JP2002212449A - Curable composition, its manufacturing method, molding method, and cured material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition having good moldability with uniform, suitable viscosity and melt characteristics, having versatility in obtaining raw material, and having industrially high utility, its manufacturing method, and a cured material obtained by curing it. SOLUTION: The curable composition can be obtained by previously subjecting a part of the carbon-carbon double bonds capable of undergoing hydrosilylation and a part of the SiH groups in a mixture containing as the essential constituents (A) an organic compound having in the molecule at least two carbon-carbon double bonds capable of undergoing hydrosilylation, (B) a silicon compound having at least two SiH groups in the molecule, and (C) a hydrosilylation catalyst to hydrosilylation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition, and more particularly to a curable composition which is uniform, has appropriate viscosity and melting properties, and has good moldability.
The present invention relates to a method for producing the same and a cured product obtained by curing the method. The present invention also relates to a method for molding a curable composition.

[0002]

2. Description of the Related Art Various curable compositions have been proposed. Among these, various proposals utilizing a hydrosilylation reaction as a curing reaction have been proposed (for example, JP-A-55-77855). However, when a siloxane compound such as a polyorganohydrogen siloxane is used as the SiH group-containing component, and an organic compound having an organic skeleton is used as the carbon-carbon double bond-containing component, these components are generally used. Is poor in compatibility, so that foaming, poor curing and the like occur, and there is a problem that mechanical properties are significantly impaired.

As means for solving this problem, SiH
As a group-containing compound, there has been proposed a method of using a reaction product (organic modified siloxane) of an organic compound having an organic skeleton and a siloxane having a SiH group (for example, Japanese Patent Application Laid-Open No. Sho 63).
Japanese Patent No. 241034, Japanese Patent No. 2732315). However, there is a problem that sufficient compatibility cannot be obtained, particularly when a highly polar organic compound is used as the carbon-carbon double bond-containing component. It is necessary to design and select a compound having good compatibility, and furthermore, the organically modified siloxane is a special compound, and it is difficult to say that various compounds are easily available. Had.

Further, when a low molecular weight compound is used as the carbon-carbon double bond-containing component or the SiH group-containing component, the viscosity of the curable composition becomes low, and the formability in press molding, cast molding, etc. becomes poor. There was also a problem that it was not always good.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a composition which is uniform, has appropriate viscosity and melting properties, has good moldability, is versatile in raw material availability, and is industrially suitable. Another object of the present invention is to provide a curable composition having high practicality, a method for producing the same, and a cured product obtained by curing the composition.

[0006]

Means for Solving the Problems In order to solve the above problems, the present inventors have made intensive studies and have found that (A) a hydrosilylatable carbon-carbon double bond has at least two carbon atoms per molecule.
(B) at least two organic compounds per molecule
A silicon compound containing two SiH groups and a part of each of the hydrosilylatable carbon-carbon double bonds and the SiH groups in a mixture containing (C) a hydrosilylation catalyst as essential components, by a hydrosilylation reaction. Curable composition that can solve the above-mentioned problems, furthermore, the curable composition obtained by removing the unreacted component (A) and / or component (B) has a high effect, The present invention has been reached.

That is, the present invention relates to (A) a method for preparing a hydrosilylatable carbon-carbon double bond in a molecule of at least 2 carbon atoms.
(B) at least two organic compounds per molecule
Compound containing two SiH groups and (C) a hydrosilylation catalyst as essential components in a mixture containing a hydrosilylatable carbon-carbon double bond and Si
It is a curable composition obtainable by previously reacting a part of each H group by a hydrosilylation reaction.

The number of hydrosilylatable carbon-carbon double bonds previously reacted by the hydrosilylation reaction is 80% of the number of hydrosilylatable carbon-carbon double bonds in the component (A) before the hydrosilylation reaction. And the number of SiH groups that are preliminarily reacted by the hydrosilylation reaction is (B) before the hydrosilylation reaction.
It is preferable that the number is 80% or less of the number of SiH groups in the component. The curable compositions are mutually incompatible (A)
It is preferable that the composition contains the component and the component (B) and is uniform. In the curable composition, it is preferable that the content of the unreacted component (A) is 10% by weight or less and / or the content of the unreacted component (B) is 10% by weight or less.

It is preferable that the component (A) and / or the component (B) is a compound containing an imide group. It is preferable that the curable composition further contains (D) a curing retarder. The component (A) is composed of C, H,
It is preferable that the compound contains only O, N, S, and halogen. The component (A) is preferably an organic compound containing at least one vinyl group in one molecule.
In the mixture containing the component (A), the component (B) and the component (C), the number (X) of the hydrosilylatable carbon-carbon double bonds contained in the component (A) and the component (B) It is preferable that the ratio of the number (Y) of the contained SiH groups is 2> Y / X, and the component (B) is a compound having a boiling point of 200 ° C. or less at normal pressure.

The present invention also relates to a method for producing the above-mentioned curable composition, comprising (A) a hydrosilylatable carbon-
Organic compounds containing at least two carbon double bonds in one molecule, (B) a silicon compound containing at least two SiH groups in one molecule, and (C) a hydrosilylation catalyst as essential components. This is a production method comprising reacting a part of each of a hydrosilylatable carbon-carbon double bond and a SiH group in a mixture by a hydrosilylation reaction in advance. In the above production method, the hydrosilylation reaction is preferably performed in the presence of a solvent.

In the above-mentioned production method, the hydrosilylation-reactive carbon-carbon double bond and a part of the SiH group are respectively reacted by a hydrosilylation reaction, and then the temperature is lowered to suppress the progress of the hydrosilylation reaction. Is preferred. In the above-mentioned production method, after a part of each of the carbon-carbon double bond capable of hydrosilylation and the SiH group is reacted by a hydrosilylation reaction, the progress of the hydrosilylation reaction is suppressed by adding a curing retarder. Is preferred. In the above production method, the hydrosilylatable carbon-carbon double bond and S
After reacting a part of each iH group by a hydrosilylation reaction, it is preferable to remove the unreacted component (A) and / or the unreacted component (B).

Furthermore, the present invention is a cured product obtained by curing the above curable composition. It is also an adhesive or a sealant containing the curable composition. Furthermore, the present invention relates to (A) an organic compound containing at least two hydrosilylatable carbon-carbon double bonds in one molecule, (B)
In a curable composition containing, as an essential component, a silicon compound containing at least two SiH groups in one molecule, and (C) a hydrosilylation catalyst, a carbon-carbon double bond and a SiH group capable of being hydrosilylatable. This is also a method for molding a curable composition, in which a part of each is reacted in advance by a hydrosilylation reaction and then molded. Hereinafter, the present invention will be described in detail.

First, the component (A) in the present invention will be described. Component (A) is an organic compound containing at least two hydrosilylatable carbon-carbon double bonds in one molecule. Such compounds include siloxane units (Si-O-) such as polysiloxane-organic block copolymers and polysiloxane-organic graft copolymers.
Not containing Si), but as constituent elements C, H,
Those composed of only N, O, S and halogen are preferred. This is because those containing a siloxane unit have problems of gas permeability and repellency. In the case of a substance containing halogen, a toxic substance may be generated at the time of combustion, so that it is more preferably composed of only C, H, N, O, and S.

The structure of component (A) is formed by bonding a skeleton portion to a hydrosilylatable carbon-bonded to the skeleton by a covalent bond (in some cases, via a divalent or higher valent substituent).
When expressed separately from a group having a carbon double bond (alkenyl group), the alkenyl group may be present anywhere in the molecule. In the present specification, “hydrosilylatable carbon-carbon double bond” refers to SiH under conventionally known conditions.
A carbon-carbon double bond capable of hydrosilylation with a group. The skeleton of the component (A), which is an organic compound, is not particularly limited, and an organic polymer skeleton or an organic monomer skeleton may be used.

Examples of the organic polymer skeleton include polyether type, polyester type, polyarylate type, polycarbonate type, saturated hydrocarbon type, polyacrylate type, polyamide type, phenol-formaldehyde type (phenol resin type), A polyimide skeleton can be used. Examples of the monomer skeleton include aromatic hydrocarbons such as phenols, bisphenols, benzene and naphthalene, aliphatic hydrocarbons, imides such as bisimides, isocyanurates, and mixtures thereof. As the alkenyl group of the component (A), Si is used.
There is no particular limitation as long as it has reactivity with the H group, but the following general formula (I)

[0016]

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An alkenyl group represented by the formula (wherein R represents a hydrogen atom or a methyl group) is preferred from the viewpoint of reactivity. Also, because it is easier to obtain raw materials,

[0018]

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Is particularly preferred. As the alkenyl group of the component (A), the following general formula (II)

[0020]

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An alkenyl group represented by the formula (wherein R represents a hydrogen atom or a methyl group) is preferred from the viewpoint that the cured product has high heat resistance. Also, because it is easier to obtain raw materials,

[0022]

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Is particularly preferred. The alkenyl group may be covalently bonded to the skeleton portion of the component (A) via a divalent or higher valent substituent, and the divalent or higher valent substituent may have 0 to 10 carbon atoms.
The substituent is not particularly limited, but a substituent containing only C, H, N, O, S, and halogen as a constituent element is preferable. Examples of these substituents include

[0024]

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[0025]

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And the like. Also, two or more of these divalent or more substituents may be connected by a covalent bond to form one divalent or more substituent. Examples of the alkenyl group covalently bonded to the skeleton as described above include a vinyl group, an allyl group, a methallyl group, an acryl group, a methacryl group, a 2-hydroxy-3- (allyloxy) propyl group, a 2-allylphenyl group, 3-allylphenyl group, 4
-Allylphenyl group, 2- (allyloxy) phenyl group, 3- (allyloxy) phenyl group, 4- (allyloxy) phenyl group, 2- (allyloxy) ethyl group,
2,2-bis (allyloxymethyl) butyl group, 3-allyloxy-2,2-bis (allyloxymethyl) propyl group,

[0027]

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And the like. As the component (A), a low-molecular-weight compound that is difficult to be expressed separately as a skeleton portion and an alkenyl group as described above can also be used. Specific examples of these low-molecular weight compounds include aliphatic chain polyene compounds such as butadiene, isoprene, octadiene, and decadiene, cyclopentadiene, cyclooctadiene, dicyclopentadiene, tricyclopentadiene,
Aliphatic cyclic polyene compounds such as norbornadiene,
Substituted aliphatic cyclic olefin compounds such as vinylcyclopentene and vinylcyclohexene are exemplified.

The hydrosilylatable carbon of the component (A)
The number of carbon double bonds may be at least two per molecule on average, but is preferably more than 2 and preferably 3 or more from the viewpoint that the heat resistance of the cured product can be further improved. More preferably, the number is particularly preferably 4 or more. When the number of hydrosilylatable carbon-carbon double bonds of the component (A) is 1 or less per molecule,
Even if it reacts with the component (B), it only forms a graft structure and does not form a crosslinked structure.

In order to further enhance the reactivity with the component (B), the component (A) is preferably an organic compound containing at least one vinyl group in one molecule, and more preferably one vinyl group. It is preferable that the organic compound contains at least two organic compounds in the molecule. (B)
In order to further increase the reactivity with the component, the component (A) is preferably an organic compound containing at least one allyl group in one molecule.

From the viewpoint of industrial availability, preferred examples of the component (A) include polybutadiene, vinylcyclohexene, cyclopentadiene, dicyclopentadiene, divinylbenzene, divinylbiphenyl, triallyl isocyanurate, trivinylcyclohexane and Examples include bisphenol A diallyl ether, 2,2'-diallyl bisphenol A, bisphenol S diallyl ether, and 2,2'-diallyl bisphenol S. From the viewpoint that the obtained cured product has high heat resistance, a compound containing an imide group is preferable as the component (A). As these compounds, for example, the following general formula (III)

[0032]

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[In the formula, R ¹ represents an aromatic group-containing tetravalent organic group having 6 to 30 carbon atoms. R ² is a divalent organic group having 6 to 30 carbon atoms containing an aromatic group, or a compound represented by the general formula (IV)

[0034]

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[0035] (wherein, ^{R 4} represents a divalent organic group having 1 to 20 carbons .R ⁵ represents a monovalent organic group having 1 to 20 carbon atoms. Plurality of ^{R 4} and R ⁵ may be the same,
They may also be different. m represents a positive integer of 1 to 20). R ³ is hydrosilylatable carbon - represents a monovalent organic group having 2-20 carbon having a carbon-carbon double bond, two R ³ may be may be the same, or different. n represents an integer of 0 to 100. An imide compound represented by the general formula (V):

[0036]

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Wherein R ¹ , R ² and n are the same as above. R ⁶ is a divalent C 2-20 carbon atom containing at least one hydrosilylatable carbon-carbon double bond. Represents an organic group, and two R ^{6 s} may be the same or different.).

In the above formulas (III) and (V), R ¹ is an aromatic group-containing 4 to 6 carbon atoms.
Represents a valent organic group. In the present specification, the “organic group” refers to an unsubstituted hydrocarbon group or a hydrocarbon group having a substituent such as a sulfonyl group, a hydroxyl group, a carbonyl group, an ether group, and a halogen group. R ¹ is composed of a tetravalent aromatic group having 6 to 30 carbon atoms or an aromatic ring bonded through a divalent group, from the viewpoint of providing a cured product having excellent heat resistance after curing. A tetravalent group having 6 to 30 carbon atoms is preferable.

Particularly preferred specific examples are pyromellitic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 3,3', 4,4'-benzophenonetetracarboxylic acid, 3,3 ', 4 4,4'-diphenylsulfonetetracarboxylic acid, 3,3 ', 4,4'-diphenylethertetracarboxylic acid, naphthalene-1,2,5,6-tetracarboxylic acid, represented by the following general formula (VI)

[0040]

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(Wherein R ⁷ is a divalent organic group having 1 to 16 carbon atoms, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, an octylene group, an isopropylene group, an isobutylene group, Phenylene group, naphthylene group, benzylene group, phenylene group,

[0042]

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And a residue obtained by removing a carboxylic acid group from a tetracarboxylic acid represented by the following formula: These may be used alone or in combination of two or more. In the general formulas (III) and (V), R ² is a divalent organic group having 6 to 30 carbon atoms containing an aromatic group, or a divalent group represented by the general formula (IV) Represents

[0044]

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In the formula, R ⁴ represents a divalent organic group having 1 to 20 carbon atoms, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, an octylene group, an isopropylene group, an isobutylene group, a phenylene group. Group, naphthylene group, benzylene group, phenethylene group and the like. R ⁵
Is a monovalent organic group having 1 to 20 carbon atoms, for example, methyl,
Represents ethyl, propyl, phenyl and the like. A plurality of R ⁴ and R ⁵ may be the same or different, and m represents a positive integer of 1 to 20. Among such R ² , an aromatic group-containing divalent organic group having 6 to 30 carbon atoms is preferable in that the heat resistance of the cured product can be further improved.

[0046] Specific examples of such ^{R 2} may, for example, 4,4'-diaminodiphenyl ether, 3,4 '
-Diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-diaminodiphenyl sulfone, 3,
3'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (2- [Aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4
-Aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 4,4'-diaminodiphenylmethane, bis (3-methyl-4-aminophenyl) methane, bis (3-chloro-4-aminophenyl) ) Methane, 4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, 3,3'-dimethoxy-
4,4'-diaminobiphenyl, 3,3'-dimethyl-
4,4'-diaminobiphenyl, 3,3'-dichloro-
4,4'-diaminobiphenyl, 2,2 ', 5,5'-
Tetrachloro-4,4'-diaminobiphenyl, 3,
3'-dicarboxy-4,4'-diaminobiphenyl,
3,3'-dihydroxy-4,4'-diaminobiphenyl, 2,4-diaminotoluene, 1,3-diaminobenzene, 1,4-diaminobenzene, 2,2'-bis [4
-(4-aminophenoxy) phenyl] propane, 2,
2'-bis [4- (4-aminophenoxy) phenyl]
Hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] sulfone, 9,9'-bis (4-aminophenyl) -10-hydroanthracene, 9,9 '
-Bis (4-aminophenyl) fluorene, ortho-tolidine sulfone; 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,5-bis (3-aminopropyl) hexamethyltrisiloxane,

[0047]

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(Wherein R ⁵ and m are the same as the examples of R ⁵ and m in the general formula (IV)), and a residue obtained by removing an amino group from a siloxane diamine such as an amino-terminated polysiloxane. can give. These may be used alone,
More than one species may be used in combination. In the general formula (III), R ³ has 2 to 2 carbon atoms having a carbon-carbon double bond.
It represents zero monovalent organic groups, and specific examples of such groups include vinyl, allyl, butenyl, pentenyl, hexenyl, octenyl, nonenyl, decenyl, undecenyl, and isopropyl. Examples thereof include a benzyl group, a 2-methyl-2-propylene group, a 2-vinylphenyl group, a 3-vinylphenyl group, a 4-vinylphenyl group and an allyloxyphenyl group.

In the above general formula (V), R ⁶ has 2 to 2 carbon atoms having at least one carbon-carbon double bond.
Represents zero divalent organic groups. Among them, a group having a carbon-carbon double bond forming a ring is preferable. As a specific example

[0050]

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And the like. The above general formula (III)
And in (V), n represents a positive integer of 0 to 100. Among these, 0 to 50 are preferable, and 0 to 20 are more preferable, from the viewpoints of excellent moldability due to good solubility and meltability, and excellent heat resistance of the obtained cured product. As these imide compounds, for example,

[0052]

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Compounds represented by (n is 0 to 10) are exemplified. From the viewpoint that the heat resistance can be further improved, the component (A) preferably contains a hydrosilylatable carbon-carbon double bond in an amount of 0.001 mol or more per 1 g of the component (A), and preferably contains 0.1 to 1 mol per gram. 005mo
l or more is more preferable, and 0.008 mol
Those containing the above are particularly preferred. Specific examples include butadiene, isoprene, vinylcyclohexene,
Cyclopentadiene, dicyclopentadiene, cyclohexadiene, decadiene, diallyl phthalate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, divinylbenzenes (purity 5
0-100%, preferably 80-100%), 1,3-diisopropenylbenzene, 1,4-
Diisopropenyl benzene and its oligomers, 1,2-polybutadiene (1,2 ratio 10-100
%, Preferably 1,2 ratio of 50 to 100%),

[0054]

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And the like. The various components (A) as described above can be used alone or as a mixture of two or more.

Next, the compound having a SiH group as the component (B) will be described. The compound having a SiH group that can be used in the present invention is not particularly limited. For example, compounds described in International Publication WO 96/15194 having at least two SiH groups in one molecule can be used.

Among these, from the viewpoint of availability, a chain and / or cyclic organopolysiloxane having at least two SiH groups in one molecule is preferable, and has good compatibility with the component (A). From the viewpoint, the following general formula (VII)

[0058]

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(Wherein R ⁸ represents an organic group having 1 to 6 carbon atoms, and n represents a number of 3 to 10), and has at least two SiH groups in one molecule. Cyclic organopolysiloxanes are preferred. The molecular weight of the component (B) is not particularly limited, and any one can be suitably used. However, a low molecular weight one is preferably used from the viewpoint that fluidity is more easily developed. Specifically, the molecular weight is 50-100,
000 is preferable, 50 to 1,000 is more preferable, and 50 to 700 is more preferable.

Specific examples of the above component (B) include 1,3,5,7-tetramethylcyclotetrasiloxane, 1,3,5,7,9-pentamethylcyclopentasiloxane, polymethylhydro Gensiloxane and the like can be mentioned. From the viewpoint that the obtained cured product has high heat resistance, a compound containing an imide group is preferable as the component (B). As these compounds, for example, the following general formula (VIII)

[0061]

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(Wherein R ¹ , R ² , and n are the same as those described in the general formula (III), and R ¹⁰ has a carbon number of 2 to 2).
Represents zero divalent organic groups, and X represents at least one Si
Represents a monovalent group containing an H group. )).

In the general formula (VIII), R ¹⁰ is a divalent organic group having 2 to 20 carbon atoms. Specific examples of such a group include a methylene group, an ethylene group, a propylene group and a butylene group. Hexylene group, octylene group, isopropylene group, isobutylene group, phenylene group, naphthylene group, benzylene group, phenethylene group and the like. In the general formula (VIII), X is a monovalent group containing at least one SiH group, and specific examples of such a group include:

[0064]

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(N represents a number of 2 to 5) and the like. As such a component (B), for example,

[0066]

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And the like. The various (B) components as described above can be used alone or in combination of two or more.

The mixing ratio of component (A) and component (B) as described above is not particularly limited, but generally, the number (X) of the hydrosilylatable carbon-carbon double bonds in component (A) and It is preferable that the ratio with respect to the number (Y) of SiH groups in the component (B) is 10 ≧ Y / X ≧ 0.1. Y
If / X> 10 or 0.1> Y / X, it is difficult to obtain sufficient compatibility. In particular, when the component (B) is a compound having a boiling point of 200 ° C. or less at normal pressure, 2> Y / X
It is preferred that When Y / X ≧ 2, a large amount of the volatile (B) component is present in the obtained curable composition, so that the moldability deteriorates and the unreacted (B) component is removed. In some cases, the resulting cured product may not have sufficient strength, and may have low heat resistance.

The present invention is particularly useful when the components (A) and (B) are incompatible with each other as described above. In this case, immiscible means not only that the liquids cannot be mixed uniformly, but also that one is a liquid and one is a gas or solid and the gas or solid is not uniformly dissolved in the liquid. Including. In addition, it includes a case where the composition is macroscopically uniform but not microscopically uniform, such as an emulsion. The temperature is not particularly limited. For example, in the case where the above-mentioned incompatible state is obtained in any limited temperature range between 20 ° C. and 200 ° C., both are considered to be incompatible. Further, that the curable composition is uniform means that the components contained in the curable composition are mutually compatible and are in a macroscopically and microscopically uniform state.

Next, the hydrosilylation catalyst as the component (C) will be described. The hydrosilylation catalyst is not particularly limited as long as it has the catalytic activity of the hydrosilylation reaction, and examples thereof include a simple substance of platinum, alumina, silica, carbon black and the like on which solid platinum is supported, chloroplatinic acid, platinum chloride Complexes of acids with alcohols, aldehydes, ketones, etc., platinum-olefin complexes (for example, Pt
_{(CH 2 = CH 2) 2} (PPh 3) 2, Pt (CH 2 =
CH ₂ ) ₂ Cl ₂ ), a platinum-vinylsiloxane complex (for example, Pt (ViMe ₂ SiOSiMe ₂ Vi) _n , P
t [(MeViSiO) ₄ ] _m ), a platinum-phosphine complex (for example, Pt (PPh ₃ ) ₄ , Pt (PB
u ₃ ) ₄ ), a platinum-phosphite complex (for example, Pt
[P (OPh) ₃ ] ₄ , Pt [P (OBu) ₃ ] ₄ )
(In the formula, Me is a methyl group, Bu is a butyl group, Vi is a vinyl group, Ph is a phenyl group, and n and m are integers.), Dicarbonyldichloroplatinum, Karstedt's catalyst, Ashby (Ash
by) US Patents 3,159,601 and 31,596
No. 62, as well as the platinum-hydrocarbon complex described in Lamoreaux.
Platinum alcoholate catalysts described in U.S. Pat. No. 2,209,72. In addition, Modic
Platinum chloride-olefin complexes described in U.S. Pat. No. 3,516,946 are also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PPh) ₃ , RhCl ₃ , and RhAl ₂ O
₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlC
l ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiC
l _4, and the like. Among these, chloroplatinic acid, a platinum-olefin complex, a platinum-vinylsiloxane complex and the like are preferable from the viewpoint of catalytic activity. These catalysts may be used alone or in combination of two or more.

The amount of the catalyst to be added is not particularly limited.
Curability and the cost of the curable composition is relatively low
(B) component 1 mole of SiH group
Ten ^-1-10^-8The molar range is preferred, more preferably
Preferably 10^-2-10^-6Range of moles.

Further, a co-catalyst can be used in combination with the above-mentioned catalyst, and examples thereof include a phosphorus compound such as triphenylphosphine, a 1,2-diester compound such as dimethyl maleate, and 2-hydroxy-2-ester. Examples include acetylene alcohol compounds such as methyl-1-butyne, sulfur compounds such as simple sulfur, and amine compounds such as triethylamine. The addition amount of the co-catalyst is not particularly limited, the catalyst 1 ^mol, preferably 10-2 to ² mols, more preferably from ¹⁰ -1 to 10 mol.

In the composition of the present invention, a curing retarder can be used as the component (D). As a curing retarder,
A compound containing an aliphatic unsaturated bond, an organic phosphorus compound,
Examples thereof include organic sulfur compounds, nitrogen-containing compounds, tin-based compounds, and organic peroxides, and these may be used in combination.

Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols, ene-yne compounds, and maleic esters. Examples of the organic phosphorus compound include triorganophosphines, diorganophosphines, organophosphones, and triorganophosphites.

Examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, thiazole, benzothiazole, benzothiazole disulfide and the like. Examples of the nitrogen-containing compound include ammonia, tetramethylethylenediamine, and the like.
Examples include secondary alkylamines, arylamines, urea, hydrazine and the like.

Examples of the tin compound include stannous halide dihydrate, stannous carboxylate and the like. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

Among these curing retarders, benzothiazole, thiazole, dimethylmalate, and 3-hydroxy-3-methyl-1-butyne are preferred from the viewpoint of good retarding activity and good raw material availability. From the viewpoint of good delay activity at high temperatures, alkylamines such as tetramethylethylenediamine are preferred.

These curing retarders can be used alone or in combination. Amount of the curing retarder, with respect to the hydrosilylation catalyst (C) 1 mol to be ^used, preferably 10 -1 to 10 ³ mols.

The curable composition of the present invention is obtained by mixing the components (A) to (C) or the components (A) to (D) as described above, and forming a hydrosilylatable carbon-carbon double in the mixture. It can be obtained by reacting each of the bond and a part of the SiH group in advance by a hydrosilylation reaction. In this case, the hydrosilylation reaction can be advanced by simply mixing the components, but can also be advanced by heating. From the viewpoint of good controllability of the reaction, the reaction is preferably advanced by heating. The reaction temperature in this case can be appropriately set according to the reaction rate, but for example, a temperature of 50 to 200 ° C. can be applied. The reaction temperature may be constant during the reaction, or may be changed over time as needed.

In carrying out the hydrosilylation reaction, various solvents may be used. When a solvent is used, the progress of the reaction becomes gentle and the control is easily performed. In this case, various solvents can be used. Examples thereof include hydrocarbon solvents such as benzene, toluene, hexane, and heptane, tetrahydrofuran, 1,4-dioxane,
Examples include ether solvents such as 3-dioxolan and diethyl ether, ketone solvents such as acetone and methyl ethyl ketone, halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane, dimethyl sulfoxide, acetonitrile, dimethylformamide and dimethylacetamide. . The solvent can be used as a mixed solvent of two or more kinds. As the solvent, from the viewpoint of good reactivity, toluene, 1,3-dioxolan,
Tetrahydrofuran and chloroform are preferred. Although the amount of the solvent used is not particularly limited, it is used (A) to (C).
For 1 g of the total of the components or the components (A) to (D), 1
Use in the range of 0 mL or less is preferable from the viewpoint that the production cost is reduced.

The curable composition of the present invention contains a hydrosilylatable carbon-carbon double bond and a SiH group. Therefore, the hydrosilylatable carbon-carbon double bond in the component (A) and all of the SiH groups in the component (B) are not reacted,
The reaction is substantially stopped when a portion of each has reacted. In this case, the terminating of the reaction means the extent that there is no problem in storage of the curable composition of the present invention (for example, the extent that 10% or less of the SiH groups remaining in the composition is consumed at room temperature / 24 hours). ) Includes the state where the reaction rate is reduced. In this case, the reaction can be stopped by lowering the temperature or by adding a curing retarder. When the reaction is stopped by lowering the temperature, the hydrosilylation reaction is carried out at a temperature higher than room temperature, and this is lowered to room temperature of, for example, 10 to 30 ° C., so that the storage stability of the curable composition is good. It is preferable from the viewpoint that there is. When the reaction is stopped by adding a curing retarder, the preferred type and amount of the curing retarder are the same as the preferred type and amount of the component (D).

The time for stopping the reaction is not particularly limited as long as the curable composition obtained does not gel, but
80% or less of the number of hydrosilylatable carbon-carbon double bonds in component (A) and 80% or less of SiH groups in component (B) It is preferable to terminate the reaction at the time when the group has reacted, and it is preferable that 60% or less of the number of hydrosilylatable carbon-carbon double bonds in the component (A) be a hydrosilylatable carbon.
60 of the number of carbon double bonds and SiH groups in component (B)
%, More preferably 3 to 60% of the number of hydrosilylatable carbon-carbon double bonds in component (A). More preferably, the reaction is terminated at the time when 60% or less of the number of SiH groups in the component (B) and the number of SiH groups in the component (B) have reacted. Most preferably, the reaction is stopped when 3 to 60% of the hydrosilylatable carbon-carbon double bonds and 3 to 60% of the number of SiH groups in the component (B) have reacted. If the timing for stopping the reaction is too early, sufficient effects such as compatibility cannot be obtained, and if it is too late, the risk of gelation during the storage period increases, which is not preferable.

In this case, the number of hydrosilylatable carbon-carbon double bonds and the number of SiH groups are analyzed by, for example, a spectroscopic method such as nuclear magnetic resonance (NMR) and infrared absorption (IR). It can be quantified and can be analyzed by gas chromatography (GC), liquid chromatography (L
It can also be analyzed and quantified by separation analysis such as C), thin layer chromatography (TLC), and molecular sieve chromatography (GPC). In addition, it can also be determined by an indirect or empirical method such as refractive index, viscosity, and tack.

After terminating the hydrosilylation reaction as described above, the unreacted component (A) and / or unreacted component (B) can be removed. If the unreacted component (A) and / or the unreacted component (B) remain in the curable composition, the compatibility becomes poor or voids are generated during curing due to the volatility of these components. It is not preferable from the viewpoint that it becomes easy. In this case, it is preferable to remove the unreacted component (A) and / or the unreacted component (B) so that each content of the uncured component is 10% by weight or less of the curable composition.
It is more preferable to remove each so as to be 5% by weight or less, and it is even more preferable to remove each so as to be 1% by weight or less. In the present specification, the “unreacted (A) component” or “unreacted (B) component”
It means that none of a plurality of "hydrosilylatable carbon-carbon double bonds" or "SiH groups" that each component has in the molecule has undergone any hydrosilylation reaction. Those that have reacted with any one of a plurality of “hydrosilylatable carbon-carbon double bonds” or “SiH groups” are not “unreacted”.

Various methods can be used for the removal. For example, normal pressure or, for example, 0.1 to 1
Devolatilization under reduced pressure such as 0 torr, activated carbon,
Examples thereof include a method by treatment with various adsorbents such as silica gel, aluminum silicate, and ion exchange resin, and a method by extraction with water, various organic solvents, and the like. Of these, a method based on devolatilization is preferred from the viewpoint of high industrial practicality.

The ratio of the number of hydrosilylatable carbon-carbon double bonds (W) to the number of SiH groups (Z) in the curable composition of the present invention is 2 ≧ W / Z ≧ 0.5 It is preferred that If W / Z> 2 or 0.5> W / Z,
In some cases, sufficient curability cannot be obtained, sufficient strength cannot be obtained, and heat resistance can be lowered.

The above operation can be performed before molding the curable composition, or can be performed after preliminary molding. For example, after the raw material mixture or the curable composition of the present invention is cast into a thin film by casting, the above-mentioned hydrosilylation reaction is performed for the first time or again to obtain the curable composition of the present invention. A molding operation such as adhesion to an adherend can be performed by molding.

The curable composition of the present invention may optionally contain an inorganic filler. The addition of the inorganic filler is effective in reducing the coefficient of linear expansion and increasing the strength of the material. As the inorganic filler, fused silica, crystalline silica, ultrafine amorphous silica, hydrophobic ultrafine silica, silica such as spherical silica, alumina, aluminum hydroxide,
Examples include talc and barium sulfate. Among these, silicas are preferred from the viewpoint that they hardly inhibit the curing reaction and the effect of reducing the linear expansion coefficient is large, and spherical silica is more preferred from the viewpoint that the viscosity when added is low.

When used for electronic materials, etc., these inorganic fillers preferably have low radiation properties to protect electronic circuits. The amount of the inorganic filler to be added is not particularly limited, but is preferably 50 to 80% by weight of the entire composition from the viewpoint that the effect of reducing the coefficient of linear expansion is high and the fluidity of the composition is good. .

Further, for the purpose of improving the properties of the curable composition of the present invention, various resins can be added. As the resin, polycarbonate resin, polyether sulfone resin, polyarylate resin, epoxy resin,
Examples thereof include a cyanate resin, a phenol resin, an acrylic resin, a polyimide resin, a polyvinyl acetal resin, a urethane resin, a polyester resin, and a silicone resin, but are not limited thereto. Various elastomers can be added as the resin.

The curable composition of the present invention can be used as it is, but a solvent can be added for the purpose of lowering the viscosity. Solvents that can be used are not particularly limited, and specific examples include hydrocarbon solvents such as benzene, toluene, hexane, and heptane, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolan, and diethyl ether. Ether solvents, ketone solvents such as acetone and methyl ethyl ketone, and halogen solvents such as chloroform, methylene chloride and 1,2-dichloroethane can be suitably used. The solvent can be used as a mixed solvent of two or more kinds. As the solvent, toluene, tetrahydrofuran, 1,3-dioxolan, and chloroform are preferred from the viewpoint of solubility and the like.
The amount of the solvent used is 0 to 1 g of the component (A) used.
Preferably used in the range of 10 mL, 0.5-5 mL
Is more preferably used, and particularly preferably used in the range of 1 to 3 mL. If the amount used is small, it is difficult to obtain the effect of using a solvent such as lowering the viscosity, and if the amount used is large, the solvent tends to remain in the material, easily causing problems such as thermal cracks, and also in terms of cost. It is disadvantageous and reduces the industrial use value.

The curable composition of the present invention may contain a coupling agent for the purpose of imparting adhesiveness. Examples of the coupling agent include an epoxy group, a methacryl group, an acryl group, an isocyanate group, an isocyanurate group, a vinyl group, a carbamate group,
A silane coupling agent having at least one functional group selected from the group consisting of SiH groups and a silicon-bonded alkoxy group can be used. Among the above functional groups, an epoxy group, a methacryl group, and an acryl group are particularly preferable in the molecule from the viewpoint of curability and adhesiveness.

Specifically, examples of the organosilicon compound having an epoxy functional group and a silicon-bonded alkoxy group include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2-glycidoxypropyltriethoxysilane.
-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl)
Ethyltriethoxysilane is mentioned. Examples of the organosilicon compound having a methacryl group or an acryl group and a silicon-bonded alkoxy group include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, Acryloxypropyltriethoxysilane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, acryloxymethyltriethoxysilane are exemplified. Of these, a silane coupling agent having an epoxy functional group and a silicon-bonded alkoxy group is preferably used from the viewpoint that the curability is not particularly hindered and the adhesion-imparting effect is high. Specifically, 3-glycidoxypropyltrimethoxysilane is particularly preferably used. These coupling agents may be used alone or in combination of two or more.

The curable composition of the present invention further comprises an antioxidant, a radical inhibitor, an ultraviolet absorber, an adhesion improver, a flame retardant, a surfactant, a storage stability improver, an ozone deterioration inhibitor, Stabilizer, thickener, plasticizer, antioxidant, heat stabilizer, conductivity-imparting agent, antistatic agent, radiation blocking agent, nucleating agent, phosphorus-based peroxide decomposer, lubricant, pigment, metal deactivator Agents, physical property modifiers, and the like can be added to the extent that the objects and effects of the present invention are not impaired.

As the curable composition of the present invention, various combinations can be used as described above. From the viewpoint of good heat resistance, the cured product obtained by curing the composition has a Tg of 50 ° C. It is preferable that the above be satisfied.
Those having a temperature of 0 ° C or higher are more preferable, and those having a temperature of 150 ° C or higher are particularly preferable. In this case, Tg can be determined, for example, from the peak temperature of tan δ measured by viscoelasticity.

The curable composition of the present invention is uniform, has appropriate viscosity and melting characteristics, and has good moldability, and can be suitably molded by various molding methods. Specific molding methods include, for example, cast molding such as cell casting and casting method, press molding, injection molding, transfer molding, potting molding, dipping molding,
Alternatively, screen printing can be performed. Further, it can also be formed by a method of dispensing and then penetrating into gaps (for example, used for underfill for semiconductors and the like). As the press molding, for example, after impregnating the raw material mixture or the curable composition of the present invention into fibers such as glass cloth and carbon cloth, the hydrosilylation reaction is further advanced as necessary, and the obtained prepreg is press-molded. It can also be molded by the method described below.

Various processes can be performed as required during molding. For example, in order to suppress voids generated during molding, it is possible to apply a process of defoaming the composition in advance by centrifugation, decompression, etc., and to perform a degassing step during press molding and various moldings under reduced pressure. To do
Defoaming treatment during molding can also be applied.

The curable composition of the present invention can be cured to obtain a cured product after performing necessary molding. The method of curing can be generally carried out by heating. The heating in this case may be heating by direct heat by heating with hot air or a mold, or heating by light such as infrared light.

The reaction temperature can be variously set. For example, a temperature of 30 to 300 ° C. can be applied, and a temperature of 100 to 250 ° C.
Is more preferable, and 150 to 200C is further preferable.
When the reaction temperature is low, the reaction time for causing a sufficient reaction is prolonged, and when the reaction temperature is high, molding tends to be difficult.

The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple steps or continuously as needed. The reaction time can also be set variously. The pressure during the reaction can be variously set as required, and the reaction can be performed at normal pressure, high pressure, or reduced pressure.

The curable composition of this reaction can be suitably used for various applications. Examples of the use include general use in which a thermosetting resin such as an epoxy resin is used. Examples of the use include an adhesive, a paint, a coating agent, a molding material (including a sheet, a film, and an FRP), and an insulating material (a printed circuit board). , An electric wire covering, etc.), a sealant, and additives to other resins and the like.

Examples of the adhesive include adhesives for electronic materials, in addition to adhesives for civil engineering, construction, automobiles, general affairs, and medical care. Among these, adhesives for electronic materials include interlayer adhesives for multilayer boards such as build-up boards,
Die bonding agents, adhesives for semiconductors such as underfills, BGA reinforcing underfills, mounting adhesives such as anisotropic conductive films (ACF), anisotropic conductive pastes (ACP), and the like.

Examples of the sealing agent include potting for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, etc., dipping, transfer mold sealing, potting sealings for ICs and LSIs such as COB, COF, TAB, and flip chips. And sealing (reinforcement underfill) when mounting IC packages such as BGA and CSP.

[0105]

EXAMPLES Examples and comparative examples of the present invention will be shown below, but the present invention is not limited by the following. (Synthesis Example 1) A stirrer, a condenser, and a dropping funnel were set in a 2 L four-necked flask. In this flask, under a nitrogen atmosphere, the following formula

[0106]

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120 g of the compound represented by the formula and 560 g of dimethylformamide were added and dissolved by stirring at room temperature. Allylamine 24.5 at a reaction liquid temperature of 20 ° C. was stirred.
g was dropped from the dropping funnel over about 15 minutes. By this operation, the temperature of the reaction solution was raised to 50 ° C. After stirring for 1 hour in a room temperature atmosphere, 86 g of acetic anhydride and 50 g of β-picoline were added. The mixture was heated and stirred at an internal temperature of 100 ° C. for 1 hour in an oil bath. After cooling, the resulting orange solution was slowly poured into 3 L of vigorously stirred methanol to reprecipitate the reaction product. The obtained beige solid was separated by filtration and reslurried and washed three times with 200 mL of methanol. The obtained solid was placed under a vacuum of 1 torr or less for 10
Drying in a vacuum oven heated to 0 ° C. afforded the product as a solid, 105 g. ^{According to 1} H-NMR, the following formula

[0108]

Embedded image

(Compound A) was obtained.

(Synthesis Example 2) 10.0 g of the compound A synthesized in Synthesis Example 1, 1, 3, 5,
18.3 g of 7-tetramethylcyclotetrasiloxane,
100 g of toluene was added and stirred at room temperature. 23.0 μL of a xylene solution of platinum vinyl siloxane complex (containing 3 wt% as platinum) was added to the obtained slurry, and 70 ° C.
The mixture was heated and stirred in an oil bath for 90 minutes. During this time, the reaction liquid gradually became transparent and uniform. After cooling, 7.0 mg of benzothiazole was added. 1 Torr of the resulting solution
Evaporation was performed under a vacuum of r or less to remove volatiles (solvent and unreacted 1,3,5,7-tetramethylcyclotetrasiloxane) to obtain a red-brown viscous liquid. ¹ H-
According to NMR, the following formula

[0111]

Embedded image

(Compound B).

Example 1 A 50 mL eggplant-shaped flask was charged with 3.0 g of Compound A and 0.83 g of 1,3,5,7-tetramethylcyclotetrasiloxane (boiling point 135 ° C.) (where Y / X is 1. 5). The mixture was mixed at room temperature, but did not dissolve and became a slurry. 30 g of toluene was further added to this mixture and mixed at room temperature, but again in a slurry state. 6.0 μL of a xylene solution of platinum vinyl siloxane complex (containing 3 wt% as platinum) was added to the obtained slurry under stirring. Place the condenser in the flask, under nitrogen, 70 ° C
And heated and stirred in an oil bath. The reaction liquid maintained a slurry state at the beginning even after heating, but the reaction liquid became transparent after 30 minutes. After 60 minutes, about 1 mL of the reaction solution was withdrawn and evaporated at 50 ° C. for 15 minutes under reduced pressure of 1 torr or less to remove volatile components, whereby a transparent and uniform curable composition was obtained. NMR analysis showed that 10% of the allyl group of compound A added first and 7% of the SiH group of 1,3,5,7-tetramethylcyclotetrasiloxane added first had hydrosilylation reaction. I understood that.

(Example 2) The curable composition obtained in Example 1 was further reacted, and the reaction was continued for 120 minutes from the start of heating.
After one minute, raise the temperature of the oil bath to 80 ° C.
The mixture was heated and stirred for minutes. When the obtained reaction liquid was evaporated to remove volatile components, a transparent and uniform curable composition was obtained. When this was analyzed by NMR, 25% of the allyl group of the compound A added first, 1,3
SiH of 5,7-tetramethylcyclotetrasiloxane
It was found that 17% of the groups had undergone a hydrosilylation reaction. When this curable composition was analyzed by gas chromatography, the content of unreacted 1,3,5,7-tetramethylcyclotetrasiloxane was 0.1% by weight or less.

Example 3 A 100 mL eggplant-shaped flask was charged with 3.0 g of Compound A, 5.5 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and 30 g of toluene (here, Y / X is 10). ). To the obtained slurry, 6.9 μL of a xylene solution of platinum vinyl siloxane complex (containing 3 wt% as platinum) was added with stirring. A condenser was placed in the flask, and the mixture was placed in a 50 ° C. oil bath for 50 minutes under nitrogen and 10 minutes in a 65 ° C. oil bath.
The mixture was heated and stirred in an oil bath at 0 ° C. for 30 minutes. During this time the reaction became clear. After adding 37 mg of benzothiazole to the obtained reaction solution, the mixture was added under reduced pressure of 1 torr or less.
When the volatile matter was removed by evaporating at 15 ° C. for 15 minutes, a transparent and uniform curable composition was obtained. When this was analyzed by NMR, it was found that two of the allyl groups of Compound A added first were
It was found that 7%, and 3% of the SiH groups of the 1,3,5,7-tetramethylcyclotetrasiloxane initially added had undergone a hydrosilylation reaction.

Example 4 The curable composition obtained in Example 3 was stored at room temperature for 48 hours and analyzed by NMR.
No further change such as the progress of the hydrosilation reaction was observed. After that, it is diluted 5 times (wt / wt) with toluene,
After heating and stirring for 15 minutes in an oil bath at 110 ° C, 1t
Evaporation was performed at 50 ° C. for 15 minutes under reduced pressure of orr to remove volatile components. NMR analysis of the obtained transparent uniform curable composition showed that 50% of the allyl groups of compound A added first and SiH groups of 1,3,5,7-tetramethylcyclotetrasiloxane added first. 5% of
Was found to undergo a hydrosilylation reaction. When this curable composition was analyzed by gas chromatography, the content of unreacted 1,3,5,7-tetramethylcyclotetrasiloxane was 0.1% by weight or less.

Example 5 A 100 mL eggplant-shaped flask was charged with 3.0 g of Compound A, 5.5 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and 30 g of toluene (here, Y / X is 10). ). To the obtained slurry, 6.9 μL of a xylene solution of platinum vinyl siloxane complex (containing 3 wt% as platinum) was added with stirring. A condenser was placed in the flask, and the mixture was heated and stirred in an oil bath at 80 ° C. for 15 minutes under nitrogen. During this time the reaction became clear. 37 mg of benzothiazole was added to the obtained reaction solution.
Was added and evaporated at 45 ° C. for 15 minutes under reduced pressure of 1 torr or less to remove volatile components, whereby a transparent and uniform curable composition was obtained. When this was analyzed by NMR, 70% of the allyl group of the compound A added first and 7% of the SiH group of the 1,3,5,7-tetramethylcyclotetrasiloxane initially added reacted with hydrosilylation. It was found to be a compound. When this curable composition was analyzed by gas chromatography, the content of unreacted 1,3,5,7-tetramethylcyclotetrasiloxane was 0.1% by weight or less.

Example 6 10.0 g of Compound A, 18.3 g of 1,3,5,7-tetramethylcyclotetrasiloxane, and 100 ml of toluene were placed in a 200 mL eggplant-shaped flask.
g (where Y / X is 10). To the obtained slurry, 23.0 μL of a xylene solution of platinum vinyl siloxane complex (containing 3 wt% as platinum) and 123.3 mg of benzothiazole were added with stirring. A condenser was placed in the flask, and the mixture was heated and stirred in a 110 ° C. oil bath for 20 minutes under nitrogen. During this time the reaction became clear. When the obtained curable composition was subjected to NMR analysis,
It was found that 95% of the allyl group of the compound A added first and 10% of the SiH group of the 1,3,5,7-tetramethylcyclotetrasiloxane added first had hydrosilylation reaction.

Example 7 The curable composition obtained in Example 6 was evaporated at 50 ° C. for 15 minutes under reduced pressure of 1 torr or less to remove volatile components, and the obtained transparent mucus was added to 50 g of toluene. Redissolved. 3 of this solution
Take 5.4 g, 12.5 g of compound A and 1
After adding 0 g, the mixture was heated and stirred in a 90 ° C. oil bath for 60 minutes. About 1 mL of the reaction solution was withdrawn and evaporated at 50 ° C. for 15 minutes under reduced pressure of 1 torr or less to remove volatile components. The reaction solution was further heated and stirred in a 110 ° C. oil bath for 60 minutes. The obtained solution is heated at 50 ° C. under a reduced pressure of 1 torr or less.
For 15 minutes to remove volatile components, and a transparent and uniform curable composition was obtained. NMR analysis showed that 31% of the total charge of allyl groups of compound A and 7% of the initially added 1,3,5,7-tetramethylcyclotetrasiloxane SiH groups were hydrosilylation reacted. I understood that. When this curable composition was analyzed by gas chromatography, unreacted 1,3,5
The content of 7-tetramethylcyclotetrasiloxane was 0.1% by weight or less.

Example 8 6.52 g of Compound A, 4.80 g of Compound B and 15.9 g of toluene were placed in a 100 mL eggplant-shaped flask. This mixture was mixed at room temperature,
There was no compatibility and a slurry was obtained. This slurry was heated and stirred in a 110 ° C. oil bath for 20 minutes. The obtained solution was evaporated at 50 ° C. for 15 minutes under reduced pressure of 1 torr or less to remove volatile components, and a transparent and uniform curable composition was obtained. According to NMR analysis, 30% of the allyl group of the compound A added first and 30% of the SiH group of the 1,3,5,7-tetramethylcyclotetrasiloxane initially added undergo hydrosilylation reaction. I understood that.

Example 9 The curable composition obtained in Example 8 was added to 1,3-dioxolane using Solid Conte.
It melt | dissolved so that nt (weight% of the composition in a solution) might be 76 weight%. This solution was cast on a PI film using a hand coater with a clearance of 225 μm, and heated in a hot air oven at 100 ° C./3 minutes and 150 ° C./3 minutes.
Cover the obtained product with a PI film and apply a surface pressure of 20 kgf.
/ Cm ² at 150 ° C. for 30 minutes. The obtained product was further heated in an oven at 200 ° C./90 minutes. When the PI film was peeled off, a cured product in the form of a transparent uniform film was obtained. Tg of the obtained cured product (t of viscoelasticity measurement)
peak temperature of anδ) was 185 ° C.

Example 10 The curable composition obtained in Example 8 was added to 1,3-dioxolane using Solid Cont.
ent (% by weight of the composition in the solution) was dissolved. This solution was cast on an electrolytic copper foil (mat surface) with a hand coater having a clearance of 225 μm,
It was heated in a hot air oven at 100 ° C./3 minutes and 150 ° C./3 minutes. Cover the obtained one with electrolytic copper foil (mat surface),
Heat pressing was performed at a surface pressure of 20 kgf / cm ² and 150 ° C. for 30 minutes. The obtained product is further heated in an oven at 200 ° C /
Heated for 90 minutes. The obtained adhesive body was in a good molded state without flowing out of the adhesive layer due to excessive fluidity during molding and without poor adhesion due to insufficient fluidity during molding.
Adhesion strength (90 ° peel strength) of copper foil of obtained adhesive
Was measured, and showed an adhesive strength of 4.2 N / cm.

Comparative Example 1 A 50 mL eggplant-shaped flask was charged with 3.0 g of Compound A and 0.83 g of 1,3,5,7-tetramethylcyclotetrasiloxane. After stirring and mixing, they were not compatible with each other and turned into a slurry state.

Comparative Example 2 A 50 mL eggplant-shaped flask was charged with 3.0 g of Compound A, 5.0 g of Compound B, and 10 g of 1,3-dioxolane, and stirred and mixed. When the obtained homogeneous solution was evaporated and the solvent was removed, an inhomogeneous state in which two components were separated was obtained.

(Comparative Example 3) 6.52 g of the compound A, 4.80 g of the compound B and 15.9 g of toluene were placed in a 100 mL eggplant-shaped flask. This slurry was cast on an electrolytic copper foil (mat surface) with a hand coater having a clearance of 225 μm, and was heated in a hot air oven at 100 ° C./3 minutes for 150 minutes.
C./3 minutes. An electrolytic copper foil (mat
Surface), and heat-pressed at 150 ° C. for 30 minutes at a surface pressure of 20 kgf / cm ² . Almost the adhesive layer flows out,
No good molded product was obtained.

[0126]

The curable composition of the present invention is uniform, has appropriate viscosity and melting properties, has good moldability, is versatile in raw material availability, and is industrially practical. Is high.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) H01L 21/52 H01L 21/52 E 23/29 23/30 R 23/31 F term (reference) 4F071 AA04 AA60 AA67 AH12 BA02 BB02 BC02 4J002 AA03W CM04W CP04X GJ00 GQ01 GQ05 4J040 DA001 DA002 DF021 DF022 DF091 DF092 EB051 EB052 ED001 ED002 EE001 EE002 EH031 EH032 EK041 EK042 EL021 EL022 HA01 HA30 HA07 HA30 HA03 HA01 HA30 HA07 HA30 HA03 HA03 HA15 4M109 AA01 BA01 BA03 CA05 CA07 CA21 EA02 EA10 EB02 EB04 EB06 EB07 EB08 EB12 EB18 EB19 EC20 GA10 5F047 BA25 BA26 BA34 BB03 BB11 BB16

Claims (18)

[Claims] 1. An organic compound containing at least two hydrosilylatable carbon-carbon double bonds in one molecule, (B) a silicon compound containing at least two SiH groups in one molecule, And (C) a hydrosilylation catalyst,
A curable composition obtainable by previously reacting a part of each of a hydrosilylatable carbon-carbon double bond and a SiH group in a mixture containing as an essential component by a hydrosilylation reaction. 2. The number of hydrosilylatable carbon-carbon double bonds previously reacted by a hydrosilylation reaction is determined by the number of hydrosilylatable carbon-carbon double bonds in the component (A) before the hydrosilylation reaction. 80% or less, and the number of SiH groups to be reacted in advance by the hydrosilylation reaction is (B) before the hydrosilylation reaction.
The curable composition according to claim 1, wherein the amount of the curable composition is 80% or less of the number of SiH groups in the component. 3. The composition according to claim 1, which contains the component (A) and the component (B) which are incompatible with each other and is uniform.
3. The curable composition according to item 1. 4. The method according to claim 1, wherein the content of the unreacted component (A) is 10% by weight or less and / or the content of the unreacted component (B) is 10% by weight or less. 3. The curable composition according to item 1. 5. The curable composition according to claim 1, wherein the component (A) and / or the component (B) is a compound containing an imide group. 6. The curable composition according to claim 1, further comprising (D) a curing retarder. 7. The component (A) comprises C, H,
The curable composition according to any one of claims 1 to 6, which is a compound containing only O, N, S, and halogen. 8. The curable composition according to claim 1, wherein the component (A) is an organic compound containing at least one vinyl group in one molecule. 9. The mixture containing component (A), component (B) and component (C), wherein the number of hydrosilylatable carbon-carbon double bonds contained in component (A) is (X)
And the ratio of the number (Y) of SiH groups contained in the component (B) is 2> Y / X, and the component (B) is a compound having a boiling point at ordinary pressure of 200 ° C. or lower. The curable composition according to claim 1. 10. A method for producing the curable composition according to claim 1, wherein (A) a hydrosilylatable carbon-carbon double bond is contained in at least two molecules per molecule. (B) a silicon compound containing at least two SiH groups in one molecule, and (C) a hydrosilylation catalyst in a mixture containing as essential components a hydrosilylation catalyst. A production method comprising reacting a part of each of a heavy bond and a SiH group by a hydrosilylation reaction in advance. 11. The production method according to claim 10, wherein the hydrosilylation reaction is carried out in the presence of a solvent. 12. A method comprising reacting a part of each of a hydrosilylatable carbon-carbon double bond and a SiH group by a hydrosilylation reaction, and then suppressing the progress of the hydrosilylation reaction by lowering the temperature. The method according to claim 10. 13. The method according to claim 1, wherein a part of each of the hydrosilylatable carbon-carbon double bond and the SiH group is reacted by a hydrosilylation reaction, and then a curing retarder is added to suppress the progress of the hydrosilylation reaction. Become,
The method according to claim 10. 14. After reacting each of the hydrosilylatable carbon-carbon double bond and a part of the SiH group by a hydrosilylation reaction, the unreacted component (A) and / or the unreacted component (B) 2. The method of claim 1, comprising removing.
14. The production method according to any one of 0 to 13. A cured product obtained by curing the curable composition according to any one of claims 1 to 9. 16. An adhesive containing the curable composition according to claim 1. Description: 17. A sealant comprising the curable composition according to claim 1. 18. An organic compound containing at least two hydrosilylatable carbon-carbon double bonds in one molecule, (B) a silicon compound containing at least two SiH groups in one molecule, And (C) a part of the hydrosilylatable carbon-carbon double bond and the SiH group in the curable composition containing the hydrosilylation catalyst as an essential component in advance by a hydrosilylation reaction, followed by molding. And a method for molding a curable composition.