. In the formula, M is a monovalent or higher metal, and n represents the valence of M.

A substituted or unsubstituted monovalent hydrocarbon group (-Z) having 9 or more carbon atoms bonded to a silicon atom is one of the characteristic structures of the organopolysiloxane of the present invention, and has an alkyl group content. It is a hydrophobic functional group introduced into the organopolysiloxane molecule in order to improve compatibility with many organic oils. In addition to the functional group represented by the general formula (1), the organopolysiloxane of the present invention has a functional group bonded to a silicon atom in the molecule. In addition, a gel-like composition having excellent compatibility, excellent thermal stability and stability over time, and thixotropic rheological properties can be formed.

The substituted or unsubstituted monovalent hydrocarbon group (-Z) having 9 or more carbon atoms bonded to the silicon atom in the organopolysiloxane of the present invention may be the same as or different from each other.
The structure of the monovalent hydrocarbon group (—Z) is selected from linear, branched, and partially branched, and a linear monovalent hydrocarbon group is preferably used. Examples of such an unsubstituted monovalent hydrocarbon group include an alkyl group, an aryl group or an aralkyl group having 9 or more carbon atoms, preferably 9 to 1000 carbon atoms. In addition, as a substituted monovalent hydrocarbon group, a perfluoroalkyl group, an aminoalkyl group, or an amidoalkyl group having 9 or more carbon atoms, preferably 9 to 1000 carbon atoms (however, an organic group represented by the general formula (1)) ), And carbinol groups. Moreover, a part of carbon atoms of the monovalent hydrocarbon group may be substituted with an alkoxy group, and examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group. Such a monovalent hydrocarbon group (—Z) is preferably a linear alkyl group, particularly preferably an alkyl group having 10 to 45 carbon atoms. A particularly preferred linear alkyl group having 10 to 45 carbon atoms is specifically a group represented by the general formula: — (CH ₂ ) _v —CH ₃ (v is a number in the range of 8 to 44). It is.

式（３）、式（４）において、Ｒ^１，Ｘ，ｐは前記と同様の基であり、Ｒは炭素原子数１〜８の非置換もしくは置換の一価炭化水素基である。非置換の一価炭化水素基としては、メチル基、エチル基、プロピル基等のアルキル基；フェニル基、トリル基、キシリル基等のアリール基；アラルキル基が例示される。置換一価炭化水素基としては、３，３，３−トリフロロプロピル基、３，３，４，４，４−ペンタフロロブチル基などのパーフルオロアルキル基；３−アミノプロピル基、３−（アミノエチル）アミノプロピル基等のアミノアルキル基；アセチルアミノアルキル基等のアミドアルキル基（ただし、一般式（１）で表される有機基は除く）が例示される。また、Ｒの一部がアルコキシ基で置換されていてもよく、アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基が例示される。Ｒは、これらの中でもアルキル基、特にメチル基が一般的に用いられる。 Moreover, it has the organic group (-Y) represented by General formula (1) couple | bonded with the silicon atom, and the substituted or unsubstituted monovalent hydrocarbon group (-Z) of 9 or more carbon atoms couple | bonded with the silicon atom. The organopolysiloxane contains at least one siloxane unit represented by the following formula (3) or formula (4).

In the formulas (3) and (4), R ¹ , X, and p are the same groups as described above, and R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms. Examples of the unsubstituted monovalent hydrocarbon group include alkyl groups such as methyl group, ethyl group, and propyl group; aryl groups such as phenyl group, tolyl group, and xylyl group; and aralkyl groups. Examples of the substituted monovalent hydrocarbon group include perfluoroalkyl groups such as 3,3,3-trifluoropropyl group, 3,3,4,4,4-pentafluorobutyl group; 3-aminopropyl group, 3- ( An aminoalkyl group such as aminoethyl) aminopropyl group; an amidoalkyl group such as acetylaminoalkyl group (excluding the organic group represented by the general formula (1)) is exemplified. A part of R may be substituted with an alkoxy group, and examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group. Among these, R is generally an alkyl group, particularly a methyl group.

（式中、Ｒ、Ｚは前記と同様の基である。）
また、本発明のオルガノポリシロキサンは、さらに式Ｒ_３ＳｉＯ_１／２，Ｒ_２ＳｉＯ_２／２，ＲＳｉＯ_３／２およびＳｉＯ_４／２で示されるシロキサン単位の１種〜４種を含んでも良い。 Furthermore, the organopolysiloxane of the present invention contains at least one siloxane unit represented by the following formula (5) or formula (6).

(In the formula, R and Z are the same groups as described above.)
The organopolysiloxane of the present invention may further contain 1 to 4 types of siloxane units represented by the formulas R ₃ SiO _1/2 , R ₂ SiO _2/2 , RSiO _3/2 and SiO _4/2. .

Organopoly having an organic group (—Y) represented by the general formula (1) bonded to a silicon atom and a substituted or unsubstituted monovalent hydrocarbon group (—Z) having 9 or more carbon atoms bonded to the silicon atom Siloxane contains at least one siloxane unit represented by the formula (3) or formula (4) in one molecule, but preferably contains two or more from the viewpoint of gelation performance, which is the object of the present invention. Furthermore, it is preferable that this organopolysiloxane contains 0.1-50 mol% of siloxane units represented by General formula (3) or (4), and 0.5-30 mol% from the point of gelation ability. Is particularly preferred. Similarly, the organopolysiloxane of the present invention contains at least one siloxane unit represented by formula (5) or formula (6) in one molecule, but is an organic oil having a high alkyl group content, which is an object of the present invention. It is preferable to include two or more in order to improve the compatibility. Moreover, it is preferable that the siloxane unit shown by Formula (5) or Formula (6) is contained 1.0 to 75 mol% from the point of gelation ability of this organopolysiloxane and the compatibility with organic oil, It is particularly preferable to contain 30 mol%.

The organopolysiloxane of the present invention has at least one organic group represented by the general formula (1) in one molecule, but preferably contains two or more from the viewpoint of gelation performance which is the object of the present invention. The organic group represented by the general formula (1) is preferably contained in an amount of 0.5% by weight or more, and more preferably 1.0% by weight or more. The molecular structure of the organopolysiloxane may be linear, branched or cyclic, but is preferably linear. Further, the bonding position of the organic group represented by the general formula (1) is not particularly limited, and when the organopolysiloxane has a linear or branched structure, the bonding position may be either a molecular chain end or a side chain. However, side chains are preferred.

In addition, the substituted or unsubstituted monovalent hydrocarbon group (-Z) having 9 or more carbon atoms bonded to the silicon atom includes two groups from the viewpoint of gelling ability of the organopolysiloxane and compatibility with organic oil. It is preferable to contain the above, and the bonding position is not particularly limited. When the organopolysiloxane has a linear or branched structure, the bonding position may be either a molecular chain terminal or a side chain, but a side chain is preferred.

式中、Ｒは前記同様の基であり、Ｙは上記一般式（１）で表される有機基、Ｚは炭素原子数９以上の置換もしくは非置換の一価炭化水素基、BはR、Ｙ、Ｚから選ばれ、ｔ＝０のとき、Bのうち少なくとも一つはＹであり、u＝０のとき、Ｂのうち少なくとも一つはＺであり、ｔ＝０かつｕ＝０であるとき、Ｂのうち一方はＹであり、他方はＺである。ｓは１０〜１０００００の整数であり、ｔは０〜５０の整数であり、uは０〜１０００である。ここで、ｔ／(ｓ＋ｔ＋ｕ)は０．１〜５％であることが好ましく、０．１〜３％がより好ましい。u／(ｓ＋ｔ＋ｕ)は１．０〜７５％であることが好ましく、５〜３０％がより好ましい。また、(ｓ＋ｔ＋ｕ)は２０〜５０００であることが、取り扱い、ゲル化能の点から特に好ましい。ケイ素原子に結合した一般式（１）で表される有機基を有するオルガノポリシロキサンは、常温で微濁〜白濁した粘稠な液体またはペースト状または固体であり、常温でペースト状または固体であることが好ましい。 Organopoly having an organic group (—Y) represented by the general formula (1) bonded to a silicon atom and a substituted or unsubstituted monovalent hydrocarbon group (—Z) having 9 or more carbon atoms bonded to the silicon atom As a typical example of siloxane, linear organopolysiloxane represented by the general formula (2) is exemplified as a suitable gelling agent.

In the formula, R is the same group as described above, Y is an organic group represented by the general formula (1), Z is a substituted or unsubstituted monovalent hydrocarbon group having 9 or more carbon atoms, B is R, Selected from Y and Z, when t = 0, at least one of B is Y, and when u = 0, at least one of B is Z, t = 0 and u = 0 Sometimes one of B is Y and the other is Z. s is an integer of 10 to 100,000, t is an integer of 0 to 50, and u is 0 to 1000. Here, t / (s + t + u) is preferably 0.1 to 5%, and more preferably 0.1 to 3%. u / (s + t + u) is preferably 1.0 to 75%, more preferably 5 to 30%. Further, (s + t + u) is particularly preferably 20 to 5000 from the viewpoint of handling and gelling ability. The organopolysiloxane having an organic group represented by the general formula (1) bonded to a silicon atom is a viscous liquid or paste or solid that is slightly turbid to white turbid at room temperature, and is pasty or solid at room temperature. It is preferable.

（式中、Ｒ^２は−ＣＯＯＨで表されるカルボキシル基もしくは−ＣＯＯＲ^４で表されるカルボン酸エステル基、Ｒ^４は炭素原子数１〜１０の一価炭化水素基、Ｘは同種もしくは異種の炭素原子数２〜１４の二価炭化水素基、ｐは０〜１０の整数である。）
(Ｍ^ｎ+)j(Ｌ^j-)ｎ （６）
（式中、Ｍは一価以上の金属、Ｌは酸素原子、またはアニオンを示し、ｎはＭの原子価、ｊはＬの価数を示す。） The organopolysiloxane having an organic group represented by the general formula (1) bonded to a silicon atom is, for example, an organic group represented by the general formula (5) and a substituted or unsubstituted monovalent having 9 or more carbon atoms. It can be produced by reacting an organopolysiloxane having both a hydrocarbon group (-Z) and a metal compound represented by the following general formula (6).

(In the formula, R ² is a carboxyl group represented by —COOH or a carboxylic acid ester group represented by —COOR ⁴ , R ⁴ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and X is the same or different. (The divalent hydrocarbon group having 2 to 14 carbon atoms, p is an integer of 0 to 10.)
(M ^{n +} ) j (L ^j− ) n (6)
(In the formula, M represents a monovalent or higher metal, L represents an oxygen atom or an anion, n represents a valence of M, and j represents a valence of L.)

（式中、Ｘは同種もしくは異種の炭素原子数2〜14の二価炭化水素基、ｐは０〜１０の整数を表す。ｐは０と１が好ましく、二価炭化水素基Ｘはアルキレン基が一般的であり、中でも炭素原子数２〜６のアルキレン基が好ましく、エチレン基またはプロピレン基が特に好ましい。）
環状カルボン酸無水物としては、コハク酸無水物、マレイン酸無水物、イタコン酸無水物、シトラコン酸無水物、アリルコハク酸無水物、フタル酸無水物、ノルボルネンジカルボン酸無水物、シクロヘキサンジカルボン酸無水物、ノネニルコハク酸無水物、デセニルコハク酸無水物が例示される。これらの中でも、ゲル化性能とゲル状組成物の透明性の点からコハク酸無水物が好ましい。アミノ官能性オルガノポリシロキサン中のアミノ基と環状カルボン酸無水物間のアミド化反応は公知であり、無溶媒または適当な溶媒存在下で発熱的に進行する。前者中のアミノ基と後者のカルボン酸無水物とのモル比はアミド基とカルボキシル基が生成しさえすれば任意であるが、アミノ基の残存量が多すぎるとゲル状組成物のべたつきが増し、ゲル化性能も低下するため、カルボン酸無水物／アミノ基＝０．５〜１の範囲が好ましく、０．９〜１の範囲がさらに好ましい。 As a synthesis method of the organopolysiloxane having an organic group represented by the general formula (5) and a substituted or unsubstituted monovalent hydrocarbon group (-Z) having 9 or more carbon atoms, A method in which an organopolysiloxane having a substituted or unsubstituted monovalent hydrocarbon group (—Z) and an amino group at the same time and a cyclic carboxylic acid anhydride are preferably used. The amino-functional organopolysiloxane is an organopolysiloxane having an amino group bonded to silicon via a divalent hydrocarbon group, and an organopolysiloxane having an organic group represented by the general formula (7) bonded to a silicon atom. Siloxane is exemplified.

(In the formula, X represents the same or different divalent hydrocarbon group having 2 to 14 carbon atoms, p represents an integer of 0 to 10. p is preferably 0 or 1, and the divalent hydrocarbon group X is an alkylene group. (In general, an alkylene group having 2 to 6 carbon atoms is preferable, and an ethylene group or a propylene group is particularly preferable.)
Examples of cyclic carboxylic acid anhydrides include succinic anhydride, maleic anhydride, itaconic anhydride, citraconic anhydride, allyl succinic anhydride, phthalic anhydride, norbornene dicarboxylic anhydride, cyclohexane dicarboxylic anhydride, Nonenyl succinic anhydride and decenyl succinic anhydride are exemplified. Among these, succinic anhydride is preferable from the viewpoint of gelation performance and transparency of the gel composition. The amidation reaction between an amino group in an amino-functional organopolysiloxane and a cyclic carboxylic anhydride is known and proceeds exothermically in the absence of a solvent or in the presence of a suitable solvent. The molar ratio between the amino group in the former and the carboxylic acid anhydride in the latter is arbitrary as long as amide groups and carboxyl groups are formed. However, if the residual amount of amino groups is too large, the stickiness of the gel composition increases. Further, since the gelling performance is also lowered, the range of carboxylic acid anhydride / amino group = 0.5 to 1 is preferable, and the range of 0.9 to 1 is more preferable.

A polyorganopolysiloxane having a substituted or unsubstituted monovalent hydrocarbon group (-Z) having 9 or more carbon atoms and an amino group represented by the formula (7) can be synthesized by a known method. . The synthesis method is not limited, but various kinds of substituted or unsubstituted monovalent hydrocarbon group (-Z) -containing polyorganosiloxane, organopolysiloxane, amino-functional organopolysiloxane having 9 or more carbon atoms can be used. Equilibrium Polymerization Method Using Organo-Catalysts, Organohydrogen Polyorganopolysiloxanes, Compounds Containing Simultaneously a Substituted or Unsubstituted Monovalent Hydrocarbon Group (-Z) and Unsaturated Groups with 9 or More Carbon Atoms and Unsaturation Preferred examples include a method of synthesizing an amino functional compound having a group by a hydrosilylation reaction in the presence of various transition metal catalysts.

As an organic group represented by General formula (5) synthesize | combined by the said method, the organic group represented by the following Formula is illustrated.

The general formula (5) in the organic group represented by the terminal carboxyl group or terminal carboxylic acid ester group of the formula ^{-COO - (M n +) 1} / n represented by metal salts of carboxylic acids (M is one or more valences When converting to an organic group represented by the general formula (1) including a metal, n represents the valence of M, the general formula (6): (M ^{n +} ) j (L ^j− ) n The metal compound represented is used. M represents a monovalent or higher valent metal, L represents an oxygen atom or an anion, n represents a valence of M, and j represents a valence of L. Examples of the metal represented by M include lithium, sodium, potassium, magnesium, calcium, barium, iron, cobalt, aluminum, nickel, copper, vanadium, molybdenum, niobium, zinc, titanium, and the like. From the viewpoint of the transparency of the gel composition formed using the gelling agent according to the present invention and the stability of the gel composition, the metal is an alkali metal such as sodium or potassium, or an alkaline earth such as magnesium or calcium. Preferred metals and aluminum are preferred. By using a monovalent alkali metal, sodium and potassium are particularly preferably used because the fluidity of the resulting gel composition changes reversibly with temperature.

Specific examples of such metal compounds include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, iron hydroxide, copper hydroxide, and zinc hydroxide. Metal alkoxides such as methoxy lithium, sodium methoxy, methoxy potassium, ethoxy lithium, ethoxy sodium, ethoxy potassium, and t-butoxy potassium; alkali metal arylates such as phenoxy lithium, phenoxy sodium, phenoxy potassium, and para methoxyphenoxy sodium; lithium, sodium Alkali metals such as potassium, alkali metal hydrides such as lithium hydride, sodium hydride, potassium hydride; methyl lithium, n-butyl lithium, sec-butyl lithium, t-butyl lithium, n-butyl Alkyl metals such as sodium, n-butylpotassium and diethylzinc; unsubstituted or substituted arylalkali metals such as phenyllithium, phenylsodium and potassium naphthalenide; copper fluoride, calcium chloride, aluminum chloride, magnesium chloride, zinc chloride Metal halides such as iron chloride, copper chloride, titanium tetrachloride, calcium bromide, aluminum bromide, magnesium bromide, zinc bromide and iron bromide; metals such as magnesium oxide, copper oxide, titanium oxide and zinc oxide Oxides; Metal carbonates such as calcium carbonate, barium carbonate, and copper carbonate; Metal sulfates such as magnesium sulfate, calcium sulfate, zinc sulfate, iron sulfate, copper sulfate, and aluminum sulfate. Among these, metal hydroxides, metal alcoholates, and metal halides are preferable from the viewpoint of reactivity, cost, and workability.

The metal compound represented by the general formula (6) can be directly reacted with a carboxylic acid or a carboxylic acid ester-modified organopolysiloxane, but a carboxylic acid or a carboxylic acid ester is reacted with a metal compound to form a metal salt. It is also possible to react with a different metal compound. Since the reaction conditions of the carboxylic acid, carboxylic acid ester, and monovalent and / or polyvalent metal salt of the carboxylic acid with the metal compound represented by the general formula (6) depend on the metal compound to be reacted, Although it cannot be defined, the reaction may be carried out by dispersing in an appropriate solvent in consideration of the reactivity of the metal compound.

The formula ^{-COO - (M n +) 1} / n represented by metal salts of carboxylic acids (M is a monovalent or more metals, n represents represents an atomic valence of M) is represented by the general formula (1) containing a The organic group (—Y) formation reaction usually proceeds easily at a temperature of about room temperature to about 100 ° C. The molar ratio of the reaction between the carboxyl group or carboxylic acid ester group contained in the organopolysiloxane having an organic group represented by the general formula (5) and the metal compound represented by the general formula (6) is arbitrary. The molar ratio of carboxyl group or carboxylic acid ester group / the metal compound is preferably in the range of 0.1 to 5.0, more preferably in the range of 0.4 to 2.0. When the molar ratio of the reaction exceeds the upper limit, the resulting organopolysiloxane having an organic group represented by the general formula (1) cannot exhibit sufficient gelling performance. This is because when the compound is used for the reaction, the system becomes strongly alkaline and the siloxane bond of the organopolysiloxane may be cleaved, and the stability of the generated gel is lowered.

Further, only a part of the terminal carboxyl group or the terminal carboxylate group of the organic group represented by the general formula (5) is represented by the general formula (6): (M ^{n +} ) j (R ^j− ) n. It can neutralize with a metal compound and can convert into the organic group (-Y) represented by General formula (1). Thereby, the softness of the gel-like composition obtained can be adjusted. For example, the general formula (6) having a neutralization amount of 80% with respect to the terminal carboxyl group or the terminal carboxylate group of the organic group represented by the general formula (5): (M ^{n +} ) j (R ^j− ) By adding the metal compound represented by n, an organopolysiloxane having an organic group represented by the general formula (1) and an organic group represented by the general formula (5) can be prepared. The gel obtained using the organopolysiloxane was prepared by adding a metal compound represented by the general formula (6) :( M ^{n +} ) j (R ^j− ) n having a neutralization amount of 100%. Compared to a gel obtained using an organopolysiloxane having an organic group represented by the formula (1), it has a soft feel.

The organopolysiloxane having an organic group (—Y) represented by the general formula (1) and a substituted or unsubstituted monovalent hydrocarbon group (—Z) having 9 or more carbon atoms is a silicone oil, non- When it is well mixed with a polar organic compound or a low polarity organic compound and then cooled to room temperature, it has a property of gelling, so it is suitable as a gelling agent for silicone oil, nonpolar organic compound or low polarity organic compound. In particular, the organopolysiloxane is excellent in compatibility with non-polar organic compounds or low-polar organic compounds having a high alkyl group content, and is therefore suitable for gelling such organic oils. Note that silicone oil, non-polar organic compound or low-polar organic compound having a low alkyl group content can be suitably gelled without any inconvenience.

Furthermore, the organopolysiloxane having an organic group (—Y) represented by the general formula (1) and a substituted or unsubstituted monovalent hydrocarbon group (—Z) having 9 or more carbon atoms is methanol, ethanol, isopropyl alcohol. Since gelation performance with respect to polar organic compounds such as the above is low, it is possible to prepare a gel-like material by utilizing this property. That is, silicone oil, a nonpolar organic compound or a low polarity organic compound and a polar organic compound are mixed, and the organic group represented by the general formula (5) and a substituted or unsubstituted one having 9 or more carbon atoms are mixed in the mixture. A liquid reaction mixture is prepared by subjecting an organopolysiloxane having a valent hydrocarbon group (-Z) and a metal compound represented by the general formula (6) to a salt formation reaction, and then the polar organic compound is distilled off under reduced pressure. By doing so, a gel-like composition can be obtained.

The gel composition of the present invention is
(A) 1 to 99% by weight of an organopolysiloxane having an organic group (—Y) represented by the general formula (1) and a substituted or unsubstituted monovalent hydrocarbon group (—Z) having 9 or more carbon atoms; (B) A silicone oil other than the component (A), a nonpolar organic compound or a low-polar organic compound is composed of 99 to 1% by weight.

In the gel composition of the present invention, the component (A) acts as a gelling agent for the component (B). The component (B) silicone oil, nonpolar organic compound or low polarity organic compound may be used alone, or a mixture comprising 2-3 of silicone oil, nonpolar organic compound and low polarity organic compound is used. Also good. The ratio of the component (A) to the component (B) is the weight percentage of the gel composition and is in the range of (A) :( B) = 1 to 99:99 to 1, but 2 to 40:98 to 60 The range of 2-30: 98-70 is more preferable.

The silicone oil does not include those corresponding to the component (A), and the structure may be any of cyclic, linear, and branched, but is hydrophobic silicone oil in terms of easy gelation. it is preferably, the viscosity at 25 ° C., usually from 0.65~100000mm ² / s, preferably a range of 0.65~10000mm ² / s. Specifically, cyclic diorganopolysiloxanes such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane; hexamethyldisiloxane, trimethylsiloxy group-blocked dimethylpolysiloxane at both ends, trimethylsiloxy group-blocked methylphenylpolysiloxane at both ends, Linear diorganopolysiloxane such as trimethylsiloxy group-blocked methylalkylpolysiloxane on both ends, branched organopolysiloxane such as methyltristrimethylsiloxysilane, ethyltristrimethylsiloxysilane, propyltristrimethylsiloxysilane, tetrakistrimethylsiloxysilane, etc. Of these, volatile linear dimethylpolysiloxane, branched methylpolysiloxane and cyclic dimethylpolysiloxane are preferred. , In particular, decamethylcyclopentasiloxane are preferred.

（一般式（８）〜（１０）において、Ｒ^２ は、水素原子、水酸基又は炭素数２から３０の一価の非置換又はフッ素置換アルキル基、アリール基、アミノ置換アルキル基、アルコキシ基及び(CH3)3SiO{(CH3)2SiO}ｈSi(CH3)2CH2CH2-で示される基から選択される基であり、具体的には、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、デシル基、ドデシル基などの飽和脂肪族炭化水素基；ビニル基、アリル基、ヘキセニル基などの不飽和脂肪族炭化水素基；シクロペンチル基、シクロヘキシル基などの飽和脂環式炭化水素基；フェニル基、トリル基、ナフチル基などの芳香族炭化水素基および、これらの基の炭素原子に結合した水素原子が部分的にハロゲン原子、エポキシ基、カルボキシル基、アミノ基、メタクリル基、メルカプト基などを含む有機基または２価の炭化水素基及び／または鎖状のポリジメチルシロキサン結合を介して結合されたトリメチルシロキシ基で置換された基が例示される。ｃは０から１０００の整数、ｄは０から１０００の整数、ｃ+ｄが１から２０００の整数、a、bは０、１、２又は３、e及びfは０〜８の整数で３≦e＋f≦８、gは１〜４の整数、hは０〜５００の整数である。） More specifically, as the silicone oil constituting part or all of the component (B), the linear organopolysiloxane represented by the following general formula (8) or the cyclic organopolysiloxane represented by the general formula (9) and the general Examples thereof include branched organopolysiloxanes represented by the formula (10).

(In the general formulas (8) to (10), R ² represents a hydrogen atom, a hydroxyl group, or a monovalent unsubstituted or fluorine-substituted alkyl group having 2 to 30 carbon atoms, an aryl group, an amino-substituted alkyl group, an alkoxy group, and ( CH3) 3SiO {(CH3) 2SiO} hSi (CH3) 2CH2CH2- is a group selected from, specifically, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, Saturated aliphatic hydrocarbon groups such as octyl group, decyl group and dodecyl group; unsaturated aliphatic hydrocarbon groups such as vinyl group, allyl group and hexenyl group; saturated alicyclic hydrocarbon groups such as cyclopentyl group and cyclohexyl group; Aromatic hydrocarbon groups such as phenyl, tolyl and naphthyl groups and hydrogen atoms bonded to carbon atoms of these groups are partially halogen atoms, epoxy groups, carboxyl groups, amino groups, methacrylic groups. And a group substituted with a trimethylsiloxy group bonded through an organic group containing a mercapto group or the like or a divalent hydrocarbon group and / or a chain-like polydimethylsiloxane bond, and c is from 0 to 1000. Integer, d is an integer from 0 to 1000, c + d is an integer from 1 to 2000, a, b are 0, 1, 2, or 3, e and f are integers from 0 to 8, and 3 ≦ e + f ≦ 8, g is (An integer of 1-4, h is an integer of 0-500.)

Specific examples of silicone oils having these structures include hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane as cyclic organopolysiloxanes. Siloxane (D6), 1,1-diethylhexamethylcyclotetrasiloxane, phenylheptamethylcyclotetrasiloxane, 1,1-diphenylhexamethylcyclotetrasiloxane, 1,3,5,7-tetravinyltetramethylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7-tetracyclohexyltetramethylcyclotetrasiloxane, tris (3,3,3-trifluoropropyl) trimethylcyclotrisiloxane 1,3,5,7-tetra (3-aminopropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (N- (2-aminoethyl) 3-aminopropyl) tetramethylcyclotetra Siloxane, 1,3,5,7-tetra (3-mercaptopropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (3-glycidoxypropyl) tetramethylcyclotetrasiloxane, 1,3, 5,7-tetra (3-methacryloxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (3-acryloxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra ( 3-carboxypropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (3-vinyloxypropyl) Tramethylcyclotetrasiloxane, 1,3,5,7-tetra (p-vinylphenyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra [3- (p-vinylphenyl) propyl] tetramethylcyclo Tetrasiloxane, 1,3,5,7-tetra [3- (p-isopropenylbenzoylamino) propyl] tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (N-methacryloyl-N-methyl-3) -Aminopropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (N-lauroyl-N-methyl-3-aminopropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (N -Acryloyl-N-methyl-3-aminopropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-te La (N, N-bis (methacryloyl) -3-aminopropyl) tetramethylcyclotetrasiloxane, 1,3,5,7-tetra (N, N-bis (lauroyl) -3-aminopropyl) tetramethylcyclotetra Siloxane is exemplified. As the linear organopolysiloxane, trimethylsiloxy group-blocked dimethylpolysiloxane with molecular chain at both ends, trimethylsiloxy group-blocked methylphenylpolysiloxane with molecular chain at both ends, trimethylsiloxy group-blocked dimethylsiloxane / methylphenylsiloxane with molecular chain at both ends Combined, trimethylsiloxy group-capped dimethylsiloxane methyl (3,3,3-trifluoropropyl) siloxane copolymer, α, ω-dihydroxypolydimethylsiloxane, α, ω-dimethoxypolydimethylsiloxane, tetramethyl Examples include -1,3-dihydroxydisiloxane, octamethyl-1,7-dihydroxytetrasiloxane, hexamethyl-1,5-diethoxytrisiloxane, hexamethyldisiloxane, and octamethyltrisiloxane.

The nonpolar organic compound or the low polarity organic compound is preferably liquid at 5 to 100 ° C. Such nonpolar organic compounds or low polarity organic compounds include, for example, hydrocarbon oils such as ozokerite, squalane, squalene, ceresin, paraffin (including heavy liquid paraffin or light liquid paraffin), paraffin wax, pristane, polyisobutylene, polybutene, Microcrystalline wax, petrolatum, etc. As animal and vegetable oils, avocado oil, linseed oil, almond oil, ibotarou, eno oil, olive oil, cacao butter, kapok wax, kaya oil, carnauba wax, liver oil, candelilla wax, beef tallow, beef leg fat, Beef bone fat, hydrogenated beef tallow, Kyonin oil, whale wax, hydrogenated oil, wheat germ oil, sesame oil, rice germ oil, rice bran oil, sugarcane wax, sasanqua oil, safflower oil, shea butter, cinnamon oil, cinnamon oil, jojoballow , Shellac low, tart Oil, soybean oil, tea seed oil, camellia oil, evening primrose oil, corn oil, lard, rapeseed oil, Japanese killi oil, nukarou, germ oil, horse fat, persic oil, palm oil, palm kernel oil, castor oil, hardened Castor oil, castor oil fatty acid methyl ester, sunflower oil, grape oil, bayberry wax, jojoba oil, macadamia nut oil, beeswax, mink oil, cottonseed oil, cotton wax, owl, owl kernel oil, montan wax, coconut oil, hardened coconut oil, tricoconut oil Fatty acid glyceride, sheep oil, peanut oil, lanolin, liquid lanolin, reduced lanolin, lanolin alcohol, hard lanolin, lanolin acetate, lanolin fatty acid isopropyl, hexyl laurate, POE lanolin alcohol ether, POE lanolin alcohol acetate, lanolin fatty acid polyethylene glycol, POE Hydrogenation Phosphoric alcohol ether, egg yolk oil, etc .; higher alcohols include lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, behenyl alcohol, hexadecyl alcohol, oleyl alcohol, isostearyl alcohol, hexyl decanol, octyldodecanol, cetostearyl alcohol , 2-decyltetradecinol, cholesterol, phytosterol, POE cholesterol ether, monostearyl glycerin ether (batyl alcohol), monooleyl glyceryl ether (ceralkyl alcohol), etc .; as ester oil, diisobutyl adipate, 2-hexyl adipate Decyl, di-2-heptylundecyl adipate, N-alkyl glycol monoisostearate, iso Isocetyl stearate, trimethylolpropane triisostearate, ethylene glycol di-2-ethylhexanoate, cetyl 2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate, pentaerythritol tetra-2-ethylhexanoate, octane Cetyl acid, octyldodecyl gum ester, oleyl oleate, octyldodecyl oleate, decyl oleate, isononyl isononanoate, neopentyl glycol dicaprate, triethyl citrate, 2-ethylhexyl succinate, amyl acetate, ethyl acetate, butyl acetate, Isocetyl stearate, butyl stearate, diisopropyl sebacate, di-2-ethylhexyl sebacate, cetyl lactate, myristyl lactate, isopropyl palmitate, palmitate 2-ethylhexyl, 2-hexyldecyl palmitate, 2-heptylundecyl palmitate, cholesteryl 12-hydroxystearylate, dipentaerythritol fatty acid ester, isopropyl myristate, 2-ethylhexyl myristate, octyldodecyl myristate, myristic acid 2-hexyldecyl, myristyl myristate, hexyldecyl dimethyloctanoate, ethyl laurate, hexyl laurate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, diisostearyl malate, etc .; Glyceryl, glyceryl triisooctanoate, glyceryl triisostearate, glyceryl triisopalmitate, glyceryl tri (capryl / caprate), monostearin Examples thereof include glyceryl acid, glyceryl di-2-heptylundecanoate, glyceryl trimyristate, and diglyceryl myristate.

The component (A) which is a gelling agent of the present invention has an advantage of excellent compatibility with the component (B) which is a nonpolar organic compound having a high alkyl group content or a low polarity organic compound, and is thermally stable. In addition, it is possible to easily form a gel composition having excellent properties and stability over time and having thixotropic rheological properties.

Such organic oils with a high alkyl group content include hydrocarbon oils such as heavy liquid paraffin, petrolatum, n-paraffin, hydrogenated polyisobutylene, ozokerite, ceresin, squalane, pristane; avocado oil, almond oil, olive oil, sesame oil, Vegetable oils such as sasanqua oil, safflower oil, soybean oil, camellia oil, corn oil, rapeseed oil, persic oil, castor oil, cottonseed oil, peanut oil, cocoa butter, palm oil, palm kernel oil, owl, coconut oil Animal fats such as mink oil, egg yolk oil, beef tallow, pork fat, hydrogenated oil; wax such as beeswax, carnauba wax, whale wax, lanolin, liquid lanolin, reduced lanolin, hard lanolin, candelilla wax, jojoba oil, microcrystalline wax Kinds: palmityl alcohol, stearyl alcohol, oleyl alcohol Higher alcohols such as lanolin alcohol, cholesterol, phytosterol, 2-hexyldecanol, isostearyl alcohol, 2-octyldodecanol; hexyl laurate, myristyl myristate, oleyl oleate, decyl oleate, octyldodecyl myristate, dimethyloctanoic acid Hexyldecyl, isononyl isononanoate, isotridecyl isononanoate, cetyl, myristyl lactate, lanolin acetate, ethylene glycol monostearate, propylene glycol monostearate, propylene glycol dioleate, glyceryl tristearate, diglyceryl dioleate, triisostearic acid Ester oils such as diglyceryl, tri-2-ethylhexanoic acid trimethylolpropane; liquid fatty acid triglyceride Id, artificial sebum (mixture of squalane and liquid fatty acid triglyceride and oleic acid). These organic oils can be mixed with the silicone oil in a ratio of 1:99 to 99: 1 to obtain the component (B) of the present invention.

As a method for preparing the gel composition of the present invention, a method of mixing the component (A) and the component (B), at least one carboxylic acid or carboxylic acid ester represented by the general formula (5) in one molecule. ( ^{Mn +} ) j ( ^Rj- ) n represented by the general formula (6) and the component (B) are mixed, and the organopolysiloxane and the metal compound are mixed in the component (B). Or a salt formation reaction in a solvent. The gel-like composition of the present invention is gel-like at room temperature, and cannot generally be said because gelation performance changes depending on the chemical structure of the component (A), but generally exhibits a liquid state at a high temperature of 50 ° C. or higher.

If the gel composition of the present invention is not liquefied at room temperature, water, lower alcohols such as ethanol, ethylene glycol and glycerin, polar liquid organic compounds such as phenols, amines and carboxylic acids are added and blended May be.

The gel composition comprising the component (A) and the component (B) is an organic group (—Y) represented by the general formula (1) contained in the component (A), particularly a monovalent or polyvalent metal salt. Type and content, content of substituted or unsubstituted monovalent hydrocarbon group (-Z) having 9 or more carbon atoms, type of silicon-bonded hydrocarbon group in component (A) and type of component (B) By adjusting, a gel composition excellent in transparency can be obtained. That is, selecting the type of X of the organic group (—Y) represented by the general formula (1) contained in the component (A), the number of p and / or the type of metal ion M ^{n +} , or (B) By selecting a silicone oil, a nonpolar organic compound or a low polarity organic compound that is colorless and transparent and has no turbid appearance as a component, a gel composition having a transparent appearance can be obtained. In order to obtain a gel composition having a transparent appearance, the component (A) in the general formula (1), X is an alkylene group, p is 0 or 1, and the metal ion M ^{n +} is a sodium ion (Na ⁺ ), An alkali metal ion such as potassium ion (K ⁺ ), or a methylpolysiloxane having an organic group which is an alkaline earth metal ion such as magnesium (Mg ²⁺ ) or calcium (Ca ²⁺ ), ) Transparency such as dimethylpolysiloxane or methylpolysiloxane having a viscosity of 0.65 to 10,000 mm ² / s at 25 ° C., liquid paraffin (including heavy liquid paraffin or light liquid paraffin), isoparaffin It is preferable that it is a nonpolar organic compound. (B) As a gel-like composition whose appearance is transparent as a component, it is preferable that the refractive index of a gel-like composition exists in the range of 1.20-1.60, and exists in the range of 1.25-1.45. It is particularly preferred.

The gelling agent of component (A) and the gel composition formed from component (A) and component (B) change the feel of application to a smooth and rich feel when blended in cosmetics. In addition, volatile silicone oils such as cyclic organopolysiloxanes having a low degree of polymerization that are easy to separate can be stably retained, so that there is an effect of improving the daily stability of cosmetics. Furthermore, the component (A) of the present invention can easily form a stable gel-like composition with an organic oil having a high alkyl group content, such as heavy liquid paraffin, and is blended in various cosmetics. In this case, there is an effect of improving the moisturizing feeling and feel.

In the cosmetics of this invention, it is preferable to mix | blend volatile silicone with the gelatinizer of this invention. Volatile silicone is rich in the effect of refreshing the touch, and when it contains a resin component such as a sunscreen agent or liquid foundation, it has a high ability to firmly fix the coating film on the skin. On the other hand, the volatile silicone may gradually separate in the container, and particularly when the tube container is filled with the volatile silicone-containing cosmetic, the volatile silicone accumulates at the tip of the tube, When the tube is used for the first time, there is a problem that only the separated volatile silicone pops out. In the cosmetic of the present invention, the combination of the gelling agent of the present invention, which is excellent in compatibility with the volatile silicone, and the volatile silicone are used in combination to suppress separation of the volatile silicone, thereby obtaining a more stable preparation. There is an excellent merit that In the cosmetic of the present invention, the blending amount of the gelling agent of the present invention and the volatile silicone ranges from 0.1 to 20% by mass of the gelling agent and 5 to 80% by mass of the volatile silicone with respect to the mass of the cosmetic. It is preferable that it exists in. Within this range, the gelling agent of the present invention is effectively compatible with volatile silicone and can exhibit a function of improving stability. The volatile silicone includes (i) volatile low molecular weight linear or cyclic methylsiloxane, (ii) volatile or nonvolatile low molecular weight linear or cyclic alkyl or arylsiloxane, or (iii) low molecular weight. A linear or cyclic functional siloxane is mentioned, and the volatile silicone is represented by the formula: (CH ₃ ) _a SiO _{(4-a) / 2} (wherein a has an average value of 2 to 3). Has an average unit. This compound contains siloxane units linked by ≡Si—O—Si≡ bond. Typical units are monofunctional “M” units (CH ₃ ) ₃ SiO _1/2 and difunctional “D” units (CH ₃ ) ₂ SiO _2/2 . Here, the presence of trifunctional “T” units CH ₃ SiO _3/2 results in the formation of volatile branched linear or cyclic methylsiloxanes. The presence of tetrafunctional “Q” units SiO _4/2 results in the formation of volatile branched linear or cyclic methylsiloxanes.

Linear volatile silicones formula: _(CH3) 3 _SiO represented by {(CH 3) 2 SiO} y Si (CH 3) 3. The value of y is 0-5. The cyclic volatile silicone is represented by the formula: {(CH ₃ ) ₂ SiO} z, and the value of z is 3 to 8, preferably 3 to 6. These volatile methylsiloxanes generally have a boiling point of less than 250 ° C. and a viscosity of 0.65 to 5.0 centistokes (mm ² / s). Some representative volatile linear methyl siloxanes (I) include hexamethyldioxy represented by the formula: (CH ₃ ) ₃ SiOSi (CH ₃ ) ₃ having a boiling point of 100 ° C. and a viscosity of 0.65 mm ² / s. siloxane (MM); boiling point 152 ° C. and a viscosity of 1.04mm2 / s _{formula: (CH 3) 3 SiO (} CH 3) 2 SiOSi (CH 3) octamethyltrisiloxane represented by ₃ (MDM); boiling point 194 ° C. And decamethyltetrasiloxane (MD ₂ M) represented by the formula: (CH ₃ ) ₃ SiO ((CH ₃ ) ₂ SiO) ₂ Si (CH ₃ ) ₃ ; boiling point 229 ° C. and viscosity 1.53 mm 2 / s 2.06mm2 / s of _{formula: (CH 3) 3 SiO (} (CH 3) 2 SiO) 3 Si dodecamethyl penta sheet represented by _{(CH 3) 3} Hexane _(MD 3 M); wherein the boiling point of 245 ° C. and a viscosity of _{2.63mm2 / s: (CH 3)} 3 SiO ((CH 3) 2 SiO) 4 Si tetradecanoyl methylhexahydrophthalic siloxanes represented by _{(CH 3) 3} (MD ₄ M); Hexadecamethylheptasiloxane represented by the formula: (CH ₃ ) ₃ SiO ((CH ₃ ) ₂ SiO) ₅ Si (CH ₃ ) _{3 having a} boiling point of 270 ° C. and a viscosity of 3.24 mm 2 / s MD ₅ M). Moreover, as a typical both-terminal trimethylsiloxy group-blocked methylalkylpolysiloxane (II), it is represented by the formula: (CH ₃ ) ₃ SiO ((CH ₃ ) (C ₈ H ₁₇ ) SiO) Si (CH ₃ ) ₃ Heptamethyloctyltrisiloxane (MDRM).

Some representative volatile cyclic methyl siloxanes (III) include hexamethylcyclotrisiloxane (D3) represented by the formula with a boiling point of 134 ° C .: {(CH ₃ ) ₂ SiO} ₃ ; boiling point of 176 ° C. and viscosity 2.3 mm ² / s formula: octamethylcyclotetrasiloxane (D4) represented by {(CH ₃ ) ₂ SiO} ₄ ; boiling point 210 ° C. and viscosity 3.87 mm ² / s formula: {(CH ₃ ) ₂ Decamethylcyclopentasiloxane (D5) represented by SiO} ₅ ; and dodecamethylcyclohexasiloxane represented by the formula: {(CH ₃ ) ₂ SiO} ₆ (boiling point 245 ° C. and viscosity 6.62 mm ² / s) D6). And some representative volatile branched methylsiloxanes (IV) and (V) include those having a boiling point of 192 ° C. and a viscosity of 1.57 mm ² / s: CH ₃ Si {OSi (CH ₃ ) ₃ } represented by ₃ heptamethyl -3 - {(trimethylsilyl) oxy} trisiloxane (M3T); viscosity 2.3 mm ² / s _wherein: hexamethyl represented by _{C 3 H 7 Si {OSi (} CH 3) 3} 3 3,3 propyl, {(trimethylsilyl) oxy} trisiloxane (M3T); formula-hexamethyl-3,3-ethyl represented by _{C2H5Si {OSi (CH 3) 3} } 3, {( trimethylsilyl) oxy} tri siloxane (M3T); wherein the boiling point of 222 ° C. and a viscosity of 2.86 mm ² / s: hexane represented by _{Si {OSi (CH 3) 3} } 4 3,3-bis {(trimethylsilyl) oxy} trisiloxane (M4 Q); and the _{formula: ((CH3) 2 SiO)} 2 {CH 3 Si (OSi (CH 3) 3) O} pentamethyl represented by {(Trimethylsilyl) oxy} cyclotrisiloxane (MD ₂ T). Among these, a combination with decamethylcyclopentasiloxane (D5) which is a cyclic pentamer dimethylpolysiloxane is particularly preferable.

The cosmetic according to the present invention is further selected from the group consisting of an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant and a semipolar surfactant as component (c). Two or more kinds of surfactants can be blended. It is preferable to blend one or more surfactants from the viewpoint of cleaning activity.

More specifically, as an anionic surfactant, saturated or unsaturated fatty acid salts (for example, sodium laurate, sodium stearate, sodium oleate, sodium linolenate, etc.), alkyl sulfates, alkylbenzene sulfonic acids (for example, hexylbenzene) Sulfonic acid, tocylbenzene sulfonic acid, dodecyl benzene sulfonic acid, etc.) and salts thereof, polyoxyalkylene alkyl ether sulfate, polyoxyalkylene alkenyl ether sulfate, polyoxyethylene alkyl sulfate ester, sulfosuccinic acid alkyl ester salt, polyoxy Alkylsulfosuccinic acid alkyl ester salts, polyoxyalkylene alkyl phenyl ether sulfates, alkane sulfonates, octyltrimethylammonium hydroxide, dode Rutrimethyl ammonium hydroxide, alkyl sulfonate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyalkylene alkyl ether acetate, alkyl phosphate, polyoxyalkylene alkyl ether phosphate, acyl glutamate, α-acyl sulfonate , Alkyl sulfonate, alkyl allyl sulfonate, α-olefin sulfonate, alkyl naphthalene sulfonate, alkane sulfonate, alkyl or alkenyl sulfate, alkyl amide sulfate, alkyl or alkenyl phosphate, alkyl amide Phosphate, alkyloylalkyl taurine salt, N-acyl amino acid salt, sulfosuccinate, alkyl ether carboxylate, amide ether carboxylate, α-sulfo fatty acid ester salt, Alanine derivatives, glycine derivatives, arginine derivatives and the like. Examples of the salt include alkali metal salts such as sodium salts, alkaline earth metal salts such as magnesium salts, alkanolamine salts such as triethanolamine salts, and ammonium salts.

As cationic surfactants, alkyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, lauryl trimethyl ammonium chloride, cetyl trimethyl ammonium chloride, tallow alkyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, stearyl trimethyl ammonium bromide, behenyl trimethyl ammonium bromide, Distearyldimethylammonium chloride, dicocoyldimethylammonium chloride, dioctyldimethylammonium chloride, di (POE) oleylmethylammonium chloride (2EO), benzalkonium chloride, alkylbenzalkonium chloride, alkyldimethylbenzalkonium chloride, benzethonium chloride, Stearyldimethylbenzylammonium chloride, lanolin-derived quaternary ammonium Salt, diethylaminoethylamide stearate, dimethylaminopropylamide stearate, amidopropyl dimethylhydroxypropylammonium chloride, stearoylcholaminoformylmethylpyridinium chloride, cetylpyridinium chloride, tall oil alkylbenzylhydroxyethylimidazolinium chloride, benzylammonium Salts are exemplified.

Nonionic surfactants include polyoxyalkylene ethers, polyoxyalkylene alkyl ethers, polyoxyalkylene fatty acid esters, polyoxyalkylene fatty acid diesters, polyoxyalkylene resin acid esters, polyoxyalkylene (cured) castor oil Polyoxyalkylene alkylphenols, polyoxyalkylene alkyl phenyl ethers, polyoxyalkylene phenyl phenyl ethers, polyoxyalkylene alkyl esters, polyoxyalkylene alkyl esters, sorbitan fatty acid esters, polyoxyalkylene sorbitan alkyl esters, Polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbit fatty acid esters, polyoxyalkylene Lysine fatty acid esters, polyglycerin alkyl ethers, polyglycerin fatty acid esters, sucrose fatty acid esters, fatty acid alkanolamides, alkyl glucosides, polyoxyalkylene fatty acid bisphenyl ethers, polypropylene glycol, diethylene glycol, polyoxyalkylene modified silicone , Polyglyceryl-modified silicone, glyceryl-modified silicone, sugar-modified silicone, fluorine-based surfactant, polyoxyethylene / polyoxypropylene block polymer, and alkylpolyoxyethylene / polyoxypropylene block polymer ether. In particular, it is preferable to blend polyoxyalkylene-modified silicone, polyglyceryl-modified silicone, glyceryl-modified silicone, and sugar-modified silicone. Since these modified silicones have the same silicone skeleton as the gelling agent of the present invention, when used in combination, there is an advantage that not only detergency but also the stability and gelling ability of cosmetics can be further improved.

Amphoteric surfactants such as imidazoline type, amide betaine type, alkyl betaine type, alkyl amide betaine type, alkyl sulfobetaine type, amide sulfobetaine type, hydroxysulfobetaine type, carbobetaine type, phosphobetaine type, aminocarboxylic acid type, amide Amino acid type amphoteric surfactants are exemplified. Specifically, 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, etc. Imidazoline-type amphoteric surfactants; alkylbetaine-type amphoteric surfactants such as lauryldimethylaminoacetic acid betaine and myristylbetaine; palm oil fatty acid amidopropyldimethylaminoacetic acid betaine, palm kernel oil fatty acid amidopropyldimethylaminoacetic acid betaine, beef tallow fatty acid amidopropyl Dimethylaminoacetic acid betaine, hardened tallow fatty acid amidopropyl dimethylaminoacetic acid betaine, lauric acid amidopropyl dimethylaminoacetic acid betaine, myristic acid amidopropyl dimethylaminoacetic acid betaine, palmitic acid Amidobetaine-type amphoteric surfactants such as dopropyldimethylaminoacetic acid betaine, stearic acid amidopropyldimethylaminoacetic acid betaine, oleic acid amidopropyldimethylaminoacetic acid betaine; alkylsulfobetaine-type amphoteric surfactants such as palm oil fatty acid dimethylsulfopropylbetaine Agents; alkylhydroxysulfobetaine-type amphoteric surfactants such as lauryldimethylaminohydroxysulfobetaine; phosphobetaine-type amphoteric surfactants such as laurylhydroxyphosphobetaine; N-lauroyl-N′-hydroxyethyl-N′-carboxymethylethylenediamine Sodium, N-oleoyl-N′-hydroxyethyl-N′-carboxymethylethylenediamine sodium, N-cocoyl-N′-hydroxyethyl-N′- Ruboxymethylethylenediamine sodium, N-lauroyl-N′-hydroxyethyl-N′-carboxymethylethylenediamine potassium, N-oleoyl-N′-hydroxyethyl-N′-carboxymethylethylenediamine potassium, N-lauroyl-N-hydroxy Ethyl-N′-carboxymethylethylenediamine sodium, N-oleoyl-N-hydroxyethyl-N′-carboxymethylethylenediamine sodium, N-cocoyl-N-hydroxyethyl-N′-carboxymethylethylenediamine sodium, N-lauroyl-N -Hydroxyethyl-N ′, N′-dicarboxymethylethylenediamine monosodium, N-oleoyl-N-hydroxyethyl-N ′, N′-dicarboxymethylethylenediamine Monosodium, N-cocoyl-N-hydroxyethyl-N ′, N′-dicarboxymethylethylenediamine monosodium, N-lauroyl-N-hydroxyethyl-N ′, N′-dicarboxymethylethylenediamine disodium, N— Amido amino acid type amphoteric surface activity such as oleoyl-N-hydroxyethyl-N ′, N′-dicarboxymethylethylenediamine disodium, N-cocoyl-N-hydroxyethyl-N ′, N′-dicarboxymethylethylenediamine disodium Agents are exemplified.

Examples of the semipolar surfactant include alkylamine oxide type surfactants, alkylamine oxides, alkylamidoamine oxides, alkylhydroxyamine oxides, and the like. Alkyldimethylamine oxide having 10 to 18 carbon atoms and 8 to 18 carbon atoms. Alkoxyethyldihydroxyethylamine oxide and the like are preferably used. Specifically, dodecyldimethylamine oxide, dimethyloctylamine oxide, diethyldecylamine oxide, bis- (2-hydroxyethyl) dodecylamine oxide, dipropyltetradecylamine oxide, methylethylhexadecylamine oxide, dodecylamidopropyl Dimethylamine oxide, cetyldimethylamine oxide, stearyl dimethylamine oxide, tallow dimethylamine oxide, dimethyl-2-hydroxyoctadecylamine oxide, lauryl dimethylamine oxide, myristyl dimethylamine oxide, stearyl dimethylamine oxide, isostearyl dimethylamine oxide, palm Fatty acid alkyldimethylamine oxide, caprylic amidopropyldimethyla Oxide, capric acid amidopropyl dimethylamine oxide, lauric acid amidopropyl dimethylamine oxide, myristic acid amidopropyl dimethylamine oxide, palmitic acid amidopropyl dimethylamine oxide, stearic acid amidopropyl dimethylamine oxide, isostearic acid amidopropyl dimethylamine oxide, Oleic acid amidopropyl dimethylamine oxide, ricinoleic acid amidopropyl dimethylamine oxide, 12-hydroxystearic acid amidopropyl dimethylamine oxide, palm fatty acid amidopropyl dimethylamine oxide, palm kernel oil fatty acid amidopropyl dimethylamine oxide, castor oil fatty acid amidopropyl Dimethylamine oxide, lauric acid amidoethyldimethyla Oxide, myristic acid amidoethyl dimethylamine oxide, palm fatty acid amidoethyl dimethylamine oxide, lauric acid amidoethyl diethylamine oxide, myristic acid amidoethyl diethylamine oxide, palm fatty acid amidoethyl diethylamine oxide, lauric acid amidoethyl dihydroxyethylamine oxide, myristic acid amide Examples include ethyl dihydroxyethylamine oxide and coconut fatty acid amidoethyl dihydroxyethylamine oxide.

The cosmetics and cosmetics of the present invention are (c) a cleansing gel, a cleansing cream, a cleansing milk, a cleansing lotion, a facial cleanser such as a facial cleanser, a hair cleanser such as a shampoo, a hair rinse, etc. It has the advantages of excellent skin and hair cleaning performance and a refreshing feel without being sticky. The amount of component (c) is preferably 1 to 20% by weight, more preferably 0.5 to 10% by weight, based on the total amount of the cosmetic or cosmetic.

The cosmetic according to the present invention may further contain a powder and / or a colorant as the component (d). If these powders and / or colorants are those used in ordinary cosmetics, their shapes (spherical, rod-like, needle-like, plate-like, indeterminate, spindle-like, etc.) and particle sizes (fog-like, Fine particles, pigment grades, etc.) and particle structures (porous, nonporous, etc.) can be used, but when these powders and / or colorants are blended as pigments, the average It is preferable to blend one type or two or more types selected from inorganic pigment powder, organic pigment powder, and resin powder having a particle diameter in the range of 1 nm to 20 μm.

Examples of the component (d) powder and / or colorant include inorganic powder, organic powder, surfactant metal salt powder (metal soap), colored pigment, pearl pigment, metal powder pigment, and the like. A composite of these pigments can also be used. Specifically, inorganic powders include titanium oxide, zirconium oxide, zinc oxide, cerium oxide, magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, sericite, Muscovite, synthetic mica, phlogopite, saucite, biotite, lithia mica, silicic acid, anhydrous silicic acid, aluminum silicate, magnesium silicate, magnesium aluminum silicate, sodium silicate, sodium magnesium silicate, calcium silicate , Barium silicate, strontium silicate, metal tungstate, hydroxyapatite, vermiculite, hydrite, bentonite, montmorillonite, hectorite, zeolite, ceramic powder, dicalcium phosphate, alumina, hydroxylation Aluminum, boron nitride, boron nitride, etc .; organic powders include polyamide powder, polyester powder, polyethylene powder, polypropylene powder, polystyrene powder, polyurethane powder, benzoguanamine powder, polymethylbenzoguanamine powder, polytetrafluoroethylene powder, polymethyl methacrylate Powder, cellulose, silk powder, nylon powder, 12 nylon, 6 nylon, silicone powder, silicone rubber powder, silicone elastomer spherical powder, polymethylsilsesquioxane spherical powder, styrene / acrylic acid copolymer, divinylbenzene Styrene copolymer, vinyl resin, urea resin, phenol resin, fluorine resin, silicon resin, acrylic resin, melamine resin, Poxy resin, polycarbonate resin, microcrystalline fiber powder, starch powder, lauroyl lysine, etc .; surfactant metal salt powders include zinc stearate, aluminum stearate, calcium stearate, magnesium stearate, zinc myristate, myristic acid Magnesium, zinc cetyl phosphate, calcium cetyl phosphate, sodium cetyl phosphate, etc .; colored pigments include inorganic red pigments such as iron oxide, iron hydroxide and iron titanate, inorganic brown pigments such as γ-iron oxide, yellow iron oxide, Inorganic yellow pigments such as ocher, inorganic black pigments such as black iron oxide and carbon black, inorganic purple pigments such as manganese violet and cobalt violet, inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide and cobalt titanate Inorganic blue pigments such as bitumen and ultramarine blue, red No. 3, Red No. 104, Red No. 106, Red No. 201, Red No. 202, Red No. 204, Red No. 205, Red No. 220, Red No. 226, Red No. 227, Red No. 228, Red No. 230, Red No. 401 , Red No. 505, Yellow No. 4, Yellow No. 5, Yellow No. 202, Yellow No. 203, Yellow No. 204, Yellow No. 401, Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 404, Green No. 3, Green No. 201, Green No. 204, Green No. 205, Orange No. 201, Orange No. 203, Orange No. 204, Orange No. 206, Orange No. 207, etc. Laked tar dyes, carminic acid, laccaic acid, calsamine, bradylin Pearl pigments include titanium oxide-coated mica, titanium oxide-coated mica, bismuth oxychloride, and titanium oxide-coated oxysalt Bismuth, titanium oxide coated talc, fish scales, titanium oxide-coated colored mica; The metal powder pigment, aluminum, gold, silver, copper, platinum, and metal powder such as stainless steel.

Furthermore, it is particularly preferable that the powder (d) and / or the colorant is subjected to a water repellency treatment. The gelling agent and the gel-like composition used in the cosmetic of the present invention have an effect of preventing these water-repellent pigments from being moved, and as a result, improve the durability of makeup and the sustainability of makeup. be able to. Moreover, since the gelatinizer of this invention can inhale not only various oil agents but sebum, it can also improve the sebum resistance of cosmetics.

Examples of such a water repellent treatment include those obtained by treating the powder and / or colorant with various water repellent surface treatment agents, such as methyl hydrogen polysiloxane treatment, silicone resin treatment, Silicone gum treatment, acrylic silicone treatment, organosiloxane treatment such as fluorinated silicone treatment, metal soap treatment such as zinc stearate treatment, silane coupling agent treatment, silane treatment such as alkylsilane treatment, perfluoroalkylsilane, perfluoroalkyl Fluorine compound treatment such as phosphate ester salt, perfluoropolyether treatment, amino acid treatment such as N-lauroyl-L-lysine treatment, oil agent treatment such as squalane treatment, acrylic treatment such as alkyl acrylate treatment, etc. Use in combination of one or more of It is possible.

The cosmetic according to the present invention may further contain a water-soluble polymer as the component (e). These water-soluble polymers can be any of amphoteric, cationic, anionic, nonionic, water-swellable clay minerals as long as they are used in ordinary cosmetics for the purpose of improving the feeling of use of cosmetics. Even one type or two or more types of water-soluble polymers can be used in combination.

Examples of amphoteric water-soluble polymers include amphoteric starch, dimethyldiallylammonium chloride derivatives (for example, acrylamide / acrylic acid / dimethyldiallylammonium chloride copolymer, acrylic acid / dimethyldiallylammonium chloride copolymer), and methacrylic acid derivatives (for example, And polymethacryloylethyldimethylbetaine, N-methacryloyloxyethyl N, N-dimethylammonium-a-methylcarboxybetaine / alkyl methacrylate copolymer, etc.).

Examples of the cationic water-soluble polymer include quaternary nitrogen-modified polysaccharides (for example, cation-modified cellulose, cation-modified hydroxyethyl cellulose, cation-modified guar gum, cation-modified locust bean gum, cation-modified starch), dimethyldiallylammonium chloride derivatives ( For example, dimethyldiallylammonium chloride / acrylamide copolymer, polydimethylmethylenepiperidinium chloride), vinylpyrrolidone derivatives (eg, vinylpyrrolidone / dimethylaminoethylmethacrylic acid copolymer salt, vinylpyrrolidone / methacrylamidepropyltrimethylammonium chloride) Copolymer, vinylpyrrolidone / methylvinylimidazolium chloride copolymer, etc.), methacrylic acid derivatives (eg, methacryloylethyldimethyl) Thanh chloride methacryloyloxyethyl trimethyl ammonium-2-hydroxyethyl methacrylate copolymer, methacryloyl ethyl dimethyl betaine chloride methacryloyloxyethyl trimethyl ammonium methacrylate methoxy polyethylene glycol copolymer) and the like.

Anionic water-soluble polymers include polyacrylic acid or its alkali metal salt, polymethacrylic acid or its alkali metal salt, hyaluronic acid or its alkali metal salt, acetylated hyaluronic acid or its alkali metal salt, methyl vinyl ether / anhydrous Water-soluble polymer of aliphatic carboxylic acid or its metal salt such as hydrolyzate of maleic acid copolymer, carboxymethyl cellulose or its alkali metal salt, methyl vinyl ether-maleic acid half ester copolymer, acrylic resin alkanolamine liquid, Examples are carboxyvinyl polymers.

Nonionic water-soluble polymers include polyvinyl pyrrolidone, highly polymerized polyethylene glycol, vinyl pyrrolidone / vinyl acetate copolymer, vinyl pyrrolidone / dimethylaminoethyl methacrylate copolymer, vinyl caprolactam / vinyl pyrrolidone / dimethylaminoethyl methacrylate copolymer Coalesce, cellulose or derivatives thereof (eg, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose), keratin and collagen or derivatives thereof, calcium alginate, pullulan, agar, gelatin, tamarind seed polysaccharide, xanthan gum, carrageenan, high Methoxyl pectin, low methoxyl pectin, guar gum, pectin, gum arabic, crystalline cellulose, Binogalactan, gum karaya, gum tragacanth, alginic acid, albumin, casein, curdlan, duran gum, dextran, quince seed gum, tragacanth gum, chitin / chitosan derivatives, starch (rice, corn, potato, wheat, etc.), keratin and collagen or derivatives thereof, etc. Natural polymer compounds are exemplified.

The water-swellable clay mineral is an inorganic water-soluble polymer and is a kind of colloid-containing aluminum silicate having a three-layer structure, and is generally exemplified by the following formula (11).
(M ¹ , M ² ) _2-3 (Si, Al) ₄ O ₁₀ (OH) ₂ M ³ _1/3 · nH ₂ O (11)
(Wherein, ^{M 1} is, Al, Fe (III), Mn (III), or a Cr (III), ^{M 2} is, Mg, Fe (II), Ni, Zn , or a Li, M ³ is K, Na or Ca)
Specific examples of such inorganic water-soluble polymers include bentonite, montmorillonite, piderite, nontronite, saponite, hectorite, aluminum magnesium silicate, and silicic anhydride, which are natural products and synthetic products. Any of these may be used.

The blending amount of the component (e) is preferably 0.01 to 25.0 weight with respect to the total amount of the cosmetic or cosmetic. If the blending amount is less than the lower limit, the viscosity and film properties become insufficient, and if it exceeds the upper limit, stickiness and the like increase, which is generally not preferred as a cosmetic.

In the cosmetic according to the present invention, one or more kinds of silicone resins can be further blended as the component (f). As the silicone resin, any silicone resin that is usually used in cosmetics can be used as long as it is not contrary to the object of the present invention, and in particular, trimethylsiloxysilicic acid, polyalkylsiloxysilicic acid, dimethylsiloxy. It preferably contains at least one selected from unit-containing trimethylsiloxysilicic acid, perfluoroalkyl group-containing polyalkylsiloxysilicic acid, polydimethylsiloxane graft acrylic copolymer, and branched carboxysiloxane dendrimer graft acrylic copolymer. . These silicone resins are preferably in the form of a gum or solid at room temperature, and are preferably oil-soluble, and particularly preferably soluble in octamethyltetrasiloxane (D4) and / or decamethylcyclopentasiloxane (D5).

Specifically, the gum-like silicone resin is a straight chain represented by the general formula (CH ₃ ) ₃ SiO {(CH ₃ ) ₂ SiO} _a {(CH ₃ ) R ³ SiO} _b Si (CH ₃ ) _3. In the silicone, R ³ is selected from a methyl group, an alkyl group having 6 to 20 carbon atoms, an amino group-containing alkyl group having 3 to 15 carbon atoms, a fluorine-substituted alkyl group, a quaternary ammonium base-containing alkyl group, a is preferably 1 to 5000 and a + b is 2500 to 25000.

The solid silicone resin is an MQ comprising any combination of trialkylsiloxy units (M units), dialkylsiloxy units (D units), monoalkylsiloxy units (T units), and tetrafunctional siloxy units (Q units). A silicone network compound which is a resin, MDQ resin, MTQ resin, MDTQ resin, TD resin, TQ resin, or TDQ resin is preferable. Further, a polydimethylsiloxane graft containing in the molecule at least one selected from the group consisting of carboxylic acid alkyl esters, pyrrolidone moieties, long-chain alkyl moieties, polyoxyalkylene moieties and fluoroalkyl moieties, and anionic moieties such as carboxylic acids Particularly preferred are type and branched carbosiloxane dendrimer graft type acrylic copolymers. Examples of the branched carbosiloxane dendrimer graft type acrylic copolymer include those listed in JP-A No. 2000-063225 and JP-A No. 2003-226611.

These silicone resins may be blended in the cosmetic alone, but can also be blended as a solvate in volatile silicone, volatile hydrocarbon oil, nonvolatile silicone, or nonvolatile hydrocarbon oil. . The blending amount when using these silicone resins is preferably 0.1 to 20% by weight, more preferably 1 to 10% by weight, based on the total amount of the cosmetic. Moreover, in order to obtain cosmetics with higher adhesiveness to the skin, it is preferable to use it as a composition comprising 50 to 500 parts by weight of a silicone resin with respect to 100 parts by weight of the silicone compound of the present invention.

The cosmetic according to the present invention may further contain a silicone elastomer as the component (g). Here, the silicone elastomer is an organopolysiloxane compound having a high degree of polymerization having a three-dimensionally cross-linked methylpolysiloxane skeleton in the main chain, and even if it has a spherical or flat particle shape, It may have the form of an oil dispersion without having a shape. In the present invention, it is a silicone elastomer having a particle shape, and the primary particle diameter by observation using an electron microscope and / or the average temporary particle diameter measured by a laser diffraction / scattering method is in the range of 0.1 to 50 μm. In addition, it is preferable to use a silicone elastomer spherical powder whose primary particles have a spherical shape. Further, the hardness of the silicone elastomer is preferably 80 or less, particularly 65 or less according to JIS type A durometer.

As a method for producing such a silicone elastomer, a cross-linking agent having a vinylic reactive site and an alkyl hydrogen polysiloxane having a hydrogen atom bonded to two or more silicon base papers are reacted under a catalyst such as chloroplatinic acid to obtain a three-dimensional The method of making it bridge | crosslink is mentioned. In the silicone elastomer of the present invention, the crosslinking agent that forms a three-dimensional crosslinked structure is alkenyl functional organopolysiloxane, α, ω-alkenyl diene, glycerin triallyl ether, polyoxyalkynylated glyceryl triallyl ether, trimethylolpropane triallyl. Examples include ethers, polyoxyalkynylated trimethylolpropane triallyl ethers, and the like having two or more vinylic reactive sites in the molecule.

Such silicone elastomers are, for example, JP-A-2-243612, JP-A-8-12545, JP-A-8-12546, JP-A-8-12524, JP-A-9-241511, JP-A-10-. No. 36219, JP-A-11-193331, JP-A-2000-281523, and the like. Specifically, Trefil E-505, 506 sold by Toray Dow Corning. , 507, 508, and the like, and cross-linked silicone powders listed in “Standards for Compositions by Cosmetic Variety” are applicable. These powders may or may not be further surface-treated. Examples of surface treatment include methyl hydrogen polysiloxane, silicone resin, metal soap, silane coupling agent, silica, and titanium oxide. Fluorine compounds such as inorganic oxides such as perfluoroalkyl silane and perfluoroalkyl phosphate ester salts.

Furthermore, it is preferable that the silicone elastomer having a particle shape is blended into the preparation in one or more forms selected from those kneaded in an oil agent, finely pulverized by a pulverizer, or an aqueous dispersion. More specifically, a silicone elastomer and one or more oily components that are liquid at room temperature selected from the group consisting of ester oils, hydrocarbon oils, higher alcohols, vegetable oils, and animal oils are kneaded or pulverized to obtain a paste-like material. And a method in which the silicone elastomer is mechanically pulverized and agglomerated to blend. A method in which the silicone elastomer is mechanically pulverized and dispersed in water by mechanical force is included.

Silicone elastomer spherical powders often have a particle size of more than 10 μm, and it was difficult to fix to the skin, but a more stable coating film was formed by using in combination with the gelling agent and gel composition of the present invention. There is a merit that can be done. Furthermore, since these powders scatter light, the blended cosmetics sometimes had a matte tone, but the gelling agent of the present invention was not combined because its surface can be coated with a glossy film. Compared to the case, some gloss can be given to the decorative coating film. As a compounding quantity of the organopolysiloxane elastomer spherical powder in the cosmetics of this invention, 0.1-30 mass% is preferable with respect to the mass of cosmetics. If the amount is less than the lower limit, there is a problem that the water slidability is weakened. If the value exceeds the upper limit, the physical strength of the coating film is decreased although the water slidability is obtained, which is not preferable because it becomes relatively weak against contact. .

The cosmetic composition according to the present invention may further contain an ultraviolet protection component as the component (h). In the present invention, inorganic and organic ultraviolet protective components can be used as the ultraviolet protective component.

The inorganic ultraviolet protection component may be formulated by blending the above inorganic powder pigment, metal powder pigment, etc. as an ultraviolet dispersant, such as titanium oxide, zinc oxide, cerium oxide, low-order titanium oxide, iron. Examples thereof include metal oxides such as doping titanium oxide, metal hydroxides such as iron hydroxide, plate-like iron oxide, metal flakes such as aluminum flakes, and ceramics such as silicon carbide. Of these, at least one selected from fine metal oxides or fine metal hydroxides having an average particle diameter in the range of 1 to 100 nm is particularly preferable. These powders are conventionally known surface treatments such as fluorine compound treatment (perfluoroalkyl phosphate treatment, perfluoroalkylsilane treatment, perfluoropolyether treatment, fluorosilicone treatment, fluorinated silicone resin treatment are preferred), silicone Treatment (methylhydrogenpolysiloxane treatment, dimethylpolysiloxane treatment, vapor phase tetramethyltetrahydrogencyclotetrasiloxane treatment is preferred), silicone resin treatment (trimethylsiloxysilicate treatment is preferred), pendant treatment (vapor phase silicone) A method of adding an alkyl chain after the treatment), silane coupling agent treatment, titanium coupling agent treatment, silane treatment (alkyl silane or alkylsilazane treatment is preferred), oil agent treatment, N-acylated lysine treatment The surface treatment is preferably performed by polyacrylic acid treatment, metal soap treatment (preferably stearic acid or myristic acid salt), acrylic resin treatment, metal oxide treatment, etc., and more preferably, a combination of these treatments. It is preferable to use it. For example, the surface of fine particle titanium oxide is coated with a metal oxide such as silicon oxide or alumina, and then surface-treated with alkylsilane. The surface treatment amount is preferably in the range of 0.1 to 50% by mass with respect to the powder mass in terms of the total surface treatment amount.

Organic UV protection components include salicylic acid such as homomenthyl salicylate, octyl salicylate, triethanolamine salicylate; paraaminobenzoic acid, ethyldihydroxypropylparaaminobenzoic acid, glycerylparaaminobenzoic acid, octyldimethylparaaminobenzoic acid, paradimethylaminobenzoic acid PABA type such as amyl, 2-ethylhexyl paradimethylaminobenzoate; 4- (2-β-glucopyranosyloxy) propoxy-2-hydroxybenzophenone, dihydroxydimethoxybenzophenone, dihydroxydimethoxybenzophenone sodium disulfonate, 2-hydroxy -4-methoxybenzophenone, hydroxymethoxybenzophenonesulfonic acid and its trihydrate, sodium hydroxymethoxybenzophenonesulfonate, -Hydroxy-4-methoxybenzophenone-5-sulfuric acid, 2,2'-dihydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2,2'4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy Benzophenone series such as -4,4'-dimethoxybenzophenone, 2-hydroxy-4-N-octoxybenzophenone; 2-ethylhexyl paramethoxycinnamate (also known as octyl paramethoxycinnamate), diparamethoxycinnamic acid Glyceryl mono-2-ethylhexanoate, methyl 2,5-diisopropylcinnamate, 2,4,6-tris [4- (2-ethylhexyloxycarbonyl) anilino] -1,3,5-triazine, tri Methyl bis (trimethylsiloxy) silylisopentyl methoxycinnamate, Cinnamic acid systems such as a mixture of isopropyl methoxycinnamate and diisopropyl cinnamate, p-methoxyhydrocinnamic acid diethanolamine salt; 2-phenyl-benzimidazole-5-sulfate, 4-isopropyldibenzoylmethane, 4-tert- Benzoylmethane such as butyl-4′-methoxydibenzoylmethane; 2-cyano-3,3-diphenylprop-2-enoic acid 2-ethylhexyl ester (also known as octocrylene), dimethoxybenzylidenedioxoimidazolidinepropionic acid 2- Ethylhexyl, 1- (3,4-dimethoxyphenyl) -4,4-dimethyl-1,3-pentanedione, sinoxate, methyl-O-aminobenzoate, 2-ethylhexyl-2-cyano-3,3-diphenyl Acrylate, 3- (4-methylben Illustrative examples include dilidene) camphor, octyltriazone, 4- (3,4-dimethoxyphenylmethylene) -2,5-dioxo-1-imidazolidinepropionate 2-ethylhexyl, their polymer derivatives, and silane derivatives. .

Furthermore, it is also possible to use those in which the organic ultraviolet protection component is sealed in a polymer powder. The polymer powder may or may not be hollow, the average primary particle diameter may be in the range of 0.1 to 50 μm, and the particle size distribution may be broad or sharp. Examples of the polymer include acrylic resin, methacrylic resin, styrene resin, polyurethane resin, polyethylene, polypropylene, polyethylene terephthalate, silicone resin, nylon, and acrylamide resin. In these polymer powders, a powder obtained by incorporating an organic ultraviolet protection component in the range of 0.1 to 30% by mass of the powder mass is preferable, and 4-tert-butyl-4′- which is a UV-A absorber is particularly preferable. It is preferable to mix methoxydibenzoylmethane.

Among the ultraviolet protection components, selected from the group consisting of fine particle titanium oxide, fine particle zinc oxide, 2-methoxyhexyl paramethoxycinnamate, 4-tert-butyl-4′-methoxydibenzoylmethane, and a benzophenone-based ultraviolet absorber. At least one kind is widely used, is easily available, and has a high UV protection effect, so that it can be suitably used. In particular, it is preferable to use an inorganic and organic ultraviolet protective component in combination, and it is more preferable to use a combination of an ultraviolet protective component corresponding to UV-A and an ultraviolet protective component corresponding to UV-B.

As a compounding quantity of the ultraviolet-ray protective component in the cosmetics of this invention, it is preferable that it is in the range of 0.1-60 mass% with respect to the mass of cosmetics by the sum total of an inorganic type and / or organic type, Especially preferably. Is 3-40 mass%. Furthermore, the blending amount of the inorganic ultraviolet protection component is preferably in the range of 0.1 to 30% by mass with respect to the mass of the cosmetic, and the organic ultraviolet absorber is 0.1 to the mass of the cosmetic. It is preferable to mix | blend in the range of -20 mass%, and as this, as a compounding quantity of (a) component (gelling agent) of this invention, it is 0.1-20 mass% with respect to the mass of cosmetics. It is preferable to mix in a range. In the range of these combinations, a more durable UV protection effect can be obtained as compared with the case where the gelling agent of the present invention is not blended. Furthermore, when the gelling agent and the gel composition of the present invention are blended, the preparation itself can be given a good moisturizing effect and gloss, and in hair cosmetics it has excellent curl retention, gloss and hair. There is an excellent effect on the unity.

In addition to the above-mentioned components, the cosmetics of the present invention usually include antibacterial and preservatives, physiologically active ingredients, pH adjusters, antioxidants, solvents, chelating agents, moisturizing ingredients, fragrances, etc. These various components can be used as long as the object of the present invention is not impaired. These components can be dissolved in the above-mentioned component (b) to form a gel-like composition and can be blended in cosmetics, or can be blended in cosmetics separately from the gelling agent or gel-like composition. .

Examples of the preservative include paraoxybenzoic acid alkyl ester, benzoic acid, sodium benzoate, sorbic acid, potassium sorbate, phenoxyethanol and the like. Antibacterial agents include benzoic acid, salicylic acid, coalic acid, sorbic acid, paraoxybenzoic acid alkyl ester, parachlorometacresol, hexachlorophene, benzalkonium chloride, chlorhexidine chloride, trichlorocarbanilide, triclosan, photosensitizer, phenoxyethanol. Etc. are exemplified.

Examples of the physiologically active ingredient used in the present invention include substances that give some physiological activity to the skin when applied to the skin. For example, anti-inflammatory agents, anti-aging agents, UV protection agents, tanning agents, antioxidants, hair growth agents, hair restorers, moisturizers, blood circulation promoters, antibacterial agents, bactericides, desiccants, cooling agents, warm feelings Agents, vitamins, amino acids, wound healing promoters, stimulus-relieving agents, analgesics, cell activators, enzyme components, and the like. Among these, natural plant extract components, seaweed extract components, and herbal medicine components are particularly preferable. In the present invention, it is preferable to blend one or more of these physiologically active ingredients.

These components include, for example, Ashitaba extract, Avocado extract, Achacha extract, Altea extract, Arnica extract, Aloe extract, Apricot extract, Apricot kernel extract, Ginkgo biloba extract, Fennel extract, Turmeric extract, Oolong tea extract, Ages extract, Echinashi leaf extract , Ogon extract, Oat extract, Auren extract, Barley extract, Hypericum extract, Odrianthus extract, Dutch mustard extract, Orange extract, Seawater dried product, Seaweed extract, Hydrolyzed elastin, Hydrolyzed wheat powder, Hydrolyzed silk, Chamomile extract, Carrot Extract, Kawaramugi Extract, Licorice Extract, Calcade Extract, Oyster Extract, Kiwi Extract, Kina Extract, Cucumber Extract, Guanosine, Gardenia Extract, Kumazasa Extract, Clara Kiss, walnut extract, grapefruit extract, clematis extract, chlorella extract, mulberry extract, gentian extract, tea extract, yeast extract, burdock extract, fermented rice bran extract, rice germ oil, comfrey extract, collagen, bilberry extract, saicin extract, psycho extract Extract Kizuta extract, hawthorn extract, elderberry extract, yarrow extract, mint extract, sage extract, mallow extract, Cucumber extract, assembly extract, soybean extract, peanut extract, thyme extract, tea extract, clove extract, chigaya extract, chimpi extract, touki extract, toshinsen extract, tonin extract, spruce extract, dokudami extract, tomato extract, natto extract, carrot extract, garlic extract , Novara extract, hibiscus extract, bacmond extract, lotus extract, parsley extract, honey, hamamelis extract, parietalia extract, toad extract, bisabolol, loquat extract, dandelion extract, fukinotou extract, bukkuri extract, butcher bloom extract, grape extract, propolis, Loofah extract, safflower extract, peppermint extract, bodaiju extract, button extract, hop extract, pine extract, maronier extract , Citrus extract, Mulberry extract, Melissa extract, Peach extract, Cornflower extract, Eucalyptus extract, Yukinoshita extract, Yuzu extract, Yakuinin extract, Artemisia extract, Lavender extract, Apple extract, Lettuce extract, Lemon extract, Astragalus extract, Rose extract, Rosemary extract , Roman chamomile extract, royal jelly extract and the like.

Biopolymers such as deoxyribonucleic acid, mucopolysaccharide, sodium hyaluronate, sodium chondroitin sulfate, collagen, elastin, chitin, chitosan, hydrolyzed eggshell membrane, glycine, valine, leucine, isoleucine, serine, threonine, phenylalanine, arginine Lysine, aspartic acid, glutamic acid, amino acids such as cystine, cysteine, methionine, tryptophan, hormones such as estradiol, etenyl estradiol, oily components such as sphingolipid, ceramide, cholesterol, cholesterol derivatives, phospholipids, ε-aminocaproic acid, Anti-inflammatory agents such as glycyrrhizic acid, β-glycyrrhetinic acid, lysozyme chloride, guaiazulene, hydrocortisone, allantoin, tranexamic acid, azulene, Vitamins A, B2, B6, C, D, E, vitamins such as calcium pantothenate, biotin, nicotinamide, vitamin C ester, active ingredients such as allantoin, diisopropylamine dichloroacetate, 4-aminomethylcyclohexanecarboxylic acid, Tocopherols, carotenoids, flavonoids, tannins, lignans, saponins, antioxidants such as butylhydroxyanisole, dibutylhydroxytoluene, phytic acid, cell activators such as α-hydroxy acids and β-hydroxy acids, γ-oryzanol, vitamin E derivatives Blood circulation promoters such as retinol, retinol derivatives, wound healing agents, cephalanthin, licorice extract, red pepper tincture, hinokitiol, garlic iodide extract, pyridoxine hydrochloride, dl-α-tocopherol, acetic acid l-α-tocopherol, nicotinic acid, nicotinic acid derivatives, calcium pantothenate, D-pantothenyl alcohol, acetyl pantothenyl ethyl ether, biotin, allantoin, isopropylmethylphenol, estradiol, ethinylesteradiol, capronium chloride, benzalkonium chloride , Diphenhydramine hydrochloride, takanal, camphor, salicylic acid, nonyl acid vanillylamide, nonanoic acid vanillylamide, piroctone olamine, pentadecanoic acid glyceryl, l-menthol, camphor, and other refreshing agents, mononitroguaiacol, resorcin, γ-aminobutyric acid, benzethonium chloride , Mexiletine hydrochloride, auxin, female hormone, cantharis tincture, cyclosporine, zinc pyrithione, hydrocortisone, minoxidis , Monostearate polyoxyethylene sorbitan, peppermint oils, hair growth agents such as Sasanishiki extract.

Examples of the pH adjuster used in the present invention include lactic acid, citric acid, glycolic acid, succinic acid, tartaric acid, dl-malic acid, potassium carbonate, sodium hydrogen carbonate, ammonium hydrogen carbonate and the like. Edetate sodium salt, sodium polyphosphate, sodium metaphosphate, phosphoric acid and the like.

Examples of the solvent used in the present invention include light liquid isoparaffin, ethers, LPG, N-methylpyrrolidone, next-generation chlorofluorocarbon and the like, in addition to water such as purified water and mineral water.

Examples of the antioxidant used in the present invention include tocopherol, butylhydroxyanisole, dibutylhydroxytoluene, phytic acid and the like; examples of the chelating agent include alanine, sodium edetate, sodium polyphosphate, sodium metaphosphate, phosphoric acid and the like. .

Moisturizing ingredients used in the present invention include glycerin, sorbitol, propylene glycol, dipropylene glycol, 1,3-butylene glycol, glucose, xylitol, maltitol, polyethylene glycol, hyaluronic acid, chondroitin sulfate, pyrrolidone carboxylate, polyoxy Examples thereof include ethylene methyl glucoside and polyoxypropylene methyl glucoside.

The cosmetics of the present invention are skin cosmetic products such as skin cleanser products, skin care products, makeup products, antiperspirant products, UV protection products; hair cleanser products, hair styling products, hair color products, nutrition Examples include hair cosmetics such as hair products and hair rinse products; bath cosmetics. Furthermore, since the gel composition of the present invention is excellent in transparency and lipophilicity, it can be easily blended into various perfumes and eau de colognes.

The skin cosmetics can be used for any part of the scalp, face (including lips, eyebrows, cheeks), fingers, nails, and whole body. Specifically, cleansing gel, cleansing cream, cleansing foam, cleansing milk, cleansing lotion, face wash cream, eye makeup remover, face wash foam, liquid soap for whole body, hand soap, gel soap, solid soap, facial rinse, body rinse , Shaving cream, sunscreen, skin care products such as anti-acne cosmetics; skin cream, scalp treatment, skin milk, milk lotion, milk, lotion, moisturizer, beauty liquid, facial pack, body powder, Skin care products such as essence and shaving lotion; foundation, make-up base, white powder, face powder, lipstick, lip balm, rim cream, lip gloss, eye shadow, eyeliner, ike Makeup products such as eyebrow, eyebrow, eyelash cosmetics, eyebrow pencil, eyebrow brush, mascara, blusher, cheek cosmetics (blusher, cheek color), nail polish, pedicure, nail color, nail lacquer, enamel remover, nail polish; Examples include antiperspirants such as deodorants; UV protection products such as sunscreen agents and suntan agents (suntan agents).

The above cosmetics for hair include shampoos, rinse-in shampoos and other hair cleaning products; hair oils, hair curl retention agents, set agents, hair creams, hair sprays, hair liquids and other hair-styling products; hair dyes, hair color sprays Hair coloring products such as hair color rinses, hair color sticks; hair tonic products such as hair tonics, hair treatments, hair packs; hair rinse products such as oil rinses, cream rinses, treatment rinses. The bath cosmetics are exemplified by bath oil, bath salt, and foam bath.

The form of the cosmetic and cosmetics according to the present invention is not particularly limited, and is liquid, W / O emulsion, O / W emulsion, W / O cream, O / W cream, solid, paste It can be preferably applied to gel, powder, multilayer, mousse, mist, granule, flake, and meteorite. In particular, the gelling agent of the present invention can provide emulsions and creamy cosmetics with excellent stability over time because the O / W and W / O oil layer portions are thickened or gelled. .

The cosmetics and cosmetic containers according to the present invention are not particularly limited, and include jars, pumps, tubes, bottles, pressure can discharge containers, pressure-resistant aerosol containers, light-shielding containers, compact containers, metal plates, stick containers, and payouts. An arbitrary container such as a container, a spray container, or a container with a partition provided with a mixed solution discharge port can be filled. Tubes tend to be separated in ordinary silicone preparations, but the cosmetics and cosmetics according to the present invention are excellent in stability, so that they can be stored stably even when filled in such tube containers. There is a merit.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these. In the examples and comparative examples, Me represents a methyl group.
[Refractive index]
The refractive index of the gel composition was measured at 25 ° C. using an Abbe refractometer (model number ER-1) manufactured by ERMA.
[Viscoelasticity]
Using a dynamic viscoelasticity test apparatus [Rheometric Dynamic Analyzer RDA-700], the storage elastic modulus G ′ and the viscosity η are measured while changing the frequency (f) while keeping the strain constant. did. The measurement conditions were as follows.
Sample diameter: 25mm
Sample thickness: 1mm
Distortion: 20%
Frequency (f): 0.1 Hz to 80 Hz

で表されるアルキル・ジメチルシロキサン・メチル（３−アミノプロピル）シロキサンコポリマー３０グラム（ＮＨ_２基：１０．２ミリモル）と無水コハク酸１．０１グラム（１０．２ミリモル）をイソプロピルアルコール３６グラム中で混合して、３０〜３５℃で５時間攪拌した。赤外吸光（ＩＲ）分析の結果、カルボン酸無水物の特性吸収が消失し、アミド基およびカルボキシル基の特性吸収が確認されたことにより、平均構造式：

で表される有機変性メチルポリシロキサンが生成していることが分かった。次いで、この反応生成物に、水酸化ナトリウムの２０重量％水溶液２．０２グラム(１０．１ミリモル)を添加して、２５℃で３０分間反応させた。次いで、ヘキサンを投入して均一溶液にした後で、低沸点成分を加熱減圧下で留去したところ、白色固体状物が得られた。ＩＲ分析の結果、該白色固体状物は、平均構造式：

で示されるケイ素原子に結合した有機基の末端にカルボン酸のナトリウム塩を有する有機変性メチルポリシロキサン（ゲル化剤１）であることが判明した。得られた白色固体状物２ｇと軽質流動パラフィン１８ｇとを９０℃で攪拌し、冷却したところ透明な硬いゲル状組成物が得られた。このゲル状組成物は、室温で３ヶ月以上安定にゲル状を維持していた。 [Example 1]
Average structural formula:

30 grams (NH ₂ groups: 10.2 mmol) and 1.01 grams (10.2 mmol) of succinic anhydride in 36 grams of isopropyl alcohol And stirred at 30 to 35 ° C. for 5 hours. As a result of infrared absorption (IR) analysis, the characteristic absorption of the carboxylic acid anhydride disappeared, and the characteristic absorption of the amide group and the carboxyl group was confirmed.

It was found that an organically modified methylpolysiloxane represented by Next, 2.02 g (10.1 mmol) of a 20 wt% aqueous solution of sodium hydroxide was added to the reaction product, and the mixture was reacted at 25 ° C. for 30 minutes. Subsequently, hexane was added to make a homogeneous solution, and then the low boiling point component was distilled off under reduced pressure by heating to obtain a white solid. As a result of IR analysis, the white solid was found to have an average structural formula:

It was found that the organic modified methylpolysiloxane (gelator 1) having a sodium salt of a carboxylic acid at the terminal of the organic group bonded to the silicon atom represented by When 2 g of the obtained white solid and 18 g of light liquid paraffin were stirred at 90 ° C. and cooled, a transparent hard gel composition was obtained. This gel composition maintained a gel state stably at room temperature for 3 months or more.

で表されるアルキル・ジメチルシロキサン・メチル（３−（２−アミノエチル）アミノプロピル）シロキサンコポリマー３０グラム（ＮＨ_２基：１０．０ミリモル）とイソプロピルアルコール３６グラム中に１．００グラム(１０．０ミリモル)の無水コハク酸を投入して窒素気流下に３０〜４０℃で５時間攪拌した。赤外吸光（ＩＲ）分析の結果、カルボン酸無水物の特性吸収は消失し、ケイ素原子に結合した有機基の末端にカルボキシル基を有する有機変性メチルポリシロキサンが生成していることが分かった。次いで、この反応生成物を室温まで冷却した後、水酸化ナトリウムの２０重量％水溶液１．９８グラム(９．９ミリモル)を添加して、室温で３０分間反応させた。次いで、ヘキサンを投入して均一溶液にした後で、低沸点成分を加熱減圧下で留去したところ、白色固体状物が得られた。ＩＲ分析の結果、該白色固体状物は、平均構造式：

で示されるケイ素原子に結合した有機基の末端にカルボン酸のナトリウム塩を有する有機変性メチルポリシロキサン（ゲル化剤２）であることが判明した。得られた白色固体状物５ｇとデカメチルシクロペンタシロキサン（Ｄ５） ２９．７ｇ、重質流動パラフィン １５．７ｇとを９０℃で攪拌し、冷却したところ透明な硬いゲル状組成物（ゲル化剤量：１０重量％）が得られた。 [Example 2]
Average structural formula:

1.00 grams (10.10) in 30 grams of alkyl dimethylsiloxane methyl (3- (2-aminoethyl) aminopropyl) siloxane copolymer (NH ₂ groups: 10.0 mmol) and 36 grams of isopropyl alcohol. 0 mmol) of succinic anhydride was added and stirred for 5 hours at 30 to 40 ° C. under a nitrogen stream. As a result of infrared absorption (IR) analysis, it was found that the characteristic absorption of the carboxylic acid anhydride disappeared, and an organically modified methylpolysiloxane having a carboxyl group at the terminal of the organic group bonded to the silicon atom was formed. The reaction product was then cooled to room temperature, and 1.98 grams (9.9 mmol) of a 20 wt% aqueous solution of sodium hydroxide was added and allowed to react at room temperature for 30 minutes. Subsequently, hexane was added to make a homogeneous solution, and then the low boiling point component was distilled off under reduced pressure by heating to obtain a white solid. As a result of IR analysis, the white solid was found to have an average structural formula:

It was proved to be an organically modified methylpolysiloxane (gelator 2) having a sodium salt of a carboxylic acid at the end of an organic group bonded to a silicon atom represented by 5 g of the obtained white solid, 29.7 g of decamethylcyclopentasiloxane (D5) and 15.7 g of heavy liquid paraffin were stirred at 90 ° C. and cooled to obtain a transparent hard gel composition (gelling agent). Amount: 10% by weight) was obtained.

上記で得た有機変性メチルポリシロキサン（ゲル化剤３）２ｇと軽質流動パラフィン１８ｇとを９０℃で攪拌し、室温に冷却したところ透明なゲル状組成物が得られた。このゲル状組成物の透明感は、実施例２で得たナトリウム塩タイプよりも透明感に優れ、柔らかいゲル感触を示した。このゲル状組成物も室温で３ヶ月間放置しても透明なゲル状を保っており、安定性が良好であった。 [Example 3]
In Example 2, the reaction and mixing were carried out under the same conditions except that 2.78 g (9.9 mmol) of a 20 wt% aqueous solution of potassium hydroxide was added instead of the 20 wt% aqueous solution of sodium hydroxide, A white solid of organically modified methylpolysiloxane represented by the following average structural formula was obtained.
Average structural formula:

When 2 g of the organically modified methylpolysiloxane (gelator 3) obtained above and 18 g of light liquid paraffin were stirred at 90 ° C. and cooled to room temperature, a transparent gel composition was obtained. The transparency of this gel composition was superior to the sodium salt type obtained in Example 2 and showed a soft gel feel. Even when this gel composition was allowed to stand at room temperature for 3 months, it kept a transparent gel and had good stability.

で表されるアルキル・ジメチルシロキサン・メチル（３−（２−アミノエチル）アミノプロピル）シロキサンコポリマー３０グラム（ＮＨ_２基：１９．５ミリモル）とイソプロピルアルコール３６グラム中に１．００グラム(１９．５ミリモル)の無水コハク酸を投入して窒素気流下に３０〜４０℃で５時間攪拌した。赤外吸光（ＩＲ）分析の結果、カルボン酸無水物の特性吸収は消失し、ケイ素原子に結合した有機基の末端にカルボキシル基を有する有機変性メチルポリシロキサンが生成していることが分かった。次いで、この反応生成物を室温まで冷却した後、水酸化ナトリウムの２０重量％水溶液３．８６グラム(１９．３ミリモル)を添加して、室温で３０分間反応させた。次いで、ヘキサンを投入して均一溶液にした後で、低沸点成分を加熱減圧下で留去したところ、白色固体状物が得られた。ＩＲ分析の結果、該白色固体状物は、平均構造式：

で示されるケイ素原子に結合した有機基の末端にカルボン酸のナトリウム塩を有する有機変性メチルポリシロキサン（ゲル化剤４）であることが判明した。得られた白色固体状物５ｇとデカメチルシクロペンタシロキサン（Ｄ５） ２９．３ｇ、重質流動パラフィン １５．７ｇとを９０℃で攪拌し、冷却したところ透明な硬いゲル状組成物（ゲル化剤量：１０重量％）が得られた。 [Example 4]
Average structural formula:

1.00 grams (19.) in 30 grams (NH ₂ groups: 19.5 mmol) of alkyl dimethylsiloxane methyl (3- (2-aminoethyl) aminopropyl) siloxane copolymer represented by 5 mmol) of succinic anhydride was added, and the mixture was stirred at 30 to 40 ° C. for 5 hours under a nitrogen stream. As a result of infrared absorption (IR) analysis, it was found that the characteristic absorption of the carboxylic acid anhydride disappeared, and an organically modified methylpolysiloxane having a carboxyl group at the terminal of the organic group bonded to the silicon atom was formed. The reaction product was then cooled to room temperature, and 3.86 grams (19.3 mmol) of a 20 wt% aqueous solution of sodium hydroxide was added and allowed to react at room temperature for 30 minutes. Subsequently, hexane was added to make a homogeneous solution, and then the low boiling point component was distilled off under reduced pressure by heating to obtain a white solid. As a result of IR analysis, the white solid was found to have an average structural formula:

It was found to be an organically modified methylpolysiloxane (gelator 4) having a sodium salt of a carboxylic acid at the end of an organic group bonded to a silicon atom represented by When 5 g of the obtained white solid substance, 29.3 g of decamethylcyclopentasiloxane (D5), and 15.7 g of heavy liquid paraffin were stirred at 90 ° C. and cooled, a transparent hard gel composition (gelling agent) Amount: 10% by weight) was obtained.

[Example 5]
In Example 2, the addition amount of a 20 wt% aqueous solution of sodium hydroxide was changed to 0.50 g (NaOH; 2.51 mmol, 90% of the number of moles relative to the amount of terminal carboxyl group neutralization). Were reacted and mixed under the same conditions to obtain a white solid which was a mixture of organically modified methylpolysiloxane.
When the organically modified methylpolysiloxane (gelator 5) obtained above (5 g), decamethylcyclopentasiloxane (D5) (29.3 g) and heavy liquid paraffin (15.7 g) were stirred at 90 ° C. and cooled to room temperature, it was transparent. A gel-like composition was obtained. Moreover, when this gel composition was compared with the gel composition prepared in Example 2, it showed a soft touch.

[Example 6]
10 g of organically modified methylpolysiloxane (gelator 1) having a sodium salt of carboxylic acid at the terminal of the organic group bonded to the silicon atom obtained in Example 1, 10 g of isopropyl alcohol, 5 g of water, and 0.56 g of calcium chloride The mixture was mixed and heated and stirred at 60 ° C. for 4 hours. To this reaction solution, 200 g of hexane and water were added to wash and remove the generated inorganic salt. Thereafter, the organic layer was removed to obtain a white solid of organically modified methylpolysiloxane (gelator 6) represented by the following average structural formula. 5 g of the obtained white solid, 29.3 g of decamethylcyclopentasiloxane (D5), and 15.7 g of heavy liquid paraffin were stirred at 90 ° C. and cooled to room temperature to obtain a transparent hard gel composition. . This gel composition maintained a gel state stably at room temperature for 3 months or more.
Average structural formula:

で表されるジメチルシロキサン・メチル（アミノプロピル）シロキサンコポリマー５グラム（ＮＨ_２基：２．５２ミリモル）と無水コハク酸０．２５グラム（２．５２ミリモル）をエタノール５グラム中で混合して、３０〜３５℃で２時間攪拌した。赤外吸光（ＩＲ）分析の結果、カルボン酸無水物の特性吸収は消失し、ケイ素原子に結合した有機基の末端にカルボキシル基を有する有機変性メチルポリシロキサンが生成していることが分かった。次いでこれに、２−アミノエタノール０．１５ｇ(２．５２ミリモル)を添加して、７０℃で１時間加熱した。次いで、エタノールを加熱減圧留去して、平均構造式：

で示される、カルボキシアミド基中のカルボキシル基がアミノエタノール中のアミノ基との塩となった有機変性オルガノポリシロキサン（ゲル化剤７）を得た。該有機変性オルガノポリシロキサン５ｇとデカメチルシクロペンタシロキサン（Ｄ５） ２９．３ｇ、重質流動パラフィン １５．７ｇとを９０℃で攪拌し、室温に冷却したが、液状でありゲル状組成物は得られなかった。 [Comparative Example 1]
Average structural formula:

5 grams (NH ₂ groups: 2.52 mmol) and 0.25 gram (2.52 mmol) succinic anhydride in 5 grams of ethanol The mixture was stirred at 30 to 35 ° C. for 2 hours. As a result of infrared absorption (IR) analysis, it was found that the characteristic absorption of the carboxylic acid anhydride disappeared, and an organically modified methylpolysiloxane having a carboxyl group at the terminal of the organic group bonded to the silicon atom was formed. Next, 0.15 g (2.52 mmol) of 2-aminoethanol was added thereto, and the mixture was heated at 70 ° C. for 1 hour. The ethanol is then distilled off under reduced pressure and the average structural formula:

Thus, an organically modified organopolysiloxane (gelator 7) in which the carboxyl group in the carboxyamide group became a salt with the amino group in aminoethanol was obtained. 5 g of the organically modified organopolysiloxane, 29.3 g of decamethylcyclopentasiloxane (D5), and 15.7 g of heavy liquid paraffin were stirred at 90 ° C. and cooled to room temperature, but a liquid gel-like composition was obtained. I couldn't.

で表されるアルキル・ジメチルシロキサン・メチル（３−（２−アミノエチル）アミノプロピル）シロキサンコポリマー３０グラム（ＮＨ_２基：１０．０ミリモル）とイソプロピルアルコール３６グラム中に１．００ｇ(１０．０ミリモル)の無水コハク酸を投入して窒素気流下に３０〜４０℃で５時間攪拌した。赤外吸光（ＩＲ）分析の結果、カルボン酸無水物の特性吸収は消失し、ケイ素原子に結合した有機基の末端にカルボキシル基を有する有機変性メチルポリシロキサンが生成していることが分かった。ＩＲ分析の結果、該ポリマーは、平均構造式：

で示される有機変性メチルポリシロキサンであった。有機変性オルガノポリシロキサン（ゲル化剤８）を得た。該有機変性オルガノポリシロキサン５ｇとデカメチルシクロペンタシロキサン（Ｄ５） ２９．３ｇ、重質流動パラフィン １５．７ｇとを９０℃で攪拌し、室温に冷却したが、液状でありゲル状組成物は得られなかった。 [Comparative Example 2]
Average structural formula:

1.00 g (10.0 g) in 30 grams (NH ₂ groups: 10.0 mmol) and 36 grams of isopropyl alcohol with alkyl dimethylsiloxane methyl (3- (2-aminoethyl) aminopropyl) siloxane copolymer represented by Mmol) of succinic anhydride was added and stirred at 30-40 ° C. for 5 hours under a nitrogen stream. As a result of infrared absorption (IR) analysis, it was found that the characteristic absorption of the carboxylic acid anhydride disappeared, and an organically modified methylpolysiloxane having a carboxyl group at the terminal of the organic group bonded to the silicon atom was formed. As a result of IR analysis, the polymer has an average structural formula:

It was organic modification methylpolysiloxane shown by these. An organically modified organopolysiloxane (gelator 8) was obtained. 5 g of the organically modified organopolysiloxane, 29.3 g of decamethylcyclopentasiloxane (D5), and 15.7 g of heavy liquid paraffin were stirred at 90 ° C. and cooled to room temperature, but a liquid gel-like composition was obtained. I couldn't.

[Example 7]
As the component (A), the organically modified methylpolysiloxane (gelator 2) described in Example 2 and as the component (B) trimethylsiloxy group-blocked dimethylpolysiloxane (6 mm ² / s), toluene, light liquid paraffin, After mixing with either isoparaffin or isododecane at a blending ratio shown in Table 1 or Table 2, the mixture was stirred at 90 ° C. and cooled to room temperature to prepare a gel composition. The results are shown in Tables 1 and 2.
In addition, the number in a table | surface shows weight%, (double-circle) of the external appearance of a gel-like composition shows a transparent gel, and (circle) shows a soft transparent gel, respectively.

*１：フェニルトリメチコンは東レ・ダウコーニング社製ＳＨ５５６を使用した
[Example 8]
7.5% by weight of organically modified methylpolysiloxane (gelator 4) described in Example 4, 60.5% by weight of decamethylpentacyclosiloxane sun (D5) and 32% by weight of various cosmetic oils at 80 ° C. for 2 hours Table 3 shows the appearance and refractive index of the gel composition obtained by heating and stirring and then cooling. Furthermore, the result of having measured the viscoelasticity data of the gel-like composition of Example 8-1 to Example 8-3 in Table 3 was shown in FIGS. In the figure, f represents frequency (Hz), G ′ represents storage elastic modulus, and η represents viscosity.

* 1: As the phenyl trimethicone, SH556 manufactured by Toray Dow Corning was used.

From Table 1 to Table 3, when an organopolysiloxane having an organic group represented by the general formula (1) is used as a gelling agent, representative nonpolar organic compounds or low polar organic compounds to be blended in cosmetics are listed. It was found that gel-like compositions can be formed and the transparency of the appearance of these gel-like compositions is very high. Moreover, even if it was a nonpolar organic compound with much alkyl group content like heavy liquid paraffin, it turned out that an external appearance is transparent and a stable gel-like composition can be obtained.
Furthermore, as shown in FIGS. 1-4, when the gel-like composition of the present invention increases the frequency (f), the viscosity (η) of the gel composition decreases and the storage elastic modulus (G ′) increases. It showed thixotropic viscoelastic properties. FIG. 4 is a result of comparison between the gel composition of Example 8-1 and the gel composition of Example 8-2, and different rheological properties are obtained by changing the oil agent (component (B)) to be formed. It shows that a gel-like composition having can sometimes be prepared.

In the examples shown below, unless otherwise specified, the term “gelator X” refers to the organically modified methylpolysiloxane (gelator X) shown in Example X above. And Moreover,% is weight%.

Example 9: Water-in-oil emulsion sunscreen (component) (wt%)
1. Gelling agent 1 5.0
2. Methyltrimethicone 25.0
3. Dimethylpolysiloxane (viscosity 6 mPa · s) 3.0
4). Carbosiloxane dendrimer graft type acrylic copolymer 3.0
5. Polyoxyethylene / methylpolysiloxane copolymer ^{* 1} 3.0
6). Tri (Capryl / Capric Acid) Glyceryl 3.0
7). Organopolysiloxane elastomer spherical powder ^{* 2} 2.0
8). Silicone-treated ultrafine titanium oxide 10.0
9. Silicone-treated ultrafine zinc oxide 10.0
10. Spherical PMMA powder 2.0
11. Dipropylene glycol 2.0
12 Deionized water remaining amount 13. Preservative appropriate amount14. Perfume
* 1: SH3772C manufactured by Toray Dow Corning Co., Ltd. was used as the polyoxyethylene / methylpolysiloxane copolymer.
* 2: Torefill E-508 manufactured by Toray Dow Corning was used as the organopolysiloxane elastomer spherical powder.

(Production method)
A: Components 1 to 7 are heated and stirred at 90 ° C. using a disper.
B: Components 8 to 10 are added to the solution prepared in A and stirred using a disper.
C: Components 11 and 12 are gradually added to the solution prepared in B at 50 ° C. to emulsify.
D: Components 13 and 14 were added to C to obtain a water-in-oil type emulsion sunscreen.
Evaluation of the feeling of use of the water-in-oil type emulsified sunscreen of Example 9 was conducted, and since the oil phase of the sunscreen was stabilized by the product of the present invention, it was excellent in aging stability and natural. It had a feeling of use and had good sebum resistance and UV protection.

Example 10: Oily foundation (component) (wt%)
1． Gelling agent 2 5.0
2. Trimethylsiloxysilicic acid 2.0
3. Decamethylpentacyclosiloxane Residual amount 4. Octyl paramethoxycinnamate 4.0
5. Methyl trimethicone * 1 10.0
6). Tri (Capryl / Capric Acid) Glyceryl 3.0
7). Caprylyl methicone * 2 1.0
8). Cross-linked polyether-modified silicone ^{* 3} 5.0
9. Alkylsilane-treated titanium oxide 10.0
10. Alkylsilane-treated zinc oxide 15.0
* 1: Methyltristrimethylone was methyltristrimethylsiloxysilane.
* 2: SS3408 manufactured by Toray Dow Corning was used as caprylyl methicone.
* 3: DC9011 manufactured by Toray Dow Corning Co., Ltd. was used as the crosslinked polyether-modified silicone.

(Production method)
A: Components 1 to 8 are heated and stirred using a disper at 90 ° C.
B: Components 9 to 11 are stirred with a disper.
C: While stirring A with a disper, B was gradually added to obtain an oily foundation.
When the oily foundation of Example 10 was evaluated for the feeling of use, the oily foundation was excellent in feeling of use without causing dripping, and excellent in long-lasting makeup.

Example 11: Emulsion foundation (W / O type)
(Ingredient) (wt%)
1. Gelling agent 2 3.0
2. Decamethylpentacyclosiloxane 8.0
3. Polyoxyethylene hydrogenated castor oil 9.0
4). Heavy liquid paraffin 5.0
5. Isononyl isononanoate 5.0
6). Dimethylpolysiloxane (viscosity 6mPa · s) 3.0
7). Dimethylsiloxane / methylpolyoxyethylenesiloxane copolymer ^{* 1} 5.0
8). Organopolysiloxane elastomer spherical powder ^{* 2} 2.0
9. Silicone-treated fine particle titanium oxide 5.0
10. Silicone-treated fine particle zinc oxide 5.0
11. Silicone-treated fine particle iron oxide 5.0
12 Propylene glycol 3.0
13. Residual amount of ion-exchanged water 14. Preservative appropriate amount15. Perfume
* 1: SH3775C manufactured by Toray Dow Corning was used as the dimethylsiloxane / methylpolyoxyethylenesiloxane copolymer.
* 2: Trefil E-508 manufactured by Toray Dow Corning was used as the organopolysiloxane elastomer spherical powder.

(Production method)
A: Components 1 to 7 are heated to 80 ° C. and dispersed uniformly.
B: Components 8 to 11 are added to A and dispersed uniformly.
C: Components 12 to 14 are mixed uniformly.
D: C is added to B at 50 ° C. and emulsified.
E: After cooling, component 15 was added to D and mixed to obtain an emulsified foundation (W / O type).
When the feeling of use of the emulsified foundation (W / O type) of Example 11 was evaluated, the emulsified foundation (W / O type) produced by this formulation had a cosmetic and wrinkle concealing effect and had a coating feel. It was smooth, easy to adjust to the skin and good stability.

Example 12: Oil cleansing gel (wash-out type)
(Composition) (%)
1. Gelling agent 4 6.0
2. Heavy liquid paraffin 30.0
3. Decamethylpentasiloxane 56.0
4). Polyoxyethylene / methylpolysiloxane copolymer ^{* 1} 5.0
5. Propylene glycol 3.0
* 1: SH3772C manufactured by Toray Dow Corning Co., Ltd. was used as the dimethylsiloxane / methylpolyoxyethylenesiloxane copolymer.

(Production method)
Ingredients 1-5 were uniformly mixed at 80 ° C. to obtain a cleansing gel.
(Evaluation method)
After applying a commercially available sebum-resistant foundation and lasting type lipstick to the skin, put an appropriate amount of the oil cleansing gel of Example 12 (wash-out type) on the coating film, and rub it with your finger to thoroughly apply the coating film. Then, it was washed with water and then washed with soap.
(Evaluation results)
By using the cleansing gel, the durable foundation applied on the skin and the lipstick were all washed away, and the gel was excellent in cleansing ability. Moreover, the feel of the gel was also a light feel excellent in thixotropy, and the usability was also excellent.

Example 13: Oil cleansing gel (wipe-off type)
(Composition) (wt%)
1. Gelling agent 3 6.0
2. Tri (Capryl / Capric Acid) Glyceryl 32.0
3. Decamethylpentasiloxane 59.0
4). Propylene glycol 3.0

(Production method)
Ingredients 1-5 were uniformly mixed at 80 ° C. to obtain a cleansing gel.
(Evaluation method)
After applying commercially available sebum-resistant oil-based foundation and lasting type lipstick to the skin, put an appropriate amount of the oil cleansing gel of Example 13 on the coating film, rubbing with a finger and thoroughly applying the coating film, then cotton Wipe off with. Further, cleansing materials produced in the same manner except that decamethylpentasiloxane was used instead of the gelling agent of Example 13 were prepared, and the same evaluation was performed.
(Evaluation results)
By using the cleansing gel, it was found that all the oil-resistant oily foundation and lipstick applied on the skin were wiped off, and the gel was excellent in cleansing ability. In addition to the light touch unique to silicone oil, the gel feel can be blended with an oil agent with a high alkyl group content, so that the feeling of use is excellent and the transparency of the gel is excellent. On the other hand, when the gelling agent was not used, it was found that a residue remained in the sebum-resistant oily foundation and the cleansing performance was insufficient. Further, when the gelling agent of the present invention was not used, the viscosity was low, dripping occurred, and the usability was poor.

Example 14: Lipstick (component) (wt%)
1. Gelling agent 2 8.0
2. Glyceryl triisostearate 20.0
3. Dimethylpolysiloxane (6 mPa · s) 5.0
4). Decamethylpentacyclosiloxane 30.0
5. Polyoxyethylene / methylpolysiloxane copolymer ^{* 1} 3.0
6). Trimethylsiloxysilicic acid 8.0
7). Alkyl-modified polysiloxane ^{* 2} 3.0
8). Methylphenylpolysiloxane 5.0
9. Silicone-treated pigment appropriate amount10. Dye proper amount11. Synthetic sodium silicate / magnesium 1.0
12 Perfume
* 1: SH3775C manufactured by Toray Dow Corning was used as the dimethylsiloxane / methylpolyoxyethylenesiloxane copolymer.
* 2: DC2503 manufactured by Toray Dow Corning was used as the alkyl-modified polysiloxane.

(Production method)
A: Components 1 to 8 were heated and stirred uniformly at 80 ° C. B: Components 9 to 12 were uniformly dispersed.
C: B was gradually added to A and filled into a brush type container to obtain a lipstick.
When the usability of the lipstick of Example 14 was evaluated, the makeup effect was highly durable, precipitation of pigments and powders did not occur, and the stability was excellent.

The result of having measured the viscoelasticity data of the gel-like composition prepared in Example 8-1. The result of having measured the viscoelasticity data of the gel-like composition prepared in Example 8-2. The result of having measured the viscoelasticity data of the gel-like composition prepared in Example 8-3. The result of having compared the viscoelasticity data of the gel-like composition prepared in Example 8-1 and Example 8-2.

Claims (22)

An organic group (—Y) represented by the general formula (1) bonded to a silicon atom and a substituted or unsubstituted monovalent hydrocarbon group (—Z) having 9 or more carbon atoms bonded to the silicon atom in the molecule A gelling agent comprising an organopolysiloxane.
General formula (1):

[In the formula, R ^{1 -COO - (M n +) 1} / n represented by metal salts of carboxylic acids (M is a monovalent or more metals, n represents represents an atomic valence of M), X is identical or different Divalent hydrocarbon group having 2 to 14 carbon atoms, p is an integer of 0 to 10. ] The gelling agent according to claim 1, wherein, in the general formula (1), M is an alkali metal and the divalent hydrocarbon group X is an alkylene group. The gelling agent according to claim 1, wherein the monovalent hydrocarbon group (-Z) is an alkyl group having 10 to 45 carbon atoms. The gelling agent according to claim 1, wherein the organopolysiloxane is a linear organopolysiloxane represented by the following general formula (2):

[Wherein, R represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms (excluding the organic group represented by the general formula (1)), and Y represents the above general formula (1). An organic group represented, Z is a substituted or unsubstituted monovalent hydrocarbon group having 9 or more carbon atoms, B is selected from R, Y, and Z, and when t = 0, at least one of B is Y And when u = 0, at least one of B is Z, and when t = 0 and u = 0, one of B is Y and the other is Z. s is an integer of 10 to 100,000, t is an integer of 0 to 50, and u is 0 to 1000. ] In the general formula (2), R is an alkyl group having 1 to 8 carbon atoms, (s + t + u) is an integer of 20 to 5000, t / (s + t + u) is 0.001 to 0.05, u The gelling agent according to claim 4, wherein / (s + t + u) is 0.001 to 0.30. The gelling agent according to any one of claims 1 to 5, wherein the gelling agent is for silicone oil, nonpolar organic compound or low polarity organic compound. (A) 1 to 99% by weight of a gelling agent according to any one of claims 1 to 6
And (B) 99 to 1% by weight of silicone oil, non-polar organic compound or low-polar organic compound
A gel-like composition comprising: The gel composition according to claim 7, wherein the silicone oil is a hydrophobic silicone oil having a viscosity at 25 ° C of 0.65 to 100,000 mm ² / s. The gel composition according to claim 7, wherein the nonpolar organic compound or the low polarity organic compound is liquid at 5 to 100 ° C. The refractive index of a gel-like composition exists in the range of 1.20-1.60, The gel-like composition of any one of Claims 7-9 characterized by the above-mentioned. Cosmetics which mix | blended the gelatinizer of any one of Claims 1-6. Cosmetics which mix | blended the gel-like composition of any one of Claims 7-10. Furthermore, (c) 1 type, or 2 or more types chosen from the group which consists of anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, and a semipolar surfactant are contained. Or the cosmetics of Claim 12. The cosmetic according to any one of claims 11 to 13, further comprising (d) a powder and / or a colorant. (D) One or more kinds of powders and / or colorants selected from the group consisting of inorganic pigment powders, organic pigment powders, and resin powders having an average particle diameter in the range of 1 nm to 20 μm. The cosmetic according to claim 14. The cosmetic according to claim 14 or 15, wherein a part or all of the component (d) is a water-repellent powder and / or a colorant. The cosmetic according to any one of claims 11 to 16, further comprising (e) a water-soluble polymer. The cosmetic according to any one of claims 11 to 17, further comprising (f) a silicone resin. The cosmetic according to any one of claims 11 to 18, further comprising (g) a silicone elastomer. The cosmetic according to any one of claims 11 to 19, further comprising (h) an ultraviolet protection component. A skin cleanser product comprising the cosmetic according to any one of claims 11 to 20. A cleansing cosmetic comprising the cosmetic according to any one of claims 11 to 20.

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