JPH06211963A - Thermosetting resin composition - Google Patents

Abstract

PURPOSE:To provide the subject composition which can give a cured product having low stress, high adhesiveness, good processability, excellent high- temperature mechanical strengths, hot water resistance and heat resistance, and low water absorptivity. CONSTITUTION:This resin composition comprises an imide compound (A) having a maleimide group of the formula, a compound (B) having at least two epoxy groups in the molecule, a compound (C) having a phenolic hydroxyl group in the molecule and a thermoplastic resin (D). A fluorine-containing compound is used as components B and/or C, and both a compound having an allylated naphthalene ring and a compound having a naphthalene ring double having bonds conjugated with the double bonds of the aromatic ring are contained in components B and/or C.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a thermosetting resin composition which gives a cured product having excellent processability and heat resistance.

[0002]

2. Description of the Related Art Thermosetting resin compositions are used as various electrical insulating materials, structural materials, adhesives, etc. as casting, impregnating, laminating and molding materials. In recent years, the usage conditions of materials have tended to be severe in each of these applications, and the heat resistance of materials has become an important requirement.

However, the thermosetting polyimide resin generally used in the thermosetting resin composition has good heat resistance, but it requires heating at a high temperature for a long time at the time of processing and is inferior in processability. It was a thing. Further, although the epoxy resin having improved heat resistance has excellent processability, it has insufficient mechanical properties at high temperature, electrical properties, long-term heat deterioration resistance, and high heat resistance.

Therefore, as a substitute material, for example, a thermosetting resin mixture containing polyimide and alkenylphenol or alkenylphenol ether (JP-A-52-994), maleimide compounds, polyallylated phenol compounds and epoxies. A heat resistant resin composition containing a resin (Japanese Patent Publication No. 57-28416) has been proposed.

However, the polyallylated phenolic compound used here has a structure in which a phenolic hydroxyl group is formed by the Claisen transition during heat curing, or the polyallyl ether compound has a structure in which a phenolic hydroxyl group is produced by the Claisen transition during heat curing. The nucleus-substituted allyl group and the hydroxyl group or ether group are located at the ortho position of the same aromatic ring, and particularly in the case of a novolac type resin composition, it tends to remain unreacted even after curing, curing characteristics at high temperature, heat resistance There was a problem with degradability. Moreover, the adhesiveness is insufficient, and it has not sufficiently satisfied 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 property, low water absorption property, and adhesiveness. The purpose is to provide.

[0007]

Means for Solving the Problems and Actions The inventors of the present invention have conducted extensive studies in order to achieve the above object, and as a result, (A) an imide compound having a maleimide group represented by the following general formula [I], (B) ) A compound having at least two epoxy groups in one molecule, (C) a compound having a phenolic hydroxyl group in one molecule, (D) a thermoplastic resin, and the components (B) and (C) described above. And a compound having a naphthalene ring containing an allyl group in either or both of the component (B) and the component (C), and a double bond conjugated to aromatic The thermosetting resin compositions each containing a compound having a naphthalene ring have a good workability at an appropriate curing rate, yet have high adhesiveness, and have high mechanical strength and hot water resistance at high temperatures. In good, it was found to give low expansion, a cured product excellent in low water absorption.

[0008]

[Chemical 3]

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. Is a compound having a fluorine atom-containing compound, 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, together with the imide group-containing compound having a maleimide group of the above formula [I], and When used together with a thermoplastic resin, the adhesiveness is improved, and a compound having an aliphatic double bond and an allyl group-containing naphthalene ring in a maleimide group-containing compound and a naphthalene ring having a double bond conjugated with an aromatic group are formed. Aliphatic double bond in the compound containing reacts at an appropriate rate to form a copolymer, and further becomes a complex by addition of a thermoplastic resin, It is therefore to finding that the thermosetting resin composition is obtained having excellent properties as described above.

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

[0011]

[Chemical 4] (However, in the formula, R ¹ 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 ² 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 that satisfies ≦ b ≦ 3 and 1 ≦ a + b <4. Further, the number of silicon atoms in one molecule is an integer of 2 to 1000, and the number of R ¹ directly linked to the silicon atoms in one molecule is an integer of 1 or more. )

Therefore, in the present invention, a compound containing the above-mentioned components (A) to (D) and containing a fluorine atom in either or both of the above-mentioned components (B) and (C) is used. A thermosetting resin composition containing both of 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 in the entire components B) and (C), and There is provided a thermosetting resin composition containing, in addition to these components, a copolymer obtained by reacting an aromatic polymer with an organopolysiloxane of the above formula [II].

The present invention will be described in more detail below. The imide compound incorporated into the thermosetting resin composition of the present invention is a compound having one or more maleimide groups represented by the following formula [I].

[0014]

[Chemical 5]

In the present invention, among the imide compounds of the above formula [I], compounds having an N-substituted maleimide group represented by the following formula [III] are particularly preferably used.

[0016]

[Chemical 6]

Here, the substituent R³ Is a divalent carbon number 6 to
20 aliphatic hydrocarbon groups or aromatic carbons having 6 to 20 carbon atoms
A hydrogenated group, for example, the following groups can be mentioned.
It

[0018]

[Chemical 7] (However, R ⁴ 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'-diphenylmethane bismaleimide, N, N'-phenylene bismaleimide,
N, N'-diphenyl ether bismaleimide, N,
N'-diphenylsulfone bismaleimide, N, N'-
Dicyclohexylmethane bismaleimide, N, N'-xylene bismaleimide, N, N'-tolylene bismaleimide, N, N'-xylylene bismaleimide, N, N '
-Diphenylcyclohexane bismaleimide, N, N '
-Dichloro-diphenylbismaleimide, N, N'-diphenylmethanebismethylmaleimide, N, N'-diphenyletherbismethylmaleimide, N, N'-diphenylsulfonebismethylmaleimide (each containing an isomer), N, N'- Ethylene bismaleimide, N,
N, N'-bismaleimide compounds such as N'-hexamethylene bismaleimide and N, N'-hexamethylene bismethyl maleimide, and the terminal obtained by adding these N, N'-bismaleimide compounds and diamines is N , N'-
A prepolymer having a bismaleimide skeleton, aniline,
Examples thereof include maleimidated products of formalin condensates and methylmaleimidated products.

Further, 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 be used.

[0021]

[Chemical 8] (However, R ⁵ is a hydrogen atom, a halogen atom or a carbon number of 1 to
4 is an alkyl group, and 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- (methacrylbicyclo [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-
Examples include 2,3-dicarboximidophenyl] methane and bis [4- (methacrylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximidophenyl)] sulfone.

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

On the other hand, the component (B) of the present invention is an epoxy compound having two or more epoxy groups in one molecule, and glycidyl such as bisphenol A type epoxy resin, phenol novolac type epoxy resin, allylphenol novolac type epoxy resin and the like. Ether type epoxy resin, triphenol alkane type epoxy resin and its polymer, naphthalene 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, biphenyl type epoxy resin, epoxy resin having a substituted or unsubstituted allyl group-containing naphthalene ring in one molecule in a part or all of epoxy resin, and double bond conjugated to aromatic group Having And an epoxy resin having at least two array type ring. Further, among these, it is preferable to use the above-mentioned epoxy resin having an allyl group-containing naphthalene ring and epoxy resin having a naphthalene ring having a double bond conjugated to an aromatic group, which results in a small expansion coefficient and low hygroscopicity. It is possible to obtain a thermosetting resin composition that gives the cured product of.

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

[0027]

[Chemical 9]

[0028]

[Chemical 10]

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

Next, the compound 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. , Naphthol type resins, phenolic resins such as biphenyl type phenolic resins, phenol aralkyl resins, and resins containing a substituted or unsubstituted allyl group-containing naphthalene ring in one molecule and a naphthalene ring having a double bond conjugated to an aromatic group. Examples thereof include a phenol resin having at least one of these, and these can be used alone or in combination of two or more.

Among the above-mentioned phenol compounds, 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, and the elastic modulus is low in the temperature range above the glass transition temperature
In addition, it is possible to obtain a thermosetting resin composition that gives a cured product with low hygroscopicity. Specific examples of the naphthalene ring-containing phenol resin include the following compounds.

[0032]

[Chemical 11]

The epoxy resin or phenol resin containing the allyl group-containing naphthalene ring and the epoxy resin or phenol resin having the naphthalene ring having a double bond conjugated to the 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 using epichlorohydrin by a conventional method.

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. Among them, 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).
It is preferably 20 parts. If it is 10 parts or less, the adhesiveness will be poor, while if it is 50 parts or more, the fluidity of the thermosetting resin composition will be poor.

Thus, in the composition of the present invention, a compound containing a fluorine atom in either or both of the epoxy compound as the component (B) and the phenol compound as the component (C) is used. Examples of such resins include the following compounds.

[0037]

[Chemical 12]

By using the above-mentioned fluorine atom-containing compound, the fluidity of the thermosetting resin composition is improved, the adhesiveness to the substrate is improved, and the water absorption becomes low. The fluorine atom-containing resin is preferably blended in an amount of 30% by weight or more as a fluorine atom content based on the total weight of the components (B) and (C).
If the content of fluorine atoms is less than 30% by weight, good adhesiveness cannot be obtained.

Further, the composition of the present invention comprises a compound having an allyl group-containing naphthalene ring in either or both of the component (B) and the component (C) and a naphthalene having a double bond conjugated to an aromatic group. And a compound having a ring, respectively. 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. Well, (B) component,
Both of the above compounds may be contained in both of the components (C) at the same time, or one component may be contained in the component (B) and the other compound may be contained in the component (C).

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
Only one of the two cannot achieve the object of the present invention.

That is, when an epoxy compound or a phenol compound 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, and the curing rate becomes slow. Therefore, there is a problem of curing failure.

On the other hand, when an epoxy compound or a phenol compound having a naphthalene ring having a double bond conjugated with an aromatic group is used alone, the radical reactivity of 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 compound having a naphthalene ring having an allyl group and a compound having a double bond conjugated to an aromatic group are used in combination to obtain a favorable molding at an appropriate curing rate. It has a sex. In this case, the ratio of the compound having a naphthalene ring having an allyl group to the compound having a double bond conjugated to an aromatic group is such that the allyl group on the naphthalene ring is a ′ (mole) and the compound conjugated to an aromatic group is two. When the heavy bond is b '(mole), the ratio b' / a 'is preferably 0.1 to 10, more preferably 0.2 to 8.
It is mixed in the range of.

In the compound containing 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. Further, if the content of the naphthalene ring exceeds 80% by weight, it may be disadvantageous in dispersibility during production, moldability and the like.

In the composition of the present invention, the total amount of the above-mentioned components (B) and (C) is 20 to 400 with respect to 100 parts (parts by weight, the same applies hereinafter) of the imide compound of the component (A).
Parts, particularly 50 to 300 parts. (B)
If the total amount of the component and the component (C) is less than 20 parts, it may be difficult to obtain a cured product having excellent processability and heat resistance. If the total amount is more than 400 parts, the glass transition temperature decreases and long-term heat resistance May get worse.

The ratio of the amount of epoxy groups contained in the component (B) (amol) to the amount of phenolic hydroxyl groups contained in the component (C) (bmol) 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.

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 the aliphatic C = C double bond (B ') in the compound containing the allyl group-containing naphthalene ring contained in the component and the component (C) and the compound having a double bond conjugated to the aromatic group The group ratio B ′ / A ′ is preferably 0.1 to 2, and particularly preferably 0.3 to 1. When B ′ / A ′ is larger than 2 and the ratio of allyl group and conjugated double bond is large, unreacted matter is increased, causing a problem in curability, resulting in poor long-term heat resistance and reliability of the cured product. In some cases, if B ′ / A ′ is less than 0.1 and the ratio of the allyl group and the conjugated double bond is small, problems may occur in moldability and mechanical strength.

The composition of the present invention preferably contains a copolymer obtained by reacting an aromatic polymer with a specific organopolysiloxane in order to impart a low stress property.

Various compounds can be used as the aromatic copolymer, and examples thereof include compounds having the following structures.

[0050]

[Chemical 13]

[0051]

[Chemical 14]

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

[0053]

[Chemical 15]

These alkenyl group-containing naphthalene resins can be obtained by an ordinary 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 of partially reacting various naphthalene skeleton-containing epoxy resins with 2-allylphenol and the like.

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

[0056]

[Chemical 16] (However, in the formula, R ¹ 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 ² 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 that satisfies ≦ b ≦ 3 and 1 ≦ a + b <4. Further, the number of silicon atoms in one molecule is an integer of 2 to 1000, and the number of R ¹ directly linked to the silicon atoms in one molecule is an integer of 1 or more. )

In this case, the substituent R ¹ is, for example, a hydrogen atom,
Organic group containing a functional group selected from hydroxyl group, amino group, epoxy group and carboxyl group, methoxy group, ethoxy group, n-propoxy group, butoxy group, methoxyethoxy group, ethoxyethoxy group and other alkoxy groups, alkenyl An oxy group and the like. R ² is, for example, an alkyl group such as a methyl group, an ethyl group, an n-propyl group or 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 [II] include the following compounds.

[0059]

[Chemical 17]

Here, the molecular weight of the organopolysiloxane of the above formula [II] is not necessarily limited, but is 100
-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 each other in the matrix, and a fine sea-island structure is formed. This is because the organopolysiloxane preferably has a molecular weight of 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 aromatic polymer and the organopolysiloxane of the formula [II] can be obtained by subjecting both compounds to an addition reaction by a usual method. In particular,
The addition reaction of an aromatic polymer with an organopolysiloxane of the formula [II] by hydrosilylation is the best method for obtaining a copolymer as set. For the addition reaction, it is preferable to use a conventionally known addition catalyst, for example, a platinum-based catalyst such as chloroplatinic acid in a catalytic amount and an inert solvent such as benzene, toluene or methyl isobutyl ketone. The reaction temperature is not particularly limited, but is preferably 60 to 120 ° C., and the reaction time is usually 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, or methyl cellosolve, or to use alcohols or phenols such as water or butanol, isopropyl alcohol, and ethanol to further accelerate the reaction, As the reaction catalyst, it is desirable to use amines such as tributylamine, 1,8-diazabicycloundecene-7, organic phosphines such as triphenylphosphine, and imidazoles such as 2-phenylimidazole.

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,
Capryl 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 (tertiary butyl peroxide) hexane,
2,5-dimethylhexyl-2,5-di (peroxybenzoate), tertiary butyl perbenzoate, tertiary butyl peracetate, tertiary butyl peroctoate, tertiary butyl peroxyisobutyrate, Examples thereof include organic peroxides such as di-tertiary butyl-di-perphthalate, and 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 accelerating the reaction between the curing catalyst and the resin. Examples of the curing accelerator include organic phosphine compounds such as triphenylphosphine, tricyclohexylphosphine, tributylphosphine, methyldiphenylphosphine, 1,2-bis (diphenylphosphino) ethane and bis (diphenylphosphino) methane, 1,8 -Tertiary amines such as diazabicyclo [5.4.0] undecene-7, imidazoles, etc. may be mentioned, and these may be used alone or in combination of two or more within a range not impairing the object of the present invention. it can.

The total amount of the curing catalyst and the curing accelerator added is 10 in total of the components (A), (B), (C) and (D).
It is preferably 0.01 to 10 parts, especially 0.1 to 2 parts, relative to 0 parts. If the amount of the catalyst is less than 0.01 part, the curability is insufficient, so good performance may not be obtained, and if it exceeds 10 parts, the curability may be accelerated and the moldability may be deteriorated.

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

As the inorganic filler, those which are usually blended with the thermosetting resin composition can be used. Examples thereof include fused silica, silica such as 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 is not particularly limited, but (A), (B),
Total amount of components (C), (D), (E) and catalyst amount 100
100 to 1000 parts, especially 200 to 700 parts per part
It is preferably within the range of parts.

The composition of the present invention may further contain various additives, if desired. 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 (γ-glycidoxypropyltrimethoxysilane, etc.), epoxysilanes, vinylsilanes, boron compounds, coupling agents such as alkyl titanates, antiaging agents, etc. One or two or more of the above 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 is 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 mixing 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.

[0072]

EFFECTS OF THE INVENTION The thermosetting resin composition of the present invention has low stress, high adhesiveness, good workability, excellent mechanical strength at high temperature and hot water resistance, heat resistance and low water absorption. It gives a cured product with excellent properties. Therefore, the composition of the present invention sufficiently satisfies the use conditions of recent thermosetting resin compositions, and various electrical insulating materials, structural materials, adhesives, powder coating materials,
It is useful as a material for semiconductor encapsulation.

[0073]

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 13, Comparative Examples 1 to 7] N,
N'-4,4'-diphenylmethane bismaleimide 40
For the parts, epoxy resin, phenolic resin of the following structure,
The curing catalyst was used in the blending amounts shown in Tables 1 to 3 and 260 parts of quartz powder, 1.5 parts of γ-glycidoxypropyltrimethoxysilane, 1.5 parts of wax E, and 1.0 part of carbon black were used. In addition, the obtained blend was uniformly melt-mixed with a hot two-roll mill to produce 20 kinds of thermosetting resin compositions (Examples 1 to 13 and Comparative Examples 1 to 7).

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 the 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 strength bar of 10 × 4 × 100 mm was molded under the condition of a molding time of 2 minutes and post-cured at 180 ° C. for 4 hours, and then measured at 215 ° C. (C) Using a test piece having a coefficient of expansion and 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 A silicon chip with a size of 2 × 6 × 0.3 mm is 4 × 1
It was adhered to a 2 × 1.8 mm SO package, and the thermosetting resin composition was molded thereon at 175 ° C. × 2 minutes and post-cured at 180 ° C. for 4 hours. 85 ℃ / 85% RH
After leaving it in the atmosphere for 24 hours and 48 hours,
It was immersed in a solder bath at 40 ° C. for 10 seconds, and the number of package cracks / total number was measured. (E) Moisture-resistant 4M DRAM chip is adhered to a 20-PIN SOJ frame, and the thermosetting resin composition is molded thereon under a molding condition of 180 ° C.
It was molded in 2 minutes and post-cured at 180 ° C. for 4 hours.
Number of aluminum wire breakages when this was left in a 121 ° C / 100% RH atmosphere for 24 hours, dipped in a solder bath at 260 ° C for 10 seconds after absorbing moisture, and then left in a 121 ° C / 100% RH atmosphere for 300 hours / Total number was measured. (F) Water absorption rate: 180 ° C, 70 kg / cm ² , molding time: 5 minutes
A disk of 0φ x 3 mm was molded and post-cured at 180 ° C for 4 hours, then it was placed in 121 ° C / 100% PCT for 24 hours.
After standing for a time, the water absorption rate 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.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

[0079]

[Chemical 18]

[0080]

[Chemical 19]

[0081]

[Chemical 20]

[0082]

[Chemical 21]

From the results of Tables 1 to 3, a thermosetting resin composition containing a maleimide compound according to the present invention, an allyl group-containing naphthalene compound, a fluorine atom-containing compound, and a naphthalene compound having a double bond conjugated with an aromatic group. The products (Examples 1 to 13) have higher flexural strength at high temperature at high glass transition point, crack resistance, and crack resistance, as compared with the thermosetting resin compositions (Comparative Examples 1 to 7) not containing these components. It was confirmed that it has excellent moisture resistance, water absorption, and adhesiveness.

[Brief description of drawings]

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

FIG. 2 is a schematic view showing a pulling direction in an adhesion test.

[Explanation of symbols]

 1 molded product 2 test piece

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication C08L 63/00 NKB 8830-4J // (C08L 63/00 83:10) (72) Inventor Takei Minoru No. 1 Hitomi, Oita, Matsuida-cho, Usui-gun, Gunma 10 Shin-Etsu Chemical Co., Ltd. Silicone Electronic Materials Research Laboratory

Claims (2)

[Claims] 1. (A) an imide compound having a maleimide group represented by the following formula [I]: (B) a compound having at least two epoxy groups in one molecule, (C) a compound having a phenolic hydroxyl group in one molecule, (D) a thermoplastic resin, and (B)
A compound containing a fluorine atom in either or both of the component and the component (C) is used, and the component (B) and the component (C) are used.
A thermosetting resin composition comprising a compound having an allyl group-containing naphthalene ring and a compound having a naphthalene ring having a double bond that is conjugated to an aromatic group in one or both of the components. 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 [II] is added. [Chemical 2] (However, in the formula, R ¹ 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 ² 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 that satisfies ≦ b ≦ 3 and 1 ≦ a + b <4. Further, the number of silicon atoms in one molecule is an integer of 2 to 1000, and the number of R ¹ directly linked to the silicon atoms in one molecule is an integer of 1 or more. )