JP2002212295A - Curable resin composition - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable composition containing a reactive imide compound. More specifically, the present invention relates to a curable composition which cures rapidly at a relatively low temperature without generating a low-boiling compound at the time of curing and gives a cured product having excellent heat resistance, chemical resistance and mechanical properties.

[0002]

2. Description of the Related Art Conventionally, many compositions have been developed as curable compositions. Among them, a curable composition utilizing a hydrosilylation reaction that proceeds at a relatively low temperature is also disclosed (JP-A-1-138230). In this composition, both the carbon-carbon double bond-containing component and the hydrosilyl group-containing component have a polyether main chain. 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, the obtained cured product has insufficient heat resistance and chemical resistance, and has disadvantages such as a large decrease in mechanical properties in a short time even at a low temperature of 100 ° C., and poor acid and solvent resistance. are doing. Therefore, it is not suitable for applications requiring heat resistance or chemical resistance, for example, applications such as coating agents around electronic components and heat-resistant adhesives.

[0003] JP-A-4-261467 discloses 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. However, since the molecular weight of the imide compound is low, the silicon content in the composition is increased, and there is a limit in improving the heat resistance.

Japanese Patent Application Laid-Open No. 6-080783 discloses a composition which gives a cured product having even higher heat resistance, using a high-molecular-weight imide compound as both a carbon-carbon double bond-containing component and a hydrosilyl group-containing component. That was disclosed. However, the raw material hydrosilyl group-containing imide compound is a special compound, and is difficult to obtain, and thus lacks industrial practicality.

[0005]

SUMMARY OF THE INVENTION In view of such circumstances, the present invention cures quickly at a relatively low temperature without generating low-boiling compounds at the time of curing, and has heat resistance, chemical resistance and mechanical strength. It is an object of the present invention to provide a cured product excellent in the above, and to provide a curable composition having high industrial practicality.
Another object of the present invention is to provide a curable composition that is easy to prepare and has excellent workability.

[0006]

Means for Solving the Problems In order to solve the above problems, the present inventors have made intensive studies and have found that an imide compound having at least two carbon-carbon double bonds in one molecule and
When a compound having at least two hydrosilyl groups in a molecule is reacted with a hydrosilylation catalyst, the compound is cured rapidly even at a relatively low temperature, and the production of a cured product is not caused because a low-boiling compound is not generated during curing. The present invention was found to provide a cured product which is easy and excellent in heat resistance, chemical resistance and mechanical properties, and completed the present invention. That is, the present invention
(A) 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 represents a monovalent organic group having 2 to 20 carbon atoms having a carbon-carbon double bond, and two R ³ 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 above. R ⁶ represents a divalent organic group having 2 to 20 carbon atoms and having at least one carbon-carbon double bond.) Two R ⁶ may be the same or different)
Characterized in that it contains at least one imide compound selected from the group consisting of the imide compounds represented by formula (I), (B) a compound having at least two hydrosilyl groups in one molecule, and (C) a hydrosilylation catalyst. Curable composition. It is. Hereinafter, the present invention will be described in detail.

In the present invention, the component (A) includes a carbon-carbon double bond-containing imide compound represented by the above general formula (I) and a carbon-carbon double bond represented by the above general formula (III). At least one imide compound selected from the group consisting of imide compounds (hereinafter, also referred to as a carbon-carbon double bond-containing imide compound) is used. The composition of the present invention comprises an imide compound (A) having a carbon-carbon double bond, for example, a vinyl group or an alkenyl group, and a catalyst (C).
Is used to react with the hydrosilyl group-containing compound (B) in the presence of to form a cured product. Since the hydrosilyl group-containing compound (B) described later has at least two hydrosilyl groups in the molecule, the compound (B) reacts with the imide compound having at least two carbon-carbon double bonds in the molecule as the component (A). To form a linear or network polymer.

When the number of carbon-carbon double bonds in the component (A) is less than 2 per molecule, the reaction with the component (B) results only in a graft structure and not in a crosslinked structure. It is difficult to obtain curability. In the curable composition of the present invention, since the compound having a carbon-carbon double bond has an imide group, a cured product excellent in heat resistance, chemical resistance and mechanical properties can be obtained.

The component (A) is not particularly limited as long as it is a compound having at least two carbon-carbon double bonds reactive with a hydrosilyl group in one molecule and containing an imide group. About 20,000 or even 5
A resin having a solubility of about 00 to about 10,000 is preferable in terms of good solubility and meltability, excellent moldability, and excellent heat resistance of the obtained cured product. Regarding the properties of the component (A), both liquid and solid components can be used without particular limitation. A material having a melting point of 250 ° C. or less is preferred from the viewpoint of good moldability.

In the above general 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, an `` organic group '' refers to a hydrocarbon group, or a sulfonyl group, a hydroxyl group, a carbonyl group,
A hydrocarbon group containing an ether group, a halogen group and the like. 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 specific examples include pyromellitic acid, 3,3 ′, 4,
4'-biphenyltetracarboxylic acid, 3,3 ', 4
4'-benzophenonetetracarboxylic acid, 3,3 ',
4,4'-diphenylsulfonetetracarboxylic acid, 3,
3 ', 4,4'-diphenylethertetracarboxylic acid, naphthalene-1,2,5,6-tetracarboxylic acid,

[0017]

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

[0019]

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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.

[0021]

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

[0023] Specific examples of such ^{R 2} may, for example, 4,4'-diaminodiphenyl ether, 3,4 '
-Diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-bis (4-aminophenoxy) biphenyl, 4,4'-diaminodiphenyl sulfone,
3'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (2- [Aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4
-Aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 4,4'-diaminodiphenylmethane, bis (3-methyl-4-aminophenyl) methane, bis (3-chloro-4-aminophenyl) ) Methane, 4,4'-diaminobiphenyl, 4,4'-diaminooctafluorobiphenyl, 3,3'-dimethoxy-
4,4'-diaminobiphenyl, 3,3'-dimethyl-
4,4'-diaminobiphenyl, 3,3'-dichloro-
4,4'-diaminobiphenyl, 2,2 ', 5,5'-
Tetrachloro-4,4'-diaminobiphenyl, 3,
3'-dicarboxy-4,4'-diaminobiphenyl,
3,3'-dihydroxy-4,4'-diaminobiphenyl, 2,4-diaminotoluene, 1,3-diaminobenzene, 1,4-diaminobenzene, 2,2'-bis [4
-(4-aminophenoxy) phenyl] propane, 2,
2'-bis [4- (4-aminophenoxy) phenyl]
Hexafluoropropane, bis [4- (4-aminophenoxy) phenyl] sulfone, 9,9'-bis (4-aminophenyl) -10-hydroanthracene, 9,9 '
-Bis (4-aminophenyl) fluorene, ortho-tolidine sulfone; 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,5-bis (3-aminopropyl) hexamethyltrisiloxane,

[0024]

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(Wherein R ⁵ and m are the same as those described above), and a residue obtained by removing an amino group from a siloxane diamine such as an amino-terminated polysiloxane. These may be used alone or in combination of two or more. In the general formula (I), R ³ represents a monovalent organic group having a carbon-carbon double bond and having 2 to 20 carbon atoms. Specific examples of such a group include a vinyl group and an allyl group. Group, butenyl group, pentenyl group, hexenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, isopropenyl group, 2-methyl-2-propyl group, 2-vinylphenyl group, 3-vinylphenyl group, 4 -Vinylphenyl group, allyloxyphenyl group and the like.

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

[0027]

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And the like. In the general formulas (I) and (III), n represents a positive integer of 1 to 100. Among them, from the viewpoints of excellent moldability due to good solubility and meltability, and excellent heat resistance of the obtained cured product, 1 to 50 is preferable, and 1 to 20 is more preferable.
As the component (A), only one type may be used, or two or more types may be mixed and used.

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.

In the reaction, an aromatic tetracarboxylic dianhydride, a diamine and a primary amine compound containing a carbon-carbon double bond are reacted in an organic solvent at a temperature of 80 ° C. or less 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.

Examples of 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. Purification methods include:
For example, methods such as washing, recrystallization, column purification, extraction (eg, Soxhlet extraction), ion exchange resin treatment, treatment with an adsorbent such as aluminum silicate, and the like can be mentioned.

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. An acid anhydride having a carbon-carbon double bond, preferably a cyclic olefin-containing acid anhydride, is used in place of the primary amine compound.

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. An acid anhydride having a carbon-carbon double bond is a carbon-carbon double bond represented by the general formula (I) with respect to a diamine newly formed by a reaction between an aromatic tetracarboxylic dianhydride and a diamine. As in the case of the bond-containing imide compound, the amount is 2 to 5 times (molar ratio, the same applies hereinafter), preferably 2 to 3 times, more preferably 2 to 3 times.
The reaction is preferably performed using 2.5 times the amount. 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:

[0038]

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And the like. Next, the compound having a hydrosilyl group as the component (B) will be described. 1
As the compound having at least two hydrosilyl groups in the molecule (hereinafter also referred to as a hydrosilyl group-containing compound), a compound which reacts with the component (A) and has at least two hydrosilyl groups in one molecule is particularly preferable. Can be used without restrictions. As such a hydrosilyl group-containing compound, a wide range of compounds can be used, and there is no particular limitation. For example, International Publication WO96 / 1519.
Compounds described in No. 4 having at least two hydrosilyl groups in one molecule can be used.

Among these, polysiloxane having at least two hydrosilyl groups in one molecule is preferable from the viewpoint of availability. Specifically, the following formula (IV) or (V)

[0041]

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(Wherein, R ⁸ represents a monovalent organic group having 1 to 10 carbon atoms, and each R ⁸ may be the same or different. P and r are two or more positive Represents an integer, q and s represent 0 or a positive integer, and satisfy 1 <p + q <50, r and s represent 0 or a positive integer, and 0 ≦ r + s
<50 is satisfied. The above p, q, r, and s simply represent the composition and do not represent the linear block copolymer. Specific examples of R ⁸ include, for example, a methyl group, a phenyl group, a methoxy group, an ethoxy group, a γ-glycidoxypropyl group, and a methyl group is preferable. )
And the like, and various polyvalent hydrogen siloxanes having a chain, branched, or cyclic shape.

In particular, a chain and / or cyclic organopolysiloxane having at least two hydrosilyl groups in one molecule is more preferable. Such organopolysiloxanes include, for example, 1,1,1,3,5,7,7,
7-octamethyltetrasiloxane, 1,1,1,3,
Chain hydrogen polysiloxanes such as 5,7,9,9,9-nonamethylpentasiloxane, 1,3,5-trimethylcyclotrisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 3,5,7,9
Cyclic hydrogensiloxane such as -pentamethylcyclopentasiloxane, polymethylhydrogensiloxane and the like. The various components (B) described above can be used alone or in combination of two or more.

In the present specification, one hydrosilyl group means a group having one Si—H bond,
A group having Si (H) ₂ is a group having at least two hydrosilyl groups. In the above hydrosilyl group-containing compound (B), 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 above-mentioned hydrosilyl group-containing compound (B) may be at least two in the molecule, but is preferably more than 2 from the viewpoint that heat resistance can be further improved, and is preferably 3 or more. Is more preferable, and the number is particularly preferably 4 or more. When the number of hydrosilyl groups contained in one molecule is less than 2, (A)
Even if it reacts with the components, only a graft structure is formed and not a crosslinked structure, so that it is difficult to obtain good curability. (B)
The molecular weight of the component hydrosilyl group-containing compound is not particularly limited, and any one can be suitably used, but the molecular weight is about 100 to 20,000, and more preferably 200 to 10,000.
It is desirable that the degree is good in terms of good solubility and meltability, excellent moldability, and excellent heat resistance of the obtained cured product.

The nature of the component (B) can be used without particular limitation, whether it is liquid or solid. From the viewpoint of good moldability, a material having a melting point of 250 ° C. or less is preferable, and a material having a melting point of 30 ° C. or less is more preferable. 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 , Na
Treatment with a reducing agent such as BH ₄ to obtain Si—Cl
A method of reducing a group to a Si—H group, (ii) a method of reacting an organic compound having a functional group X with a compound having both a functional group Y and a hydrosilyl group that reacts with the functional group X,
(Iii) a method of selectively hydrosilylating a compound containing a carbon-carbon double bond with a polyhydrosilane compound having at least two hydrosilyl groups so that the hydrosilyl groups remain in the compound molecules even after the reaction, (iv)
A method of thermally decomposing a high-molecular-weight SiH-containing compound may be used. Among them, the method (iii) is preferred from the viewpoints of simplicity of the reaction and good yield. The method (iv) is preferable from the viewpoint of the availability of raw materials.

The combination of component (A) / component (B) as described above includes those listed as specific examples of component (A) or mixtures thereof / the ones listed as specific examples of component (B), or Various combinations of these various mixtures can be mentioned. 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, but is not limited to the carbon-carbon double bond in the component (A). Thus, the hydrosilyl group in the component (B) has a molar ratio of 0.5 to 1
The ratio is preferably 0 times, more preferably 0.5 to 5 times. If 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 ( Ashby)
Platinum-hydrocarbon complexes described in U.S. Pat. Nos. 3,159,601 and 3,159,662, and platinum alcoholate catalysts described in U.S. Pat. No. 3,220,972 to Lamoreaux. In addition, Modic US Patent No. 3
The platinum chloride-olefin complexes described in 516946 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 , TiCl ₄
And the like. Among these, chloroplatinic acid, a platinum-olefin complex, and a platinum-vinylsiloxane complex 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 carbon-carbon double bond of the component (A).
More preferably, it is in the range of 10 ⁻³ to 10 ⁻⁶ mol. 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. Further, the hydrosilylation catalyst is generally expensive and corrosive, and a large amount of hydrogen gas may be generated to cause foaming of the cured product. Therefore, it is preferable not to use the hydrosilylation catalyst in an amount exceeding 10 ^-1 mol.

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 maleate, 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.

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 a compound containing an aliphatic unsaturated bond, an organic phosphorus compound, an organic sulfur compound, a nitrogen-containing compound, a tin-based compound, and an organic peroxide. These may be used in combination. Examples of the compound containing an aliphatic unsaturated bond include propargyl alcohols, ene-yne compounds, and maleic esters. As organophosphorus compounds, triorganophosphines,
Diorganophosphines, organophosphones,
Examples thereof include triorganophosphites. Examples of the organic sulfur compound include organomercaptans, diorganosulfides, hydrogen sulfide, benzothiazole, benzothiazole disulfide, and the like. Examples of the nitrogen-containing compound include ammonia, primary and secondary alkylamines such as tetramethylethylenediamine, arylamines, urea, and hydrazine. Examples of the tin compound include stannous halide dihydrate, stannous carboxylate, and the like. Examples of the organic peroxide include di-t-butyl peroxide, dicumyl peroxide, benzoyl peroxide, and t-butyl perbenzoate.

Among these curing retarders, benzothiazole, dimethyl malate and 3-hydroxy-3-methyl-1-butyne are preferred from the viewpoint of good retarding activity and good raw material availability. From the viewpoint of good delay activity at high temperatures, alkylamines such as tetramethylethylenediamine are preferred. These curing retarders can be used alone or in combination. Amount of the curing retarder, with respect to hydrosilylation catalyst 1 mole to be ^used, preferably 10 -1 to 10 ³ mols, more preferably from 1 to 50 mol.

The components (A) / (B) /
As the combination of the component (C), those listed as specific examples of the component (A) or various mixtures thereof / those listed as specific examples of the component (B) or various mixtures thereof /
Various combinations of those listed as specific examples of the component (C) or various mixtures thereof can be given. Among these combinations, at least one of the component (A) and the component (B) is a liquid, and a combination showing good compatibility and solubility with the other two components is a uniform composition. Is preferred from the viewpoint of obtaining

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 such as dissolution, kneading,
A mixture obtained by a method such as impregnation, support, or melting may be used as the composition, or a solution dissolved in an appropriate solvent may be used as the composition. Such solvents include hexane, toluene, hydrocarbon solvents such as xylene, methanol, alcohol solvents such as ethylene glycol, diethyl ether, tetrahydrofuran,
Ether solvents such as 1,4-dioxane, 1,3-dioxolan, ethylene glycol dimethyl ether, and anisole; ester solvents such as ethyl acetate and methyl benzoate; and halogenated carbonization such as methylene chloride, chloroform, dichlorobenzene, and dibromoethane. Hydrogen solvents and the like can be mentioned. The amount of the solvent used is not particularly limited as long as it does not interfere with the operation, but the component (A)
The sum of the concentrations of the components (B) and (C) is 1 to
60% (% by weight, hereinafter the same), more preferably 1 to 40
% Is preferably used.

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).

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 and the component (B). The reaction temperature can be variously set, for example, a temperature of 30 to 300 ° C. can be applied,
250 ° C is more preferable, and 150 to 200 ° C is still more preferable. 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 reaction may be carried out at a constant temperature, but the temperature may be changed in multiple stages or continuously as needed. The reaction time can also be set variously. The pressure during the reaction can also be set variously as necessary,
The reaction can be carried out under high or reduced pressure.

At any stage before, during or after curing, a treatment other than heating, such as pre-curing or centrifugal defoaming, is performed within a range that does not significantly impair the reactivity of the composition and the physical properties of the cured product. Processing, vacuum devolatilization, B-stage, cooling and solidification, ultrasonic treatment, light irradiation, and the like can also be added. It is preferable to perform a devolatilization treatment from the viewpoint that foaming hardly occurs in the cured product and good moldability is obtained. From the viewpoint of adjusting the viscosity and compatibility of the blend to improve the moldability, a part of the carbon-carbon double bond in the component (A) and a part of the hydrosilyl group in the component (B) are used. After the reaction, it is desirable to perform a so-called B-stage, in which the progress is stopped before the reaction is completed.

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 curing conditions. The cured product obtained by curing the composition of the present invention has excellent heat resistance,
Since it has chemical resistance and mechanical properties, it can be used for various molded article materials. As a specific example, it can be used for a plastic molding material, a fiber reinforced plastic, a heat-resistant resin film, a foam material, a plastic cell, an optical component, a printed circuit board, an electric insulating material, and the like, in addition to applications where a polyimide resin is usually used.

Since the composition of the present invention has a property of giving a cured product having excellent heat resistance, chemical resistance and mechanical properties after curing, the composition of the present invention can be used for various uses. Specific examples include, for example, adhesives, wire coatings, sealing agents such as elements, paints, building materials such as sealings,
It can be used for resin modifiers, coating agents, anticorrosion agents, packaging and the like.

[0061]

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 an L three-necked flask,

[0062]

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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.

[0064]

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An imide compound having a carbon-carbon double bond (having a molecular weight of 9412) was obtained. (Example 1) In a two-necked flask equipped with a cooling tube under a nitrogen stream,

[0066]

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1.0 g of the imide compound represented by the formula (3.0
mmol) and 1,3,5,7-tetramethylcyclotetrasiloxane (KF-990, manufactured by Shin-Etsu Chemical Co., Ltd.)
2) Add 1.83 g (30 mmol) and add toluene 10
g Pt vinyl catalyst (Deguss)
a, PTVTS) 2.30 μl (0.000304 mm
ol) and heated at 70 ° C. for 2 hours. After 0.689 mg (0.00510 mmol) of benzothiazole was added thereto, 1,3,5,7-tetramethylcyclotetrasiloxane unreacted with toluene was distilled off under reduced pressure. A composition containing 0.0053 mol of Si-H groups per gram was obtained. To 1.7 g of this composition, 84.7 g (9.0 mmol) of the imide compound synthesized in Synthesis Example 1 was added and dissolved in 200 g of tetrahydrofuran to obtain a uniform curable composition. This composition was cast on a polyimide film by a solution dripping method, and was cured by heating at 200 ° C. in an oven to obtain a cured product.

Example 2 470 mg (0.0500 mmol) of the imide compound synthesized in Synthesis Example 1 and polymethyl hydrogen siloxane (manufactured by Shin-Etsu Chemical Co., Ltd.)
KF-99) (6.0 mg, 0.0024 mmol) was dissolved in tetrahydrofuran (2.0 g), and a 3 wt% Pt vinyl catalyst (Degussa, PTVTS) was dissolved in toluene.
9.05 μl of a 0-fold diluted solution was added to obtain a uniform composition. This composition was applied to a flat copper foil, and after evaporating the solvent, the composition was cured by heating in an oven at 200 ° C. for 1 hour. A film-like cured product without tack was obtained.

[0069]

The curable composition of the present invention has the above-mentioned constitution, has excellent industrial practicality, does not generate a low-boiling compound at the time of curing, cures quickly at a relatively low temperature, Provides a cured product with excellent heat resistance, chemical resistance and mechanical properties. Further, the curable composition of the present invention can be easily prepared because the step of synthesizing a special compound such as a hydrosilyl group-containing imide compound can be omitted. Further, since the curable composition of the present invention is composed of a low-viscosity liquid component, it is excellent in workability.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4J031 AA57 AA59 AB04 AC13 AE15 AF11 AF13 AF24 AF26 4J043 PA04 QB31 RA34 RA35 RA36 RA37 SA05 SA06 SB01 SB02 TA22 TB01 TB02 UA122 UA131 UA132 UA262 UB012 UB022 UB121A ZB02 ZB48

Claims (2)

[Claims] (A) 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 represents a monovalent organic group having 2 to 20 carbon atoms having a carbon-carbon double bond, and two R ³ 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 carbon-carbon double bond. The two R ⁶ may be the same, or at least one imide compound selected from the group consisting of imide compounds represented by the different may be), (B) at least two hydrosilyl in a molecule A curable composition comprising: a compound having a group; and (C) a hydrosilylation catalyst. 2. Component (B) contains at least 2 components per molecule.
The curable composition according to claim 1, which is a polysiloxane having one hydrosilyl group.