JP2006016554A - Taurine-modified organopolysiloxane and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a new taurine-modified organopolysiloxane in which a taurine residue is bonded by a connecting group having poor hydrolyzability even in the presence of an acid or alkali and to provide a method for efficiently producing the new taurine-modified organopolysiloxane. <P>SOLUTION: The taurine-modified organopolysiloxane comprises at least one taurine residue bonded to a silicon atom in an organopolysiloxane. The method for producing the taurine-modified organopolysiloxane comprises reacting (A) taurine, a taurine derivative in which one hydrogen atom bonded to a nitrogen atom in the molecule is substituted with a 1-40C monofunctional hydrocarbon group or a salt thereof with (B) an epoxy group-containing organopolysiloxane. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a novel taurine-modified organopolysiloxane and an efficient production method thereof.

The taurine-modified organopolysiloxane that binds a taurine residue to a silicon atom in the organopolysiloxane includes an organopolysiloxane having a polyether chain having a halogenated alkylacyloxy group at the terminal, taurine, and nitrogen-bonded hydrogen in the molecule. A taurine derivative in which one atom is substituted with a monovalent hydrocarbon group having 1 to 40 carbon atoms, or a taurine-modified organopolysiloxane bonded to a taurine residue by an ester bond-containing polyether group obtained by reaction with a salt thereof (See U.S. Pat. No. 5,280,099), an organopolysiloxane having a carboxyl group and taurine, a taurine derivative in which one nitrogen atom-bonded hydrogen atom in the molecule is substituted with a monovalent hydrocarbon group having 1 to 40 carbon atoms, or Tau can be obtained by amide bond obtained by reaction with these salts. There are known taurine-modified organopolysiloxanes (see US Pat. No. 5,286,830). These taurine-modified organopolysiloxanes have taurine residues bonded by ester bonds or amide bonds. Therefore, there is a possibility that taurine may be separated by hydrolysis with acid or alkali.
US Pat. No. 528,0099 US Pat. No. 5,286,830

  The present invention relates to a novel taurine-modified organopolysiloxane in which a taurine residue is bonded with a linking group having poor hydrolyzability even in the presence of an acid or an alkali, and a method for efficiently producing such a novel taurine-modified organopolysiloxane. The purpose is to provide.

（式中、Ｒ³はアルキレン基である。）
で示される基、または一般式：

（式中、Ｒ³は前記と同じである。）
で示される基であり、Ｒ¹は水素原子または炭素数１〜４０の一価炭化水素基であり、Ｍは水素原子、Ｎａ、Ｋ、Ｌｉ、またはＮＨ₄であり、ａは１または２である。｝
で示されるタウリン残基を少なくとも１個結合することを特徴とする。 The taurine-modified organopolysiloxane of the present invention has a general formula:
(—X—) _a N (R ¹ ) _(2-a) —CH ₂ CH ₂ —SO ₃ M
{Wherein X is a general formula:
_{^{-R 2 -CH 2 CH (OH)}} -CH 2 -
(In the formula, R ² is an alkylene group, an alkyleneoxy group, or a polyalkyleneoxy group.)
A group represented by the general formula:
_{^{-R 2 -CH 2 CH (CH 2}} OH) -
(Wherein R ² is the same as described above.)
A group represented by the general formula:

(In the formula, R ³ is an alkylene group.)
Or a group represented by the general formula:

(Wherein, R ³ are as defined above.)
R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 40 carbon atoms, M is a hydrogen atom, Na, K, Li, or NH ₄ , and a is 1 or 2 is there. }
It is characterized by binding at least one taurine residue represented by

  The method for producing a taurine-modified organopolysiloxane of the present invention comprises: (A) taurine, a taurine derivative in which one nitrogen atom-bonded hydrogen atom in the molecule is substituted with a monovalent hydrocarbon group having 1 to 40 carbon atoms, or a salt thereof. And (B) an epoxy group-containing organopolysiloxane.

  The taurine-modified organopolysiloxane of the present invention is a novel compound in which a taurine residue is bonded with a linking group that is poorly hydrolyzable even in the presence of an acid or alkali, and the production method of the present invention is such a novel compound. It is characterized in that a modified organopolysiloxane can be produced efficiently.

で示される基、または一般式：

で示される基である。式中のＲ²はアルキレン基、アルキレンオキシ基、またはポリアルキレンオキシ基であり、このアルキレン基としては、メチレン基、エチレン基、プロピレン基、ブチレン基が例示され、このアルキレンオキシ基としては、メチレンオキシ基、エチレンオキシ基、プロピレンオキシ基が例示され、このポリアルキレンオキシ基としては、プロピレンオキシポリ（エチレンオキシ）基、プロピレンオキシポリ（エチレンオキシ）ポリ（プロピレンオキシ）基が例示される。また、式中のＲ³はアルキレン基であり、前記Ｒ²と同様のアルキレン基が例示される。また、式中のＲ¹は水素原子または炭素数１〜４０の一価炭化水素基であり、Ｒ¹の一価炭化水素基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、デシル基、ドデシル基、ミリスチル基、パルミチル基、ステアリル基等のアルキル基；ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基、オレイル基等のアルケニル基；シクロペンチル基、シクロヘキシル基等のシクロアルキル基；フェニル基、トリル基、キシリル基、ナフチル基等のアリール基；ベンジル基、フェネチル基等のアラルキル基；クロロメチル基、３−クロロプロピル基、３,３,３−トリフロロプロピル基等のハロゲン化アルキル基が例示される。また、式中のＭは水素原子、Ｎａ、Ｋ、Ｌｉ、またはＮＨ₄である。また、式中のａは１または２である。なお、式中のａが１である場合、本発明のタウリン変性オルガノポリシロキサンは、一分子中のケイ素原子に、上記のタウリン残基を結合したオルガノポリシロキサンであり、式中のａが２である場合、本発明のタウリン変性オルガノポリシロキサンは、一分子中のケイ素原子と他のケイ素原子に、上記のタウリン残基を結合したオルガノポリシロキサン、あるいはオルガノポリシロキサン中のケイ素原子と他のオルガノポリシロキサン中のケイ素原子に、上記のタウリン残基を結合した架橋構造を有するオルガノポリシロキサンである。 The taurine-modified organopolysiloxane of the present invention has a general formula:
(—X—) _a N (R ¹ ) _(2-a) —CH ₂ CH ₂ —SO ₃ M
It is characterized by binding at least one taurine residue represented by X in the formula is a general formula:
_{^{-R 2 -CH 2 CH (OH)}} -CH 2 -
A group represented by the general formula:
_{^{-R 2 -CH 2 CH (CH 2}} OH) -
A group represented by the general formula:

Or a group represented by the general formula:

It is group shown by these. R ² in the formula is an alkylene group, an alkyleneoxy group, or a polyalkyleneoxy group. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group. Examples include an oxy group, an ethyleneoxy group, and a propyleneoxy group. Examples of the polyalkyleneoxy group include a propyleneoxypoly (ethyleneoxy) group and a propyleneoxypoly (ethyleneoxy) poly (propyleneoxy) group. Moreover, R < ³ > in a formula is an alkylene group, and the alkylene group similar to said R < ² > is illustrated. R ¹ in the formula is a hydrogen atom or a monovalent hydrocarbon group having 1 to 40 carbon atoms, and examples of the monovalent hydrocarbon group for R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. Alkyl groups such as hexyl group, heptyl group, octyl group, decyl group, dodecyl group, myristyl group, palmityl group, stearyl group; alkenyl groups such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, oleyl group Cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group, tolyl group, xylyl group and naphthyl group; aralkyl groups such as benzyl group and phenethyl group; chloromethyl group, 3-chloropropyl group, 3, Illustrative are halogenated alkyl groups such as 3,3-trifluoropropyl group. M in the formula is a hydrogen atom, Na, K, Li, or NH ₄ . Moreover, a in the formula is 1 or 2. When a in the formula is 1, the taurine-modified organopolysiloxane of the present invention is an organopolysiloxane in which the above taurine residue is bonded to a silicon atom in one molecule, and a in the formula is 2 The taurine-modified organopolysiloxane of the present invention is an organopolysiloxane in which the above taurine residue is bonded to a silicon atom and another silicon atom in one molecule, or a silicon atom in an organopolysiloxane An organopolysiloxane having a crosslinked structure in which the taurine residue is bonded to a silicon atom in the organopolysiloxane.

で示されるエポキシ含有基、または一般式：

で示されるエポキシ含有基であり、一分子中の少なくとも１個のＲは前記タウリン残基である。Ｒの一価炭化水素基としては、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、デシル基、ドデシル基、ミリスチル基、パルミチル基、ステアリル基等のアルキル基；ビニル基、アリル基、ブテニル基、ペンテニル基、ヘキセニル基、オレイル基等のアルケニル基；シクロペンチル基、シクロヘキシル基等のシクロアルキル基；フェニル基、トリル基、キシリル基、ナフチル基等のアリール基；ベンジル基、フェネチル基等のアラルキル基；クロロメチル基、３−クロロプロピル基、３,３,３−トリフロロプロピル基等のハロゲン化アルキル基が例示される。また、Ｒのタウリン残基において、式中のＸ、Ｒ¹、Ｍ、およびａは前記と同様である。また、式中のｂは１.５〜２.１の数である。また、Ｒのエポキシ含有基において、式中のＲ²はアルキレン基、アルキレンオキシ基、またはポリアルキレンオキシ基であり、前記と同様の基が例示され、また、式中のＲ³はアルキレン基であり、前記と同様の基が例示される。 Such taurine-modified organopolysiloxane has, for example, an average formula:
R _b SiO _{(4-b) / 2}
Can be shown. In the formula, R is a substituted or unsubstituted monovalent hydrocarbon group.
(—X—) _a N (R ¹ ) _(2-a) —CH ₂ CH ₂ —SO ₃ M
Taurine residue represented by the general formula:

Or an epoxy-containing group represented by the general formula:

And at least one R in one molecule is the taurine residue. Examples of monovalent hydrocarbon groups for R include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, myristyl, palmityl, stearyl, etc. Alkyl group; alkenyl group such as vinyl group, allyl group, butenyl group, pentenyl group, hexenyl group, oleyl group; cycloalkyl group such as cyclopentyl group, cyclohexyl group; aryl such as phenyl group, tolyl group, xylyl group, naphthyl group Groups: aralkyl groups such as benzyl and phenethyl groups; halogenated alkyl groups such as chloromethyl, 3-chloropropyl, and 3,3,3-trifluoropropyl. In the taurine residue of R, X, R ¹ , M, and a in the formula are the same as described above. Moreover, b in a formula is a number of 1.5-2.1. Further, in the epoxy-containing group of R, R ² in the formula is an alkylene group, an alkyleneoxy group, or a polyalkyleneoxy group, and examples thereof are the same as those described above, and R ^{3 in} the formula is an alkylene group. Yes, the same groups as described above are exemplified.

  The method for producing such a taurine-modified organopolysiloxane is not particularly limited. (A) Taurine, a taurine derivative in which one nitrogen atom-bonded hydrogen atom in a molecule is substituted with a monovalent hydrocarbon group having 1 to 40 carbon atoms, Alternatively, it is preferable to react these salts with (B) an epoxy group-containing organopolysiloxane.

The taurine as the component (A), a taurine derivative in which one nitrogen atom-bonded hydrogen atom in the molecule is substituted with a monovalent hydrocarbon group having 1 to 40 carbon atoms, or a salt thereof,
NH _a (R ¹ ) _(2-a) —CH ₂ CH ₂ —SO ₃ M
Indicated by R ¹ in the above formula is a hydrogen atom or a monovalent hydrocarbon group having 1 to 40 carbon atoms, and examples of the monovalent hydrocarbon group for R ¹ include the same groups as described above. M in the above formula is a hydrogen atom, Na, K, Li, or NH ₄ . Further, a in the above formula is 1 or 2. Specific examples of such component (A) include taurine, taurine sodium, N-methyl taurine, and N-methyl taurine sodium.

で示されるエポキシ含有基、または一般式：

で示されるエポキシ含有基であり、一分子中の少なくとも１個のＲ'は前記いずれかのエポキシ含有基である。式中のＲ²はアルキレン基、アルキレンオキシ基、またはポリアルキレンオキシ基であり、前記と同様の基が例示される。また、式中のＲ³はアルキレン基であり、前記と同様の基が例示される。また、式中のｂは１.５〜２.１の数である。 The (B) component epoxy group-containing organopolysiloxane is not particularly limited as long as it has at least one epoxy group bonded to a silicon atom in one molecule. The bonding position of the epoxy group is not limited, and examples thereof include a molecular chain terminal and / or a molecular chain side chain. The molecular structure of such an organosiloxane is not particularly limited, and examples thereof include linear, cyclic, branched, and partially branched linear, preferably linear. Such an epoxy group-containing organopolysiloxane has, for example, an average formula:
R ' _b SiO _{(4-b) / 2}
Indicated by R ′ in the formula is a substituted or unsubstituted monovalent hydrocarbon group,

Or an epoxy-containing group represented by the general formula:

And at least one R ′ in one molecule is any of the epoxy-containing groups described above. R ² is an alkylene group wherein an alkylene group or a polyalkyleneoxy group, the same groups are exemplified. R ³ in the formula is an alkylene group, and examples thereof are the same groups as described above. Moreover, b in a formula is a number of 1.5-2.1.

  Such an epoxy group-containing organopolysiloxane can be prepared, for example, by subjecting a silicon atom-bonded hydrogen atom-containing organopolysiloxane and an alkenyl group-containing epoxy compound to an addition reaction in the presence of a platinum catalyst.

In the method for producing a taurine-modified organopolysiloxane of the present invention, the nitrogen atom-bonded hydrogen atom in the component (A) reacts with the epoxy group in the component (B) to generate a nitrogen-carbon bond and a hydroxyl group. This reaction is usually carried out by using component (A) as an aqueous solution or an aqueous alcohol solution such as methanol, ethanol, propanol, etc., and dropping or mixing component (B), and bringing both components into contact with each other in the solution. During the reaction, it is preferable to maintain the reaction system at pH 8 to 12, particularly pH 9 to 11. For this purpose, alkaline substances such as sodium hydroxide, potassium hydroxide, lithium hydroxide, aqueous ammonia, triethylamine, and triethanolamine are added. If necessary, drop or mix in the reaction solution. During the reaction, the pH in the reaction system is maintained in the above-mentioned range because the nitrogen atom-bonded hydrogen atom in the component (A) reacts with the epoxy group in the component (B) so that the reaction rate is lower than pH 8. This is because the siloxane bond in the component (B) is hydrolyzed at pH 12 or higher. The reaction proceeds even at room temperature, but is accelerated by increasing the temperature. However, since the hydrolysis of the siloxane bond in the component (B) is promoted when the temperature is increased while the pH is high, the temperature is preferably at most 80 ° C. The component (B) is usually a liquid or a solid and may be used as it is, but a solution such as water, methanol, ethanol, propanol, ethyl ether, acetone, dioxane, tetrahydrofuran, acetonitrile, or a mixture thereof. It is preferable to use a solution. The progress of this reaction can be confirmed by measuring the modified group and residual epoxy group produced by the reaction of the amino group and epoxy group of the taurine derivative by ¹³ C-NMR analysis.

  Moreover, the method of performing reaction of (A) component and (B) component in an emulsion dispersion liquid is also illustrated. The reaction of the component (A) and the component (B) in the emulsified dispersion is usually performed by dropping or mixing the emulsified dispersion of the component (B) into the aqueous solution of the component (A) and mixing both components in the emulsified dispersion. Done by contacting. The emulsified dispersion of component (B) used in this method is usually prepared using an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant. These surfactants are not particularly limited as long as they do not inhibit the reaction between the component (A) and the component (B), and can be used alone or in combination.

  Examples of the anionic surfactant include N-acyl-sarcosine salts, N-acyl glutamic acid and salts thereof, alkanesulfonic acid and salts thereof, α-olefin sulfonic acid and salts thereof, alkylsulfuric acid and salts thereof, and higher fatty acid esters. Sulfonic acids and salts thereof, dialkylsulfosuccinic acid and salts thereof, acylmethyl taurine and salts thereof, polyoxyethylene alkyl ether sulfuric acid and salts thereof, fatty acid salts, alkyl polyether carboxylic acids and salts thereof, alkyl phosphoric acid and salts thereof, Examples thereof include polyoxyethylene alkyl ether phosphoric acid and salts thereof, alkylallyl sulfonic acid and salts thereof, and acylated hydrolyzed collagen peptide salts.

  Examples of the cationic surfactant include, for example, ethyl lanolin sulfate fatty acid aminopropylethyldimethylammonium chloride, alkyltrimethylammonium chloride, oalkyldihydroxyethylmethylammonium chloride, γ-gluconamidopropyldimethylhydroxyethylammonium chloride, dialkyldimethylammonium chloride. , Di (polyoxyethylene) alkylmethylammonium chloride, stearoylcholaminoformylmethylpyridinium chloride, cetylpyridinium chloride, alkyldimethylethylammonium chloride, tri (polyoxyethylene) alkylammonium chloride, benzalkonium chloride, benzethonium chloride, polychloride Oxyethylene polyoxypropylene diethyl methyl ammonium, polyoxypropylene chloride Le diethylammonium, lauroyl Kola amino formyl methyl pyridinium chloride, alkyl bromide isoquinolinium solution, bromide alkyltrimethylammonium include alkyltrimethylammonium saccharin.

  Examples of the nonionic surfactant include ethylene glycol fatty acid esters, polyethylene glycol fatty acid esters, propylene glycol fatty acid esters, polypropylene glycol fatty acid esters, glycol fatty acid esters, trimethylolpropane fatty acid esters, penta Erythlit fatty acid esters, glucoside derivatives, glycerin alkyl ether fatty acid esters, trimethylolpropaneoxyethylene alkyl ethers, fatty acid amides, alkylolamides, alkylamine oxides, lanolin and its derivatives, castor oil derivatives , Hardened castor oil derivatives, sterols and derivatives thereof, polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ether , Polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, polyoxyethylene alkylolamides, polyoxyethylene diethanolamine fatty acid esters, polyoxyethylene trimethylolpropane fatty acid esters, polyoxyethylene alkyl ether fatty acid esters , Polyoxyethylene polyoxypropylene glycols, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene polyoxypropylene polyhydric alcohol ethers, glycerin fatty acid esters, polyglycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters Sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sucrose fatty acid esters, polyoxy Ethylene group-containing organopolysiloxane, polyoxyethylene polyoxypropylene group-containing organopolysiloxanes.

  Examples of the amphoteric surfactant include 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, sodium alkylhydroxyethylimidazolinium betaine, alkyldiaminoethylethylglycine hydrochloride, stearyldimethylamino Betaine acetate, bis (stearyl-N-hydroxyethylimidazoline) chloroacetic acid complex, alkyl-N-carboxymethoxyethyl-N-carboxymethylimidazolinium disodium hydroxide, coconut oil alkyl-N-carboxymethoxyethyl-N-carboxyl Methylimidazolinium disodium lauryl sulfate, alkylbetaine, triethanolamine laurylaminopropionate, sodium β-laurylaminopropionate, lauryl-N- Carboxymethyl methoxyethyl -N- carboxymethyl imidazolinium disodium dodecanoyl sarcosine, lauryl di aminoethyl glycine sodium, lauryl dimethylamino acetic acid betaine, lauric acid amidopropyl betaine solution.

  The method for preparing the emulsified dispersion of component (B) is not particularly limited, and examples thereof include a method in which component (B), a surfactant and water are uniformly mixed and emulsified with high shear. Moreover, the average particle diameter of the emulsified dispersion liquid of (B) component in that case is not specifically limited.

In the reaction of the component (A) and the component (B) in the emulsified dispersion, it is preferable to maintain the pH in the reaction system at 8 to 12, particularly 9 to 11, and for this purpose, sodium hydroxide, potassium hydroxide, water An alkaline substance such as lithium oxide, aqueous ammonia, triethylamine, or triethanolamine is dropped or mixed into the reaction solution as necessary. During the reaction, the pH in the reaction system is maintained in the above range because the amino group in the component (A) reacts with the epoxy group in the component (B) to be alkaline at pH 8 or higher. Desirably, at pH 12 or higher, the siloxane bond in the component (B) is hydrolyzed. The reaction proceeds even at room temperature and can be accelerated by heating. However, when the temperature is increased at a high pH, hydrolysis of the siloxane bond in the component (B) is promoted or an emulsified dispersion. Is unstable, it is preferable to heat to 90 ° C. or lower. The progress of this reaction can be confirmed by measuring the modified group and residual epoxy group produced by the reaction of the amino group and epoxy group of the taurine derivative by ¹³ C-NMR analysis.

  In the production method of the present invention, after reacting the component (A) and the component (B), filtration is performed as necessary, unreacted components are separated, and, if necessary, low-boiling substances such as organic solvents are heated under reduced pressure. The desired taurine-modified organopolysiloxane can be purified by distilling off under pressure.

  The taurine-modified organopolysiloxane of the present invention and the production method thereof will be described in detail with reference to examples.

で示されるポリオキシエチレンモノアリルモノグリシジルエーテルとをそれらのヒドロシリル基と不飽和基との当量比が１：１.２になるような原料比で秤量し、更に白金と１,３−ジビニル−１,１,３,３−テトラメチルジシロキサンとの錯体（白金金属が反応原料の合計重量に対して４ｐｐｍになる量）を加えて反応温度８０℃で５時間攪拌した。得られたこのポリマーはＮＭＲおよびＩＲの結果、平均式：
(ＣＨ₃)_1.98(Ｅp)_0.04ＳiＯ_0.99
で示され、式中、Ｅpは、式：

で示されるエポキシ含有基であるエポキシ基含有オルガノポリシロキサンであることが判明した。 [Reference Example 1]
Average formula:
(CH ₃ ) _1.98 H _0.04 SiO _0.99
A dimethylsiloxane / methylhydrogensiloxane copolymer having both ends of the molecular chain blocked with a trimethylsiloxy group represented by the formula:

The polyoxyethylene monoallyl monoglycidyl ether represented by the formula (1) is weighed in such a raw material ratio that the equivalent ratio of the hydrosilyl group to the unsaturated group is 1: 1.2, and platinum and 1,3-divinyl- A complex with 1,1,3,3-tetramethyldisiloxane (amount in which platinum metal is 4 ppm with respect to the total weight of the reaction raw materials) was added and stirred at a reaction temperature of 80 ° C. for 5 hours. The obtained polymer was analyzed by NMR and IR, and the average formula:
(CH ₃ ) _1.98 (Ep) _0.04 SiO _0.99
Where Ep is the formula:

It was found that the epoxy group-containing organopolysiloxane is an epoxy-containing group represented by

で示されるポリオキシエチレンモノアリルモノグリシジルエーテルとをそれらのヒドロシリル基と不飽和基との当量比が１：１．２になるような原料比で秤量し、更に白金と１,３−ジビニル−１,１,３,３−テトラメチルジシロキサンとの錯体（白金金属が反応原料の合計重量に対して４ｐｐｍになる量）を秤量して反応温度８０℃で５時間攪拌した。得られたこのポリマーはＮＭＲおよびＩＲの結果、平均式：
(ＣＨ₃)_1.98(Ｅp)_0.04ＳiＯ_0.99
で示され、式中、Ｅpは、式：

で示されるエポキシ含有基であるエポキシ基含有オルガノポリシロキサンであることが判明した。 [Reference Example 2]
Average formula:
(CH ₃ ) _1.98 H _0.04 SiO _0.99
A dimethylpolysiloxane having both ends of the molecular chain blocked with dimethylhydrogensiloxy groups, represented by the formula:

The polyoxyethylene monoallyl monoglycidyl ether represented by the formula (1) is weighed at a raw material ratio such that the equivalent ratio of the hydrosilyl group to the unsaturated group is 1: 1.2, and platinum and 1,3-divinyl- A complex with 1,1,3,3-tetramethyldisiloxane (amount in which platinum metal is 4 ppm based on the total weight of the reaction raw materials) was weighed and stirred at a reaction temperature of 80 ° C. for 5 hours. The obtained polymer was analyzed by NMR and IR, and the average formula:
(CH ₃ ) _1.98 (Ep) _0.04 SiO _0.99
Where Ep is the formula:

It was found that the epoxy group-containing organopolysiloxane is an epoxy-containing group represented by

で示されるポリオキシエチレンモノアリルモノグリシジルエーテルとをそれらのヒドロシリル基と不飽和基との当量比が１：１.２になるような原料比で秤量し、更に白金と１,３−ジビニル−１,１,３,３−テトラメチルジシロキサンとの錯体（白金金属が反応原料の合計重量に対して４ｐｐｍになる量）を秤量して反応温度８０℃で５時間攪拌した。得られたこのポリマーはＮＭＲおよびＩＲの結果、平均式：
(ＣＨ₃)_2.07(Ｅp)_0.07ＳiＯ_0.93
で示され、式中、Ｅpは、式：

で示されるエポキシ含有基であるエポキシ基含有オルガノポリシロキサンであることが判明した。 [Reference Example 3]
Average formula:
(CH ₃ ) _2.07 H _0.07 SiO _0.93
A dimethylpolysiloxane having one end of a molecular chain blocked with a trimethylsiloxy group and the other end of a molecular chain blocked with a dimethylhydrogensiloxy group, represented by the formula:

The polyoxyethylene monoallyl monoglycidyl ether represented by the formula (1) is weighed in such a raw material ratio that the equivalent ratio of the hydrosilyl group to the unsaturated group is 1: 1.2, and platinum and 1,3-divinyl- A complex with 1,1,3,3-tetramethyldisiloxane (amount in which platinum metal is 4 ppm based on the total weight of the reaction raw materials) was weighed and stirred at a reaction temperature of 80 ° C. for 5 hours. The obtained polymer was analyzed by NMR and IR, and the average formula:
(CH ₃ ) _2.07 (Ep) _0.07 SiO _0.93
Where Ep is the formula:

It was found that the epoxy group-containing organopolysiloxane is an epoxy-containing group represented by

で示されるアリルグリシジルエーテル１８.５ｇを秤量し、更に白金と１,３−ジビニル−１,１,３,３−テトラメチルジシロキサンとの錯体（白金金属が反応原料の合計重量に対して４ｐｐｍになる量）を秤量して反応温度８０℃で５時間攪拌した。得られたポリマーはＮＭＲおよびＩＲの結果、平均式：
(ＣＨ₃)_1.87(ＥＯ)_0.07(Ｅp)_0.08ＳiＯ_0.99
で示され、式中、ＥＯは、式：
−Ｃ₃Ｈ₆Ｏ(Ｃ₂Ｈ₄Ｏ)₂₂(Ｃ₃Ｈ₆Ｏ)₂₂ＣＨ₃
で示されるポリオキシアルキレン残基であり、Ｅpは、式：

で示されるエポキシ含有基であるエポキシ基含有オルガノポリシロキサンであることが判明した。 [Reference Example 4]
Average formula:
(CH ₃ ) _1.87 H _0.15 SiO _0.99
And 92.3 g of a dimethylsiloxane / methylhydrogensiloxane copolymer having both ends of the molecular chain blocked with a trimethylsiloxy group represented by the formula:
CH ₂ = CHCH ₂ O (C ₂ H ₄ O) ₂₂ (C ₃ H ₆ O) ₂₂ CH ₃
197.0 g of polyoxyethylene polyoxypropylene monoallyl monomethyl ether represented by the formula:

18.5 g of allyl glycidyl ether represented by formula (1) and a complex of platinum and 1,3-divinyl-1,1,3,3-tetramethyldisiloxane (4 ppm relative to the total weight of the reaction raw materials) And the mixture was stirred at a reaction temperature of 80 ° C. for 5 hours. As a result of NMR and IR, the obtained polymer has an average formula:
(CH ₃ ) _1.87 (EO) _0.07 (Ep) _0.08 SiO _0.99
Where EO is the formula:
_{-C 3 H 6 O (C 2} H 4 O) 22 (C 3 H 6 O) 22 CH 3
Wherein Ep is a compound represented by the formula:

It was found that the epoxy group-containing organopolysiloxane is an epoxy-containing group represented by

で示されるタウリン残基、または式：

で示されるタウリン残基であるタウリン変性ポリオルガノシロキサンであることを確認した。 [Example 1]
25.0 g of an epoxy group-containing organopolysiloxane prepared in Reference Example 1, the formula:
_{CH 3 -NH-CH 2 CH 2} -SO 3 Na
1.76 g of sodium N-methyltaurine represented by the formula (equivalent ratio of epoxy group to amino group of 1: 1), 18.2 g of ethanol and 5.0 g of ion-exchanged water were added to a separator, equipped with a condenser, a nitrogen inlet and a stirrer. Weighed into a bull flask and mixed it. At this time, the mixed solution had a pH of 9.5. The mixture was heated to 80 ° C. and reacted for 2 hours. After cooling, ethanol and water of the obtained mixed solution were volatilized at room temperature to obtain a sticky grease-like polymer. When ¹³ C-NMR analysis of this polymer was carried out, the peak of the epoxy group disappeared, and the epoxy group and the amino group in taurine were found at 42.9, 49.0, 53.6, 60.7, 67.6 ppm. Since a peak derived from the reaction of was produced, this polymer has an average formula:
(CH ₃ ) _1.98 (Tu) _0.04 SiO _0.99
Where Tu is the formula:

A taurine residue represented by the formula:

It confirmed that it was a taurine modified polyorganosiloxane which is a taurine residue shown by these.

で示されるタウリン残基、または式：

で示されるタウリン残基であり、さらに、式：

で示されるタウリン残基、式：

で示されるタウリン残基、または式：

で示されるタウリン残基によって、一分子中のケイ素原子と他のケイ素原子、あるいは、オルガノポリシロキサン中のケイ素原子と他のオルガノポリシロキサン中のケイ素原子とを部分架橋したタウリン変性ポリオルガノシロキサンであることを確認した。 [Example 2]
25.0 g of an epoxy group-containing organopolysiloxane prepared in Reference Example 2, the formula:
_{NH 2 -CH 2 CH 2 -SO 3} H
1.22 g of taurine represented by the formula (equivalent ratio of epoxy group to amino group is 1: 1), 1.94 g of 20% aqueous sodium hydroxide solution, 18.4 g of ethanol, and 3.5 g of ion-exchanged water were introduced into a condenser and introduced into nitrogen Weighed into a separable flask equipped with a mouth and a stirrer and mixed. This mixed solution had a pH of 10.0. The mixture was heated to 80 ° C. with stirring and held for 2 hours. After cooling, ethanol and water of the obtained mixed solution were volatilized at room temperature to obtain a sticky raw rubber-like polymer. When this polymer was subjected to ¹³ C-NMR analysis, there was no peak derived from residual epoxy groups, and 45.3, 51.0, 52.2, 52.7, 67.6 ppm, etc. Since a peak derived from the reaction with the amino group was generated, this polymer has an average formula:
(CH ₃ ) _1.98 (Tu) _0.04 SiO _0.99
In the formula, Tu represents the formula:

A taurine residue represented by the formula:

A taurine residue represented by the formula:

A taurine residue represented by the formula:

A taurine residue represented by the formula:

A taurine-modified polyorganosiloxane in which a silicon atom in one molecule and another silicon atom, or a silicon atom in an organopolysiloxane and a silicon atom in another organopolysiloxane are partially crosslinked by a taurine residue represented by I confirmed that there was.

で示されるタウリン残基、または式：

で示されるタウリン残基であり、さらに、式：

で示されるタウリン残基、式：

で示されるタウリン残基、または式：

で示されるタウリン残基によって、オルガノポリシロキサン中のケイ素原子と他のオルガノポリシロキサン中のケイ素原子とを部分架橋したタウリン変性ポリオルガノシロキサンであることを確認した。 [Example 3]
25.0 g of an epoxy group-containing organopolysiloxane prepared in Reference Example 3, the formula:
NH ₂ —CH ₂ CH ₂ —SO ₃ Na
2.52 g of sodium taurine, 17.5 g of ethanol and 5.04 g of ion-exchanged water represented by the above formula were weighed and mixed in a separable flask equipped with a condenser, a nitrogen inlet and a stirrer. This mixed solution had a pH of 10.0. The mixture was heated to 80 ° C. with stirring and held for 2 hours. After cooling, ethanol and water of the obtained mixed solution were volatilized at room temperature to obtain a highly viscous polymer having tackiness. When this polymer was subjected to ¹³ C-NMR analysis, there was no peak derived from the residual epoxy group, and there was no difference between the epoxy group and the amino group in taurine at 45.4, 52.0, 52.4, 67.4 ppm, etc. Since a peak derived from the reaction was generated, this polymer has an average formula:
(CH ₃ ) _2.07 (Tu) _0.07 SiO _0.93
Where Tu in the formula is the formula:

A taurine residue represented by the formula:

A taurine residue represented by the formula:

A taurine residue represented by the formula:

A taurine residue represented by the formula:

It was confirmed that the taurine residue was a taurine-modified polyorganosiloxane in which a silicon atom in an organopolysiloxane and a silicon atom in another organopolysiloxane were partially crosslinked.

で示されるタウリン残基または式：

で示されるタウリン残基、および式：

で示される未反応のエポキシ含有基、さらには、式：

で示されるタウリン残基、式：

で示されるタウリン残基、または式：

で示されるタウリン残基によって、一分子中のケイ素原子と他のケイ素原子、あるいは、オルガノポリシロキサン中のケイ素原子と他のオルガノポリシロキサン中のケイ素原子とを部分架橋したタウリン変性ポリオルガノシロキサンであることを確認した。また、４３.９ｐｐｍと５０.８ｐｐｍの残存エポキシ基のピークより、エポキシ変性オルガノポリシロキサン中のエポキシ基とタウリン中のアミノ基との反応率を算出したところ、４６％であった。 [Example 4]
30.0 g of an epoxy group-containing organopolysiloxane prepared in Reference Example 1, 3.5 g of polyoxyethylene (5 mol) alkyl (C _12-14 ) ether, polyoxyethylene (9 mol) alkyl (C _12-14 ) ether 3.5 g, 0.9 g of sodium N-lauroylmethyltaurine and 32.1 g of ion-exchanged water were weighed into a glass beaker and mixed with a propeller stirrer to obtain a uniform emulsion. This emulsion is transferred to a separable flask equipped with a condenser, nitrogen inlet and stirrer, where the formula:
NH ₂ —CH ₂ CH ₂ —SO ₃ H
A mixed solution of 1.64 g of taurine represented by the formula (equivalent ratio of epoxy group and amino group is 1: 1), 2.63 g of 20% -aqueous sodium hydroxide and 25.7 g of ion-exchanged water was added. This mixed solution had a pH of 9.5. The emulsion was heated to 50 ° C. and stirred for 2 hours. After cooling, 20 g of hexane and 20 g of methanol were added to 10 g of the obtained emulsion, and the polymer was extracted. After discarding the solvent layer, the polymer layer was dried at room temperature to obtain an adhesive high-viscosity polymer. When this polymer was subjected to ¹³ C-NMR analysis, a peak derived from the reaction between an epoxy group and an amino group in taurine was generated at 58.3 ppm.
(CH ₃ ) _1.98 (Y) _0.04 SiO _0.99
Where Y is the formula:

A taurine residue or a formula:

A taurine residue represented by the formula:

And an unreacted epoxy-containing group represented by the formula:

A taurine residue represented by the formula:

A taurine residue represented by the formula:

A taurine-modified polyorganosiloxane in which a silicon atom in one molecule and another silicon atom, or a silicon atom in an organopolysiloxane and a silicon atom in another organopolysiloxane are partially crosslinked by a taurine residue represented by I confirmed that there was. The reaction rate between the epoxy group in the epoxy-modified organopolysiloxane and the amino group in taurine was calculated from the peaks of the remaining epoxy groups of 43.9 ppm and 50.8 ppm, and was 46%.

で示されるタウリン残基、または式：

で示されるタウリン残基であるタウリン変性オルガノポリシロキサンであることを確認した。 [Example 5]
47.4 g of the epoxy group-containing organopolysiloxane prepared in Reference Example 4 and the formula:
_{CH 3 -NH-CH 2 CH 2} -SO 3 Na
N-methyl taurine sodium 2.6g, ethanol 40.0g, and ion-exchanged water 7.4g were weighed into a separable flask equipped with a condenser, a nitrogen inlet and a stirrer, and mixed uniformly. At this time, the mixed solution had a pH of 10.0. The mixture was heated to 80 ° C. with stirring and held for 4 hours. After cooling, ethanol and water of the obtained mixed solution were volatilized at room temperature to obtain a sticky grease-like polymer. When this polymer was subjected to ¹³ C-NMR analysis, there was no peak derived from the residual epoxy group, and there was no difference between the epoxy group and the amino group in taurine at 45.4, 52.0, 52.4, 67.4 ppm, etc. Since a peak derived from the reaction was generated, this polymer has an average formula:
(CH ₃ ) _1.87 (EO) _0.07 (Tu) _0.08 SiO _0.99
Where EO is the formula:
_{-C 3 H 6 O (C 2} H 4 O) 22 (C 3 H 6 O) 22 CH 3
In the formula, Tu is a polyoxyalkylene residue represented by the formula:

A taurine residue represented by the formula:

It confirmed that it was a taurine modified organopolysiloxane which is a taurine residue shown by these.

The taurine-modified organopolysiloxane of the present invention sufficiently exhibits the excellent characteristics of organopolysiloxane and the excellent characteristics of taurine. Therefore, additives such as cosmetics and paints, various coating agents, and organic resin molding Useful as release agents, organic resin modifiers, lubricants, softeners, etc., and base materials such as hair, skin, nails, metals, organic resins, inorganic resins, glass, ceramics, fillers, building materials, fibers, paper Application to is illustrated.

Claims (6)

The silicon atom in the organopolysiloxane has a general formula:
(—X—) _a N (R ¹ ) _(2-a) —CH ₂ CH ₂ —SO ₃ M
{Wherein X is a general formula:
_{^{-R 2 -CH 2 CH (OH)}} -CH 2 -
(In the formula, R ² is an alkylene group, an alkyleneoxy group, or a polyalkyleneoxy group.)
A group represented by the general formula:
^{_{-R 2 -CH 2 CH (CH 2}} OH) -
(Wherein R ² is the same as described above.)
A group represented by the general formula:

(In the formula, R ³ is an alkylene group.)
Or a group represented by the general formula:

(Wherein R ³ is the same as described above.)
In a group represented, R ¹ is hydrogen atom or a monovalent hydrocarbon group having a carbon number of 1 to 40, M is a hydrogen atom, Na, K, and Li or NH, _4, a is 1 or 2 is there. }
A taurine-modified organopolysiloxane which binds at least one taurine residue represented by Taurine-modified organopolysiloxane has an average formula:
R _b SiO _{(4-b) / 2}
[Wherein R represents a substituted or unsubstituted monovalent hydrocarbon group, a general formula:
(—X—) _a N (R ¹ ) _(2-a) —CH ₂ CH ₂ —SO ₃ M
{Wherein X is a general formula:
_{^{-R 2 -CH 2 CH (OH)}} -CH 2 -
(In the formula, R ² is an alkylene group, an alkyleneoxy group, or a polyalkyleneoxy group.)
A group represented by the general formula:
_{^{-R 2 -CH 2 CH (CH 2}} OH) -
(Wherein R ² is the same as described above.)
A group represented by the general formula:

(In the formula, R ³ is an alkylene group.)
Or a group represented by the general formula:

(Wherein R ³ is the same as described above.)
R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 40 carbon atoms, M is a hydrogen atom, Na, K, Li, or NH ₄ , and a is 1 or 2 is there. }
Taurine residue represented by the general formula:

(Wherein R ² is the same as described above.)
Or an epoxy-containing group represented by the general formula:

(Wherein R ³ is the same as described above.)
Wherein at least one R in the organopolysiloxane is the taurine residue, and b is a number from 1.5 to 2.1. ]
The taurine-modified organopolysiloxane according to claim 1, wherein   (A) Taurine, a taurine derivative in which one nitrogen atom-bonded hydrogen atom in the molecule is substituted with a monovalent hydrocarbon group having 1 to 40 carbon atoms, or a salt thereof, and (B) an epoxy group-containing organopolysiloxane. A method for producing a taurine-modified organopolysiloxane, which comprises reacting at least one taurine residue with a silicon atom in an organopolysiloxane. The component (A) has the general formula:
NH _a (R ¹ ) _(2-a) —CH ₂ CH ₂ —SO ₃ M
(In the formula, R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 40 carbon atoms, M is a hydrogen atom, Na, K, Li, or NH ₄ , and a is 1 or 2.)
The taurine represented by the above, a taurine derivative in which one nitrogen-bonded hydrogen atom in the molecule is substituted with a monovalent hydrocarbon group having 1 to 40 carbon atoms, or a salt thereof. A method for producing taurine-modified organopolysiloxane. (B) component is average formula:
R ' _b SiO _{(4-b) / 2}
{Wherein R ′ represents a substituted or unsubstituted monovalent hydrocarbon group or a general formula:

(In the formula, R ² is an alkylene group, an alkyleneoxy group, or a polyalkyleneoxy group.)
Or an epoxy-containing group represented by the general formula:

(In the formula, R ³ is an alkylene group.)
Wherein at least one R ′ in one molecule is any one of the epoxy-containing groups described above, and b is a number of 1.5 to 2.1. }
The method for producing a taurine-modified organopolysiloxane according to claim 3, characterized in that it is an epoxy group-containing organopolysiloxane represented by formula (1). The method for producing a taurine-modified organopolysiloxane according to claim 3, wherein the reaction is carried out in water or in an alcohol aqueous solution.