JP2014152321A - Organic functional group-containing polyether modified alkoxy siloxane, and production method thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide organosiloxane that contains an organic functional group, a polyether group, and an alkoxy group in one molecule, and enables free adjustment of the numbers of the groups to thereby improve compatibility of the organosiloxane and the organic resin and also allow control of affinity with an inorganic substrate surface.SOLUTION: There is provided organosiloxane represented by average composition formula (1) and containing an organic functional group, a polyether group and an alkoxy group, in one molecule. In the average composition formula (1), Y is an organic group containing at least one kind selected from a mercapto group, an epoxy group, a (meth)acryloxy group, an alkenyl group and an amino group, Z is an organic group containing a polyether group, Ris a monovalent hydrocarbon group containing no aliphatic unsaturated bond, Ris an alkyl group, a, b, c, d and e are numbers satisfying 0.01≤a<1, 0.01≤b<1, 0≤c<1, 0.1≤d≤2, 0≤e≤1 as well as 0.1≤d+e≤2 and 1<a+b+c+d+e≤3.

Description

  The present invention relates to resin curing agents, resin modifiers, paint modifiers, adhesion modifiers, fiber surface treatment agents, inorganic materials (inorganic pigments for paints, inorganic fillers for plastics, inorganic powders for cosmetics) The present invention relates to an organic functional group-containing polyether-modified alkoxysiloxane that is suitably used as a surface treating agent for glass, concrete, etc., and a method for producing the same. Furthermore, this invention relates to the resin composition containing this alkoxysiloxane.

  Silicone oligomer type coupling agents containing an organic functional group such as epoxy group, mercapto group, (meth) acryloxy group, alkenyl group, haloalkyl group, amino group and alkoxysilyl group in one molecule are paints, coating agents, It is a useful material for applications such as resin modification.

  For example, when an organic resin having reactivity with the organic functional group of the coupling agent is reacted with the coupling agent, an alkoxysilyl group is introduced into the organic resin. As a result, the organic resin is modified, and adhesion and adhesiveness with the inorganic base material are greatly improved (Patent Documents 1 to 3: Japanese Patent Laid-Open Nos. 09-040908, 09-040911, and Japanese Patent Laid-Open No. 09). -111188).

  In recent years, silicone oligomer type coupling agents in which an organic functional group such as an epoxy group, a carboxy group, a hydroxyl group, an amino group, a polyether group, and an alkoxysilyl group are co-modified on the side chain of silicone oil have been developed. It has been reported and applied to applications such as adhesives, primers, and adhesives. By introducing a polyether group into the molecule of the coupling agent, it becomes possible to improve the compatibility between the coupling agent and the organic resin, and to improve the adhesion between the organic resin and the inorganic base material. In this material, addition of a polyether group is performed by reacting a Si-H group-containing organosiloxane with a polyether compound containing a reactive double bond under a platinum catalyst (Patent Documents 4 and 5). : JP 05-043696 A, JP 07-331206 A).

  However, this reaction has a problem that when a plurality of polyether groups are introduced into one siloxane molecule, the reactivity decreases as the amount of introduction increases, the reaction is not completed, and unreacted polyether remains. is there. In addition, since a platinum catalyst is used, coloring due to the catalyst occurs, and there is a problem that it cannot be used depending on the application. Furthermore, in the presence of an organic functional group that is an additive poison such as a mercapto group, the reactivity between the polyether compound containing a reactive double bond and a Si—H group under a platinum catalyst is reduced, and the polyether Introduction of the group becomes difficult. That is, this method has a problem that co-modification with a polyether cannot be performed depending on the organic functional group to be selected.

JP 09-040908 A JP 09-040911 A Japanese Patent Laid-Open No. 09-111188 Japanese Patent Laid-Open No. 05-043696 JP 07-331206 A

  The present invention has been made in view of the above circumstances, and includes a novel organic functional group-containing polyether-modified alkoxysiloxane having reduced unreacted polyether residue and coloring caused by a platinum catalyst, a method for producing the same, and the alkoxysiloxane. It aims at providing the resin composition to contain.

  As a result of intensive studies to achieve the above object, the present inventor is obtained by partial cohydrolysis and polycondensation of an alkoxysilane containing an organic functional group and an alkoxysilane containing a polyether group. The present inventors have found that the above problems can be solved by an organic functional group-containing polyether-modified alkoxysiloxane, and have completed the present invention.

（式中、Ｙは、メルカプト基、エポキシ基、（メタ）アクリロキシ基、アルケニル基及びアミノ基から選ばれる少なくとも１種を含有する有機基を示す。Ｚは、ポリエーテル基を含有する有機基を示す。Ｒ¹は、脂肪族不飽和結合を有さない置換又は非置換の炭素原子数１〜８の一価炭化水素基を示す。Ｒ²は、炭素原子数１〜４のアルキル基を示す。ａ、ｂ、ｃ、ｄ、ｅは、０．０１≦ａ＜１、０．０１≦ｂ＜１、０≦ｃ＜１、０．１≦ｄ≦２、０≦ｅ≦１であって、かつ０．１≦ｄ＋ｅ≦２及び１＜ａ＋ｂ＋ｃ＋ｄ＋ｅ≦３を満たす数を示す。）
なお、前記平均組成式（１）におけるＹが、メルカプト基を含有する有機基であることが好ましい。
また、前記平均組成式（１）におけるＺが、下記式（２）で表されるポリエーテル基を含有する有機基であることが好ましい。

（式中、Ｒ³は、炭素原子数１〜１０の二価炭化水素基を示す。Ｒ⁴は、炭素原子数２〜１０の二価炭化水素基を示す。Ｒ⁵は、水素原子、炭素原子数１〜６の一価炭化水素基、又は下記式（３）で表される有機基を示す。Ｒ⁶は、水素原子又はヒドロキシ基を示す。ｆ、ｇは、０又は１の整数を示す。ｈ、ｉは、０以上の整数を示す。ただし、ｈ、ｉの少なくとも１つは、１以上の整数である。）

（式中、Ｒ⁷は、炭素原子数１〜４の一価炭化水素基を示す。）
また、前記式（２）で表されるポリエーテル基を含有する有機基において、ｇ＝１であることが好ましい。 That is, the present invention provides an organosiloxane which is represented by the following average composition formula (1) and contains an organic functional group, a polyether group and an alkoxy group in one molecule.

(In the formula, Y represents an organic group containing at least one selected from a mercapto group, an epoxy group, a (meth) acryloxy group, an alkenyl group and an amino group. Z represents an organic group containing a polyether group. R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms which does not have an aliphatic unsaturated bond, and R ² represents an alkyl group having 1 to 4 carbon atoms. A, b, c, d, e are 0.01 ≦ a <1, 0.01 ≦ b <1, 0 ≦ c <1, 0.1 ≦ d ≦ 2, 0 ≦ e ≦ 1, And a number satisfying 0.1 ≦ d + e ≦ 2 and 1 <a + b + c + d + e ≦ 3.)
In addition, it is preferable that Y in the said average compositional formula (1) is an organic group containing a mercapto group.
Moreover, it is preferable that Z in the said average composition formula (1) is an organic group containing the polyether group represented by following formula (2).

(In the formula, R ³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms. R ⁴ represents a divalent hydrocarbon group having 2 to 10 carbon atoms. R ⁵ represents a hydrogen atom or carbon. A monovalent hydrocarbon group having 1 to 6 atoms or an organic group represented by the following formula (3): R ⁶ represents a hydrogen atom or a hydroxy group, and f and g are integers of 0 or 1. H and i represent an integer of 0 or more, provided that at least one of h and i is an integer of 1 or more.)

(In the formula, R ⁷ represents a monovalent hydrocarbon group having 1 to 4 carbon atoms.)
Moreover, in the organic group containing the polyether group represented by the formula (2), it is preferable that g = 1.

（式中、Ｙ、Ｚ、Ｒ¹、Ｒ²は、それぞれ上記と同様の内容を示す。ｐ、ｑは、０〜２の整数を示す。ｒは、０〜３の整数を示す。） The present invention further provides a resin composition containing the organosiloxane.
The resin composition of the present invention preferably contains the organosiloxane in an amount of 0.001 to 5 parts by mass with respect to 100 parts by mass of the acrylic polymer.
Furthermore, regarding the organosiloxane of the present invention, at least one kind of alkoxysilane containing an organic functional group represented by the following general formula (4) and at least one kind of polyether group represented by the following general formula (5): A process for producing the organosiloxane, comprising: partially co-hydrolyzing and polycondensing, if necessary, an alkoxysilane represented by the following general formula (6): provide.

(In the formula, Y, Z, R ¹ and R ² each have the same contents as above. P and q represent an integer of 0 to 2. r represents an integer of 0 to ^3. )

（式中、Ｒ¹、Ｒ²、ｐは、それぞれ上記と同様の内容を示す。Ｒ⁸は、炭素原子数１〜１０の二価炭化水素基を示す。） In addition, it is preferable that the alkoxysilane containing the organic functional group represented by said Formula (4) is an alkoxysilane containing the mercapto group represented by following formula (7).

(In the formula, R ¹ , R ² and p each have the same contents as above. R ⁸ represents a divalent hydrocarbon group having 1 to 10 carbon atoms.)

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、ｆ、ｇ、ｈ、ｉ、ｑは、上記と同様の内容を示す。） Moreover, it is preferable that the alkoxysilane containing the polyether group represented by the said Formula (5) is a compound of the structure represented by following formula (8).

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , f, g, h, i, and q have the same contents as described above.)

The partial cohydrolysis and polycondensation of the alkoxysilane represented by the general formulas (4) to (6) are preferably performed in a ketone solvent, and more preferably in diacetone alcohol.
The organosiloxane of the present invention is preferably used as a resin modifier, a paint modifier, an adhesion modifier between materials, a fiber surface treatment agent, and a surface treatment agent for inorganic materials.
Moreover, it is preferable that the resin composition containing this organosiloxane is used as a pressure-sensitive adhesive composition for liquid crystal elements.

The organosiloxane of the present invention contains an organic functional group, a polyether group, and an alkoxy group in the molecule, and the number of each functional group can be freely adjusted. Thereby, the compatibility between the organosiloxane and the organic resin can be improved, and the affinity with the surface of the inorganic base material can be controlled.
When the organosiloxane is used in applications such as resin curing agents, resin modifiers, paint modifiers, and organic-inorganic material adhesion improvers, the adhesion and adhesion between organic and inorganic materials is improved. It is possible to adjust freely.
Moreover, according to the production method of the present invention, a polyether group can be efficiently introduced into the molecule without using an addition reaction under a platinum catalyst. Thereby, the residue of unreacted polyether is suppressed and the original characteristic of a product is fully exhibited. In addition, coloring caused by the platinum catalyst can be suppressed. Further, even in the presence of an organic functional group that becomes an additive poison such as a mercapto group, a polyether group can be efficiently introduced into the molecule.

（式中、Ｙは、メルカプト基、エポキシ基、（メタ）アクリロキシ基、アルケニル基及びアミノ基から選ばれる少なくとも１種を含有する有機基を示す。Ｚは、ポリエーテル基を含有する有機基を示す。Ｒ¹は、脂肪族不飽和結合を有さない置換又は非置換の炭素原子数１〜８の一価炭化水素基を示す。Ｒ²は、炭素原子数１〜４のアルキル基を示す。ａ、ｂ、ｃ、ｄ、ｅは、０．０１≦ａ＜１、０．０１≦ｂ＜１、０≦ｃ＜１、０．１≦ｄ≦２、０≦ｅ≦１であって、かつ０．１≦ｄ＋ｅ≦２及び１＜ａ＋ｂ＋ｃ＋ｄ＋ｅ≦３を満たす数を示す。） The present invention will be described in detail below.
The organopolysiloxane of the present invention is an organic functional group-containing polyether-modified alkoxysiloxane represented by the following average composition formula (1): an organic functional group contained in one molecule, a polyether group, and an alkoxy group. The number can be adjusted freely.

(In the formula, Y represents an organic group containing at least one selected from a mercapto group, an epoxy group, a (meth) acryloxy group, an alkenyl group and an amino group. Z represents an organic group containing a polyether group. R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms which does not have an aliphatic unsaturated bond, and R ² represents an alkyl group having 1 to 4 carbon atoms. A, b, c, d, e are 0.01 ≦ a <1, 0.01 ≦ b <1, 0 ≦ c <1, 0.1 ≦ d ≦ 2, 0 ≦ e ≦ 1, And a number satisfying 0.1 ≦ d + e ≦ 2 and 1 <a + b + c + d + e ≦ 3.)

  Here, Y is an organic group having at least one selected from a mercapto group, an epoxy group, a (meth) acryloxy group, an alkenyl group, and an amino group. These functional groups are usually bonded to a silicon atom via a linking group. Examples of the linking group include an ether bond (—O—), a thioether bond (—S—), and an imino group (—NH—). A linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, an arylene ring having 6 to 12 carbon atoms, a group in which these are bonded, or the like, which may have an aromatic ring such as a hetero atom or a phenylene group. Examples thereof include alkylene such as methylene, ethylene, trimethylene, hexamethylene and decamethylene, and a divalent hydrocarbon group having an aromatic ring such as methylphenylethyl. The alkenyl group may be bonded to the silicon atom via a linking group, or may be directly bonded to the silicon atom.

  Examples of the organic group having a mercapto group include a mercaptomethyl group, a 3-mercaptopropyl group, a 6-mercaptohexyl group, a 10-mercaptodecyl group, and a (4-mercaptomethyl) phenylethyl group, and an organic group having an epoxy group The groups include glycidoxymethyl group, 3-glycidoxypropyl group, 5,6-epoxyhexyl group, 9,10-epoxydecyl group, 2- (3,4-epoxycyclohexyl) ethyl group, 2- ( 3,4-epoxy-4-methylcyclohexyl) propyl group and the like, and examples of the organic group having a (meth) acryloxy group include an acryloxymethyl group, a 3-acryloxypropyl group, and a 6-acryloxyhexyl group. 10-acryloxydecyl group, methacryloxymethyl group, 3-methacryloxypropyl group, 6- Examples include a acryloxyhexyl group, a 10-methacryloxydecyl group, and the organic group having an alkenyl group includes a vinyl group, an allyl group, a 5-hexenyl group, a 9-decenyl group, a 3-vinyloxypropyl group, p- A styryl group, a cyclohexenylethyl group, and the like are exemplified. As an organic group having an amino group, an aminomethyl group, a 3-aminopropyl group, a 6-aminopropyl group, an N-methyl-3-aminopropyl group, an N, N- Dimethyl-3-aminopropyl group, N-phenyl-3-aminopropyl group, N- (2-aminoethyl) -3-aminopropyl group, N- (6-aminohexyl) -3-aminopropyl group, N- (Vinylbenzyl) -2-aminoethyl-3-aminopropyl group and the like are exemplified.

  In the organopolysiloxane of the present invention, when it is an organic group having a mercapto group, an epoxy group, or a (meth) acryloxy group among the above-mentioned organic functional groups, it is suitable for various uses because of its high reactivity, and is preferable. In particular, those having a mercapto group or an epoxy group have a high utility value and are more preferable.

  Z in the average composition formula (1) is an organic group containing a polyether group. The polyether group has an effect of improving the compatibility between the organosiloxane and the organic resin, an effect of controlling the affinity with the surface of the inorganic base material, and the like. The polyether group is usually bonded to a silicon atom via a linking group. Examples of the linking group include hetero bonds such as an ether bond (—O—), a thioether bond (—S—), and an imino group (—NH—). Examples include linear, branched or cyclic alkylene groups having 1 to 12 carbon atoms which may have an aromatic ring such as an atom or phenylene group, such as methylene, ethylene, trimethylene, hexamethylene, decamethylene, etc. A divalent hydrocarbon group having an aromatic ring such as alkylene and methylphenylethyl.

（式中、Ｒ³は、炭素原子数１〜１０、好ましくは３〜８のアルキレン基等の二価炭化水素基を示す。Ｒ⁴は、炭素原子数２〜１０、好ましくは２〜８のアルキレン基等の二価炭化水素基を示す。Ｒ⁵は、水素原子、炭素原子数１〜６のアルキル基等の一価炭化水素基、又は下記式（３）で表される有機基を示す。Ｒ⁶は、水素原子又はヒドロキシ基を示す。ｆ、ｇは、０又は１の整数を示す。ｈ、ｉは、０以上の整数を示す。ただし、ｈ、ｉの少なくとも１つは、１以上の整数である。）

（式中、Ｒ⁷は、炭素原子数１〜４のアルキル基等の一価炭化水素基を示す。） As a monovalent hydrocarbon group containing a polyether group, the structure of following formula (2) is preferable.

(In the formula, R ³ represents a divalent hydrocarbon group such as an alkylene group having 1 to 10 carbon atoms, preferably 3 to 8 carbon atoms. R ⁴ has 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms. R ⁵ represents a hydrogen atom, a monovalent hydrocarbon group such as an alkyl group having 1 to 6 carbon atoms, or an organic group represented by the following formula (3). R ⁶ represents a hydrogen atom or a hydroxy group, f and g represent an integer of 0 or 1. h and i represent an integer of 0 or more, provided that at least one of h and i is 1 (It is an integer above.)

(In the formula, R ⁷ represents a monovalent hydrocarbon group such as an alkyl group having 1 to 4 carbon atoms.)

  The polyether group portion is of ethylene oxide type (hereinafter referred to as EO type), propylene oxide type (hereinafter referred to as PO type), ethylene oxide-propylene oxide type (hereinafter referred to as EO-PO type). Any of them may be used, and in the case of the EO-PO type, any of random, block, and alternate may be used.

  In this case, h is preferably 0 to 50, more preferably 1 to 25, still more preferably 5 to 15, and i is preferably 0 to 50, more preferably 0 to 25, still more preferably 0 to 10. H + i is preferably 1 to 50, more preferably 1 to 25, still more preferably 5 to 15.

（Ｒ³、Ｒ⁵、Ｒ⁶、ｈ、ｉは、上記と同様の内容を示す。） In the formula (2), when g = 0, a structure represented by the following formula (9) is taken.

(R ³ , R ⁵ , R ⁶ , h, i have the same contents as above.)

Examples of this structure include 3- [poly (ethylene glycol) monomethyl ether] propyl group, 3- [poly (propylene glycol) monomethyl ether] propyl group, and 3- [poly (ethylene glycol-propylene glycol) monomethyl ether] propyl. Group, 3- [poly (ethylene glycol-propylene glycol) monoacetyl ether] propyl group, and the like, and specifically include an organic group represented by the following formula.

（Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、ｈ、ｉは、上記と同様の内容を示す。） In the formula (2), when g = 1 and f = 0, the structure is represented by the following formula (10).

(R ³ , R ⁴ , R ⁵ , R ⁶ , h, i have the same contents as above.)

Specific examples of the compound having this structure include organic groups represented by the following formulas.

（Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、ｈ、ｉは、上記と同様の内容を示す。ただし、ここでのＲ⁴は、炭素原子２〜３の二価炭化水素基を示す。） In the formula (2), when g = 1 and f = 1, the structure is represented by the following formula (11).

(R ³ , R ⁴ , R ⁵ , R ⁶ , h, i represent the same contents as described above, provided that R ⁴ represents a divalent hydrocarbon group having 2 to 3 carbon atoms.)

Specific examples of the compound having this structure include organic groups represented by the following formulas.

R ¹ in the average composition formula (1) has an effect of controlling the compatibility with the resin composition. Specifically, it represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms which does not have an aliphatic unsaturated bond. Alkyl such as methyl, ethyl, propyl, isopropyl, 1-methylpropyl, butyl, isobutyl, t-butyl, hexyl, octyl, phenyl, tolyl, benzyl, phenylethyl Groups, aryl groups, aralkyl groups, etc., and haloalkyl groups such as chloromethyl group, 3-chloropropyl group, 6-chlorohexyl group, 10-chlorodecyl group, bromomethyl group, 3-bromopropyl group, etc. . From the viewpoint of the influence of steric hindrance on the reactivity of the organic functional group and the cost, it is particularly preferable to use a methyl group.

  Moreover, the organosiloxane of the present invention contains an alkoxy group in the molecule. When an inorganic base material such as glass is surface-treated with the organosiloxane, this alkoxy group reacts with —OH group present on the surface of the inorganic base material, and a chemical bond is formed between the organosiloxane and the inorganic base material. The Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group, and at least one selected from these groups can be used.

  Furthermore, in the average composition formula (1), a, b, c, d, and e are 0.01 ≦ a <1, 0.01 ≦ b <1, 0 ≦ c <2, 0.1 ≦ d <. 2, 0 ≦ e ≦ 1, and a number satisfying 0.1 ≦ d + e ≦ 2 and 1 <a + b + c + d + e ≦ 3.

  Here, the coefficient a is a numerical value representing the degree of substitution of the organic functional group with respect to the silicon atom, but if this is too small, the characteristic due to the reactivity of the organic functional group that should be originally exhibited when the organopolysiloxane is used. On the other hand, since it is difficult to make the degree of substitution of the organic functional group greater than 1 from the viewpoint of synthesis and cost, it is necessary to make the range 0.01 ≦ a <1, preferably 0. 0.1 ≦ a <1, more preferably 0.1 ≦ a ≦ 0.8.

  The coefficient b is a numerical value representing the degree of substitution of a monovalent hydrocarbon group having a polyether group with respect to a silicon atom. If this is too small, the compatibility with an organic resin is insufficient when the organopolysiloxane is used. Or the affinity and reactivity to the inorganic base material cannot be controlled. On the other hand, if the degree of substitution is 1 or more, the reactivity between the organic functional group and the resin may decrease, or the reactivity between the alkoxy group and the inorganic base material may decrease. It is necessary to set the range of 01 ≦ b <1, preferably 0.1 ≦ b <1, more preferably 0.1 ≦ b ≦ 0.8.

  The coefficient c is a numerical value representing the degree of substitution of a monovalent hydrocarbon group having 1 to 8 carbon atoms with respect to silicon atoms, and is appropriately introduced as necessary in order to control the compatibility with the organic resin. The If the degree of substitution is 1 or more, there may be inconveniences such as loss of compatibility with the resin or inhibition of the reaction between the organic functional group and the organic resin. Therefore, it is necessary to set the range of 0 ≦ c <1, preferably 0.1 ≦ c <1, more preferably 0.1 ≦ c ≦ 0.8.

  The coefficient d indicates the degree of substitution of alkoxy groups for silicon atoms. The degree of substitution can be arbitrarily set according to the purpose of use, but it is necessary that the range is 0.1 ≦ d <2. Preferably, the ranges are 0.1 ≦ d ≦ 1.8 and 0.2 ≦ d ≦ 1.5.

  The coefficient e is a numerical value representing the degree of substitution of the hydroxyl group with respect to the silicon atom, that is, the silanol group content. This silanol group can be subjected to a silylation reaction or a condensation reaction, and imparts hydrophilicity to the organopolysiloxane. However, from the viewpoint of ensuring the storage stability of the organopolysiloxane mixed composition, it is preferably as small as possible. Therefore, it is necessary to set the range of 0 ≦ e ≦ 1, preferably 0 ≦ e ≦ 0.5, and more preferably 0 ≦ e ≦ 0.2.

  The sum (a + b + c + d + e) of the coefficients described above is a numerical value for determining [4- (a + b + c + d + e)] / 2 indicating the degree of condensation of the organopolysiloxane represented by the average composition formula (1). It is necessary to set the range of a + b + c + d + e ≦ 3. The degree of polymerization of the organopolysiloxane can range from a dimer having 2 silicon atoms to a polymer having about several hundred silicon atoms. If the content of the monomer in the inside increases, the original intended purpose of the silicone alkoxy oligomer may be impaired, and if the average degree of polymerization is too large, it becomes a high-viscosity product, a paste or a solid, and handling becomes complicated. The average degree of polymerization is preferably in the range of 3 to 100, and more preferably in the range of 3 to 50. From this point of view, the above (a + b + c + d + e) is preferably in the range of 1.5 ≦ a + b + c + d + e ≦ 2.67, more preferably 2.0 ≦ a + b + c + d + e ≦ 2.67.

  The organopolysiloxane containing an organic functional group, a polyether group and an alkoxy group represented by the average composition formula (1) in one molecule may be any number as long as a to e satisfy the above ranges. , Branched, annular, and a combination of these.

  Moreover, it is preferable that the polystyrene conversion weight average molecular weight by the gel permeation chromatography (GPC) of the organosiloxane of this invention is 400-35,000, More preferably, it is 400-10,000, More preferably, it is 450- 5,000.

（式中、Ｙ、Ｚ、Ｒ¹、Ｒ²は、それぞれ上記と同様の内容を示す。ｐ、ｑは、０〜２の整数を示す。ｒは、０〜３の整数を示す。） Next, the organopolysiloxane containing an organic functional group, a polyether group, and an alkoxy group represented by the average composition formula (1) of the present invention in one molecule is, for example, at least one of the following general formulas (4) ) And an alkoxysilane containing a polyether group represented by the following general formula (5), and if necessary, a general formula (6) Can be produced by a method of partial cohydrolysis and polycondensation.

(In the formula, Y, Z, R ¹ and R ² each have the same contents as above. P and q represent an integer of 0 to 2. r represents an integer of 0 to ^3. )

（式中、Ｒ¹、Ｒ²、Ｒ⁸、ｐは、それぞれ上記と同様の内容を示す。Ｒ⁸は炭素原子数１〜１０、好ましくは１〜６のアルキレン基等の二価炭化水素基である。） As the organic functional group-containing alkoxysilane represented by the general formula (4), an alkoxysilane containing a mercapto group represented by the following formula (12) is preferably used.

(Wherein R ¹ , R ² , R ⁸ and p each have the same contents as above. R ⁸ is a divalent hydrocarbon group such as an alkylene group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. .)

  The mercapto group-containing alkoxysilane represented by the above formula (12) includes, among others, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldiethoxy. It is preferable to use at least one selected from silane.

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、ｆ、ｇ、ｈ、ｉ、ｑは、それぞれ上記と同様の内容を示す。） As the alkoxysilane containing a polyether group represented by the general formula (5), an alkoxysilane containing a polyether group represented by the following formula (13) is preferably used.

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , f, g, h, i, and q have the same contents as described above.)

  The compound represented by the above formula (13) has a structure in which an organic group containing a polyether group represented by the above formula (2) and an alkoxysilyl group are bonded.

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁵、Ｒ⁶、ｈ、ｉ、ｑは、それぞれ上記と同様の内容を示す。） In the above formula (13), when g = 0, a structure represented by the following formula (14) is taken.

(In the formula, R ¹ , R ² , R ³ , R ⁵ , R ⁶ , h, i, and q have the same contents as described above.)

（式中、Ｒ¹、Ｒ²、ｐは、それぞれ上記と同様の内容を示す。）

（式中、Ｒ⁵、Ｒ⁶、ｈ、ｉは、それぞれ上記と同様の内容を示す。Ｒ⁹は、単結合又は炭素原子数１〜８のアルキレン基等の二価炭化水素基を示す。） The alkoxysilane containing a polyether group represented by the above formula (14) includes an ≡Si—H group-containing alkoxysilane represented by the following formula (15) and a polyether group represented by the following formula (16): And a compound containing a reactive double bond can be produced by a hydrosilylation reaction in the presence of a platinum catalyst.

(In the formula, R ¹ , R ² and p each have the same contents as above.)

(In the formula, R ⁵ , R ⁶ , h and i each have the same contents as above. R ⁹ represents a single bond or a divalent hydrocarbon group such as an alkylene group having 1 to 8 carbon atoms. )

Specifically, for example, a compound containing an ≡Si—H group-containing trimethoxysilane represented by the following formula (17), a polyether group represented by the following formula (18) and a reactive double bond. By carrying out hydrosilylation reaction in the presence of a platinum catalyst, trimethoxysilane containing various organic functional groups represented by the following formula (19) can be produced.

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、ｈ、ｉ、ｑは、それぞれ上記と同様の内容を示す。）

（式中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、ｈ、ｉ、ｑは、それぞれ上記と同様の内容を示す。ただし、ここでのＲ⁴は、炭素原子数１〜３の二価炭化水素基を示す。） In the above formula (13), when g = 1, a polyether group and an alkoxysilyl group are bonded by a linking group having an —S— bond. When f = 0, a structure represented by the following formula (20) is taken, and when f = 1, a structure represented by the following formula (21) is obtained.

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , h, i, and q have the same contents as described above.)

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , h, i, and q each have the same contents as above, where R ⁴ is the number of carbon atoms. 1 to 3 divalent hydrocarbon groups.)

（式中、Ｒ¹、Ｒ²、Ｒ⁸、ｐは、それぞれ上記と同様の内容を示す。）

（式中、Ｒ⁵、Ｒ⁶、Ｒ⁹、ｈ、ｉは、それぞれ上記と同様の内容を示す。） The compound represented by the above formula (20) comprises an alkoxysilane containing a mercapto group represented by the following formula (12), a polyether group represented by the following formula (16) and a reactive double bond. The compound to be contained can be produced by an addition reaction in the presence of a radical generator.

(In the formula, R ¹ , R ² , R ⁸ and p each have the same contents as above.)

(In the formula, R ⁵ , R ⁶ , R ⁹ , h and i each have the same contents as above.)

Specifically, for example, a compound containing a trimethoxysilane containing a mercapto group represented by the following formula (22), a polyether group represented by the following formula (23) and a reactive double bond, By performing an addition reaction in the presence of a radical generator, trimethoxysilane containing a polyether group represented by the following formula (24) can be produced.

（式中、Ｒ⁵、Ｒ⁶、ｈ、ｉは、それぞれ上記と同様の内容を示す。Ｒ¹⁰は、水素原子又はメチル基を示す。） The compound represented by the above formula (21) comprises an alkoxysilane containing a mercapto group represented by the above formula (12), a polyether group represented by the following formula (25) and a reactive double bond. The compound can be produced by addition reaction in the presence of a radical generator.

(In the formula, R ⁵ , R ⁶ , h and i each have the same contents as above. R ¹⁰ represents a hydrogen atom or a methyl group.)

Specifically, for example, a compound containing a trimethoxysilane containing a mercapto group represented by the formula (22), a polyether group represented by the following formula (26) and a reactive double bond, By performing an addition reaction in the presence of a radical generator, trimethoxysilane containing a polyether group represented by the following formula (27) can be produced.

  Since the alkoxysilane containing the polyether group represented by the formulas (20) and (21) does not use a platinum catalyst in the production process, it is more platinum than the compound represented by the formula (14). There is no coloration caused by the catalyst, and a product with less color is obtained. Therefore, this is mixed with an alkoxysilane containing an organic functional group represented by the formula (4) and, if necessary, an alkoxysilane represented by the formula (6), and partially cohydrolyzed and polycondensed. The organosiloxane obtained in this way can also be reduced in color.

  Further, as the alkoxysilane represented by the general formula (6), specifically, as r = 0 alkoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, Tetraisobutoxysilane and the like, as r = 1 alkoxysilane, methyl group, ethyl group, propyl group, isopropyl group, 1-methylpropyl group, butyl group, isobutyl group, t-butyl group, hexyl group, octyl group, phenyl Trimethoxysilane, triethoxysilane, tripropoxysilane, triisopropoxysilane, tributoxysilane, triisobutoxysilane, etc. having a group, tolyl group, benzyl group, phenylethyl group, etc. Dimethoxysilane, dimethyl Distearate silane, dimethyl dipropoxy silane, dimethyl dibutoxy silane, methyl ethyl dimethoxy silane, diphenyl dimethoxy silane, diphenyl diethoxy silane, and the like.

From the viewpoint of availability of raw materials and cost, p in the general formula (4) is 0, that is, trialkoxysilane containing an organic functional group, and q in the general formula (5) is 0, that is, It is preferable to use a trialkoxysilane containing a polyether group and R ¹ in the general formula (6) is a methyl group and r is 1 and / or 0, that is, methyltrialkoxysilane and tetraalkoxysilane.

  The mixing ratio of the above-mentioned alkoxysilane containing an organic functional group, an alkoxysilane containing a polyether group, and an alkoxysilane is not particularly limited, but an alkoxysilane containing an organic functional group and an alkoxy containing a polyether group If the compounding ratio of silane is too small, the inherent properties of the present organopolysiloxane cannot be exhibited, and it is necessary to have at least one organic functional group and polyether group in one molecule. From this, the Si atom equivalent molar ratio of the three components is preferably in the range of 1 to 99: 1 to 99: 0 to 98, and more preferably in the range of 10 to 90:10 to 90: 0 to 90. More preferably.

  In addition, the blending order and mixing method of these various raw materials, and the method of performing partial cohydrolysis and polycondensation are not particularly limited, and based on a conventionally known method, for example, an alkoxysilane containing an organic functional group described above and In addition, it can be obtained by performing partial cohydrolysis and polycondensation reaction by adding water in the presence of a hydrolysis and condensation reaction catalyst in a mixture of an alkoxysilane containing a polyether group and an alkoxysilane, At this time, an appropriate organic solvent can be used as necessary.

  Various conventionally known catalysts can be used as the hydrolysis and condensation reaction catalyst used. Specific examples include organic acids such as acetic acid, trifluoroacetic acid, butyric acid, oxalic acid, maleic acid, citric acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, etc. Inorganic acids, basic compounds such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate, sodium acetate, potassium acetate, ammonia, ammonium hydroxide, triethylamine, and fluorine-containing compounds such as potassium fluoride and ammonium fluoride Examples thereof include organometallic compounds such as compounds, tetraisopropyl titanate, tetrabutyl titanate, dioctyltin dilaurate, and aluminum chelates. The above catalyst may be used alone or in combination of two or more kinds, but the amount of the catalyst used is 0.0001 to 10 mol% with respect to the number of moles of Si atoms present in the whole raw material. It is preferable to set it as a range, and it is more preferable to set it as a range of 0.001-3 mol% further.

  As described above, the degree of polymerization of each organopolysiloxane of the present invention may be from a dimer having 2 silicon atoms to a polymer having about several hundred silicon atoms, but water used for partial hydrolysis and polycondensation. The average degree of polymerization is determined by the amount. If water is added in excess, the corresponding alkoxy group is hydrolyzed to form a resin having a lot of branched structures, and the desired silicone alkoxy oligomer cannot be obtained. Therefore, the amount of hydrolyzed water must be determined strictly. For example, when the alkoxysilane raw material used is a monomer having one silicon atom, in order to prepare an organopolysiloxane having an average polymerization degree of Z, (Z-1) What is necessary is just to perform partial hydrolysis and polycondensation using water.

  At this time, an organic solvent such as alcohols, ethers, esters, and ketones may be used as necessary. Specific examples of these organic solvents include alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol and propylene glycol monomethyl ether, ethers such as diethyl ether and dipropyl ether, methyl acetate, ethyl acetate and acetoacetic acid. Examples include esters such as ethyl, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and acetyl acetone, and diacetone alcohol. Moreover, you may use together nonpolar solvents, such as hexane, toluene, and xylene, with the said solvent. In particular, it is preferable to use ketones such as methyl ethyl ketone, methyl isobutyl ketone, and acetyl acetone, and diacetone alcohol is particularly preferable.

  The amount of the organic solvent used may be in the range of 0 to 1,000 parts by mass with respect to 100 parts by mass in total of the alkoxysilane as a raw material, its partial hydrolyzate and its condensate, but the amount used is small. The reaction system at the start of hydrolysis may not be uniform, and if it is too much, not only the effect of addition is not seen, but also the pot yield is lowered and economically disadvantageous, so 10 to 500 mass. Part range, more preferably 20 to 200 parts by mass.

  As an actual operation in partial (co) hydrolysis and polycondensation reaction, a predetermined amount of water or a mixed solution of water / organic solvent is dropped into a mixed system composed of an alkoxysilane raw material, a catalyst and an organic solvent, or an alkoxysilane raw material It is preferable that a predetermined amount of a mixed solution of water / catalyst or a mixed solution of water / catalyst / organic solvent is dropped into a mixed system composed of the organic solvent. Each reaction may be carried out in the temperature range of 0 to 150 ° C., but in general, the reaction proceeds slowly at a temperature lower than room temperature, and is not practical, and even when the temperature is too high, an epoxy group, a mercapto group, etc. In view of adverse effects on the organic functional group such as thermal decomposition of acryloxy group and thermal polymerization of acryloxy group, the temperature is preferably in the range of 20 to 130 ° C. After the reaction, the catalyst is removed by neutralization, adsorption, filtration, etc. of the catalyst used, and purified by distillation of the used organic solvent and by-product alcohol and low-boiling substances. Siloxane can be obtained.

  The organopolysiloxane of the present invention can be suitably used as a resin modifier, a paint modifier, an adhesion modifier between materials, a fiber surface treatment agent, a surface treatment agent for inorganic materials, and the like. The organopolysiloxane of the present invention can be used by being contained in a resin composition, for example, a resin composition having an acrylic polymer as a base resin.

  For example, as a resin modifier, organic materials such as rubber and plastic, metal, silica, quartz, talc, clay, zinc oxide, iron oxide, titanium oxide, aluminum oxide, calcium carbonate, aluminum hydroxide, mica, carbon black It is used for adhesion with inorganic materials such as inorganic fillers, and the like, and reinforced plastics and high-strength elastomers having high weather resistance and heat resistance are obtained. In addition, it is blended in a coating resin made of polyester resin, acrylic resin or the like as a coating modifier, and enables coating with excellent weather resistance, durability and heat resistance to metal, wood, concrete and the like. Furthermore, as the surface modifier of the fiber, the raw materials include natural fibers such as wool, silk, hemp, cotton and asbestos, regenerated fibers such as rayon, cupra and acetate, polyester, polyester ether, polyacrylonitrile, vinylon, polychlorinated Any fiber such as organic synthetic fibers such as vinylidene, polyvinyl chloride, polyethylene, and polypropylene, inorganic synthetic fibers such as glass fibers and carbon fibers, and any form such as woven fabric, knitted fabric, non-woven fabric, resin processed fabric, etc. Even if it is a thing, the surface of the fiber can be processed and a weather resistance, durability, etc. are provided to this fiber.

  Moreover, the organopolysiloxane of the present invention is suitably used as an adhesion modifier between an organic material and an inorganic material. For example, the resin composition containing the organosiloxane of the present invention is suitably used as a pressure-sensitive adhesive composition for liquid crystal elements, and has an adhesive property, durability, and reworkability in the adhesion between a liquid crystal cell and a polarizing plate. Coexistence is possible. The resin composition used here is not particularly limited, but an acrylic polymer is particularly preferably used. Usually, a (co) polymer formed from an acrylic monomer such as (meth) acrylic acid ester, a functional group-containing acrylic monomer, or the like is used. For example, (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (Meth) acrylate, cyclohexyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, etc. can be mentioned. These can be used alone or in combination.

  The acrylic polymer used in the present invention has a repeating unit derived from the above (meth) acrylic acid ester in an amount of usually 60 to 99% by mass, preferably 80 to 98% by mass. The functional group-containing acrylic monomer includes acrylic acid, methacrylic acid, β-carboxyethyl acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and chloro-2-hydroxypropyl (meth). Examples thereof include acrylate, diethylene glycol mono (meth) acrylate, dimethylaminoethyl (meth) acrylate, and glycidyl (meth) acrylate. These can be used alone or in combination.

  The acrylic polymer used in the present invention has a repeating unit derived from the functional group-containing acrylic monomer in an amount of usually 1 to 20% by mass, preferably 2 to 10% by mass. The acrylic polymer used in the present invention may have a repeating unit derived from a monomer other than the above (meth) acrylic acid ester and the functional group-containing acrylic monomer. And a repeating unit derived from a styrene monomer and a repeating unit derived from a vinyl monomer. Examples of the styrenic monomer include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, triethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene, and other alkyl styrenes; Halogenated styrenes such as chlorostyrene, bromostyrene, dibromostyrene and iodostyrene; and nitrostyrene, acetylstyrene and methoxystyrene. Vinyl monomers include vinyl pyridine, vinyl pyrrolidone, vinyl carbazole, divinyl benzene, vinyl acetate and acrylonitrile; conjugated diene monomers such as butadiene, isoprene and chloroprene; vinyl halides such as vinyl chloride and vinyl bromide; vinylidene chloride And vinylidene halides such as These monomers can be used alone or in combination.

  The repeating unit derived from the other monomer in the acrylic polymer used in the present invention is usually contained in an amount of 0 to 20% by mass, preferably 0 to 10% by mass. In particular, the acrylic polymer used in the present invention preferably has at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, a glycidyl group, and an amide group. The acrylic polymer having such a group has good reactivity with the polymer-type silane coupling agent constituting the adhesive composition of the present invention or a crosslinking agent blended as required. The acrylic polymer used in the present invention usually has a weight average molecular weight of 100,000 to 1,500,000, preferably 300,000 to 800,000.

  In addition, in the resin composition which uses an acrylic polymer as a base resin, the organopolysiloxane of the present invention is 0.001 to 5 parts by mass, particularly 0.001 to 1 part by mass with respect to 100 parts by mass of the acrylic polymer. It is preferable to use in.

  The present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to the following examples.

In addition, the analysis of the organopolysiloxane obtained by the synthesis example was implemented by the method shown below.
(1) The average degree of polymerization of the organopolysiloxane was calculated from the weight average molecular weight determined by gel permeation chromatography (GPC) analysis based on a calibration curve prepared from a polystyrene standard sample.
(2) The alkoxy group content in the organopolysiloxane is measured by an alkali cracking-gas chromatography (GC) analysis method [see Silicone Handbook, pages 792-793 (published by Nikkan Kogyo Shimbun)], and the average composition formula ( The coefficient d in 1) and (2) was obtained.
(3) The structure analysis of the organopolysiloxane is carried out by silicon nuclear magnetic resonance spectrum ( ²⁹ Si-NMR) analysis and proton nuclear magnetic resonance spectrum ( ¹ H-NMR) analysis, and the average composition formula (1), The coefficients a, b, c, and e in (2) were obtained.
(4) The mercapto group equivalent of organopolysiloxane is titration method of acetic acid / potassium iodide / potassium iodate added-sodium thiosulfate solution [see Analytical Chemistry Handbook, Revised Second Edition, pages 432-433 (issued by Maruzen Co., Ltd.)] Measured according to

[Example 1] (Synthesis of mercapto group-containing polyether-modified methoxysiloxane-1)
In a 1 L flask equipped with a stirrer, cooling condenser, thermometer and dropping funnel, 25.0 g (12.7 × 10 ⁻² mol) of 3-mercaptopropyltrimethoxysilane, represented by the following formula (19) Charge 28.8 g (4.25 × 10 ⁻² mol) of polyether group-containing trimethoxysilane and 17.0 g of diacetone alcohol, and add 0.05N hydrochloric acid aqueous solution with stirring at an internal temperature of 20-30 ° C. 67 g (water: 14.8 × 10 ⁻² mol, hydrochloric acid: 1.34 ×× 10 ⁻⁴ mol) was added dropwise over 30 minutes, followed by further aging for 2 hours.

表１に、上記した分析結果から求めた重量平均分子量、平均重合度、前記平均組成式（１）における各係数と、メルカプト基当量を示す。 Next, 1.91 g of a 1% methanol solution of sodium acetate (sodium acetate: 2.33 × 10 ⁻⁴ mol) was added, and the mixture was heated to 70 ° C. and aged for 2 hours.
Subsequently, heating under reduced pressure for 2 hours under the conditions of 100 ° C. and 10 mmHg, the residual alcohol component and the low boiling point component were distilled off, followed by filtration to obtain a liquid organosiloxane 1 having a nonvolatile content of 99.0%. (Yield: 42.7 g, Yield: 91%).
This organopolysiloxane 1 has an average composition formula (1), wherein Y is a 3-mercaptopropyl group, Z is an organic group containing a polyether group represented by the following formula (28), and R ¹ is a methyl group It is.

Table 1 shows the weight average molecular weight, the average degree of polymerization, each coefficient in the average composition formula (1), and the mercapto group equivalent determined from the above analysis results.

上記に生成した液体について、ＴＨＦ溶媒下でのＧＰＣ（Ｇｅｌ Ｐｅｒｍｅａｔｉｏｎ Ｃｈｒｏｍａｔｏｇｒａｐｈｙ）測定を行った。その結果、保持時間２８分〜３４分の範囲において、生成物ピークを確認した。なお、保持時間３６分〜３８分の範囲において、３−メルカプトプロピルトリメトキシシラン由来のピークは、およそ消失していた。また、上記に生成した液体について、¹Ｈ−ＮＭＲ測定を行った。その結果として、４．７〜６．０ｐｐｍの範囲において、反応前に存在していた上記式（２３）で表されるアリル化ポリエーテルのアリル基由来ピークが消失していた。下記式（２９）で表されるポリエーテル基含有アルコキシシランが生成していると推定された。

[Example 2] (Synthesis of mercapto group-containing polyether-modified methoxysiloxane-2)
In a 1 L flask equipped with a stirrer, a cooling condenser, a thermometer, and a dropping funnel, 12.5 g (6.36 × 10 ⁻² mol) of 3-mercaptopropyltrimethoxysilane and the following formula (23) After charging 35.4 g (6.36 × 10 ⁻² mol) of allylated polyether, PERBUTYL-O [manufactured by NOF Corporation: t-butylperoxy-2-ethylhexanoate] was added while stirring. 0.5 g was added and aging was performed at 65 ° C. for 2 hours.

About the liquid produced | generated above, GPC (Gel Permeation Chromatography) measurement in THF solvent was performed. As a result, a product peak was confirmed in the retention time range of 28 minutes to 34 minutes. Note that the peak derived from 3-mercaptopropyltrimethoxysilane was almost disappeared in the range of 36 minutes to 38 minutes. Moreover, the < ¹ > H-NMR measurement was performed about the produced | generated liquid above. As a result, in the range of 4.7 to 6.0 ppm, the allyl group-derived peak of the allylated polyether represented by the above formula (23), which existed before the reaction, disappeared. It was estimated that a polyether group-containing alkoxysilane represented by the following formula (29) was generated.

表１に、上記した分析結果から求めた重量平均分子量、平均重合度、前記平均組成式（１）における各係数と、メルカプト基当量を示す。 Next, 37.5 g (19.1 × 10 ⁻² mol) of 3-mercaptopropyltrimethoxysilane, 17.4 g (12.8 × 10 ⁻² mol) of methyltrimethoxysilane, While adding 44.0 g of acetone alcohol and stirring at an internal temperature of 20-30 ° C., 6.3 g of 0.05N hydrochloric acid aqueous solution (water: 35.0 × 10 ⁻² mol, hydrochloric acid: 3.15 ×× 10 ^{− 4} mol) was added dropwise over 30 minutes and aged for 2 hours. Subsequently, 4.50 g of a 1% methanol solution of sodium acetate (sodium acetate: 5.49 × 10 ⁻⁴ mol) was added, the temperature was raised to 70 ° C., and aging was performed for 2 hours.
Next, under reduced pressure at 100 ° C. and 10 mmHg for 2 hours, the residual alcohol component and the low boiling point component are distilled off, followed by filtration to obtain a liquid organosiloxane 2 having a nonvolatile content of 98.9%. Obtained (yield: 77.1 g, yield: 90%).
This organopolysiloxane 2 has an average composition formula (1) in which Y is a 3-mercaptopropyl group, Z is an organic group containing a polyether group represented by the following formula (30), and R ¹ is a methyl group It is.

Table 1 shows the weight average molecular weight, the average degree of polymerization, each coefficient in the average composition formula (1), and the mercapto group equivalent determined from the above analysis results.

表１に、上記した分析結果から求めた重量平均分子量、平均重合度、前記平均組成式（１）における各係数と、メルカプト基当量を示す。 [Example 3] (Synthesis of mercapto group-containing polyether-modified methoxysiloxane-3)
In Synthesis Example 2, 35.4 g (6.36 × 10 ⁻² mol) of the allylated polyether represented by the formula (23) was converted into 31.6 g of methoxypolyethylene glycol monomethacrylate represented by the following formula (31). Except for changing to (6.37 × 10 ⁻² mol), the same operation as above was performed to obtain organosiloxane 3 having a nonvolatile content of 99.1% (yield: 72.1 g, yield: 88 %).

Table 1 shows the weight average molecular weight, the average degree of polymerization, each coefficient in the average composition formula (1), and the mercapto group equivalent determined from the above analysis results.

[Comparative Example 1] Synthesis of mercapto group-containing polyether-modified methoxysiloxane-4
A 1 L flask equipped with a stirrer, a cooling condenser, and a thermometer was charged with 98.2 g (0.50 mol) of 3-mercaptopropyltrimethoxysilane and 60.0 g (0.25 mol) of tetramethyltetrahydrocyclotetrasiloxane. Thereafter, 0.08 g of trifluoromethanesulfonic acid was added with stirring, and equilibrated at room temperature for 4 hours. After the equilibration was completed, 0.57 g of a solid basic neutralizing agent represented by Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O was added to the system and stirred for 2 hours. After the sum treatment, filtration purification was performed to obtain a liquid product A (mercapto group-containing methylhydrogenmethoxysiloxane) (yield: 150 g, yield: 95%).
Here, GPC measurement in a toluene solvent was performed on the product A. As a result, a product peak was confirmed in the retention time range of 28 minutes to 38 minutes. Note that the peak derived from 3-mercaptopropyltrimethoxysilane was almost disappeared in the range of retention time of 37 minutes to 39 minutes. Moreover, in the range of retention time 35 minutes-37 minutes, the peak derived from tetramethyltetrahydrocyclotetrasiloxane has disappeared approximately.
Next, the mercapto equivalent of product A was measured. As a result, 307 g / mol (set value: 316 g / mol), a value substantially close to the set value, was obtained.
Next, according to the following measuring method, the content of ≡Si—H group in 1 g of product A was measured. As a result, 6.25 × 10 ⁻³ mol / g (set value: 6.32 × 10 ⁻³ mol / g) was obtained, which is a value substantially close to the set value.

次に、上記生成物Ａ５０ｇ（１５．８×１０^-2ｍｏｌ）に対し、前記式（２３）で表されるアリル化ポリエーテル１７６ｇ（３１．７×１０^-2ｍｏｌ）を仕込んだ後、撹拌を加えながら、塩化白金酸のトルエン溶液（Ｐｔ濃度：０．５質量％）１．００ｇを添加し、９０℃まで昇温して３時間熟成を行って、生成物Ｂを得た。
ここで、反応前後において、サンプル１ｇ中に含有する≡Ｓｉ−Ｈ基の量を測定した。下記に、その結果を示す。
（反応前）１．３９×１０^-3ｍｏｌ／ｇ
（反応後）１．３４×１０^-3ｍｏｌ／ｇ
サンプル１ｇ中に含有する≡Ｓｉ−Ｈ基の量は、反応前後において、４％程度の減少量にとどまった。
ここで、生成物Ｂのトルエン溶媒下でのＧＰＣ測定を行った。その結果、反応前と比較して、出現ピークに顕著な変化がみられなかった。
以上のことから、白金触媒存在下において、メルカプト基含有メチルハイドロジェンメトキシシロキサンと前記式（２３）で表されるアリル化ポリエーテルとのヒドロシリル化反応は、ほとんど進行しないと推定される。 <Measurement method>
10 g of butanol was added to 1 g of a sample, and 20 g of 20% by mass NaOH aqueous solution was added while stirring. The content of ≡SiH was calculated from the amount of hydrogen gas (≡SiH + H ₂ O → ≡SiOH + H ₂ ↑) generated at this time.
From the above results, it was estimated that the mercapto group-containing methylhydrogenmethoxysiloxane of product A had an average composition of the following formula (32).

Next, with respect to 50 g (15.8 × 10 ⁻² mol) of the product A, 176 g (31.7 × 10 ⁻² mol) of the allylated polyether represented by the formula (23) was charged and stirred. , 1.00 g of a toluene solution of chloroplatinic acid (Pt concentration: 0.5 mass%) was added, the temperature was raised to 90 ° C., and aging was performed for 3 hours to obtain a product B.
Here, the amount of ≡Si—H groups contained in 1 g of the sample was measured before and after the reaction. The results are shown below.
(Before reaction) 1.39 × 10 ⁻³ mol / g
(After reaction) 1.34 × 10 ⁻³ mol / g
The amount of ≡Si—H group contained in 1 g of the sample was reduced by about 4% before and after the reaction.
Here, GPC measurement of the product B in a toluene solvent was performed. As a result, no significant change was observed in the appearance peak compared to before the reaction.
From the above, it is presumed that the hydrosilylation reaction between the mercapto group-containing methylhydrogenmethoxysiloxane and the allylated polyether represented by the formula (23) hardly proceeds in the presence of a platinum catalyst.

比較例１と同様、前記生成物Ａ（メルカプト基含有メチルハイドロジェンメトキシシロキサン）と、上記式（３３）で表されるアリル化ポリエーテルとの反応前後において、サンプル１ｇ中に含有する≡Ｓｉ−Ｈ基の量を測定した。下記に、その結果を示す。
（反応前）１．０７×１０^-3ｍｏｌ／ｇ
（反応後）１．０４×１０^-3ｍｏｌ／ｇ
サンプル１ｇ中に含有する≡Ｓｉ−Ｈ基の量は、反応前後において、３％程度の減少量にとどまった。
ここで、反応後のサンプルについて、トルエン溶媒下でのＧＰＣ測定を行った。その結果、反応前と比較して、出現ピークに顕著な変化がみられなかった。
以上のことから、白金触媒存在下において、メルカプト基含有メチルハイドロジェンメトキシシロキサンと前記式（３３）で表されるアリル化ポリエーテルとのヒドロシリル化反応は、ほとんど進行しないと推定される。 [Comparative Example 2] Synthesis of mercapto group-containing polyether-modified methoxysiloxane-5
In Comparative Example 1, 176 g (31.7 × 10 ⁻² mol) of the allylated polyether represented by the formula (23) was converted to 244 g (31.8 × 10 8) of the allylated polyether represented by the following formula (33). The same operation as described above was performed except that it was changed to ^-2 mol).

Similar to Comparative Example 1, ≡Si— contained in 1 g of sample before and after the reaction between the product A (mercapto group-containing methylhydrogenmethoxysiloxane) and the allylated polyether represented by the above formula (33). The amount of H groups was measured. The results are shown below.
(Before reaction) 1.07 × 10 ⁻³ mol / g
(After reaction) 1.04 × 10 ⁻³ mol / g
The amount of ≡Si—H group contained in 1 g of the sample was reduced by about 3% before and after the reaction.
Here, the GPC measurement in the toluene solvent was performed about the sample after reaction. As a result, no significant change was observed in the appearance peak compared to before the reaction.
From the above, it is presumed that the hydrosilylation reaction between the mercapto group-containing methylhydrogenmethoxysiloxane and the allylated polyether represented by the formula (33) hardly proceeds in the presence of a platinum catalyst.

Claims (13)

An organosiloxane represented by the following average composition formula (1), which contains an organic functional group, a polyether group and an alkoxy group in one molecule.

(In the formula, Y represents an organic group containing at least one selected from a mercapto group, an epoxy group, a (meth) acryloxy group, an alkenyl group and an amino group. Z represents an organic group containing a polyether group. R ¹ represents a substituted or unsubstituted monovalent hydrocarbon group having 1 to 8 carbon atoms which does not have an aliphatic unsaturated bond, and R ² represents an alkyl group having 1 to 4 carbon atoms. A, b, c, d, e are 0.01 ≦ a <1, 0.01 ≦ b <1, 0 ≦ c <1, 0.1 ≦ d ≦ 2, 0 ≦ e ≦ 1, And a number satisfying 0.1 ≦ d + e ≦ 2 and 1 <a + b + c + d + e ≦ 3.)   The organosiloxane according to claim 1, wherein Y in the average composition formula (1) is an organic group containing a mercapto group. The organosiloxane according to claim 1 or 2, wherein Z in the average composition formula (1) is an organic group containing a polyether group represented by the following formula (2).

(In the formula, R ³ represents a divalent hydrocarbon group having 1 to 10 carbon atoms. R ⁴ represents a divalent hydrocarbon group having 2 to 10 carbon atoms. R ⁵ represents a hydrogen atom or carbon. A monovalent hydrocarbon group having 1 to 6 atoms or an organic group represented by the following formula (3): R ⁶ represents a hydrogen atom or a hydroxy group, and f and g are integers of 0 or 1. H and i represent an integer of 0 or more, provided that at least one of h and i is an integer of 1 or more.)

(In the formula, R ⁷ represents a monovalent hydrocarbon group having 1 to 4 carbon atoms.)   4. The organosiloxane according to claim 3, wherein g = 1 in the organic group containing a polyether group represented by the formula (2).   A resin composition comprising the organosiloxane according to any one of claims 1 to 4.   A resin composition comprising the organosiloxane according to any one of claims 1 to 4 in an amount of 0.001 to 5 parts by mass with respect to 100 parts by mass of an acrylic polymer. At least one alkoxysilane containing an organic functional group represented by the following general formula (4), at least one alkoxysilane containing a polyether group represented by the following general formula (5), and The production of the organosiloxane according to any one of claims 1 to 4, wherein at least one alkoxysilane represented by the following general formula (6) is partially cohydrolyzed and polycondensed. Method.

(In the formula, Y, Z, R ¹ and R ² each have the same contents as above. P and q represent an integer of 0 to 2. r represents an integer of 0 to ^3. ) 8. The organosiloxane according to claim 7, wherein the alkoxysilane containing an organic functional group represented by the formula (4) is an alkoxysilane containing a mercapto group represented by the following formula (7). Production method.

(In the formula, R ¹ , R ² and p each have the same contents as above. R ⁸ represents a divalent hydrocarbon group having 1 to 10 carbon atoms.) The method for producing an organosiloxane according to claim 7 or 8, wherein the alkoxysilane containing a polyether group represented by the formula (5) is a compound having a structure represented by the following formula (8). .

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , f, g, h, i, and q have the same contents as described above.)   The method for producing an organosiloxane according to any one of claims 7 to 9, wherein partial cohydrolysis and polycondensation are performed in a ketone solvent.   The method for producing an organosiloxane according to any one of claims 7 to 10, wherein partial cohydrolysis and polycondensation are performed in diacetone alcohol.   The organosiloxane according to any one of claims 1 to 4, which is used as a resin modifier, a paint modifier, an adhesion modifier between materials, a fiber surface treatment agent, or a surface treatment agent of an inorganic material.   The resin composition according to claim 5 or 6, which is used as a pressure-sensitive adhesive composition for a liquid crystal element.