JP2005232359A - Oligoamide-modified organopolysiloxane, its production process, and gelatinous composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new oligoamide-modified organopolysiloxane capable of thickening/gelling silicone oil or a nonpolar organic compound liquid without the aid of water, its production process and a gelatinous composition of silicone oil or a nonpolar organic compound liquid. <P>SOLUTION: This new oligoamide-modified organopolysiloxane comprises a specific organic group containing an amide group where a silicon atom and an amide group are linked through a nitrogen atom, an oxygen atom or a sulfur atom. This gelatinous composition comprises the oligoamide-modified organopolysiloxane and the silicone oil or the nonpolar organic compound liquid. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a novel oligoamide-modified organopolysiloxane containing a specific amide group-containing organic group and capable of thickening and gelling silicone oil and nonpolar liquid organic compounds, and a method for producing the same. The present invention further relates to a gel composition comprising the oligoamide-modified organopolysiloxane and a silicone oil or a nonpolar liquid organic compound.

Silicone oil, particularly low viscosity silicone oil, is blended in many cosmetics because of its excellent progress, refreshing feeling, lubricity, water repellency and high safety. However, silicone oils generally have poor compatibility with other oils, and it has been difficult to prepare products with excellent stability. For example, even if a wax is blended in order to obtain a gel-like product based on a low-viscosity silicone oil, a product having excellent stability cannot be obtained, and the appearance is cloudy. Further, when cross-linked silicone is used, there is a drawback that the sticky feeling remains and the original refreshing feeling of the silicone oil is lost.
Patent Document 1 proposes a polyether-grafted polysiloxane as a gelling agent for silicone oil, but this gelling agent needs to be used in combination with an appropriate amount of water. For this reason, there has been a demand for a compound capable of gelling silicone oil without deteriorating the feel of silicone oil and without adding water.
In Patent Document 2 and Patent Document 3, an organopolysiloxane / polyamide block copolymer is proposed as a thickener. However, these publications do not describe a graft copolymer in which an amide group-containing organic group is graft-bonded to a siloxane chain. Further, the copolymer described in the publication has a silicon atom and an amide group (—CONH—) bonded by an alkylene group, and the silicon atom and the amide group are bonded through a nitrogen atom, an oxygen atom, or a sulfur atom. Copolymers are not described. Further, in this publication, organopolysiloxane / polyamide is synthesized by a method in which both ends SiH group-blocked dimethylpolysiloxane and undecylenic acid are reacted to synthesize both ends carboxyl group-blocked dimethylpolysiloxane and then this is amidated with an organic diamine. Manufactures block copolymers. However, this method has a drawback that a special reaction apparatus is required because a high temperature of 150 ° C. or higher is required for the amidation reaction.
JP 7-215817 A JP 2000-38450 A Special table 2001-512164 gazette

  The present invention contains a specific amide group-containing organic group in which a silicon atom and an amide group are bonded via a nitrogen atom, an oxygen atom or a sulfur atom, and thickens and gels silicone oil and nonpolar liquid organic compounds. It is an object of the present invention to provide a novel oligoamide-modified organopolysiloxane that can be used, a method for producing the same, and a gel composition comprising the oligoamide-modified organopolysiloxane and silicone oil or a nonpolar liquid organic compound.

一般式（２）：

［式中、R¹は脂肪族不飽和結合を含まない二価炭化水素基であり、R²は水素原子、一価炭化水素基またはアシル基であり、R⁴はメチル基または水素原子であり、R⁵は脂肪族不飽和結合を含まない一価炭化水素基、ジアルキルアミノアルキル基または水素原子である。Xは式：

（式中、R³は脂肪族不飽和結合を含まない一価炭化水素基または水素原子である。）から選択される基であり、Yは水素原子または一般式（３）：

（式中、R⁵は前記と同じである。）で示されるアミド基である。mは０または１であるが、mが１の場合にYは水素原子であり、mが０の場合にYは上記一般式（３）で示されるアミド基である。nは１〜100の整数である。］
また、本発明は、（ａ）ケイ素原子に結合した、
一般式：−R¹−Z、または、一般式：−R¹−NH−R¹−Z
［式中、R¹は前記と同じであり、Zは式：

（式中、R³は前記と同じである。）から選択される活性水素含有基である。］
で示される活性水素含有有機基を一分子中に少なくとも一個有するオルガノポリシロキサンと、
（ｂ）アルカリ金属、アルカリ金属水素化物、アルカリ土類金属、アルカリ土類金属水素化物、アルカリ金属もしくはアルカリ土類金属を含有する有機金属化合物から選択される金属または金属化合物を反応させて（ａ）成分中の活性水素をメタル化し、次いで、
（ｃ）一般式（４）：

（式中、R⁴およびR⁵は前記と同じである。）で示されるアクリルアミド化合物を重合させて、
（ｄ）有機酸、無機酸、ハロゲン化炭化水素、ハロゲン化アシルから選択される重合停止剤で反応を終了することを特徴とする上記オリゴアミド変性オルガノポリシロキサンの製造方法に関する。
さらに本発明は、（Ａ）ケイ素原子に結合した、上記一般式（１）または一般式（２）で示されるアミド基含有有機基を一分子中に少なくとも一個含有するオリゴアミド変性オルガノポリシロキサンと
（Ｂ）シリコーンオイルまたは非極性液体有機化合物
からなることを特徴とするゲル状組成物に関する。 The present invention relates to an oligoamide-modified organopolysiloxane characterized in that it contains at least one amide group-containing organic group represented by the following general formula (1) or general formula (2) bonded to a silicon atom in one molecule. .
General formula (1):

General formula (2):

[Wherein R ¹ is a divalent hydrocarbon group not containing an aliphatic unsaturated bond, R ² is a hydrogen atom, a monovalent hydrocarbon group or an acyl group, and R ⁴ is a methyl group or a hydrogen atom. , R ⁵ is a monovalent hydrocarbon group, dialkylaminoalkyl group or hydrogen atom that does not contain an aliphatic unsaturated bond. X is the formula:

(Wherein R ³ is a monovalent hydrocarbon group or a hydrogen atom that does not contain an aliphatic unsaturated bond), and Y is a hydrogen atom or the general formula (3):

(Wherein R ⁵ is the same as defined above). m is 0 or 1, but when m is 1, Y is a hydrogen atom, and when m is 0, Y is an amide group represented by the above general formula (3). n is an integer of 1-100. ]
Further, the present invention provides (a) bonded to a silicon atom,
General formula: -R ¹ -Z or General formula: -R ¹ -NH-R ¹ -Z
[Wherein R ¹ is as defined above, and Z is the formula:

(Wherein R ³ is the same as defined above) and is an active hydrogen-containing group. ]
An organopolysiloxane having at least one active hydrogen-containing organic group represented by
(B) reacting a metal selected from an alkali metal, an alkali metal hydride, an alkaline earth metal, an alkaline earth metal hydride, an alkali metal or an organic metal compound containing an alkaline earth metal or a metal compound (a ) Metallize active hydrogen in the component, then
(C) General formula (4):

(Wherein R ⁴ and R ⁵ are as defined above), and an acrylamide compound is polymerized,
(D) The present invention relates to a method for producing the above oligoamide-modified organopolysiloxane, characterized in that the reaction is terminated with a polymerization terminator selected from organic acids, inorganic acids, halogenated hydrocarbons, and acyl halides.
Furthermore, the present invention relates to (A) an oligoamide-modified organopolysiloxane containing at least one amide group-containing organic group represented by the above general formula (1) or general formula (2) bonded to a silicon atom in one molecule ( B) The present invention relates to a gel composition comprising a silicone oil or a nonpolar liquid organic compound.

  The oligoamide-modified organopolysiloxane of the present invention is characterized in that it can thicken and gel silicone oil and nonpolar liquid organic compounds without using water together. Further, the method for producing an oligoamide-modified organopolysiloxane of the present invention is characterized in that it can be produced with good productivity under mild conditions. The gel-like product of the present invention is excellent in storage stability and can be blended in various industrial products, pharmaceuticals, cosmetics, health care products, and house hold care products.

から選択される基である。R³は脂肪族不飽和結合を含まない一価炭化水素基または水素原子であり、一価炭化水素基としては上記R⁵で例示した基が挙げられる。これらの中でも、−NH−基が好ましい。Yは水素原子または一般式（３）：

（R⁵は前記と同じである。）で示されるアミド基である。mは０または１である。なお、mが０の場合は、本発明の製法で使用される（ｃ）アクリルアミド化合物中の炭素−炭素二重結合がそのまま重合してポリアクリルアミドが生成した場合であるので、Yは上記一般式（３）で示されるアミド基である。一方、mが１の場合は、（ｃ）アクリルアミド化合物の異性化重合が進行した場合であるので、Yは水素原子である。（ｃ）アクリルアミド化合物中の2個のR⁵のうち1個以上が水素原子の場合には、一般に、上記した二種類の重合反応が進行して、１分子中に、ｍ＝０のアミド基含有有機基とｍ＝１のアミド基含有有機基が混在することがある。nは１〜100の整数であり、１〜30が好ましく、１〜10がより好ましい。このような上記一般式（１）または一般式（２）で示されるアミド基含有有機基として具体的には、次式で示される有機基が挙げられる。下式中、n¹及びn²は０または正の整数であり、n¹＋n²＝nである。

このようなアミド基含有有機基の結合位置は、主鎖となるシロキサン骨格の側鎖でも末端でもよく、その両方でもよい。また本発明オルガノポリシロキサン中、上記アミド基含有有機基の含有率は０．０１〜２０重量％であることが好ましく、０．１〜１０重量％であることがより好ましい。 The oligoamide-modified organopolysiloxane of the present invention contains at least one amide group-containing organic group represented by the above general formula (1) or general formula (2) bonded to a silicon atom in one molecule. . In the above formula, R ¹ is a divalent hydrocarbon group that does not contain an aliphatic unsaturated bond, and is an alkylene group such as a methylene group, an ethylene group, a propylene group, a methylethylene group, a butylene group, or a hexylene group; An arylene group is illustrated. Among these, an alkylene group is preferable, and an alkylene group having 10 or less carbon atoms is more preferable. R ² is a hydrogen atom, a monovalent hydrocarbon group or an acyl group. Examples of the monovalent hydrocarbon group include alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tertiary butyl group. Groups; aryl groups such as phenyl, tolyl and xylyl; aralkyl groups such as phenethyl and the like; alkenyl groups such as vinyl, allyl and methallyl. Examples of the acyl group include an acetyl group, a propionyl group, a methacryloyl group, and a benzoyl group. Among these, a hydrogen atom is preferable. R ⁴ is a methyl group or a hydrogen atom, preferably a hydrogen atom. R ⁵ is a monovalent hydrocarbon group not containing an aliphatic unsaturated bond, a dialkylaminoalkyl group or a hydrogen atom, and the monovalent hydrocarbon group not containing an aliphatic unsaturated bond is a methyl group, an ethyl group or a propyl group. And alkyl groups such as isopropyl group, butyl group, isobutyl group and tertiary butyl group; aryl groups such as phenyl group, tolyl group and xylyl group; and aralkyl groups such as phenethyl group. Examples of the dialkylaminoalkyl group include a dimethylaminoethyl group, a diethylaminoethyl group, and a diisopropylaminoethyl group. Among these, a hydrogen atom is preferable. X is the formula:

Is a group selected from R ³ is a monovalent hydrocarbon group or a hydrogen atom that does not contain an aliphatic unsaturated bond, and examples of the monovalent hydrocarbon group include the groups exemplified above for R ⁵ . Among these, -NH- group is preferable. Y is a hydrogen atom or general formula (3):

(R ⁵ is the same as above). m is 0 or 1. In addition, when m is 0, since (c) the carbon-carbon double bond in the acrylamide compound used in the production method of the present invention is polymerized as it is to produce polyacrylamide, Y represents the above general formula. It is an amide group represented by (3). On the other hand, when m is 1, Y is a hydrogen atom since (c) isomerization polymerization of an acrylamide compound has proceeded. (C) When one or more of the two R ^{5 in} the acrylamide compound is a hydrogen atom, in general, the above-described two kinds of polymerization reactions proceed, and m = 0 amide group in one molecule The containing organic group and the amide group-containing organic group of m = 1 may be mixed. n is an integer of 1 to 100, preferably 1 to 30, and more preferably 1 to 10. Specific examples of the amide group-containing organic group represented by the general formula (1) or the general formula (2) include organic groups represented by the following formula. In the following formula, n ¹ and n ² are 0 or a positive integer, and n ¹ + n ² = n.

The bonding position of such an amide group-containing organic group may be a side chain or a terminal of the siloxane skeleton as the main chain, or both. In the organopolysiloxane of the present invention, the content of the amide group-containing organic group is preferably 0.01 to 20% by weight, and more preferably 0.1 to 10% by weight.

で表されるジオルガノポリシロキサンが挙げられる。上式中、Ｒは炭素原子数1〜8の非置換もしくは置換の一価炭化水素基または有機官能性基である。一価炭化水素基としては、メチル基、エチル基、プロピル基等のアルキル基；フェニル基、トリル基、キシリル基等のアリール基；アラルキル基が例示される。有機官能性基としては、アミノプロピル基、アミノエチルアミノプロピル基等のアミノ基含有有機基；メトキシ基、エトキシ基、プロポキシ基等のアルコキシ基；メルカプトプロピル基等のメルカプト基含有有機基；ヒドロキシプロピル基等の水酸基含有有機基；アセチルアミノアルキル基が例示される。これらの中でもアルキル基、とりわけメチル基が一般的であるが、その一部が有機官能性基で置換されていてもよい。AはＲまたは上記一般式（１）もしくは一般式（２）で示されるアミド基含有有機基であり、Ａの少なくとも一個は該アミド基含有有機基である。ｘは５〜１００００の整数であり、１０〜５０００が好ましい。ｙは０〜５０の整数であり、１〜３０が好ましい。なお、上記アミド基含有有機基がシロキサン側鎖にグラフト結合している場合には、ｙ／(ｘ＋ｙ)が０．１〜１０モル％であることが好ましく、０．５〜７モル％がより好ましい。 The molecular structure of the siloxane skeleton constituting the main chain of the organopolysiloxane of the present invention may be cyclic, linear, partially branched linear, or branched, with linear being preferred. The weight average molecular weight of the organopolysiloxane of the present invention is preferably in the range of 5,000 to 1,000,000, and more preferably in the range of 10,000 to 500,000. The property at 25 ° C. is usually a slightly turbid to cloudy viscous liquid or a pasty solid. Specifically, such an organopolysiloxane of the present invention has the general formula (5):

The diorganopolysiloxane represented by these is mentioned. In the above formula, R is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 8 carbon atoms or an organic functional group. Examples of the monovalent hydrocarbon group include alkyl groups such as methyl group, ethyl group, and propyl group; aryl groups such as phenyl group, tolyl group, and xylyl group; and aralkyl groups. Examples of the organic functional group include amino group-containing organic groups such as aminopropyl group and aminoethylaminopropyl group; alkoxy groups such as methoxy group, ethoxy group and propoxy group; mercapto group-containing organic groups such as mercaptopropyl group; A hydroxyl group-containing organic group such as a group; and an acetylaminoalkyl group. Among these, an alkyl group, particularly a methyl group, is common, but a part thereof may be substituted with an organic functional group. A is R or an amide group-containing organic group represented by the general formula (1) or (2), and at least one of A is the amide group-containing organic group. x is an integer of 5 to 10,000, preferably 10 to 5,000. y is an integer of 0-50, and 1-30 are preferable. When the amide group-containing organic group is grafted to the siloxane side chain, y / (x + y) is preferably 0.1 to 10 mol%, more preferably 0.5 to 7 mol%. preferable.

（R³は前記と同じである。）から選択される活性水素含有基である。］で示される活性水素含有有機基を一分子中に少なくとも一個有するオルガノポリシロキサンと、
（ｂ）アルカリ金属、アルカリ金属水素化物、アルカリ土類金属、アルカリ土類金属水素化物、アルカリ金属もしくはアルカリ土類金属を含有する有機金属化合物から選択される金属または金属化合物を反応させて（ａ）成分中の活性水素をメタル化し、次いで、
（ｃ）一般式（４）：

（R⁴およびR⁵は前記と同じである。）で示されるアクリルアミド化合物を重合させて、
（ｄ）有機酸、無機酸、ハロゲン化炭化水素、ハロゲン化アシルから選択される重合停止剤で反応を終了する方法により製造することができる。 Such oligoamide-modified organopolysiloxane of the present invention is, for example,
(A) General formula: —R ¹ —Z or general formula: —R ¹ —NH—R ¹ —Z bonded to a silicon atom [wherein R ¹ is the same as defined above, and Z is a formula:

(Wherein R ³ is the same as defined above). An organopolysiloxane having at least one active hydrogen-containing organic group represented by the formula:
(B) reacting a metal selected from an alkali metal, an alkali metal hydride, an alkaline earth metal, an alkaline earth metal hydride, an alkali metal or an organic metal compound containing an alkaline earth metal or a metal compound (a ) Metallize active hydrogen in the component, then
(C) General formula (4):

(R ⁴ and R ⁵ are the same as described above)
(D) It can be produced by a method in which the reaction is terminated with a polymerization terminator selected from organic acids, inorganic acids, halogenated hydrocarbons, and acyl halides.

  Examples of the active hydrogen-containing organic group in component (a) include an aminopropyl group, a methylaminopropyl group, an aminoethyliminopropyl group, a mercaptopropyl group, and a hydroxypropyl group. Examples of the molecular structure of the organopolysiloxane include linear, cyclic and branched structures, with the linear structure being preferred. In particular, a linear organopolysiloxane having an amino group-containing organic group such as an aminopropyl group, a methylaminopropyl group, or an aminoethyliminopropyl group is preferred.

  The component (b) reacts with Z in the component (a), that is, an active hydrogen-containing group, to cause a metalation reaction, thereby producing a metalated organopolysiloxane in which the active hydrogen is substituted with the metal in the component (b). Specific examples of the component (b) include alkali metals such as lithium, sodium and potassium; alkaline earth metals such as magnesium and calcium; alkali metal hydrides such as lithium hydride, sodium hydride and potassium hydride; hydrogenation Examples include alkaline earth metal hydrides such as magnesium and calcium hydride; and organometallic compounds containing alkali metals or alkaline earth metals such as methyllithium, butyllithium, phenyllithium, and grinder reagents. Of these, organometallic compounds are preferred, and organolithium compounds are more preferred. Component (b) is preferably used in such an amount that it is completely consumed in the reaction with component (a) and no unreacted material remains. This is because if the component (b) remains during the polymerization of the component (c), the polymerization of the components (c) proceeds and the amount of the homopolymer of the component (c) increases.

  The component (c) is anionically polymerized using a metallated organopolysiloxane obtained by the reaction of the components (a) and (b) as an initiator. Specifically, acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-methylmethacrylamide, N, N-dimethylmethacrylamide, N- (dimethylamino) ethylacrylamide, N- (dimethylamino) ) Ethyl methacrylamide, bis-N, N- (dimethylamino) ethyl acrylamide, bis-N, N- (dimethylamino) ethyl methacrylamide are exemplified. There is no restriction | limiting in particular in the usage-amount of (c) component. However, if used in a large amount, the amount of homopolymer of component (c) increases due to chain transfer reaction, so it must be 100 moles or less per mole of active hydrogen in the organopolysiloxane used for component (a). Is preferred.

  The component (d) stops anionic polymerization by reacting with the anionic polymerization growth terminal. That is, when an organic acid or an inorganic acid is used, the polymerization is stopped in a form in which the growing anion reacts with the proton. When halogenated hydrocarbons are used, the polymerization stops when the growing anion reacts with the cation of the residue excluding the halogen ions. When acyl halides are used, the growing anion reacts with the acyl cation. In this way, the polymerization stops. Specific examples of the component (d) include organic acids such as acetic acid, propionic acid and acrylic acid; inorganic acids such as hydrochloric acid, carbonic acid and phosphoric acid; halogenated carbonization such as allyl chloride, allyl bromide and benzyl chloride. Hydrogen; acyl halides such as acetyl chloride and benzoyl chloride are exemplified. Of these, organic acids are preferred.

  The reaction between the component (a) and the component (b) is preferably performed at a temperature of 30 ° C. or lower in order to suppress a side reaction that causes the component (b) to cleave the siloxane bond in the component (a). The polymerization reaction of the metallated organopolysiloxane obtained by the reaction between the component (a) and the component (b) and the component (c) is preferably performed at a temperature of 0 to 150 ° C. for 50 to 1 hour. The reaction proceeds at 100 ° C or lower. Moreover, it is preferable to use a solvent in order to perform a polymerization reaction smoothly. Solvents that can be used are aprotic solvents such as aromatics such as toluene and xylene; aliphatics such as hexane and heptane; ethers such as tetrahydrofuran and diethyl ether. In order to completely stop the polymerization after completion of the polymerization reaction, it is necessary to add the component (d) having a neutralization equivalent or more. This reaction is an acid-base reaction and normally proceeds smoothly even at a temperature below room temperature, and the polymerization is stopped almost instantaneously. Further, with the termination of polymerization, a salt by neutralization reaction and a homopolymer of component (c) by chain transfer reaction are by-produced. If the reaction solution becomes extremely thick after the polymerization is stopped, add the minimum amount of alcohol such as methanol or ethanol to lower the viscosity of the reaction solution, and filter off the neutralized salt and the homopolymer of component (c). To do. The oligoamide-modified organopolysiloxane of the present invention can be obtained from the filtrate by distilling off low-boiling substances under reduced pressure while heating.

  Such an oligoamide-modified organopolysiloxane of the present invention is a novel organopolysiloxane having a specific amide group-containing organic group in which a silicon atom and an amide group are bonded via a nitrogen atom, an oxygen atom or a sulfur atom, It is useful as a gelling agent for silicone oils, particularly hydrophobic silicone oils and nonpolar liquid organic compounds. In particular, the organopolysiloxane of the present invention is suitable as a gelling agent for decamethylcyclopentasiloxane. It is not necessary to use water at the time of gelation. Further, the production method of the present invention does not have an amidation reaction step performed at a high temperature, and the reaction proceeds under mild conditions of 100 ° C. or less. For this reason, it has the characteristic that it can manufacture with sufficient productivity, without utilizing a special reaction apparatus.

The gel composition of the present invention comprises the oligoamide-modified organopolysiloxane (A) and (B) silicone oil or a nonpolar liquid organic compound. (B) As a silicone oil of a component, hydrophobic silicone oils other than the said (A) component are mentioned. Specifically, a hydrophobic silicone oil having a viscosity at 25 ° C. of 0.65 to 100,000 mm ² / s is preferable, and examples thereof include cyclic, linear, and branched organopolysiloxanes. Specifically, cyclic diorganopolysiloxanes such as octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane; hexamethyldisiloxane, trimethylsiloxy group-blocked dimethylpolysiloxane at both ends, trimethylsiloxy group-blocked methylphenylpolysiloxane at both ends, Examples include linear diorganopolysiloxanes such as trimethylsiloxy group-blocked methylalkylpolysiloxanes at both ends. Among these, cyclic dimethylpolysiloxane is preferable, and decamethylcyclopentasiloxane is more preferable. Nonpolar liquid organic compounds include liquid paraffin, petrolatum, n-paraffin, isoparaffin, ozokerite, ceresin, microcrystalline wax, squalane, pristane, and other hydrocarbon oils; avocado oil, almond oil, olive oil, sesame oil, sasanqua oil, Vegetable oils such as safflower oil, soybean oil, camellia oil, corn oil, rapeseed oil, persic oil, castor oil, cottonseed oil, peanut oil, cocoa butter, palm oil, palm kernel oil, owl, palm oil, etc .; mink oil Animal oils such as egg yolk oil, beef tallow, pork fat, hardened oil; waxes such as beeswax, carnauba wax, whale wax, lanolin, liquid lanolin, reduced lanolin, hard lanolin, candelilla wax, jojoba oil; palmityl alcohol, stearyl Alcohol, oleyl alcohol, lanolin alcohol, Higher alcohols such as lesterol, phytosterol, 2-hexyldecanol, isostearyl alcohol, 2-octyldodecanol; cetyl octoate, isopropyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, oleyl oleate , Decyl oleate, octyldodecyl myristate, hexyl decyl dimethyloctanoate, cetyl lactate, myristyl lactate, diethyl phthalate, dibutyl phthalate, lanolin acetate, ethylene glycol monostearate, propylene glycol monostearate, propylene glycol dioleate, Glyceryl monostearate, glyceryl monooleate, glyceryl tri-2-ethylhexanoate, tri-2-ethylhexanoic acid tri Ester oils such as Chi trimethylolpropane; liquid fatty acid triglyceride, and the like artificial sebum (mixture of squalane and liquid fatty acid triglyceride and oleic acid). (B) A component may use these compounds individually by 1 type, and may use 2 or more types of mixtures. (B) The viscosity in 25 degreeC of a component is the range of 0.65-100000 mm < ² > / s normally, and the range of 5-10000 mm < ² > / s is preferable. The ratio of the component (A) to the component (B) is in the range of (A) :( B) = 1 to 99:99 to 1% by weight, but preferably in the range of 1 to 30:99 to 70% by weight. The gel composition of the present invention is in a gel form at 25 ° C., and gelation performance varies depending on the chemical structure of the component (A). However, the gel composition is generally liquid at high temperatures of 50 ° C. or higher. If the composition of the present invention is not liquefied at 25 ° C., the composition of the present invention is polar liquid such as water, alcohols such as ethanol, ethylene glycol and glycerin, phenols, amines and carboxylic acids. An organic compound may be added and blended.

  Hereinafter, the present invention will be described in detail by way of examples.

で示される両末端アミノプロピル基封鎖ジメチルポリシロキサン７グラム（NH₂基：3．18ミリモル）にトルエン７グラムを混合した後、共沸脱水を行って反応系中の水分を除いた。次いでこれを10℃まで冷却して、氷水冷しながら3．18ミリモルのn−ブチルリチウムを15℃以下で滴下した。滴下終了後、室温で0.5時間攪拌して、上記ジメチルポリシロキサン中のアミノプロピル基が、式：−（ＣＨ_２）_３−ＮＨＬｉで示される基に変化したメタル化ジメチルポリシロキサンを得た。次いで、式：

で示されるアクリルアミド1．13グラム(15．9ミリモル)を投入して90℃で４時間攪拌したところ、反応溶液が乳白色になった。これを冷却して0．29グラム(4．8ミリモル)の酢酸を投入すると、反応溶液は著しく増粘した。４グラムのエタノールを添加したところ低粘度化して白色沈殿が析出したため、滅菌ろ過して無色透明な濾液を得た。得られた濾液中の低沸点物を加熱減圧留去したところ、白濁した粘稠な液体6．6グラムが得られた。赤外吸光分析、核磁気共鳴分析の結果、この液体は、平均構造式：

［式中、Ｂは、式：

または、式：

（n¹、n²は０または正の整数であり、０＜n¹＋n²≦５である。）で示されるアミド基含有有機基である。］で表される、アミド基含有有機基がシロキサン鎖両末端に結合した直鎖状のオリゴアミド変性ジメチルポリシロキサンであることが判明した。
このようにして得られたオリゴアミド変性ジメチルポリシロキサンにデカメチルシクロペンタシロキサンを混合して加熱し、上記オリゴアミド変性ジメチルポリシロキサン濃度が15重量％の溶液を調製した。この溶液を室温まで冷却したところ、微濁したゲルが得られた。このゲルは室温で６ヶ月経過後も分離することなくゲル性状を維持しており、安定性が良好であった。 [Example 1]
Average structural formula:

7 grams (NH ₂ group: 3.18 mmol) of both-end aminopropyl group-blocked dimethylpolysiloxane represented by the formula ( ₂ ) was mixed with toluene, and azeotropic dehydration was performed to remove water in the reaction system. Next, this was cooled to 10 ° C., and 3.18 mmol of n-butyllithium was added dropwise at 15 ° C. or lower while cooling with ice water. After completion of the dropwise addition, the mixture was stirred at room temperature for 0.5 hour to obtain a metalated dimethylpolysiloxane in which the aminopropyl group in the dimethylpolysiloxane was changed to a group represented by the formula: — (CH ₂ ) ₃ —NHLi. Then the formula:

When 1.13 g (15.9 mmol) of acrylamide represented by the formula (1) was added and stirred at 90 ° C. for 4 hours, the reaction solution became milky white. When this was cooled and 0.29 grams (4.8 mmol) of acetic acid was added, the reaction solution thickened significantly. When 4 grams of ethanol was added, the viscosity was reduced and a white precipitate was precipitated, and sterilized filtration gave a colorless and transparent filtrate. When low boiling point substances in the obtained filtrate were distilled off under reduced pressure under heating, 6.6 g of a cloudy viscous liquid was obtained. As a result of infrared absorption analysis and nuclear magnetic resonance analysis, this liquid has an average structural formula:

[Wherein B is the formula:

Or the formula:

(N ¹ and n ² are 0 or a positive integer, and 0 <n ¹ + n ² ≦ 5). It was found that the amide group-containing organic group represented by the formula is a linear oligoamide-modified dimethylpolysiloxane having both ends of the siloxane chain bonded.
The oligoamide-modified dimethylpolysiloxane thus obtained was mixed with decamethylcyclopentasiloxane and heated to prepare a solution having an oligoamide-modified dimethylpolysiloxane concentration of 15% by weight. When this solution was cooled to room temperature, a slightly turbid gel was obtained. This gel maintained its gel properties without separation even after 6 months at room temperature, and had good stability.

で示されるジメチルシロキサン・メチル(3−アミノプロピル)シロキサンコポリマー9．4グラム（NH₂基：4．75ミリモル）にトルエン16グラムを混合した後、共沸脱水を行って反応系中の水分を除いた。次いでこれを14℃まで冷却して、氷水冷しながら4．75ミリモルのn−ブチルリチウムを18℃以下で滴下した。滴下終了後、室温で0．5時間攪拌して、上記コポリマー中の3−アミノプロピル基が式：−（ＣＨ_２）_３−ＮＨＬｉで示される基に変化したメタル化オルガノポリシロキサンを得た。次いで、式：

で示されるアクリルアミド1．35グラム(19ミリモル)を投入して90〜95℃で４時間攪拌したところ、反応溶液が乳白色になった。これを冷却して0．34グラム(5．7ミリモル)の酢酸を投入すると、反応溶液は著しく増粘した。４グラムのエタノールを添加したところ低粘度化して白色沈殿が析出したため、滅菌ろ過して無色透明な濾液を得た。得られた濾液中の低沸点物を加熱減圧留去したところ、白濁したペースト8．8グラムが得られた。赤外吸光分析、核磁気共鳴分析の結果、このペーストは、平均構造式：

［式中、Ｄは、式：

または、式：

（n¹、n²は０または正の整数であり、０＜n¹+n²≦４である。）で示されるアミド基含有有機基である。］で表される、アミド基含有有機基がシロキサン側鎖にグラフト結合してなる直鎖状のオリゴアミド変性オルガノポリシロキサンであることが判明した。
このようにして得られたオリゴアミド変性オルガノポリシロキサンにデカメチルシクロペンタシロキサンを混合して加熱し、上記オリゴアミド変性オルガノポリシロキサン濃度が5重量％の溶液を調製した。この溶液を室温まで冷却したところ、ほぼ透明なゲルが得られた。このゲルは室温で６ヶ月経過後も分離することなくゲル性状を維持しており、安定性が良好であった。
また、上記で得られたオリゴアミド変性オルガノポリシロキサンに、25℃における粘度が5ｍｍ^２／ｓの両末端トリメチルシロキシ基封鎖ポリジメチルシロキサンを混合して加熱し、上記オリゴアミド変性オルガノポリシロキサン濃度が5重量％の溶液を調製した。この溶液を室温まで冷却したところ、ほぼ透明なゲルが得られた。このゲルは室温で６ヶ月経過後も分離することなくゲル性状を維持しており、安定性が良好であった。 [Example 2]
Average structural formula:

After mixing 9.4 grams (NH ₂ groups: 4.75 mmol) of dimethylsiloxane / methyl (3-aminopropyl) siloxane copolymer represented by formula (16) with toluene, azeotropic dehydration was performed to remove moisture in the reaction system. Excluded. Next, this was cooled to 14 ° C., and 4.75 mmol of n-butyllithium was added dropwise at 18 ° C. or lower while cooling with ice water. After completion of the dropwise addition, the mixture was stirred at room temperature for 0.5 hours to obtain a metalated organopolysiloxane in which the 3-aminopropyl group in the copolymer was changed to a group represented by the formula: — (CH ₂ ) ₃ —NHLi. Then the formula:

When 1.35 g (19 mmol) of acrylamide represented by the formula (1) was added and stirred at 90 to 95 ° C. for 4 hours, the reaction solution became milky white. When this was cooled and 0.34 grams (5.7 mmol) of acetic acid was added, the reaction solution thickened significantly. When 4 grams of ethanol was added, the viscosity was reduced and a white precipitate was precipitated, and sterilized filtration gave a colorless and transparent filtrate. When low boiling point substances in the obtained filtrate were distilled off under reduced pressure under heating, 8.8 g of a cloudy paste was obtained. As a result of infrared absorption analysis and nuclear magnetic resonance analysis, this paste has an average structural formula:

[Wherein D is the formula:

Or the formula:

(N ¹ and n ² are 0 or a positive integer, and 0 <n ¹ + n ² ≦ 4). The amide group-containing organic group represented by the following formula was found to be a linear oligoamide-modified organopolysiloxane formed by graft bonding to the siloxane side chain.
The oligoamide-modified organopolysiloxane thus obtained was mixed with decamethylcyclopentasiloxane and heated to prepare a solution having the oligoamide-modified organopolysiloxane concentration of 5% by weight. When this solution was cooled to room temperature, an almost transparent gel was obtained. This gel maintained its gel properties without separation even after 6 months at room temperature, and had good stability.
In addition, the oligoamide-modified organopolysiloxane obtained above was mixed with a tridimethylsiloxy group-blocked polydimethylsiloxane having a viscosity of 5 mm ² / s at 25 ° C. and heated so that the oligoamide-modified organopolysiloxane concentration was 5 wt. % Solution was prepared. When this solution was cooled to room temperature, an almost transparent gel was obtained. This gel maintained its gel properties without separation even after 6 months at room temperature, and had good stability.

  Since the oligoamide-modified organopolysiloxane of the present invention can thicken and gel silicone oil and nonpolar liquid organic compounds without using water together, it improves the stability, feel and feel of products using these. Has the advantage. In addition, the gel composition of the present invention has excellent storage stability, and improves the feel, feel and stability when blended into various industrial products such as liquid and paste, pharmaceuticals, cosmetics, health care products, and household care products. Let It can also be used as car wax, surface treatment agent, mold release agent, lubricant, resin additive and the like.

2 is an infrared absorption spectrum of the oligoamide-modified dimethylpolysiloxane obtained in Example 1. 2 is an infrared absorption spectrum of the oligoamide-modified organopolysiloxane obtained in Example 2.

Claims (8)

An oligoamide-modified organopolysiloxane containing at least one amide group-containing organic group represented by the following general formula (1) or general formula (2) bonded to a silicon atom in one molecule.
General formula (1):

General formula (2):

[Wherein R ¹ is a divalent hydrocarbon group not containing an aliphatic unsaturated bond, R ² is a hydrogen atom, a monovalent hydrocarbon group or an acyl group, and R ⁴ is a methyl group or a hydrogen atom. , R ⁵ is a monovalent hydrocarbon group, dialkylaminoalkyl group or hydrogen atom that does not contain an aliphatic unsaturated bond. X is the formula:

(Wherein R ³ is a monovalent hydrocarbon group or a hydrogen atom that does not contain an aliphatic unsaturated bond), and Y is a hydrogen atom or the general formula (3):

(Wherein R ⁵ is the same as defined above). m is 0 or 1, but when m is 1, Y is a hydrogen atom, and when m is 0, Y is an amide group represented by the above general formula (3). n is an integer of 1-100. ] The oligoamide-modified organopolysiloxane according to claim 1, wherein the amide group-containing organic group represented by the general formula (1) or the general formula (2) is grafted to the siloxane chain. The oligoamide-modified organopolysiloxane according to claim 1, wherein the amide group-containing organic group represented by the general formula (1) or the general formula (2) is bonded to a siloxane chain end. The oligoamide modification | denaturation of any one of Claims 1-3 whose content rate of the amide group containing organic group shown by General formula (1) or General formula (2) is 0.01 to 20 weight%. Organopolysiloxane. The oligoamide-modified organopolysiloxane according to any one of claims 1 to 4, which is a gelling agent for silicone oil or a nonpolar liquid organic compound. (A) bonded to a silicon atom;
General formula: -R ¹ -Z or General formula: -R ¹ -NH-R ¹ -Z
[Wherein R ¹ is as defined above, and Z is the formula:

(Wherein R ³ is the same as defined above) and is an active hydrogen-containing group. ]
An organopolysiloxane having at least one active hydrogen-containing organic group represented by
(B) reacting a metal selected from an alkali metal, an alkali metal hydride, an alkaline earth metal, an alkaline earth metal hydride, an alkali metal or an organic metal compound containing an alkaline earth metal or a metal compound (a ) Metallize active hydrogen in the component, then
(C) General formula (4):

(Wherein R ⁴ and R ⁵ are as defined above), and an acrylamide compound is polymerized,
(D) The method for producing an oligoamide-modified organopolysiloxane according to claim 1, wherein the reaction is terminated with a polymerization terminator selected from organic acids, inorganic acids, halogenated hydrocarbons, and acyl halides. (A) an oligoamide-modified organopolysiloxane containing at least one amide group-containing organic group represented by the following general formula (1) or general formula (2) bonded to a silicon atom in one molecule;
General formula (1):

General formula (2):

[Wherein R ¹ is a divalent hydrocarbon group not containing an aliphatic unsaturated bond, R ² is a hydrogen atom, a monovalent hydrocarbon group or an acyl group, and R ⁴ is a methyl group or a hydrogen atom. , R ⁵ is a monovalent hydrocarbon group, dialkylaminoalkyl group or hydrogen atom that does not contain an aliphatic unsaturated bond. X is the formula:

(Wherein R ³ is a monovalent hydrocarbon group or a hydrogen atom that does not contain an aliphatic unsaturated bond), and Y is a hydrogen atom or the general formula (3):

(Wherein R ⁵ is the same as defined above). m is 0 or 1, but when m is 1, Y is a hydrogen atom, and when m is 0, Y is an amide group represented by the above general formula (3). n is an integer of 1-100. ]
And (B) a gel composition comprising silicone oil or a nonpolar liquid organic compound. The gel composition according to claim 7, wherein the silicone oil as component (B) is a hydrophobic silicone oil.

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