JP2017014320A - Method for producing cross-linking silicon compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method capable of mass-producing a cross-linking silicon compound including a silsesquioxane skeleton having a molecular weight in a fixed range at the main chain of a silicon based polymer.SOLUTION: Provided is a method for producing a cross-linking silicon compound where a silsesquioxane unit-containing compound represented by Formula (1) is brought into an equilibrium polymerization reaction with either or both of a linear siloxane unit compound and a cyclic siloxane unit compound, including an aging step where aging is performed to the silsesquioxane unit-containing compound which is a raw material of a cross-linking silicon compound and to the feed total mass of either or both of the linear siloxane unit compound and the cyclic siloxane unit compound in the presence of water of 0.5 to 15 mass%, in which the aging step is performed so as to be held to a temperature of above 0 to below 100°C.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a crosslinkable silicon compound containing a silsesquioxane skeleton in the main chain of a silicon polymer.

The cured product of a curable silicon compound having a silsesquioxane group has optical properties, electrical properties, heat resistance, and gas permeability as compared with ordinary silicon compounds such as siloxane and its polymers. In some cases, it exhibits unique characteristics in various characteristics such as mechanical strength. Such a curable silicon compound having a silsesquioxane group and a cured product thereof are further used particularly in the fields of transparent films such as lenses and protective films, and electrical and optical sealing materials. Be expected.
Until now, by giving a reactive functional group to a silsesquioxane skeleton or a silicon-based polymer containing the same, a crosslinkable siloxane polymer that enables secondary crosslinking, and the end of the crosslinkable siloxane polymer are A crosslinked silicone film formed of all siloxane polymers has been studied (Patent Document 1).
In the equilibration polymerization reaction for producing the silicon polymer, the reaction is generally carried out under dehydration conditions in the presence of an acid or an alkali catalyst. In this reaction method, after the catalyst and the raw material react to form a catalyst adduct, the polymerization reaction proceeds. It is also known that moisture has a function as a reaction terminator, and it is known that at the end of the reaction, the polymerization reaction can be stopped by adding water (Non-patent Document 1).
It is also known that by taking out by-product water out of the system, the equilibrium shifts and the cycle of silicon polymer formation proceeds (Patent Document 2).
In addition, an example in which the activity / inactivity of an alkali (base) catalyst is controlled by moisture has been reported (Patent Document 3).

JP 2010-116464 A JP 2009-191207 A JP 2000-198849 A

Eugene G. EG Tochow, translated by Shozo Miki and Masao Tsuchagawa “Silicon and Silicones” Springer Fairlark Tokyo, June 20, 1990, p. 89

The present inventors have developed a novel crosslinkable silicon compound containing a silsesquioxane skeleton in the main chain of a silicon-based polymer.
In the sequential synthesis reaction, it is possible to obtain a crosslinkable polymer (crosslinkable silicon compound) having a certain quality, that is, having a molecular weight in a certain range, but strictness is required for reaction conditions and operations.
On the other hand, in the equilibration polymerization reaction under dehydration conditions, the progress of the reaction is unstable, and the polymerization may proceed to the high molecular weight body or may not proceed at all.
In this way, it is difficult to easily mass-produce crosslinkable silicon compounds of constant quality in sequential synthesis reactions, and it is difficult to control the reaction in equilibrium polymerization reactions. It was difficult to mass-produce the crosslinkable silicon compound.
In view of the above problems, the present invention provides a production method capable of easily mass-producing a crosslinkable silicon compound having a silsesquioxane skeleton in the main chain of a silicon-based polymer having a certain range of molecular weight.

As a result of the inventors' diligent research, in the equilibration polymerization reaction system, when synthesizing a crosslinkable silicon compound, a cage silsesquioxane as a raw material reacts with a catalyst to produce a catalyst adduct. Since the catalyst adduct is stable, it was speculated that the progress of the subsequent polymerization reaction is governed by the amount of water remaining in the system.
As a result of further intensive studies, it was found that after the initial catalyst adduct formation, the polymerization reaction proceeds due to the presence of an amount of water within a predetermined range. It has been found that there is an appropriate range for the amount of water, and if the amount falls below the lower limit, the polymerization reaction does not proceed or the molecular weight of the resulting crosslinkable silicon compound becomes unstable. Moreover, when exceeding an upper limit, it discovered that a water | moisture content acts as a reaction terminator also in this equilibration polymerization reaction system, and stops a polymerization reaction.
Furthermore, it has been found that the molecular weight reached (the molecular weight that has reached the equilibrium state) can be controlled by the polymerization temperature with respect to the polymerization temperature when carrying out the equilibration polymerization reaction.
As described above, the present inventors have made a crosslinkable silicon compound having a molecular weight in a certain range by allowing a predetermined amount of water to be present in the system and carrying out an equilibration polymerization reaction under conditions of a predetermined temperature range. It was found that can be obtained stably.
Based on the above knowledge, the present invention provides a production method capable of easily mass-producing a constant quality crosslinkable silicon compound. That is, the present invention provides the inventions represented by the following [1] to [10].

[1] In the presence of a catalyst and water, equilibrate one or both of the compound represented by the following formula (2) and the compound represented by the following formula (3) with the compound represented by the following formula (1). A method for producing a crosslinkable silicon compound comprising polymerizing reaction,
Preparation of one or both of the compound represented by the following formula (1), the compound represented by the following formula (2) and the compound represented by the following formula (3), which is a raw material of the crosslinkable silicon compound Including an aging step of aging in the presence of 0.5% by mass to 15% by mass of water based on the total mass,
The aging step is carried out at a temperature exceeding 0 ° C. and less than 100 ° C., wherein the method for producing a crosslinkable silicon compound (however, R ¹ , R ⁵ in the following formula (1), and the formula: (At least one of R ^{2 in} (2) includes hydrogen or a crosslinkable functional group having 2 to 40 carbon atoms).

（式（１）中、Ｒ⁰は独立して炭素数５〜２０のアリール又は炭素数５若しくは６のシ
クロアルキルを表し；
Ｒ³は独立して水素、又は−（Ｓｉ（Ｒ⁵）₂−Ｏ）_p−Ｓｉ（Ｒ⁵）₂−ＯＨ（ｐは独立して０〜３０の整数を表す）を表し；
Ｒ¹及びＲ⁵は独立して、水素若しくは炭素数２〜４０のアルケニルである架橋性官能基
、又は炭素数１〜４０のアルキル、任意の水素が独立してハロゲン若しくは炭素数１〜２０のアルキルで置き換えられてもよい炭素数６〜２０のアリール、又はアリールにおける任意の水素が独立してハロゲン若しくは炭素数１〜２０のアルキルで置き換えられてもよい炭素数７〜２０のアリールアルキルを表し；
前記炭素数１〜４０のアルキルにおいて、任意の水素は独立してフッ素で置き換えられてもよく、任意の−ＣＨ₂−は独立して−Ｏ−又は炭素数５〜２０のシクロアルキレンで
置き換えられてもよく；
前記アリール又はアリールアルキルの置換基である炭素数１〜２０のアルキルにおいて、任意の水素は独立してフッ素で置き換えられてもよく、任意の−ＣＨ₂−は独立して−
Ｏ−、炭素数５〜２０のシクロアルキレン又はフェニレンで置き換えられてもよく；
前記アリールアルキルのアルキレンにおいて、その炭素数は１〜１０であり、任意の水素は独立してフッ素で置き換えられてもよく、そして任意の−ＣＨ₂−は独立して−Ｏ−
、−ＣＨ＝ＣＨ−は炭素数５〜２０のシクロアルキレンで置き換えられてもよい。）

(In the formula (1), R ⁰ independently represents aryl having 5 to 20 carbon atoms or cycloalkyl having 5 or 6 carbon atoms;
R ³ independently represents hydrogen, or — (Si (R ⁵ ) ₂ —O) _p —Si (R ⁵ ) ₂ —OH (p independently represents an integer of 0 to 30);
R ¹ and R ⁵ are independently a crosslinkable functional group which is hydrogen or alkenyl having 2 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms, and any hydrogen is independently halogen or having 1 to 20 carbon atoms. Represents an aryl having 6 to 20 carbon atoms which may be replaced by alkyl, or an arylalkyl having 7 to 20 carbon atoms in which any hydrogen in aryl may be independently replaced by halogen or alkyl having 1 to 20 carbon atoms ;
In the alkyl having 1 to 40 carbon atoms, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — may be independently replaced with —O— or cycloalkylene having 5 to 20 carbon atoms. May be;
In the alkyl having 1 to 20 carbon atoms which is a substituent of the aryl or arylalkyl, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — is independently —
May be replaced by O-, C5-C20 cycloalkylene or phenylene;
In the arylalkyl alkylene, the carbon number thereof is 1 to 10, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — is independently —O—.
, -CH = CH- may be replaced by a cycloalkylene having 5 to 20 carbon atoms. )

（式（２）中、ｋは独立して０〜３０の整数を表し；
Ｒ²は前記式（１）のＲ¹と同様に定義され；
Ｒ⁴は、独立して、水酸基、水素若しくは炭素数２〜４０のアルケニルである架橋性官
能基、炭素数１〜４０のアルキル、ハロゲン、炭素数１〜１５のアシル、炭素数１〜１５のアルコキシル、炭素数１〜１５のオキシム、置換基を有していてもよいアミノ、置換基を有していてもよい炭素数１〜１５のアミド、置換基を有していてもよいアミノキシ、又は置換基を有していてもよい炭素数２〜１５のビニルアルコール残基を表し；
置換基を有するアミノ及びアミノキシでは、置換基の炭素数は１〜１５である。）

(In formula (2), k independently represents an integer of 0 to 30;
R ² is defined in the same manner as R ^{1 in} formula (1);
R ⁴ is independently a cross-linkable functional group which is a hydroxyl group, hydrogen or alkenyl having 2 to 40 carbon atoms, alkyl having 1 to 40 carbon atoms, halogen, acyl having 1 to 15 carbon atoms, or 1 to 15 carbon atoms. Alkoxyl, oxime having 1 to 15 carbon atoms, amino optionally having substituent (s), amide having 1 to 15 carbon atoms optionally having substituent (s), aminoxy optionally having substituent (s), or Represents an optionally substituted vinyl alcohol residue having 2 to 15 carbon atoms;
In amino and aminoxy having a substituent, the substituent has 1 to 15 carbon atoms. )

（式（３）中、ｈは３〜６の整数を表し；Ｒ²は前記式（１）のＲ¹と同様に定義される。）

(In formula (3), h represents an integer of 3 to 6; R ² is defined in the same manner as R ^{1 in} formula (1)).

[2] The method for producing a crosslinkable silicon compound according to [1], comprising reacting the compound represented by the formula (1) with the compound represented by the formula (2).
[3] The method for producing a crosslinkable silicon compound according to [1], comprising reacting the compound represented by the formula (1) with the compound represented by the formula (3).
[4] The method includes reacting the compound represented by the formula (1) with the compound represented by the formula (2) and the compound represented by the formula (3) [1] The manufacturing method of the crosslinkable silicon compound as described in 2. above.
[5] In any one of [1] to [4], in the aging step, the water content is 0.5% by mass or more and 10% by mass or less based on the total mass of the raw material of the crosslinkable silicon compound. A method for producing a crosslinkable silicon compound according to claim 1.
[6] In the aging step, the amount of the catalyst used is 0.7% by mass or more and 40% by mass or less based on the total mass of the raw material of the crosslinkable silicon compound [1] to [5] The manufacturing method of the crosslinkable silicon compound in any one of these.
[7] One or both of a silsesquioxane group represented by the following formula (8) or (9), a group represented by the following formula (10) and a group represented by the following formula (11), A production method according to any one of [1] to [6], wherein a crosslinkable silicon compound is produced.

（式（８）及び式（９）中、Ｒ⁰は独立して炭素数６〜２０のアリール又は炭素数５又
は６のシクロアルキルを表し；
式（８）中、Ｒ³は独立して水素、又は−（Ｓｉ（Ｒ⁵）₂−Ｏ）_p−Ｓｉ（Ｒ⁵）₂−ＯＨ（ｐは独立して０〜３０の整数を表す）を表し；
式（８）及び式（９）中、Ｒ¹及びＲ⁵は独立して、水素若しくは炭素数２〜４０のアルケニルである架橋性官能基、炭素数１〜４０のアルキル、任意の水素が独立してハロゲン若しくは炭素数１〜２０のアルキルで置き換えられてもよい炭素数６〜２０のアリール、又はアリールにおける任意の水素が独立してハロゲン若しくは炭素数１〜２０のアルキル
で置き換えられてもよい炭素数７〜２０のアリールアルキルを表し；
式（１０）及び式（１１）中、Ｒ^２はＲ¹と同様に定義され；
式（１１）中、Ｒ⁴は、独立して、水酸基、水素若しくは炭素数２〜４０のアルケニルで
ある架橋性官能基、炭素数１〜４０のアルキル、ハロゲン、炭素数１〜１５のアシル、炭素数１〜１５のアルコキシル、炭素数１〜１５のオキシム、置換基を有していてもよいアミノ、置換基を有していてもよい炭素数１〜１５のアミド、置換基を有していてもよいアミノキシ、又は置換基を有していてもよい炭素数２〜１５のビニルアルコール残基を表し；
前記炭素数１〜４０のアルキルにおいて、任意の水素は独立してフッ素で置き換えられてもよく、任意の−ＣＨ₂−は独立して−Ｏ−又は炭素数５〜２０のシクロアルキレンで
置き換えられてもよく；
前記アリール又はアリールアルキルの置換基である炭素数１〜２０のアルキルにおいて、任意の水素は独立してフッ素で置き換えられてもよく、任意の−ＣＨ₂−は独立して−
Ｏ−、炭素数５〜２０のシクロアルキレン又はフェニレンで置き換えられてもよく；
前記アリールアルキルのアルキレンにおいて、その炭素数は１〜１０であり、任意の水素は独立してフッ素で置き換えられてもよく、そして任意の−ＣＨ₂−は独立して−Ｏ−
、−ＣＨ＝ＣＨ−又は炭素数５〜２０のシクロアルキレンで置き換えられてもよく；
置換基を有するアミノ及びアミノキシでは、置換基の炭素数は１〜１５であり；
かつ、Ｒ¹、Ｒ⁵、及びＲ²の少なくとも１種が水素若しくは炭素数２〜４０のアルケニル
である架橋性官能基を含む。）

(In Formula (8) and Formula (9), R ⁰ independently represents aryl having 6 to 20 carbon atoms or cycloalkyl having 5 or 6 carbon atoms;
In Formula (8), R ³ is independently hydrogen, or — (Si (R ⁵ ) ₂ —O) _p —Si (R ⁵ ) ₂ —OH (p independently represents an integer of 0 to 30). Represents;
In formula (8) and formula (9), R ¹ and R ⁵ are independently hydrogen or a crosslinkable functional group that is alkenyl having 2 to 40 carbon atoms, alkyl having 1 to 40 carbon atoms, and arbitrary hydrogen is independent. And an aryl having 6 to 20 carbon atoms which may be replaced by halogen or alkyl having 1 to 20 carbon atoms, or any hydrogen in aryl may be independently replaced by halogen or alkyl having 1 to 20 carbon atoms. Represents arylalkyl having 7 to 20 carbon atoms;
In formula (10) and formula (11), R ² is defined in the same manner as R ¹ ;
In formula (11), R ⁴ is independently a hydroxyl group, hydrogen or a crosslinkable functional group which is alkenyl having 2 to 40 carbon atoms, alkyl having 1 to 40 carbon atoms, halogen, acyl having 1 to 15 carbon atoms, C1-C15 alkoxyl, C1-C15 oxime, Substituent amino, Substituent C1-C15 amide, Substituent Represents an aminoxy which may be substituted, or a vinyl alcohol residue having 2 to 15 carbon atoms which may have a substituent;
In the alkyl having 1 to 40 carbon atoms, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — may be independently replaced with —O— or cycloalkylene having 5 to 20 carbon atoms. May be;
In the alkyl having 1 to 20 carbon atoms which is a substituent of the aryl or arylalkyl, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — is independently —
May be replaced by O-, C5-C20 cycloalkylene or phenylene;
In the arylalkyl alkylene, the carbon number thereof is 1 to 10, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — is independently —O—.
, -CH = CH- or cycloalkylene having 5 to 20 carbon atoms may be substituted;
In amino and aminoxy having a substituent, the substituent has 1 to 15 carbon atoms;
And, including R ^1, R ^5, and at least one crosslinkable functional group is alkenyl having hydrogen or 2 to 40 carbon atoms R ^2. )

[8] The method for producing a crosslinkable silicon compound according to [7], wherein a crosslinkable silicon compound represented by the following formula (12) is produced.

（式（１２）中、ｍは独立して０〜３０の整数を表し；ｎは１〜１，０００の整数を表し；Ｒ⁰は前記式（８）及び（９）のＲ⁰と同じであり；Ｒ¹及びＲ²は前記式（８）〜（１１）のＲ¹及びＲ²とそれぞれ同じであり；かつ、Ｒ¹及び／又はＲ²が1個以上の水素若し
くは炭素数２〜４０のアルケニルである架橋性官能基を含む。）

(In the formula (12), m independently represents an integer of 0 to 30; n represents an integer of 1 to 1,000; R ⁰ is the same as R ^{0 in the} formulas (8) and (9). There; R ¹ and R ² are respectively the same as R ¹ and R ² in the formula (8) to (11); and, R ¹ and / or R ² 2 to 40 carbon one or more hydrogen or carbon A crosslinkable functional group that is an alkenyl of

[9] The method for producing a crosslinkable silicon compound according to any one of [1] to [8], wherein R ⁰ is phenyl.
[10] The method for producing a crosslinkable silicon compound according to [8] or [9], wherein m is 2 or more and 10 or less.

  By the production method of the present invention, a crosslinkable silicon compound having a molecular weight in a certain range and containing a silsesquioxane skeleton in the main chain of the silicon polymer can be easily mass-produced. This also facilitates application of the siloxane polymer and silicone film to the actual material by crosslinking of the crosslinkable silicon compound, which is excellent from the viewpoint of practical use. Applications of the siloxane polymer and silicone film include optical applications (resin, film, LED sealing material, contact lens).

In the present invention, in the presence of a catalyst and water, one or both of the compound represented by the following formula (2) and the compound represented by the following formula (3) is balanced with the compound represented by the following formula (1). A method for producing a crosslinkable silicon compound comprising a polymerization reaction, the compound represented by the following formula (1) as a raw material of the crosslinkable silicon compound, the compound represented by the following formula (2), and In the presence of 0.5% by mass or more and 15% by mass or less of water with respect to the total mass of one or both of the compounds represented by the following formula (3), the temperature is maintained at a temperature higher than 0 ° C. and lower than 100 ° C. (Wherein at least one of R ¹ and R ⁵ in the following formula (1) and R ² in the formula (2) is one or more hydrogen or carbon atoms 2 to 40 crosslinkable functional groups that are alkenyl).

（式（１）中、Ｒ⁰は独立して炭素数５〜２０のアリール又は炭素数５若しくは６のシ
クロアルキルを表し；
Ｒ³は独立して水素、又は−（Ｓｉ（Ｒ⁵）₂−Ｏ）_ｐ−Ｓｉ（Ｒ⁵）₂−ＯＨ（ｐは独立
して０〜３０の整数を表す）を表し；
Ｒ¹は独立して水素若しくは炭素数２〜４０のアルケニルである架橋性官能基、又は炭
素数１〜４０のアルキル、任意の水素が独立してハロゲン若しくは炭素数１〜２０のアルキルで置き換えられてもよい炭素数６〜２０のアリール、又はアリールにおける任意の水素が独立してハロゲン若しくは炭素数１〜２０のアルキルで置き換えられてもよい炭素数７〜２０のアリールアルキルを表し；
前記炭素数１〜４０のアルキルにおいて、任意の水素は独立してフッ素で置き換えられてもよく、任意の−ＣＨ₂−は独立して−Ｏ−又は炭素数５〜２０のシクロアルキレンで
置き換えられてもよく；
前記アリール又はアリールアルキルの置換基である炭素数１〜２０のアルキルにおいて、任意の水素は独立してフッ素で置き換えられてもよく、任意の−ＣＨ₂−は独立して−
Ｏ−、炭素数５〜２０のシクロアルキレン又はフェニレンで置き換えられてもよく；
前記アリールアルキルのアルキレンにおいて、その炭素数は１〜１０であり、任意の水素は独立してフッ素で置き換えられてもよく、そして任意の−ＣＨ₂−は独立して−Ｏ−
、−ＣＨ＝ＣＨ−は炭素数５〜２０のシクロアルキレンで置き換えられてもよい。）

(In the formula (1), R ⁰ independently represents aryl having 5 to 20 carbon atoms or cycloalkyl having 5 or 6 carbon atoms;
R ³ independently represents hydrogen or — (Si (R ⁵ ) ₂ —O) _p —Si (R ⁵ ) ₂ —OH (p independently represents an integer of 0 to 30);
R ¹ is independently a crosslinkable functional group that is hydrogen or alkenyl having 2 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms, and any hydrogen is independently replaced by halogen or alkyl having 1 to 20 carbon atoms. Optionally represents aryl having 6 to 20 carbon atoms, or any hydrogen in aryl independently represents halogen or arylalkyl having 7 to 20 carbon atoms which may be substituted with alkyl having 1 to 20 carbon atoms;
In the alkyl having 1 to 40 carbon atoms, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — may be independently replaced with —O— or cycloalkylene having 5 to 20 carbon atoms. May be;
In the alkyl having 1 to 20 carbon atoms which is a substituent of the aryl or arylalkyl, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — is independently —
May be replaced by O-, C5-C20 cycloalkylene or phenylene;
In the arylalkyl alkylene, the carbon number thereof is 1 to 10, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — is independently —O—.
, -CH = CH- may be replaced by a cycloalkylene having 5 to 20 carbon atoms. )

（式（２）中、ｋは独立して０〜３０の整数を表し；
Ｒ²は前記式（１）のＲ¹と同様に定義される基であり；
Ｒ⁴は、独立して、水酸基、水素若しくは炭素数２〜４０のアルケニルである架橋性官
能基、炭素数１〜４０のアルキル、ハロゲン、炭素数１〜１５のアシル、炭素数１〜１５のアルコキシル、炭素数１〜１５のオキシム、置換基を有していてもよいアミノ、置換基を有していてもよい炭素数１〜１５のアミド、置換基を有していてもよいアミノキシ、又は置換基を有していてもよい炭素数２〜１５のビニルアルコール残基を表し；
置換基を有するアミノ及びアミノキシでは、置換基の炭素数は１〜１５である。）

(In formula (2), k independently represents an integer of 0 to 30;
R ² is a group defined in the same manner as R ^{1 in the} formula (1);
R ⁴ is independently a cross-linkable functional group which is a hydroxyl group, hydrogen or alkenyl having 2 to 40 carbon atoms, alkyl having 1 to 40 carbon atoms, halogen, acyl having 1 to 15 carbon atoms, or 1 to 15 carbon atoms. Alkoxyl, oxime having 1 to 15 carbon atoms, amino optionally having substituent (s), amide having 1 to 15 carbon atoms optionally having substituent (s), aminoxy optionally having substituent (s), or Represents an optionally substituted vinyl alcohol residue having 2 to 15 carbon atoms;
In amino and aminoxy having a substituent, the substituent has 1 to 15 carbon atoms. )

（式（３）中、ｈは３〜６を表し；Ｒ²は前記式（２）のＲ²と同様に定義される基である。）

(In formula (3), h represents 3 to 6; R ² is a group defined in the same manner as R ^{2 in} formula (2)).

The silsesquioxane group-containing silicon compound used in the present invention will be described.
The silsesquioxane represented by the formula (1) includes a compound represented by the formula (4) and a compound represented by the formula (5) as described in JP-A-2006-222207. It is obtained by reacting and hydrolyzing. Here, X represents halogen or hydrogen. The compound represented by formula (4) is also hydrolyzed from the compound represented by formula (6) in the presence of sodium hydroxide and water, as described in JP-A-2006-222207. Obtained by condensation polymerization. The reaction at this time may be in the presence or absence of an organic solvent.

The silicon compound that reacts with the crosslinkable silsesquioxane group-containing silicon compound used in the present invention will be described.
Examples of the crosslinkable silicon compound that reacts with the crosslinkable silsesquioxane group-containing silicon compound used in the present invention include a linear siloxane represented by the formula (2) and / or a cyclic represented by the formula (3). Of siloxane.

（式（２）中、ｋは独立して０〜３０の整数を表し；
Ｒ²は前記式（１）のＲ¹と同様に定義される基であり；
Ｒ⁴は、独立して、水酸基、水素若しくは炭素数２〜４０のアルケニルである架橋性官
能基、炭素数１〜４０のアルキル、ハロゲン、炭素数１〜１５のアシル、炭素数１〜１５のアルコキシル、炭素数１〜１５のオキシム、置換基を有していてもよいアミノ、置換基を有していてもよい炭素数１〜１５のアミド、置換基を有していてもよいアミノキシ、又は置換基を有していてもよい炭素数２〜１５のビニルアルコール残基を表し；
置換基を有するアミノ及びアミノキシでは、置換基の炭素数は１〜１５である。）

(In formula (2), k independently represents an integer of 0 to 30;
R ² is a group defined in the same manner as R ^{1 in the} formula (1);
R ⁴ is independently a cross-linkable functional group which is a hydroxyl group, hydrogen or alkenyl having 2 to 40 carbon atoms, alkyl having 1 to 40 carbon atoms, halogen, acyl having 1 to 15 carbon atoms, or 1 to 15 carbon atoms. Alkoxyl, oxime having 1 to 15 carbon atoms, amino optionally having substituent (s), amide having 1 to 15 carbon atoms optionally having substituent (s), aminoxy optionally having substituent (s), or Represents an optionally substituted vinyl alcohol residue having 2 to 15 carbon atoms;
In amino and aminoxy having a substituent, the substituent has 1 to 15 carbon atoms. )

  In the formula (2), k is preferably 0 to 9, more preferably 0 to 5, and still more preferably 1 to 3, from the viewpoint of availability as a compound.

The substituent which R ⁴ may have is a compound represented by formulas (1) and (2) or a compound represented by formulas (1) to (3) as a crosslinkable silicon compound. This is a substituent that acts as a terminal terminator during the equilibration reaction in the case of synthesizing by an equilibration reaction, or a substituent that can generate silanol by hydrolysis and bond to the silsesquioxane moiety through a siloxane bond. As such substituents, for example, substituents that act as end terminators include hydroxyl groups, hydrogen or crosslinkable functional groups that are alkenyl having 2 to 40 carbon atoms, and alkyls, which produce silanols by hydrolysis. Examples of substituents include acyl, alkoxyl such as methoxy, and oxime.

（式（３）中、Ｒ²は式（１）におけるＲ²と同様に定義される基であり、ｈは３〜６の整数である。）

(In the formula (3), R ² is a group defined as for R ² in Formula (1), h is an integer from 3 to 6.)

In the formula (3), h represents 3 to 6; R ² is defined the same as R ² in the formula (2). H in Formula (3) is preferably 3 or 4 from the viewpoint of easy availability of the compound.

The production method of the present invention will be described.
In the production method of the present invention, in the presence of a catalyst and water, the compound represented by formula (1) is equilibrated with one or both of the compound represented by formula (2) and the compound represented by formula (3). A method for producing a crosslinkable silicon compound comprising a polymerization reaction, wherein the compound represented by formula (1) is a raw material of the crosslinkable silicon compound, and the compound represented by formula (2) and formula (3) A aging step of aging in the presence of 0.5% by mass or more and 15% by mass or less of water based on the total mass of one or both of the compounds represented by formula (1).
In the reaction system of the production method of the present invention, the amount of water in the aging step is the difference between the amount of water input into the reaction system and the amount of water extracted from the reaction system, and is represented by the formula (1) that is a raw material for the crosslinkable silicon compound. 0.5 mass% or more, preferably 1 mass% or more, based on the total mass of one or both of the compound represented by formula (2) and the compound represented by formula (2) and the compound represented by formula (3) More preferably, it is 1.5% by mass or more. Moreover, an upper limit is 15 mass% or less, Preferably it is 10 mass% or less, More preferably, it is 8 mass% or less.
Note that the amount of water charged into the reaction system includes the water contained in the catalyst.

In the production method of the present invention, the aging step is carried out while maintaining the temperature above 0 ° C and below 100 ° C.
In the reaction system of the production method of the present invention, the polymer does not elongate at 0 ° C. or lower, and the reaction progress becomes unstable at 100 ° C. or higher. It is presumed that when the aging temperature approaches the boiling point of water, the amount of water in the system decreases and the equilibration polymerization reaction of this system becomes unstable. From the viewpoint of controlling the water concentration in the reaction system, the aging step is preferably performed under temperature conditions exceeding 0 ° C.
The present inventors have found that when the equilibration polymerization reaction is performed, the ultimate molecular weight (molecular weight reaching the equilibrium state) can be controlled by the polymerization temperature. In the production method of the present invention, the polymer can be most elongated in the aging temperature range of 40 ° C. to 50 ° C. to produce a high molecular weight polymer. Under conditions of lower or higher temperatures than 40 ° C., smaller molecular weight polymers can be produced. The temperature of the aging step may be determined according to the desired molecular weight within the range of more than 0 ° C. and less than 100 ° C.
As described above, in the production method of the present invention, not only the molecular weight is controlled by the raw material and the catalyst concentration, but also the molecular weight can be controlled by the aging temperature.

  In the production method of the present invention, one or both of the compound represented by the formula (2) and the compound represented by the formula (3) are added to the compound represented by the formula (1) under the conditions of a normal polymerization reaction. The reaction is carried out underneath, followed by equilibrium polymerization in the aging step.

For example, the reaction of the compound represented by the formula (1) and the compound represented by the formula (2) generates a crosslinkable silicon compound represented by the formula (12 ′). This reaction is represented by the following reaction formula.
This reaction is usually performed at 40 to 150 ° C. in the presence of a strong acid or in the presence of a base such as triethylamine. M in the formula (12 ′) can be determined by the type of the chain siloxane. N in the formula (12 ′) is adjusted depending on the reaction conditions (temperature, concentration of the compound represented by the formula (1), etc.). According to this reaction, a crosslinkable silicon compound in which a silsesquioxane group which may have a crosslinkable functional group and a siloxane group which may have a crosslinkable functional group are alternately arranged is obtained. Can do.

  The reaction between the compound represented by the formula (1) and the compound represented by the formula (3) is represented by the following reaction formula. According to this reaction, a crosslinkable silicon compound in which silsesquioxane groups which may have a crosslinkable functional group and units having a siloxane group which may have a crosslinkable functional group are alternately arranged. Can be obtained.

  In this reaction, a disiloxane compound can be used as a terminal terminator. In this case, the crosslinkable silicon compound is obtained by refluxing the compound represented by the formula (1), the compound represented by the formula (3) and the compound represented by the formula (2) at 0 ° C. And obtained by aging at a temperature of less than 100 ° C. The reaction of the compound represented by the formula (1) with the compound represented by the formula (3) and the compound represented by the formula (2) is represented by the following reaction formula. According to this reaction, the silsesquioxane group which may have a crosslinkable functional group and the siloxane group which may have a crosslinkable functional group are alternately arranged, and the crosslinkable functional group is at the terminal. A crosslinkable silicon compound which may have

Also, the compound of formula (3) is obtained by reacting the silsesquioxane represented by formula (1) with the compound of formula (2 ′) to obtain a compound of formula (7). And the compound of formula (12) may be synthesized.

(In formula (2 ′), k ′ independently represents an integer of 0 to 30;
R ² is a group defined in the same manner as R ^{1 in} formula (1);
X is a halogen. )

(In the formula (7), l ′ and l ″ are independently integers from 0 to 14 and smaller than m, and m− (l ′ + l ″) − 2> 0).
Of these, l ′ and l ″ are preferably integers of 0 to 3.

  In the crosslinkable silicon compound of formula (12 ') obtained by the reaction described above, m in the formula may give a plurality of integers instead of a single one. In this case, m may be a mixture of polymers having an integer of 4 or more. That is, when the crosslinkable silicon compound obtained by the production method of the present invention is a mixture of polymers giving a plurality of m, m may be expressed by a decimal number instead of an integer.

  In this reaction system, one or both of the compound represented by the formula (1), the compound represented by the formula (2), and the compound represented by the following formula (3), which are raw materials for the crosslinkable silicon compound The molar ratio of the charge of is the ratio of the total mole of the compound represented by formula (1) to the total mole of the compound represented by formula (2) or the compound represented by formula (3) below. Is preferably 1: 1 or more and 1: 8 or less, more preferably 1: 1 or more and 1: 2 or less.

In this reaction system, a strong acid or a strong base is usually used as a catalyst. In the method for producing a crosslinkable silicon compound in the present invention, a strong acid is preferable as the catalyst in consideration of the stability during the reaction of silsesquioxane in each of the reactions described above. Examples of such a catalyst include hydrochloric acid, sulfuric acid, fluorosulfuric acid, p-toluenesulfonic acid monohydrate, trifluoromethanesulfonic acid, activated clay, and sulfonic acid ion exchange resin. Among these, p-toluenesulfonic acid monohydrate, trifluoromethanesulfonic acid, activated clay, and sulfonic acid ion exchange resins are more preferable.
As a commercially available product, RCP-160M (strongly acidic cation exchange resin, manufactured by Mitsubishi Chemical Corporation) can be used.

The amount of the catalyst used is not particularly limited as long as it is an amount sufficient to promote the equilibration polymerization reaction. From the viewpoint of promoting the reaction, preferably 0.5% by mass or more, more preferably 0.7% by mass or more, and further preferably 0.9% by mass or more, based on the total mass of the raw material of the crosslinkable silicon compound. It is. Further, from the viewpoint of cost effectiveness and polymerization stability, it is preferably 40% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less.

  In the above reaction, it is preferable to use a solvent. Any solvent can be used as long as it is a solvent that can dissolve the compound represented on the left side of the reaction formula in the above formula and does not react with an acid or base compound used as a catalyst. For example, a hydrocarbon solvent such as hexane or heptane. , Aromatic hydrocarbon solvents such as benzene, toluene and xylene, ether solvents such as diethyl ether, tetrahydrofuran (THF), dioxane and cyclopentyl methyl ether, and halogenated hydrocarbon solvents such as methylene chloride and carbon tetrachloride Etc. The solvent may be one kind or a mixture of two or more kinds.

  As described above, the production method of the present invention enables mass production of a cross-linkable silicon compound having a certain quality by simply controlling the amount of water and the temperature. Moreover, since the control of the amount of water and the temperature does not require any special changes to existing production equipment, it is possible to provide a cross-linkable silicon compound having a certain quality at a low cost.

  A crosslinkable silicon compound containing a silsesquioxane skeleton in the main chain of a silicon-based polymer obtained by the production method of the present invention as described above is a silsesquioxane represented by the following formula (8) or (9). It consists of an oxan group and one or both of a group represented by the following formula (10) and a group represented by the following formula (11). In this specification, “consisting of” means “having a partial structure”.

In Formula (8), R ³ is independently hydrogen, or — (Si (R ⁵ ) ₂ —O) _p —Si (R ⁵ ) ₂ —OH (p independently represents an integer of 0 to 30). Represents.
In Formula (8) and Formula (9), R ⁰ independently represents aryl having 6 to 20 carbon atoms or cycloalkyl having 5 or 6 carbon atoms. Any two of R ⁰ may be the same or different. R ⁰ is preferably phenyl from the viewpoint of obtaining various characteristics such as optical characteristics and the ease of synthesis.

In formula (8) and formula (9), R ¹ and R ⁵ are independently a crosslinkable functional group, carbon or alkenyl having 2 to 40 carbon atoms, which can be added to silicon of other compounds. An alkyl having a number of 1 to 40, an arbitrary hydrogen may be independently replaced by a halogen or an alkyl having a carbon number of 1 to 20, or an aryl having a carbon number of 6 to 20, or an arbitrary hydrogen in an aryl is independently a halogen or a carbon This represents an arylalkyl having 7 to 20 carbon atoms which may be substituted with an alkyl having 1 to 20 carbon atoms.

In the alkyl having 1 to 40 carbon atoms, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — may be independently replaced with —O— or cycloalkylene having 5 to 20 carbon atoms. May be. In the alkyl having 1 to 20 carbon atoms which is a substituent of the aryl or arylalkyl, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — is independently —O—, It may be replaced with cycloalkylene having 5 to 20 carbon atoms or phenylene. Further, in the alkylene of the arylalkyl, the carbon number thereof is 1 to 10, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — is independently —O—, — CH = CH- or C5-C20 cycloalkylene may be substituted.

  The crosslinkable functional group is a functional group bonded to silicon in the crosslinkable silicon compound that can be added to silicon in other compounds. The crosslinkable functional groups may all be the same or different in one crosslinkable silicon compound. As said crosslinkable functional group, hydrogen or a C2-C40 alkenyl is mentioned, for example, As a specific group at this time, a C2-C40 alkenyl or hydrogen is mentioned, for example. The crosslinkable functional group is preferably hydrogen or vinyl from the viewpoint of ease of synthesis.

R ¹ may all be the same or different. R ¹ excluding the crosslinkable functional group is preferably methyl, for example, from the viewpoint of ease of synthesis.

In formula (10) and formula (11), R ² is defined in the same manner as R ¹ . R ² may all be the same or different. R ² excluding the crosslinkable functional group is preferably methyl, for example, from the viewpoint of ease of synthesis.

In formula (11), R ⁴ is independently a hydroxyl group, hydrogen or a crosslinkable functional group which is alkenyl having 2 to 40 carbon atoms, alkyl having 1 to 40 carbon atoms, halogen, acyl having 1 to 15 carbon atoms, carbon An alkoxyl having 1 to 15 carbon atoms, an oxime having 1 to 15 carbon atoms, an amino optionally having a substituent, an amide having 1 to 15 carbon atoms optionally having a substituent, and a substituent; Represents an aminoxy which may have a substituent or a vinyl alcohol residue having 2 to 15 carbon atoms which may have a substituent, and in the amino and aminoxy having a substituent, the substituent has 1 to 15 carbon atoms.
. R ⁴ may be the same as or different from each other in the same manner as R ¹ . R ⁴ excluding the crosslinkable functional group is preferably methyl, for example, from the viewpoint of ease of synthesis.

At least one of R ¹ , R ⁵ , R ² and R ⁴ contains one or more crosslinkable functional groups. In the crosslinkable silicon compound, the crosslinkable functional groups may be arranged uniformly or may be arranged unevenly. The number of the crosslinkable functional groups in the crosslinkable silicon compound can be appropriately determined according to desired physical properties and applications of the siloxane polymer that is a cross-linked product of the crosslinkable functional groups. For example, from the viewpoint of increasing the mechanical strength of the siloxane polymer film, the number of crosslinkable functional groups is preferably 1 to 60, more preferably 1 to 30 per 10,000 molecular weight. More preferably, it is 16.

  Examples of the crosslinkable silicon compound include a compound comprising a silsesquioxane group having the crosslinkable functional group and a siloxane group not having the crosslinkable functional group, or a silsesquioxane having no crosslinkable functional group. Examples thereof include a compound comprising an oxane group and a siloxane group having a crosslinkable functional group, and a compound comprising a silsesquioxane group having the crosslinkable functional group and a siloxane group having the crosslinkable functional group. Examples of the siloxane group having a crosslinkable functional group include a group composed of a group of the formula (10) having the crosslinkable functional group and a group of the formula (11) having no crosslinkable functional group, A group comprising the group of formula (10) having no functional group and the group of formula (11) having the crosslinkable functional group, and the group of formula (10) having the crosslinkable functional group and the crosslink And a group comprising a group of formula (11) having a functional functional group.

The molecular weight of the crosslinkable silicon compound is preferably 10,000 to 200,000, more preferably 30,000 to 150,000, and more preferably 40,000 to 120,000 in terms of weight average molecular weight (Mw). More preferably. The number of silsesquioxane groups in the crosslinkable silicon compound is preferably 1 to 8 and more preferably 4 to 8 per 10,000 molecular weight from the viewpoint of obtaining a high hardness siloxane polymer by crosslinking. Preferably, it is 6-8.

More specifically, examples of the crosslinkable silicon compound include compounds represented by the following formula (12). R ¹ and / or R ² in the formula (12) includes one or more crosslinkable functional groups.

In formula (12), m independently represents an integer of 0 to 30, and n represents an integer of 1 to 1,000. m is preferably 0 to 30 and preferably 2 to 10 from the viewpoint of the ease of synthesis and the effect of the ratio of the silsesquioxane moiety and the siloxane moiety on the physical properties of the compound of formula (12). Is more preferable, and it is more preferable that it is 2-8. Further, n is determined from the following mathematical formula (1) in conjunction with the determination of the molecular weight and m.
Molecular weight = {A + (B × m + C)} × n + terminal H ₂ O Formula (1)
A: Silsesquioxane unit B: Siloxane unit C: —O—Si (R ² ) ₂ —

<Siloxane polymer>
A siloxane polymer can be obtained from the crosslinkable silicon compound produced by the production method of the present invention and the crosslinkable compound capable of causing a crosslinking reaction with the crosslinkable silicon compound.

  As a raw material of the siloxane polymer, the crosslinkable compound may be one kind or two or more kinds, a silicon compound, or a non-silicon compound such as a normal organic compound. The crosslinkable compound may be a compound that crosslinks with the crosslinkable functional group of the crosslinkable silicon compound, or may be a compound that crosslinks with another portion of the crosslinkable silicon compound. The crosslinkable compound can be determined based on the type of the crosslinkable silicon compound and the form of crosslinking with the crosslinkable silicon compound.

For example, the crosslinkable silicon compound has a hydroxyl group (for example, R ⁵ is a hydroxyl group,
In the case of the compound represented by the formula (12), the crosslinkable compound is a condensed crosslinkable silicon compound having three or more groups or atoms that cause a condensation reaction with a hydroxyl group in the crosslinkable silicon compound. be able to. Examples of such a condensation-crosslinking silicon compound include methyltrimethoxysilane, methyltris (methylethylketoxime) silane, and methyltriacetoxysilane. In the case of using the condensed crosslinkable silicon compound, for example, the crosslinkable silicon compound can be crosslinked by placing the crosslinkable composition at room temperature in an atmosphere of water such as normal air.

For example, when the crosslinkable silicon compound is the first crosslinkable silicon compound having hydrogen as a crosslinkable functional group, the crosslinkable compound has 2 to 4 carbon atoms as the crosslinkable functional group.
A second crosslinkable silicon compound having 0 alkenyl can be used.

  Furthermore, the crosslinkable compound may be a compound that reacts with a crosslinkable functional group or other portion in the crosslinkable silicon compound by another reaction mechanism such as radical polymerization. Examples of such a crosslinkable compound include compounds having an unsaturated hydrocarbon group such as a vinyl group when the crosslinkable silicon compound has an alkenyl having 2 to 40 carbon atoms as a crosslinkable functional group. Examples of such compounds include acrylic monomers such as methacrylic acid, methyl methacrylate, 2-hydroxyethyl methacrylate, acrylic acid, butyl acrylate, 2-hydroxyethyl acrylate, and vinyl monomers such as vinyl acetate. Can be mentioned.

  The ratio of the crosslinkable compound to the crosslinkable silicon compound as a component of the siloxane polymer is 1 to 100 with respect to 100 parts by mass of the crosslinkable silicon compound from the viewpoint of physical properties of the obtained siloxane polymer and silicone film. It is preferable that it is a mass part, It is more preferable that it is 2-50 mass parts, It is further more preferable that it is 5-20 mass parts.

  A crosslinkable silicon compound produced by the production method of the present invention and the crosslinkable compound can be contained to obtain a crosslinkable composition. Since the crosslinkable silicon compound has the crosslinkable functional group, for example, a mixture of two or more crosslinkable silicon compounds each having one or more of hydrogen and alkenyl groups as the crosslinkable functional group. Can be cured by a crosslinking reaction such as a hydrosilylation reaction.

  Further, for example, when the crosslinkable silicon compound has a hydroxyl group, it can be crosslinked and cured by using the condensation crosslinkable silicon compound. In the case of using a condensation crosslinkable silicon compound, the crosslinkable silicon compound and the crosslinkable compound may be crosslinked only by crosslinking by the condensation reaction with the condensation crosslinkable silicon compound, or in addition to a crosslinking reaction such as a hydrosilylation reaction. Furthermore, the crosslinkable silicon compound and the crosslinkable compound may be crosslinked by a condensation reaction with the condensation crosslinkable silicon compound.

  The ratio of the crosslinkable compound to the crosslinkable silicon compound in the crosslinkable composition is 1 with respect to 100 parts by mass of the crosslinkable silicon compound from the viewpoint of the characteristics of the siloxane polymer and silicone film obtained by crosslinking and curing. It is preferably ˜40 parts by mass, more preferably 3 to 25 parts by mass, and even more preferably 5 to 15 parts by mass.

  The crosslinkable composition may further contain a solvent. Such a solvent is preferably a solvent that can dissolve both the crosslinkable silicon compound and the crosslinkable compound and that does not condense with the crosslinkable silicon compound or the crosslinkable compound. Examples of such solvents include hydrocarbon solvents such as hexane and heptane, aromatic hydrocarbon solvents such as benzene, toluene and xylene, ether solvents such as diethyl ether, tetrahydrofuran (THF) and dioxane, and chloride. Examples thereof include halogenated hydrocarbon solvents such as methylene and carbon tetrachloride, and ester solvents such as ethyl acetate. The solvent may be a single solvent or two or more solvents.

  The content of the solvent is preferably an amount such that the content of the crosslinkable silicon compound and the crosslinkable compound is 20 to 80% by mass, and from 30 to 70% by mass, from the viewpoint of applicability. It is more preferable that the amount is 40 to 60% by mass.

Moreover, the said crosslinkable composition may further contain the adjuvant for the bridge | crosslinking by a crosslinkable functional group. Such an auxiliary agent can be determined based on the type of the crosslinkable functional group. For example, a crosslinkable composition containing a first crosslinkable silicon compound having hydrogen as a crosslinkable functional group and a second crosslinkable silicon compound having alkenyl having 2 to 40 carbon atoms as a crosslinkable functional group. In that case, in addition to the solvent described above, a hydrosilylation catalyst may be further contained.

  As the hydrosilylation catalyst, a platinum catalyst usually used in a hydrosilyl reaction can be used. Examples of such a platinum catalyst include chloroplatinic acid and karsted catalyst. In the crosslinkable composition, the content of the hydrosilylation catalyst is preferably 0.1 to 1,000 ppm, more preferably 0.5 to 200 ppm, and further preferably 1 to 50 ppm. .

  The film of the crosslinkable composition containing the crosslinkable silicon compound produced by the production method of the present invention can be cured to obtain a silicone film. The film | membrane of a crosslinkable composition can be formed by the well-known method apply | coated to a board | substrate or a sheet | seat. Further, the curing of the film of the crosslinkable composition can be determined based on the conditions for crosslinking with the crosslinkable functional group. For example, when the crosslinkable functional group is hydrogen and alkenyl having 2 to 40 carbon atoms, the silicone film can be formed by heating the crosslinkable composition or the film thereof to 50 to 150 ° C. for 1 to 15 hours.

  For example, when the crosslinkable silicon compound is a compound of the formula (12), the silicone film is a crosslinkable siloxane having a main chain formed entirely from silanol in which siloxane chains and silsesquioxane are alternately arranged. It is comprised by the crosslinked material of a polymer. Such a silicone film has excellent effects in various physical properties such as solubility, heat resistance, mechanical strength, optical permeability, gas permeability, dielectric constant, flame retardancy, adhesiveness, workability, and a wide range of applications. Expected to be used.

  For example, the application of electrical / electronic materials in the silicone film obtained from the crosslinkable silicon compound produced by the production method of the present invention includes coating agents for substrates such as metal elution prevention films, gas barrier films and antireflection films, liquid sealing Agents, light-emitting diode encapsulants, interlayer insulating films, antifouling coating agents, microlenses, light guide plates, optical waveguide materials and other optical elements, display substrates, printed wiring boards, and the like. Also, it is expected to be used for optical resins, optical films, contact lenses and the like.

  The crosslinkable silicon compound produced by the production method of the present invention can be confirmed by the molecular weight by GPC or the presence of peaks of silsesquioxane part and siloxane part by NMR. The siloxane polymer and silicone film obtained from the crosslinkable silicon compound produced by the production method of the present invention are confirmed by, for example, changes in heat resistance and solubility in a solvent when produced from a raw material containing the crosslinkable silicon compound. can do. For example, the formation of siloxane polymers and silicone films can be confirmed by not melting when heated to 120 ° C. or by the product being insoluble in acetone.

In addition, the weight average molecular weight of each of the aforementioned compounds in the present invention can be determined by GPC, and more specifically can be determined under the following conditions.
<GPC measurement conditions>
The measurement conditions for GPC measurement are shown below.
<Measurement conditions>
Column: Showex Denko Co., Ltd. Shodex KF804L, Shodex KF805L, 2 in series Mobile phase: THF
Flow rate: 1.0 ml / min
Temperature: 40 ° C
Detector: RI
Molecular weight standard sample: polystyrene with known molecular weight

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited only to the Example illustrated below.

<Example 1>
A cooling tube, a mechanical stirrer, a Dean-Stark tube, an oil bath, and a thermometer protective tube were attached to a 100 mL flask, and the inside of the flask was purged with nitrogen. DD (Me) -OH (formula (13) 5.0 g, octamethylcyclotetrasiloxane (D4) 2.5 g, RCP-16
0.5 g of 0M (strongly acidic cation exchange resin, manufactured by Mitsubishi Chemical Corporation: water content 23.4 mass%) and 51.0 mL of dehydrated toluene were placed in a flask. Reflux for 1 hour, toluene 22.
4 mL and 0.12 g of water contained in 23.4 mass% in RCP-160M were extracted. After completion of the reflux, the mixture was cooled to 80 ° C., 0.55 g of pure water was added and aging was carried out at 80 ° C., and equilibrium was reached in 5 hours. After cooling to room temperature, RCP-160M was filtered off, and the obtained filtrate was washed once with water. Thereafter, the solvent and low boiling point components of the filtrate were distilled off, and the resulting crude product was purified by reprecipitation with heptane. The obtained white viscous liquid was vacuum dried at 40 ° C. to obtain 2.5 g of a white solid. ^{According to 1} H-NMR and GPC analysis, the obtained white solid is the target compound represented by the formula (14), and each constituent unit (silsesquioxane unit and dimethylsiloxane unit) in the formula (1) is alternately arranged. It was found that the average siloxane chain length was 4.0 in terms of the number of Si atoms. From the GPC analysis, the number average molecular weight of the target product was Mn = 29,500, and the weight average molecular weight was Mw = 48,700. ^When calculated from the average siloxane chain length and the weight average molecular weight Mw obtained by ¹ H-NMR and GPC analysis, n was 33 and m was 3.0. The results are shown in Table 1. In Table 1, the amount of water in the reaction system (H ₂ O / total charge) is a value obtained from the following mathematical formula (2). Note that the amount of water charged into the reaction system includes the water contained in the catalyst.
Moisture content (H ₂ O / total charge)
= {(Amount of water charged into the reaction system) / (addition amount of DD (Me) -OH + addition amount of D4)} × 100 Formula (2)

<Example 2>
A cooling tube, a mechanical stirrer, and a thermometer protection tube were attached to the 100 mL flask, and the inside of the flask was purged with nitrogen. DD (Me) -OH (formula (13)) 5.0 g, octamethylcyclotetrasiloxane (D4) 2.5 g, RCP-160M (strongly acidic cation exchange resin, manufactured by Mitsubishi Chemical Corporation): water content 23. 4 mass%) 0.5 g, dehydrated toluene 28.6 mL
Was placed in a flask. Only reflux was performed for 1 hour, and toluene / water was not extracted. After refluxing, the mixture was cooled to 80 ° C. and aged at 80 ° C. to reach equilibrium in 5 hours. After completion of aging, the mixture was cooled to room temperature, and RCP-160M was filtered off. The obtained filtrate was washed with water once. Thereafter, the solvent and low-boiling components were distilled off from the filtrate, and the resulting crude product was purified by reprecipitation with heptane. The obtained white viscous liquid was vacuum dried at 40 ° C. to obtain 1.7 g of a white solid. ^{According to 1} H-NMR and GPC analysis, the obtained white solid is the target compound represented by the formula (14), and each constituent unit (silsesquioxane unit and dimethylsiloxane unit) in the formula (1) alternates. It was found that the average siloxane chain length with a polymer bonded to was 4.1 on average in terms of the number of Si atoms. From the GPC analysis, the number average molecular weight of the target product was Mn = 31,500, and the weight average molecular weight was Mw = 58,800. ^When calculated from the average siloxane chain length and weight average molecular weight Mw obtained by ¹ H-NMR and GPC analysis, n was 40 and m was 3.1. The results are shown in Table 1.

<Example 3>
Add 25.0 g of DD (Me) -OH (formula (13)) to a 500 mL three-necked flask, and assemble Dean-Stark tube, reflux tube, thermometer, and synthesizer (EYELA RCH-20L and EYELA aluminum block bath) The apparatus was heated and dried under reduced pressure at 120 ° C. and 10 mbar for 3 hours. The inside of the flask was replaced with nitrogen and allowed to cool to room temperature, and then 250 mL of toluene, 0.8 g of p-toluenesulfonic acid monohydrate and 12.5 g of octamethylcyclotetrasiloxane (D4) were added and refluxed to start azeotropic dehydration. did. After confirming that no water droplets were generated in the toluene in the Dean-Stark tube, 125 mL of toluene was extracted from the Dean-Stark tube over about 30 minutes. After allowing to cool to 80 ° C., 0.76 mL of water was added and the mixture was aged at 50 ° C. for 24 hours to reach an equilibrium molecular weight. After cooling to room temperature, the mixture was transferred to a separatory funnel to remove the acid catalyst and washed with a saturated aqueous sodium hydrogen carbonate solution. The aqueous layer became pH 9 by washing twice with a saturated aqueous solution of sodium bicarbonate. Furthermore, it washed with water until the aqueous layer became neutral. The organic layer was concentrated by an evaporator to obtain a white oily crude product. It melt | dissolved in the minimum amount of toluene, and it was dripped slowly in hexane, and stirred. The supernatant and the precipitate were separated by decantation, and the precipitate was vacuum-dried to obtain 24.3 g of a white solid. ^{From the 1} H-NMR analysis and the GPC analysis, the obtained white solid is the target product (formula (14)), and each constituent unit (silsesquioxane unit and dimethylsiloxane unit) in formula (14) is alternately arranged. It was a polymer formed by bonding, and the average siloxane chain length was found to be 3.4 on average in terms of the number of Si atoms. According to GPC analysis, the obtained white solid had a weight average molecular weight of Mw = 75,200. In the formula (1), m =
2.4, n = 53. The results are shown in Table 1.

<Example 4>
The conditions were the same as in Example 3 except that the aging temperature was changed to 60 ° C. The polymer molecular weight reached equilibrium at an aging time of 24 hours. ^{From the 1} H-NMR analysis and the GPC analysis, the obtained white solid is the target product (formula (14)), and each constituent unit (silsesquioxane unit and dimethylsiloxane unit) in formula (14) is alternately arranged. It was a polymer formed by bonding, and the average siloxane chain length was found to be 3.4 on average in terms of the number of Si atoms. According to GPC analysis, the obtained white solid had a weight average molecular weight of Mw = 64,400, and in formula (14), m = 2.
4. It was found that n = 45. The results are shown in Table 1.

<Example 5>
The conditions were the same as in Example 3 except that the aging temperature was changed to 70 ° C. The polymer molecular weight reached equilibrium at an aging time of 24 hours. ^{From the 1} H-NMR analysis and the GPC analysis, the obtained white solid is the target product (formula (14)), and each constituent unit (silsesquioxane unit and dimethylsiloxane unit) in formula (14) is alternately arranged. It was a polymer formed by bonding, and the average siloxane chain length was found to be 3.4 on average in terms of the number of Si atoms. According to GPC analysis, the obtained white solid had a weight average molecular weight of Mw = 52,800, and in the formula (14), m = 2,
4. It was found that n = 37. The results are shown in Table 1.

<Example 6>
The same conditions as in Example 3 were used except that the aging temperature was changed to 80 ° C. The polymer molecular weight reached an equilibrium at a aging time of 40 hours. ^{From the 1} H-NMR analysis and the GPC analysis, the obtained white solid is the target product (formula (14)), and each constituent unit (silsesquioxane unit and dimethylsiloxane unit) in formula (13) is alternately It was a polymer formed by bonding, and the average siloxane chain length was found to be 3.4 on average in terms of the number of Si atoms. According to GPC analysis, the obtained white solid had a weight average molecular weight of Mw = 42,500, and in formula (14), m = 2.
4. It was found that n = 30. The results are shown in Table 1.

<Example 7>
The test was carried out under the same conditions as in Example 3, except that p-toluenesulfonic acid monohydrate was changed to 0.5-fold mol and the aging temperature was changed to 50 ° C. The polymer molecular weight reached equilibrium at an aging time of 216 hours. ^{From the 1} H-NMR analysis and GPC analysis, the obtained white solid is the target product (formula (14)), and each structural unit (silsesquioxane and dimethylsiloxane unit) in formula (14) is bonded alternately. It was found that the average siloxane chain length was 3.4 in terms of the number of Si atoms. The weight average molecular weight of the obtained white solid was found to be Mw = 76,000 by GPC analysis, and it was found that m = 2.4 and n = 53 in formula (13). The results are shown in Table 1.

<Example 8>
A cooling tube, a mechanical stirrer, an oil bath, and a thermometer protection tube were attached to a 100 mL flask, and the inside of the flask was replaced with nitrogen. DD (Me) -OH (formula (13)) 10 g, octamethylcyclotetrasiloxane (D4) 5.0 g, RCP-160M (strongly acidic cation exchange resin, manufactured by Mitsubishi Chemical Corporation): water content 30.3 mass% ) 1.0 g and dehydrated toluene 35.0 mL were placed in a flask. Only refluxing was performed for 1 hour, and no toluene / water extraction was performed. After refluxing, the mixture was cooled to 90 ° C. and aged at 90 ° C. for 5 hours to reach equilibrium. After completion of aging, the mixture was cooled to room temperature, and RCP-160M was filtered off. The obtained filtrate was washed with water once. Thereafter, the solvent and low-boiling components were distilled off from the filtrate, and the resulting crude product was purified by reprecipitation with heptane. The obtained white viscous liquid was vacuum-dried at 40 ° C. to obtain 9.2 g of a white solid. ^{According to 1} H-NMR and GPC analysis, the obtained white solid is the target compound represented by the formula (14), and each constituent unit (silsesquioxane unit and dimethylsiloxane unit) in the formula (1) alternates. It was found that the average siloxane chain length with the polymer formed by bonding to was 4.4 on average in terms of the number of Si atoms. From the GPC analysis, the number average molecular weight of the target product was Mn = 23,900, and the weight average molecular weight was Mw = 54,200. ^When calculated from the average siloxane chain length and the weight average molecular weight Mw obtained by ¹ H-NMR and GPC analysis, n was 44 and m was 3.4. The results are shown in Table 1.

<Example 9>
A cooling tube, a mechanical stirrer, an oil bath, and a thermometer protection tube were attached to a 100 mL flask, and the inside of the flask was replaced with nitrogen. DD (Me) -OH (formula (13)) 3.0 g, octamethylcyclotetrasiloxane (D4) 1.5 g, RCP-160M (strongly acidic cation exchange resin, manufactured by Mitsubishi Chemical Corporation): water content 29. 4 mass%) 0.31 g and dehydrated toluene 10.4 mL were placed in a flask. Only reflux was performed for 1 hour, and toluene / water was not extracted. After refluxing, the mixture was rapidly cooled to 25 ° C. and aged at 25 ° C. for 26 hours, and reached equilibrium in 26 hours. After aging, RCP-160M was filtered off. The obtained filtrate was washed with water once. Thereafter, the solvent and low-boiling components were distilled off from the filtrate, and the resulting crude product was purified by reprecipitation with heptane. The obtained white viscous liquid was vacuum-dried at 40 ° C. to obtain 2.1 g of a white solid. ^{According to 1} H-NMR and GPC analysis, the obtained white solid was represented by the formula (14)
There is a polymer in which each structural unit (silsesquioxane unit and dimethylsiloxane unit) in formula (1) is alternately bonded, and the average siloxane chain length is 4 on average in terms of the number of Si atoms. .7. From the GPC analysis, the number average molecular weight of the target product was Mn = 27,000, and the weight average molecular weight was Mw = 58,800. ¹ H-NMR and G
When calculated from the average siloxane chain length and weight average molecular weight Mw obtained by PC analysis, n was 44 and m was 3.7. The results are shown in Table 1.

<Example 10>
DD (Me) -OH 40 g was added to a 500 mL three-necked flask, and a Dean-Stark tube, reflux tube, thermometer, and synthesizer (EYELA RCH-20L and EYELA aluminum block thermostatic bath) were assembled, and the conditions were 120 ° C. and 1 kPa. The apparatus was heated and dried under reduced pressure for 3 hours. The inside of the flask was replaced with nitrogen and allowed to cool to room temperature, and then 400 mL of toluene, 1.3 g of p-toluenesulfonic acid monohydrate and 20 g of octamethylcyclotetrasiloxane were added and refluxed to start azeotropic dehydration. After confirming that no water droplets were generated in the toluene in the Dean-Stark tube, 195 mL of toluene was extracted from the Dean-Stark tube over about 30 minutes. After allowing to cool to 80 ° C., 1.2 mL (68 mmol) of water was added and ripened at 40 ° C., reaching equilibrium in 24 hours. After cooling to room temperature, the reaction solution was sampled and transferred to a separatory funnel to remove the acid catalyst and washed with a saturated aqueous sodium hydrogen carbonate solution. The aqueous layer became pH 9 by washing twice with a saturated aqueous solution of sodium bicarbonate. Furthermore, it washed with water until the aqueous layer became neutral. The organic phase was analyzed by GPC, but the progress of polymerization could not be confirmed. The solvent is distilled off and vacuum-dried at 40 ° C. From ¹ H-NMR analysis and GPC analysis, each of the structural units (silsesquioxane and dimethylsiloxane unit) in the formula (14) is a polymer that is randomly bonded. The average siloxane chain length was found to be 3.4 on average in terms of the number of Si atoms. The weight average molecular weight of the obtained white solid was found to be Mw = 76,300 by GPC analysis, and it was found that m = 2.4 and n = 54 in formula (14). The results are shown in Table 1.

<Comparative Example 1>
A cooling tube, a mechanical stirrer, a Dean-Stark tube, and a thermometer protective tube were attached to a 100 mL flask, and the inside of the flask was purged with nitrogen. DD (Me) -OH (formula (13)) 15 g, octamethylcyclotetrasiloxane (D4) 7.1 g, RCP-160M (strongly acidic cation exchange resin, manufactured by Mitsubishi Chemical Corporation): water content 23.4 wt% ) 1.5 g and 141 mL of dehydrated toluene were placed in a flask. Reflux for 1 hour, 53 mL of toluene and RCP-1
0.4 g of water contained in 23.4 mass% in 60M was extracted. After completion of the reflux, the mixture was cooled to 80 ° C., and 3.4 g of pure water was added and aged for 8 hours. Unreacted. Further, the number average molecular weight of the product after aging was Mn = 10,600, and the weight average molecular weight was Mw = 30,600. The results are shown in Table 1.

<Comparative example 2>
A cooling tube, a mechanical stirrer, a Dean-Stark tube, and a thermometer protective tube were attached to a 100 mL flask, and the inside of the flask was purged with nitrogen. DD (Me) -OH (formula (13)) 5.0 g, octamethylcyclotetrasiloxane (D4) 2.4 g, RCP-160M (strongly acidic cation exchange resin, manufactured by Mitsubishi Chemical Corporation): water content 23. 4 wt%) 0.5 g and dehydrated toluene 47 mL were placed in a flask. Reflux for 1 hour, and 21 mL of toluene and RC
In order to extract 0.12 g of water contained in 23.4 mass% in P-160M, the mixture was refluxed for 8 hours and then cooled to 80 ° C. Subsequently, the mixture was aged at 80 ° C. for 3 hours, but from GPC analysis, the polymerization had hardly progressed before aging, and DD (Me) —OH was 80% unreacted. The number average molecular weight of the product after aging was Mn = 8,340, and the weight average molecular weight was Mw = 35,700. The results are shown in Table 1.

<Comparative Example 3>
Add 100 g of DD (Me) -OH to a 3 L flask and assemble the Dean-Stark tube, reflux tube, thermometer, mantle heater, peripheral pump, and nitrogen line, and heat and vacuum dry the device at 120 ° C, 20 mbar for 3 hours. went. In order to remove moisture from the system after replacing the inside of the flask with nitrogen and allowing to cool to room temperature, adding 1000 mL of dehydrated toluene, 64.1 g of p-toluenesulfonic acid monohydrate, and 100 g of octamethylcyclotetrasiloxane, The mixture was refluxed and azeotropic dehydration was started. After confirming that no water droplets were generated in toluene in the Dean-Stark tube, they were extracted and refluxed for another 20 hours. After allowing to cool to room temperature, it was transferred to a separatory funnel to remove the acid catalyst and washed with water until the aqueous layer became neutral. The organic layer was concentrated by an evaporator to obtain a white oily crude product. It melt | dissolved in the minimum amount of toluene, it was dripped slowly in hexane, a supernatant liquid and a precipitate were separated by decantation, and the precipitate was vacuum-dried and 135g of white solid was obtained. ¹ H-NMR analysis and GPC analysis show the target product (formula (14)), and each structural unit (silsesquioxane and dimethylsiloxane unit) in formula (14) is bonded alternately. The polymer was found to have an average siloxane chain length of 4.1 on average in terms of Si atoms. GPC analysis showed that the obtained white solid had a weight average molecular weight of Mw = 245,000, and in formula (14), m = 3.1 and n = 167. The results are shown in Table 1.

<Comparative example 4>
Add 100 g of DD (Me) -OH to a 2 L flask and assemble the Dean Stark tube, reflux tube, thermometer, mantle heater, peripheral pump, and nitrogen line, and heat and vacuum dry the device at 120 ° C., 20 mbar for 3 hours. went. After the inside of the flask was replaced with nitrogen and allowed to cool to room temperature, dehydrated toluene 1000 mL, p-toluenesulfonic acid monohydrate 64.1 g, octamethylcyclotetrasiloxane (D4) 100 g (337 mmol) were added,
The mixture was refluxed and azeotropic dehydration was started. After confirming that no water droplets were generated in the toluene in the Dean-Stark tube, they were extracted and refluxed for another 20 hours. After allowing to cool to room temperature, it was transferred to a separatory funnel to remove the acid catalyst and washed with water until the aqueous layer became neutral. The organic layer was concentrated by an evaporator to obtain 160 g of a white oily crude product. Although it melt | dissolved in the minimum amount toluene and dripped slowly in hexane and stirred, precipitation did not arise. The crude product is a polymer in which each structural unit (silsesquioxane and dimethylsiloxane unit) in formula (14) is bonded alternately by ¹ H-NMR analysis and GPC analysis, and the average siloxane chain length is Si. The average number of atoms was found to be 3.8. The weight average molecular weight of the obtained white solid was found to be Mw = 9,200 by GPC analysis, and it was found that m = 2.8 and n = 6 in formula (14). The results are shown in Table 1.

<Comparative Example 5>
A cooling tube, a mechanical stirrer, an oil bath, and a thermometer protection tube were attached to a 100 mL flask, and the inside of the flask was replaced with nitrogen. DD (Me) -OH (formula (13)) 10 g, octamethylcyclotetrasiloxane (D4) 5.0 g, RCP-160M (strongly acidic cation exchange resin, manufactured by Mitsubishi Chemical Corporation): moisture content 29.9 mass% ) 1.0 g and dehydrated toluene 35.0 mL were placed in a flask. Only reflux was performed for 1 hour, and toluene / water was not extracted. After refluxing, it was cooled to −5 ° C. with a low-temperature constant temperature bath and aged at −5 ° C. for 21 hours, but the molecular weight did not increase in the aging process. After aging, RCP-160M was filtered off. The obtained filtrate was washed with water once. Thereafter, the solvent and low-boiling components were distilled off from the filtrate, and the resulting crude product was purified by reprecipitation with heptane. The resulting white viscous liquid was vacuum dried at 40 ° C. to obtain 8.0 g of a white solid. ^{According to 1} H-NMR and GPC analysis, the obtained white solid is the target compound represented by the formula (14), and each constituent unit (silsesquioxane unit and dimethylsiloxane unit) in the formula (1) alternates. It was found that the average siloxane chain length was 4.5 in terms of the number of Si atoms. From the GPC analysis, the number average molecular weight of the target product was Mn = 19,300, and the weight average molecular weight was Mw = 36,000. ^When calculated from the average siloxane chain length and the weight average molecular weight Mw obtained by ¹ H-NMR and GPC analysis, n was 26 and m was 3.5. The results are shown in Table 1.

From Examples 1 to 10 in which the aging step was performed in the presence of an amount of water within a predetermined range, it was shown that a stable and constant quality crosslinkable silicon compound can be easily obtained by the production method of the present invention. It was done.
On the other hand, Comparative Example 1 performed under the condition where the water content was excessive showed that the polymerization hardly proceeded even after the aging step, and that DD (Me) -OH was 20% unreacted.
Further, in Comparative Example 2 in which the aging step was performed after removing moisture in the system, the polymerization hardly proceeded even after the aging step, and DD (Me) -OH was 80% unreacted.
From Comparative Example 3 and Comparative Example 4 in which the aging step was not performed, it was shown that polymers having greatly different molecular weights were formed despite the same synthesis conditions.
Further, Comparative Example 5 showed that the molecular weight did not elongate under the condition that the aging temperature was lowered to -5 ° C.

  The cured product of a curable silicon compound having a silsesquioxane group has optical properties, electrical properties, heat resistance, and gas permeability as compared with ordinary silicon compounds such as siloxane and its polymers. In some cases, it exhibits unique characteristics in various characteristics such as mechanical strength. Therefore, the curable silicon compound having a silsesquioxane group and a cured product thereof are more effectively used in the fields of transparent films such as lenses and protective films, and electrical and optical sealing materials. Be expected. The present invention is very useful because a silicon compound that is useful in this way can be manufactured with a constant quality and can be easily mass-produced.

Claims (10)

In the presence of a catalyst and water, the compound represented by the following formula (1) is allowed to undergo an equilibrium polymerization reaction with one or both of the compound represented by the following formula (2) and the compound represented by the following formula (3). A method for producing a crosslinkable silicon compound comprising:
Preparation of one or both of the compound represented by the following formula (1), the compound represented by the following formula (2) and the compound represented by the following formula (3), which is a raw material of the crosslinkable silicon compound Including an aging step of aging in the presence of 0.5% by mass to 15% by mass of water based on the total mass,
The aging step is carried out at a temperature exceeding 0 ° C. and less than 100 ° C., wherein the method for producing a crosslinkable silicon compound (however, R ¹ , R ⁵ in the following formula (1), and the formula: (At least one of R ^{2 in} (2) includes hydrogen or a crosslinkable functional group having 2 to 40 carbon atoms).

(In the formula (1), R ⁰ independently represents aryl having 5 to 20 carbon atoms or cycloalkyl having 5 or 6 carbon atoms;
R ³ independently represents hydrogen, or — (Si (R ⁵ ) ₂ —O) _p —Si (R ⁵ ) ₂ —OH (p independently represents an integer of 0 to 30);
R ¹ and R ⁵ are independently a crosslinkable functional group which is hydrogen or alkenyl having 2 to 40 carbon atoms, or alkyl having 1 to 40 carbon atoms, and any hydrogen is independently halogen or having 1 to 20 carbon atoms. Represents an aryl having 6 to 20 carbon atoms which may be replaced by alkyl, or an arylalkyl having 7 to 20 carbon atoms in which any hydrogen in aryl may be independently replaced by halogen or alkyl having 1 to 20 carbon atoms ;
In the alkyl having 1 to 40 carbon atoms, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — may be independently replaced with —O— or cycloalkylene having 5 to 20 carbon atoms. May be;
In the alkyl having 1 to 20 carbon atoms which is a substituent of the aryl or arylalkyl, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — is independently —
May be replaced by O-, C5-C20 cycloalkylene or phenylene;
In the arylalkyl alkylene, the carbon number thereof is 1 to 10, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — is independently —O—.
, -CH = CH- may be replaced by a cycloalkylene having 5 to 20 carbon atoms. )

(In formula (2), k independently represents an integer of 0 to 30;
R ² is defined in the same manner as R ^{1 in} formula (1);
R ⁴ is independently a cross-linkable functional group which is a hydroxyl group, hydrogen or alkenyl having 2 to 40 carbon atoms, alkyl having 1 to 40 carbon atoms, halogen, acyl having 1 to 15 carbon atoms, or 1 to 15 carbon atoms. Alkoxyl, oxime having 1 to 15 carbon atoms, amino optionally having substituent (s), amide having 1 to 15 carbon atoms optionally having substituent (s), aminoxy optionally having substituent (s), or Represents an optionally substituted vinyl alcohol residue having 2 to 15 carbon atoms;
In amino and aminoxy having a substituent, the substituent has 1 to 15 carbon atoms. )

(In formula (3), h represents an integer of 3 to 6; R ² is defined in the same manner as R ^{1 in} formula (1)).   2. The method for producing a crosslinkable silicon compound according to claim 1, comprising reacting the compound represented by the formula (1) with the compound represented by the formula (2).   The method for producing a crosslinkable silicon compound according to claim 1, comprising reacting the compound represented by the formula (1) with the compound represented by the formula (3).   The compound represented by the formula (1) is reacted with the compound represented by the formula (2) and the compound represented by the formula (3). A method for producing a crosslinkable silicon compound.   5. The moisture content is 0.5% by mass or more and 10% by mass or less based on the total charged mass of the raw material of the crosslinkable silicon compound in the aging step. A process for producing a crosslinkable silicon compound.   6. The method according to claim 1, wherein the amount of the catalyst used is 0.7% by mass or more and 40% by mass or less based on the total mass of the raw material of the crosslinkable silicon compound in the aging step. The manufacturing method of the crosslinkable silicon compound as described in 2. above. Crosslinking comprising a silsesquioxane group represented by the following formula (8) or (9) and one or both of a group represented by the following formula (10) and a group represented by the following formula (11) The manufacturing method of any one of Claims 1-6 which manufactures a property silicon compound.

(In Formula (8) and Formula (9), R ⁰ independently represents aryl having 6 to 20 carbon atoms or cycloalkyl having 5 or 6 carbon atoms;
In Formula (8), R ³ is independently hydrogen, or — (Si (R ⁵ ) ₂ —O) _p —Si (R ⁵ ) ₂ —OH (p independently represents an integer of 0 to 30). Represents;
In formula (8) and formula (9), R ¹ and R ⁵ are independently hydrogen or a crosslinkable functional group that is alkenyl having 2 to 40 carbon atoms, alkyl having 1 to 40 carbon atoms, and arbitrary hydrogen is independent. And an aryl having 6 to 20 carbon atoms which may be replaced by halogen or alkyl having 1 to 20 carbon atoms, or any hydrogen in aryl may be independently replaced by halogen or alkyl having 1 to 20 carbon atoms. Represents arylalkyl having 7 to 20 carbon atoms;
In formula (10) and formula (11), R ² is defined in the same manner as R ¹ ;
In formula (11), R ⁴ is independently a hydroxyl group, hydrogen or a crosslinkable functional group which is alkenyl having 2 to 40 carbon atoms, alkyl having 1 to 40 carbon atoms, halogen, acyl having 1 to 15 carbon atoms, C1-C15 alkoxyl, C1-C15 oxime, Substituent amino, Substituent C1-C15 amide, Substituent Represents an aminoxy which may be substituted, or a vinyl alcohol residue having 2 to 15 carbon atoms which may have a substituent;
In the alkyl having 1 to 40 carbon atoms, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — may be independently replaced with —O— or cycloalkylene having 5 to 20 carbon atoms. May be;
In the alkyl having 1 to 20 carbon atoms which is a substituent of the aryl or arylalkyl, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — is independently —
May be replaced by O-, C5-C20 cycloalkylene or phenylene;
In the arylalkyl alkylene, the carbon number thereof is 1 to 10, any hydrogen may be independently replaced with fluorine, and any —CH ₂ — is independently —O—.
, -CH = CH- or cycloalkylene having 5 to 20 carbon atoms may be substituted;
In amino and aminoxy having a substituent, the substituent has 1 to 15 carbon atoms;
And, including R ^1, R ^5, and at least one crosslinkable functional group is alkenyl having hydrogen or 2 to 40 carbon atoms R ^2. ) The method for producing a crosslinkable silicon compound according to claim 7, wherein a crosslinkable silicon compound represented by the following formula (12) is produced.

(In the formula (12), m independently represents an integer of 0 to 30; n represents an integer of 1 to 1,000; R ⁰ is the same as R ^{0 in the} formulas (8) and (9). There; R ¹ and R ² are respectively the same as R ¹ and R ² in the formula (8) to (11); and, R ¹ and / or R ² 2 to 40 carbon one or more hydrogen or carbon A crosslinkable functional group that is an alkenyl of The method for producing a crosslinkable silicon compound according to any one of claims 1 to 8, wherein ^R0 is phenyl.   The method for producing a crosslinkable silicon compound according to claim 8 or 9, wherein m is 2 or more and 10 or less.