JPH05320515A - Curable composition - Google Patents

Abstract

PURPOSE:To obtain a curable composition, comprising a specific imide compound, a compound having plural C-C double bonds and a hydrosilylating catalyst, rapidly curable at low temperatures, excellent in heat and chemical resistance/and mechanical strength and useful as electronic parts, etc. CONSTITUTION:The objective composition comprises (A) an imide compound, having two or more hydrosilyl groups in the molecule and expressed by formula I [R<0> is 6-30C bivalent organic group having aromatic group) or formula II [R<2> is 1-20C bivalent organic group; R<3> is methyl or phenyl; (k) is 1-20]; R<1> is 1-20C organic group containing one or more hydroxysilyl groups], (B) a compound having two or more C-C double bonds in the molecule such as 1,3-butadiene and (C) a hydrosilylating catalyst such as chloroplatinic acid. Furthermore, the components (A) to (B) are preferably blended so as to provide Si-H groups at a ratio of the components (A) to (B) so as to provide 0.5-5 times molar ratio based on the C-C double bonds.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a curable composition containing a reactive imide compound. More specifically, it relates to a curable composition which does not generate a low boiling point compound during curing, is rapidly cured at a relatively low temperature, and gives a cured product having excellent heat resistance, chemical resistance and mechanical properties after curing.

[0002]

2. Description of the Related Art Many curable compositions have been developed so far. Among them, a curable composition utilizing a hydrosilylation reaction that proceeds at a relatively low temperature has been disclosed (JP-A-1-138230). In the composition, a cured product having a good appearance with little generation of low-boiling point compounds is obtained at the time of curing, but both the alkenyl group-containing component and the hydrosilyl group-containing component, which are essential components of the composition, have a main chain of poly It is an ether, and the obtained cured product does not have sufficient heat resistance, chemical resistance, etc., and mechanical properties are greatly reduced in a short time even at a temperature of 100 ° C, acid resistance,
It has drawbacks such as poor solvent resistance. Therefore, it is unsuitable for applications where heat resistance and chemical resistance are required, such as coating agents for electronic parts and heat resistant adhesives.

[0003]

SUMMARY OF THE INVENTION The present invention provides rapid curing at relatively low temperatures without the formation of low boiling compounds during curing,
An object of the present invention is to provide a curable composition which gives a cured product having excellent heat resistance, chemical resistance and mechanical strength after curing.

[0004]

Means for Solving the Problems As a result of intensive studies on the above problems, the inventors have found that (A) an imide compound having at least two hydrosilyl groups in the molecule,
A curable composition comprising (B) a compound having at least two carbon-carbon double bonds in the molecule, and (C) a hydrosilylation catalyst is rapidly cured even at a relatively low temperature, and has a low viscosity during curing. Since it is not accompanied by the generation of a boiling point compound, it is easy to prepare a cured product, and it is found that it gives a cured product having excellent heat resistance, chemical resistance, and mechanical properties after curing,
The present invention has been completed.

The present invention relates to (A) an imide compound having at least two hydrosilyl groups in the molecule, (B) a compound having at least two carbon-carbon double bonds in the molecule, and (C) hydrosilylation. The present invention relates to a curable composition containing a catalyst.

[0006]

The composition of the present invention utilizes that a compound having a hydrosilyl group reacts with a compound having a carbon-carbon double bond in the presence of a catalyst to form a cured product. It provides a cured product having excellent heat resistance, chemical resistance and mechanical properties after curing.

The imide compound (A) used in the present invention has the general formula (I):

[0008]

[Chemical 4]

(In the formula, R ⁰ is a divalent organic group containing an aromatic group having 6 to 30 carbon atoms, or a general formula (II):

[0010]

[Chemical 5]

(R ² is a divalent organic group having 1 to 20 carbon atoms,
R ³ represents a methyl group or a phenyl group, two R ² and a plurality of R ³ may be the same or different, and k represents a positive integer of 1 to 20).
R ¹ is a C 1-20 organic group containing at least one hydrosilyl group, and two R ¹
May be the same or different), or an imide compound represented by the general formula (III):

[0012]

[Chemical 6]

(In the formula, R ⁴ is a tetravalent organic group containing an aromatic group having 6 to 30 carbon atoms, R ⁵ is a divalent organic group having 1 to 20 carbon atoms, and Y is at least one. An imide compound and the like, which represents a group containing a hydrosilyl group, and two R ⁵ and Y may be the same or different.

R ^{0 of the} compound represented by the general formula (I)
Contains an aromatic group having 6 to 30 carbon atoms and a group represented by the general formula (II), the cured product obtained after curing has excellent heat resistance and chemical resistance.

The divalent group represented by R ⁰ is a divalent group obtained by removing an amino group from a diamino compound, and specific examples thereof include 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-aminophenyl) 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, orthotolidine sulfone, 1,3-bis (3 -Aminopropyl) tetramethyldisiloxane, 1,5-bis (3-aminopropyl) hexamethyltrisiloxane, and general formula (IV):

[0016]

[Chemical 7]

Examples thereof include a residue obtained by removing an amino group from a diamine such as an amino-terminated polysiloxane represented by the formula (wherein R ³ and k are the same as above), and these groups may be contained alone. It may well contain two or more kinds.

R ¹ is a divalent organic group having at least one hydrosilyl group and having 1 to 20 carbon atoms, and preferably has a structure in which a group having a hydrosilyl group is directly bonded to carbon atoms constituting a ring. It is a divalent organic group, and more preferable specific examples include the following structural formulas:

[0019]

[Chemical 8]

It is at least one group selected from and two R ¹ 's in the general formula (I) may be the same or different.

W is a group containing at least one hydrosilyl group, and W in the formula may be the same as or different from each other. To specifically exemplify such a group,

[0022]

[Chemical 9]

A hydrosilyl group having one silicon atom such as

[0024]

[Chemical 10]

Groups containing 2-3 silicon atoms, such as

[0026]

[Chemical 11]

(In the formula, R ⁶ is H, OSi (CH ₃ ) ₃
And a group selected from organic groups having 1 to 10 carbon atoms, and each R ⁶ may be the same or different. m and n are
It is a positive integer and 2 <m + n <50. ),

[0028]

[Chemical 12]

(Wherein R ⁶ is the same as above, m is a positive integer, n is 0 or a positive integer, 2 <m + n <50, p is a positive integer, q is 0 or a positive integer, and 2 ≦ p + q ≦ 4) and the like, and groups derived from various linear, branched, or cyclic polyvalent hydrogen siloxanes.

When two or more hydrosilyl group-containing groups are present in the same molecule, they may be the same or different from each other. The total number of hydrosilyl groups contained in the hydrosilyl group-containing imide compound represented by the general formula (I) may be at least two in one molecule, but is preferably 2 to 15 and preferably 3 to 12. Especially preferred. When the number of the hydrosilyl groups is less than 2, the hydrosilyl group-containing imide compound is mixed with a compound having at least two carbon-carbon bonds in the molecule in the presence of a hydrosilylation catalyst to cure by hydrosilylation reaction. When it is applied, it often causes curing failure. Further, when the number of the hydrosilyl groups is more than 15, the storage stability of the imide compound is deteriorated, and moreover, a large amount of the hydrosilyl groups remains in the cured product even after curing, causing voids and cracks.

In the general formula (II), R ² has 1 carbon atom.
To 20 divalent organic groups, and specific examples thereof include methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group, isopropylene group,
A linear or branched divalent hydrocarbon group such as an isobutylene group, a phenylene group, a naphthylene group,

[0032]

[Chemical 13]

And the like.

In the general formula (III), R ⁴ is a tetravalent organic group containing an aromatic group having 6 to 30 carbon atoms,
In particular, a tetravalent group having an aromatic ring having a carbon number of 6 to 30 and a tetravalent aromatic group bonded through a divalent group gives a cured product having excellent heat resistance after curing. Preferred and particularly preferred specific examples are pyromellitic acid,
3,3 ', 4,4'-biphenyltetracarboxylic acid, 3,3',
4,4'- Benzophenonetetracarboxylic acid, 3,3 ', 4,4
´-Diphenylsulfone tetracarboxylic acid, 3,3´, 4,4
´-Diphenyl ether tetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane, naphthalene-1,2,5,6-tetracarboxylic acid, etc. These can be used alone or as a mixture of two or more kinds.

R ⁵ is a divalent organic group having 1 to 20 carbon atoms, and specific examples thereof include the same groups as R ² in the general formula (II).

Examples of Y are the same as those described above for W.

Specific examples of the imide compound of the present invention are shown below, but the imide compound of the present invention is not limited to these specific examples.

As the compound represented by the general formula (I),

[0039]

[Chemical 14]

[0040]

[Chemical 15]

[0041]

[Chemical 16]

Examples of the compound represented by the general formula (III) include

[0043]

[Chemical 17]

[0044]

[Chemical 18]

[0045]

[Chemical 19]

[0046]

[Chemical 20]

And the like.

The method for producing the hydrosilyl group-containing imide compound represented by the general formulas (I) and (III) is not particularly limited, and various methods can be used. For example, an imide compound having a Si-Cl group in the molecule is used as Li
A method of treating a compound with a reducing agent such as AlH ₄ and NaBH ₄ to reduce the Si—Cl group in the compound to a Si—H group, an imide compound having a functional group X in the molecule, and the functional group in the molecule. A method for reacting a compound having a reactive functional group Z and a hydrosilyl group at the same time, by selectively hydrosilylating a polyhydrosilane compound having at least two hydrosilyl groups with respect to an imide compound having a carbon-carbon double bond After the reaction, the hydrosilyl group may remain in the molecule of the compound. Among these, the method of reacting an imide compound having a carbon-carbon double bond with a polyhydrosilane compound is particularly preferable from the viewpoints of easy availability of raw materials, easy reaction, and good yield.

When the imide compound having a carbon-carbon double bond, which is a reaction component, is produced by the above-mentioned method, the diamine component (1) and the cyclic olefin-containing acid of the compound of the general formula (I) are used. A method of reacting an anhydride with an organic polar solvent to obtain a solution of amic acid, and then (a) thermally imidizing the solution of the amic acid, or (b) a solution of the amic acid. A method of chemically imidizing the above with a dehydrating agent such as acetic anhydride, or (c) contacting the solution of the amic acid with water or a poor solvent for the amic acid such as a hydrocarbon to precipitate the amic acid Examples of the method include precipitation and heating, or (2) a method in which a diisocyanate component and a cyclic olefin-containing acid anhydride are reacted in an organic polar solvent to directly obtain an imide compound. Wear.

An imide compound containing two cyclic olefins in the same molecule can be produced by any of these methods and is not particularly limited, but the production apparatus and production process are simpler or easier. And because it is easy to obtain the raw materials used,
The method (1) (a), that is, the method in which a diamine component and a cyclic olefin-containing acid anhydride are reacted in an organic polar solvent and then heated to obtain an imide is preferable.

When obtaining the compound of the general formula (III), a reaction similar to the above-mentioned (1) and (2) can be used.

The hydrosilylation reaction between the imide compound having a carbon-carbon double bond and the polyhydrosilane compound is carried out by the imide compound having a carbon-carbon double bond obtained above and a polyhydrosilyl compound such as diethylsilane or phenyl. Silanes such as silane and diphenylsilane, 1,1,1,3,5,7,7,7-octamethyltetrasiloxane,
Chain hydrogen polysiloxanes such as 1,1,1,3,5,7,9,9,9-nonamethylpentasiloxane, 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7- Cyclic hydrogen polysiloxanes such as tetramethylcyclotetrasiloxane and carbon-carbon 2 in the presence of a hydrosilylation catalyst.
The polyhydrosilyl compound is added in an amount of 2 to 5 times (molar ratio) with respect to the heavy bond.

The reaction is generally carried out in the temperature range of 0 to 150 ° C., and if necessary, a hydrocarbon solvent such as hexane, heptane, benzene, toluene, xylene, methanol, ethanol, propanol, ethylene glycol, 1, Alcohol solvents such as 4-butanediol, 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, benzoin Appropriate organic solvents such as ester solvents such as methyl acidate and ethyl benzoate, halogenated hydrocarbon solvents such as methylene chloride, chloroform, ethylene chloride and chlorobenzene, or a mixture of two or more kinds thereof may be used.

The imide compound thus obtained is a white or yellowish brown liquid at room temperature or a solid having a melting point of 150 ° C. or lower, and is an alcohol solvent such as methanol, ethanol, propanol, ethylene glycol or 1,4-butanediol. Ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, anisole, etc., esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl benzoate, ethyl benzoate, etc. System 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,
Formamide solvents such as N, N-diethylformamide,
N, N-dimethylacetamide, N, N-diethylacetamide and other acetamide solvents, N-methyl-2-pyrrolidone,
Pyrrolidone solvents such as N-acetyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, phenol, o-cresol, m-
Soluble in phenolic solvents such as cresol, p-cresol, xylenol, halogenated phenols, catechol, pyridine, hexamethylphosphoramide, γ-butyrolactone and mixtures of two or more of these, pentane, hexane, heptane, benzene. It is insoluble or extremely insoluble in hydrocarbon solvents such as toluene, toluene and xylene, and water.

The hydrosilyl group-containing imide compound used in the present invention may increase viscosity or gel during storage due to moisture. In order to prevent this phenomenon, a compound containing an aliphatic unsaturated bond in the imide compound,
A storage stability improver such as an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin compound, an organic peroxide can be contained.

The amount of the above-mentioned storage stability improver to be used can be selected almost arbitrarily as long as it is uniformly dispersed, but it is 10 ⁻⁶ to 10 ^{−6 with respect} to 1 mol of the hydrosilyl group-containing imide compound.
It is preferably used in the range of 10 ^-1 mol. If it is less than 10 ^-6 mol, the effect of storage stability is not fully exerted, and 10 ^-1 mol
The above may impede curing. The storage stability improvers may be used alone or in combination of two or more.

The compound having at least two carbon-carbon double bonds in the molecule which is the component (B) is not particularly limited, and compounds represented by the general formulas (V) to (VIII) are used. .

That is, the general formula (V):

[0059]

[Chemical 21]

(In the formula, R ⁷ is a hydrogen atom or a methyl group,
R ⁸ is a divalent organic group having 2 to 20 carbon atoms and may have one or more ether bonds, and R ⁹ is 1 to 30 carbon atoms.
Aromatic or aliphatic monovalent to tetravalent organic group, a is 1
A compound having an ether bond represented by the general formula (VI):

[0061]

[Chemical formula 22]

(Wherein R ⁷ , R ⁸ and a are the same as above,
¹⁰ represents a monovalent to tetravalent organic group having 1 to 30 carbon atoms), a compound having an ester bond represented by the general formula (VII):

[0063]

[Chemical formula 23]

(Wherein R ⁷ and a are the same as defined above, and R ¹¹ is a monovalent to tetravalent organic group having 2 to 50 carbon atoms), a hydrocarbon compound represented by the general formula (VIII) :

[0065]

[Chemical formula 24]

(Wherein R ⁷ , R ⁸ and a are the same as above,
¹² is a compound having a carbonate bond represented by 1 to 4 valent organic groups having 1 to 30 carbon atoms.

In the general formulas (V), (VI) and (VIII), R ⁸ is a divalent organic group having 2 to 20 carbon atoms and may have one or more ether bonds. In particular,

[0068]

[Chemical 25]

And the like.

In the general formula (V), R ⁹ has 1 to 30 carbon atoms.
Represents one aromatic or aliphatic monovalent to tetravalent organic group, and specific examples include

[0071]

[Chemical formula 26]

[0072]

[Chemical 27]

And the like.

In the general formula (VI), R ¹⁰ has 1 carbon atom.
~ 30 represents a monovalent to tetravalent organic group, and specific examples thereof include

[0075]

[Chemical 28]

[0076]

[Chemical 29]

And the like.

In the general formula (VII), R ¹¹ is a monovalent to tetravalent organic group having 2 to 50 carbon atoms, and specific examples thereof include

[0079]

[Chemical 30]

[0080]

[Chemical 31]

And the like.

In the general formula (VIII), R ¹² is a monovalent to tetravalent organic group having 1 to 30 carbon atoms, and specific examples thereof include

[0083]

[Chemical 32]

[0084]

[Chemical 33]

[0085]

[Chemical 34]

And the like.

Specific examples of the compound represented by the component (B) having at least two carbon-carbon double bonds in the molecule include 1,3-butadiene, 1,5-hexadiene, 1,
Hydrocarbon compounds such as 9-decadiene, o-divinylbenzene, m-divinylbenzene, p-divinylbenzene, bisphenol A-diallyl ether, bisphenol P-
Examples thereof include ether compounds such as diallyl ether, ester compounds such as diallyl terephthalate and diallyl isophthalate, and carbonate compounds such as diallyl carbonate.

The ratio of the component (A) and the component (B) in the curable composition is 0.5 to 10 times, and more preferably 0.5 to 10 times the molar ratio of the Si-H group to the carbon-carbon double bond. 5
It is preferable to mix them in a double amount. If the amount is less than 0.5 times, the curing does not proceed sufficiently and a good cured product cannot be obtained. Further, if the amount is more than 10 times, the storage stability of the mixture of the component (A) and the component (B) becomes poor, and moreover, a large amount of hydrosilyl group remains in the cured product even after curing, causing voids and cracks. It is easy to become.

The hydrosilylation catalyst which is the component (C) of the composition of the present invention includes platinum simple substance, solid platinum supported on a simple substance such as alumina, silica, carbon black, chloroplatinic acid, chloroplatinic acid chloride. complexes with alcohols, aldehydes, ketones, etc., platinum - olefin complexes _{(e.g., Pt (CH 2 = CH 2} ) 2 (PPh 3) 2, P
_{t (CH 2 = CH 2)} 2 Cl 2); platinum - vinylsiloxane complex (e.g., Pt _n (ViMe ₂ SiOSiM
_{e 2 Vi) m, Pt [} (MeViSiO) 4] m), platinum - phosphine complex (e.g., Pt (PPh _{3) 4,}
Pt (PBu) ₄ ), platinum-phosphite complex (for example, Pt [P (OPh) ₃ ] ₄ ) (in the formula, Me represents a methyl group, Bu represents a butyl group, Vi represents a vinyl group, and Ph represents a phenyl group. , M, n represent integers), dicarbonyldichloroplatinum, and Ashby U.S. Pat.
Platinum-hydrocarbon composites described in 3159601 and 3159662, and Lamore (Lamore
aux) in U.S. Pat. No. 3,220,972 and the platinum alcoholate catalysts. In addition, the platinum chloride-olefin composites described in Modic US Pat. No. 3,516,946 are also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ and RhAl ₂
O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlCl
₃ , PdCl ₂ .2H ₂ O, NiCl ₂ , TiCl _{4 and the} like. These catalysts may be used alone or in combination of two or more. From the viewpoint of catalytic activity, chloroplatinic acid, a platinum-olefin complex, and a platinum vinylsiloxane complex are preferable.

The catalyst amount is not particularly limited,
For component (B) carbon-carbon double bond 1 mol, 10 ^-1
It is preferably used in the range of -10 ^-8 mol, preferably in the range of 10 ^-3 -10 ^-6 mol. If it is less than 10 ^-8 mol, curing will not proceed sufficiently. Further, the hydrosilylation catalyst is generally expensive and corrosive, and there is a possibility that a large amount of hydrogen gas is generated and the cured product foams. Therefore, it is preferable not to use 10 ^-1 mol or more.

When both the components (A) and (B) are liquid at room temperature and are compatible with each other,
The composition can be obtained by directly mixing the component (A), the component (B), and the component (C).

When the components (A) and / or (B) of the composition of the present invention are solids, the components (A), (B), and (C) are replaced with suitable organic compounds. solvent,
For example, hydrocarbon solvents such as hexane, heptane, benzene, toluene, xylene, alcohol solvents such as methanol, ethanol, propanol, ethylene glycol, 1,4-butanediol, diethyl ether, tetrahydrofuran, 1,4-dioxane, ethylene. Ether solvent such as glycol dimethyl ether, ethylene glycol diethyl ether, anisole, methyl acetate,
Ester-based solvents such as ethyl acetate, propyl acetate, butyl acetate, methyl benzoate and ethyl benzoate, halogenated hydrocarbon solvents such as methylene chloride, chloroform, ethylene chloride and chlorobenzene, dimethyl sulfoxide,
Sulfoxide solvents such as diethyl sulfoxide, N, N-
Formamide solvents such as dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N,
N-diethylacetamide and other acetamide solvents, N-
Methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N-
Pyrrolidone-based solvent such as vinyl-2-pyrrolidone, phenol-based solvent such as phenol, o-cresol, m-cresol, p-cresol, xylenol, halogenated phenol, catechol, or pyridine, hexamethylphosphoramide, γ-butyrolactone Also, a solution prepared by dissolving a mixture of two or more of these alone or a mixture of two or more thereof can be used as the composition.

The amount of the solvent used is not particularly limited as long as it does not hinder the work, but is preferably (A).
The total concentration of the components, the components (b) and (C) is 1 to 60% (weight%, the same applies hereinafter), more preferably 1 to 50%, and further 1 to 40%. Is preferred.

The composition of the present invention may further contain an adhesion improver, a physical property adjuster, a storage stability improver, a plasticizer, if necessary.
Filler, anti-aging agent, ultraviolet absorber, metal deactivator,
Various additives such as an ozone deterioration inhibitor, a light stabilizer, an amine radical chain inhibitor, a phosphorus peroxide decomposer, a lubricant, a pigment, and a foaming agent can be appropriately added. The total amount of the additives is not particularly limited as long as it does not significantly deteriorate the properties of the cured product, but is preferably 1 to 300 parts by weight with respect to 100 parts by weight of the imide compound.

To cure the composition of the present invention, a temperature range of 50 ° C. or higher and a decomposition temperature of the component (A) or the component (B) or lower, preferably 50 to 350 ° C., more preferably 50 to 300 ° C.
It is preferable to perform the treatment in the temperature range of ° C for 1 minute to 30 hours. If the treatment temperature is too high, local heat generation or foaming occurs during curing, which makes it difficult to obtain a good cured product, which is not preferable. When the composition is an organic solvent solution, by distilling off or volatilizing the organic solvent before curing of the composition, during curing, or at any stage after curing, the above curing conditions may be applied. , A cured product can be obtained.

The resin 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 parts that are easily exposed to high temperatures. It is preferably used as a coating material.

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Synthesis Example 1 (Synthesis 1 of hydrosilyl group-containing imide compound) 2,3-dicarboxy-bicyclo [2.2.1] hept-5-
32.8 g (0.20 mol) of ene dianhydride was dissolved in 200 ml of N, N-dimethylacetamide (hereinafter, abbreviated as DMAc).
4,4'-diaminodiphenyl ether at room temperature 20.0
Approximately 30 g (0.10 mol) dissolved in 200 ml DMAc
Slowly added over minutes. After the addition was completed, stirring was continued for 20 minutes to obtain an amic acid solution.

Subsequently, the obtained amic acid solution was heated to reflux, and heating and stirring was continued for another 3 hours. After allowing to cool, the reaction solution was poured into a large amount of methanol to precipitate the product, which was then filtered. The obtained needle crystals of the imide compound were washed with methanol and dried under reduced pressure at room temperature for several hours.

52.2 g of 1,3,5,7-tetramethylcyclotetrasiloxane was charged into a 500 ml four-necked flask, and 1.02 of a 10% ethanol solution of H ₂ PtCl ₆ .6H ₂ O was added thereto.
ml was added. A solution prepared by dissolving 10 g of the imide compound in 1 liter of chlorobenzene was slowly added dropwise to this solution at room temperature over about 30 minutes. After the dropping was completed, the reaction was carried out at 100 ° C for 40 hours. After the reaction, chlorobenzene and unreacted 1,3,5,
After 7-tetramethylcyclotetrasiloxane was distilled off, the product was dried under reduced pressure at room temperature for several hours to obtain 17.2 g of the desired imide compound (IX) having a hydrosilyl group.

[0102]

[Chemical 35]

Synthesis Example 2 (Synthesis 2 of Hydrosilyl Group-Containing Imide Compound) Under a nitrogen stream, 1,2,3,6-tetrahydrophthalic anhydride 30.4 g (0.20
mol) was dissolved in 200 ml of DMAc. At room temperature
DMAc of 10.8 g (0.10 mol) of 4,4'-diaminobenzene
The solution dissolved in 200 ml was added slowly over about 30 minutes. After the addition was completed, stirring was continued for 20 minutes to obtain an amic acid solution.

Subsequently, the same treatment as in Synthesis Example 1 was carried out to obtain an imide compound.

63.8 g of 1,3,5,7-tetramethylcyclotetrasiloxane was charged into a 500 ml four-necked flask, and 1.33 of a 10% ethanol solution of H ₂ PtCl ₆ .6H ₂ O was added thereto.
ml was added. Chlorobenzene 500 with 10 g of the imide compound
The solution dissolved in ml was slowly added dropwise at room temperature over about 30 minutes. After the dropping was completed, the reaction was carried out at 50 ° C. for 15 hours. After the reaction, chlorobenzene and unreacted 1,3,5,7-tetramethylcyclotetrasiloxane were distilled off, followed by vacuum drying at room temperature for several hours to obtain 20.7 g of the desired imide compound (X) having a hydrosilyl group. I got it.

[0106]

[Chemical 36]

Synthesis Example 3 (Synthesis 3 of Hydrosilyl Group-Containing Imide Compound) 33.2 g (0.20 mol) of 2,3-dicarboxy-7-oxabicyclo [2.2.1] hept-5-ene dianhydride under a nitrogen stream. To DMAc
It was dissolved in 200 ml. 24.8 g (0.10 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane at room temperature
Was dissolved in 200 ml of DMAc and gradually added over about 30 minutes. After the addition was completed, stirring was continued for 20 minutes to obtain an amic acid solution.

Subsequently, the same treatment as in Synthesis Example 1 was carried out to obtain an imide compound.

1,3,5-trimethylcyclotrisiloxane 3
3.1 g was charged into a 500 ml four-necked flask, and H ₂ was added to it.
0.92 ml of a 10% ethanol solution of PtCl ₆ .6H ₂ O was added. A solution prepared by dissolving 10 g of the imide compound in 500 ml of chlorobenzene was slowly added dropwise at room temperature over about 30 minutes. After the dropping was completed, the reaction was carried out at 50 ° C. for 15 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 15.3 g of a desired hydrosilyl group-containing imide compound (XI).

[0110]

[Chemical 37]

Synthesis Example 4 (Synthesis 4 of Hydrosilyl Group-Containing Imide Compound) 26.2 g (0.12 mol) of pyromellitic dianhydride was added to D under a nitrogen stream.
It was dissolved in 350 ml of MAc. Allylamine 1 at room temperature
1.4 g (0.20 mol) was added slowly over about 30 minutes.
After the addition was completed, stirring was continued for 20 minutes to obtain an amic acid solution.

Subsequently, the obtained amic acid solution was heated to reflux, and heating and stirring was continued for another 3 hours. After cooling, the reaction solution was poured into a large amount of methanol to precipitate the product, which was then filtered. The obtained needle crystals were washed with methanol and dried under reduced pressure at room temperature for several hours.

65.0 g of 1,3,5,7-tetramethylcyclotetrasiloxane was charged into a 500 ml four-necked flask, and 0.25 ml of H ₂ PtCl ₆ .6H ₂ O 10% ethanol solution was charged therein.
added. 10 g of the imide compound obtained above at room temperature
Was dissolved in 200 ml of chloroform, and the solution was slowly added dropwise over about 30 minutes. After the dropping was completed, the reaction was carried out at 50 ° C. for 15 hours. After the reaction, chloroform and unreacted 1,3,5,7-tetramethylcyclotetrasiloxane were distilled off, followed by drying under reduced pressure at room temperature for several hours to obtain 23.1 g of the desired imide compound (XII) having a hydrosilyl group. I got it.

[0114]

[Chemical 38]

The compound (XII) was a viscous liquid at room temperature.

¹ H NMR (CDCl ₃ ) δ: 0.18
(S, 24H, SiCH ₃ ), 0.62 (t, 4H, SiCH
₂ ), 1.76 (m, 4H, CH ₂ CH ₂ CH ₂ ), 3.74
(T, 4H, NCH ₂ ), 4.68 (s, 6H, SiH),
8.27 (s, 2H, aromatic).

Synthesis Example 5 (Synthesis 5 of Hydrosilyl Group-Containing Imide Compound) 32.2 g (0.10 mol) of 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride was dissolved in 350 ml of DMAc under a nitrogen stream. . Approximately 11.4 g (0.20 mol) of allylamine at room temperature
Gradually added over 30 minutes. After the addition was completed, stirring was continued for 20 minutes to obtain an amic acid solution.

Subsequently, the same treatment as in Synthesis Example 4 was carried out to obtain an imide compound.

59.6 g of 1,3,5,7-tetramethylcyclotetrasiloxane was charged into a 500 ml four-necked flask, and 0.25 ml of H ₂ PtCl ₆ .6H ₂ O 10% ethanol solution was charged therein.
added. 10 g of the imide compound obtained above at room temperature
Was dissolved in 200 ml of chloroform, and the solution was slowly added dropwise over about 30 minutes. After the dropping was completed, the reaction was carried out at 50 ° C. for 15 hours. After the reaction, chloroform and unreacted 1,3,5,7-tetramethylcyclotetrasiloxane were evaporated and then dried under reduced pressure at room temperature for several hours to obtain 20.8 g of an intended imide compound (XIII) having a hydrosilyl group. .

[0120]

[Chemical Formula 39]

Synthesis Example 6 (Synthesis 6 of Hydrosilyl Group-Containing Imide Compound) 35.8 g (0.10 mol) of 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride was dissolved in 350 ml of DMAc under a nitrogen stream. did. 23.8 g (0.20 m) of p-aminostyrene at room temperature
ol) dissolved in 100 ml of DMAc was gradually added over about 30 minutes. After the addition was completed, stirring was continued for 20 minutes to obtain an amic acid solution.

Subsequently, the same treatment as in Synthesis Example 4 was carried out to obtain an imide compound.

1,3,5-trimethylcyclotrisiloxane 3
2.1 g was charged into a 500 ml four-necked flask, and H ₂ was added to it.
0.25 ml of 10% PtCl ₆ .6H ₂ O ethanol solution was added. At room temperature, a solution prepared by dissolving 10 g of the imide compound obtained above in 200 ml of chloroform was slowly added dropwise over about 30 minutes. After completion of the dropping, reaction was carried out at 50 ° C. for 10 hours. After the reaction, chloroform and unreacted 1,3,5-trimethylcyclotrisiloxane were evaporated and then dried under reduced pressure at room temperature for several hours to obtain 14.3 g of an intended imide compound (XIV) having a hydrosilyl group.

[0124]

[Chemical 40]

Example 1 1.30 g of the imide compound (IX) synthesized in Synthesis Example 1 and the formula (X
V):

[0126]

[Chemical 41]

1.0 g of the carbon-carbon double bond-containing compound represented by: was dissolved in 18 g of chloroform, and H ₂ Pt was added thereto.
A thermosetting composition was obtained by adding 3.2 μl of a 10% ethanol solution of Cl ₆ .6H ₂ O. The composition was stored at 50 ° C. for 1 day and then treated at 100 ° C. for 1 hour to obtain a cured product. The appearance and gel fraction (weight fraction of chloroform-insoluble matter) of the obtained cured product are shown in Table 1.

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

Example 2 1.4 g of the imide compound (X) synthesized in Synthesis Example 2 and the formula (XV
I):

[0130]

[Chemical 42]

1.0 g of the carbon-carbon double bond-containing compound represented by: was dissolved in 10 g of chloroform, and H ₂ P was added thereto.
3.0 μL of 10% ethanol solution of tCl ₆ .6H ₂ O was blended to obtain a thermosetting composition. The composition was stored at 50 ° C. for 1 day and then treated at 100 ° C. for 1 hour to obtain a cured product. The appearance and gel fraction of the obtained cured product are shown in Table 1.

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

Example 3 1.9 g of the imide compound (X) synthesized in Synthesis Example 2 and the compound of the formula (XVI
I):

[0134]

[Chemical 43]

1.0 g of the carbon-carbon double bond-containing compound represented by: was dissolved in 15 g of chloroform, and H ₂ Pt was added thereto.
A thermosetting composition was obtained by blending 6.0 μl of 10% Cl ₆ .6H ₂ O ethanol solution. The composition at 50 ° C.
It was stored for a day and then treated at 100 ° C. for 1 hour to obtain a cured product. The appearance and gel fraction of the obtained cured product are shown in Table 1.

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

Example 4 1.5 g of the imide compound (XI) synthesized in Synthesis Example 3 and the formula (X
VIII):

[0138]

[Chemical 44]

A carbon-carbon double bond-containing compound represented by 1.0 g was dissolved in 10 g of chloroform, and H ₂ P was added thereto.
3.0 μL of 10% ethanol solution of tCl ₆ .6H ₂ O was blended to obtain a thermosetting composition. The composition was stored at 50 ° C. for 1 day and then treated at 100 ° C. for 1 hour to obtain a cured product. The appearance and gel fraction of the obtained cured product are shown in Table 1.

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

Example 5 1.7 g of the imide compound (XI) synthesized in Synthesis Example 3 and the formula (X
VI) a carbon-carbon double bond-containing compound 1.0 g
Was dissolved in 10 g of chloroform, and H ₂ PtCl ₆
3.0 μl of 6% H ₂ O 10% ethanol solution was blended to obtain a thermosetting composition. The composition was stored at 50 ° C. for 1 day and then treated at 100 ° C. for 1 hour to obtain a cured product. The appearance and gel fraction of the obtained cured product are shown in Table 1.

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

Example 6 3.1 g of the imide compound (XI) synthesized in Synthesis Example 3 and the formula (X
IX):

[0144]

[Chemical formula 45]

A carbon-carbon double bond-containing compound represented by 1.0 g was dissolved in 10 g of chloroform, and H ₂ P was added thereto.
A thermosetting composition was obtained by mixing 1.8 μl of 10% tCl ₆ .6H ₂ O ethanol solution. The composition was stored at 50 ° C. for 1 day and then treated at 100 ° C. for 1 hour to obtain a cured product. The appearance and gel fraction of the obtained cured product are shown in Table 1.

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

Example 7 0.94 g of the imide compound (XII) obtained in Synthesis Example 4 and the formula (XV)
1.06 g of the carbon-carbon double bond-containing compound represented by is dissolved in 18 g of chloroform, and H ₂ PtCl ₆ · 6H is dissolved therein.
_A thermosetting composition was obtained by mixing 6.0 μl of a 10% ethanol solution of ₂ O. Storing the composition at 50 ° C. for 1 day,
After that, it was treated at 100 ° C. for 1 hour to obtain a cured product. The appearance and gel fraction of the obtained cured product are shown in Table 1.

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

Example 8 1.0 g of the imide compound (XIII) synthesized in Synthesis Example 5 and the formula
Carbon-carbon double bond-containing compound represented by (XVI) 0.74
g was dissolved in 10 g of chloroform, and H ₂ PtCl ₆ was dissolved therein.
A curable composition was prepared by mixing 3.0 μl of 6H ₂ O 10% ethanol solution. The composition was stored at 50 ° C. for 1 day and then treated at 100 ° C. for 1 hour to obtain a cured product. The appearance and gel fraction of the obtained cured product are shown in Table 1.

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

Example 9 0.94 g of the imide compound (XIII) synthesized in Synthesis Example 5 and the formula
Compound containing carbon-carbon double bond represented by (XVII) 1.3
g was dissolved in 15 g of chloroform, and H ₂ PtCl ₆ was dissolved therein.
A curable composition was prepared by mixing 6.0 μl of a 6% H ₂ O 10% ethanol solution. The composition was stored at 50 ° C. for 1 day and then treated at 100 ° C. for 1 hour to obtain a cured product. The appearance and gel fraction of the obtained cured product are shown in Table 1.

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

Example 10 1.2 g of the imide compound (XIV) synthesized in Synthesis Example 6 and the formula (X
Compound containing carbon-carbon double bond represented by VIII) 0.68
g was dissolved in 10 g of chloroform, and H ₂ PtCl ₆ was dissolved therein.
A curable composition was prepared by mixing 3.0 μl of 6H ₂ O 10% ethanol solution. The composition was stored at 50 ° C. for 1 day and then treated at 100 ° C. for 1 hour to obtain a cured product. The appearance and gel fraction of the obtained cured product are shown in Table 1.

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

Example 11 1.0 g of the imide compound (XIV) synthesized in Synthesis Example 6 and the formula (X
Compound containing carbon-carbon double bond represented by VI) 0.43 g
Was dissolved in 10 g of chloroform, and H ₂ PtCl ₆
A curable composition was prepared by mixing 1.8 μl of 6H ₂ O 10% ethanol solution. The composition was stored at 50 ° C. for 1 day and then treated at 100 ° C. for 1 hour to obtain a cured product.
The appearance and gel fraction of the obtained cured product are shown in Table 1.

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

Example 12 1.0 g of the imide compound (XIV) synthesized in Synthesis Example 6 and the formula (X
IX) carbon-carbon double bond-containing compound 0.24 g
Was dissolved in 10 g of chloroform, and H ₂ PtCl ₆
A curable composition was prepared by mixing 1.8 μl of 6H ₂ O 10% ethanol solution. The composition was stored at 50 ° C. for 1 day and then treated at 100 ° C. for 1 hour to obtain a cured product.
The appearance and gel fraction of the obtained cured product are shown in Table 1.

The obtained cured product was subjected to TGA measurement using a differential thermal balance TG-DTA manufactured by Rigaku Denki Co., Ltd. under a nitrogen stream. Table 1 shows the 5% and 10% weight loss temperatures obtained there. Table 2 shows the results of 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 about 8000) and 1 g of polypropylene glycol having a 1,3,5,7-tetramethylcyclotetrasiloxy group at both ends (molecular weight about 8000) Mixed with H ₂ Pt
A curable composition was prepared by blending 4 μl of a 10% ethanol solution of Cl ₆ .6H ₂ O. The composition was stored in an oven kept at 100 ° C. for 1 hour to obtain a cured product. The appearance and gel fraction of the obtained cured product are shown in Table 1.

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

[0161]

[Table 1]

[0162]

[Table 2]

From Table 1, it can be seen that the resin obtained by curing the composition of the present invention has excellent heat resistance. Further, it can be seen from Table 2 that the resin obtained by curing the composition of the present invention has excellent chemical resistance.

[0164]

EFFECTS OF THE INVENTION The curable composition of the present invention can be easily made into a cured product having various shapes, and the obtained cured product has excellent heat resistance and chemical resistance.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Kazuya Yonezawa 5-12-11 Tsutsujigaoka, Tarumi-ku, Kobe-shi, Hyogo

Claims (3)

[Claims] 1. An (I) imide compound having at least two hydrosilyl groups in the molecule, (B) a compound having at least two carbon-carbon double bonds in the molecule, and (C) a hydrosilylation catalyst. Curable composition containing. 2. An imide compound having at least two hydrosilyl groups in the molecule has the general formula (I): (In the formula, R ⁰ is a divalent organic group having an aromatic group having 6 to 30 carbon atoms, or a compound represented by the general formula (II): (R ² represents a divalent organic group having 1 to 20 carbon atoms, R ³ represents a methyl group or a phenyl group, two R ² and a plurality of R ³
May be the same or different, and k represents a positive integer of 1 to 20),
R ¹ is an organic group having 1 to 20 carbon atoms containing at least one hydrosilyl group, and two R ¹ may be the same or different). 1. The curable composition according to 1. 3. An imide compound having at least two hydrosilyl groups in the molecule is represented by the general formula (III): (In the formula, R ⁴ contains an aromatic group having 6 to 30 carbon atoms;
Valent organic group, R ⁵ is a divalent organic group having 1 to 20 carbon atoms, Y
Represents a group containing at least one hydrosilyl group,
The two curable compositions according to claim 1, wherein the two R ⁵ and Y each may be the same or different).