JP3359360B2 - Curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition containing a reactive imide compound. More specifically, it cures quickly at a relatively low temperature without the generation of low-boiling compounds during curing, and has excellent heat resistance, chemical resistance after curing,
The present invention relates to a curable composition that gives a cured product having mechanical properties.

[0002]

2. Description of the Related Art Conventionally, many compositions have been developed as curable compositions. Among them, a curable composition utilizing a hydrosilylation reaction which proceeds at a relatively low temperature is also disclosed (JP-A-1-138230). When the composition is used, a low-boiling compound is hardly generated at the time of curing, and a compound having a good appearance can be obtained. However, the main chain of both the alkenyl group-containing component and the hydrosilyl group-containing component is composed of polyether, and the obtained curing is obtained. The products have insufficient heat resistance, chemical resistance, etc., and have drawbacks such as a large decrease in mechanical properties in a short time even at a temperature of 100 ° C., and poor acid resistance and solvent resistance. Therefore, it is not suitable for applications requiring heat resistance and chemical resistance, for example, applications such as coating agents around electronic components and heat-resistant adhesives.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a cured product which cures rapidly at a relatively low temperature without generating a low-boiling compound at the time of curing, and has excellent heat resistance, chemical resistance and mechanical strength after curing. It is intended to provide a curable composition to be provided.

[0004]

Means for Solving the Problems As a result of intensive studies on such problems, the present inventors have found that at least two molecules are present in a molecule.
When an imide compound having two hydrosilyl groups and a compound having at least two carbon-carbon double bonds in the molecule are reacted with each other using a hydrosilylation catalyst, the compound is rapidly cured even at a relatively low temperature, and a low-boiling compound is obtained during curing. It has been found that the production of a cured product is easy because of not causing the occurrence of the cured product, and a cured product having excellent heat resistance, chemical resistance and mechanical properties is provided after curing, and the present invention has been completed.

That is, the present invention provides (A) a compound represented by the general formula (I):

[0006]

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Wherein R ¹ is a tetravalent organic group containing an aromatic group having 6 to 30 carbon atoms, and R ² is a divalent organic group containing an aromatic group having 6 to 30 carbon atoms. Or the general formula (II):

[0008]

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(R ⁴ is a divalent organic group having 1 to 20 carbon atoms,
R ⁵ represents a monovalent organic group having 1 to 20 carbon atoms, and a plurality of R ⁴ and R ⁵ may be the same or different; l is a positive integer of 1 to 20 R ³ is a divalent organic group having 1 to 20 carbon atoms, Y is an organic group having 1 to 20 carbon atoms including at least one hydrosilyl group, and two R ³ and Y may be the same, or different Tei may, n imide compound is represented by representing) an integer from 1 to 100 and the general formula (II
I):

[0010]

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Wherein R ¹ , R ² , and n are the same as above, and R ⁶ is a divalent organic group having 1 to 20 carbon atoms containing at least one hydrosilyl group; ^At least one imide compound selected from imide compounds represented by the following general formula (IV):

Embedded image (Wherein, R ⁸ is a hydrogen atom or a methyl group, and R ⁹ is
A divalent organic group having a prime number of 2 to 20;
R ¹⁰ may have 1 to 30 carbon atoms.
An aromatic or aliphatic divalent to tetravalent organic group, a is 2 to 4
A compound having an ether bond represented by
Object, general formula (V):

Embedded image (Wherein, R ⁸ and R ⁹ are the same as described above, and R ¹¹ has 1 carbon atom)
~ 30 monovalent to tetravalent organic groups, b represents an integer of 1 to 4
Compound having an ester bond represented by the general formula
(VI):

Embedded image (Wherein R ⁸ and a are the same as described above, and R ¹² has 2 carbon atoms.
Represents up to 50 divalent to tetravalent organic groups)
A hydrogen-based compound and a compound represented by the general formula (VII):

Embedded image (Wherein R ⁸ , R ⁹ and a are the same as above, and R ¹³ is a carbon atom
Represents an organic group having 1 to 30 divalent to tetravalent organic groups)
Compound having a carbonate bond, 1,3-butadiene
, Bisphenol A diallyl ether, bisphenol
P diallyl ether, diallyl terephthalate, dia
Ryl isophthalate or diallyl carbonate
Have at least two carbon-carbon double bonds in the molecule
And a compound containing no imide group , and (C) a hydrosilylation catalyst, and a hydrosilyl (Si—H) group in the component (A).
Is a molar ratio with respect to the carbon-carbon double bond in the component (B).
0.5 to 10 times the amount of component (C) used in component (B)
The present invention relates to a curable composition having an amount of 10 ^{< -1} > to 10 < ^-8> mol per mol of carbon-carbon double bond .

[0012]

In the present invention, the component (A) is represented by the general formula (I):

[0013]

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Wherein R ¹ is a tetravalent organic group containing an aromatic group having 6 to 30 carbon atoms, and R ² is a divalent organic group containing an aromatic group having 6 to 30 carbon atoms. Or the general formula (II):

[0015]

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(R ⁴ is a divalent organic group having 1 to 20 carbon atoms,
R ⁵ represents a monovalent organic group having 1 to 20 carbon atoms, and a plurality of R ⁴ and R ⁵ may be the same or different; l is a positive integer of 1 to 20 2)
R ³ is a divalent organic group having 1 to 20 carbon atoms, Y is an organic group having 1 to 20 carbon atoms containing at least one hydrosilyl group, and two R ³ and Y are the same. And n may represent an integer of 1 to 100), and an imide compound represented by the general formula (I
II):

[0017]

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(Wherein R ¹ , R ² , and n are the same as described above; R ⁶ is a divalent organic group having 1 to 20 carbon atoms containing at least one hydrosilyl group; ⁶ may be the same or different), and at least one imide compound selected from imide compounds represented by the following formula (hereinafter, also referred to as a hydrosilyl group-containing imide compound) is used.

The composition of the present invention utilizes the fact that the hydrosilyl group-containing imide compound reacts with a compound having a carbon-carbon double bond, for example, an alkenyl group, in the presence of a catalyst to form a cured product. Since there is an imide group in the hydrosilyl group-containing imide compound, a cured product having particularly excellent heat resistance, chemical resistance and mechanical properties after curing can be obtained.

The hydrosilyl group-containing imide compound as the component (A) used in the present invention has at least 2
, Preferably 2 to 15, more preferably 3 to 12 hydrosilyl groups. Since the hydrosilyl group-containing imide compound (A) has at least two hydrosilyl groups in the molecule, it reacts with a compound having at least two carbon-carbon double bonds in the molecule, which is the component (B) described below. , A linear or network polymer. If the number of hydrosilyl groups contained in one molecule is less than 2, curing failure often occurs. On the other hand, if the number of hydrosilyl groups is too large, the storage stability of the hydrosilyl group-containing imide compound (A) becomes poor, and a large amount of hydrosilyl groups remains in the cured product even after curing, causing voids and cracks. Becomes

The hydrosilyl group-containing imide compound (A) is not particularly limited as long as it is an imide compound having at least two hydrosilyl groups in the molecule, but has a molecular weight of about 500 to 20,000, more preferably about 500 to 10,000. These are preferred in that they have good moldability due to good solubility and meltability, and have excellent heat resistance of the resulting cured product.

The above general formulas (I) and (III)
In the formula, R ¹ is a tetravalent organic group containing an aromatic group having 6 to 30 carbon atoms, and particularly, R ¹ is bonded via a tetravalent aromatic group having 6 to 30 carbon atoms or a divalent group. A tetravalent group comprising an aromatic ring is preferred from the viewpoint of providing a cured product having excellent heat resistance after curing. Particularly preferred specific examples are pyromellitic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 3,3', 4,4'-benzophenonetetracarboxylic acid, 3,3 ', 4,4' -Diphenylsulfonetetracarboxylic acid, 3,3 ', 4,4'-diphenylethertetracarboxylic acid, and residues obtained by removing carboxylic acid groups from naphthalene-1,2,5,6-tetracarboxylic acid. These may be used alone or in combination of two or more.

The above general formulas (I) and (III)
In the formula, R ² is a divalent organic group containing an aromatic group having 6 to 30 carbon atoms, or a general formula (II):

[0024]

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(R ⁴ is a divalent organic group having 1 to 20 carbon atoms,
R ⁵ represents a monovalent organic group having 1 to 20 carbon atoms, and a plurality of R ⁴ and R ⁵ may be the same or different; l is a positive integer of 1 to 20 Represents a group represented by the following formulas. Specific examples of such a group include, 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'-diaminodiphenyl sulfone, 3,3'-diaminobenzophenone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (2-aminophenoxy) phenyl] sulfone, 1,
4-bis (4-aminophenoxy) benzene, 1,3-bis (4-
Aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, bis [4- (4-aminophenoxy) phenyl] ether, 4,4′-diaminodiphenylmethane,
Bis (3-ethyl-4-aminophenyl) methane, 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, 2,2'-bis (4-amino Phenyl) propane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (3-hydroxy-4-aminophenyl) propane, 2,2'-bis (3-
Hydroxy-4-aminophenyl) hexafluoropropane, 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,

[0026]

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(Wherein R ⁵ and l are the same as those described above), and a residue obtained by removing an amino group from a siloxane diamine such as an amino group-terminated polysiloxane. These may be used alone or in combination of two or more.

R ³ is a divalent organic group having 1 to 20 carbon atoms. Specific examples of such a group include, for example, a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and an octylene group. , An isopropylene group, an isobutylene group, a phenylene group, a naphthylene group, a benzylene group and a phenethylene group.

In the general formula (II), R ⁴ is a divalent organic group having 1 to 20 carbon atoms.
Examples include methylene, ethylene, propylene, butylene, hexylene, octylene, isopropylene, isobutylene, phenylene, naphthylene, benzylene, phenethylene and the like.

Y in the general formula (I) is a group containing at least one hydrosilyl group. Specific examples of such a group include, for example,

[0031]

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A hydrosilyl group having one silicon atom (in the case of --SiH ₃ ,
Will be included),

[0033]

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A group containing two or three silicon atoms, such as

[0035]

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Wherein R ⁷ is H, OSi (CH ₃ ) ₃
And a group selected from organic groups having 1 to 10 carbon atoms,
A plurality of R ^{7 s} may be the same or different; m and n are positive integers and satisfy 2 <m + n <50);

[0037]

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(Where R ⁷ is the same as above, p is a positive integer q is 0 or a positive integer, 2 ≦ p + q ≦ 4, k is a positive integer, r is 0 or a positive integer, And 2 ≦ k + r <
And groups derived from various polyvalent hydrogensiloxanes having a chain, a branch, or a ring shown in 50).

When two or more hydrosilyl group-containing groups are present in the same molecule, they may be the same or different.

In the general formula (III), R ⁶ is a divalent organic group having 1 to 20 carbon atoms containing at least one hydrosilyl group, preferably a hydrosilyl group directly bonded to a ring-forming carbon atom. Is a divalent organic group having a structure in which a group having is bonded. Preferred specific examples of such groups include structural formulas:

[0041]

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(Y is the same as described above). Two R ⁶ present in the imide compound represented by the general formula (III) may be the same or different.

Next, a method for producing the hydrosilyl group-containing imide compound represented by the general formula (I), which is one of the components (A) used in the present invention, will be described.

The method for producing the hydrosilyl group-containing imide compound represented by the general formula (I) is not particularly limited, and it can be produced by any method.

For example, a method in which an imide compound having a Si—Cl group in the molecule is treated with a reducing agent such as LiAlH ₄ or NaBH ₄ to reduce the Si—Cl group in the compound to a Si—H group, A method of reacting an imide compound having a functional group Z and a compound having a functional group Y ′ and a hydrosilyl group simultaneously reacting with the above functional group in a molecule, at least for an imide compound having a carbon-carbon double bond. A method of selectively hydrosilylating a polyhydrosilane compound having two hydrosilyl groups so that the hydrosilyl group remains in the molecule of the compound after the reaction can be considered. Among them, the method is particularly preferable in terms of easy availability of raw materials, simple reaction, and high yield.

In the above-mentioned method, as a method for producing an imide compound having a carbon-carbon double bond (for example, an alkenyl group) as a reaction component, for example, first, an aromatic tetracarboxylic dianhydride and a diamine are used. Reaction in an organic polar solvent followed by a carbon-carbon double bond containing 1
Reacting a secondary amine compound to obtain a polyamic acid solution,
Then, (i) a method of thermally imidizing by heating the polyamic acid solution, or (ii) a method of chemically imidizing by reacting a dehydrating agent such as acetic anhydride on the polyamic acid solution, Alternatively, (iii) a method of contacting a solution of the polyamic acid with a poor solvent for amic acid such as water or hydrocarbon to precipitate amic acid as a precipitate and heating the precipitate.

An imide compound having a carbon-carbon double bond can be produced by any of these methods, and is not particularly limited. However, the production apparatus and production steps are simpler or easier. Since the raw materials to be used are easily available, the method (i), that is, the reaction of the aromatic tetracarboxylic dianhydride with the diamine in an organic polar solvent, followed by the carbon-carbon double bond-containing 1 It is preferable to obtain a polyamic acid solution by reacting a secondary amine and then obtain a imide compound by heating.

The reaction is carried out by reacting tetracarboxylic dianhydride, diamine and a primary amine compound containing a carbon-carbon double bond in a solvent at a temperature of 80 ° C. or less as described above to obtain a solution of amic acid. It is preferable to heat this to 100 to 250 ° C.

The carbon-carbon double bond-containing primary amine compound to be used is 2 to 5 times (molar ratio) the acid anhydride newly formed by the reaction between the tetracarboxylic dianhydride and the dian. The same applies hereinafter), preferably 2 to 3 times, more preferably 2 to 2.5 times the amount. When the amount of the carbon-carbon double bond-containing primary amine compound is 2
If less than twice the amount, unreacted acid anhydride remains,
The yield of the desired imide compound is undesirably reduced. When used in an amount exceeding 5 times, the amount of remaining unreacted diamine decreases, but the excess carbon-carbon 2
It is not preferable because it becomes difficult to remove the primary amine compound containing a heavy bond.

Preferred tetracarboxylic dianhydrides are tetracarboxylic dianhydrides based on the groups mentioned as specific examples of R ¹ . As the diamine to be used, a diamine based on the group mentioned as a specific example of R ² is preferable.

Preferred primary amine compounds containing a carbon-carbon double bond include, for example, allylamine, butenylamine, o-aminostyrene, m-aminostyrene and p-aminostyrene.
Examples include aminostyrene, o-allyloxyaniline, m-allyloxyaniline, and p-allyloxyaniline.

Examples of the organic polar solvent include sulfoxide solvents such as dimethylsulfoxide and diethylsulfoxide, N, N-dimethylformamide, N, N
-Formamide solvents such as diethylformamide,
Acetamide solvents such as N, N-dimethylacetamide, N, N-diethylacetamide, N-methyl-2-
Pyrrolidone, N-acetyl-2-pyrrolidone, pyrrolidone-based solvents such as N-vinyl-2-pyrrolidone, phenol, o-cresol, m-cresol, p-cresol, xylenol, halogenated phenol, phenol-based solvents such as catechol, Examples include pyridine, hexamethylphosphoramide, γ-butyrolactone, and a mixture of two or more of these.

Since the imide compound thus produced has a carbon-carbon double bond, a hydrosilyl group can be introduced by the method described above to obtain the hydrosilyl group-containing imide compound used in the present invention. it can.

The imide compound having a carbon-carbon double bond usually has a melting point of 250 ° C. or less.

Next, the method for producing the hydrosilyl group-containing imide compound represented by the general formula (III) will be described.

The method for producing the hydrosilyl group-containing imide compound represented by the general formula (III) is not particularly limited, and it can be produced in the same manner as in the case of the hydrosilyl group-containing imide compound represented by the general formula (I).

In the production of the hydrosilyl group-containing imide compound represented by the general formula (III), the carbon-carbon double bond-containing primary compound used in the production of the hydrosilyl group-containing imide compound represented by the general formula (I) is used. A cyclic olefin-containing acid anhydride is used in place of the amine compound.

The cyclic olefin-containing acid anhydride used is:
As in the case of the hydrosilyl group-containing imide compound represented by the general formula (I), the diamine newly formed by the reaction between the tetracarboxylic dianhydride and the dian is 2 to 5 times (molar ratio) The same applies hereinafter), preferably 2 to
The reaction is preferably carried out using a 3-fold amount, more preferably 2-2.5-fold amount.

Preferred tetracarboxylic dianhydrides and diamines are the same as those for the hydrosilyl group-containing imide compound represented by the general formula (I).

On the other hand, preferred cyclic olefin-containing acid anhydrides include:

[0061]

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And the like.

The imide compound which is a reaction product of the cyclic olefin-containing acid anhydride, diamine and tetracarboxylic dianhydride generally has a melting point of 250 ° C. or less.

Since the imide compound thus produced has a carbon-carbon double bond, a hydrosilyl group can be introduced by the above-described method to give the hydrosilyl group-containing imide compound used in the present invention.

The hydrosilyl group-containing imide compound (A) used in the present invention generally has a melting point of 250 ° C. or less,
Hydrocarbon solvents such as hexane, heptane, benzene, toluene and xylene, alcohol solvents such as methanol, ethanol, propanol, ethylene glycol and 1,4-butanediol, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol Ether solvents such as dimethyl ether, ethylene glycol diethyl ether and anisole; ester solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl benzoate and ethyl benzoate; methylene chloride, chloroform, ethylene chloride, chlorobenzene and the like Halogenated hydrocarbon solvents, dimethyl sulfoxide,
Sulfoxide-based solvents such as diethylsulfoxide, N,
Formamide solvents such as N-dimethylformamide and N, N-diethylformamide; acetamido solvents such as N, N-dimethylacetamide and N, N-diethylacetamide; N-methyl-2-pyrrolidone; N-acetyl-2- Pyrrolidone, pyrrolidone-based solvents such as N-vinyl-2-pyrrolidone, phenol, o-cresol,
Soluble in phenolic solvents such as m-cresol, p-cresol, xylenol, halogenated phenol, catechol, pyridine, hexamethylphosphoramide, γ-butyrolactone, a mixture of two or more of these, and insoluble in water It is. Further, since it has a hydrosilyl group in the molecule, 0 to 30 in the presence of a hydrosilylation catalyst.
Reacts readily with carbon-carbon double bonds such as alkenyl groups at a temperature of 0 ° C.

The hydrosilyl group-containing imide compound (A) used in the present invention has a hydrosilyl group, and may increase in viscosity or gelation due to the incorporation of moisture.
To prevent this, the hydrosilyl group-containing imide compound (A) may be used to store an aliphatic unsaturated bond-containing compound, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound, an organic peroxide, or the like. A stability improver may be contained. The amount of the storage stability improver can be selected almost arbitrarily as long as it is uniformly dispersed, but is preferably 10 ^-6 to 10 ^{-1 based on} 1 mol of the hydrosilyl group-containing imide compound (A).
It is preferably used in the mol range. If the amount is less than 10 ^-6 mol, the storage stability of the imide compound is not sufficiently improved,
If it exceeds 10 ^-1 mol, it will hinder the curing. The storage stability improver may be used alone, or two or more kinds may be used in combination.

In the present invention, a compound having at least two carbon-carbon double bonds in a molecule (hereinafter referred to as an alkenyl compound (hereinafter referred to as an alkenyl compound) is used as a component (component (B)) that reacts with the hydrosilyl group-containing imide compound (A). B)
Is used.

[0068] alkenyl compound (B) is at least 2 carbons in the molecule - has a carbon double bond, Ri compound der containing no imide group, specific examples thereof are, for example, the following
Compounds represented by general formulas (IV) to (VII)
Is raised .

[0069]

That is, the general formula (IV):

[0071]

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Wherein R ⁸ is a hydrogen atom or a methyl group; R ⁹ is a divalent organic group having 2 to 20 carbon atoms;
R ¹⁰ may have an aromatic bond or an aliphatic di- or tetra-valent organic group having 1 to 30 carbon atoms, and a represents an integer of 2 to 4). A compound having an ether bond represented by the general formula (V):

[0073]

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(Wherein R ⁸ and R ⁹ are the same as described above;
R ¹¹ is a C 1-30 organic group having 1 to 4 valences, b is 1 to 4
A compound having an ester bond represented by the general formula (VI):

[0075]

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(Wherein R ⁸ and a are the same as described above;
^{And 12} is a hydrocarbon compound represented by a divalent to tetravalent organic group having 2 to 50 carbon atoms, and a compound represented by the general formula (VI
I):

[0077]

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Wherein R ⁸ , R ⁹ and a are as defined above, and R ¹³ represents a divalent to tetravalent organic group having 1 to 30 carbon atoms and having a carbonate bond . in Oh <br/> Ru.

R ⁹ in the general formulas (IV), (V) and (VII) is a divalent organic group having 2 to 20 carbon atoms.
Is a group which may have more than one ether bond,
As a specific example,

[0080]

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And the like.

In the general formula (IV), R ¹⁰ has 1 carbon atom
It is an aromatic or aliphatic divalent to tetravalent organic group of up to 30. Specific examples include, for example,

[0083]

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[0084]

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And the like.

In the general formula (V), R ¹¹ is a monovalent to tetravalent organic group having 1 to 30 carbon atoms.

[0087]

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[0088]

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And the like.

R ¹² in the general formula (VI) is a divalent to tetravalent organic group having 2 to 50 carbon atoms.

[0091]

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[0092]

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R ¹³ in the general formula (VII) is
Although it is a divalent or tetravalent organic group having 1 to 30 carbon atoms, specific examples thereof include, for example,

[0094]

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[0095]

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[0096]

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And the like.

[0098] Other specific examples of the alkenyl compound (B), 1, 3-butadiene, bisphenol A Jiarirue
Ter, bisphenol P diallyl ether, diallylte
Lephthalate, diallyl isophthalate, diallyl car
Bonate. 1,5-hexadiene, 1,9-decadiene, o-divinylbenzene, m-divinylbenzene,
p-Divinylbenzene and the like are represented by the general formula (VI)
Ru Examples der hydrocarbon compound that.

In the present invention, a hydrosilylation catalyst (C) as a component (C) is used as a catalyst for reacting the imide compound (A) with the alkenyl compound (B).

Specific examples of the hydrosilylation catalyst (C) include, for example, a substance in which solid platinum is supported on a simple substance of platinum, alumina, silica, carbon black, etc., chloroplatinic acid, chloroplatinic acid and alcohol, aldehyde, Complexes with ketones and the like, 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 (eg, Pt _n (ViMe ₂ SiOSiMe ₂ V)
i) _m , Pt [(MeViSiO) ₄ ] _m ), platinum-phosphine complex (for example, Pt (PPh ₃ ) ₄ , Pt
(PBu) ₄ ), a platinum-phosphite complex (for example,
Pt [P (OPh) ₃ ] ₄ ) (where Me is a methyl group,
Bu is a butyl group, Vi is a vinyl group, Ph is a phenyl group, m and n are integers), dicarbonyldichloroplatinum, and Ashby U.S. Pat.
Platinum-hydrocarbon composites described in U.S. Pat. Nos. 601 and 3159662; and platinum alcoholate catalysts described in Lamoreaux U.S. Pat. No. 3,209,972. 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, for example, RhCl (PPh ₃ ) ₃ , RhCl ₃ , R
hAl ₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ ,
AlCl ₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , Ti
Cl _{4 and the} like.

These catalysts may be used alone or in combination of two or more. In terms of catalytic activity,
Preference is given to chloroplatinic acid, platinum-olefin complexes and platinum vinylsiloxane complexes.

The ratio of the component (A) to the component (B) in the curable composition is preferably 0.5 to 10 times, more preferably, a molar ratio of the hydrosilyl (Si—H) group to the carbon-carbon double bond. It is preferable to mix them in an amount of 0.5 to 5 times. If the amount is less than 0.5 times, curing does not proceed sufficiently,
It becomes difficult to obtain a good cured product. On the other hand, if the amount is more than 10 times, the stability of the component (A) becomes poor, and furthermore, a large amount of hydrosilyl groups remains in the cured product even after curing, which tends to cause voids and cracks.

The amount of the hydrosilylation catalyst (C) used
Is preferably 10 ^-1 to 10 ^-8 mol, and more preferably ^{1 -1} to 10 ^-8 mol, per mol of a carbon-carbon double bond such as an alkenyl group of the component ( B )
It is preferably used in the range of 10 ^-3 to 10 ^-6 mol. If the amount of the hydrosilylation catalyst used is less than 10 ^-8 mol, curing will not sufficiently proceed, and the hydrosilylation catalyst is generally expensive and corrosive. Further, since a large amount of hydrogen gas may be generated to cause foaming of the cured product, it is preferable not to use more than 10 ^-1 mol.

When component (A) and component (B) used in the composition of the present invention are solid, component (A),
Component (B) and component (C) are converted to a suitable organic solvent, for example, a hydrocarbon solvent such as hexane, heptane, benzene, toluene and xylene, and an alcohol such as methanol, ethanol, propanol, ethylene glycol and 1,4-butanediol. System solvents, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ether solvents such as anisole, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl benzoate, ethyl benzoate, etc. Ester solvents, halogenated hydrocarbon solvents such as methylene chloride, chloroform, ethylene chloride and chlorobenzene, sulfoxide solvents such as dimethyl sulfoxide and diethyl sulfoxide, N, N-dimethylformamide, , N- formamide solvents such as dimethylformamide, N, N- dimethylacetamide, N, acetamide solvents such as N- diethylacetamide, N- methyl-2-pyrrolidone, N- acetyl -2
-Pyrrolidone solvents such as pyrrolidone, N-vinyl-2-pyrrolidone, phenol solvents such as phenol, o-cresol, m-cresol, p-cresol, xylenol, halogenated phenol, catechol, pyridine, hexamethylphosphoramide , Γ-butyrolactone, etc., alone or in a mixture of two or more thereof may be used as the composition.

The composition of the present invention may further contain, if necessary, an adhesion improver, a physical property modifier, a storage stability improver, a plasticizer, a filler, an antioxidant, an ultraviolet absorber, and a metal deactivator. Various additives such as an ozone deterioration inhibitor, a light stabilizer, an amine-based radical chain inhibitor, a phosphorus-based peroxide decomposer, a lubricant, a pigment, and a foaming agent may be appropriately added. The total amount of the additives is not particularly limited as long as the properties of the cured product are not significantly reduced, but is preferably 1 to 300 parts with respect to 100 parts of the hydrosilyl group-containing imide compound (A).

For curing the composition of the present invention, the temperature is preferably from 50 ° C.
Temperature range below the decomposition temperature of component (A) or component (B), preferably 50-350 ° C, more preferably 50-300 ° C.
It only needs to be processed in the temperature range of 1 minute to 30 hours. If the treatment temperature is too high, local heat generation or foaming occurs during curing, and it becomes difficult to obtain a good cured product, which is not preferable. When the composition is an organic solvent solution, the organic solvent is distilled off or volatilized at any stage before or during the curing of the composition, and the cured product is obtained by allowing the composition to reach the above-described curing conditions. You can get.

The cured product obtained by curing the composition of the present invention has excellent heat resistance, chemical resistance, and mechanical properties, and can be used in various applications such as resin modifiers and sites that are easily exposed to high temperatures. It is suitably used for a coating material of the like.

Next, the composition of the present invention will be described based on examples.

Synthesis Example 1 (Synthesis of Hydrosilyl Group-Containing Imide Compound) Under a nitrogen stream, a 3,3 ', 4,4'-diphenylsulfonetetracarboxylic acid was placed in a 1000 cc four-necked flask equipped with a mechanical stirrer, a ball condenser, and a thermometer. 35.8 g of acid 2 anhydride (0.10
mol) and 270 g of N-methyl-2-pyrrolidone (NMP) were added to prepare a uniform solution. To this solution, 14.6 g (0.050 mol) of 1,3-bis (3-aminophenoxy) benzene was added with NMP.
A solution dissolved in 60.0 g was added using a funnel at room temperature, and stirring was continued at room temperature for 1 hour. Then, 5.7 g (0.10 mol) of allylamine was added dropwise to the reaction solution at room temperature, and the mixture was further stirred for 30 minutes, and then heated in an oil bath at 200 ° C. until the internal temperature reached 165 to 170 ° C. Heating was continued at this temperature for a further 5 hours. After cooling, the total amount of the reaction solution was reduced to 1900
Pour into ml of methanol. The resulting precipitate was filtered, washed with methanol, and dried at 80 ° C. under reduced pressure.
41.4 g of an imide compound having a carbon-carbon double bond was obtained.

[0111] 1,3,5,7-tetramethylcyclotetrasiloxane 5.0 g was charged into a four-necked flask 200 ml, there H ₂ PtCl ₆ · 6H ₂ O 10% ethanol solution 1.00
ml was added. At room temperature, a solution prepared by dissolving 10 g of the obtained carbon-carbon double bond-containing imide compound in 90 g of chloroform was slowly dropped over about 30 minutes. After dropping,
The reaction was performed at 60 ° C. for 10 hours. After the reaction, chloroform and unreacted 1,3,5,7-tetramethylcyclotetrasiloxane are evaporated and then dried under reduced pressure at room temperature for several hours to obtain the desired hydrosilyl group-containing imide compound (VIII)
14.9g was obtained.

[0112]

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Synthesis Example 2 (Synthesis of Hydrosilyl Group-Containing Imide Compound) 1,3-bis (3-aminophenoxy) benzene (APB) was placed in a 1000 cc four-necked flask equipped with a mechanical stirrer, a lens cooling tube, and a thermometer under a nitrogen stream. ) 29.2 g (0.10 mol), NMP120
g was added to prepare a homogeneous solution. 3,3 ′,
4,4'-benzophenonetetracarboxylic dianhydride 16.1
g (0.050 mol) in 145.0 g of NMP was added at room temperature, and stirring was continued at room temperature for 1 hour. Next, a solution of 16.4 g (0.10 mol) of 2,3-dicarboxyl-bicyclo [2.2.1] hept-5-ene dianhydride in 140 g of NMP was added dropwise to the reaction solution at room temperature, and the mixture was further stirred for 30 minutes. After continuing,
The mixture was heated in an oil bath at 200 ° C until the internal temperature reached 165 to 170 ° C. Heating was continued at this temperature for a further 5 hours.

Thereafter, 46.8 g of a carbon-carbon double bond-containing imide compound was obtained in the same manner as in Synthesis Example 1.

[0115] 1,3,5,7-tetramethylcyclotetrasiloxane 4.4 g was charged into a four-necked flask 500 ml, there H ₂ PtCl ₆ · 6H ₂ O 10% ethanol solution 0.91
ml was added. At room temperature, a solution obtained by dissolving 10 g of the obtained imide compound having a carbon-carbon double bond in 90 g of chlorobenzene was slowly dropped over about 30 minutes. After the completion of the dropwise addition, the reaction was carried out at 100 ° C. for 40 hours. After the reaction, chlorobenzene and unreacted 1,3,5,7-tetramethylcyclotetrasiloxane are evaporated and then dried under reduced pressure at room temperature for several hours to obtain the desired hydrosilyl group-containing imide compound (I
X) 14.2 g was obtained.

[0116]

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Synthesis Example 3 (Synthesis of Hydrosilyl Group-Containing Imide Compound) 1,3-Bis (3-aminopropyl) tetramethyldimethylamine was placed in a 1000 cc four-necked flask equipped with a mechanical stirrer, a lens cooling tube, and a thermometer under a stream of nitrogen. Siloxane 24.8g (0.10mo
l), 120 g of NMP was added to prepare a uniform solution. here
3,3 ', 4,4'-diphenylsulfonetetracarboxylic acid 2
A solution of 29.7 g (0.083 mol) of an anhydride dissolved in 270.0 g of NMP was added at room temperature, and stirring was continued at room temperature for 1 hour. Next, 5.5 g (0.033 g) of 2,3-dicarboxyl-7-oxabicyclo [2.2.1] hept-5-ene dianhydride was added to the reaction solution at room temperature.
mol) dissolved in 50 g of NMP was added dropwise, and stirring was continued for another 30 minutes.
Heated to 170 ° C. Heating was continued at this temperature for a further 5 hours. Thereafter, the same treatment as in Synthesis Example 1 was carried out to obtain 49.4 g of an imide compound having a carbon-carbon double bond.

1,3,5-trimethylcyclotrisiloxane 1.
1 g was charged into a 500 ml four-necked flask, and H ₂ P
tCl ₆ · 6H ₂ O 10% ethanol was added 0.33ml of. At room temperature, a solution in which 10 g of the obtained imide compound having a carbon-carbon double bond was dissolved in 90 g of chlorobenzene was slowly dropped over about 30 minutes. After dropping,
The reaction was performed at 100 ° C. for 40 hours. After the reaction, chlorobenzene and unreacted 1,3,5-trimethylcyclotrisiloxane were evaporated, and then dried under reduced pressure at room temperature for several hours to obtain 10.8 g of the desired hydrosilyl group-containing imide compound (X).

[0119]

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Example 1 2.0 g of the hydrosilyl group-containing imide compound (VIII) synthesized in Synthesis Example 1 and a compound of the formula (XI):

[0121]

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[0122] The allyl group-containing compound 1.1 g represented by dissolving in chloroform 18 g, there H ₂ PtCl ₆ · ₆
A thermosetting composition was obtained by mixing 35.0 μL of a 10% ethanol solution of H ₂ O. The composition was heated at 25 ° C / 10 mmHg for 1 hour.
After storage for 1 day, the mixture was treated at 150 ° C. for 1 hour to prepare a cured product.

Using a differential thermal balance TG-DTA manufactured by Rigaku Denki Co., Ltd., the cured product was subjected to T
GA measurements were performed. Table 1 shows the obtained 5% and 10% weight loss temperatures. Table 2 shows the results of the appearance evaluation after the cured product was immersed in N, N-dimethylformamide and 10% hydrochloric acid at room temperature for 10 days.

Example 2 2.0 g of the hydrosilyl group-containing imide compound (VIII) synthesized in Synthesis Example 1 and a compound of the formula (XII):

[0125]

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[0126] The allyl group-containing compound 0.87g represented by dissolving in chloroform 18 g, there H ₂ PtCl ₆ · ₆
A thermosetting composition was obtained by mixing 35.0 μL of a 10% ethanol solution of H ₂ O. The composition was heated at 25 ° C / 10 mmHg for 1 hour.
After storage for 1 day, the mixture was treated at 150 ° C. for 1 hour to prepare a cured product.

Using a differential thermal balance TG-DTA manufactured by Rigaku Electric Co.,
GA measurements were performed. Table 1 shows the obtained 5% and 10% weight loss temperatures. Table 2 shows the results of the appearance evaluation after the cured product was immersed in N, N-dimethylformamide and 10% hydrochloric acid at room temperature for 10 days.

Example 3 2.0 g of the hydrosilyl group-containing imide compound (IX) synthesized in Synthesis Example 2 and a compound of the formula (XIII):

[0129]

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[0130] The allyl group-containing compound 0.39g represented by dissolving in chloroform 18 g, there H ₂ PtCl ₆ · ₆
A thermosetting composition was obtained by mixing 30.0 μL of a 10% ethanol solution of H ₂ O. The composition was heated at 25 ° C / 10 mmHg for 1 hour.
After storage for 1 day, the mixture was treated at 150 ° C. for 1 hour to prepare a cured product.

Using a differential thermal balance TG-DTA manufactured by Rigaku Electric Co.,
GA measurements were performed. Table 1 shows the obtained 5% and 10% weight loss temperatures. Table 2 shows the results of the appearance evaluation after the cured product was immersed in N, N-dimethylformamide and 10% hydrochloric acid at room temperature for 10 days.

Example 4 4.0 g of the hydrosilyl group-containing imide compound (X) synthesized in Synthesis Example 3 and a compound of the formula (XIV):

[0133]

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[0134] The allyl group-containing compound 0.23g represented by dissolving in chloroform 18 g, there H ₂ PtCl ₆ · ₆
16.0 μL of a 10% ethanol solution of H ₂ O was blended to obtain a thermosetting composition. The composition was heated at 25 ° C / 10 mmHg for 1 hour.
After storage for 1 day, the mixture was treated at 150 ° C. for 1 hour to prepare a cured product.

Using a differential thermal balance TG-DTA manufactured by Rigaku Electric Co.,
GA measurements were performed. Table 1 shows the obtained 5% and 10% weight loss temperatures. Table 2 shows the results of the appearance evaluation after the cured product was immersed in N, N-dimethylformamide and 10% hydrochloric acid at room temperature for 10 days.

Comparative Example 1 3 g of polypropylene glycol having an allyl group at both ends (molecular weight of about 8000) and 1 g of polypropylene glycol having a 1,3,5,7-tetramethylcyclotetrasiloxy group at both ends (molecular weight of about 8000) Mixed with H ₂ P
to prepare a curable composition by blending 10% ethanol solution 4μL of tCl ₆ · 6H ₂ O. The composition was stored in an oven maintained at 100 ° C. for 1 hour to prepare a cured product.

Using a differential thermal balance TG-DTA manufactured by Rigaku Denki Co., Ltd., the obtained cured product was exposed to nitrogen under a stream of nitrogen.
GA measurements were performed. Table 1 shows the obtained 5% and 10% weight loss temperatures. Table 2 shows the results of the appearance evaluation after the cured product was immersed in N, N-dimethylformamide and 10% hydrochloric acid at room temperature for 10 days.

[0138]

[Table 1]

[0139]

[Table 2]

From Table 1, it can be seen that the cured product of the composition of the present invention has excellent heat resistance. Table 2 shows that the cured product of the composition of the present invention has excellent chemical resistance.

[0141]

The imide compound containing a hydrosilyl group (A)
And alkenyl compound (B) and hydrosilylation catalyst (C)
The curable composition of the present invention containing (1) and (2) can be easily formed into cured products of various shapes, and the obtained cured product has extremely excellent heat resistance and chemical resistance.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kazuya Yonezawa 5-12-11 Tsutsujigaoka, Tarumizu-ku, Kobe City, Hyogo Prefecture (56) References JP-A 1-318037 (JP, A) JP-A 2-75644 (JP) JP-A-4-261467 (JP, A) JP-A-5-320515 (JP, A) JP-A-5-320516 (JP, A) (58) Fields studied (Int. Cl. ⁷ , DB Name) C08G 77/455 C08G 73/10 C08L 83/05 C08L 83/08

Claims (1)

(57) [Claims] (A) General formula (I): (Wherein R ¹ is a group containing an aromatic group having 6 to 30 carbon atoms)
A bivalent organic group, R ² is a divalent organic group containing an aromatic group having 6 to 30 carbon atoms, or a general formula (II): (R ⁴ is a divalent organic group having 1 to 20 carbon atoms, R ⁵ is
Represents up to 20 monovalent organic groups, and a plurality of R ⁴ and R ⁵ may be the same or different; l is 1 to 20
A divalent organic group represented by R ³
Represents a divalent organic group having 1 to 20 carbon atoms, Y represents an organic group having 1 to 20 carbon atoms including at least one hydrosilyl group,
Two R ³ and Y may be the same or different
And n represents an integer of 1 to 100) and an imide compound represented by the general formula (III): (Wherein, R ¹ , R ² , and n are the same as those described above, and R ⁶ is a C ¹ to C ² containing at least one hydrosilyl group)
A valent organic group, at least one imide compound selected from represented by the imide compound in the two R ⁶ may be the same or may be or different), (B) the general formula (IV ): (Wherein, R ⁸ is a hydrogen atom or a methyl group, and R ⁹ is
A divalent organic group having a prime number of 2 to 20;
R ¹⁰ may have 1 to 30 carbon atoms.
An aromatic or aliphatic divalent to tetravalent organic group, a is 2 to 4
A compound having an ether bond represented by
Compound, general formula (V): (Wherein, R ⁸ and R ⁹ are the same as described above, and R ¹¹ has 1 carbon atom)
~ 30 monovalent to tetravalent organic groups, b represents an integer of 1 to 4
Compound having an ester bond represented by the general formula
(VI): (Wherein R ⁸ and a are the same as described above, and R ¹² has 2 carbon atoms.
Represents up to 50 divalent to tetravalent organic groups)
Hydrogen compound, general formula (VII): (Wherein R ⁸ , R ⁹ and a are the same as above, and R ¹³ is a carbon atom
Represents an organic group having 1 to 30 divalent to tetravalent organic groups)
Compound having a carbonate bond, 1,3-butadiene
, Bisphenol A diallyl ether, bisphenol
P diallyl ether, diallyl terephthalate, dia
Ryl isophthalate or diallyl carbonate
Have at least two carbon-carbon double bonds in the molecule
And a compound containing no imide group , and (C) a hydrosilylation catalyst, and a hydrosilyl (Si—H) group in the component (A).
Is a molar ratio with respect to the carbon-carbon double bond in the component (B).
0.5 to 10 times the amount of component (C) used in component (B)
A curable composition having an amount of 10 ^{< -1} > to 10 < ^-8> mol per mol of carbon-carbon double bond .