JP2014098147A - Siloxane compound, and curable composition and cured body comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition which has an obtained cured body showing sufficient heat resistance and can be also molded so that no bubbles remain in the cured body, and a siloxane compound used in the preparation of the composition.SOLUTION: A siloxane compound is basket-formed polysiloxane having a specific substituent, wherein the specific substituent is an N-containing organosilicon group such as an azido group, or an organosilicon group having an alkyne group.

Description

  The present invention relates to a curable siloxane compound, a curable composition containing the siloxane compound, and a cured product using the composition.

  Encapsulants used for LSI (Large Scale Integration) elements equipped with a plurality of semiconductors and LED (Light Emitting Diode) elements that convert electricity into light are required to have appropriate fluidity in a non-solvent liquid state, and In addition, the property of not foaming at the time of molding and curing is required. Until now, investigations have been made mainly on epoxy resins and silicone resins as the sealing material. However, although the epoxy resin is inexpensive and excellent in mechanical strength, there is a problem that the heat resistance is as low as about 150 ° C. Moreover, although the heat resistance of silicone resin is up to about 200 ° C. and has better heat resistance than epoxy resin, the amount of water vapor and oxygen permeation is higher than that of epoxy resin, and metal parts used for wiring of LED elements and LSI elements are There was a problem that it deteriorated with time. Therefore, these epoxy resins and silicone resins cannot be applied to next-generation power semiconductor encapsulants and high-power LED encapsulants that require further high heat resistance, low water vapor permeability, and low oxygen permeability. There was a problem. In order to solve this problem, organic-inorganic hybrid materials have been studied (for example, Patent Documents 1 to 3).

  However, in the dehydration condensation reaction between silanol groups, which is generally known as the curing reaction of organic-inorganic hybrid materials, water is by-produced during curing, so it is difficult to mold without leaving bubbles in the cured body. The cured product obtained by leaving a lowering of mechanical strength. Therefore, a method has been proposed in which an addition reaction such as hydrosilylation is used for curing instead of a condensation reaction.

  However, since the curing reaction by hydrosilylation can suppress foaming in the cured body, it is particularly used for the curing reaction of LED encapsulants. However, since the chemical bond formed by curing is an ethylene bond, There was a problem that heat resistance was inferior to the siloxane bond formed by the dehydration condensation reaction.

  In addition, since a cross-linking reaction by an organic group is used, there is no silanol group, which causes a problem that adhesion strength to glass or a metal substrate is lowered.

JP 2004-123936 A JP 2005-325174 A JP2006-022207

  Cured composition formed by curing reaction exhibits sufficient heat resistance and can be molded without leaving bubbles in the cured product, siloxane compound for preparing the curable composition, and the curing A cured product obtained from the adhesive composition is provided.

  As a result of intensive studies, the present inventors have focused on a ring structure formation reaction with higher heat resistance, not a polymerization reaction due to an ethylene bond with low heat resistance, as a crosslinking (curing) reaction of a siloxane compound. The present invention was completed by synthesizing a curable siloxane compound to be prepared, preparing a curable composition using the same, and further curing the curable composition to obtain a cured product.

  That is, the present invention includes the following invention 1 to invention 17.

[Invention 1]
General formula (1)

(In Formula (1), each X is independently X1 or X2, the number a of X1 is an integer of 2 to 8, the number b of X2 is an integer of 0 to 6, and the sum of a and b. Is 8. In formulas X1 and X2, R ¹ , R ² , R ³ , R ⁴ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl having 6 to 12 carbon atoms. A hydrogen atom of these hydrocarbon groups may be substituted with a fluorine atom.

R ⁵ is independently selected from the formulas (1-1) to (1-4)

(In formulas (1-2) and (1-4), R ⁷ is an organic group containing a hydroxyl group, an alkoxy group, an ester group or a trialkylsilyl group, and R ⁸ and R ⁹ are each independently a hydroxyl group, An organic group containing an alkoxy group, an ester group, or a trimethylsilyl group.)
An organic group having one or more substituents selected from m and n are each independently an integer of 1 to 4. )
A siloxane compound represented by

[Invention 2]
The siloxane compound of the invention 1, wherein R ⁵ is an organic group having an azide group (formula (1-1)).

[Invention 3]
R ⁵ represents the formula (3) or (4)

(In formulas (3) and (4), v and w are each independently an integer of 0 to 6. A represents a phenylene group, a naphthylene group, or a biphenylene group, and any of these aromatic hydrocarbon groups. These hydrogen atoms may be substituted with fluorine atoms, and may be substituted with alkyl groups having 1 to 6 carbon atoms, perfluoroalkyl groups having 1 to 6 carbon atoms, and cyano groups.)
The siloxane compound of the invention 1 or 2 represented by these.

[Invention 4]
The siloxane compound according to any one of Inventions 1 to 3, wherein R ⁵ is represented by Formula (5) or (6).

[Invention 5]
General formula (2)

(In Formula (2), X is each independently X3 or X4, the number c of X3 is an integer of 2 to 8, the number d of X4 is an integer of 0 to 6, and The sum is 8. In Formulas X3 and X4, R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a group having 6 to 12 carbon atoms. It is an aryl group, and any number of hydrogen atoms contained in these hydrocarbon groups may be substituted with fluorine atoms.

R ¹⁴ is independently selected from formulas (2-1) to (2-6).

(In the formulas (2-1) to (2-6), R ^16A is a single bond, an alkylene group having 1 to 8 carbon atoms, or an arylene group having 6 to 12 carbon atoms, and R ^16B and R ¹⁷ are each independently , A hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 18 carbon atoms, and R ¹⁸ and R ¹⁹ are each independently a fluoroalkyl group having 1 to 6 carbon atoms, a cyano group, or an ester group. R ²⁰ is an alkylene group having 1 to 6 carbon atoms or an aryl group having 6 to 18 carbon atoms, and R ²¹ and R ²² are each independently a trifluoromethanesulfonyl group, a trimethylsilyl group, an iodine atom, or a bromine atom. .)
Is an organic group having one or more substituents selected from p, and p and q are each independently an integer of 1 to 4. )
A siloxane compound represented by

[Invention 6]
The siloxane compound of the invention 5, wherein R ¹⁴ is an organic group having a terminal acetylene group.

[Invention 7]
R ¹⁴ represents formulas (7) to (11)

(Wherein x, y and z are each independently an integer of 0 to 6. B represents a phenylene group, a naphthylene group or a biphenylene group, and any number of hydrogen atoms in these aromatic hydrocarbon groups. May be substituted with a fluorine atom, and may be substituted with an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms, or a cyano group, and R ²⁷ and R ²⁸ are each independently Represents a dialkylsilylene group or an alkylene group having 1 to 6 carbon atoms.)
The siloxane compound of the invention 5 or 6 represented by these.

[Invention 8]
R ¹⁴ represents the formulas (12) to (18).

Any one siloxane compound of invention 5-7 represented by these.

[Invention 9]
The curable composition containing any one siloxane compound of invention 1-4 and any one siloxane compound of invention 5-8.

[Invention 10]
Any one of the siloxane compounds of the inventions 1 to 4, and the general formula (19)

(In the formula (19), R ²³ and R ²⁴ are each independently an organic group containing an amino group, an aromatic ring, a heterocyclic ring, a siloxane group, or a silazane group, or a hydrogen atom, and h is an integer of 2 to 4. there. However ^{R 23, R 24} can not both be a hydrogen atom. in ^{addition, R 23} and ^{R 24} mutually, an alkylene group, vinylene group, ethynylene group, a ring as an aromatic ring or heterocyclic linking groups, (It may be formed.)
The curable composition containing the alkyne compound represented by these.

[Invention 11]
Any one of the siloxane compounds of Inventions 1 to 4, and the general formula (20)

(In Formula (20), R ²⁶ is an organic group containing a siloxane group, and i is an integer of 2 to 3)
The curable composition containing the maleimide compound represented by these.

[Invention 12]
Any one of the siloxane compounds of inventions 5 to 8 and the general formula (21)

(In formula (21), R ²⁵ represents an organic group containing at least an amino group, an aromatic ring, a heterocyclic ring, a siloxane group, or a silazane group, and j represents an integer of 2 to 4.)
The curable composition containing the azide compound represented by these.

[Invention 13]
Alkyne compounds are represented by the general formulas (22) to (24).

(In Formula (22), aa is an integer of 1-4. In Formula (23), ab is an integer of 0-10. In Formula (24), ac is an integer of 1-2, ad is 2. An integer of ˜3, and ac and ad satisfy the formula ac + ad = 3)
The curable composition of the invention 10 represented by these.

[Invention 14]
Alkyne compounds are represented by formulas (25) to (27)

The curable composition of invention 10 or 13, which is one compound selected from the group consisting of:

[Invention 15]
The maleimide compound is represented by formula (28) or formula (29)

The curable composition of invention 11, which is one compound selected from:

[Invention 16]
Furthermore, the curable composition of any one of invention 9-15 containing a curing catalyst.

[Invention 17]
The curable composition according to any one of Inventions 9 to 16, further comprising inorganic fine particles.

[Invention 18]
A cured product obtained by curing the curable composition according to any one of Inventions 9 to 17.

[Invention 19]
The hardened | cured material of the invention 18 obtained by heat-processing and hardening | curing.

  The curable composition containing the siloxane compound of the present invention has a high heat resistance due to the formation of a ring structure in the curing reaction, and a cured product free from cracks and containing bubbles therein is obtained.

  In this specification, the siloxane compound represented by the general formula (1) may be represented as “siloxane compound (1)”, and the siloxane compound represented by the general formula (2) may be represented as “siloxane compound (2)”.

  Below, the siloxane compound of this invention, the curable composition containing the same, and the hardening body produced from the curable composition are demonstrated in order.

<1. Siloxane compound>
[Siloxane compound (1)]
One of the siloxane compounds of the present invention is represented by the general formula (1)

[Wherein, X is independently X1 or X2, the number a of X1 is an integer of 1 to 8, the number b of X2 is an integer of 0 to 7, and the sum of a and b is 8 It is.

R ¹ , R ² , R ³ , R ⁴ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and the hydrogen atoms of these hydrocarbon groups are It may be substituted with a fluorine atom.

R ⁵ is an organic group having one or more substituents selected from formulas (1-1) to (1-4)

(Wherein R ⁷ is an organic group containing a hydroxyl group, an alkoxy group, an ester group or a trialkylsilyl group, and R ⁸ and R ⁹ each independently represents a hydroxyl group, an alkoxy group, an ester group or a trialkylsilyl group. Contains organic groups.)
And m and n are each independently an integer of 1 to 4. ]
(Hereinafter, it may be expressed as “siloxane compound (1)”).

In R ¹ , R ² , R ³ , R ⁴ and R ⁶ , the alkyl group having 1 to 8 carbon atoms specifically includes a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, and n-butyl. Group or sec-butyl group. Specific examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a biphenyl group, and a naphthyl group. Among them, a methyl group and a phenyl group are preferable from the viewpoint of synthesis and availability, and those in which all of R ¹ , R ² , R ³ , and R ⁴ are methyl groups are particularly preferable.

R ⁵ is an organic group having one or more substituents selected from formulas (1-1) to (1-4). This substituent corresponds to one reactive group responsible for the curing reaction in obtaining a cured product from the curable composition of the present invention described later.

In R ⁷ , specific examples of the alkoxy group include a methoxy group, an ethoxy group, and an isopropoxy group. Among these, a methoxy group is preferable from the viewpoint of synthesis and availability.

Specific examples of the ester group in R ⁷ include a methyl ester group and an ethyl ester group. More specifically, examples include a methyl acetoacetate group, an ethyl acetoacetate group, an isopropyl acetoacetate group, an n-butyl acetoacetate group, and an isobutyl acetoacetate group.

Specific examples of the trialkylsilyl group in R ⁷ include a trimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a triisopropyl group, a tert-butyldimethylsilyl group, and a tert-butyldiphenylsilyl group.

Specific examples of the alkoxy group in R ⁸ and R ⁹ include a methoxy group, an ethoxy group, and an isopropoxy group. Among these, a methoxy group is preferable from the viewpoint of synthesis and availability.

Specific examples of the ester group in R ⁸ and R ⁹ include a methyl ester group and an ethyl ester group.

Specific examples of the trialkylsilyl group in R ⁸ and R ⁹ include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, triisopropyl group, tert-butyldimethylsilyl group, and tert-butyldiphenylsilyl group. .

R ⁵ preferably has an azide group represented by the formula (1-1) from the viewpoint of synthesis and availability. Specifically, a group represented by the formula (3), a group represented by the formula (4)

(In formulas (3) and (4), v and w are each independently an integer of 0 to 6. A represents a phenylene group, a naphthylene group, or a biphenylene group, and any number of hydrogens in these groups. The atom may be substituted with a fluorine atom, and may be substituted with an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms, or a cyano group.)
Etc. Specific examples of the group represented by formula (3) or formula (4) include groups represented by the following.

Of these, the groups represented below are particularly preferred.

The siloxane compound (1) is preferably a compound represented by the following.

  When the number of X1 in the formula is 1, the siloxane compound (1) does not contribute to the formation of the skeleton of the cured product, but is effectively used for capping the cured product end. Curing obtained from a curable composition containing at least the siloxane compound (1) and a siloxane compound (2), alkyne compound (19), and / or maleimide compound (20) described later when the number of X1 is 2 or more The body skeleton can be formed.

[Siloxane compound (2)]
One of the siloxane compounds of the present invention is represented by the general formula (2)

[In Formula (2), each X is independently X3 or X4, the number c of X3 is an integer of 2 to 8, the number d of X4 is an integer of 0 to 6, and The sum is eight. In formulas X3 and X4, R ¹⁰ , R ¹¹ , R ¹² , R ^13, and R ¹⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms. The hydrogen atom of the hydrogen group may be substituted with a fluorine atom. R ¹⁴ represents formulas (2-1) to (2-6).

Is an organic group having one or more substituents selected from: p and q are each independently an integer of 1 to 4. R ^16A is a single bond, an alkylene group, or an arylene group, and R ^16B and R ¹⁷ are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 18 carbon atoms, R ¹⁸ and R ¹⁹ are each independently a fluoroalkyl group having 1 to 6 carbon atoms, a cyano group, or an ester group, and R ²⁰ is an alkylene group having 1 to 6 carbon atoms or an arylene group having 6 to 18 carbon atoms. Each of R ²¹ and R ²² is a trifluoromethanesulfonyl group, a trimethylsilyl group, an iodine atom, or a bromine atom. ]
It is represented by

In R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁵ , the alkyl group having 1 to 8 carbon atoms may be linear, branched or cyclic, and specifically includes a methyl group, ethyl Group, 1-propyl group, 2-propyl group, n-butyl group or sec-butyl group. Specific examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a biphenyl group, and a naphthyl group. Among them, a methyl group and a phenyl group are preferable from the viewpoint of synthesis and availability, and those in which all of R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are methyl groups are particularly preferable.

R ¹⁴ is an organic group containing a substituent that reacts with R ⁵ in the siloxane compound (1), and this substituent is responsible for a curing reaction in obtaining a cured product from the curable composition of the present invention. It corresponds to one reactive group.

In R ^16A , the alkylene group may be chain, branched, or cyclic, and specific examples include a methylene group, an ethylene group, a propylene group, an isopropylene group, and a cyclohexylene group. Furthermore, an arbitrary number of hydrogen atoms of the alkylene group may be substituted with fluorine atoms. Specific examples include a difluoromethylene group, a tetrafluoroethylene group, an n-hexafluoropropylene group, and an n-octafluorobutylene group.

In R ^16A , the arylene group specifically includes a phenylene group and a naphthylene group. Further, an arbitrary number of hydrogen atoms of the arylene group may be substituted with fluorine atoms. Specific examples include a tetrafluorophenylene group.

In R ^16B and R ¹⁷ , the alkyl group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and specifically includes a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group. Group, n-butyl group or sec-butyl group. Specific examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a biphenyl group, and a naphthyl group. Among these, a methyl group and a phenyl group are preferable from the viewpoint of synthesis and availability, and a methyl group is particularly preferable.

Specific examples of the fluoroalkyl group having 1 to 6 carbon atoms in R ¹⁸ and R ¹⁹ include a trifluoromethyl group, a pentafluoroethyl group, an n-heptafluoropropyl group, and an n-nonafluorobutyl group. Examples of the ester group include a methyl ester group, an ethyl ester group, an n-propyl ester group, an isopropyl ester group, and an n-butyl ester group. R ¹⁸ and R ¹⁹ are preferably a trifluoromethyl group, an n-nonafluorobutyl group, a methyl ester group, an ethyl ester group, or a cyano group.

In R ²⁰ , examples of the alkylene group having 1 to 6 carbon atoms include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, and an n-hexylene group. Specific examples of the arylene group having 6 to 18 carbon atoms include a biphenylene group and a naphthylene group. Of these, a methylene group, an ethylene group, and an n-propylene group are preferable.

R ¹⁴ is a group containing an ethynyl group, in which R ^16A in the structure represented by formula (2-1) is a single bond and R ^16B is a hydrogen atom because of ease of synthesis and availability. It is preferable.

Examples of groups containing ethynyl groups include those of formulas (7) to (11)

(Wherein x, y and z are each independently an integer of 0 to 6. B represents a phenylene group, a naphthylene group or a biphenylene group, and any number of hydrogen atoms in these aromatic hydrocarbon groups. May be substituted with a fluorine atom, and may be substituted with an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms, or a cyano group, and R ²⁷ and R ²⁸ are each independently Represents a dialkylsilylene group or an alkylene group having 1 to 6 carbon atoms.)
Is mentioned.

In R ²⁷ and R ²⁸ , the dialkylsilylene group is a group in which a hydrogen atom in a silylene group (—SiH ₂ —) is substituted with two alkyl groups having 1 to 6 carbon atoms, specifically, a dimethylsilylene group, diethyl Examples thereof include a silylene group and a methylethylsilylene group. The alkylene group having 1 to 6 carbon atoms may be chain, branched, or cyclic, and specifically includes a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, Examples thereof include n-hexylene group.

Specific examples of R ¹⁴ include groups represented by the following.

Of these, the groups represented below are particularly preferred.

The siloxane compound (2) is preferably a compound represented by the following.

    When the number of X3 in the formula is 1, the siloxane compound (2) does not contribute to the formation of the skeleton of the cured product, but is effectively used for capping the cured product end. When the number of X3 is 2 or more, the skeleton of a cured product obtained from a curable composition containing at least the siloxane compound (2) and the siloxane compound (1) and / or the azide compound (21) described later Can be formed.

<2. Method for producing siloxane compound>
Although an example of the manufacturing method of the siloxane compound of this invention is demonstrated below, it is not limited to this. The siloxane compound (1) and the siloxane compound (2) can be produced from a common intermediate raw material. This common intermediate material has the formula (30)

(Wherein X is independently X5 or X6, the number e of X5 is an integer of 2 to 8, the number f of X6 is an integer of 0 to 6, and the sum of e and f is 8) R ⁴⁰ , R ⁴¹ , R ⁴² and R ⁴³ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 12 carbon atoms, (The hydrogen atom may be substituted with a fluorine atom. S and t are each independently an integer of 1 to 4.)
(Hereinafter, sometimes referred to as “siloxane compound (30)”).

In R ⁴⁰ , R ⁴¹ , R ⁴² and R ⁴³ , the alkyl group having 1 to 8 carbon atoms may be linear, branched or cyclic, and specifically includes a methyl group, an ethyl group, 1 -Propyl group, 2-propyl group, n-butyl group or sec-butyl group. Specific examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a biphenyl group, and a naphthyl group. Among these, a methyl group and a phenyl group are preferable from the viewpoint of synthesis and availability, and those in which all of R ⁴⁰ , R ⁴¹ , R ⁴² and R ⁴³ are methyl groups are particularly preferable.

The manufacturing method of a siloxane compound (30) is not specifically limited. For example, it can be obtained by reacting a siloxane compound represented by the formula (31) (hereinafter sometimes referred to as “siloxane compound (31)”) with two types of disiloxane compounds under acidic conditions. The reaction formula is shown below.

(Wherein R ^W , R ^X , R ^Y , and R ^Z are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 8 carbon atoms. (Part of the hydrogen atoms of the alkyl group may be a hydroxy group.)
In R ^W , R ^X , R ^Y and R ^Z , the alkyl group having 1 to 4 carbon atoms is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl. Group and the like. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group. Examples of those in which some hydrogen atoms of the alkyl group having 1 to 4 carbon atoms are hydroxy groups include hydroxymethyl group, 1-hydroxyethyl group, 1-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxyethyl group 2-hydroxypropyl group, 2-hydroxybutyl group, 3-hydroxypropyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like.

As an example of the siloxane compound (30), in the siloxane compound (30), s = 1, t = 1, X5 / X6 = 4/4, the siloxane compound represented by the formula (32) (hereinafter referred to as “siloxane compound ( 32) ".)).

(In formula (32), each X is independently X5 or X6, and the number of X5 and X6 is 4, respectively.)
Hereinafter, the production method of the siloxane compound (1) and the siloxane compound (2) will be described by taking the siloxane compound (32) as an example, but the present invention is not limited to this, and the number ratio of X5 / X6 Can be appropriately adjusted in the production step of the siloxane compound (32) from the siloxane compound (31).

[Method for Producing Siloxane Compound (32)]
Hereinafter, the manufacturing method of a siloxane compound (32) is demonstrated. The siloxane compound (32) is synthesized by the following two-step reaction using tetraethoxysilane (hereinafter sometimes referred to as “TEOS”) as a starting material.

  The production of the siloxane compound (31) from the first stage TEOS will be described. The siloxane compound (31) can be produced according to the method described in Non-Patent Document 1 (I. Hasegawa et al., Chem. Lett., Pp. 1319 (1988)). Specifically, a siloxane compound (31) is obtained by adding TEOS to an aqueous solution of quaternary ammonium hydroxide and stirring at room temperature.

  Specific examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and choline. Among them, it is preferable to use choline because it is obtained as a solid and is excellent in solubility in alcohol as a reaction solvent in the silylation of the next reaction for obtaining the siloxane compound (31).

  Next, the production of the siloxane compound (32) from the second stage siloxane compound (31) will be described. The siloxane compound (32) is obtained by reacting the siloxane compound (31) with a silylating agent. Examples of the silylating agent include halogenated dialkylsilanes such as chlorodimethylsilane and disiloxanes such as hexamethyldisiloxane. Specifically, for example, the siloxane compound (32) is obtained by reacting an alcohol solution of siloxane compound (31), tetramethyldisiloxane, and hexamethyldisiloxane in the presence of an acid. The alcohol used is preferably methanol, ethanol, or 2-propanol, and the acid is preferably hydrochloric acid or nitric acid.

  The reaction between the siloxane compound (31) and chlorodimethylsilane is described in Non-Patent Document 1, and the reaction with disiloxane is disclosed in Patent Document 4 (Japanese Patent Laid-Open No. 2007-15991).

  The ratio of X5 and X6 in the siloxane compound (32) can be adjusted by the ratio of tetramethyldisiloxane and hexamethyldisiloxane used in this second stage reaction.

In addition to the mixture of tetramethyldisiloxane and hexamethyldisiloxane, the disiloxane compound is represented by the following formula (34):

(In Formula (34), R ^I each independently represents a monovalent organic group, and R ^II represents both a hydrogen atom or each independently a monovalent organic group.)
A mixture of two or more of the disiloxane compounds represented by may be used. When both R ^II are hydrogen atoms, the siloxane compound (32) can be produced with only one kind.

  Specific examples of the disiloxane compound represented by the formula (34) include 1,1,3,3-tetraisopropyldisiloxane, 1,1,3,3-tetraphenyldisiloxane, 1,1,3, 3-tetravinyldisiloxane, 1,3-bis ((acryloxymethyl) phenethyl) tetramethyldisiloxane, 1,3-bis (2-aminoethylaminomethyl) tetramethyldisiloxane, 1,3-bis (3 -Aminopropyl) tetramethyldisiloxane, bis ((bicycloheptenyl) ethyl) tetramethyldisiloxane, 1,3-bis (3-carboxypropyl) tetramethyldisiloxane, bis (3-chloroisobutyl) tetramethyldisiloxane 1,3-bis (chloromethyl) tetramethyldisiloxane, 1,3-bis (cyanopropyl) teto Methyldisiloxane, bis (2- (3,4-epoxycyclohexyl) ethyl) tetramethyldisiloxane, 1,3-bis (glycidoxypropyl) tetramethyldisiloxane, 1,3-bis (hydroxybutyl) tetramethyl Disiloxane, 1,3-bis (hydroxypropyl) tetramethyldisiloxane, 1,3-bis (methacrylamidepropyl) tetramethyldisiloxane, 1,3-bis (3-methacryloxypropyl) tetramethyldisiloxane, bis (Methoxytriethyleneoxypropyl) tetramethyldisiloxane, bis (nonafluorohexyl) tetramethyldisiloxane, bis (tridecafluoro-1,1,2,2-tetrahydrooctyl) tetramethyldisiloxane, 1,3-bis (Triethoxysilylethyl) te Lamethyldisiloxane, 1,3-bis (trifluoropropyl) tetramethyldisiloxane, 1,3-diallyltetramethyldisiloxane, 1,3-dichloro-1,3-diphenyl-1,3-dimethyldisiloxane, 1,3-dichlorotetramethyldisiloxane, 1,3-dichlorotetraphenyldisiloxane, 1,3-diethyltetramethyldisiloxane, 1,3-diethynyltetramethyldisiloxane, 1,3-dimethyltetramethoxydisiloxane 1,3-diphenyltetramethyldisiloxane, 1,3-divinyl-1,3-dimethyl-1,3-dichlorodisiloxane, 1,3-divinyl-1,3-diphenyl-1,3-dimethyldisiloxane 1,3-divinyltetraethoxydisiloxane, 1,3-divinyltetramethyldisilo Xane, 1,3-divinyltetraphenyldisiloxane, hexaethyldisiloxane, hexamethyldisiloxane, hexaphenyldisiloxane, hexavinyldisiloxane, 1,1,3,3-tetracyclopentyldichlorodisiloxane, 1,1, 3,3-tetraethoxy-1,3-dimethyldisilosan, 1,3-tetramethyl-1,3-diethoxydisiloxane, 1,1,3,3-tetraphenyldimethyldisiloxane, 1,1, Examples include 3,3-tetravinyldimethyldisiloxane, 1-allyl-1,1,3,3-tetramethyldisiloxane, 3-aminopropylpentamethyldisiloxane, and chloromethylpentamethyldisiloxane.

  Among these, in order to improve the heat resistance of the cured product, it is useful to introduce a large number of phenyl groups, and 1,1,3,3-tetraphenyldisiloxane is preferably used.

When using the said disiloxane compound (34), the siloxane compound (30) which has group X corresponding to each siloxane structure is obtained. For example, when 1,1,3,3-tetraphenyldisiloxane and hexamethyldisiloxane are used in combination, a derivative of the siloxane compound (32) represented by the formula (35) (hereinafter referred to as “siloxane compound (35)”) May be expressed). In formula (35), X is each independently X5 or X6, and the number of X5 and X6 is 4, respectively.

[Production Method of Siloxane Compound (1)]
Next, a method for producing a siloxane compound (1) from a siloxane compound (32), which is an example of a siloxane compound (30), which is an intermediate raw material, via a halide siloxane compound will be described. A halide siloxane compound represents a chloride siloxane compound, a bromide siloxane compound, or an iodide siloxane compound. Here, the siloxane compound (37A) is passed from the siloxane compound (32) via the benzyl chloride siloxane compound represented by the formula (36A) (hereinafter sometimes referred to as “benzyl chloride siloxane compound (36A)”). The synthesis method for obtaining the above will be described, but even when the types of X5 and X6 and the ratio of the numbers thereof are different, those methods can be easily understood by those skilled in the art from this description. In addition, the positional relationship of the functional groups X5 and X6 in X of various siloxane compounds synthesized from the siloxane compound (32) corresponds to the siloxane compound (32). In addition, when it is necessary to specifically describe the X5, X5A and X5B may be used. In formula (36A), X is each independently X5 or X6, and the number of X5 and X6 is 4, respectively.

  A method for obtaining the benzyl chloride siloxane compound (36A) from the siloxane compound (32) will be described.

  First, the siloxane compound (32) is dissolved in the following solvent, 4-chloromethylstyrene and a metal catalyst are added, and room temperature (in particular, an atmospheric temperature that is not heated or cooled, usually about 15 to 30 ° C. The same applies hereinafter. )), The hydrosilylation reaction proceeds to obtain the benzyl chloride siloxane compound (36A). Instead of 4-chloromethylstyrene, 3-chloromethylstyrene and 2-chloromethylstyrene can be used, and benzyl chloride siloxane compounds corresponding to the respective compounds can be obtained.

  The solvent is not particularly limited as long as it dissolves the siloxane compound (32) and does not react with the siloxane compound and does not inactivate the metal catalyst. For example, toluene, tetrahydrofuran, methylene chloride, chloroform and the like can be mentioned. Of these, toluene and tetrahydrofuran are preferred.

  The metal catalyst only needs to have a catalytic action for promoting the hydrosilylation reaction, and is selected from the group consisting of platinum compounds, palladium compounds, and rhodium compounds. Specifically, platinum compounds such as platinum-carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, or platinum-octylaldehyde complex, containing palladium or rhodium instead of platinum Palladium compounds and rhodium compounds to be used, and these may be used alone or in combination of two or more. Of these, platinum compounds are preferred because of their good reactivity and availability.

  As described above, a benzylsiloxane compound can be obtained by the same method for the siloxane compound (32) obtained from various disiloxane compounds other than tetramethyldisiloxane and hexamethyldisiloxane and derivatives thereof. Is possible.

Next, from the benzyl chloride siloxane compound (36A), among the siloxane compounds (1), as an example of a compound in which R ⁵ has a substituent of the formula (1-1), an azido siloxane compound represented by the formula (37A) ( Hereinafter, a production method for obtaining “azidosiloxane compound (37A)”) will be described.

Benzyl chloride siloxane compound (36A) is dissolved in the following solvent, sodium azide (NaN ₃ ) and diphenylphosphoric acid azide (DPPA) are added, and the desired reaction proceeds by stirring in the temperature range of 20 to 50 ° C. As a result, an azidosiloxane compound (37A) is obtained.

  The solvent is not particularly limited as long as it dissolves the benzyl chloride siloxane compound (36A) and does not inhibit the desired reaction progress. For example, N, N-dimethylformamide, tetrahydrofuran, toluene and the like can be mentioned. Of these, N, N-dimethylformamide is preferable.

  As described above, an azidosiloxane compound can be obtained by the same method for benzylsiloxane compounds obtained from various disiloxane compounds other than tetramethyldisiloxane and hexamethyldisiloxane.

The azidosiloxane compound (37A) is included in the siloxane compound (1) and corresponds to a suitable compound.

  In the reaction for obtaining the benzyl chloride siloxane compound (36A), 4-chlorostyrene is used instead of 4-chloromethylstyrene, whereby a siloxane compound represented by the formula (36B) (hereinafter referred to as “siloxane compound ( 36B) ").) Is obtained. Instead of 4-chlorostyrene, 4-bromostyrene or 3-chlorostyrene can be used, and a corresponding halide siloxane compound can be obtained.

  Next, the siloxane compound (36B) is diazotized according to a method described in a non-patent document (J. Chem. Soc. Trans. 119, 2008) and reacted with a sulfonamide such as an alkylsulfonamide. A siloxane compound represented by the formula (37B) (hereinafter sometimes referred to as “siloxane compound (37B)”) can be obtained.

The azidosiloxane compound (37B) is one of the compounds included in the siloxane compound (1).

[Synthesis Method of Siloxane Compound (2)]
Next, the manufacturing method of the siloxane compound (2) from the siloxane compound (32) which is an example of the siloxane compound (30) which is an intermediate raw material through the halide siloxane compound will be described. Here, from the benzyl chloride siloxane compound (36A) which is an example of a halide siloxane compound, among the siloxane compounds (2), R ¹⁴ is an example of a compound having a substituent of formula (2-1). A production method for obtaining an alkynesiloxane compound represented by the formula (hereinafter sometimes referred to as “alkynesiloxane compound (38)”) will be described. The same method can be applied to other compounds in which R ¹⁴ has a substituent of formula (2-1), or compounds having substituents of other formulas (2-2) to (2-6). In the alkyne siloxane compound (38), the benzyl chloride siloxane compound (36A) is dissolved in the following solvent, propargyl alcohol (structural formula: HC≡C—CH ₂ OH) and sodium hydride are added, and the temperature is 20 to 50 ° C. By stirring in the temperature range, the desired reaction can proceed and be obtained.

  The solvent is not particularly limited as long as it dissolves the benzyl chloride siloxane compound (36A) and does not inhibit the desired reaction progress. For example, N, N-dimethylformamide, tetrahydrofuran, toluene and the like can be mentioned. Of these, N, N-dimethylformamide is preferable.

Sodium hydride has the action of extracting the hydrogen atom of the hydroxyl group of propargyl alcohol (structural formula: HC≡C—CH ₂ OH) and replacing it with sodium. Sodium, sodium methoxide, sodium ethoxide, sodium (tert-butoxide) and the like can be used. Among these, sodium hydride having high versatility is preferable.

  As described above, an azidosiloxane compound can be obtained by the same method for benzylsiloxane compounds obtained from various disiloxane compounds other than tetramethyldisiloxane and hexamethyldisiloxane.

  The alkyne siloxane compound (38) is included in the siloxane compound (2) and corresponds to a suitable compound.

Moreover, as one of the suitable alkyne siloxane compounds contained in the siloxane compound (2), the following formula (39)

And a siloxane compound (hereinafter, sometimes referred to as “siloxane compound (29)”). Among the siloxane compounds (39), R ⁴⁰ , R ⁴¹ , R ⁴² and R ⁴³ are methyl groups, and the following formula (39-S)

(Hereinafter, sometimes referred to as “siloxane compound (39-S)”) is preferable. The siloxane compound (39) is obtained by using a 1,3-diethynyldisiloxane compound and a 1,3-dimethyldisiloxane compound in a reaction under acidic conditions of the siloxane compound (31) and two types of disiloxane compounds. can get. The reaction formula is shown below.

<3. Curable composition>
The curable composition of the present invention will be described. The said curable composition contains a siloxane compound (1) or a siloxane compound (2) at least, and may contain both.

When both the siloxane compound (1) and the siloxane compound (2) are included in the composition, a curable composition can be formed with them, which is particularly preferable. Further, the curable composition of the present invention has the following general formula (19) instead of part or all of the siloxane compound (2) in the composition.

(In the formula (19), R ²³ and R ²⁴ are each independently an organic group containing an amino group, an aromatic ring, a heterocyclic ring, a siloxane group, or a silazane group, or a hydrogen atom, and h is an integer of 2 to 4. there. However ^{R 23, R 24} can not both be a hydrogen atom. in ^{addition, R 23} and ^{R 24} mutually, an alkylene group, vinylene group, ethynylene group, a ring as an aromatic ring or heterocyclic linking groups, (It may be formed.)
The alkyne compound represented by these may be included.

Specific examples of the alkyne compound include 1,3-butadiyne, 1,4-pentadiyne, 1,5-hexadiyne, 1,6-heptadiine, 1,7-octadiyne, diprop-2-ynyl ether, dipropargylamine, Tripropargylamine, 2,5-diethynyl-2,5-dimethyltetrahydrofuran, propiolic acid (2-propynyl) ester, tetra (2-propynyloxymethyl) methane, 3-prop-2-ynyloxy-2,2-bis ( Prop-2-ynyloxymethyl) propan-1-ol, 5,5-diprop-2-ynylpyrimidine-2,4,6-trione, diprop-2-ynylmalonic acid diethyl ester, 2-prop-2- Inylpent-4-ynoic acid, hepta-1,6-diin-4-ol, 4-prop-2-ynyl Puta-1,6-diin-4-ol, 4-propylhepta-1,6-diin-4-ol, 3,3-diprop-2-ynylpentane-2,4-dione, 1,3-diethynylbenzene 1,3,5-tris (prop-2-ynyloxy) benzene, 1,2,3-tris (prop-2-ynyloxy) benzene, 2,4,6-tris (propargylamino) -1,3,5 -Triazine, 1,8-diethynylnaphthalene, 4-phenylhepta-1,6-diin-4-ol, 2- (1-prop-2-ynylbut-3-ynyl) quinoline, 1,3-diethynyltetra Examples include methyldisiloxane. Among them, as an alkyne compound suitable for improving the heat resistance, transparency and adhesion of the cured product, 1,3-diethynylbenzene represented by the following formula (25), 1 represented by the formula (26) , 3-diethynyltetramethyldisiloxane, and tripropargylamine represented by the formula (27).

The curable composition of the present invention has the following general formula (20) instead of a part or all of the siloxane compound (2) in the composition.

(In Formula (20), R ²⁹ is an organic group containing a siloxane group, and i is an integer of 2 to 3)
It may contain the maleimide compound represented by these.

Specific examples of the maleimide compound include, for example, formula (28) and formula (29)

The maleimide compound represented by these is mentioned.

Further, the curable composition of the present invention has the following general formula (21) instead of a part or all of the siloxane compound (1).

(In the formula (21), R ²⁵ represents an organic group containing an amino group, aromatic ring, heterocyclic ring, siloxane group, or silazane group, and j represents an integer of 2 to 4.)
The azide compound represented by these may be included.

  Specific examples of the azide compound include 1,3-diazidopropane, 1,4-diazidobutane, 1,5-diazidopentane, 1,6-diazidohexane, cis / trans-1,2-diazidocyclohexane. Pentane, trans-1,3-diazidocyclopentane, 3,6-diazidocyclohexene, 1,2-bis (azidomethyl) benzene, tris (2-azidoethyl) amine, N, N′-bis (2-azidoethyl) -N '-(2-bromoethyl) amine, 2- [bis (2-azidoethyl) amino] ethanol, erythro-1,2,3,4-tetraazidobutane, pentaerythrityl tetraazide, 3-azido-2, 2-bisazidomethylpropan-1-ol, 1,3-diazido-2-azidomethyl-2-methylpropane, 1-azido-2,2-bis Didomethyl-3-propoxypropane, 1-azido-2,2-bisazidomethyldecane, 1-azido-2,2-bisazidomethyldodecane, 1-azido-2,2-bisazidomethyltetradecane, α, α, α-tris (azidomethyl) toluene, 1-azido-3- (3-azido-2,2-bisazidomethylpropoxy) -2,2-bisazidomethylpropane, 2-nitro-2-azidomethyl-1,3- Diazidopropane, 2-amino-2-azidomethyl-1,3-diazidepropane, 2,2-bis (azidomethyl) -1,3-propanediol, 2,4,6-tris (3-azidopropylamino) -1,3,5-triazine, 2,4,6-tris (2-azidoethylamino) -1,3,5-triazine.

  The blending ratio of the curable composition is adjusted by the ratio of substituents involved in the curing reaction described later and the boiling point of the compound having the substituent. The compounds are classified into a group (A) consisting of siloxane compound (1) and azide compound (21) and a group (B) consisting of siloxane compound (2), alkyne compound (19) and maleimide compound (20). The ratio of the number of substituents involved in the curing reaction contained in group (A) to the number of substituents involved in the curing reaction contained in group (B) is from 5: 1 to 1: 5. Adjust so that it is within the range. Here, the substituents involved in the curing reaction included in the group (A) are specifically the formulas (1-1) to (1-4) in the siloxane compound (1), and the alkyne compound ( 19) represents an alkenyl group, and the maleimide compound (20) represents a carbon-carbon double bond site of the maleimide group. Specifically, the substituents involved in the curing reaction included in the group (B) are formulas (2-1) to (2-6) of the siloxane compound (2), and in the azide compound (21) An azido group.

  As an example of the blending ratio of the curable composition, a siloxane compound (1) having the formula (1-1) as a substituent involved in the curing reaction and a siloxane compound (2) having the formula (2-1) are shown. . The compounding ratio of the curable composition is adjusted by the ratio of the azide group in the siloxane compound (1) and the alkynyl group in the siloxane compound (2) and the boiling point of each compound. Basically, 1 part of the azide group is blended so that the alkynyl group is 1 part. However, if the boiling point of the compound is low relative to the curing temperature and volatilizes, blending of the azide group and alkynyl group The ratio is blended in the range of 5: 1 to 1: 5.

  In the curable composition of the present invention, a curing catalyst can be added for the purpose of lowering the curing temperature or shortening the curing time. The curing catalyst of the present invention refers to an inorganic compound or organometallic compound composed of at least a Group 12 element, Group 13 element or transition metal element, which acts as a catalyst in the curing reaction. Specific examples include a copper (I) compound, tris (2,3,4,5,6-pentafluorophenyl) borane, silver acetate, and chlorobis (triphenylphosphinyl) cyclopentadienyl ruthenium. Examples include copper compounds. Specific examples of the copper (I) compound include copper iodide (I), copper bromide (I), copper chloride (I), tetrakisacetonitryl copper (I) hexafluorophosphate, triphenylphosphine copper (I) bromide , Copper (I) triflate, copper (I) tetrafluoroborate, copper acetate (I), copper nitrate (I), copper (I) acetylacetonate, and ethylenediaminetetraacetic acid dicopper.

  Furthermore, it is also possible to use a mixture that produces copper (I) ions under certain reaction conditions. For example, copper sulfate (II), copper chloride (II), copper nitrate (II), copper carbonate (II) or copper acetate (II), diisopropylamine, triethylamine, diisopropylethylamine, pentamethyldiethylenetriamine, tris [(1 -Benzyl-1H-1,2,3-triazol-4-yl) methyl] amine (TBTA), tris (carboxyethyl) phosphane, and the like. Instead of the copper (II) salt, a copper element can be used.

  The addition amount of the curing catalyst is in the range of 0.00001 mass% to 5 mass%, preferably 0.001 mass% to 2 mass%, based on the total mass of the curable composition.

  In addition, to the extent that the cured product obtained from the curable composition of the present invention does not impair the intended performance of the present invention, the curable composition of the present invention includes viscosity adjustment in potting molding, heat resistance of the cured product. In addition, inorganic fine particles may be added for the purpose of improving transparency and the like. Examples of such inorganic fine particles include silicon dioxide fine particles, colloidal silica, silica filler, aluminum oxide, zinc oxide, tungsten zirconium phosphate and the like, and silicon dioxide fine particles are particularly preferable. In order not to impair the transparency of the cured body, the particle size of these inorganic fine particles is preferably 50 μm or less. As the silicon dioxide fine particles, trade name Tospearl (made by Momentive Performance Materials Japan GK), trade name Wacker HDK (made by Asahi Kasei Wacker Silicon Co., Ltd.), trade name Aerosil (made by Nippon Aerosil Co., Ltd.), fused silica FB (Manufactured by Electrochemical Industry Co., Ltd.).

The curable composition of the present invention preferably has fluidity from the viewpoint of ease of handling when preparing a cured body described later and ease of molding of the cured body. If both of the siloxane compound (1) and the siloxane compound (2) in the curable composition of the present invention are not fluid, or if the curable composition is not fluid or low, both are A solvent may be appropriately used for mixing. When one or both of the siloxane compound (1) and the siloxane compound (2) is a fluid liquid, the curable composition does not necessarily contain a solvent. Specific examples of the solvent used include ethyl acetate, acetonitrile, acetone, diethyl ether, diisopropyl ether, tetrahydrofuran, pentane, hexane, toluene, methanol, ethanol, isopropanol, dimethylformamide, dimethylacetamide, dichloromethane, chloroform, and the like. .

<4. Production of cured body>
Next, the cured body of the present invention will be described. The cured product of the present invention can be prepared from the curable composition of the present invention. By heat-treating the curable composition of the present invention, the curing reaction of the curable composition described later proceeds, and as a result, a homogeneous cured body having high heat resistance and no bubbles remaining is obtained. When the solvent is contained in the curable composition of the present invention, if the heat treatment is performed as it is, bubbles may remain in the obtained cured product. Therefore, it is preferable to remove the solvent from the curable composition before the heat treatment. In the heat treatment, the curing temperature is preferably 50 ° C. or higher and 300 ° C. or lower, more preferably 100 ° C. or higher and 200 ° C. or lower. If the curing temperature is lower than 100 ° C., it is difficult to obtain a desired hardness. Curing proceeds as the temperature is raised, but if the curing temperature is higher than 300 ° C., cracks may occur, which is not practical. The curing time is preferably 0.5 hours or more and 10 hours or less, more preferably 1 hour or more and 4 hours or less. If the curing time is shorter than 0.5 hours, the curing reaction may not proceed completely, and if it is longer than 10 hours, it is not practical.

In the curing reaction for obtaining the cured product of the present invention, the organic groups of the siloxane compound (1) and / or the siloxane compound (2) contained in the curable composition are involved. In the siloxane compound (1), a substituent selected from the formulas (1-1) to (1-4) in R ⁵ is a site involved in the curing reaction, and in the siloxane compound (2), the formula in R ¹⁴ A substituent selected from (2-1) to (2-6) is a site involved in the curing reaction.

  When the alkyne compound (13) is contained in the curable composition instead of part or all of the siloxane compound (2), the ethynyl site of the alkyne compound (19) is involved in the curing reaction, and the siloxane compound (2 ) Plays the same role as the substituent (formula (2-1)).

  When the maleimide compound (20) is contained in the curable composition instead of a part or all of the siloxane compound (2), the carbon-carbon double bond in the maleimide compound (20) is involved in the curing reaction. And plays the same role as the substituent (formula (2-5)) in the siloxane compound (2).

  On the other hand, when the azide compound (21) is contained in the curable composition instead of a part or all of the siloxane compound (1), the azide part of the azide compound (21) is involved in the curing reaction, and the siloxane compound It plays the same role as the substituent (formula (1-1)) in (1).

The curing reaction for obtaining the cured product of the present invention involves the type of substituent selected from the formulas (1-1) to (1-4) in R ⁵ of the siloxane compound (1), the R of the siloxane compound (2). ¹⁴ is represented by formulas (K-1) to (K-7), for example, depending on the combinations shown below, depending on the types of substituents selected from formulas (2-1) to (2-6). Ring structures containing nitrogen atoms, such as triazole rings. In the formula, the wavy line represents a portion of the partial structure of the substrate that has no structural change in the curing reaction. Me in the formula represents a methyl group, but these Me is only an example of a substituent and may be another substituent. R ^{16 to} R ¹⁹ represent a substituent as described above.

  The cured product of the present invention is useful as a sealing material for semiconductors and a sealing material for high-luminance light-emitting elements such as LEDs that require high heat resistance.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by these Examples.

  The physical properties of the siloxane compound, composition, and cured product obtained in this example were evaluated by the methods shown below.

[NMR (nuclear magnetic resonance) measurement]
Using a nuclear magnetic resonance apparatus (manufactured by JEOL Ltd.) having a resonance frequency of 400 MHz, ¹ H-NMR and ²⁹ Si-NMR were measured.

[Thermogravimetry-Differential thermal analysis]
Using ThermoPlus TG8120 (product name, manufactured by Rigaku Corporation) as a thermogravimetric-differential thermal simultaneous measurement device (Thermogravimetric / Differential Thermal Analysis, hereinafter abbreviated as TG-DTA), the cured product was obtained at 5 ° C./min in the air. Heating to 500 ° C. at a rate of temperature rise, the heat resistance was evaluated with T _d5 being the temperature at which the mass decreased by 5%.

[Preparation Example 1]
<Synthesis of Siloxane Compound (40)>
To a 1 L three-necked flask equipped with a thermometer and a reflux condenser were added 1290 g (6200 mmol) of tetraethoxysilane and 1500 g (7200 mmol) of a 50% by weight aqueous choline hydroxide solution, and room temperature (about 20 ° C., hereinafter the same in the examples) ) For 12 hours. After the stirring was completed, 600 mL of 2-propanol was added and the mixture was further stirred for 30 minutes. After cooling to 3 ° C., the precipitated solid was separated by filtration and washed with 2 propanol, and then dried to obtain octa (2-hydroxyethyltrimethylammonium) silsesquioxane / 37 hydrate (hereinafter referred to as “white powder”). "It may be called" siloxane compound (40-S). ") 1190 g was obtained. The yield was 78%.

The structural formula of octa (2-hydroxyethyltrimethylammonium) silsesquioxane is shown below.

[NMR measurement results]
¹ H NMR (solvent: deuterated methanol, reference material: tetramethylsilane); δ 3.23 (s, 9H), 3.48-3.51 (m, 2H), 4.02-4.05 (m, 2H) )
[Preparation Example 2]
<Synthesis of Siloxane Compound (32)>
To a 1 L three-necked flask equipped with a thermometer and a reflux condenser were added 666 g of toluene, 71 g of methanol, 56.4 g (420 mmol) of tetramethyldisiloxane as a silylating agent, and 102.3 g (630 mmol) of hexamethyldisiloxane as 3 ° C. Until cooled. Subsequently, 69 mass% and 173 g of nitric acid were added dropwise over 30 minutes while stirring. After stirring for 30 minutes, a solution obtained by dissolving 200 g (105 mmol) of octa (2-hydroxyethyltrimethylammonium) silsesquioxane 37 hydrate, which is the siloxane compound (40-S) prepared in Preparation Example 1, in 146 g of methanol. The mixture was heated to room temperature with stirring, and stirred at room temperature for 12 hours to carry out a silylation reaction. After completion of stirring, the aqueous layer was removed, and the organic layer was washed 3 times with 250 g of water. The organic layer was dried over 25 g of magnesium sulfate, and magnesium sulfate was filtered off and concentrated under reduced pressure. The product was washed with methanol and dried to obtain 79.9 g (74.1 mmol) of tetra (hydrodimethylsiloxy) tetra (trimethylsiloxy) silsesquioxane as a siloxane compound (32) as a white powder. The yield was 71%.

The structural formula of tetra (hydrodimethylsiloxy) tetra (trimethylsiloxy) silsesquioxane, which is the siloxane compound (32), is shown below.

[NMR measurement results]
¹ H NMR (solvent: deuterated chloroform, reference material: tetramethylsilane); δ 0.15 (s, 36H), 0.25 (s, 24H), 4.73 (s, 4H)
[Preparation Example 3]
<Production of benzyl chloride siloxane compound (36A)>
In a 2 L three-necked flask equipped with a thermometer and a reflux condenser, the siloxane compound (32) prepared in Preparation Example 2: 35 g (32.5 mmol) of tetra (hydrodimethylsiloxy) tetra (trimethylsiloxy) silsesquioxane, 4- (Chloromethyl) styrene 21.5 g (141 mm 1) and toluene 675 mL were added, and then platinum (0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (Cursted catalyst) 3 225 mg of a mass% xylene solution was added with stirring, and the mixture was heated and stirred in a 70 ° C. oil bath. After stirring for 2 hours, the reaction solution was transferred to a 1 L eggplant flask and concentrated under reduced pressure. The product was purified by a silica gel column (eluent; hexane: ethyl acetate = 9: 1) to obtain 47.9 g (28.4 mmol) of the benzyl chloride siloxane compound (36A). The yield was 87%. The ratio of X5A + X5B and X2 which are functional groups of the siloxane compound (36A) was X5: X6 = 4: 4 in terms of the average value of the respective numbers, and the ratio of X5A and X5B was 2.4: 1.6.

The structural formula of the benzyl chloride siloxane compound (36A) is shown below.

[NMR measurement results]
¹ H NMR (solvent: deuterated chloroform, reference material: tetramethylsilane); δ 0.05-1.15 (m, 60H), 0.91 (brs, 4.8H), 1.39 (brs, 4.8H) ), 2.27 (brs, 1.6H), 2.67 (brs, 4.8H), 4.55 (s, 8H), 7.09-7.26 (m, 16H),
²⁹ Si NMR (solvent: deuterated chloroform, reference material: tetramethylsilane); δ 12.9, 12.5, 10.6, −108.9
[Example 1]
<Production of Azidosiloxane Compound (37A)>
To a 1 L three-necked flask equipped with a thermometer, 10 g (5.94 mmol) of the benzyl chloride siloxane compound (36A) prepared in Preparation Example 3 was added, and the inside of the reaction vessel was purged with nitrogen. After adding 400 mL of dimethylformamide to the reaction vessel, the solution was stirred, and 8.35 g (128 mmol) of sodium azide was added little by little under a nitrogen stream. After stirring for 2 hours, the reaction solution was transferred to a 2 L separatory funnel, 400 mL of water and 500 mL of diisopropyl ether were added, extraction operation was performed, and the organic layer was separated. The obtained organic layer was washed with 200 mL of water three times, dried over magnesium sulfate, and concentrated under reduced pressure to obtain 47.9 g (28.4 mmol) of the azidosiloxane compound (37A) as a product. The yield was 97%. The ratio of X5A + X5B and X6, which are functional groups of the siloxane compound (37A), was X5: X6 = 4: 4 in terms of the average value of the respective numbers, and the ratio of X5A and X5B was 2.4: 1.6.

The structural formula of the azidosiloxane compound (37A) is shown below.

[NMR measurement results]
¹ H NMR (solvent: deuterated chloroform, reference material: tetramethylsilane); δ 0.05-1.16 (m, 60H), 0.96 (brs, 4.8H), 1.41 (brs, 4.8H) ), 2.28 (brs, 1.6H), 2.69 (brs, 4.8H), 4.28 (s, 8H), 7.00-7.27 (m, 16H),
²⁹ Si NMR (solvent: deuterated chloroform, reference material: tetramethylsilane); δ 12.6, 12.3, 10.5, −109.1
[Example 2]
<Synthesis of Siloxane Compound (39-S)>
In a 1 L three-necked flask equipped with a thermometer and a reflux condenser, 67 g of toluene, 7.1 g of methanol, 11.5 g (63.0 mmol) of 1,3-ethynyltetramethyldisiloxane, 10.2 g (63.0 mmol) of hexamethyldisiloxane ) Was added and cooled to 3 ° C. Next, 17.3 g of 69 mass% nitric acid was added dropwise over 30 minutes with stirring. After stirring for 30 minutes, 20.0 g of octa (2-hydroxyethyltrimethylammonium) silsesquioxane 37 hydrate, which is the siloxane compound (40-S) prepared in Preparation Example 1, was added to 14.6 g of methanol. 5 mmol) was added, and the mixture was heated to room temperature with stirring, and stirred at room temperature for 12 hours to carry out a silylation reaction. After completion of the stirring, the aqueous layer was removed, and the organic layer was washed 3 times with 25 g of water. The organic layer was dried over 2.5 g of magnesium sulfate, and magnesium sulfate was filtered off and concentrated under reduced pressure. The product was washed with methanol and dried to obtain 11.0 g of a siloxane compound represented by the following formula (39-S) as a white solid. The yield was 90%. The ratio of X5 and X6 is X5: X6 = 4: 4 in terms of the average value of each number.

The structural formula of tetra (ethynyldimethylsiloxy) tetra (trimethylsiloxy) silsesquioxane (39-S), which is one type of siloxane compound (39), is shown below.

[NMR measurement results]
¹ H NMR (solvent: deuterated chloroform, reference material: tetramethylsilane); δ 0.14 (s, 36H), 0.35 (s, 24H), 2.43 (s, 4H)
[Example 3]
<Synthesis of Alkynesiloxane Compound (38)>
To a 100 mL three-necked flask equipped with a thermometer, 1.0 g of 50-70 mass% sodium hydride wetted with oil was added, and the inside of the reaction vessel was purged with nitrogen. After adding 20 mL of hexane to the reaction vessel and stirring for 5 minutes, the reaction vessel was allowed to stand for 10 minutes, and the operation of sucking the supernatant with a syringe was performed 3 times. Next, the reaction vessel was dried under reduced pressure and purged with nitrogen, and then 20 mL of tetrahydrofuran was added.

  The reaction vessel was bathed in an ice bath, and the solution was cooled to 3 ° C., and then 200 mg (3.6 mmol) of propargyl alcohol was added dropwise, and the mixture was stirred for 30 minutes while still in the ice bath. Thereafter, a solution prepared by dissolving 5.6 g (3.3 mmol) of the benzyl chloride siloxane compound (36A) prepared in Preparation Example 3 in 5 mL of tetrahydrofuran was added dropwise to the reaction solution, and the ice bath was removed and stirred for 2 hours.

  After 2 hours, the reaction solution was cooled again to 3 ° C. with an ice bath, and 20 mL of distilled water was carefully added dropwise, followed by stirring for 30 minutes. The solution was transferred to a 200 mL separatory funnel, 50 mL of diisopropyl ether was added, extraction operation was performed, and the organic layer was separated. The obtained organic layer was washed twice with 10 mL of water, dried over 1 g of magnesium sulfate, and concentrated under reduced pressure to produce 5.23 g (2.97 mmol) of an alkynesiloxane compound (38) represented by the following structural formula. It was obtained as a product. The yield was 90%. The ratio of X5A + X5B and X6, which are functional groups of the alkynesiloxane compound (38), was an average value of each number, and X5A + X5B: X6 = 4: 4, and the ratio of X5A and X5B was 2.4: 1.6. .

The structural formula of the alkynesiloxane compound (38) is shown below.

[NMR measurement results]
¹ H NMR (solvent: deuterated chloroform, reference material: tetramethylsilane); δ 0.05-1.17 (m, 60H), 0.95 (brs, 4.8H), 1.42 (brs, 4.8H) ), 2.27 (brs, 1.6H), 2.45 (brs, 4H), 2.70 (brs, 4.8H), 4.15 (s, 8H), 4.57 (s, 8H) , 7.05-7.28 (m, 16H),
²⁹ Si NMR (solvent: deuterated chloroform, reference material: tetramethylsilane); δ 12.8, 12.4, 10.5, −109.0
[Example 4]
<Synthesis of Alkynesiloxane Compound (41)>

  11.77 g (27.4 mmol) of the azidosiloxane compound (37A) was taken into a 500 mL eggplant flask (240.34 g) equipped with a rotor, and 1,3-diethynyl-1,1,3,3-tetramethyldisiloxane was taken. After adding 50.16 g (550 mmol), 112 mL of toluene was added to prepare a reaction solution. Conduct a transmission IR measurement with the reaction solution sandwiched between two NaCl plates with a PTFE ring of 0.05 mm as a spacer, and confirm the azide group in the reaction solution based on the difference spectrum from the previously measured transmission IR spectrum of toluene Went.

  While stirring the reaction solution, the reaction was performed in an oil bath at 110 ° C. for 2 hours. After returning the reaction solution to room temperature, the presence of an azido group in the reaction solution was analyzed as described above. As a result, the peak of the azide group disappeared completely. Toluene was distilled off with an evaporator and dried under reduced pressure at 80 ° C. for 6 hours to obtain 16.30 g of alkyne-substituted siloxane (41) in a yield of 95%.

Analytical data of the obtained alkyne-substituted siloxane (41) are shown below.

IR (ATR method): 3277, 2036 cm ⁻¹ , ethynyl group
¹ H-NMR (deuterated solvent: deuterated chloroform, reference material: deuterated chloroform): 7.8-7.4 (m), 7.3-6.8 (bs), 5.48 (s), 2.62 (S), 2.27 (s), 2.4-2.1 (s), 1.37 (s), 0.88 (s), 0.42 (s), 0.4-(-0 .1) (m)
¹³ C-NMR (deuterated solvent: deuterated chloroform, reference material: deuterated chloroform): 145.1, 144.4, 133.1, 131.8, 130.7, 129.0, 127.7, 127.4, 127.2, 126.3, 123.0, 92.4, 88.5, 52.9, 52.5, 30.2, 28.3, 19.2, 13.8, 1.6, 0.00. 9, 0.5, -0.7
²⁹ Si-NMR (deuterated solvent: deuterated chloroform, reference material: Si-110 ppm in POSS skeleton): 11.5, 9.7, -6.1, -18.5
GPC: Mw5347, Mn3811, Mw / Mn1.40
Analysis of acetylene equivalent: 0.3828 g of alkyne-substituted siloxane (41) was taken into a sample bottle, 0.0027 g of 1,3,5-trioxane was added, and completely dissolved in 0.6 mL of deuterated chloroform. This was measured by ¹ H-NMR solution was calculated acetylene equivalents from the integral value of the ethynyl group of the integrated value and 2.27ppm of 1,3,5-trioxane of 5.14ppm, 1.1 × 10 ^- It was ³ mol / g.

[Example 5]
<Synthesis of Alkynesiloxane Compound (42)>

  To a 300 mL eggplant flask (183.88 g) equipped with a rotor, 9.04 g (20.6 mmol) of the azidosiloxane compound (37A) was added, and 90 mL of toluene was added to make a solution, and then 19.50 g (414 mmol) of propargyl ether. ) Was added to obtain a reaction solution. Conduct a transmission IR measurement with the reaction solution sandwiched between two NaCl plates with a PTFE ring of 0.05 mm as a spacer, and confirm the azide group in the reaction solution based on the difference spectrum from the previously measured transmission IR spectrum of toluene Went.

  While stirring the reaction solution, the reaction was performed in an oil bath at 110 ° C. for 2 hours. After returning the reaction solution to room temperature, the presence of an azido group in the reaction solution was analyzed as described above. As a result, the peak of the azide group disappeared completely. Toluene was distilled off with an evaporator and dried under reduced pressure at 80 ° C. for 7 hours to obtain 10.68 g of alkyne-substituted siloxane (42) in a yield of 96%.

Analytical data of the obtained alkyne-substituted siloxane (42) are shown below.

IR (ATR method): 3292 cm ⁻¹ , 2119 cm ⁻¹ (ethynyl group)
¹ H-NMR (deuterated solvent: deuterated chloroform, reference material: deuterated chloroform): 7.62 (s), 7.45 (m), 7.3-6.7 (bs), 5.51 (m), 5.42 (m), 4.66 (s), 4.48 (s), 4.17 (s), 4.04 (s), 2.61 (s), 2.48 (s), 2 .43 (s), 2.22 (s), 1.34 (s), 0.88 (s), 0.4-(-0.3) (m)
¹³ C-NMR (deuterated solvent: deuterated chloroform, reference material: deuterated chloroform): 144.6, 143.9, 134.1, 132.0, 131.4, 130.4, 128.5, 128.0, 127.7, 127.4, 127.2, 124.8, 122.4, 78.9, 78.1, 75.6, 74.7, 62.6, 58.7, 57.0, 56. 9, 56.0, 53.5, 51.7, 30.4, 28.4, 19.3, 13.9, 1.1, -0.6, -1.9, -3.2
²⁹ Si-NMR (heavy solvent: deuterated chloroform, reference material: Si-110 ppm in POSS skeleton): 11.6, 9.7
GPC: Mw4657, Mn3364, Mw / Mn1.38
Analysis of acetylene equivalent: 0.1970 g of alkyne-substituted siloxane XX-2 was taken into a sample bottle, 0.00191 g of 1,3,5-trioxane was added and completely dissolved in 0.6 mL of deuterated chloroform. The ¹ H-NMR of this solution was measured, and the acetylene equivalent was calculated from the sum of the integral value of 5.13 ppm 1,3,5-trioxane and the integral value of 4.7-4.0 ppm propargyl ether. 1.6 × 10 ⁻³ mol / g.

[Example 6]
<Preparation of curable compositions 1-18>
At least the produced azidosiloxane compound (37A), one type selected from the group consisting of the alkynesiloxane compounds (38), (39-S), (41) and (42), and formulas (25) to The curable composition 1,3,5,7,9,13-18 which further contains 1 or more types from the group which consists of three types of alkyne compounds represented by (27) was produced. Compositions 2, 4, 6, 8, and 10-12 obtained by further adding a copper catalyst to the curable composition were similarly prepared. The results are shown in Table 1.

Note 1: Azidosiloxane compound, alkynesiloxane compound, alkyne compound, and copper catalyst represent mass content ratios in each curable composition.

Note 2: Among the alkyne siloxane compounds, () indicates the distinction between the alkyne siloxane compounds (38), (39-S), (41), and (42).

Note 3: Among alkyne compounds, A represents 1,3-diethynylbenzene, B represents 1,3-diethynyl-1,1,3,3-tetramethyldisiloxane, and C represents tripropargylamine.

Note 4: The copper catalyst is an acetonitrile solution in which 3.3% by mass of copper (II) iodide is dissolved.

[Example 7]
<Preparation of curable compositions 19-24>
Curable composition containing at least the produced azidosiloxane compound (37A) and further comprising bismaleimide compounds (28) and (29) produced from the production methods described in JP-A No. 04-366126 and US2007205399, respectively. 19-24 were produced. The results are shown in Table 2.

Note 1: The azidosiloxane compound (37A) and the bismaleimide compound represent the mass content ratio in each curable composition.

Note 2: Among the bismaleimide compounds, () indicates the distinction between the bismaleimide compounds (28) and (29).

[Example 8]
<Production and evaluation of cured body>
Each of the curable compositions 1 to 24 shown in Table 1 was poured into a glass sample tube having a diameter of 10 mm and heated in a heating furnace at 150 ° C. for 1 hour to obtain cured bodies (H-1) to (H-18). ) (A cylinder having a diameter of 10 mm and a height of 3 mm). Table 3 shows the results of evaluating the appearance and heat resistance of the cured bodies (H-1) to (H-18).

Note 1: Heat resistance indicates a 5% weight loss temperature (in-air, 5 ° C./min heating rate) in the TG-DTA analysis of the cured bodies (H-1) to (H-24).

  In the obtained cured products (H-1) to (H-24), no foaming and cracks were observed, there was no tackiness (tackiness), and the appearance was good. About heat resistance, the 5% weight reduction | decrease temperature in TG-DTA analysis was observed over 305-390 degreeC, and heat resistance was favorable.

  Next, Comparative Examples 1 and 2 that are not within the scope of the present invention will be described.

[Comparative Example 1]
<Preparation of curable compositions I and II>
Curable compositions I and II containing at least a siloxane compound (32) and a platinum catalyst and further containing divinylbenzene or 1,3-divinyltetramethyldisiloxane as a vinyl compound were prepared. The results are shown in Table 4.

Note 1: A siloxane compound (32) and a vinyl compound represent a mass content ratio in each curable composition, and a platinum catalyst represents a ratio in the curable composition.

Note 2: Among vinyl compounds, A represents divinylbenzene (manufactured by Tokyo Chemical Industry, product number, D0958), and B represents 1,3-divinyltetramethyldisiloxane.

Note 3: The platinum catalyst is a platinum (0) 1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex xylene solution.

[Comparative Example 2]
<Production and Evaluation of Cured Products HI and H-II>
Under the same conditions as for obtaining the cured products (H-1) to (H-24) of the present invention, cured products HI and H-II were obtained from the curable compositions I and II, respectively. Table 5 shows the results of evaluating the appearance and heat resistance of the cured bodies (HI) to (H-II).

  From the above results, cured bodies HI and H-II that are not in the category of the present invention had good appearance without foaming and cracking, but heat resistance was observed over 260 to 280 ° C., and the cured product of the present invention. It turned out that the heat resistance (305-390 degreeC) of a body (H-1)-(H-24) is excellent.

Claims (19)

General formula (1)

(In Formula (1), each X is independently X1 or X2, the number a of X1 is an integer of 2 to 8, the number b of X2 is an integer of 0 to 6, and the sum of a and b. Is 8. In formulas X1 and X2, R ¹ , R ² , R ³ , R ⁴ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl having 6 to 12 carbon atoms. A hydrogen atom of these hydrocarbon groups may be substituted with a fluorine atom.
R ⁵ is independently selected from the formulas (1-1) to (1-4)

(In formulas (1-2) and (1-4), R ⁷ is an organic group containing a hydroxyl group, an alkoxy group, an ester group or a trialkylsilyl group, and R ⁸ and R ⁹ are each independently a hydroxyl group, An organic group containing an alkoxy group, an ester group, or a trimethylsilyl group.)
An organic group having one or more substituents selected from m and n are each independently an integer of 1 to 4. )
A siloxane compound represented by The siloxane compound according to claim 1, wherein R ⁵ is an organic group having an azide group (formula (1-1)). R ⁵ represents the formula (3) or (4)

(In formulas (3) and (4), v and w are each independently an integer of 0 to 6. A represents a phenylene group, a naphthylene group, or a biphenylene group, and any of these aromatic hydrocarbon groups. These hydrogen atoms may be substituted with fluorine atoms, and may be substituted with alkyl groups having 1 to 6 carbon atoms, perfluoroalkyl groups having 1 to 6 carbon atoms, and cyano groups.)
The siloxane compound of Claim 1 or 2 represented by these. The siloxane compound according to any one of claims 1 to 3, wherein R ⁵ is represented by formula (5) or (6).

General formula (2)

(In Formula (2), X is each independently X3 or X4, the number c of X3 is an integer of 2 to 8, the number d of X4 is an integer of 0 to 6, and The sum is 8. In Formulas X3 and X4, R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁵ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a group having 6 to 12 carbon atoms. It is an aryl group, and any number of hydrogen atoms contained in these hydrocarbon groups may be substituted with fluorine atoms.
R ¹⁴ is independently selected from formulas (2-1) to (2-6).

(In the formulas (2-1) to (2-6), R ^16A is a single bond, an alkylene group having 1 to 8 carbon atoms, or an arylene group having 6 to 12 carbon atoms, and R ^16B and R ¹⁷ are each independently , A hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 18 carbon atoms, and R ¹⁸ and R ¹⁹ are each independently a fluoroalkyl group having 1 to 6 carbon atoms, a cyano group, or an ester group. R ²⁰ is an alkylene group having 1 to 6 carbon atoms or an aryl group having 6 to 18 carbon atoms, and R ²¹ and R ²² are each independently a trifluoromethanesulfonyl group, a trimethylsilyl group, an iodine atom, or a bromine atom. .)
Is an organic group having one or more substituents selected from p, and p and q are each independently an integer of 1 to 4. )
A siloxane compound represented by The siloxane compound according to claim 5, wherein R ¹⁴ is an organic group having a terminal acetylene group. R ¹⁴ represents formulas (7) to (11)

(Wherein x, y and z are each independently an integer of 0 to 6. B represents a phenylene group, a naphthylene group or a biphenylene group, and any number of hydrogen atoms in these aromatic hydrocarbon groups. May be substituted with a fluorine atom, and may be substituted with an alkyl group having 1 to 6 carbon atoms, a perfluoroalkyl group having 1 to 6 carbon atoms, or a cyano group, and R ²⁷ and R ²⁸ are each independently Represents a dialkylsilylene group or an alkylene group having 1 to 6 carbon atoms.)
The siloxane compound of Claim 5 or 6 represented by these. R ¹⁴ represents the formulas (12) to (18).

The siloxane compound of any one of Claims 5-7 represented by these.   A curable composition containing the siloxane compound according to any one of claims 1 to 4 and the siloxane compound according to any one of claims 5 to 8. The siloxane compound according to any one of claims 1 to 4, and a general formula (19)

(In the formula (19), R ²³ and R ²⁴ are each independently an organic group containing an amino group, an aromatic ring, a heterocyclic ring, a siloxane group, or a silazane group, or a hydrogen atom, and h is an integer of 2 to 4. there. However ^{R 23, R 24} can not both be a hydrogen atom. in ^{addition, R 23} and ^{R 24} mutually, an alkylene group, vinylene group, ethynylene group, a ring as an aromatic ring or heterocyclic linking groups, (It may be formed.)
The curable composition containing the alkyne compound represented by these. The siloxane compound according to any one of claims 1 to 4, and the general formula (20)

(In Formula (20), R ²⁹ is an organic group containing a siloxane group, and i is an integer of 2 to 3)
The curable composition containing the maleimide compound represented by these.
The siloxane compound according to any one of claims 5 to 8, and a general formula (21)

(In formula (21), R ²⁵ represents an organic group containing at least an amino group, an aromatic ring, a heterocyclic ring, a siloxane group, or a silazane group, and j represents an integer of 2 to 4.)
The curable composition containing the azide compound represented by these. Alkyne compounds are represented by the general formulas (22) to (24).

(In Formula (22), aa is an integer of 1-4. In Formula (23), ab is an integer of 0-10. In Formula (24), ac is an integer of 1-2, ad is 2. An integer of ˜3, and ac and ad satisfy the formula ac + ad = 3)
The curable composition of Claim 10 represented by these. Alkyne compounds are represented by formulas (25) to (27)

The curable composition of Claim 10 or 13 which is 1 type of compounds selected from these. The maleimide compound is represented by formula (28) or formula (29)

The curable composition of Claim 11 which is 1 type of compounds selected from.   Furthermore, the curable composition of any one of Claims 9-15 containing a curing catalyst.   The curable composition according to any one of claims 9 to 16, further comprising inorganic fine particles.   A cured product obtained by curing the curable composition according to claim 9.   The hardened | cured material of Claim 18 obtained by heat-processing and hardening.