JPH1081748A - Production of polyimide-containing polyhydric phenolic resin, epoxy resin composition using the same resin and its cured substance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin excellent in performances of heat resistance, high toughness and high adhesiveness, useful as a hardener for an epoxy resin, by carrying out the polymerization reaction of a polyimide in a polyhydric phenolic resin. SOLUTION: (B) An acid anhydride (preferably pyromellitic acid dianhydride) is reacted with (C) a diamine compound [preferably bis(3-aminopropyl) polymethylsiloxane] and imidated while carrying out a dehydration reaction in the presence of (A) a polyhydric phenolic resin containing two or more phenolic hydroxyl groups in one molecule [preferably an aralkyl resin of the formula (A is an alkyl-substituted or nonsubstituted benzene ring or naphthalene ring; R1 and R2 are each H or a 1-6C hydrocarbon; (p) is 1 or 2; (m) is 0-15) to give the objective resin. Consequently, the objective resin capable of providing a cured material not lowering a glass transition temperature and mechanical strength and being combined with an epoxy resin is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to heat resistance, high toughness,
The present invention relates to a method for producing a polyimide-containing polyhydric phenolic resin exhibiting excellent performance such as high adhesiveness and useful as a curing agent for an epoxy resin, and an epoxy resin composition and a cured product thereof.

[0002]

2. Description of the Related Art Hitherto, phenol novolaks, phenol aralkyl resins and the like have been widely used as curing agents for epoxy resin compositions used in the fields of powder coatings, semiconductor encapsulating materials and the like. However, the cured product obtained therefrom is generally brittle, and has problems in adhesion to various substrates, adhesion, and the like. As a method for overcoming the above problems, a method of adding a rubber or elastomer component has been studied (Journal of Material Science, 21, 2462).
(1986)). However, these methods have problems such as a decrease in glass transition point and a decrease in mechanical strength.

As a method for solving the above problem, a composite with polyimide having excellent thermal and mechanical properties can be considered. In general, since polyimide has high heat resistance and good electrical and mechanical properties as an organic polymer compound, polyimide is widely used as a protective material, an insulating material or an adhesive, a film, and a structural material in the field of electronic devices. However, in general, polyimide has a high melting point or glass transition point and often exceeds or is close to its thermal decomposition temperature, making it difficult to melt-mold and, for the same reason, epoxy resin by melt-mixing etc. It is also difficult to form a composite with other materials.

[0004] For this reason, proposals regarding fusible polyimide polymers are often made. For example, JP-A-61-203132 proposes a crystalline silicone imide copolymer. Also, JP-A-61-25
No. 0031 proposes a special pyromellitic imide copolymer as a meltable polyimide copolymer. However, in the above-mentioned JP-A-61-203132,
The melting point of the copolymer is from 140 to 2 as far as the working examples are concerned.
The temperature is 10 ° C., and according to JP-A-61-250031, the copolymer must be heated to 400 ° C. by a melt press in order to form a film. Therefore, even with these materials, it has been difficult to form a composite with another material such as an epoxy resin by a method such as melt mixing.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an epoxy which exhibits excellent properties such as heat resistance, high toughness and high adhesion without lowering the glass transition point and mechanical strength of the cured product. An object of the present invention is to provide a method for producing a polyimide-containing polyhydric phenolic resin which is particularly useful as a resin curing agent.

[0006]

SUMMARY OF THE INVENTION Generally, polyimide is
Although the melting point is high and it is difficult to form a composite with other materials such as epoxy resin, the present invention provides a method for conducting a polymerization reaction of polyimide in a polyhydric phenolic resin which is generally used as a curing agent for epoxy resin. As a result, it has been found that polyimide produced by polymerization is uniformly melted or dispersed in the polyhydric phenolic resin, and the present invention has been accomplished.

That is, the present invention provides an imidization reaction by reacting an acid anhydride with a diamine compound in the presence of a polyhydric phenolic resin containing two or more phenolic hydroxyl groups in one molecule, and performing a dehydration reaction. And a method for producing a polyimide-containing polyhydric phenolic resin.

[0008] The present invention is also an epoxy resin composition characterized in that the polyimide-containing polyhydric phenolic resin is used as a part or all of a curing agent component for an epoxy resin.

Further, the present invention is a cured epoxy resin obtained by curing the epoxy resin composition.

The polyimide-containing polyhydric phenolic resin of the present invention is obtained by reacting an acid anhydride with a diamine compound in the presence of a polyhydric phenolic resin, and performing an imidization reaction while performing a dehydration reaction. . In this case, the polyhydric phenolic resin to be used may be a resin containing two or more phenolic hydroxyl groups in one molecule, and examples thereof include bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, and 4,4′-biphenol. , 2,2'-biphenol, hydroquinone, resorcinol, divalent phenolic compounds such as naphthalene diol, tris- (4-hydroxyphenyl) methane,
Trivalent or more phenols represented by 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak, naphthol novolak, polyvinylphenol, and the like; further, phenols and naphthols; Alternatively, dihydric phenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, 4,4′-biphenol, 2,2′-biphenol, hydroquinone, resorcinol, naphthalene diol, etc. are converted into formaldehyde, acetaldehyde, benzaldehyde, p-hydroxyl. Examples include polyhydric phenolic compounds synthesized by reaction with a condensing agent such as benzaldehyde, p-xylylene glycol, p-xylylene glycol dimethyl ether. Preferably, a phenol novolak obtained by condensation of phenols and formaldehyde, a novolak resin such as cresol novolak, or an aralkyl resin obtained by reacting a phenol or naphthol with a condensing agent such as p-xylylene glycol dimethyl ether. No.

When the polyimide-containing polyhydric phenolic resin of the present invention is used as an epoxy resin curing agent, if a novolak resin is used as a synthetic raw material, a cured product having excellent moldability and heat resistance can be obtained, and an aralkyl resin can be used. Then
In particular, a cured product having excellent moisture resistance is obtained. The softening point of these polyhydric phenolic resins is not particularly limited, but is usually preferably in the range of 40C to 150C.

Here, the aralkyl resin is represented by the following general formula (1): a phenolic hydroxyl group-containing compound having an alkyl-substituted or unsubstituted benzene ring or naphthalene ring; Is obtained by reacting

Embedded image (In the formula, A represents an alkyl-substituted or unsubstituted benzene ring or naphthalene ring, and when two or more are contained in one molecule, they may be the same or different. R ₁ and R _{2 each} represent a hydrogen atom or a carbon atom. Represents a hydrocarbon group of 1 to 6, p represents an integer of 1 or 2, and m represents a number of 0 to 15)

As the phenolic hydroxyl group-containing compound,
For example, phenol, o-cresol, m-cresol,
Benzene ring-containing compounds such as p-cresol, ethylphenols, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, isopropylphenols, tert-butylphenol, phenylphenols, catechol, resorcinol, hydroquinone, , 1-
Examples include naphthalene ring-containing compounds such as naphthol, 2-naphthol, and naphthalene diols.

As the aromatic crosslinking agent, o-form, m-form
-Or p-form, but preferably m-form or p-form. Specifically, p-xylylene glycol, α, α′-dimethoxy-p-xylene, α, α′-
Diethoxy-p-xylene, α, α′-diisopropyl-p-xylene, α, α′-dibutoxy-p-xylene, m-xylylene glycol, α, α′-dimethoxy-m-xylene, α, α′- Diethoxy-m-xylene, α, α′-diisopropoxy-m-xylene, α,
α'-dibutoxy-m-xylene, 1,4-di (2-hydroxy-2-ethyl) benzene, 1,4-di (2-methoxy-2-ethyl) benzene, 1,4-di (2-hydroxy -2-ethyl) benzene, 1,4-di (2-ethoxy-2-ethyl) benzene, 1,4-di (2-isopropoxy-2-ethyl) benzene, 1,4-di (2-hydroxy- 2-propyl) benzene, 1,4-di (2-
Methoxy-2-propyl) benzene, 1,4-di (2-
(Hydroxy-2-propyl) benzene, 1,4-di (2
-Ethoxy-2-propyl) benzene, 1,4-di (2
-Isopropoxy-2-propyl) benzene, 1,3-
Di (2-hydroxy-2-ethyl) benzene, 1,3-
Di (2-methoxy-2-ethyl) benzene, 1,3-di (2-hydroxy-2-propyl) benzene, 1,3-
Di (2-methoxy-2-propyl) benzene, 1,2-
Divinylbenzene, 1,3-divinylbenzene, 1,4
-Divinylbenzene, 1,2-di (2-propenyl) benzene, 1,3-di (2-propenyl) benzene, 1,
4-di (2-propenyl) benzene and the like.

When the phenolic hydroxyl group-containing compound is reacted with the aromatic crosslinking agent, the molar ratio of the two is preferably 1 mol or less, more preferably 0.1 to 0.1 mol, per mol of the phenolic hydroxyl group-containing compound. The range is 9 moles. If the amount of the aromatic cross-linking agent is less than 0.1 mol, the amount of the unreacted phenolic hydroxyl group-containing compound becomes large, which is not industrially preferable. If it exceeds 0.9 mol, the softening point of the resin becomes high, which hinders the molding workability. Cause.

The preferred softening point of the aralkyl-type polyhydric phenolic compound used in the present invention is from 40 to 150 ° C, more preferably from 50 to 120 ° C. If it is lower than this, there is a problem of blocking during storage, and if it is higher than this, there is a problem in kneadability and moldability in preparing the epoxy resin composition. The melt viscosity at 150 ° C. is preferably 20 centipoise or less, more preferably 5 centipoise or less. If it is higher than this, there is a problem in kneadability and moldability during preparation of the epoxy resin composition.

Preferred examples of the aralkyl polyhydric phenolic compound used in the present invention include phenol or naphthols, p-xylylene glycol or α, α'-.
There are phenol aralkyl-type resins and naphthol aralkyl-type resins obtained by condensation with dimethoxy-p-xylene, and Mirex XL-225-3L, XL manufactured by Mitsui Toatsu Chemicals, Inc.
-225-LL, XL-225-L, MEH-7800 manufactured by Meiwa Kasei Co., Ltd., SN-180 manufactured by Nippon Steel Chemical Co., Ltd., and the like.

As the acid anhydride used to obtain the polyimide-containing polyhydric phenolic resin of the present invention, most tetracarboxylic acid anhydrides used in synthesizing ordinary polyimides can be used. For example, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 3,3 ′, 4
4'-biphenyltetracarboxylic dianhydride, 2,
2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, bis (2,3-dicarboxyphenyl) -methane dianhydride, Bis (3,4-dicarboxyphenyl)
-Methane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -propane dianhydride, bis (3,4-dicarboxyphenyl) -ether dianhydride, bis (3,4
-Dicarboxyphenyl) sulfone dianhydride, 3,
3 ', 4,4'-tetracarboxybenzoyloxybenzene dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, thiophene -2,3,4,5-tetracarboxylic dianhydride, pyrazine-2,3,5,6-
Tetracarboxylic dianhydride, pyridine-2,3,5,6
-Tetracarboxylic dianhydride and the like. One of these carboxylic dianhydrides may be used, or two or more compounds may be used in combination.

Among the above-mentioned acid anhydrides, pyromellitic dianhydride, 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3 , 3 ', 4,4'-Biphenyltetracarboxylic dianhydride and bis (3,4-dicarboxyphenyl) sulfone dianhydride are suitably selected. Above all, bis (3,4-dicarboxyphenyl) sulfone dianhydride is preferable in order to improve the compatibility with an epoxy resin as a thermoplastic polyimide.

As the acid anhydride, phthalic anhydride, 4-chlorophthalic anhydride, tetrachlorophthalic anhydride, 4-hydroxyphthalic anhydride, naphthalic anhydride, naphthalic anhydride, A dicarboxylic anhydride such as maleic acid may be used.

The diamine component is selected from aromatic diamines, heterocyclic diamines, aliphatic diamines, diaminopolysiloxanes and the like.

As the aromatic diamines, for example, o-,
diaminotoluenes such as m- and p-phenylenediamine, 2,4-diaminotoluene, 1,4-diamino-2
-Methoxybenzene, 2,5-diaminoxylenes,
1,3-diamino-4-chlorobenzene, 1,4-diamino-2,5-dichlorobenzene, 1,4-diamino-
2-bromobenzene, 1,3-diamino-4-isopropylbenzene, N, N'-diphenyl-1,4-phenylenediamine, 4,4'-diaminodiphenyl-2,2
-Propane, 4,4'-diaminodiphenylmethane,
2,2′-diaminostilbene, 4,4′-diaminostilbene, 4,4′-diaminodiphenyl ether,
3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 4,4′-di (meth-aminophenoxy) diphenyl sulfone, 4,4'-di (para-aminophenoxy)
Diphenyl sulfone, 4,4'-diaminobenzoic acid phenyl ester, benzidine, 2,2'-dimethylbenzidine, 2,2'-diaminobenzophenone, 4,4'-
Diaminobenzophenone, 4,4′-diaminobenzyl, 4- (4′-aminophenylcarbamoyl) -aniline, bis (4-aminophenyl) -phosphine oxide, bis (4-aminophenyl) -methyl-phosphine oxide, bis ( 3-aminophenyl) -methylsulfine oxide, bis (4-aminophenyl) -phenylphosphine oxide, bis (4-aminophenyl) -cyclohexylphosphine oxide, N, N-bis (4-
Aminophenyl) -N-methylamine, 4,4′-diaminodiphenylurea, 1,5-diaminonaphthalene,
1,8-diaminonaphthalene, 1,5-diaminoanthraquinone, diaminofluoranthene, bis (4-aminophenyl) -diethylsilane, bis (4-aminophenyl) -dimethylsilane, 2,2-bis [4- ( 4-aminophenoxy) phenyl] propane, bis [4- (4-
Aminophenoxy) phenyl] sulfone, 4,4'-bis (4-aminophenoxy) phenyl, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4
-Aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 2,2-bis [4- (4-
Aminophenoxy) phenyl] hexafluoropropane and the like.

The heterocyclic diamines include, for example, 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-S-triazine, 2,7-diaminodibenzofuran, and 3,7-diamino Phenothiazine, 2,4-diamino-6-phenyl S-triazine and the like can be mentioned.

Further, as the aliphatic diamine, for example, dimethyldiamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 2,2-diamine Dimethylpropylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine,
4,4′-dimethylheptamethylenediamine, 3-methylheptamethylenediamine, 3-methoxyheptamethylenediamine, 5-methylnonamethylenediamine, 2,1
1-diaminododecane, 1,12-diaminooctadecane, 1,2-bis (3-aminopropoxy) -ethane,
N, N'-dimethylethylenediamine, N, N'-diethyl-1,3-diaminopropane, N, N'-dimethyl-1,6-diaminohexane, and the like.

Further, examples of diaminopolysiloxanes include the following.

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The above diamines such as aromatic diamines, heterocyclic diamines, aliphatic diamines and diaminopolysiloxanes may be used alone or in combination of two or more.

Among the above diamine compounds, aromatic diamines are preferred from the viewpoint of improving the heat resistance of the obtained polyimide. In order to further improve the compatibility with an epoxy resin by using a thermoplastic polyimide, 2,2-bis [4- (4-aminophenoxy) phenyl] propane and bis (3-aminopropyl) polymethylsiloxane are preferable. .

The molar ratio between the tetracarboxylic anhydride and the diamine compound can be appropriately adjusted according to the intended use of the polyimide-containing polyhydric phenolic resin. The molar ratio of tetracarboxylic anhydride / diamine compound is 0.8 to 1.2 when importance is placed on heat resistance and mechanical strength, and when importance is placed on blendability with epoxy resin and melt mixing property,
0.2 to 0.8, and in consideration of moldability (particularly fluidity) after forming the epoxy resin composition, 1.2 to 5.0.
And can also be used as a low molecular weight polyimide compound.

The polyimide-containing polyhydric phenolic resin of the present invention can be obtained by reacting an acid anhydride and a diamine compound in the presence of a polyhydric phenolic resin. Although not limited, the total amount of the acid anhydride compound and the diamine compound is usually 5 to 200 parts by weight based on 100 parts by weight of the polyhydric phenolic resin. If the amount is less than this, the effect of improving the physical properties of the polyimide when the epoxy resin is cured is small. If the amount is more than this, the viscosity rise during the synthesis of the polyimide is large, and handling during synthesis becomes difficult.

Regarding the order of addition of the tetracarboxylic acid anhydride and the diamine compound to the reaction system, the tetracarboxylic acid anhydride and the diamine compound may be added simultaneously and reacted, or may be added to the total amount of the tetracarboxylic acid anhydride. After the specific diamine compound is added and reacted first, the remaining diamine compound may be further added and reacted. Conversely, a part of the tetracarboxylic anhydride may be added to the entire amount of the diamine compound and reacted first, and then the remaining tetracarboxylic anhydride may be added and reacted.

The imidation reaction is carried out while stirring and dehydrating by heating. The reaction temperature is usually from 100 to
300 ° C. If it is lower than this, the reaction time will be longer,
If it is higher than this, a decomposition reaction of the polyhydric phenolic resin used as a reaction medium occurs. The reaction time is usually from 1 to 40.
Time range.

In the imidization reaction, a solvent may be used. As the solvent, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylphosphoramide, methylformamide, N -Acetyl-2-
Pyrrolidone, ethylene glycol monomethyl ether,
Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, cresol, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, tetrahydrofuran, N-acetyl-2-pyrrolidone , N-methyl-ε-caprolactam, tetrahydrothiophenedioxod (sulfolane)
And the like. Further, the imidization reaction can be performed in a mixed solvent of the above solvents.

Further, in order to carry out dehydration quickly, an aromatic solvent such as benzene, toluene and xylene may be used as an azeotropic solvent. Further, the reaction may be performed under reduced pressure in order to quickly perform dehydration.

The polyimide-containing polyhydric phenolic resin obtained by the above reaction is suitable as a curing agent for an epoxy resin, and an epoxy resin composition can be obtained by combining this with an epoxy resin. The epoxy resin used at this time is not particularly limited, but is selected from those having two or more epoxy groups in one molecule. For example, bisphenol A, dihydroxydiphenylmethanes, dihydroxydiphenylsulfones, dihydroxydiphenylsulfides, fluorenebisphenol, dihydroxybiphenyls,
Divalent phenols such as hydroquinones and resorcinol, or tris- (4-hydroxyphenyl) methane;
Novolak resin obtained by condensing 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane or a phenolic compound such as phenol, cresol and naphthol with aldehydes such as formaldehyde, acetaldehyde and benzaldehyde, and further phenol , Cresol, polyglycidyl etherified polyphenolic compounds such as aralkyl resins such as naphthol,
And glycidyl ether compounds derived from halogenated bisphenols such as tetrabromobisphenol A. The above epoxy resins may be used alone or in combination of two or more.

Further, the epoxy resin composition of the present invention may contain an inorganic filler. In this case, from the viewpoint of increasing the filling of the inorganic filler, the epoxy resin to be used is selected from epoxy resins having excellent low viscosity. For example, 3,3 ′, 5,5′-tetramethyl-4,
4'-dihydroxydiphenylmethane, 3,3 ', 5
5'-tetramethyl-4,4'-dihydroxybiphenyl, 2,5-ditert-butylhydroquinone,
1,4-bis (3-methyl-4-hydroxycumyl) benzene, 3,3 ′, 5,5′-tetramethyl-4,4 ′
Diglycidyl ethers such as dihydroxydiphenyl sulfide, 3,3′-ditert-butyl-5,5′-dimethyl-4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl ether, 1,6-naphthalenediol And the like.

Examples of the inorganic filler include fused silica, crystalline silica, alumina, magnesia, titanium oxide, calcium carbonate, glass fiber, talc and the like. Among them, fused silica is preferably used from the viewpoint of low thermal expansion and the like. The shape of the fused silica may be either crushed or spherical, but from the viewpoint of improving solder heat resistance, crushed silica having an average particle size of 15 μm or less, and an average particle size of 40 μm.
m or less, and spherical silica having an average particle diameter of 2 μm or less are used in combination as appropriate. The compounding amount of the inorganic filler is usually 30 to 95% by weight, but when used for a semiconductor encapsulant, it is preferably in the range of 65 to 95% by weight from the viewpoint of improving solder heat resistance.

The epoxy resin composition of the present invention may be used by mixing a known curing agent in addition to the polyimide-containing polyhydric phenolic resin of the present invention. As the curing agent to be mixed and used, all those generally known as curing agents for epoxy resins can be used, and examples thereof include an acid anhydride type, an amine type, and a phenol type, and preferably have a phenolic hydroxyl group. A phenolic curing agent,
Examples include phenol novolak, cresol novolak, phenol aralkyl resin, polyvinyl phenol, naphthol novolak, naphthol aralkyl resin, naphthalene diol novolak, and naphthalene diol aralkyl resin.

When other curing agents are mixed and used, the polyimide-containing polyhydric phenolic resin according to the present invention is used in all curing agents in view of high heat resistance, toughness, and improvement in mechanical strength caused by polyimide. It is preferable to use 10% by weight or more.

Further, the epoxy resin composition of the present invention includes:
Usually, a curing accelerator is blended. As a curing accelerator,
All conventionally known curing accelerators can be used. For example, amines such as benzyldimethylamine, 1,8-diaza-bicyclo (5,4,0) undecene-7, imidazoles such as 2-ethyl-4-methylimidazole, organic phosphines such as triphenylphosphine, Lewis acids and the like. These curing accelerators are used as a mixture of two or more as necessary. Usually, the amount of the curing accelerator used is 0.1 to 10 parts by weight based on 100 parts by weight of the epoxy resin.

Further, if necessary, the epoxy resin composition of the present invention may contain a coupling agent, a wax, a flame retardant, a low stress agent, a pigment, a release agent, a lubricant and the like.

Further, the epoxy resin composition of the present invention may contain an oligomer or a high molecular compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene maron resin, and phenoxy resin. Good.

[0042]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, since the imidation reaction is carried out in the presence of a polyhydric phenol, a phenol resin in which a phenol resin and a polyimide resin are uniformly mixed can be obtained. In addition, it is not clear whether the hydroxyl group of the phenol resin reacts with the acid anhydride to form an ester bond during the imidization reaction, but even if such a reaction occurs, there is almost no decrease in the physical properties, and rather, the dissolution occurs. It is considered that effects such as improvement of the properties are produced.

[0043]

The present invention will be described more specifically with reference to the following examples. Example 1 [Production of Polyimide-Containing Polyphenolic Resin A] A softening point of 7 was placed in a 2-liter glass separable flask.
Phenol novolak 47 having a hydroxyl equivalent of 104 at 5 ° C.
3.2 g, bis (3,4-dicarboxyphenyl) sulfone dianhydride 85.69 g, 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane 63.57 g,
62.11 g of bis (3-aminopropyl) polymethylsiloxane having a molecular weight of 750 and 315 g of mixed xylene were charged, and heated to 150 ° C. with slow stirring. Then, the stirring rotation speed was set to 30 rpm, and the mixture was heated to 165 ° C.
The reaction was performed for 8 hours. During this time, generated water was removed from the system by azeotropic distillation with xylene. After the reaction, the remaining xylene was distilled off under reduced pressure to obtain 621.6 g of a polyimide-containing polyhydric phenolic resin A. The obtained polyimide-containing polyhydric phenolic resin A had a softening point of 103 ° C. and a melt viscosity at 150 ° C. measured by an ICI cone-plate viscometer of 7.4 poise. FIG. 1 shows the infrared absorption spectrum.

Example 2 [Preparation of Polyimide-Containing Polyphenolic Resin B] A 2-liter glass separable flask was charged with a softening point of 7
Phenol novolak 71 having a hydroxyl equivalent of 104 at 5 ° C.
0.1 g, bis (3,4-dicarboxyphenyl) sulfone dianhydride 96.23 g, 2,2-bis [4- (4-
86.38 g of aminophenoxy) phenyl] propane,
93.89 g of bis (3-aminopropyl) polymethylsiloxane having a molecular weight of 750, 40.0 g of phthalic anhydride,
470 g of mixed xylene was charged and reacted in the same manner as in Example 1 to obtain a polyimide-containing polyhydric phenolic resin B99.
9.5 g were obtained. The obtained polyimide-containing polyhydric phenolic resin B had a softening point of 77.5 ° C. and a melt viscosity at 150 ° C. measured with an ICI cone-plate viscometer of 8.9 poise.

Example 3 [Production of Polyimide-Containing Polyphenolic Resin C] A 2-liter glass separable flask was charged with a softening point of 8
Phenol aralkyl resin 7 with 5 ° C and hydroxyl equivalent 170
10.1 g, bis (3,4-dicarboxyphenyl) sulfone dianhydride 118.30 g, 2,2-bis [4-
(4-aminophenoxy) phenyl] propane 104.
36 g, 93.84 g of bis (3-aminopropyl) polymethylsiloxane having a molecular weight of 1234 and 470 g of mixed xylene were charged and reacted in the same manner as in Example 1 to obtain 1002.4 g of a polyimide-containing polyhydric phenolic resin C. The softening point of the obtained polyimide-containing polyhydric phenolic resin C was 123 ° C.

Example 4 [Production of polyimide-containing polyhydric phenolic resin D] A softening point of 7 was placed in a 2-liter separable glass flask.
Phenol novolak 47 having a hydroxyl equivalent of 104 at 5 ° C.
3.8 g, pyromellitic acid 47.6 g, molecular weight 750
Bis (3-aminopropyl) polymethylsiloxane 1
Example 1 was prepared by charging 63.8 g and 470 g of mixed xylene.
Was carried out in the same manner as in the above to obtain 621.8 g of a polyimide-containing polyhydric phenolic resin D62. The softening point of the resulting polyimide-containing polyhydric phenolic resin D was 87.5 ° C.
The melt viscosity at 150 ° C. measured with a CI cone plate viscometer was 0.9 poise. FIG. 2 shows the infrared absorption spectrum.

Example 5 [Preparation of Polyimide-Containing Polyphenolic Resin E] A softening point of 7 was placed in a 2-liter separable glass flask.
Phenol novolak 47 having a hydroxyl equivalent of 104 at 5 ° C.
3.8 g, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride 63.2 g, bis of molecular weight 750
(3-aminopropyl) polymethylsiloxane 147.
2 g and 470 g of mixed xylene were charged and reacted in the same manner as in Example 1 to obtain a polyimide-containing polyhydric phenolic resin E.
621.8 g were obtained. The obtained polyimide-containing polyhydric phenolic resin E had a softening point of 87.5 ° C. and a melt viscosity at 150 ° C. measured with an ICI cone-plate viscometer of 0.9 poise.

Example 6 [Production of Polyimide-Containing Polyphenolic Resin F] A 2-liter glass separable flask was charged with a softening point of 8
71.Og of 2-naphthol aralkyl resin having 4 ° C hydroxyl equivalent 204, bis (3,4-dicarboxyphenyl)
111.5 g of sulfone dianhydride, 2,2-bis [4-
(4-aminophenoxy) phenyl] propane 90.5
g, 20.6 g of phthalic anhydride and 470 g of mixed xylene were charged and reacted in the same manner as in Example 1 to obtain 729.5 g of a polyimide-containing polyhydric phenolic resin F. The softening point of the obtained polyimide-containing polyhydric phenolic resin F is 10
The melt viscosity at 150 ° C. measured at 2.5 ° C. with an ICI cone plate viscometer was 8.2 poise.

Examples 7 to 12 and Comparative Examples 1 and 2 Bisphenol A type epoxy resin (Epikote 828 made by Yuka Shell: epoxy resin X) as an epoxy resin component
And a polyimide-containing polyhydric phenolic resin A to F obtained in Examples 1 to 6 as a curing agent using an o-cresol novolak type epoxy resin (epoxy resin Y) having a softening point of 71 ° C. and an epoxy equivalent of 197, and a softening point. A phenol novolak (curing agent M) at 68 ° C. was used, and triphenylphosphine was used as a curing accelerator.
The kneading was carried out according to the formulation shown in Table 1 to prepare an epoxy resin composition.
These epoxy resin compositions were molded at 150 ° C.
After performing post-curing at 5 ° C. for 12 hours to prepare a cured product test piece, it was subjected to various physical property measurements. Adhesive strength is 35μm
After forming the sample on the copper foil of No. 1, the peel strength in the 90-degree direction was measured. The glass transition point and the coefficient of linear expansion were determined at a heating rate of 10 ° C. using a mechanical thermal analyzer. The water absorption was determined by a pressure cooker tester from the weight change rate after 96 hours at 133 ° C. and 3 atm. Table 2 shows the results.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

When the polyimide-containing polyhydric phenolic resin of the present invention is used as an epoxy resin curing agent, heat resistance, high toughness, high adhesion, etc. can be obtained without lowering the glass transition point and mechanical strength of the cured product. It exhibits excellent performance and is suitably used as a base resin in various applications such as molding materials, laminate materials, and coating materials.

[Brief description of the drawings]

FIG. 1 is a drawing showing an infrared absorption spectrum of a polyimide-containing polyhydric phenolic resin A of Example 1.

FIG. 2 is a drawing showing an infrared absorption spectrum of a polyimide-containing polyhydric phenolic resin D of Example 4.

Claims (7)

[Claims] An imidation reaction is carried out by reacting an acid anhydride with a diamine compound in the presence of a polyhydric phenolic resin containing two or more phenolic hydroxyl groups in one molecule, and performing a dehydration reaction. A method for producing a polyimide-containing polyhydric phenolic resin, comprising: 2. The method for producing a polyimide-containing polyhydric phenolic resin according to claim 1, wherein the polyhydric phenolic resin is a novolak resin obtained by condensation of a phenol and formaldehyde. 3. The method for producing a polyimide-containing polyhydric phenolic resin according to claim 1, wherein the polyhydric phenolic resin is an aralkyl resin represented by the following general formula (1). Embedded image (In the formula, A represents an alkyl-substituted or unsubstituted benzene ring or naphthalene ring, and when two or more are contained in one molecule, they may be the same or different. R ₁ and R _{2 each} represent a hydrogen atom or a carbon atom. Represents a hydrocarbon group of 1 to 6, p represents an integer of 1 or 2, and m represents a number of 0 to 15) 4. An acid anhydride comprising pyromellitic dianhydride,
3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride The method for producing a polyimide-containing polyhydric phenolic resin according to claim 1, which is at least one acid anhydride selected from the group consisting of: 5. The method according to claim 1, wherein the diamine compound is 2,2-bis [4-
2. The method for producing a polyimide-containing polyhydric phenolic resin according to claim 1, which comprises (4-aminophenoxy) phenyl] propane or bis (3-aminopropyl) polymethylsiloxane. 6. An epoxy resin composition comprising an epoxy resin and a curing agent, wherein the polyimide-containing polyhydric phenolic resin according to claim 1 is used as a part or all of a curing agent component. 7. A cured product obtained by curing the epoxy resin composition according to claim 6.