JP2002212296A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable composition excellent in molding properties, not generating a low-boiling compound on curing, rapidly curable at a relatively low temperature and giving a cured product excellent in heat resistance, chemical resistance and mechanical strength. SOLUTION: The curable composition comprises (A) an imide compound bearing at least two hydrosilylatable carbon-carbon double bonds in the molecule, (B) an imide compound bearing at least two hydrosilyl groups in the molecule and (C) a hydrosilylation catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable composition containing a reactive imide compound. More specifically, a cured product having excellent heat resistance, chemical resistance, and mechanical properties characteristic of a polyimide resin after curing is quickly cured at a relatively low temperature without generation of a low-boiling compound upon curing. And a curable composition having excellent moldability.

[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 that 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 during curing, and a compound having a good appearance can be obtained. However, since both the main chains of the carbon-carbon double bond-containing component and the hydrosilyl group-containing component are made of polyether, the obtained cured product has insufficient heat resistance, chemical resistance, etc., and is short even at a temperature of 100 ° C. It has drawbacks such as a significant decrease in mechanical properties over time, poor acid resistance and poor solvent resistance. Therefore, it is not suitable for applications requiring heat resistance and chemical resistance, for example, applications such as a resin for semiconductor encapsulation and a heat resistant adhesive.

A composition which gives a cured product having excellent heat resistance and chemical resistance by using an imide compound as a carbon-carbon double bond-containing component (JP-A-4-261467) is known. Since the compatibility between the double bond-containing component and the hydrosilyl group-containing component is poor, there are problems that a large amount of solvent is required for preparing the composition and that both components are easily phase-separated during thermosetting.

As a composition having excellent compatibility, a composition using a high-molecular-weight imide compound for both a carbon-carbon double bond-containing component and a hydrosilyl group-containing component (Japanese Patent Application Laid-open No.
080783), but it is difficult to mold at a curing temperature or lower due to a high thermal softening point.

[0005]

SUMMARY OF THE INVENTION In view of the above-mentioned circumstances, the present invention provides a method of curing rapidly at a relatively low temperature without generation of a low-boiling compound or phase separation of components at the time of curing. Giving a cured product with chemical resistance and mechanical properties,
An object of the present invention is to provide a curable composition having excellent moldability.

[0006]

That is, the present invention provides:
(A) an imide compound containing at least two hydrosilylatable carbon-carbon double bonds in the molecule, (B) an imide compound having at least two hydrosilyl groups in the molecule, and (C) a hydrosilylation catalyst A curable composition comprising: wherein the component (A) has the general formula (I):

[0007]

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

[0009]

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[0010] (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 has a carbon number of 2 to 2 having a hydrosilylatable carbon-carbon double bond.
It represents zero or a monovalent organic group, two R ³ may be may be the same, or different. n represents an integer of 1 to 100. And an imide compound represented by the general formula (III):

[0011]

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Wherein R ¹ , R ² and n are the same as defined above. R ⁶ is a divalent C 2-20 carbon atom having at least one hydrosilylatable carbon-carbon double bond. A curable composition containing at least one imide compound selected from the group consisting of imide compounds represented by the following general formula: wherein R ⁶ may be the same or different. is there. In the present invention, the above (B)
As a component, general formula (IV):

[0013]

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(Wherein, R ⁷ represents an aromatic group-containing tetravalent organic group having 6 to 30 carbon atoms. R ⁸ represents 1 carbon atom.
Represents up to 20 divalent organic groups. Y represents a monovalent group containing at least one hydrosilyl group. Two R ⁸ and Y may be the same or different) and an imide compound represented by the general formula (V):

[0015]

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(Wherein R ⁹ is a divalent organic group having 6 to 30 carbon atoms containing an aromatic group, or a compound represented by the above general formula (I)
It represents a divalent organic group represented by I). R ¹⁰ is a C 1-20 C 2 containing at least one hydrosilyl group.
It is preferable to use at least one imide compound selected from the group consisting of imide compounds represented by a valent organic group, and two R ^{10 s} may be the same or different. The present invention is also a cured product obtained by curing the curable composition. Hereinafter, the present invention will be described in detail.

The composition of the present invention comprises a compound (A) having a hydrosilylatable carbon-carbon double bond, for example, a vinyl group or an alkenyl group, in the presence of a hydrosilyl group-containing compound (B) and a catalyst (C). And that a cured product is produced by the reaction. Since the hydrosilyl group-containing imide compound (B) contains at least two hydrosilyl groups in the molecule, the imide compound having at least two hydrosilylatable carbon-carbon double bonds in the molecule as the component (A) To form a linear or network polymer. When the number of hydrosilylatable carbon-carbon double bonds in the component (A) is 1 or less per molecule or when the number of hydrosilyl groups in the component (B) is 1 or less per molecule, Also, since only a graft structure is formed and not a crosslinked structure, good curability is hardly obtained.

A typical hydrosilyl group-containing compound conventionally used is, for example, a polysiloxane compound such as polymethylhydrogensiloxane. However, in general, the imide compound and the polysiloxane compound have low compatibility, and it is difficult to obtain a uniform composition, or the composition is likely to be phase-separated during curing, resulting in poor curing. Since the composition of the present invention has an imide group in both the component (A) and the component (B), the compatibility of both components is high and the phase separation during curing is suppressed.

In this specification, the term "compatible" means that two or more components are compatible with each other to form a uniform mixture. In the present specification, `` compatible '' means that when all of a plurality of components to be mixed are in a liquid state, a uniform liquid mixture without phase separation, emulsification, precipitation, or the like when these are mixed is used. Means that at least one or more of the components to be mixed is a solid, and when the composition is heated to liquefy the solid component, a uniform liquid mixture is obtained, or In a suitable solvent means that a homogeneous solution is obtained.
Mixtures that do not meet any of these conditions, such as emulsified suspensions, are incompatible.

The component (A) in the present invention will be described. The component (A) is not particularly limited as long as it has at least two carbon-carbon double bonds capable of hydrosilylation in one molecule and contains the imide compound represented by the above general formula (I) or (III). Absent. Here, the carbon-carbon double bond capable of hydrosilylation refers to a carbon-carbon double bond capable of hydrosilylation with a SiH group under conventionally known general conditions.

The molecular weight of the component (A) is, for example, 500 to
About 20,000, and more preferably about 500 to 10,000 are excellent in moldability because of good solubility and meltability, and,
It is preferable from the viewpoint that the obtained cured product has excellent heat resistance. When the molecular weight is too low, the heat resistance of the obtained cured product tends to be low. If the molecular weight is too high, the modulus of elasticity of the composition may be high and moldability may be impaired.

In the above formulas (I) and (III), 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 and an aromatic ring bonded via a divalent group, from the viewpoint of providing a cured product having excellent heat resistance after curing. A tetravalent organic group having 6 to 30 carbon atoms is preferable.

Particularly preferred examples include 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, 2,2-bis (3,4-di Carboxyphenyl) propane, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane,

[0024]

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(In the formula, R ¹¹ is a group having 2 to 16 carbon atoms.)
Organic group such as methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group, isopropylene group, isobutylene group, phenylene group, naphthylene group, benzylene group, phenethylene group,

[0026]

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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 above general formulas (I) and (III), R ² represents an aromatic group-containing divalent organic group having 6 to 30 carbon atoms, or 2 represented by the following general formula (II)
Represents a valent organic group.

[0028]

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In the formula, R ⁴ is a divalent organic group having 1 to 20 carbon atoms, for example, methylene, ethylene, propylene, butylene, hexylene, octylene, isopropylene, isobutylene, phenylene. Group, naphthylene group, benzylene group, phenethylene group and the like. R ⁵
Represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms, such as a methyl group, a phenyl group, and a γ-glycidoxypropyl group. When R ⁵ is hydrogen, it can also contribute to the curing reaction as a reactive hydrosilyl group. Among such R ^5, a monovalent organic group having 1 to 20 carbon atoms consisting of only a carbon atom and a hydrogen atom, such as a methyl group and a phenyl group, is particularly preferred. Multiple R ⁴ and R
⁵ may be the same or different. m
Represents a positive integer of 1 to 20.

In the above general formulas (I) and (III), R ² is an aromatic group-containing 2 to 6 carbon atoms.
Represents a valent organic group or a group represented by the general formula (II). Specific examples of such a group include residues obtained by removing an amino group from various diamine compounds. 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'-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 '
Residues obtained by removing amino groups from diamine compounds such as -bis (4-aminophenyl) fluorene and ortho-tolidine sulfone; and 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,5-bis (3 -Aminopropyl) hexamethyltrisiloxane,

[0031]

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(Where R⁵And m are the same as above)
Siloxane diamines such as amino-terminated polysiloxanes
And a residue obtained by removing an amino group from an amino acid. This
Una R ²Among which 6 to 30 carbon atoms containing an aromatic group
Is that the divalent organic group can further improve the heat resistance of the cured product.
Preferred in terms of

In the above general formula (I), R ³ is a group having 2 carbon atoms having a hydrosilylatable carbon-carbon double bond.
Represents up to 20 monovalent organic groups; specific examples of such groups include vinyl, allyl, butenyl, pentenyl, hexenyl, octenyl, nonenyl, decenyl, undecenyl, Isopropenyl group, 2-methyl-2-propyl group, 2-vinylphenyl group, 3-vinylphenyl group, 4-vinylphenyl group, 3,5-divinylphenyl group, 4-allyloxyphenyl group, 4-ali And a roxycyclohexyl group.

In the above general formula (III), R ⁶ is
Represents a divalent organic group having 2 to 20 carbon atoms having at least one hydrosilylatable carbon-carbon double bond.
Among them, a divalent organic group having 2 to 20 carbon atoms and containing a cyclic olefin is preferable. As a specific example,

[0035]

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And the like. In the general formulas (I) and (III), n represents a positive integer of 1 to 100. Above all, from the viewpoint of good moldability due to good solvent solubility and compatibility with the component (B), and excellent heat resistance of the obtained cured product, 1 to 50 is preferable, and 1 to 20 is more preferable. preferable. As the component (A), only one type may be used, or two or more types may be mixed and used. In the present invention, the component (A) may be one or more of the compounds described above, or may be other carbon-
It may further contain a compound containing a carbon double bond. Examples of such a carbon-carbon double bond-containing compound include bisphenol A diallyl ether, 2,2 ',
4,4'-tetraallylbisphenol A, triallyl isocyanurate and the like can be mentioned.

Next, a method for producing the carbon-carbon double bond-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 carbon-carbon double bond-containing imide compound represented by the general formula (I) is not particularly limited, and can be produced by any method. Specifically, for example, first, an aromatic tetracarboxylic dianhydride and a diamine are reacted in an organic solvent, and then a carbon-carbon double bond-containing primary amine compound is reacted to obtain a polyamic acid solution. Then, (i) a method of imidization by heating the polyamic acid solution, (ii) a method of imidating the polyamic acid solution by reacting a dehydrating agent such as acetic anhydride, or (iii) a polyamide. A method of contacting a solution of an acid with a poor solvent for amic acid (for example, water or a hydrocarbon) to precipitate a polyamic acid as a precipitate and heating the precipitate is exemplified.

By any of these methods, the carbon-carbon double bond-containing imide compound represented by the general formula (I) can be produced, and there is no particular limitation. Is more convenient or easy, and the raw materials to be used are easily available.
I.e., reacting an aromatic tetracarboxylic dianhydride with a diamine in an organic solvent, and subsequently reacting a carbon-carbon double bond-containing primary amine compound to obtain a polyamic acid solution. A method of obtaining an imide compound by heating is preferable.

The reaction is carried out by reacting an aromatic tetracarboxylic dianhydride, a diamine and a primary amine compound containing a carbon-carbon double bond in an organic solvent at a temperature of 80 ° C. or lower to obtain a polyamic acid solution. Is preferably heated to 100 to 250 ° C. The amounts of the aromatic tetracarboxylic dianhydride and the diamine are changed according to the desired value of n. For example, when it is desired to obtain a compound represented by the formula (I) in which n is 9, the molar ratio is 10: 9.

The primary amine compound having a carbon-carbon double bond is generally used in an amount of 2 to 5 with respect to the acid anhydride newly formed by the reaction of the aromatic tetracarboxylic dianhydride with the diamine.
The reaction is carried out using a double amount (molar ratio, hereinafter the same), preferably 2 to 3 times, more preferably 2 to 2.5 times. Carbon-
If the amount of the primary amine compound containing a carbon double bond is less than twice the amount of the unreacted acid anhydride, the yield of the desired imide compound is undesirably reduced. Also, 5
If the amount is more than twice, the amount of the remaining unreacted acid anhydride decreases, but it is not preferable because it becomes difficult to remove the excessively used carbon-carbon double bond-containing primary amine compound.

[0041] As the aromatic tetracarboxylic acid dianhydride, aromatic tetracarboxylic acid dianhydride was based groups listed as specific examples of the R ¹ are preferred. Examples of the diamine, diamines which was based groups listed as specific examples of the R ² are preferred. Primary amine compounds containing a carbon-carbon double bond include allylamine, butenylamine,
Examples include o-aminostyrene, m-aminostyrene, p-aminostyrene, o-allyloxyaniline, m-allyloxyaniline, and p-allyloxyaniline.

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

The imide compound containing a carbon-carbon double bond obtained by the above-mentioned production method may be used without purification or may be used after purification. Generally amine compounds,
Since the imide compound may inhibit hydrosilylation, it is preferable to use the purified product in that the reactivity of the obtained composition is improved. Examples of the purification method include methods such as washing, recrystallization, column purification, extraction (for example, Soxhlet extraction), ion exchange resin treatment, treatment with an adsorbent such as aluminum silicate, and the like.

Next, the carbon represented by the general formula (III)
The method for producing the carbon double bond-containing imide compound will be described. The method for producing the carbon-carbon double bond-containing imide compound represented by the general formula (III) is not particularly limited, and may be the same as that of the carbon-carbon double bond-containing imide compound represented by the general formula (I). Can be manufactured. The general formula (II
In the method for producing the carbon-carbon double bond-containing imide compound represented by I), the carbon-carbon double bond-containing imide compound used for producing the carbon-carbon double bond-containing imide compound represented by the general formula (I) is used. Olefin-containing acid anhydrides are used instead of primary amine compounds.

The amounts of the aromatic tetracarboxylic dianhydride and the diamine are varied depending on the desired value of n. For example, when it is desired to obtain a compound represented by the formula (III) in which n is 9, the molar ratio is 9:10. The acid anhydride having a carbon-carbon double bond capable of hydrosilylation is obtained by reacting an aromatic tetracarboxylic dianhydride with a diamine to form a carbon dioxide represented by the general formula (I) with respect to a diamine newly formed. -As in the case of the imide compound containing a carbon double bond,
The reaction is preferably carried out in an amount of up to 5 times (molar ratio, the same applies hereinafter), preferably 2 to 3 times, more preferably 2 to 2.5 times. Preferred tetracarboxylic dianhydrides and diamines are also the same as those of the carbon-carbon double bond-containing imide compound represented by the general formula (I). On the other hand, preferred cyclic olefin-containing acid anhydrides include:

[0046]

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And the like. Next, the component (B) will be described. In the present invention, as the component (B), a compound represented by the general formula (IV):

[0048]

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Wherein R ⁷ is a tetravalent organic group having 6 to 30 carbon atoms containing an aromatic group, R ⁸ is a divalent organic group having 1 to 20 carbon atoms, and Y is at least one An imide compound represented by a monovalent group containing a hydrosilyl group, and two R ⁸ and Y may be the same or different from each other), and a general formula (V):

[0050]

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(Wherein, R ⁹ is a divalent organic group having 6 to 30 carbon atoms containing an aromatic group or a divalent organic group represented by the general formula (II), and R ¹⁰ is at least one of Represents a divalent organic group having 1 to 20 carbon atoms including a hydrosilyl group,
At least one imide compound selected from the imide compounds represented by the formula (I) wherein two R ¹⁰ may be the same or different.

The hydrosilyl group-containing imide compound that can be used in the present invention contains at least two hydrosilyl groups having hydrosilylation activity in one molecule and is represented by the above general formula (IV) or (V). Is not particularly limited as long as the molecular weight is 300 to 500, for example.
It is preferably about 0, and more preferably about 400 to 2,000, because the resulting composition has excellent compatibility and the obtained cured product has excellent heat resistance. If the molecular weight is too high, the modulus of elasticity of the resulting composition will be high, and moldability will be impaired. The properties of the component (B)
Liquid substances can also be used without particular limitation.

In the present specification, one hydrosilyl group is a group containing one Si—H bond.
A group containing Si (H) ₂ becomes a group containing two hydrosilyl groups. The hydrosilyl group-containing compound (B)
In the above, when two or more hydrosilyl group-containing groups are present in the same molecule, those groups may be the same or different.

The number of hydrosilyl groups in the hydrosilyl group-containing compound (B) may be at least two in the molecule, but is preferably 2 to 50, particularly preferably 3 to 15. If the number of hydrosilyl groups contained in one molecule is less than 2, curing failure often occurs. When the number of the hydrosilyl groups is more than 50, the storage stability of the composition is deteriorated, and after curing, a large amount of unreacted hydrosilyl groups remains in the cured product to lower the chemical resistance and the mechanical properties. Cause

In the general formula (IV), R ⁷ is a tetravalent organic group having 6 to 30 carbon atoms containing an aromatic group, but does not contain an imide group. Especially carbon number 6 ~
A tetravalent group composed of 30 tetravalent aromatic groups or an aromatic ring bonded via a divalent group is preferred in that a cured product having excellent heat resistance is obtained after curing. Specific examples of such a group include the same groups as the specific examples of R ¹ in the general formula (I). These may be used alone or in combination of two or more.

In the general formula (IV), R ⁸ is a divalent organic group having 1 to 20 carbon atoms, but does not include an imide group. Specific examples of such a group include, for example, a methylene group, an ethylene group, a propylene group, a butylene group,
Examples include a hexylene group, 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 (IV), Y is a group containing at least one hydrosilyl group. Specific examples of such _{groups, -Si (H) n (CH} 3) 3-n, -Si (H) n (C
_{2 H 5) 3-n,} -Si (H) n (C 6 H 5)
_{3-n (n = 1~3)} , - SiH 2 (C 6 H 13) 1 piece having hydrosilyl groups to silicon atoms, such _{as, -Si (CH 3) 2 Si} (CH 3) 2 H, -Si (CH
_{3) 2 CH 2 CH 2 Si} (CH 3) 2 H, -Si (CH
_{3) 2 Si (CH 3)} H 2, -Si (CH 3) 2 -C 6
_{H 4 -Si (CH 3) 2} H, -Si (CH 3) 2 NHS
_{i (CH 3) 2 H,} -Si (CH 3) 2 N [Si (CH
₃ ) ₂ H] ₂ , —Si (CH ₃ ) ₂ OC (CH ₃ ) = N
_{Si (CH 3) 2 H,} -Si (CH 3) 2 N = C (CH
₃ ) a group having two silicon atoms such as OSi (CH ₃ ) ₂ H;

[0058]

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(Wherein R ¹² represents a monovalent organic group having 1 to 10 carbon atoms, and each R ¹² may be the same or different; p is a positive integer; q is 0 or Represents a positive integer and satisfies 1 <p + q <50, r and s represent 0 or a positive integer, and satisfies 0 ≦ r + s <50;
Specific examples of R ¹² include, for example, a methyl group, a phenyl group, a trimethylsiloxy group, a γ-glycidoxypropyl group, and the like;
Examples include groups derived from various cyclic polyvalent hydrogen siloxanes. Of these groups,

[0060]

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The group represented by the following is particularly preferred.

In the general formula (V), R ⁹ is an aromatic group-containing divalent organic group having 6 to 30 carbon atoms or a divalent organic group represented by the general formula (II). There is
It does not contain an imide group. Specific examples of such R ⁹ include the same groups as the specific examples of R ² in formula (III). These may be used alone or in combination of two or more.

In the general formula (V), R ¹⁰ is a divalent organic group having 1 to 20 carbon atoms having at least one hydrosilyl group, but does not include an imide group. Among these, a group having a cycloalkane structure bonded to a hydrosilyl group-containing group is preferable. As a specific example

[0064]

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(Wherein, W represents a group containing at least one hydrosilyl group). Specific examples of W include the same groups as those described above as specific examples of Y. The various (B) components as described above can be used alone or in combination of two or more.

The method for producing the component (B) is not particularly limited, and any method may be used. For example, (i) an organic compound having a Si—Cl group in a molecule is LiAlH ₄ , NaB
A method of treating the compound with a reducing agent such as H ₄ to reduce the Si—Cl group to a Si—H group, (ii) an organic compound having a functional group X in the molecule, A method of reacting a compound having both a functional group Y and a hydrosilyl group which reacts with X, and (iii) selectively hydrosilylating a polyhydrosilane compound having at least two hydrosilyl groups with respect to a compound containing a carbon-carbon double bond. Thus, a method of leaving a hydrosilyl group in the compound molecule after the reaction can be considered. Among them, the method (iii) is preferred from the viewpoints of simplicity of the reaction and good yield.

In the case of the method (iii), the polyhydrosilane compound is preferably used in an amount of 1 to 20 with respect to the carbon-carbon double bond-containing compound in the presence of a hydrosilylation catalyst.
The reaction is performed using a double amount, more preferably 2 to 5 times (molar ratio). The reaction is preferably performed in a temperature range of 0 to 150 ° C. If necessary, an appropriate organic solvent may be used. Specific examples of the organic solvent that can be used include, for example, hydrocarbon solvents such as hexane, toluene, and xylene, methanol, alcohol solvents such as ethylene glycol, diethyl ether, tetrahydrofuran,
Ether solvents such as 4-dioxane, 1,3-dioxolan, ethylene glycol dimethyl ether and anisole; ester solvents such as ethyl acetate and methyl benzoate; and halogenated hydrocarbon solvents such as methylene chloride, chloroform and dichlorobenzene. can give.

In the case of the method (iii), specific examples of the polyhydrosilane compound as a reaction component include silanes such as diethylsilane, phenylsilane and diphenylsilane, 1,1,1,3,5,7 , 7,7-
Octamethyltetrasiloxane, 1,1,1,3,5
Chain hydrogen polysiloxanes such as 7,9,9,9-nonamethylpentasiloxane, cyclic hydrogens such as 1,3,5-trimethylcyclotrisiloxane and 1,3,5,7-tetramethylcyclotetrasiloxane And polysiloxane. The carbon-carbon double bond-containing compound as a reaction component may be synthesized by the same method as that of the component (A) carbon-carbon double bond-containing imide compound, or by another method. You may.

The above-mentioned combinations of component (A) / component (B) include those listed as specific examples of component (A) and mixtures thereof / the ones listed as specific examples of component (B). Various combinations of these various mixtures can be mentioned. From the viewpoint that the compatibility of the obtained composition is excellent, the one represented by the general formula (IV) among those listed as specific examples of the component (A) / the ones listed as specific examples of the component (B) is used. In the combination that was
And a combination of R ¹ = R ⁷ , or a combination of those listed as specific examples of component (A) / the ones listed as specific examples of component (B) represented by general formula (V) And a combination in which R ² = R ⁹ is preferred.

The mixing ratio of the component (A) and the component (B) in the curable composition is not particularly limited as long as the physical properties of the cured product are not significantly impaired. (B) The molar ratio is 0.5 to 1 with respect to the hydrosilylatable carbon-carbon double bond in the component.
It is preferable to mix them so that the amount becomes 0 times, more preferably 0.5 to 5 times. When the amount is less than 0.5 times or more than 10 times, sufficient curability is hardly obtained, sufficient strength may not be obtained, and heat resistance may be lowered.

Next, the hydrosilylation catalyst as the component (C) will be described. In the present invention, a hydrosilylation catalyst as the component (C) is used as a catalyst for reacting the imide compound (A) with the hydrosilyl group-containing compound (B). 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 hydrosilylation catalyst (C) is not particularly limited, but is preferably in the range of 10 ^-1 to 10 ^-8 mol per mol of the hydrosilylatable carbon-carbon double bond of the component (A). , More preferably, 10 ^-3 to 10
^-6 mole range. Alternatively, the range is preferably from 10 ^-1 to 10 ^-8 mol, more preferably from 10 ^-2 to 10 ^-6 mol, per 1 mol of the hydrosilyl group of the component (B). If the amount of the catalyst used is less than 10 ^-8 mol, curing will not sufficiently proceed. Also, hydrosilylation catalysts are generally expensive and corrosive. In addition, 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.

Further, a co-catalyst can be used in combination with the above-mentioned catalyst, and examples thereof include phosphorus compounds such as triphenylphosphine, 1,2-diester compounds such as dimethyl malate, and 2-hydroxy-2- compounds. 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.

The components (A) / (B) /
As the combination of the component (C), those listed as specific examples of the component (A) and their various mixtures / the ones listed as specific examples of the component (B) and their various mixtures / specific examples of the component (C) And various combinations thereof.
When at least one of the component (A), the component (B), and the component (C) used in the present invention is a solid, they are prepared by an appropriate method, for example, dissolution, kneading, impregnation, support, melting, etc. May be used as a composition, or a solution dissolved in an appropriate solvent may be used as the composition. The amount of the solvent used is not particularly limited as long as it does not interfere with the operation.

A curing retarder can be used for the purpose of improving the storage stability of the composition of the present invention or for controlling the reactivity of the hydrosilylation reaction in the production process. Examples of the curing retarder include compounds containing an aliphatic unsaturated bond, organic phosphorus compounds, organic sulfur compounds, nitrogen-containing compounds, tin compounds, organic peroxides, and the like.
These may be used in combination. Compounds containing an aliphatic unsaturated bond include propargyl alcohols, en-
In compounds and maleic acid esters are exemplified. Examples of the organic phosphorus compound include triorganophosphines, diorganophosphines, organophosphones, and triorganophosphites. Examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, benzothiazole disulfide, and the like. As the nitrogen-containing compound, ammonia, primary to tertiary alkylamines such as tetramethylethylenediamine,
Examples include 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-perbenzoic acid.
Butyl and the like are exemplified.

Among these curing retarders, benzothiazole, dimethyl maleate, and 3-hydroxy-3-methyl-1-butyne are preferred from the viewpoint of good delay activity and availability of raw materials. Alkylamines such as tetramethylethylenediamine are preferred from the viewpoint of good delay activity at high temperatures.

These curing retarders can be used alone or in combination. Amount of the curing retarder, with respect to hydrosilylation catalyst 1 mole to be ^used, preferably 10 -1 to 10 ³ mols, more preferably from 1 to 50 mol.

The composition of the present invention further comprises an antioxidant, a radical inhibitor, an ultraviolet absorber, an adhesion improver, a flame retardant, a filler, a surfactant, a storage stability improver, an ozone deterioration inhibitor, Light stabilizer, thickener, plasticizer, antioxidant, heat stabilizer, conductivity imparting agent, antistatic agent, radiation blocking agent, nucleating agent, phosphorus peroxide decomposer, lubricant, pigment, metal inert An agent, a physical property adjusting agent, a foaming agent, a compatibilizing agent, and the like can be added within a range that does not impair the object and effect of the present invention. The total amount of the additives is not particularly limited as long as the physical properties of the cured product are not significantly reduced, but is preferably 1 to 300 parts by weight based on 100 parts by weight of the imide compound (A).

The method of preparing the composition of the present invention is not particularly limited as long as a uniform mixture can be obtained, and can be carried out by any method. (A) component, (B) component,
The order of mixing the component (C), the solvent, the cocatalyst, the various additives, and the like, and the apparatus and equipment used for the mixing can also be arbitrarily set. For example, in an organic solvent, the component (A), a curing retarder,
The composition may be prepared by adding the component (B), the adhesion improver, and the component (C) in this order, and then dissolving the mixture by centrifugal stirring. Alternatively, the component (A), the component (C), the flame retardant, The composition may be prepared by adding the component (B) in small portions to the mixture obtained by kneading the agent in rolls several times.

The temperature and pressure during the mixing operation can be set arbitrarily. In terms of preventing the curing reaction from proceeding during mixing,
The temperature of the composition is 100 ° C. or less, more preferably 50 ° C.
It is preferable to work while keeping the following.

Since the composition of the present invention is excellent in moldability, it can be molded into any shape by an appropriate molding method. The molding method is not particularly limited and can be performed by any method. For example, a method such as extrusion, casting, casting, roll, and press can be used. The shapes of the molded composition and the cured product are not particularly limited, and for example, can be molded into any shape such as a rod, a sphere, a plate, a film, a gear, and a housing. By heating and curing the composition after or at the same time as the composition is molded, a cured product of any shape can be obtained.

To cure the composition of the present invention, (A)
It is only necessary to perform heat treatment in a temperature range not higher than the decomposition temperature of the component or the component (B). Although various reaction temperatures can be set, for example, a temperature of 30 to 300 ° C. can be applied,
50 ° C. is more preferred. When the reaction temperature is low, the reaction time for sufficiently reacting is prolonged, and when the reaction temperature is high, local heat generation or foaming occurs during curing, so that molding processing becomes difficult and it becomes difficult to obtain a good cured product. Not preferred.

The curing reaction may be carried out in one stage, or the curing reaction may be carried out several times by stopping the progress of the reaction in the middle. After reacting a part of the hydrosilylatable carbon-carbon double bond in the component (A) and a part of the hydrosilyl group in the component (B), the progress is stopped before the curing reaction is completed. A so-called B stage can be performed. From the viewpoint of improving the moldability by adjusting the elastic modulus and compatibility of the composition, it is preferable to perform the B-stage.

The reaction may be carried out at a constant temperature, but the temperature may be changed in multiple stages or continuously as required. 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.

At any stage before, during or after curing, a process other than heating, such as drying, pre-curing, or centrifuging, is performed so long as the reactivity of the composition is not significantly impaired and the physical properties of the cured product are not significantly impaired. Defoaming treatment, defoaming under reduced pressure, cooling and solidification, ultrasonic treatment, light irradiation and the like can also be added.
From the viewpoint that foaming hardly occurs in the cured product and good moldability is obtained, it is preferable to perform drying and / or defoaming treatment.

When the composition is an organic solvent solution,
An organic solvent is distilled off or volatilized at any stage before, during or after curing of the composition, and a cured product can be obtained by satisfying the above-mentioned curing conditions.

The composition of the present invention is excellent in moldability and gives a cured product having excellent heat resistance, chemical resistance and mechanical properties after curing. Therefore, the composition of the present invention is used for various applications. be able to. As a specific example, it can be used for, for example, a heat-resistant adhesive, an electric wire coating agent, a sealant for a semiconductor element, a powder coating, a sealing, a resin modifier, a coating agent, a corrosion prevention treatment agent, and packaging.

Since the cured product obtained by curing the composition of the present invention has excellent heat resistance, chemical resistance, and mechanical properties, the cured product obtained from the composition of the present invention can be used in various molded articles. Can be used. Specific examples include applications where polyimide resins are commonly used, plastic molding materials, fiber-reinforced plastics, heat-resistant resin films,
It can be used for a foam material, a plastic cell, an optical component, a printed circuit board, an electric insulating material, and the like.

[0090]

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 condenser tube and a dropping funnel were attached under a nitrogen stream.
In a three-necked L flask, formula (VI)

[0091]

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The tetracarboxylic dianhydride 7 represented by
0.8 g was added, and 250 g of dimethylformamide was added, and the mixture was stirred and dissolved. At room temperature (25 ° C), the bis [4-
(4-Aminophenoxy) phenyl] sulfone 47.8
g of dimethylformamide was added dropwise from a dropping funnel. A solution of 2.8 g of allylamine in 40 g of dimethylformamide was dropped from the dropping funnel. β-picoline 3
After dropping 5.0 g from the dropping funnel, acetic anhydride 60.0 g was added.
g was dropped from the dropping funnel. The mixture was heated in an oil bath and stirred at an internal temperature of 100 ° C. for 90 minutes. After cooling, the obtained orange solution was gradually poured into 2,000 ml of vigorously stirred methanol to cause reprecipitation. The solid was filtered off with filter paper and washed with methanol in reslurry. The obtained individual is
It dried under reduced pressure for 2 hours in the vacuum dryer heated at 0 degreeC. Chemical formula (VII)

[0093]

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A carbon-carbon double bond-containing imide compound represented by the following formula was obtained.

(Synthesis Example 2) A 500 ml four-necked flask equipped with a condenser and a dropping funnel was purged with nitrogen, and the tetracarboxylic dianhydride represented by the above formula (VI) was added.
03 g was added, dimethylformamide 220 g was added, and the mixture was stirred and dissolved. At room temperature (30 ° C.), 10.40 g of allylamine was dropped from the dropping funnel over about 15 minutes.
After stirring at room temperature for 1 hour, acetic anhydride 36.0 g,
Then, 21.0 g of β-picoline was added dropwise from the dropping funnel over about 3 minutes. Heated in a 100 ° C. oil bath for 1 hour. After the resulting orange solution was allowed to cool, it was gradually poured into 900 ml of vigorously stirred methanol for reprecipitation. Chemical formula (VIII)

[0096]

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A carbon-carbon double bond-containing imide compound represented by the following formula was obtained.

In a two-necked flask equipped with a cooling tube, 1.0 g (3.0 mmol) of this imide compound and 1, 3, 5, 7
1.83 g of tetramethylcyclotetrasiloxane (3
0 mmol), and dissolved in 10 g of toluene. A platinum-vinyl catalyst (manufactured by Degussa, PTVTS-3.0) was added.
X) 2.30 μl (0.000304 mmol) was added, and the mixture was heated at 70 ° C. for 2 hours under a nitrogen stream. 0.689 mg (0.00510 mmol) of benzothiazole
After that, toluene and unreacted 1,3,5,7-tetramethylcyclotetrasiloxane were distilled off under reduced pressure. Chemical formula (IX)

[0099]

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And a platinum vinyl catalyst of 8.2 × 10 ⁻⁷ mo
A product containing 1 / g was obtained. Si of this product
The -H value was 0.0053 mol / g.

Example 1 1.7 g of a product containing a hydrosilyl group-containing imide compound synthesized in Synthesis Example 2 and a platinum-vinyl catalyst was added to 84.7 g of a carbon-carbon double bond-containing imide compound synthesized in Synthesis Example 1. (9.0 mmol) was added and dissolved in 200 g of tetrahydrofuran to obtain a uniform curable composition solution. This composition was cast on a copper foil by a solution dripping method, and the solvent was evaporated to form a film. This is heated to 200 ° C in an oven to cure,
A film-shaped cured product was obtained.

Example 2 1.2 g of a product containing a hydrosilyl group-containing imide compound synthesized in Synthesis Example 2 and a platinum-vinyl catalyst was compounded by the chemical formula (X)

[0103]

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10.0 g of the imide compound having a carbon-carbon double bond and 32 mg of benzothiazole represented by
-Dissolved in 7.1 g of dioxolane to obtain a uniform curable composition solution. This solution was applied on a polyimide film using a bar coater, and then heated to 150 ° C. to evaporate the solvent, thereby forming a transparent and uniform resin layer having a thickness of 100 μm. This polyimide film with resin layer and copper foil
The resin layer was thermally cured by pressing at a temperature of ° C, and the polyimide film and the copper foil were bonded.

Comparative Example 1 12.3 g of a carbon-carbon double bond-containing imide compound represented by the above formula (X) and polymethyl hydrogen siloxane (Shin-Etsu Chemical Co., Ltd.)
(KF99) 0.85 g and platinum vinyl catalyst 0.20
μl was dissolved in 60 g of THF. This was applied to a polyimide film and the solvent was allowed to evaporate spontaneously. When this was heated to 200 ° C. with a press, polymethyl hydrogen siloxane permeated around the imide compound, and a good cured product could not be obtained.

Comparative Example 2 33.0 g of a carbon-carbon double bond-containing imide compound represented by the chemical formula (VIII) synthesized in Synthesis Example 2 and a hydrosilyl group-containing imide compound represented by the chemical formula (IX) 19. 0 g of dioxolan 5
Dissolved in 0.0 g. When this was applied to a copper foil and the solvent was allowed to evaporate spontaneously, a yellowish-white imide compound powder was partially deposited and could not be formed into a resin layer having a uniform thickness.

Comparative Example 3 50 g of the carbon-carbon double bond-containing imide compound represented by chemical formula (VII) and 6.4 g of 1,3,5,7-tetramethylcyclotetrasiloxane synthesized in Synthesis Example 1 were used. 250 g of 1,3-dioxolan
, And 0.2 ml of a platinum-vinyl catalyst was added, and the mixture was reacted at 70 ° C. for 1 hour under a nitrogen stream. After 60 mg of benzothiazole was added thereto, volatiles were distilled off under reduced pressure to obtain a product having a SiH value of 0.000815 mol / g. 16.5 g of this product, 8.0 g of a carbon-carbon double bond-containing imide compound represented by the chemical formula (X), and benzothiazole 25
mg was dissolved in 150 g of 1,3-dioxolan to obtain a uniform curable composition solution. This solution was cast on a polyimide film using a bar coater. As the solvent evaporates, warping and cracking occur, making it difficult to form a resin layer having a uniform thickness. The polyimide film with the resin layer and the copper foil were pressed at 150 ° C. and 200 ° C., but the fluidity of the composition was low and the polyimide and the copper foil could not be bonded.

[0108]

Since the curable composition of the present invention has the above-mentioned constitution, it is excellent in moldability, and does not involve generation of low-boiling compounds or phase separation of components at the time of curing. It cures and gives a cured product having excellent heat resistance, chemical resistance and mechanical properties after curing.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J031 AA57 AA59 AB04 AC13 AD01 AD03 AD05 AE15 AF11 AF13 AF24 AF26 4J043 PA04 QB31 RA34 RA35 RA36 RA37 SA05 SA06 SA49 SB01 SB02 TA22 TB01 TB02 UA122 UA131 UA132 UA262 UB012 UB012 UB012 UB012 UB012 UB302 XA13 YB40 ZB01 ZB02 ZB48

Claims (3)

[Claims] (1) an imide compound having at least two hydrosilylatable carbon-carbon double bonds in a molecule, (B) an imide compound having at least two hydrosilyl groups in a molecule, and C) A curable composition containing a hydrosilylation catalyst, wherein the component (A) has the general formula (I): [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 (I
I): embedded image (In the formula, R ⁴ represents a divalent organic group having 1 to 20 carbon atoms. R ⁵ represents a monovalent organic group having 1 to 20 carbon atoms. A plurality of R ⁴ and R ⁵ are the same. And m may 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 1 to 100. ]
And an imide compound represented by the general formula (III): (Wherein R ¹ , R ² and n are the same as above. R
⁶ represents a divalent organic group having 2 to 20 carbon atoms having at least one hydrosilylatable carbon-carbon double bond. Curable composition comprising at least one imide compound selected from the group consisting of imide compounds represented by the formula (I) wherein two R ^{6 s} may be the same or different. . 2. Component (B) represented by the general formula (IV): (Wherein, R ⁷ represents an aromatic group-containing tetravalent organic group having 6 to 30 carbon atoms. R ⁸ represents 2 to 4 carbon atoms having 1 to 20 carbon atoms.)
Represents a valent organic group. Y represents a monovalent group containing at least one hydrosilyl group. Two R ⁸ and Y may be the same or different) and an imide compound represented by the general formula (V): (Wherein, ^{R 9} is a divalent organic group having 6 to 30 carbon atoms containing an aromatic group, or, ^{.R 10} representing a divalent organic group represented by general formula (II), Represents a divalent organic group having 1 to 20 carbon atoms including at least one hydrosilyl group,
Two R ¹⁰ may be the same, or curable composition according to claim 1 using at least one imide compound selected from the group consisting of imide compounds represented by different or may be) . 3. A cured product obtained by curing the curable composition according to claim 1 or 2.