JP4800681B2 - Gelling agent and gel composition - Google Patents

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, 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.

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.

JP 7-215817 A JP-A-10-158150 JP-A-8-109263

The present invention relates to a gelling agent capable of gelling silicone oil, nonpolar organic compounds and low polar organic compounds without using water, and a gel having excellent thermal stability and stability over time, and thixotropic rheological properties. An object is to provide a 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 an organopolysiloxane having an organic group represented by the general formula (1) bonded to a silicon atom

[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
The present inventors have found that a gel-like composition consisting of is useful in solving the above-mentioned problems, and have 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ことを特徴とする〔１〕または〔２〕に記載のゲル化剤。

［式中、Aは一般式（１）で表される有機基、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）、BはRまたはAから選択される基であり、ｔ＝０のとき、Bのうち少なくとも一つはAである。ｓは１０〜１０００００の整数であり、ｔは０〜５０の整数である。］
〔４〕 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が１００〜１０００の整数であり、ｔ／(ｓ＋ｔ)が０．１〜５％であることを特徴とする〔３〕に記載のゲル化剤。
〔５〕 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〕〜〔４〕のいずれかに記載のゲル化剤。
〔６〕 シリコーンオイルが疎水性シリコーンオイルである〔５〕に記載のゲル化剤。
〔７〕 （Ａ）〔１〕〜〔４〕のいずれかに記載のゲル化剤 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疎水性シリコーンオイルである〔７〕に記載のゲル状組成物。
〔９〕 疎水性シリコーンオイルが揮発性である〔８〕に記載のゲル状組成物。
〔１０〕 非極性有機化合物または低極性有機化合物が油脂である、〔７〕に記載のゲル状組成物。
〔１１〕 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〕〜〔１０〕のいずれかに記載のゲル状組成物。」に関する。 The present invention is “[1] A gelling agent comprising an organopolysiloxane having an organic group represented by the general formula (1) bonded to a silicon atom.

[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] or [2], which is a linear organopolysiloxane represented by the general formula (2).

[Wherein, A is an organic group represented by the general formula (1), R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms (provided that the organic group is represented by the general formula (1) B is a group selected from R or A, and when t = 0, at least one of B is A. s is an integer of 10 to 100,000, and t is an integer of 0 to 50. ]
[4] In General Formula (2), R is an alkyl group having 1 to 8 carbon atoms, s is an integer of 100 to 1000, and t / (s + t) is 0.1 to 5%. The gelling agent according to [3], which is characterized.
[5] The gelling agent according to any one of [1] to [4], which is for silicone oil, nonpolar organic compound, or low polarity organic compound.
[6] The gelling agent according to [5], wherein the silicone oil is a hydrophobic silicone oil.
[7] (A) 1 to 99% by weight of a gelling agent according to any one of [1] to [4] and (B) 99 to 1% by weight of silicone oil, nonpolar organic compound or low polar organic compound
[7] The gel composition according to [7], wherein the silicone oil is a hydrophobic silicone oil.
[9] The gel composition according to [8], wherein the hydrophobic silicone oil is volatile.
[10] The gel composition according to [7], wherein the nonpolar organic compound or the low polarity organic compound is an oil or fat.
[11] The gel composition according to any one of [7] to [10], wherein the gel composition has a refractive index in the range of 1.20 to 1.60. ".

The gelling agent of the present invention can gel silicone oil, nonpolar organic compounds and low polar organic compounds with good thermal stability and temporal stability without using water together. The gel composition according to the present invention has thixotropic rheological properties and is excellent in thermal stability and stability over time.

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 is an organopolysiloxane having an organic group represented by the general formula (1) bonded to a silicon atom.

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.

式（３）、式（４）において、Ｒ，Ｒ^１，Ｘ，ｐは前記と同様である。 The organopolysiloxane having an organic group represented by the general formula (1) bonded to the silicon atom contains at least one siloxane unit represented by the following formula (3) or formula (4).

In the formulas (3) and (4), R, R ¹ , X, and p are the same as described above.

The gelling agent 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 . In the formula, 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.

The organopolysiloxane having an organic group represented by the general formula (1) bonded to a silicon atom contains at least one siloxane unit represented by the formula (3) or (4) in one molecule. It is preferable to include two or more from the viewpoint of the gelation performance which is the object. 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.

The organopolysiloxane having an organic group represented by the general formula (1) bonded to a silicon atom has at least one organic group represented by the general formula (1) in one molecule, and is an object of the present invention. From the viewpoint of gelling performance, it is preferable to contain two or more, preferably 0.5% by weight or more, and more preferably 1.0% by weight or more of the organic group represented by the general formula (1). Particularly preferred. 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.

で表されるジオルガノポリシロキサンが挙げられる。上式中、Ｒは前記どおりであり、
Aは一般式（１）で表される有機基であり、BはRまたはAであり、ｔ＝０のとき、Bのうち少なくとも一つはAである。ｓは１０〜１０００００の整数であり、１００〜１００００が好ましい。ｔは０〜５０の整数であり、１〜３０が好ましい。また、ｔ／(ｓ＋ｔ)は０．１〜５％であることが好ましく、０．１〜３％がより好ましい。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。 As a typical example of the linear organopolysiloxane having an organic group represented by the general formula (1) bonded to a silicon atom, the general formula (2):

The diorganopolysiloxane represented by these is mentioned. In the above formula, R is as described above,
A is an organic group represented by the general formula (1), B is R or A, and when t = 0, at least one of B is A. s is an integer of 10-100,000, and 100-10000 is preferable. t is an integer of 0 to 50, preferably 1 to 30. Further, t / (s + t) is preferably 0.1 to 5%, and more preferably 0.1 to 3%. 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 paste 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 represented by, for example, an organopolysiloxane having an organic group represented by the general formula (5) and the following general formula (6). It can manufacture by making the metal compound made to react.

(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 method for synthesizing the organopolysiloxane having an organic group represented by the general formula (5), a known method of reacting an amino-functional organopolysiloxane with a cyclic carboxylic acid anhydride is 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.

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. In addition, when using an organopolysiloxane having only an organic group having an amino alcohol salt other than a metal salt, the heat resistance is low, and when producing a cosmetic using the gelling agent itself and the gelling agent, If it is maintained at a temperature of 110 ° C. or more for several hours, a dehydration reaction occurs, and there is a problem that a desired gelling ability cannot be exhibited when cooled.

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; calcium carbonate, barium carbonate, metal salts such as copper carbonate; magnesium sulfate, calcium sulfate, zinc sulfate, iron sulfate, copper sulfate, sulfuric acid metal salts such as 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 reaction for forming an organic group 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 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 represented by the general formula (1) has a property of gelling when it is well mixed with silicone oil, nonpolar organic compound or low polar organic compound under heating and then cooled to room temperature. Therefore, it is suitable as a gelling agent for silicone oil, non-polar organic compound or low-polar organic compound.

Furthermore, since the organopolysiloxane having an organic group represented by the general formula (1) has low gelling performance with respect to a polar organic compound such as methanol, ethanol, isopropyl alcohol, etc., a gel-like material is prepared using this property. It is also possible. That is, silicone oil, a nonpolar organic compound or a low polarity organic compound and a polar organic compound are mixed, and the organopolysiloxane having an organic group represented by the general formula (5) in the mixture and the general formula (6) A gel-like composition can be obtained by carrying out a salt formation reaction with the metal compound to be prepared to prepare a liquid reaction mixture and then distilling off the polar organic compound under reduced pressure.

The gel composition of the present invention is
(A) 1 to 99% by weight of an organopolysiloxane having an organic group represented by the general formula (1) and (B) silicone oil other than the component (A), a nonpolar organic compound or a low polar organic compound 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) and the component (B) is in the range of (A) :( B) = 1 to 99:99 to 1% by weight, preferably in the range of 2 to 40:98 to 60% by weight, A range of 2 to 30:98 to 70% by weight 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.

Nonpolar organic compounds or low polar organic compounds include carbonized hexane, heptane, toluene, xylene, mesitylene, liquid paraffin, petrolatum, n-paraffin, isoparaffin, isododecane, hydrogenated polyisobutylene, ozokerite, ceresin, squalane, pristane, etc. Hydrogen: avocado oil, almond oil, olive oil, sesame oil, 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 Vegetable oils such as nuclear oil, molasses and coconut oil; animal oils such as mink oil, egg yolk oil, beef tallow, pork fat, hydrogenated oil; beeswax, carnauba wax, whale wax, lanolin, liquid lanolin, reduced lanolin, hard Lanolin, candelilla wax, jojoba oil, microcrystalline Waxes such as wax; higher alcohols such as palmityl alcohol, stearyl alcohol, oleyl alcohol, lanolin alcohol, cholesterol, phytosterol, 2-hexyldecanol, isostearyl alcohol, 2-octyldodecanol; methyl formate, ethyl formate, ethyl acetate , Propyl acetate, butyl acetate, cetyl octanoate, isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, oleyl oleate, decyl oleate, octyldodecyl myristate, hexyldecyl dimethyloctanoate, Cetyl lactate, myristyl lactate, diethyl phthalate, dibutyl phthalate, lanolin acetate, ethylene glycol monostearate, propylene monostearate Glycerol, propylene glycol dioleate, glyceryl monostearate, glyceryl monooleate, glyceryl tri-2-ethylhexanoate, trimethylolpropane tri-2-ethylhexanoate; liquid fatty acid triglycerides, artificial sebum (squalane and liquid And a mixture of fatty acid triglyceride and oleic acid).

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 a type and content of the organic group represented by the general formula (1) contained in the component (A), particularly a monovalent or polyvalent metal salt. By adjusting the type of silicon-bonded hydrocarbon group in component (A) and the type of component (B), a gel composition having excellent transparency can be obtained. That is, selecting the type of X of the organic group represented by the general formula (1) contained in the component (A), the number of p and / or the type of the metal ion M ^{n +} , or the appearance as the component (B) By selecting a colorless, transparent and non-turbid silicone oil, a nonpolar organic compound or a low polar organic compound, 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⁺ ), The component is preferably dimethylpolysiloxane or methylpolysiloxane having a viscosity at 25 ° C. of 0.65 to 10,000 mm ² / s. (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.

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 a temperature of 25 ° C. using an Abbe refractive index (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：１１．０ミリモル）と無水コハク酸１．１０グラム（１１．０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２．２グラム(１０．８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であることが判明した。得られた白色固体状物２ｇとデカメチルペンタシクロシロキサン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。このゲル状組成物の屈折率は１．３９７０であった。 [Example 1]
Average structural formula:

30 grams of dimethylsiloxane methyl (3-aminopropyl) siloxane copolymer (NH ₂ groups: 11.0 mmol) and 1.10 grams (11.0 mmol) of succinic anhydride were mixed in 36 grams of isopropyl alcohol. And it stirred at 30-35 degreeC 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, 2.2 g (10.8 mmol) of a 20 wt% aqueous solution of sodium hydroxide was added to the reaction product and 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 to be an organically modified methylpolysiloxane having a sodium salt of a carboxylic acid at the terminal of an organic group bonded to a silicon atom represented by When 2 g of the obtained white solid and 18 g of decamethylpentacyclosiloxane 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. The refractive index of this gel composition was 1.3970.

で表される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１０グラム（ＮＨ_２基：２．８２ミリモル）とイソプロピルアルコール２０グラム中に０．２８グラム(２．８２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０．５６グラム(２．７９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であることが判明した。得られた白色固体状物２ｇとデカメチルペンタシクロシロキサン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（ゲル化剤量：１０重量％）が得られた。同様に、得られた白色固体状物１．５ｇとデカメチルペンタシクロシロキサン１８．５ｇを９０℃で攪拌し、冷却したところ、ゲル化剤量が１０重量％のゲル状組成物と比べて柔らかい感触のゲル状組成物（ゲル化剤量：７．５重量％）が得られた。これらのゲル状組成物の屈折率は１．３９８０であった。 [Example 2]
Average structural formula:

In represented by dimethyl siloxane-methyl (3- (2-aminoethyl) aminopropyl) siloxane copolymer 10 g (NH ₂ groups: 2.82 mmol) 0.28 g (2.82 mmol of isopropyl alcohol 20 g in ) Succinic anhydride was added and 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. Then, the reaction product was cooled to room temperature, 0.56 g (2.79 mmol) of a 20 wt% aqueous solution of sodium hydroxide was added, and the mixture was reacted 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 having a sodium salt of a carboxylic acid at the terminal of an organic group bonded to a silicon atom represented by When 2 g of the obtained white solid and 18 g of decamethylpentacyclosiloxane were stirred at 90 ° C. and cooled, a transparent hard gel composition (amount of gelling agent: 10% by weight) was obtained. Similarly, when 1.5 g of the obtained white solid and 18.5 g of decamethylpentacyclosiloxane were stirred at 90 ° C. and cooled, the amount of the gelling agent was softer than that of the gel-like composition with 10% by weight. A feelable gel composition (gelling agent amount: 7.5% by weight) was obtained. These gel compositions had a refractive index of 1.3980.

上記で得た有機変性メチルポリシロキサン２ｇとデカメチルペンタシクロシロキサン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。このゲル状組成物の屈折率は１．３９８１であった。 [Example 3]
In Example 2, the reaction and mixing were carried out under the same conditions except that 0.784 g (2.79 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 obtained above and 18 g of decamethylpentacyclosiloxane 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. The refractive index of this gel composition was 1.3981.

上記で得た有機変性メチルポリシロキサン２ｇとデカメチルペンタシクロシロキサン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。 [Example 4]
In Example 2, the reaction and mixing were carried out under the same conditions except that 0.54 g (NaOCH ₃ ; 2.79 mmol) of a 28 wt% aqueous solution of sodium methoxide was added instead of the 20 wt% aqueous solution of sodium hydroxide. Thus, 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 obtained above and 18 g of decamethylpentacyclosiloxane were stirred at 90 ° C. and cooled to room temperature, a transparent gel composition was obtained.

上記で得た有機変性メチルポリシロキサン２ｇとデカメチルペンタシクロシロキサン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。このゲル状組成物を実施例２で調製したゲル状組成物と比較すると柔らかい感触を示した。またこのゲル状組成物の屈折率は１．３９８０であった。 [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 methylpolysiloxanes represented by the following average structural formula (i) to average structural formula (iv).
Average structural formula:

When 2 g of the organically modified methylpolysiloxane obtained above and 18 g of decamethylpentacyclosiloxane were stirred at 90 ° C. and cooled to room temperature, a transparent gel composition was obtained. When this gel composition was compared with the gel composition prepared in Example 2, it showed a soft feel. The refractive index of this gel composition was 1.3980.

[Example 6]
10 g of organically modified methylpolysiloxane having a sodium salt of carboxylic acid at the end of the organic group bonded to the silicon atom obtained in Example 1, 10 g of isopropyl alcohol, 5 g of water, and 0.33 g of calcium chloride were mixed at 60 ° C. Stir with heating for 4 hours. To this reaction solution, 200 g of hexane and water were added to wash and remove the generated inorganic salt. Then, the organic layer was removed to obtain a white solid of organically modified methylpolysiloxane represented by the following average structural formula. When 2 g of the obtained white solid and 18 g of decamethylpentacyclosiloxane were stirred at 90 ° C. and cooled to room temperature, a transparent hard gel composition was obtained. This gel composition maintained a gel state stably at room temperature for 3 months or more. The refractive index of this gel composition was 1.3978.
Average structural formula:

[Example 7]
(A) The gelling agent obtained in Example 2 as component (A) and either terminal trimethylsiloxy group-blocked dimethylpolysiloxane (6 mm ² / s), toluene, hexane, isoparaffin, or isododecane as component (B) at 90 ° C. Table 1 and Table 2 show the results of preparing the gel composition by stirring at rt and cooling to room temperature.
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.

で表される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。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ので反応を終了し、２０gのデカメチルシクロペンタシロキサンを投入した。次いでエタノールを加熱減圧下で留去することにより、低粘度の液体が得られた。この液体は、平均構造式：

で示される有機変性メチルポリシロキサンとデカメチルシクロペンタシロキサンの混合物であり、上記の有機変性メチルポリシロキサン濃度は２０重量％であった。この混合物を室温（２５℃）まで冷却したが液状であり、ゲル状物は得られなかった。 [Comparative Example 1]
Average structural formula:

5 grams of dimethylsiloxane methyl (3- (2-aminoethyl) aminopropyl) siloxane copolymer represented by the formula (NH ₂ group: 2.52 mmol) and 0.25 grams (2.52 mmol) of succinic anhydride were added to ethanol. Mix in 5 grams and stir at 30-35 ° C. for 2 hours. As a result of 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. Therefore, the reaction was terminated, and 20 g of decamethylcyclopentasiloxane was added. Subsequently, ethanol was distilled off under heating and reduced pressure to obtain a low-viscosity liquid. This liquid has the average structural formula:

A mixture of organically modified methylpolysiloxane and decamethylcyclopentasiloxane represented by the above formula, and the concentration of the above organically modified methylpolysiloxane was 20% by weight. Although this mixture was cooled to room temperature (25 ° C.), it was liquid and a gel-like product was not obtained.

[Example 8]
The result of having measured the viscoelasticity data of the gel-like composition prepared in Example 1, Example 2, and Example 3 was shown in FIG. In the figure, f represents frequency (Hz), G ′ represents storage elastic modulus, and η represents viscosity.
From FIG. 1, it was found that when the frequency was increased, the viscosity (η) of the gel composition was decreased, and thixotropic viscoelastic characteristics were exhibited. Moreover, it turned out that the gel-like composition of an Example has high storage elastic modulus (G '), and is excellent in gelatinization ability.

The gelling agent of the present invention is useful as a gelling agent for silicone oils, particularly hydrophobic silicone oils, nonpolar organic compounds and low polar organic compounds. Furthermore, the gel composition of the present invention can be blended into various industrial products such as liquid and paste, pharmaceuticals, cosmetics, health care products, and household care products, thereby improving their feel, feel and stability. Has the advantage of The gel composition of the present invention can also be used as a car wax, a surface treatment agent, a mold release agent, a lubricant, a resin additive, and an emulsion stabilizer.

The measurement result of the viscoelasticity of the gel-like composition prepared in Example 1, Example 2, and Example 3 is shown.

Claims (11)

Gelling agent comprising an organopolysiloxane having an organic group represented by the general formula (1) bonded to a silicon atom

[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 or 2, which is a linear organopolysiloxane represented by the general formula (2).

[Wherein, A is an organic group represented by the general formula (1), R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms (provided that the organic group is represented by the general formula (1) B is R or A, and when t = 0, at least one of B is A. s is an integer of 10 to 100,000, and t is an integer of 0 to 50. ] In the general formula (2), R is an alkyl group having 1 to 8 carbon atoms, s is an integer of 100 to 1000, and t / (s + t) is 0.1 to 5%. The gelling agent according to claim 3. The gelling agent according to any one of claims 1 to 4, wherein the gelling agent is for silicone oil, nonpolar organic compound, or low polarity organic compound. The gelling agent according to claim 5, wherein the silicone oil is a hydrophobic silicone oil. (A) 1 to 99% by weight of the gelling agent according to any one of claims 1 to 4 and (B) silicone oil, nonpolar organic compound or low polar organic compound 99 to 1% by weight
A gel-like composition comprising: 8. The gel composition according to claim 7, wherein the silicone oil is a hydrophobic silicone oil. The gel composition according to claim 8, wherein the hydrophobic silicone oil is volatile. The gel composition according to claim 7, wherein the nonpolar organic compound or the low polarity organic compound is an oil or fat. The gel composition according to any one of claims 7 to 10, wherein the refractive index of the gel composition is in the range of 1.20 to 1.60.

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