JP6012403B2 - Organosiloxane derivative composition - Google Patents

Description

  The present invention relates to a novel organosiloxane derivative composition, and particularly to improvement of the gelling ability of the silicone oil.

  Conventionally, as a gelling agent for liquid organic compounds such as oil, 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. are known. It has been. These gelling agents are effective as gelling agents for organic solvents, animal and vegetable oils, mineral oils and the like, but silicone oils could not be gelled. Therefore, means for gelling both the silicone oil and the compound simultaneously and stably has been limited.

  On the other hand, particularly low viscosity silicone oils are used for various applications because of their excellent progress, refreshing feeling, lubricity, water repellency, safety, and the like, and are widely used especially in cosmetics. However, since such silicone oils generally have low compatibility with other oils, it has been difficult to prepare products with excellent stability. For example, in the case of low-viscosity silicone oil, even if it is mixed with wax to make a gel product, it does not become a stable composition, and the appearance becomes cloudy. Then, there was a problem that the sticky feeling remained and the original refreshing feeling of the silicone oil was lost.

  To date, various means have been proposed for the problem of gelation of silicone oil. For example, Patent Document 1 discloses a polyether graft type organopolysiloxane as a gelling agent for silicone oil. This gelling agent requires a specific amount of water to be used in combination, and the resulting composition is obtained. The product is not satisfactory in terms of its feel and stability over time.

In recent years, various structures and uses have been proposed for organopolysiloxane derivatives having a specific structure containing a carboxyl group as materials excellent in usability, stability, and rheology.
For example, in Patent Document 2, an organosiloxane having a carboxylic acid polyvalent metal salt-modified group obtained by adding an equivalent amount of a polyvalent metal ion as a cation valence to a carboxylic acid group is gelled into silicone oil. The use as an agent is disclosed. However, the gelation performance was not always satisfactory.
Patent Document 3 discloses a gel composition comprising a monovalent metal salt of a carboxylic acid group-containing organosiloxane derivative having a specific structure, a monovalent aliphatic alcohol having 10 to 30 carbon atoms, and water.

Patent Document 4 discloses an invention in which an organosiloxane that is a divalent or trivalent metal salt of a terminal carboxyl group of a carboxylic acid group-containing organosiloxane derivative having a specific structure is used as a surface treatment agent.
However, these derivatives can be used as gelling or surface treatment agents for water, but are not suitable for use as oil-based thickening or gelling agents.
Furthermore, Patent Documents 5 and 6 propose polyorganosiloxane having an amide group-containing carboxylic acid metal salt in the molecule as a gelling agent for silicone oil. However, a large amount of the gelling agent needs to be mixed with the oil at a high temperature for a long time, and further improvement has been demanded.

JP 07-215817 A Japanese Patent Laid-Open No. 08-109263 WO2009 / 025146 WO2009 / 022621 JP 2007-332295 A JP 2007-001996 A

  The present invention has been made in view of the above problems of the prior art, and an object thereof is to provide an organosiloxane derivative composition capable of stably gelling an oil agent in a small amount.

  As a result of intensive studies by the present inventors in order to solve the problems of the prior art, silicone oil can be gelled by using an organosiloxane derivative composition having a specific structure containing a carboxyl group. The present gel-like composition was found to have excellent thermal stability and stability over time, and the present invention was completed.

（上記式中、Ｒ^１〜Ｒ^３は、少なくとも１つが−Ｏ−Ｓｉ（Ｒ^４）_３で表される官能基（Ｒ^４は、炭素数１〜６のアルキル基又はフェニル基のいずれかである）、又は−Ｏ−Ｓｉ（Ｒ^５）_２−Ｘ^１で表される官能基（Ｒ^５は、炭素数１〜６のアルキル基又はフェニル基のいずれかであり、Ｘ^１はｉ＝１のときの下記一般式（３）で示される官能基である）であり、その他のＲ^１〜Ｒ^３は同一又は異なっていてもよい置換又は非置換の１価炭化水素基である。Ｍは１種類以上のｎ価の金属陽イオンであり、ｎは２以上の数である。ｓは０．１＜ｓ≦１．０の数であり、ｔは０．０５＜ｔ≦１．０の数であり、ｎ×ｓ−ｔ＝１の関係を満たす。Ａは、Ｃ_ｑＨ_２ｑで表される直鎖状又は分岐鎖状のアルキレン基であり、ｑは０〜２０の整数である。また、平均一般式（２）で表されるオルガノシロキサン誘導体の１分子中に含まれるケイ素原子（Ｓｉ）の平均合計数は２〜１００である。）

（上記式中、Ｒ^６は、水素原子、炭素数１〜６のアルキル基又はフェニル基のいずれかであり、Ｒ^７及びＲ^８は、炭素数１〜６のアルキル基又はフェニル基のいずれかである。Ｂは、一部に分岐を有してよいＣ_ｒＨ_２ｒで表される直鎖状又は分岐鎖状のアルキレン基であり、ｒは２〜２０の整数である。ｉはＸ^ｉで示されるシリルアルキル基の階層を示し、階層数がｎのとき１〜ｎの整数であり、階層数ｎは１〜１０の整数であり、ａｉはｉがいずれのときも０〜２の整数であり、Ｘ^ｉ＋１はｉがｎ未満のときは該シリルアルキル基であり、ｉ＝ｎのときはメチル基である。）

（式中、Ｒ^９〜Ｒ^１２は、同一又は異なっていてもよい置換又は非置換の１炭化水素基であり、Ｍは１種類以上のｎ価の金属陽イオンであり、ｎは２以上の数である。ｓは０．１＜ｓ≦１．０の数であり、ｔは０．０５＜ｔ≦１．０の数であり、ｎ×ｓ−ｔ＝１の関係を満たす。Ａは、Ｃ_ｑＨ_２ｑで表される直鎖状又は分岐鎖状のアルキレン基であり、ｑは０〜２０の整数である。ｐは０〜２０の数である。） That is, the first subject of the present invention is an organosiloxane derivative composition having a functional group represented by the following average general formula (1).
(Chemical formula 1)
_{^{- (CH 2) 2 -A-}} COO - (M n +) s (OH -) t (1)
(In the above formula, A is a linear or branched alkylene group represented by C _q H _2q , and q is an integer of 0 to 20. M is one or more n-valent metal positive ions. N is a number of 2 or more, s is a number of 0.1 <s ≦ 1.0, t is a number of 0.05 <t ≦ 1.0, and n × s−t = 1 is satisfied.)
Moreover, in the said organosiloxane derivative composition, the derivative composition represented by the following average general formula (2) or the following average general formula (4) is suitable.

(In the above formula, at least one of R ^{1 to} R ³ is a functional group represented by —O—Si (R ⁴ ) ₃ (R ⁴ is either a C 1-6 alkyl group or a phenyl group) Or a functional group represented by —O—Si (R ⁵ ) ₂ —X ¹ (R ⁵ is either an alkyl group having 1 to 6 carbon atoms or a phenyl group, and X ¹ is i = 1. The other R ^{1 to} R ³ are substituted or unsubstituted monovalent hydrocarbon groups which may be the same or different, and M is a functional group represented by the following general formula (3) 1 or more types of n-valent metal cations, n is a number of 2 or more, s is a number of 0.1 <s ≦ 1.0, and t is 0.05 <t ≦ 1.0. And satisfies the relationship of n × s−t = 1, A is a linear or branched alkylene group represented by C _q H _2q , and q is 0-20. The average total number of silicon atoms (Si) contained in one molecule of the organosiloxane derivative represented by the average general formula (2) is 2 to 100.)

(In the above formula, R ⁶ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R ⁷ and R ⁸ are either an alkyl group having 1 to 6 carbon atoms or a phenyl group. B is a linear or branched alkylene group represented by C _r H _2r which may be partially branched, and r is an integer of 2 to 20. i is X ^i. The number of layers is an integer of 1 to n when the number of layers is n, the number of layers n is an integer of 1 to 10, and ai is an integer of 0 to 2 when i is any X ^{i + 1} is the silylalkyl group when i is less than n, and the methyl group when i = n.)

(Wherein R ^{9 to} R ¹² are substituted or unsubstituted monohydrocarbon groups which may be the same or different, M is one or more n-valent metal cations, and n is 2 or more. S is a number satisfying 0.1 <s ≦ 1.0, t is a number satisfying 0.05 <t ≦ 1.0, and satisfies the relationship of n × s−t = 1. , C _q H _2q represents a linear or branched alkylene group, q is an integer of 0 to 20. p is a number of 0 to 20.)

In the organosiloxane derivative composition, M ^{n +} is preferably a divalent metal cation, a trivalent metal cation, or a mixture thereof.
In the organosiloxane derivative composition, M ^{n +} contains zinc ions (Zn ²⁺ ) and / or aluminum ions (Al ³⁺ ), and
It is preferable that t is a number of 0.1 <t ≦ 0.8.

The organosiloxane derivative composition is an organosiloxane derivative composition represented by the average general formula (2),
R ¹ and R ² are functional groups represented by —O—Si (R ⁴ ) ₃ (R ⁴ is an alkyl group having 1 to 6 carbon atoms);
It is preferable that R ³ is a monovalent hydrocarbon group having 1 to 10 carbon atoms and q is an integer of 6 to 20.
The organosiloxane derivative composition is an organosiloxane derivative composition represented by the average general formula (4),
R ^{9 to} R ¹² are groups selected from the group consisting of substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, aryl groups, and aralkyl groups, q is an integer of 6 to 20, and p is 1 A number of ~ 20 is preferred.

The third subject of the present invention is an oil gelling agent comprising the organosiloxane derivative composition or the organosiloxane derivative composition.
The oil gelling agent is preferably used for liquid oil.

  The fourth subject of the present invention is a gel composition comprising (A) the oil gelling agent and (B) a liquid oil other than the component (A).

The fifth subject of the present invention is:
(A) an organosiloxane derivative composition having a functional group represented by the following average general formula (5);
(Chemical formula 5)
_{- (CH 2) 2 -A-} COOM '(5)
(In the above formula, A is a linear or branched alkylene group represented by C _q H _2q , and q is an integer of 0 to 20. M ′ is a hydrogen atom or a monovalent metal atom. is there.)
(B) an aqueous solution containing a polyvalent metal cation M ^{n +} (M ^{n +} represents a cation of one or more n-valent metals M, and n is a number of 2 or more);
(C) an aqueous solution containing hydroxide ions;
It is a manufacturing method of the organosiloxane derivative composition characterized by mixing.

Moreover, in the said manufacturing method, the mixing amount of (b) component with respect to said (a) component is more than 0.1 equivalent and 1.0 equivalent or less in substance amount ratio, and (c) with respect to said (a) component It is preferable that the mixing amount of the components is more than 0.05 equivalent and 1.0 equivalent or less in terms of the substance amount ratio.
In the production method, it is preferable that the component (a) is mixed with the component (b) prepared in advance in an aqueous solution, and then the component (c) is mixed.
In the production method, M ′ in the component (a) is a monovalent metal atom, and the polyvalent metal cation M ^{n + in the} component (b) is zinc ion (Zn ²⁺ ) or aluminum ion. (Al ³⁺ ) is preferred.

（上記式中、Ｒ^１〜Ｒ^３は、少なくとも１つが−Ｏ−Ｓｉ（Ｒ^４）_３で表される官能基（Ｒ^４は、炭素数１〜６のアルキル基又はフェニル基のいずれかである）、又は−Ｏ−Ｓｉ（Ｒ^５）_２−Ｘ^１で表される官能基（Ｒ^５は、炭素数１〜６のアルキル基又はフェニル基のいずれかであり、Ｘ^１はｉ＝１のときの下記一般式（７）で示される官能基である）であり、その他のＲ^１〜Ｒ^３は同一又は異なっていてもよい置換又は非置換の１価炭化水素基である。Ｍは水素原子又は１価の金属原子である。Ａは、Ｃ_ｑＨ_２ｑで表される直鎖状又は分岐鎖状のアルキレン基であり、ｑは０〜２０の整数である。また、平均一般式（６）で表されるオルガノシロキサン誘導体の１分子中に含まれるケイ素原子（Ｓｉ）の平均合計数は２〜１００である。）

（上記式中、Ｒ^６は、水素原子、炭素数１〜６のアルキル基又はフェニル基のいずれかであり、Ｒ^７及びＲ^８は、炭素数１〜６のアルキル基又はフェニル基のいずれかである。Ｂは、一部に分岐を有してよいＣ_ｒＨ_２ｒで表される直鎖状又は分岐鎖状のアルキレン基であり、ｒは２〜２０の整数である。ｉはＸ^ｉで示されるシリルアルキル基の階層を示し、階層数がｎのとき１〜ｎの整数であり、階層数ｎは１〜１０の整数であり、ａｉはｉがいずれのときも０〜２の整数であり、Ｘ^ｉ＋１はｉがｎ未満のときは該シリルアルキル基であり、ｉ＝ｎのときはメチル基である。）

（式中、Ｒ^９〜Ｒ^１２は、同一又は異なっていてもよい置換又は非置換の１炭化水素基であり、Ｍは水素原子又は１価の金属原子である。Ａは、Ｃ_ｑＨ_２ｑで表される直鎖状又は分岐鎖状のアルキレン基であり、ｑは０〜２０の整数である。ｐは０〜２０の数である。） Moreover, in the said manufacturing method, it is suitable that the said (a) component is a composition represented by the following average general formula (6) or the following average general formula (8).

(In the above formula, at least one of R ^{1 to} R ³ is a functional group represented by —O—Si (R ⁴ ) ₃ (R ⁴ is either a C 1-6 alkyl group or a phenyl group) Or a functional group represented by —O—Si (R ⁵ ) ₂ —X ¹ (R ⁵ is either an alkyl group having 1 to 6 carbon atoms or a phenyl group, and X ¹ is i = 1. The other R ^{1 to} R ³ are substituted or unsubstituted monovalent hydrocarbon groups which may be the same or different, and M is a functional group represented by the following general formula (7) A is a hydrogen atom or a monovalent metal atom, A is a linear or branched alkylene group represented by C _q H _2q , and q is an integer of 0 to 20. The average total number of silicon atoms (Si) contained in one molecule of the organosiloxane derivative represented by (6) is 2 to 2. 00 a is.)

(In the above formula, R ⁶ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R ⁷ and R ⁸ are either an alkyl group having 1 to 6 carbon atoms or a phenyl group. B is a linear or branched alkylene group represented by C _r H _2r which may be partially branched, and r is an integer of 2 to 20. i is X ^i. The number of layers is an integer of 1 to n when the number of layers is n, the number of layers n is an integer of 1 to 10, and ai is an integer of 0 to 2 when i is any X ^{i + 1} is the silylalkyl group when i is less than n, and the methyl group when i = n.)

(In the formula, R ^{9 to} R ¹² are substituted or unsubstituted monohydrocarbon groups which may be the same or different, and M is a hydrogen atom or a monovalent metal atom. A is C _q H _2q. And q is an integer of 0 to 20. p is a number of 0 to 20.)

  According to the present invention, liquid oil can be gelled in a small amount without using water. In addition, the gel composition according to the present invention has thixotropic rheological properties, is excellent in thermal stability and stability over time, and is useful in various fields that require gelled oil.

Hereinafter, preferred embodiments of the present invention will be described.
First, the organosiloxane derivative composition according to the present invention will be described.
The organosiloxane derivative composition used in the present invention has a functional group represented by the following average general formula (1).
(Chemical 9)
_{^{- (CH 2) 2 -A-}} COO - (M n +) s (OH -) t (1)

The functional group represented by the average general formula (1) is directly bonded to the silicon atom of the organosiloxane. That is, the organosiloxane derivative composition of the present invention is an organosiloxane modified with the above functional group.
The “average general formula” means that the organosiloxane derivative contained in the organosiloxane derivative composition forms, on average, a structure represented by the general formula.
In the above average formula (1), A is a linear or branched alkylene group represented by _{C q} H2 q, q is an integer of 0 to 20. That is, when q = 0, the carboxyl-modified group is bonded to silicon of the organosiloxane through the ethylene group. In addition, in this invention, when the value of q exceeds the said upper limit, it may be inferior to a feeling in use.

In the above average general formula (1), M ^{n +} is a cation of one or more n-valent metals M, and n is a number of 2 or more. In the present invention, M ^{n +} is preferably a divalent metal cation, a trivalent metal cation, or a mixture thereof. Examples of the divalent metal cation include calcium ion (Ca ²⁺ ), magnesium ion (Mg ²⁺ ), manganese ion (Mn ²⁺ ), barium ion (Ba ²⁺ ), iron ion (Fe ²⁺ ), and nickel (II). An ion (Ni ^<2+> ), a zinc ion (Zn ^<2+> ), a copper (II) ion (Cu ^<2+> ) etc. are mentioned. Examples of the trivalent metal cation include aluminum ions (Al ³⁺ ), iron (III) ions (Fe ³⁺ ), and chromium (III) ions (Cr ³⁺ ). In the present invention, it is particularly preferable that zinc ions (Zn ²⁺ ) and aluminum ions (Al ³⁺ ) are included.

In the above average general formula (1), s represents the average number of metal cations added per molecule of the organosiloxane derivative, and is a number of 0.1 <s ≦ 1.0, preferably 0.2 < The number is s <0.85. t represents the average number of hydroxide ions added per molecule of the organosiloxane derivative, and is a number of 0.05 <t ≦ 1.0, preferably 0.1 <t ≦ 0.8. Particularly preferably, the number is 0.3 <t ≦ 0.8.
Moreover, s and t satisfy the relationship of n × s−t = 1. That is, in the above average general formula (1), the metal cation is added in an amount to neutralize the carboxylate ion and the hydroxide ion, and the hydroxide ion neutralizes the metal cation together with the carboxylate ion. The amount to be added is added.

上記一般式（Ｉ）において、ｎは０以上、好ましくは０〜１０の整数であり、最も好適には１〜３である。Ｒ^１〜Ｒ^８は水素原子、炭化水素基、水酸基、アルコキシ基等であり、それぞれ異なっていてもよい。
したがって、本発明のオルガノシロキサン誘導体の一実施形態は、上記一般式（Ｉ）で表される鎖状オルガノシロキサンのケイ素原子との結合基、すなわち、Ｒ^１〜Ｒ^８のいずれか１つ以上が上記平均一般式（１）で示される官能基に置き換わった化合物を包含する。 The structure of the organosiloxane to which the functional group is bonded is not limited as long as it has a structure in which an organic group is added to a siloxane bond (Si-O-Si), but various chain organosiloxanes are particularly preferably applied. obtain.
Examples of the chain organosiloxane include those represented by the following formula (I).

In the said general formula (I), n is 0 or more, Preferably it is an integer of 0-10, Most preferably, it is 1-3. R ^{1 to} R ⁸ are a hydrogen atom, a hydrocarbon group, a hydroxyl group, an alkoxy group, and the like, and may be different from each other.
Therefore, in one embodiment of the organosiloxane derivative of the present invention, at least one of R ^{1 to} R ⁸ is a bonding group with a silicon atom of the chain organosiloxane represented by the general formula (I). The compound which substituted the functional group shown by the said average general formula (1) is included.

上記平均一般式（２）で表されるオルガノシロキサン誘導体組成物は、上記平均一般式（１）で表される官能基で変性されたオルガノシロキサン誘導体組成物であり、誘導体１分子中のケイ素原子（Ｓｉ)の平均合計数が２〜１００の範囲にあることを特徴とするものである。
上記平均一般式（２）において、Ｒ^１〜Ｒ^３は、少なくとも１つが−Ｏ−Ｓｉ（Ｒ^４）_３で表される官能基（Ｒ^４は、炭素数１〜６のアルキル基又はフェニル基のいずれかである）、又は−Ｏ−Ｓｉ（Ｒ^５）_２−Ｘ^１で表される官能基（Ｒ^５は、炭素数１〜６のアルキル基又はフェニル基のいずれかであり、Ｘ^１はｉ＝１のときの下記一般式（３）で示される官能基である）である。なお、Ｒ^１〜Ｒ^３において、その全てが前記官能基のいずれかであってもよい。あるいは、Ｒ^１〜Ｒ^３の少なくとも１つが前記官能基であれば、その他のＲ^１〜Ｒ^３は、同一または異なっていてもよい置換又は非置換の一価炭化水素基のいずれかであってもよい。 In the present invention, the organosiloxane derivative composition having a functional group represented by the above average general formula (1) is preferably a derivative composition represented by the following average general formula (2) or the following average general formula (4). is there.

The organosiloxane derivative composition represented by the above average general formula (2) is an organosiloxane derivative composition modified with the functional group represented by the above average general formula (1), and silicon atoms in one molecule of the derivative The average total number of (Si) is in the range of 2 to 100.
In the average general formula (2), at least one of R ^{1 to} R ³ is a functional group represented by —O—Si (R ⁴ ) ₃ (R ⁴ is an alkyl group having 1 to 6 carbon atoms or a phenyl group. Or a functional group represented by —O—Si (R ⁵ ) ₂ —X ¹ (R ⁵ is either an alkyl group having 1 to 6 carbon atoms or a phenyl group, and X ¹ Is a functional group represented by the following general formula (3) when i = 1). Note that all of R ^{1 to} R ³ may be any of the functional groups. Alternatively, if at least one of the functional groups of R ¹ to R ^3, other R ¹ to R ³ may be either the same or may be different substituted or unsubstituted monovalent hydrocarbon group Also good.

In the functional group represented by —O—Si (R ⁴ ) ₃ , R ⁴ is either an alkyl group having 1 to 6 carbon atoms or a phenyl group. Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, pentyl, neopentyl, cyclopentyl, hexyl and the like. Examples include linear, branched or cyclic alkyl groups. Examples of the functional group represented by —O—Si (R ⁴ ) ₃ include —O—Si (CH ₃ ) ₃ , —O—Si (CH ₃ ) ₂ (C ₂ H ₅ ), and —O—Si. (CH ₃ ) ₂ (C ₃ H ₇ ), —O—Si (CH ₃ ) ₂ (C ₄ H ₉ ), —O—Si (CH ₃ ) ₂ (C ₅ H ₁₁ ), —O—Si (CH ₃ ) ₂ (C ₆ H ₁₃ ), —O—Si (CH ₃ ) ₂ (C ₆ H ₅ ), and the like. The functional group is preferably a trialkylsiloxy group, and most preferably a trimethylsiloxy group.

The functional group represented by —O—Si (R ⁵ ) ₂ —X ¹ is an organosiloxy group having a dendrimer structure, and R ⁵ is either an alkyl group having 1 to 6 carbon atoms or a phenyl group. It is. X ¹ is a functional group represented by the following general formula (3) when i = 1.

In the general formula (3), R ⁶ is any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R ⁷ and R ⁸ are an alkyl group or phenyl group having 1 to 6 carbon atoms. One of them. R ^{6 to} R ⁸ are preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably all methyl groups. B is a linear or branched alkylene group represented by C _r H _2r which may be partially branched, and r is an integer of 2 to 20. Examples of the alkylene group having 2 to 20 carbon atoms as B include linear alkylene groups such as ethylene group, propylene group, butylene group and hexylene group; methylmethylene group, ethylethylene group, 1-methylpentylene group, 1, A branched alkylene group such as a 4-dimethylbutylene group is exemplified. Among these, an ethylene group or a hexylene group is preferable.

In the general formula (3), i specifies the generation of a silylalkyl group represented by X ^i, the number of layers, i.e., the number of repetitions of the silylalkyl group is an integer ranging from 1~n time n. The hierarchy number n is an integer of 1 to 10. X ^{i + 1} is the silylalkyl group when i is less than n, and is a methyl group (—CH ₃ ) when i = n. ai is an integer of 0 to 2 when i = 1, and is a number of less than 3 when i is 2 or more. ai is preferably 1 or less, particularly preferably 0.
That is, when the layer n of the dendrimer structure is 1, the silylalkyl group of the formula (3) is

で示され、デンドリマー構造の階層ｎが２である場合、式（３）のシリルアルキル基は、

When the hierarchy n of the dendrimer structure is 2, the silylalkyl group of the formula (3) is

で示され、デンドリマー構造の階層ｎが３である場合、式（３）のシリルアルキル基は、

And when the hierarchy n of the dendrimer structure is 3, the silylalkyl group of the formula (3) is

で示されるものである。

It is shown by.

The functional group represented by —O—Si (R ⁵ ) ₂ —X ¹ is particularly preferably a functional group in which the number n of tiers of the silylalkyl group represented by the following general formula (III) is 1, or the following general group A functional group in which the number n of layers of the silylalkyl group represented by the formula (IV) is 2 is exemplified.

Moreover, in said average general formula (2), in R < ¹ > -R < ³ >, at least 1 is the functional group represented by the said -O-Si (R < ⁴ >) ₃ , or -O-Si (R < ⁵ >). _As long as it is any of the functional groups represented by _2- X ¹ , the other R ^{1 to} R ³ may be either substituted or unsubstituted monovalent hydrocarbon groups which may be the same or different. Good. Examples of the unsubstituted monovalent hydrocarbon group represented by R ^{1 to} R ³ include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, pentyl, neopentyl, cyclopentyl, Examples include linear, branched or cyclic alkyl groups such as hexyl; aryl groups such as phenyl, tolyl and xylyl groups; and aralkyl groups. Examples of the substituted monovalent hydrocarbon group represented by R ^{1 to} R ³ include perfluoroalkyl groups such as 3,3,3-trifluoropropyl group, 3,3,4,4,4-pentafluorobutyl group; 3 -An aminoalkyl group such as aminopropyl group and 3- (aminoethyl) aminopropyl group; and an amidoalkyl group such as acetylaminoalkyl group are exemplified. Further, a part of the hydrocarbon groups of R ^{1 to} R ³ may be substituted with a hydroxyl group, an alkoxy group, a polyether group or a perfluoropolyether group. As the alkoxy group, a methoxy group, an ethoxy group, a propoxy group Is exemplified.

In said average general formula (2), one or two of R < ¹ > -R < ³ > is the functional group represented by said -O-Si (R < ⁴ >) ₃ , or -O-Si (R < ⁵ >) _2- X. ^In the case of any one of the functional groups represented by ¹ , the other R ^{1 to} R ³ are preferably a linear or branched alkyl group having 1 to 6 carbon atoms, and a methyl group or an ethyl group is Particularly preferred. In particular, in R ^{1 to} R ³ in the average general formula (2), all or two of them are functional groups represented by the aforementioned —O—Si (R ⁴ ) ₃ , or —O—Si (R ⁵ ) ₂ —X. ¹ is preferable, and the other R ^{1 to} R ³ are preferably a methyl group or an ethyl group.

M ^{n +} is a cation of one or more n-valent metals M, and n is a number of 2 or more. In the present invention, M ^{n +} is preferably a divalent metal cation, a trivalent metal cation, or a mixture thereof. Examples of the divalent metal cation include calcium ion (Ca ²⁺ ), magnesium ion (Mg ²⁺ ), manganese ion (Mn ²⁺ ), barium ion (Ba ²⁺ ), iron ion (Fe ²⁺ ), and nickel (II). An ion (Ni ^<2+> ), a zinc ion (Zn ^<2+> ), a copper (II) ion (Cu ^<2+> ) etc. are mentioned. Examples of the trivalent metal cation include aluminum ions (Al ³⁺ ), iron (III) ions (Fe ³⁺ ), and chromium (III) ions (Cr ³⁺ ). In the present invention, it is particularly preferable that zinc ions (Zn ²⁺ ) and aluminum ions (Al ³⁺ ) are included.

In the above average general formula (2), s represents the average number of metal cations added per molecule of the organosiloxane derivative, and is a number of 0.1 <s ≦ 1.0, preferably 0.25 < The number is s <0.85. t represents the average number of metal cations added per molecule of the organosiloxane derivative, and is a number of 0.05 <t ≦ 1.0, preferably 0.1 <t ≦ 0.8.
Moreover, s and t satisfy the relationship of n × s−t = 1. That is, in the above average general formula (2), the metal cation is added in an amount to neutralize the carboxylate ion and the hydroxide ion, and the hydroxide ion neutralizes the metal cation together with the carboxylate ion. The amount to be added is added.

A is a linear or branched alkylene group represented by C _q H _2q , and q is an integer of 0-20. When q = 0, the organosiloxane derivative composition represented by the average general formula (2) is a derivative composition represented by the following average general formula (2 ′), and the carboxyl-modified group is an ethylene group. It is bonded to silicon via In this invention, when the value of q exceeds the said upper limit, it may be inferior to a feeling in use.
R ¹ R ² R ³ Si— (CH ₂ ) ₂ —COO ⁻ (M ^{n +} ) _s (OH ⁻ ) _t (2 ′)

  Moreover, the organosiloxane derivative composition represented by the above average formula (2) is characterized in that the average total number of silicon atoms in one molecule of the derivative is in the range of 2 to 100. The average total number of silicon atoms is preferably in the range of 2 to 10, particularly preferably in the range of 3 to 5. On the other hand, if the total number of silicon atoms in one molecule of the derivative exceeds the upper limit, it may not function sufficiently as an oil gelling agent.

More specifically, as the organosiloxane derivative composition represented by the above average general formula (2), R ¹ and R ² are functional groups (R ⁴ is represented by —O—Si (R ⁴ ) _3. An organosiloxane derivative composition in which R ³ is a linear or branched alkyl group having 1 to 6 carbon atoms, and the value of q is 6 to 12. Are preferably used.

The organosiloxane derivative composition represented by the average general formula (4) is an organosiloxane derivative composition in which both ends of the molecular chain are modified with alkyl carboxyl groups.
In the general formula (3), in the formula, R ^{9 to} R ¹² are selected from any of substituted or unsubstituted monovalent hydrocarbon groups which may be the same or different. The unsubstituted monovalent hydrocarbon group represented by R ^{9 to} R ¹² is a straight chain such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, or a dodecyl group. Chain or branched alkyl group; linear or branched alkenyl group such as allyl group and hexenyl group; cycloalkyl group such as cyclopentyl group and cyclohexyl group; aryl group such as phenyl group, tolyl group and naphthyl group An aralkyl group such as a benzyl group, a phenylethyl group, a phenylpropyl group, a naphthylmethyl group, or a naphthylethyl group; The substituted monovalent hydrocarbon groups represented by R ^{9 to} R ¹² are such that hydrogen atoms bonded to carbon atoms of these groups are partially hydroxyl groups, halogen atoms, epoxy groups, amino groups, methacryl groups, mercapto groups, alkoxy groups. A group substituted with an organic group such as a polyether group or a perfluoropolyether group, and a per group such as a 3,3,3-trifluoropropyl group or a 3,3,4,4,4-pentafluorobutyl group. Examples include fluoroalkyl groups; aminoalkyl groups such as 3-aminopropyl group and 3- (aminoethyl) aminopropyl group; and amidealkyl groups such as acetylaminoalkyl group. R ^{9 to} R ¹² are preferably an alkyl group having 1 to 20 carbon atoms, an aryl group and an aralkyl group, and 90 mol% or more of R ^{9 to} R ^{12 in} one molecule is a methyl group and / or a phenyl group. It is particularly preferred.

M ^{n +} is a cation of one or more n-valent metals M, and n is a number of 2 or more. In the present invention, M ^{n +} is preferably a divalent metal cation, a trivalent metal cation, or a mixture thereof. Examples of the divalent metal cation include calcium ion (Ca ²⁺ ), magnesium ion (Mg ²⁺ ), manganese ion (Mn ²⁺ ), barium ion (Ba ²⁺ ), iron ion (Fe ²⁺ ), and nickel (II). An ion (Ni ^<2+> ), a zinc ion (Zn ^<2+> ), a copper (II) ion (Cu ^<2+> ) etc. are mentioned. Examples of the trivalent metal cation include aluminum ions (Al ³⁺ ), iron (III) ions (Fe ³⁺ ), and chromium (III) ions (Cr ³⁺ ). In the present invention, it is particularly preferable that zinc ions (Zn ²⁺ ) and aluminum ions (Al ³⁺ ) are included.

In the average general formula (4), s represents the average number of metal cations added per molecule of the organosiloxane derivative, and is a number of 0.1 <s ≦ 1.0, preferably 0.25 < The number is s <0.80. t represents the average number of hydroxide ions added per molecule of the organosiloxane derivative, and is a number of 0.05 <t ≦ 1.0, preferably 0.1 <t ≦ 0.8. .
Moreover, s and t satisfy the relationship of n × s−t = 1. That is, in the above average formula (4), the metal cation is added in an amount that neutralizes the carboxylate ion and the hydroxide ion, and the hydroxide ion neutralizes the metal cation together with the carboxylate ion. The amount to be added is added.

A is a linear or branched alkylene group represented by C _q H _2q , and q is an integer of 0-20. In addition, when q = 0, the organosiloxane derivative composition represented by the average general formula (4) is a derivative composition represented by the following average general formula (4 ′), and the carboxyl-modified group is an ethylene group. It bonds with silicon.
(Chemical formula 19)
^{_{MOOC- (CH 2) 2 - (}} SiR 9 R 10 -O) p -SiR 11 R 12 - (CH 2) 2 -COO - (M n +) s (OH -) t (4 ')

  In the said average general formula (4), p shows the average degree of polymerization of disubstituted polysiloxane, and is a number of 0-20. In this invention, it is more preferable that p is 1-20, and it is especially preferable that it is 1-10. On the other hand, if p exceeds the upper limit, it may not function sufficiently as an oil gelling agent.

In the organosiloxane derivative composition represented by the average general formula (4), R ^{9 to} R ¹² are groups selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an aryl group, and an aralkyl group. , Q is an integer of 6 to 20, and an organosiloxane derivative composition in which p is a number of 1 to 20 is preferably used.

The organosiloxane derivative composition having a functional group represented by the average general formula (1) is:
(A) an organosiloxane derivative composition having a functional group represented by the following average general formula (5);
(Chemical formula 20)
_{- (CH 2) 2 -A-} COOM '(5)
(In the above formula, A is a linear or branched alkylene group represented by C _q H _2q , and q is an integer of 0 to 20. M ′ is a hydrogen atom or a monovalent metal atom. is there.)
(B) an aqueous solution containing a polyvalent metal cation M ^{n +} (M ^{n +} represents a cation of one or more n-valent metals M, and n is a number of 2 or more);
(C) an aqueous solution containing hydroxide ions;
It can manufacture by mixing.

Hereinafter, the components (a) to (c) will be described.
Component (a) The component (a) is an organosiloxane derivative composition having a functional group represented by the average general formula (5). The functional group represented by the average general formula (5) is directly bonded to the silicon atom of the organosiloxane, and the structure of the organosiloxane is an organo group having the functional group represented by the average general formula (1) to be produced. This is reflected in the organosiloxane part of the siloxane derivative composition. Therefore, the organosiloxane to which the functional group represented by the average general formula (5) is bonded is similar to the functional group represented by the average general formula (1) in the siloxane bond (Si—O—Si). If it has the structure which added, it will not specifically limit, For example, the various chain | strand organosiloxane represented by the said general formula (I) may be applied.

In the functional group represented by the average general formula (5), A is reflected in the A portion of the functional group represented by the average general formula (1). Accordingly, A in the average general formula (5) is a linear or branched alkylene group represented by C _q H _2q as in the case of the functional group represented by the average general formula (1), and q Is an integer of 0-20.
In the average general formula (5), M ′ is a hydrogen atom or a monovalent metal atom. Examples of monovalent metal atoms include Li, Na, and K.

The organosiloxane derivative composition represented by the above average general formula (5) is, for example, an organosiloxane represented by the above general formula (I) in a silicon atom into which the functional group of the average general formula (1) is introduced. A trimethylsilyl group 1 which is a protective group is obtained by subjecting a compound having a bonded hydrogen atom to a trimethylsilyl derivative having a vinyl terminus represented by CH═CH ₂ -A-COOSiMe ₃ in the presence of a platinum catalyst. By adding at least 1 mol or more of monohydric alcohol such as methanol, water or a mixture thereof and heating per mole, it can be produced by a deprotection step by alcoholysis. In addition, A is a group similar to the above, and when M ′ is a monovalent metal atom, it further includes a neutralization step with a compound containing a corresponding metal (M ′) ion. As an example, this is a step of neutralizing the carboxyl group (—COOH) by adding an aqueous solution of sodium hydroxide (NaOH), potassium hydroxide (KOH) or the like.

  In particular, in the present invention, an organosiloxane derivative composition represented by the following average general formula (6) or (8) is preferably used as the component (a). By using the organosiloxane derivative composition represented by the following average general formula (6) as the component (a), the organosiloxane derivative composition represented by the above average general formula (2) can be obtained. By using the organosiloxane derivative composition represented by the general formula (8) as the component (a), the organosiloxane derivative composition represented by the average general formula (4) can be obtained.

In the average general formula (6), at least one of R ^{1 to} R ³ is a functional group represented by —O—Si (R ⁴ ) ₃ (R ⁴ is an alkyl group having 1 to 6 carbon atoms or a phenyl group. Or a functional group represented by —O—Si (R ⁵ ) ₂ —X ¹ (R ⁵ is either an alkyl group having 1 to 6 carbon atoms or a phenyl group, and X ¹ Is a functional group represented by the following general formula (7) when i = 1), and other R ^{1 to} R ³ are substituted or unsubstituted monovalent hydrocarbon groups which may be the same or different. is there. M ′ is a hydrogen atom or a monovalent metal atom. A is a linear or branched alkylene group represented by C _q H _2q , and q is an integer of 0-20. Moreover, the average total number of silicon atoms (Si) contained in one molecule of the derivative of the organosiloxane derivative composition represented by the general formula (6) is 2 to 100.

In the general formula (7), ^{R 6} is a hydrogen atom, an alkyl group or a phenyl group having 1 to 6 carbon atoms, ^{R 7} and ^{R 8} is an alkyl group or a phenyl group having 1 to 6 carbon atoms One of them. B is a linear or branched alkylene group represented by C _r H _2r which may be partially branched, and r is an integer of 2 to 20. i specifies the generation of a silylalkyl group represented by X ^i, an integer of 1~n when the number of layers is n, the number of layers n is an integer of from 1 to 10, even when ai is i is either 0 X ^{i + 1} is an silylalkyl group when i is less than n, and a methyl group when i = n.

In said average general formula (8), R < ⁹ > -R < ¹² > is the same or different substituted or unsubstituted 1 hydrocarbon group, and M 'is a hydrogen atom or a monovalent metal atom. A is a linear or branched alkylene group represented by C _q H _2q , and q is an integer of 0-20. p is a number from 0 to 20. )

In addition, the organosiloxane derivative composition represented by the average general formula (6) can be easily obtained by the following steps (1) to (3).
Step (1):
(Chemical formula 24)
HSi (—O—SiR ₂ H) _f R ^L _3-f
(In the formula, R is either an alkyl group having 1 to 6 carbon atoms or a phenyl group, R ^L is a substituted or unsubstituted monovalent hydrocarbon group which may be the same or different, and f is 1 carboxylic acid trimethylsilyl derivative having the organosilane having a dimethylsiloxy group represented by to 3 of an _integer), the vinyl end represented by _{CH = CH 2 -A-COOSiMe 3} ( wherein, a is the same group) And an addition reaction in the presence of a platinum-based transition metal catalyst to obtain an intermediate (1-1) of the following general formula.
(Chemical formula 25)
^{_{Si (-O-SiR 2 H)}} f R L 3-f - (CH 2) 2 -A-COOSiMe 3 (1-1)

Step (2):
(Chemical Formula 26)
R ^B Si (O—R ⁶ ) _ai (OSiR ⁷ R ⁸ —X ^{i + 1} ) _3-ai
(In the formula, R ^B is a linear or branched alkenyl group represented by C _r H _2r , and r is an integer of 2 to 20. R ⁶ , R ⁷ , R ⁸ , X ^{i + 1} , ai is the same group and number as described above) and an addition reaction in the presence of a platinum-based catalyst with an organosilane having an alkenyl group represented by the following general formula (1-2):
(Chemical 27)
_{^{Si {-OSiR 2 -B-Si (}} O-R 6) ai (OSiR 7 R 8 -X i + 1) 3-ai} f R L 3-f - (CH 2) 2 -A-COOSiMe 3 (1-2 )

Step (3):
The intermediate (1-2) is deprotected by alcoholysis by adding at least 1 mol of monohydric alcohol such as methanol, water or a mixture thereof to 1 mol of the trimethylsilyl group as a protecting group and heating. Process.
In addition, in the functional group represented by the average general formula (5), when M ′ is a monovalent metal atom, a neutralization step with a compound containing a corresponding metal (M ′) ion is further included. As an example, this is a step of neutralizing the carboxyl group (—COOH) by adding an aqueous solution of sodium hydroxide (NaOH), potassium hydroxide (KOH) or the like.

Moreover, the organosiloxane derivative composition represented by the average general formula (8) is:
(Chemical formula 28)
_{^{H- (SiR 9 R 10 -O)}} p -SiR 11 R 12 -H
(Wherein R ^{9 to} R ¹² are the same groups as described above, and p is a number from 0 to 20).
In respect organohydrogenpolysiloxane 1 mol having a molecular chain terminal silicon-bonded hydrogen atoms indicated, and a carboxylic acid trimethylsilyl derivative having a vinyl end represented by at least two moles of CH = CH 2 _{-A-COOSiMe 3} In addition, by performing an addition reaction in the presence of a platinum-based catalyst and adding at least 1 mol of monohydric alcohol such as methanol, water or a mixture thereof to 1 mol of a trimethylsilyl group as a protecting group, the alcoholysis is decomposed. Can be produced by the deprotection step. In addition, A is a group similar to the above, and when M is a metal atom or an organic cation, it further includes a neutralization step with a compound containing a corresponding metal ion (M ^{n +} ) or a basic organic compound.
Specifically, this is a step of neutralizing the carboxyl group (—COOH) by adding an aqueous solution of sodium hydroxide (NaOH), potassium hydroxide (KOH) or the like.

  The platinum-based catalyst used in the above production is a hydrosilylation reaction catalyst of silicon-bonded hydrogen atoms and alkenyl groups. Chloroplatinic acid, alcohol-modified chloroplatinic acid, platinum olefin complex, platinum ketone complex, platinum vinylsiloxane Complex, platinum tetrachloride, platinum fine powder, alumina or silica carrier with solid platinum, platinum black, platinum olefin complex, platinum alkenylsiloxane complex, platinum carbonyl complex, platinum catalyst Examples thereof include thermoplastic organic resin powders such as methyl methacrylate resin, polycarbonate resin, polystyrene resin, and silicone resin. Preferable is 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex of platinum or chloroplatinic acid.

(B) Component The component (b) in the present invention is an aqueous solution containing a polyvalent metal cation M ^{n +} . M ^{n +} is reflected in M ^{n +} in the organosiloxane derivative composition having a functional group represented by the average general formula (1) produced by this method. Therefore, M ^{n + in the} component (b) also represents one or more cations of the n-valent metal M as in the case of the average general formula (1), and n is a number of 2 or more. In the present invention, M ^{n +} is preferably a divalent metal cation, a trivalent metal cation, or a mixture thereof. Examples of the divalent metal cation include calcium ion (Ca ²⁺ ), magnesium ion (Mg ²⁺ ), manganese ion (Mn ²⁺ ), barium ion (Ba ²⁺ ), iron ion (Fe ²⁺ ), and nickel (II). An ion (Ni ^<2+> ), a zinc ion (Zn ^<2+> ), a copper (II) ion (Cu ^<2+> ) etc. are mentioned. Examples of the trivalent metal cation include aluminum ions (Al ³⁺ ), iron (III) ions (Fe ³⁺ ), and chromium (III) ions (Cr ³⁺ ). In the present invention, it is particularly preferable that zinc ions (Zn ²⁺ ) and aluminum ions (Al ³⁺ ) are included.
Examples of the aqueous solution containing M ^{n +} include calcium chloride, magnesium chloride, manganese chloride, barium chloride, iron chloride, (II), iron chloride (III), nickel chloride, zinc chloride, copper chloride (II), An aqueous solution of chloride such as aluminum chloride; an aqueous solution of sulfate such as calcium sulfate, barium sulfate, aluminum sulfate, iron (II) sulfate, iron (III) sulfate, nickel sulfate, zinc sulfate, copper (II) sulfate, aluminum sulfate ; Aqueous solutions of nitrates such as calcium nitrate, barium nitrate, aluminum nitrate, iron (III) nitrate, zinc nitrate, copper nitrate (II), aluminum nitrate; calcium phosphate, zinc phosphate, aluminum phosphate, iron (II) phosphate, etc. Phosphate aqueous solution; calcium hydroxide, barium hydroxide, zinc hydroxide, aluminum hydroxide, hydroxide Examples thereof include aqueous solutions of hydroxides such as iron (II), iron (III) hydroxide, and copper (II) hydroxide, and these can be used alone or in combination. In the present invention, in particular, an aqueous solution containing zinc ions and aluminum ions (for example, zinc chloride, aluminum chloride, zinc sulfate, aluminum sulfate, zinc nitrate, aluminum nitrate, zinc phosphate, aluminum phosphate, zinc hydroxide, hydroxide) Aluminum, etc.), in particular zinc chloride, aluminum chloride and zinc sulfate are preferred.

Component (c) The component (c) is an aqueous solution containing hydroxide ions, specifically, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide, zinc hydroxide, water Examples include aluminum oxide, iron (II) hydroxide, iron (III) hydroxide, copper (II) hydroxide, and sodium hydroxide is particularly preferable.

When the component (a) is added to the component (b) (aqueous solution), the specific functional group portion which is an active part has an anionic property, which reacts with the polyvalent metal cation ionized from the component (b). Form a metal soap. By neutralizing the metal soap with the component (c), an organosiloxane derivative composition having a functional group represented by the general formula (1) is generated.
Accordingly, the present invention can be obtained by mixing the component (a) with the component (b) and the component (c) prepared in advance in an aqueous solution. In this case, the order of mixing is not particularly limited, and after mixing and reacting the component (a) with the component (b), it may be mixed with the component (c) or the three components may be mixed and reacted at the same time. In consideration of reaction efficiency, it is more preferable to mix the component (a) with the component (b) prepared in advance in an aqueous solution, and then mix the component (c).
The mixing amount of the component (b) is greater than 0.1 equivalent and less than 1.0 equivalent in terms of the substance equivalent ratio with respect to the functional group represented by the average general formula (5) in the component (a). The mixing amount of the component is preferably greater than 0.05 equivalent and less than or equal to 1.0 equivalent in terms of the substance amount ratio with respect to the functional group. When the mixing amount is smaller than the above range, the organopolysiloxane derivative composition may not be sufficiently formed, and even if it is excessively mixed, the organopolysiloxane derivative composition exceeding a certain amount is not generated.

The above-described organosiloxane derivative composition according to the present invention can be used for oil gelation as an oil gelling agent.
In addition, the gel-like composition obtained by gelatinizing an oil agent with the organosiloxane derivative composition of the present invention is a composition having a gel structure inside the system. The presence or absence of the gel structure may be determined by a conventionally known method, for example, an X-ray diffraction method. The gel composition has thixotropic rheological properties. In the present invention, it is considered that a gel is formed by the interaction between the metal ion and the carboxylic acid moiety and the intermolecular interaction with the hydroxide ion (—OH) in water. As a result, the appearance is thickened, the fluidity of the oil is lost, and a gel-like product is formed that is uniform and flexible throughout.

The gel composition of the present invention is particularly
(A) an oil gelling agent comprising the organosiloxane derivative composition;
(B) A liquid oil other than the component (A) is included.
In the gel composition of the present invention, the component (A) is an oil gelling agent composed of the above-described organosiloxane derivative composition according to the present invention, and acts as a gelling agent for the component (B).
The said (A) component can be mix | blended in 1-99 weight% with respect to a gel-like composition, Preferably it is 2-40 weight%.

  In the gel composition of the present invention, the component (B) is not particularly limited as long as it is a hydrophobic substance that exhibits a liquid state (ie, has fluidity) as the whole component (B) at room temperature (25 ° C.). One type or a combination of two or more types can be blended. Therefore, the component (B) may be a liquid hydrophobic substance such as liquid oil or a combination thereof, or a liquid hydrophobic substance (solid oil etc.) that is solid at room temperature (25 ° C.). When used in combination with a functional substance or the like to form a liquid, it can be used as the component (B) in the gel composition of the present invention. In such a case, if necessary, the components may be dispersed and mixed using mechanical force, or the components may be heated and melted before use.

Examples of the hydrophobic substance as described above include silicone oil and various organic compounds.
The silicone oil may be cyclic, linear or branched, and the viscosity at 25 ° C. is usually in the range of 0.65 to 100,000 mm ² / s, preferably 0.65 to 10,000 mm ^2. / S range. Specifically, cyclic diorganopolysiloxanes such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane; hexamethyldisiloxane, trimethylsiloxy group-blocked dimethylpolysiloxane at both ends, trimethylsiloxy group-blocked methylphenylpolysiloxane at both ends, Linear diorganopolysiloxanes such as trimethylsiloxy-blocked methylalkylpolysiloxanes at both ends; branched organopolysiloxanes such as methyltristrimethylsiloxysilane, ethyltristrimethylsiloxysilane, propyltristrimethylsiloxysilane, tetrakistrimethylsiloxysilane, etc. Among these, volatile linear dimethylpolysiloxane, branched methylpolysiloxane and cyclic dimethylpolysiloxane are preferable.

  Examples of organic compounds include hydrocarbons such as hexane, heptane, toluene, xylene, mesitylene, liquid paraffin, petrolatum, n-paraffin, isoparaffin, isododecane, polybutene, ozokerite, ceresin, squalane, pristane, α-olefin oligomers; Avocado oil, almond oil, macadamia nut 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 kernel oil, molasses, coconut oil; animal oils such as mink oil, egg yolk oil, beef tallow, pork fat, hardened oil; beeswax, carnauba wax, whale wax, lanolin, liquid lanolin, reduced lanolin, hard Lanolin, candelilla wax, jojoba oil, my Waxes such as locrystallin wax; myristyl alcohol, isostearyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol, lanolin alcohol, cholesterol, phytosterol, 2-hexyldecanol, isostearyl alcohol, 2-octyldodecanol, decyltetradecanol Higher alcohols such as methyl formate, ethyl formate, ethyl acetate, propyl acetate, butyl acetate, cetyl 2-ethylhexanoate, methyl castor oil fatty acid, isopropyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, diisopropyl sebacate , Diethyl sebacate, butyl stearate, hexyl laurate, myristyl myristate, oleyl oleate, decyl oleate, Octyldodecyl ristinate, hexyldecyl dimethyloctanoate, oleyl lactate, cetyl lactate, octyl dodecyl lactate, myristyl lactate, diethyl phthalate, dibutyl phthalate, lanolin acetate, ethylene glycol monostearate, propylene glycol monostearate, propylene oleate Glycol, glyceryl monostearate, glyceryl sesquioleate, glyceryl tri-2-ethylhexanoate, glyceryl tri (capryl / caprate), glyceryl tricaprylate, trimethylolpropane tri-2-ethylhexanoate, diisostearyl malate, diisostearate Glyceryl acid, propylene glycol isostearate, glyceryl triisostearate, trimethylolpropane triisostearate, di-2-ene Ruhexanoic acid neopentyl glycol, dicaprylic acid neopentyl glycol, dicapric acid neopentyl glycol, di-2-ethylhexanoic acid ethylene glycol, isodecylbenzoate, dicaprylic acid propylene glycol, isononanoic acid isononyl, tetra-2-ethylhexanoic acid pentaerythritol, Esters such as di-2-ethylhexyl succinate, ethylene glycol dicaprate, polyethylene glycol dilaurate, ethylene glycol palmitate, ethylene glycol oleate, tetra (behenic acid / benzoic acid / ethylhexanoic acid) pentaerythritol, trioctanoin, etc. Oil; Fatty acids such as isostearic acid, oleic acid, linoleic acid; liquid fatty acid triglyceride, artificial sebum (squalane and liquid fatty acid triglyceride) Mixtures of id and oleic acid).

In the present invention, it is particularly preferable to use octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, liquid paraffin, and butyl acetate from the viewpoint of easy gelation.
The said (B) component can be mix | blended in 1-99 weight% with respect to a gel-like composition.

The gel composition according to the present invention can be prepared by mixing the component (A) and the component (B). In addition, for example, the synthesis of the component (A) by the above-described method for producing an organosiloxane derivative composition is performed in the component (B), or the synthesis of the component (A) is performed in an arbitrary solvent, and the component (B) Can also be prepared by mixing them.
As the solvent, as long as the gel state in the composition of the present invention is not impaired, for example, lower alcohols such as water, ethanol, ethylene glycol and glycerin; phenols; amines; highly polar liquid organics such as carboxylic acids Compounds can also be used.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to these.
The structures of organosiloxane derivative compositions (Examples 1 to 6 and Comparative Examples 1 to 4) used in Examples and Comparative Examples are shown below and their synthesis methods. Each compound is composed of ¹ H, ¹³ C, ²⁹ Si-NMR (NMR apparatus: Fourier Transform Nuclear Magnetic Resonance Spectrometer JEOL
JNM-EX400 (manufactured by JEOL Ltd.)).

<Example 1>
Synthesis Method 1400 g of a 1% sodium hydroxide (NaOH) aqueous solution was prepared in a flask equipped with a stirrer, a thermometer, and a condenser, and heated to 70 ° C. After adding 145.5 g of compound A obtained by the following synthesis method at 70 ° C., the mixture was further stirred for 1 hour while maintaining the temperature. Thereafter, 231.6 g of an aqueous 25% zinc sulfate heptahydrate (ZnSO ₄ .7H ₂ O) solution was added at 70 ° C., and the mixture was further stirred for 1 hour to precipitate zinc soap. Thereto was added 65.1 g of 5% aqueous sodium hydroxide solution, and the mixture was stirred at 70 ° C. for 1 hour to confirm that it was neutral (neutralization reaction was completed), and then cooled to remove water.
The obtained product was dissolved by heating in an excessive amount of ion-exchanged water, and water was separated five times to wash zinc hydroxide and by-product salt (Na ₂ SO ₄ ).
Thereafter, the product was dried at 105 ° C. under reduced pressure to obtain a transparent to white solid substance. As a result of the analysis, the material is a carboxyl-modified organosiloxane derivative moiety derived from a compound A ^'R Si _-C 10 _H 20 -COO ^- "If it is abbreviated to as an average composition formula" ^R Si _-C 10 _{H 20} - COO ⁻ (Zn ²⁺ ) _5/8 (OH ⁻ ) _¼ ”was contained.
The neutralization reaction formula is as follows.
(Chemical 29)
8R ^Si —C ₁₀ H ₂₀ —COONa + 5ZnSO ₄ + 2NaOH → 3Zn (O—C (═O) —C ₁₀ H ₂₀ —R ^Si ) ₂ +2 (R ^Si —C ₁₀ H ₂₀ — (C═O) —O—Zn -OH) + _5Na 2 SO ₄

(Method for Synthesizing Compound A)
In a flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 100 g of 1,1,1,3,5,5,5-heptamethyltrisiloxane, platinum-1,3-divinyl-1,1,3 0.02 g of a toluene solution of 3,3-tetramethyldisiloxane complex was added, and 105 g of trimethylsilyl undecylate was added dropwise so as to maintain the range of 70-100 ° C. After completion of the dropwise addition, the mixture was aged for 2 hours at 100 ° C., and the completion of the reaction was confirmed using gas chromatography. The low boiling point component was distilled off under reduced pressure. Thereafter, methanol and water were added, and the mixture was aged for 5 hours under reflux to perform deprotection. Thereafter, the low boiling point component was removed again under reduced pressure to obtain Compound A. As a result of analysis, it was confirmed that the compound A was represented by the following chemical structural formula.

<Example 2>
Synthesis Method 1400 g of a 1% sodium hydroxide (NaOH) aqueous solution was prepared in a flask equipped with a stirrer, a thermometer, and a condenser, and heated to 70 ° C. After adding 145.5 g of compound A obtained by the said manufacturing method at 70 degreeC, it stirred for further 1 hour, maintaining this temperature. Thereafter, 119.28 g of a 25% aqueous solution of zinc chloride (ZnCl ₂ ) was added at 70 ° C., and further stirred for 1 hour to precipitate zinc soap. Thereto was added 65.1 g of 5% aqueous sodium hydroxide solution, and the mixture was stirred at 70 ° C. for 1 hour to confirm that it was neutral (neutralization reaction was completed), and then cooled to remove water.
The obtained product was dissolved by heating in an excess amount of ion-exchanged water, and water was separated five times to wash zinc hydroxide and a by-product salt (NaCl).
Thereafter, the product was dried at 105 ° C. under reduced pressure to obtain a transparent to white solid substance. As a result of analysis, when the carboxyl-modified organosiloxane derivative portion derived from Compound A is abbreviated as “R ^Si —C ₁₀ H ₂₀ —COO ⁻ ”, the average composition formula “R ^Si —C ₁₀ H ₂₀ — COO ⁻ (Zn ²⁺ ) _5/8 (OH ⁻ ) _¼ ”was contained.
The neutralization reaction formula is as follows.
(Chemical Formula 31)
8R ^Si —C ₁₀ H ₂₀ —COONa + 5ZnCl ₂ + 2NaOH → 3Zn (O—C (═O) —C ₁₀ H ₂₀ —R ^Si ) ₂ +2 (R ^Si —C ₁₀ H ₂₀ — (C═O) —O—Zn -OH) +10 NaCl

<Example 3>
Synthesis Method 1400 g of a 1% sodium hydroxide (NaOH) aqueous solution was prepared in a flask equipped with a stirrer, a thermometer, and a condenser, and heated to 70 ° C. After adding 145.5 g of compound A obtained by the said manufacturing method at 70 degreeC, it stirred for further 1 hour, maintaining this temperature. Thereafter, 127 g of a 25% zinc chloride (ZnCl ₂ ) aqueous solution was added at 70 ° C., and the mixture was further stirred for 1 hour to precipitate zinc soap. 86.8g of 5% sodium hydroxide aqueous solution was added there, and it stirred at 70 degreeC for 1 hour, and after confirming that it was neutral (neutralization reaction was completed), it cooled and removed water.
The obtained product was dissolved by heating in an excess amount of ion-exchanged water, and water was separated five times to wash zinc hydroxide and a by-product salt (NaCl).
Thereafter, the product was dried at 105 ° C. under reduced pressure to obtain a transparent to white solid substance. As a result of analysis, when the carboxyl-modified organosiloxane derivative portion derived from Compound A is abbreviated as “R ^Si —C ₁₀ H ₂₀ —COO ⁻ ”, the average composition formula “R ^Si —C ₁₀ H ₂₀ — COO ⁻ (Zn ²⁺ ) _2/3 (OH ⁻ ) _1/3 ”was contained.
The neutralization reaction formula is as follows.
(Chemical Formula 32)
6R ^Si —C ₁₀ H ₂₀ —COONa + 4ZnCl ₂ + 2NaOH → 2Zn (O—C (═O) —C ₁₀ H ₂₀ —R ^Si ) ₂ +2 (R ^Si —C ₁₀ H ₂₀ — (C═O) —O—Zn -OH) + 8NaCl

<Example 4>
Synthesis Method 1400 g of a 1% sodium hydroxide (NaOH) aqueous solution was prepared in a flask equipped with a stirrer, a thermometer, and a condenser, and heated to 70 ° C. After adding 145.9 g of compound A obtained by the said manufacturing method at 70 degreeC, it stirred for further 1 hour, maintaining this temperature. Thereafter, 277.9 g of a 25% zinc sulfate (ZnSO ₄ ) aqueous solution was added at 70 ° C., and the mixture was further stirred for 1 hour to precipitate zinc soap. 130.4g of 5% sodium hydroxide aqueous solution was added there, and it stirred at 70 degreeC for 1 hour, and after confirming that it was neutral (neutralization reaction was completed), it cooled and removed water.
The obtained product was dissolved by heating in an excessive amount of ion-exchanged water, and water was separated five times to wash zinc hydroxide and by-product salt (Na ₂ SO ₄ ).
Thereafter, the product was dried at 105 ° C. under reduced pressure to obtain a transparent to white solid substance. As a result of analysis, when the carboxyl-modified organosiloxane derivative portion derived from Compound A is abbreviated as “R ^Si —C ₁₀ H ₂₀ —COO ⁻ ”, the average composition formula “R ^Si —C ₁₀ H ₂₀ — COO ⁻ (Zn ²⁺ ) _3/4 (OH ⁻ ) _1/2 ”was contained.
The neutralization reaction formula is as follows.
(Chemical Formula 33)
4R ^Si —C ₁₀ H ₂₀ —COONa + 3ZnSO ₄ + 2NaOH → Zn (O—C (═O) —C ₁₀ H ₂₀ —R ^Si ) ₂ +2 (R ^Si —C ₁₀ H ₂₀ — (C═O) —O—Zn -OH) + _3Na 2 SO ₄

<Example 5>
Synthesis Method 1400 g of a 1% sodium hydroxide (NaOH) aqueous solution was prepared in a flask equipped with a stirrer, a thermometer, and a condenser, and heated to 70 ° C. After adding 145.9 g of compound A obtained by the said manufacturing method at 70 degreeC, it stirred for further 1 hour, maintaining this temperature. Thereafter, 135.2 g of a 25% aluminum chloride hexahydrate (AlCl ₃ .6H ₂ O) aqueous solution was added at 70 ° C., and the mixture was further stirred for 1 hour to precipitate aluminum soap. 52.1g of 5% sodium hydroxide aqueous solution was added there, and it stirred at 70 degreeC for 1 hour, and after confirming that it was neutral (neutralization reaction was completed), it cooled and removed water.
The obtained product was dissolved by heating in an excess amount of ion-exchanged water, and water was separated five times to wash zinc hydroxide and a by-product salt (NaCl).
Thereafter, the product was dried at 105 ° C. under reduced pressure to obtain a transparent to white solid substance. As a result of analysis, when the carboxyl-modified organosiloxane derivative portion derived from Compound A is abbreviated as “R ^Si —C ₁₀ H ₂₀ —COO ⁻ ”, the average composition formula “R ^Si —C ₁₀ H ₂₀ — COO ⁻ (Al ³⁺ ) _2/5 (OH ⁻ ) _1/5 ”was contained.

<Example 6>
Synthesis Method 1400 g of a 1% sodium hydroxide (NaOH) aqueous solution was prepared in a flask equipped with a stirrer, a thermometer, and a condenser, and heated to 70 ° C. The compound B141.9g obtained by the following manufacturing method was added at 70 degreeC, and also it stirred for 1 hour, maintaining this temperature. Thereafter, 127 g of a 25% zinc chloride (ZnCl ₂ ) aqueous solution was added at 70 ° C., and the mixture was further stirred for 1 hour to precipitate zinc soap. 86.8g of 5% sodium hydroxide aqueous solution was added there, and it stirred at 70 degreeC for 1 hour, and after confirming that it was neutral (neutralization reaction was completed), it cooled and removed water.
The obtained product was dissolved by heating in an excess amount of ion-exchanged water, and water was separated five times to wash zinc hydroxide and a by-product salt (NaCl).
Thereafter, the product was dried at 105 ° C. under reduced pressure to obtain a transparent to white solid substance. As a result of the analysis, the material was prepared, the carboxyl-modified organosiloxane derivative moiety derived from a B ^'R Si _-C 10 _H 20 -COO ^- "If it is abbreviated to as an average composition formula" ^R Si _-C 10 _{H 20} - COO ⁻ (Zn ²⁺ ) _2/3 (OH ⁻ ) _1/3 ”was contained.

(Synthesis Method of Compound B)
In a flask equipped with a stirrer, reflux condenser, dropping funnel and thermometer, 596.3 g (4.45 mol) of 1,1,3,3-tetramethyldisiloxane was charged, and 74.8 g of 1-hexene ( 0.89 mol) and 0.07 g of a toluene solution of platinum-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex was added dropwise at 70 ° C. over 2 hours. After completion of the dropwise addition, the mixture was aged for 1 hour, and then excess 1,1,3,3-tetramethyldisiloxane was distilled off under reduced pressure. To this reaction mixture, 250.6 g (0.98 mol) of trimethylsilyl undecylate was dropped at 85 ° C. to completely react silicon-bonded hydrogen atoms (Si—H) in tetramethyldisiloxane. After completion of the reaction, the low boiling point was distilled off under reduced pressure. Thereafter, methanol was added, and after refluxing for 2 hours, the low boiling point was removed under reduced pressure to obtain Compound B. As a result of analysis, it was confirmed that the compound B was represented by the following chemical structural formula.

<Comparative Example 1>
The following compound A obtained in the above-described method for synthesizing compound A was defined as comparative example 1.

<Comparative example 2>
The following salt obtained by neutralizing the compound A with sodium hydroxide was used as Comparative Example 2.

<Comparative Example 3>
The following salt obtained by neutralizing Compound A with aminomethylpropanol (AMP) was used as Comparative Example 3.

<Comparative example 4>
The following salt obtained by neutralizing the compound A with zinc chloride was used as Comparative Example 4.

The following oil gelation test was conducted using Examples 1-6 and Comparative Examples 1-3.
Oil gelation test (A) The above Examples 1 to 6 and Comparative Examples 1 to 310 parts were mixed with (B) liquid oil (decamethylpentasiloxane, trimethylsiloxy group-blocked dimethylpolysiloxane at both ends (6 mm ² / s (25 ° C.)). ), Liquid paraffin, butyl acetate) and 90 parts at 70 ° C. and cooled to room temperature to obtain each composition. The appearance of the obtained composition was evaluated according to the following criteria. The results are shown in Table 1 below.
(Evaluation criteria by appearance)
◯: The composition is gel.
X: The composition is in a liquid state, or (A) and (B) are separated.

  As shown in Table 1 above, the organopolysiloxane derivative of the present invention having a functional group having a specific structure was suitable for any oil agent.

Claims (7)

An organosiloxane derivative composition, which is a composition represented by the following average formula (2):

(In the above formula, R ^{1 to} R ³ are functional groups in which one or two are represented by —O—Si (R ⁴ ) ₃ (R ⁴ is an alkyl group having 1 to 6 carbon atoms or a phenyl group. Or a functional group represented by —O—Si (R ⁵ ) ₂ —X ¹ (R ⁵ is either an alkyl group having 1 to 6 carbon atoms or a phenyl group, and X ¹ is and other R ^{1 to} R ³ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, and Mn + is a zinc ion. (Zn ² +) and / or aluminum ions (Al ³ +) , s is a number of 0.1 <s ≦ 1.0, t is a number of 0.1 <t ≦ 0.8 , satisfy n × s-t = 1 relationship .A _is a linear or branched alkylene group represented by C _{q H 2q,} q is the 6-20 integer That. The average total number of silicon atoms contained in one molecule of the organosiloxane derivative represented by the average general formula (2) (Si) is 2 to 100.)

(In the above formula, R ⁶ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R ⁷ and R ⁸ are either an alkyl group having 1 to 6 carbon atoms or a phenyl group. B is a linear or branched alkylene group represented by C _r H _2r which may be partially branched, and r is an integer of 2 to 20. i is X ^i. The number of layers is an integer of 1 to n when the number of layers is n, the number of layers n is an integer of 1 to 10, and ai is an integer of 0 to 2 when i is any X ^{i + 1} is the silylalkyl group when i is less than n, and the methyl group when i = n.) An organosiloxane derivative represented by the average general formula (2),
R ¹ and R ² are functional groups represented by —O—Si (R ⁴ ) ₃ (R ⁴ is an alkyl group having 1 to 6 carbon atoms);
The organosiloxane derivative composition according to claim 1 , wherein R ³ is a monovalent hydrocarbon group having 1 to 10 carbon atoms, and q is an integer of 6 to 20. An oil gelling agent comprising the organosiloxane derivative according to claim 1 . 4. The oil gelling agent according to claim 3, wherein the oil gelling agent is for liquid oil. (A) the oil gelling agent according to claim 3 or 4 ,
(B) liquid oil other than the component (A),
A gel-like composition comprising: (A) a composition represented by the following average general formula (6):

(In the above formula, R ^{1 to} R ³ are functional groups in which one or two are represented by —O—Si (R ⁴ ) ₃ (R ⁴ is either an alkyl group having 1 to 6 carbon atoms or a phenyl group) Or a functional group represented by —O—Si (R ⁵ ) ₂ —X ¹ (R ⁵ is either an alkyl group having 1 to 6 carbon atoms or a phenyl group, and X ¹ is i And the other R ^{1 to} R ³ are monovalent hydrocarbon groups having 1 to 10 carbon atoms, and M ′ is a hydrogen atom. Or A is a linear or branched alkylene group represented by C _q H _2q , and q is an integer of 6 to 20. In addition, the average general formula (6 The average total number of silicon atoms (Si) contained in one molecule of the organosiloxane derivative represented by 2) is 2 to 100.)

(In the above formula, R ⁶ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and R ⁷ and R ⁸ are either an alkyl group having 1 to 6 carbon atoms or a phenyl group. B is a linear or branched alkylene group represented by C _r H _2r which may be partially branched , and r is an integer of 2 to 20. i is X ^i. The number of layers is an integer of 1 to n when the number of layers is n, the number of layers n is an integer of 1 to 10, and ai is an integer of 0 to 2 when i is any X ^{i + 1} is the silylalkyl group when i is less than n, and the methyl group when i = n.)
(B) an aqueous solution in which the polyvalent metal cation Mn + contains zinc ions (Zn ² +) or aluminum ions (Al ³ +) ;
(C) an aqueous solution containing hydroxide ions ,
The mixing amount of the component (b) with respect to the component (a) is more than 0.1 equivalent and 1.0 equivalent or less in a substance amount ratio, and
The method for producing an organosiloxane derivative composition, wherein the mixing amount of the component (c) with respect to the component (a) is mixed in a substance amount ratio of more than 0.05 equivalent and not more than 1.0 equivalent . The method for producing an organosiloxane derivative composition according to claim 6 , wherein the component (a) is mixed with the component (b) prepared in advance in an aqueous solution, and then the component (c) is mixed. .