JP2692517B2 - Thermosetting resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermosetting resin composition which gives a cured product excellent in workability, adhesiveness and heat resistance.

[0002]

2. Description of the Related Art Thermosetting resin compositions are used as materials for casting, impregnation, lamination, and molding, as various electric insulating materials, structural materials, adhesives, and the like. In recent years, the use conditions of the materials in these applications tend to be strict, and the heat resistance of the materials has become an important requirement.

[0003] However, thermosetting polyimide resins generally used in thermosetting resin compositions have good heat resistance, but require long-time heating at a high temperature during processing, resulting in poor processability. Was something. Epoxy resins with improved heat resistance are excellent in processability but insufficient in high-temperature mechanical properties, electrical properties, long-term heat deterioration resistance, and high heat resistance.

[0004] Therefore, as alternative materials, for example, a thermosetting resin mixture containing polyimide and alkenylphenol or alkenylphenol ether (JP-A-52-994), a maleimide compound, a polyallylated phenol compound and an epoxy compound A heat-resistant resin composition containing a resin (JP-B-57-28416) has been proposed.

However, the polyallylated phenolic compound used here is a compound obtained by subjecting a polyallyl ether compound to Claisen transition or having a structure in which a phenolic hydroxyl group is generated by Claisen transition during heat curing. The nucleus-substituted allyl group and the hydroxyl group or the ether group are located at the ortho position of the same aromatic ring, and particularly in the case of a novolak-type resin composition, they tend to remain unreacted even after curing, and have high-temperature curing properties and heat resistance. There was a problem in deterioration and the like. In addition, the adhesiveness was insufficient, and did not sufficiently satisfy the usage conditions of recent materials.

The present invention has been made in view of the above circumstances, and provides a thermosetting resin composition which gives a cured product having good workability and excellent heat resistance, low thermal expansion, low water absorption, and adhesion. The purpose is to provide.

[0007]

Means for Solving the Problems and Actions The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, (A) an imide compound having a maleimide group represented by the following formula [I], (B) A resin having at least two epoxy groups in one molecule, (C) a resin having a phenolic hydroxyl group in one molecule, (D) a thermoplastic resin, and the following general formula in the component (B): A compound having a resin represented by [II] and having an allyl group-containing naphthalene ring and a compound having a naphthalene ring having a double bond conjugated to an aromatic group in the entire components (B) and (C) A thermosetting resin composition containing both of them has good processability at an appropriate curing rate, and has high adhesiveness, and also has good mechanical strength and hot water resistance at high temperature, low expansion and low water absorption. Excellent cured product It was found to be obtained.

[0008]

Embedded image (However, in the formula, R ¹ is the same or different group selected from a hydrogen atom, a halogen atom and an alkyl group having 1 to 5 carbon atoms, m
Is an integer of 0 to 4, and q is an integer of 0 to 5. )

That is, although a compound having a maleimide group generally has a large effect of imparting heat resistance, a thermosetting resin composition containing this compound has problems in long-term heat resistance, adhesiveness, water absorption, and processability. Together with the imide group-containing compound having a maleimide group of the above formula [I], the above formula [II]
With a biphenyl type epoxy resin represented by, a compound having an allyl group-containing naphthalene ring and a compound having a naphthalene ring having a double bond conjugated with an aromatic group, and a thermoplastic resin in combination, the adhesiveness is improved, The aliphatic double bond in the maleimide group-containing compound and the compound having the allyl group-containing naphthalene ring and the aliphatic double bond in the compound containing the naphthalene ring having a double bond conjugated with the aromatic group are at an appropriate rate. React to form a copolymer,
Furthermore, it was found that a thermoplastic resin was added to form a composite, and therefore a thermosetting resin composition having the above-described excellent properties can be obtained.

Further, in addition to the above components, a copolymer obtained by reacting an aromatic polymer with an organopolysiloxane represented by the following compositional formula [III] is added to the above thermosetting resin composition. It was also found that the stress property can be reduced, and the present invention was completed.

[0011]

Embedded image (However, in the formula, R ² represents an organic group, an alkoxy group or an alkenyloxy group containing any functional group selected from a hydrogen atom, a hydroxyl group, an amino group, an epoxy group and a carboxyl group, and R ³ is a substituted group. Alternatively, it represents an unsubstituted monovalent hydrocarbon group, and a and b are 0.001 ≦ a ≦ 1, 1
It is a positive number satisfying ≦ b ≦ 3 and 1 ≦ a + b <4. Further, the number of silicon atoms in one molecule is an integer of 2 to 1,000, and the number of R ² directly linked to the silicon atom in one molecule is an integer of 1 or more. )

Therefore, the present invention contains the above-mentioned components (A) to (D), and includes the resin represented by the above formula [II] in the above-mentioned component (B), as well as the above-mentioned components (B) and (C). ) A thermosetting resin composition containing both a compound having an allyl group-containing naphthalene ring and a compound having an aromatically conjugated double bond in the entire component, and an aromatic compound in addition to these components. Group polymer and the above formula [II
There is provided a thermosetting resin composition to which a copolymer obtained by reacting the organopolysiloxane of I] is added.

Hereinafter, the present invention will be described in more detail. The imide compound to be added to the thermosetting resin composition of the present invention is a compound having at least one maleimide group represented by the following formula [I].

[0014]

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In the present invention, among the imide compounds having a maleimide group of the above formula [I], the following formula [I
A compound having an N-substituted maleimide group represented by V] is preferably used.

[0016]

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Here, the substituent R ⁴ is a divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms or a divalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and examples thereof include the following groups. be able to.

[0018]

Embedded image (However, R ⁵ is an alkyl group having 1 to 4 carbon atoms or a halogen atom, and an integer of c ≧ 1. The same applies hereinafter.)

Specific examples of the compound having such an N-substituted maleimide group include N, N'-diphenylmethanebismaleimide, N, N'-phenylenebismaleimide,
N, N'-diphenyl ether bismaleimide, N,
N'-diphenylsulfone bismaleimide, N, N'-
Dicyclohexylmethane bismaleimide, N, N'-xylene bismaleimide, N, N'-tolylenbismaleimide, N, N'-xylylenebismaleimide, N, N '
-Diphenylcyclohexanebismaleimide, N, N '
-Dichloro-diphenylbismaleimide, N, N'-diphenylmethanebismethylmaleimide, N, N'-diphenyletherbismethylmaleimide, N, N'-diphenylsulfonebismethylmaleimide (each including isomers), N, N'- Ethylene bismaleimide, N,
N, N'-bismaleimide compounds such as N'-hexamethylenebismaleimide, N, N'-hexamethylenebismethylmaleimide, and the terminal obtained by adding these N, N'-bismaleimide compounds and diamines have N , N'-
A prepolymer having a bismaleimide skeleton, aniline,
A maleimidated product of methyl formalin, a methylmaleimidated product, and the like can be exemplified.

As the imide compound, a compound represented by the following formula, a mono-substituted maleimide, a tri-substituted maleimide, or a mixture of a tetra-substituted maleimide and a substituted bismaleimide can also be used.

[0021]

Embedded image (However, R ⁵ is a hydrogen atom, a halogen atom or a C 1 -C 1
The alkyl group of 4, d is an integer of 1 ≦ d ≦ 20. )

Further, it is also possible to use a compound obtained by modifying the above maleimide compound with silicone.

Furthermore, N-methyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-allyl-allylbicyclo [2.2.1]
Hept-5-ene-2,3-dicarboximide, N-
(2-ethylhexyl) -allylbicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide,
N-cyclohexyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-phenyl-allylbicyclo [2.2.1] hept-5-ene-2,3- Dicarboximide, N-benzyl-allylbicyclo [2.2.1] hept-5-ene-2,3-
Dicarboximide, N, N'-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-
Dicarboximide), N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide), N, N'-dodecamethylene-bis (allylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximide), bis [4-
(Allylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboximidophenyl)]-methane, bis [4- (methacrylicicyclo [2.2.1] hept-
5-ene-2,3-dicarboximidophenyl)]-
Methane, N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), bis [4- (allylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximidophenyl) ether, bis [4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximidophenyl) )] Sulfone, N-allyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3
-Dicarboximide, N- (2-ethylhexyl)-
Allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-phenyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,
3-dicarboximide, N, N'-hexamethylene-
Bis (allylmethylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximide), bis [4-allylmethylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboximidophenyl] methane and bis [4- (methacrylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximidophenyl)] sulfone are also exemplified.

In the present invention, one of these imide compounds may be used alone or two or more of them may be used in combination. Among them, N-substituted trimaleimide, N-substituted bismaleimide, In particular, N, N'-diphenylmethane bismaleimide is preferably used.

On the other hand, the component (B) of the present invention is an epoxy resin having two or more epoxy groups in one molecule, and glycidyl such as bisphenol A type epoxy resin, phenol novolac type epoxy resin and allylphenol novolac type epoxy resin. Ether type epoxy resin, triphenol alkane type epoxy resin and its polymer, naphthalene type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, phenol aralkyl type epoxy resin, glycidyl ester type epoxy resin,
Alicyclic epoxy resin, heterocyclic epoxy resin, halogenated epoxy resin, epoxy resin having a substituted or unsubstituted allyl group-containing naphthalene ring in one molecule in part or all of the epoxy resin, aromatic group An epoxy resin having at least one naphthalene ring having a conjugated double bond (eg, 1-propylene group, 1-butylene group, etc.) can be used. Among these, it is preferable to use the above-mentioned epoxy resin having an allyl group-containing naphthalene ring and an epoxy resin having a naphthalene ring having a double bond conjugated to an aromatic group, which results in a small expansion coefficient and low hygroscopic curing. A thermosetting resin composition that gives a product can be obtained.

Specific examples of the naphthalene ring-containing epoxy resin include the following compounds.

[0027]

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[0028]

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The above epoxy resins may be used alone or in admixture of two or more.

The thermosetting resin composition of the present invention contains a biphenyl type epoxy resin represented by the following formula [II] in the epoxy resin of the above-mentioned component (B). Good flowability and improved adhesion to the substrate.

[0031]

Embedded image (However, in the formula, R ¹ is the same or different group selected from a hydrogen atom, a halogen atom and an alkyl group having 1 to 5 carbon atoms, m
Is an integer of 0 to 4, and q is an integer of 0 to 5. )

Specific examples of the epoxy resin represented by the formula [II] include the following compounds.

[0033]

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The compounding amount of the epoxy resin represented by the formula [II] is 50% by weight or less in the epoxy resin as the component (B),
It is particularly preferable to set it in the range of 20 to 30% by weight. 5
If it is blended in an amount of more than 0% by weight, the epoxy resin represented by the formula [II] is bifunctional, so that the glass transition temperature may be lowered and problems such as heat resistance may occur.

Next, the resin having a phenolic hydroxyl group in one molecule of the component (C) of the present invention acts as a curing agent. For example, novolac type phenol resin, resol type phenol resin, triphenol alkane type resin. , Phenol resins such as naphthol type resins and biphenyl type phenol resins, phenol aralkyl resins, phenol resins containing a substituted or unsubstituted allyl group-containing naphthalene ring in one molecule, and a double bond conjugated to an aromatic group (for example, 1 A phenol resin having at least one naphthalene ring having a propylene group, a 1-butylene group, etc.), and these can be used alone or in combination of two or more.

Among the above-mentioned phenol resins, it is preferable to use a phenol resin having an allyl group-containing naphthalene ring and a phenol resin having a naphthalene ring having a double bond conjugated to an aromatic group, as the curing agent.
Due to this, the expansion coefficient is small, the glass transition temperature is high,
It is possible to obtain a thermosetting resin composition that has a low elastic modulus in a temperature range of the glass transition temperature or higher and that gives a cured product with low hygroscopicity. Specific examples of the naphthalene ring-containing phenol resin include the following compounds.

[0037]

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It should be noted that these epoxy resin or phenol resin containing an allyl group-containing naphthalene ring and epoxy resin or phenol resin having a naphthalene ring having a double bond conjugated to an aromatic group should be synthesized by a usual method. For example, after allyl etherification of a phenol resin, a Claisen rearrangement reaction is performed to obtain an allyl group-containing phenol resin, which is further rearranged using an alkali catalyst to be conjugated with an aromatic group. A phenol resin having a double bond (propenyl group) can be obtained. Further, the desired epoxy compound can be obtained by a conventional method using epichlorohydrin.

In the composition of the present invention, the total amount of the above-mentioned components (B) and (C) is 20 to 400 relative to 100 parts (parts by weight, the same applies hereinafter) of the imide compound of the component (A).
Parts, particularly preferably 50 to 300 parts. (B)
If the total amount of component (C) and component (C) is less than 20 parts, it may be difficult to obtain a cured product having excellent workability and heat resistance. May be worse.

The ratio of the amount of epoxy groups (amol) contained in the component (B) to the amount of phenolic hydroxyl groups contained in the component (C) (b mol) is a / b = 0.5 to 1 It is desirable to be in the range of 0.5, and if a / b is out of the above range, it may be disadvantageous in terms of curability and low stress.

Examples of the thermoplastic resin as the component (D) of the present invention include styrene-butadiene-methyl methacrylate copolymer (MBS resin), styrene-ethylene-butene-styrene copolymer (SBS resin), polybutadiene rubber. , Polyisoprene rubber, styrene-butadiene-vinylpyridine copolymer, acrylonitrile-butadiene-
Styrene copolymer (ABS resin), acrylonitrile
Styrene copolymer (AS resin), styrene-isoprene copolymer, vinylidene fluoride resin, carboxy-modified butadiene-acrylonitrile copolymer, thermoplastic resin nylon, polybutylene terephthalate resin, polybutene
1, polyvinylhexyl resin, polyvinyl acetoacetal resin, polyvinyl butyral resin, polyvinyl formal resin, polyvinyl ether resin, polyester elastomer, polyurethane-methyl methacrylate copolymer and the like polymers, among which styrene-butadiene-methacrylic acid. A methyl copolymer is preferred.

These thermoplastic resins are contained in an amount of 10 to 50 parts, particularly 10 to 100 parts, relative to 100 parts of the imide compound as the component (A).
Preferably it is 20 parts. If it is 10 parts or less, the adhesiveness may deteriorate, while if it is 50 parts or more, the fluidity of the thermosetting resin composition may deteriorate.

Thus, the composition of the present invention has the above-mentioned (A),
(B), (C) and (D) are blended, and the compound containing an allyl group-containing naphthalene ring in the whole of (B) component and (C) component is conjugated with an aromatic group. And a compound having a naphthalene ring having a double bond. That is, at least one of the component (B) and the component (C) simultaneously contains a compound having an allyl group-containing naphthalene ring and a compound having a naphthalene ring having a double bond conjugated to an aromatic group. Alternatively, both of the above compounds may be simultaneously contained in both the component (B) and the component (C), and one compound in the component (B), (C)
The component may contain the other compound.

As described above, the composition of the present invention comprises a compound containing an allyl group-containing naphthalene ring and a naphthalene ring having a double bond conjugated to an aromatic group in the entire components (B) and (C). Containing both the compound and
The object of the present invention cannot be achieved by only one of the two.

That is, when an epoxy resin or a phenolic resin having a naphthalene ring having an allyl group is used alone, the radical reactivity between the vinyl group of the allyl group and the vinyl group of the imide compound is low, so the curing speed becomes slow. Therefore, there is a problem of curing failure.

On the other hand, when an epoxy resin or a phenol resin having a naphthalene ring having a double bond conjugated to an aromatic group is used alone, the radical reactivity between the vinyl group of the conjugated double bond and the vinyl group of the imide group is increased. Therefore, since the curing rate is too high, there is a problem in that the moldability is unfilled.

In the composition of the present invention, a resin having a naphthalene ring having an allyl group and a resin having a double bond conjugated to an aromatic group are used in combination to obtain a good molding at an appropriate curing rate. It has a sex. In this case, the ratio of the resin having a naphthalene ring having an allyl group to the resin having a double bond conjugated to an aromatic group is such that the allyl group on the naphthalene ring is a ′ (mole) and the resin conjugated to an aromatic group is two. When the heavy bond is b '(mol), the ratio of b' / a 'is preferably 0.1 to 10, and more preferably 0.2 to 8.

In the compound having an allyl group-containing naphthalene ring and the compound having a naphthalene ring having a double bond conjugated to an aromatic group, the substituted or unsubstituted naphthalene ring has a component (B) and a component (C). It is desirable to mix such that the content of the naphthalene ring is less than 10% by weight based on 100 parts by weight of the total weight of the components. Since the effect of lowering the elastic modulus in the temperature range is not remarkable, the crack resistance may not be sufficiently improved. If the naphthalene ring content exceeds 80% by weight, dispersibility during production,
Further, it may be disadvantageous in terms of moldability.

Further, in the present invention, the aliphatic C═C double bond (A ′) and (B) in the imide compound of the component (A) are used.
With aliphatic C = C double bond (B ') in compound containing allyl group-containing naphthalene ring and compound having double bond conjugated to aromatic group contained in component (C) It is preferable that the base ratio B ′ / A ′ is 0.1 to 2, particularly 0.3 to 1. When B '/ A' is larger than 2 and the ratio of the allyl group and the conjugated double bond is large, the unreacted material increases, causing a problem in the curability and deteriorating the long-term heat resistance and reliability of the cured product. In some cases, when B '/ A' is smaller than 0.1 and the ratio between the allyl group and the conjugated double bond is small, problems may occur in the moldability and mechanical strength.

The composition of the present invention is preferably blended with a copolymer obtained by reacting an aromatic polymer with a specific organopolysiloxane, if necessary, in order to impart low stress.

As the aromatic copolymer, various compounds may be used, and examples thereof include compounds having the following structures.

[0052]

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[0053]

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Further, an alkenyl group-containing naphthalene resin represented by the following formula can be used as the aromatic polymer.

[0055]

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These alkenyl group-containing naphthalene resins can be obtained by a usual synthetic method. For example, a naphthalene skeleton-containing phenol resin is reacted with allyl glycidyl ether to introduce an alkenyl group into the molecule,
It can be easily obtained by a method such as partially reacting 2-allylphenol or the like with various naphthalene skeleton-containing epoxy resins.

On the other hand, the organopolysiloxane is represented by the following composition formula [III].

[0058]

Embedded image (However, in the formula, R ² represents an organic group, an alkoxy group or an alkenyloxy group containing any functional group selected from a hydrogen atom, a hydroxyl group, an amino group, an epoxy group and a carboxyl group, and R ³ is a substituted group. Alternatively, it represents an unsubstituted monovalent hydrocarbon group, and a and b are 0.001 ≦ a ≦ 1, 1
It is a positive number satisfying ≦ b ≦ 3 and 1 ≦ a + b <4. Further, the number of silicon atoms in one molecule is an integer of 2 to 1,000, and the number of R ² directly linked to the silicon atom in one molecule is an integer of 1 or more. )

In this case, the substituent R ² is, for example, a hydrogen atom,
An organic group containing a functional group selected from a hydroxyl group, an amino group, an epoxy group and a carboxyl group, an alkoxy group such as a methoxy group, an ethoxy group, an n-propoxy group, a butoxy group, a methoxyethoxy group, and an ethoxyethoxy group; And an oxy group. R ³ is, for example, an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an alkenyl group such as a vinyl group or an allyl group, an aryl group such as a phenyl group or a tolyl group, a benzyl group or a phenyl group. An aralkyl group such as an ethyl group, or a chloromethyl group obtained by substituting a part or all of hydrogen atoms of these groups with a halogen atom, an alkoxysilyl group or the like, 3,
It is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms such as a 3,3-trifluoropropyl group, a trimethoxysilylethyl group, and a methyldimethoxysilylethyl group.

Specific examples of the organopolysiloxane of the above formula [III] include the following compounds.

[0061]

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Here, the molecular weight of the organopolysiloxane of the above formula [III] is not necessarily limited, but 10
0-70000 is preferable. This is because when the obtained copolymer is blended with a thermosetting resin composition, the copolymer of the aromatic polymer and the organopolysiloxane is not compatible with the matrix, and forms a fine sea-island structure. This is because the molecular weight of the organopolysiloxane is suitably 100 to 70,000. When the molecular weight is less than 100, flexibility may not be imparted when the copolymer obtained is blended in a thermosetting resin composition, or a high glass transition temperature may not be obtained. When it exceeds the above range, the molecular weight of the organopolysiloxane copolymer becomes large, the compatibility with the thermosetting resin is lost, the copolymer is separated, and the flexural strength as a physical property may be reduced.

The copolymer of the above aromatic polymer and the organopolysiloxane of the formula [III] can be obtained by subjecting both compounds to an addition reaction by a usual method. In particular, the addition reaction of the aromatic polymer and the organopolysiloxane of the formula [III] by hydrosilylation is the most excellent method for obtaining the copolymer as set. In the addition reaction, a conventionally known addition catalyst, for example, a platinum-based catalyst such as chloroplatinic acid is used in a catalytic amount, and an inert solvent such as benzene, toluene, and methyl isobutyl ketone is preferably used.
The reaction temperature is not particularly limited, but is preferably from 60 to 120 ° C, and the reaction time is usually from 30 minutes to 24 hours. Further, a copolymer of an aromatic polymer and aminopolysiloxane or epoxypolysiloxane can be obtained by reacting the respective components at room temperature or high temperature, but both are mixed in a uniform or nearly uniform state. For example, it is desirable to use a solvent such as methyl isobutyl ketone, toluene, dioxane, and methyl cellosolve, and water or butanol to further accelerate the reaction,
Alcohols and phenols such as isopropyl alcohol and ethanol are used, amines such as tributylamine and 1,8-diazabicycloundecene-7 as reaction catalysts, organic phosphines such as triphenylphosphine and 2-phenyl. It is desirable to use imidazoles such as imidazole.

In the composition of the present invention, the crosslinking bond between the imide compound having the maleimide group of the formula [I], the compound having an allyl group-containing naphthalene ring and the compound having a double bond conjugated to an aromatic group is completed. Therefore, it is preferable to add a curing catalyst.

In this case, as the curing catalyst, for example, benzoyl peroxide, parachlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide,
Caprylic peroxide, lauroyl peroxide,
Acetyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, bis (1-
(Hydroxycyclohexyl peroxide), hydroxyheptyl peroxide, tertiary butyl hydroperoxide, p-methane hydroperoxide, cumene hydroperoxide, di-tertiary butyl peroxide, dicumyl peroxide, 2,5-dimethyl −
2,5-di (tert-butyl peroxide) hexane,
2,5-dimethylhexyl-2,5-di (peroxybenzoate), tertiary butyl perbenzoate, tertiary butyl peracetate, tertiary butyl peroctoate, tertiary butyl peroxyisobutyrate, Organic peroxides such as di-tert-butyl-di-perphthalate can be mentioned, and one of these can be used alone or in combination of two or more.

Further, it is preferable to use various curing accelerators for the purpose of promoting the crosslinking reaction. Examples of the curing accelerator include triphenylphosphine, tricyclohexylphosphine, tributylphosphine, methyldiphenylphosphine, 1,2-bis (diphenylphosphino).
Organic phosphine compounds such as ethane and bis (diphenylphosphino) methane, 1,8-diazabicyclo [5.
4.0] Tertiary amines such as undecene-7, imidazoles and the like can be mentioned, and these can be used alone or in combination of two or more within a range not impairing the object of the present invention.

The total blending amount of the curing catalyst and the curing accelerator is 10 (A), (B), (C) and (D).
The amount is preferably 0.01 to 10 parts, particularly preferably 0.1 to 2 parts with respect to 0 parts. When the amount of the catalyst is less than 0.01 part, the curability is insufficient, so that good performance may not be obtained. On the other hand, when the amount exceeds 10 parts, the curability is increased, and the moldability may be deteriorated.

Furthermore, the composition of the present invention may optionally contain an inorganic filler.

As the inorganic filler, those which are usually blended in the thermosetting resin composition can be used. Examples thereof include silicas such as fused silica and crystalline silica, alumina, carbon black, mica, clay, kaolin and glass. Examples thereof include beads, glass fibers, aluminum nitride, silicon carbide, zinc oxide, antimony trioxide, calcium carbonate, aluminum hydroxide, beryllium oxide, boron nitride, titanium oxide, iron oxide and the like.

One of these inorganic fillers may be used alone, or two or more thereof may be used in combination. The compounding amount thereof is not particularly limited, but (A), (B),
The total amount of the components (C) and (D) and the catalyst amount is 100 to 1000 parts, and particularly preferably 200 to 800 parts.

The composition of the present invention may further contain various additives if necessary. For example, organic synthetic rubber, fine powder of a cured product of silicone gel or silicone rubber, waxes such as carnauba wax, release agents such as fatty acids such as stearic acid and metal salts thereof, carbon black, cobalt blue, pigments such as red iron oxide, Flame retardants such as antimony oxide and halogen compounds, surface treatment agents (aminopropyltrimethoxysilane, methacryloxytrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, etc.), epoxysilanes, vinylsilanes, boron compounds, alkyls One or more coupling agents such as titanate, antiaging agents, and other additives can be blended.

In the production of the thermosetting resin composition of the present invention, predetermined amounts of the above-mentioned components are uniformly stirred and mixed, and kneaded by a kneader, roll, extruder or the like which has been heated to 70 to 95 ° C. in advance. It can be obtained by methods such as cooling, crushing, and the like. Here, there is no particular limitation on the order of compounding the components.

The thermosetting resin composition of the present invention can be suitably used as a molding material, a powder coating material, an adhesive agent, etc., and can also seal semiconductor devices such as ICs, LSIs, transistors, thyristors and diodes. It can also be used effectively for manufacturing and printed circuit boards.

[0074]

The thermosetting resin composition of the present invention has low stress, high adhesiveness, good workability, and excellent mechanical strength and hot water resistance at high temperatures, heat resistance, and low water absorption. Gives cured products with excellent properties. Therefore, the composition of the present invention sufficiently satisfies the recent use conditions of the thermosetting resin composition, and various electric insulating materials, structural materials, adhesives, powder coating materials,
It is useful as a semiconductor sealing material.

[0075]

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, all parts are parts by weight.

[Examples 1 to 14, Comparative Examples 1 to 5] N,
N'-4,4'-diphenylmethane bismaleimide 40
Parts, epoxy resin, phenol resin, styrene-
A butadiene MMA copolymer, a butyral resin, and a curing catalyst were used in the amounts shown in Table 1, and 260 parts of quartz powder, 1.5 parts of γ-glycidoxypropyltrimethoxysilane, 1.5 parts of wax E, 1.0 part of carbon black was added, and the obtained blend was uniformly melt-mixed with a hot two-roll to produce 19 kinds of thermosetting resin compositions (Examples 1 to 14 and Comparative Examples 1 to 5). did.

The following tests (a) to (g) were conducted on these thermosetting resin compositions. The results are shown in Tables 1 to 3.
Shown in (A) Spiral flow value Using a mold conforming to EMMI standard, 175 ° C, 70
It was measured under the condition of kg / cm ² . (B) Mechanical strength (flexural strength and flexural modulus) 180 ° C, 70 kg / cm according to JIS-K6911
^{2. A} bending rod of 10 × 4 × 100 mm was molded under the condition of molding time of 2 minutes, and post-cured at 180 ° C. for 4 hours, and measured at 215 ° C. (C) Using a test piece having a glass transition temperature of 4 mmφ × 15 mm, the value when the temperature was raised at a rate of 5 ° C./min was measured by a deratometer. (D) Crack resistance after moisture absorption soldering 4 × 1 silicon chips having a size of 2 × 6 × 0.3 mm
The thermosetting resin composition was bonded to a 2 × 1.8 mm SO package, molded at 175 ° C. for 2 minutes, and post-cured at 180 ° C. for 4 hours. 85 ° C / 85% RH
After standing for 24 and 48 hours in an atmosphere of
It was immersed in a solder bath at 40 ° C. for 10 seconds, and the number of package cracks / total number was measured. (E) A moisture-resistant 4M DRAM chip is bonded to a 20-pin SOJ frame, and a thermosetting resin composition is formed thereon at a molding condition of 180 ° C. ×
It was molded in 2 minutes and post-cured at 180 ° C. for 4 hours.
This was left to stand in a 121 ° C / 100% RH atmosphere for 24 hours to absorb moisture, then immersed in a solder bath at 260 ° C for 10 seconds, and then left to stand in a 121 ° C / 100% RH atmosphere for 300 hours. The number of wire breaks / total number was measured. (F) Water absorption of 180 ° C., 70 kg / cm ² , molding time of 2 minutes 5
A 0φ × 3 mm disc was molded and post-cured at 180 ° C. for 4 hours.
It was left for a while, and the water absorption was measured. (G) Test piece with adhesiveness of 0.5 x 20 x 20 mm (42 alloy)
A molded product having a shape as shown in FIG. 2 was molded at 175 ° C. for 2 minutes and after-cured at 180 ° C. for 4 hours to obtain a molded product. The obtained molded product was pulled in the direction of the arrow shown in the drawing, and the adhesive force (kg) was measured.

[0078]

[Table 1]

[0079]

[Table 2]

[0080]

[Table 3]

[0081]

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[0082]

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[0083]

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[0084]

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From the results shown in Tables 1 to 3, the heat of blending the biphenyl type epoxy resin according to the present invention, the maleimide compound, the allyl group-containing naphthalene compound, the naphthalene resin having a double bond that is conjugated to an aromatic group, and the thermoplastic resin are shown. The curable resin compositions (Examples 1 to 14) have higher bending strength at high temperature at high glass transition point than the thermosetting resin compositions (Comparative Examples 1 to 5) not containing these components, It was confirmed that it is excellent in crack resistance, moisture resistance, water absorption and adhesiveness.

[Brief description of the drawings]

FIG. 1 is a schematic view of a molded product used for an adhesion test.

FIG. 2 is a schematic diagram showing a tensile direction in an adhesion test.

[Explanation of symbols]

 1 Molded product 2 Test piece

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Minoru Takei Minoru 1 Hitomi, Oita, Matsuida-cho, Usui-gun, Gunma Prefecture Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory (56) Reference JP-A-5-43658 ( JP, A) JP 5-43659 (JP, A) JP 5-222164 (JP, A) JP 5-112630 (JP, A) JP 4-300914 (JP, A) JP Flat 4-300915 (JP, A)

Claims (2)

(57) [Claims] (A) an imide compound having a maleimide group represented by the following formula [I]: (B) a resin having at least two epoxy groups in one molecule, (C) a resin having a phenolic hydroxyl group in one molecule, (D) a thermoplastic resin, and the following in the component (B): General formula [II] (However, in the formula, R ¹ is the same or different group selected from a hydrogen atom, a halogen atom and an alkyl group having 1 to 5 carbon atoms, m
Is an integer of 0 to 4, and q is an integer of 0 to 5. And a compound having an allyl group-containing naphthalene ring and a compound having a naphthalene ring having a double bond that is aromatically conjugated, in the entire components (B) and (C). A thermosetting resin composition comprising: 2. The thermosetting resin composition according to claim 1, wherein a copolymer obtained by reacting an aromatic polymer with an organopolysiloxane represented by the following composition formula [III] is added. Embedded image (However, in the formula, R ² represents an organic group, an alkoxy group or an alkenyloxy group containing any functional group selected from a hydrogen atom, a hydroxyl group, an amino group, an epoxy group and a carboxyl group, and R ³ is a substituted group. Alternatively, it represents an unsubstituted monovalent hydrocarbon group, and a and b are 0.001 ≦ a ≦ 1, 1
It is a positive number satisfying ≦ b ≦ 3 and 1 ≦ a + b <4. Further, the number of silicon atoms in one molecule is an integer of 2 to 1,000, and the number of R ² directly linked to the silicon atom in one molecule is an integer of 1 or more. )