JPH0730165B2 - Epoxy resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to an epoxy resin composition, and more particularly to an epoxy resin composition suitable for lamination and molding.

<Prior art> Laminated boards and I used for industrial equipment and consumer equipment.
Epoxy resin was used to seal semiconductor elements such as C and LSI.

<Problems to be Solved by the Invention> However, due to the low heat resistance of the cured product, the laminated plate has a large dimensional change in the vertical direction with respect to the base material, and there are problems of plating connection reliability and smear. It was In addition, the thermal expansion of IC and ISI encapsulation materials is large, and when connecting parts such as IC and LSI to a circuit, there is a problem that cracks are generated by the heat of solder.

In order to improve the heat resistance of the cured product, a method of using an aromatic imide compound as a curing agent can be considered.

Aromatic imide compounds are generally produced from aromatic tetracarboxylic acid anhydrides and aromatic diamines as raw materials,
Pyromellitic dianhydride or benzophenone tetracarboxylic dianhydride is well known as a typical aromatic tetracarboxylic acid. However, the aromatic imide compounds obtained by using these acid anhydrides have poor compatibility with epoxy resins, and it was difficult to improve performance by using them as a curing agent for epoxy resins. . Further, these imide compounds have extremely low solubility in ordinary low-boiling organic solvents, and require a high-boiling solvent for dissolution, and from this standpoint it is difficult to use them together with an epoxy resin.

<Means for Solving Problems> From the above facts, the inventors of the present invention have diligently studied an imide compound having excellent solubility and compatibility, and as a result, have shown that [In the formula, R ₁ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ₂ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms,
Represents an alkoxy group or a hydroxyl group. ] Found that the imide compound having a structural unit represented by, is very soluble in various organic solvents and epoxy resins, further, by using the imide compound in combination with an epoxy resin, the heat resistance is low, the size The present invention has been completed by finding that the problems such as large changes and cracking due to heat can be solved.

That is, the present invention relates to an epoxy resin and the following general formula (I)
Is an epoxy resin composition containing an imide compound represented by the following as an essential component, and a cured product thereof has excellent heat resistance that has never been obtained.

[In the formula, X represents an —NH ₂ group and / or an —OH group, and Ar ₁ ,
Ar ₂ is independently an aromatic residue, R ₁ is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ₂ is a hydrogen atom, and 1 carbon atom
~ 20 represents an alkyl group, an alkoxy group or a hydroxyl group, and m and n represent a number from 0 to 30. ] In more detail about the Ar ₁ and Ar _2, Ar ₁ and A
Each r ₂ is independently a mononuclear or polynuclear divalent aromatic residue, and the aromatic ring includes those substituted with a lower alkyl group, halogen, lower alkoxy group, etc. and those not substituted. . More specifically, Ar ₁ and Ar ₂ are both aromatic amine residues, Ar ₂ is an aromatic diamine residue, and Ar ₁ is an aromatic monoamine or diamine residue. Exemplifying these aromatic amines,
For aromatic diamines 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylpropane, 4,
4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 2,4-toluenediamine, 2,6-
Toluene diamine, m-phenylenediamine, p-phenylenediamine, benzidine, 4,4'-diaminodiphenyl sulfide, 3,3'-dichloro-4,4'-diaminodiphenyl sulfone, 3,3'-dichloro-4, 4'-diaminodiphenylpropane, 3,3'-dimethyl-4,4'diaminodiphenylmethane, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl , 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene,
1,4-bis (4-aminophenoxy) benzene, 2,2-bis (4-aminophenoxyphenyl) propane, 4,4 ′
-Bis (4-aminophenoxy) diphenylsulfone, 4,4'bis (3-aminophenoxy) diphenylsulfone, 9,9'-bis (4-aminophenyl) anthracene, 9,9'-bis (4-aminophenyl) ) Fluorene, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 2,4-diaminoanisole, bis (3-aminophenyl) methylphosphine oxide, 3,3'-diaminobenzophenone, o-toluidine sulfone, Four,
4'-methylene-bis-o-chloroaniline, tetrachlorodiaminodiphenylmethane, m-xylylenediamine, p-xylylenediamine, 4,4'-diaminostilbene, 5-amino-1- (4'-aminophenyl- 1,3,
3-trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, 5-amino-6-methyl-1- (3'-amino-4'-methylphenyl) -1,3,3-Trimethylindane, 7-amino-6-methyl-1- (3'-amino-4'-methylphenyl) -1,3,3-trimethylindane, 6-amino-5
-Methyl-1- (4'-amino-3'-methylphenyl) -1,3,3-trimethylindane, 6-amino-7-
Methyl-1- (4'-amino-3'-methylphenyl)
There is one kind or two or more kinds such as -1,3,3-trimethylindane.

On the other hand, regarding aromatic monoamines, o-aminophenol, m-aminophenol, p-aminophenol,
6-amino-m-cresol, 4-amino-m-cresol, 2,2- (4-hydroxyphenyl-4-aminophenyl) -propane, 2,2- (4-hydroxyphenyl-2'-methyl-4) ′ -Aminophenyl) -propane,
2,2- (3-methyl-4-hydroxyphenyl-4'-
Aminophenyl) -propane, 3-amino-1-naphthol, 8-amino-2-naphthol, 5-amino-1-
There are one kind or two or more kinds of naphthol, 4-amino-2-methyl-1-naphthol and the like.

Although R ₁ and R ₂ are as described above, R ₁ is particularly preferably an alkyl group having 1 to 3 carbon atoms. R ₂ is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

Further, m and n in the general formula (1) are as described above, but preferably m and n are numbers from 0 to 8, particularly preferably 0 to 4.

The method for producing the unend functional imide compound used in the present invention will be illustrated.

When X in the formula (1) is —NH ₂ , the above aromatic diamine and the formula [In the formula, R ₁ and R ₂ are the same as described above. ] The compound shown below (hereinafter referred to as B ₁ and the isomers as the Y component or the Z component, respectively) can be synthesized by carrying out a usual imidization reaction with excess aromatic diamine.

When X in the formula (1) is -OH, the above aromatic monoamine having an -OH group and the above aromatic diamine are
To B _1, the molar ratio of aromatic diamine / B ₁ is (m + n) / (m
+ N + 1) and the molar ratio of aromatic monoamine / B ₁ is 2 /
(M + n + 1) (m and n are the same as described above), and a usual imidization reaction can be performed to synthesize.

Although the method for synthesizing the terminal functional imide compound used in the present invention has been illustrated above, the method is not limited to these.

Here, exemplifying the synthesis method of B ₁ , [In the formula, R ₁ and R ₂ are the same as described above. ] A compound represented by (hereinafter referred to as B ₃ ) and maleic anhydride are reacted at a molar ratio of 1/2 in the absence of a radical polymerization catalyst and in the presence or absence of a radical polymerization inhibitor. To be Examples of B ₃ include styrene, α-methylstyrene, α, p-dimethylstyrene, α, m-dimethylstyrene, isopropylstyrene, vinyltoluene and p.
-T-butylstyrene, p-isopropenylphenol, m-isopropenylphenol, 1-methoxy-3
-Isopropenylbenzene, 1-methoxy-4-isopropenylbenzene, vinyl xylene and the like may be used alone or in combination.

The terminal functional type imide compound used in the present invention thus obtained is soluble at a high concentration in a low boiling solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl cellosolve, ethyl cellosolve, methylene chloride and chloroform. Furthermore, the compatibility with the epoxy resin is excellent.

The epoxy resin used in the present invention is a compound having two or more epoxy groups in the molecule, and is exemplified by bisphenol A, bisphenol F, hydroquinone, resorcin, phloroglysin, tris- (4-hydroxyphenyl) methane, 1, Glycidyl ether compounds derived from divalent or trivalent or more phenols such as 1,2,2-tetrakis (4-hydroxyphenyl) ethane or halogenated bisphenols such as tetrabromobisphenol A, phenol, o-cresol, etc. Novolak epoxy resin derived from novolak resin, which is the reaction product of phenol and formaldehyde, and aniline,
p-aminophenol, m-aminophenol, 4-amino-m-cresol, 6-amino-m-cresol,
4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-
Aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, 2,2-bis (4-aminophenoxyphenyl) propane, p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, p-xylylenediamine, m-xylylenediamine, 1,4-cyclohexane-bis (methylamine), 1,3-cyclohexane-bis (Methylamine),
5-amino-1- (4'-aminophenyl) -1,3,3-
Amine-based epoxy resin derived from trimethylindane, 6-amino-1- (4'-aminophenyl) -1,3,3-trimethylindane, p-oxybenzoic acid, m-
Oxybenzoic acid, terephthalic acid, glycidyl ester compounds derived from aromatic carboxylic acids such as isophthalic acid, hydantoin epoxy resins derived from 5,5-dimethylhydantoin, etc., 2,2'-bis (3, Fats such as 4-epoxycyclohexyl) propane, 2,2-bis [4 (2,3-epoxypropyl) cyclohexyl] propane, vinylcyclohexenedioxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate Cyclic epoxy resin, other, triglycidyl isocyanurate, 2,4,6-triglycidoxy-S-
One or more of triazine and the like can be mentioned.

The composition of the present invention contains the epoxy resin and the terminal functional imide compound described above as essential components, and if necessary, known epoxy resin curing agents and curing accelerators, fillers, flame retardants, reinforcing materials, surface treatment agents, A pigment or the like can be used in combination.

Known epoxy curing agents include amine-based curing agents such as the above-mentioned aromatic amines and aliphatic amines such as xylylenediamine, polyphenol compounds such as phenol novolac and cresol novolac, and further acid anhydrides, dicyandiamide, hydrazide compounds and the like. It is illustrated. Regarding the ratio of the epoxy resin (A) and the terminal functional imide compound (B), the total of (B) and other curing agents is 0.8 g equivalent to 1.2 g equivalent to 1 g equivalent of (A).

As a curing accelerator, benzyldimethylamine, 2,4,6-
Amines such as tris (dimethylaminomethyl) phenol and 1,8-diazabicycloundecene, and imidazole compounds such as 2-ethyl-4-methylimidazole,
A boron trifluoride amine complex etc. can be illustrated. Examples of the filler include silica and calcium carbonate, and examples of the flame retardant include aluminum hydroxide, antimony trioxide, red phosphorus and the like. As a reinforcing agent, glass fiber, polyester fiber,
Illustrative are woven fabrics, non-woven fabrics, mats, papers made of organic fibers and inorganic fibers such as polyamide fibers and alumina fibers, or combinations thereof.

<Effects of the Invention> The composition according to the present invention comprising the components described above gives a cured product having an extremely high heat resistance which has never been obtained, and has a high industrial value as a laminate or a molding material.

<Examples> Hereinafter, the present invention will be described in more detail with reference to Examples.

Reference Example-1 [Synthesis of Raw Material B ₁ ] 110.3 g (1.125 mol) of maleic anhydride was added to a 500 ml four-necked flask equipped with a stirrer, a thermometer, and a cooling condenser.
N, N'-diphenyl-1,4-phenylenediamine 3.90 g,
Charge 100 g of toluene and 50 g of methyl isobutyl ketone. Subsequently, the temperature was raised to 120 ° C., 59.1 g (0.5 mol) of α-methylstyrene was added dropwise over 8 hours while maintaining the same temperature, and the temperature was kept at the same temperature for another 2 hours after completion of the addition. After the reaction, 50 g of toluene and 25 g of methyl isobutyl ketone were added and cooled to precipitate crystals. The crystals were separated, washed with toluene several times, and then dried to obtain 55.7 g of powder crystals close to white.

In this product, the purity of B ₁ by GPC was 97.2%, the composition ratio of the isomers of B ₁ by GC was Y component / Z component 0.45 / 0.55, and the melting point was 206 to 208 ° C.

Reference Example-2 [Synthesis of Raw Material B ₁ ] In a 500 ml four-necked flask equipped with a stirrer, a thermometer, and a cooling condenser, 98.1 g (1 mol) of maleic anhydride and N, N ′ were added.
Charge 3.90 g of diphenyl-1,4-phenylenediamine and 150 g of xylene. Subsequently, the temperature was raised to 145 ° C, and while maintaining the same temperature, α-methylstyrene 5
9.1 g (0.5 mol) was added dropwise, and after completion of the addition, the temperature was kept at the same temperature for 2 hours. After the reaction, 75 g of methyl isobutyl ketone was added and cooled to precipitate crystals. The crystals were separated, washed with toluene several times, and then dried to obtain 50.4 g of powder crystals close to white.

In this product, the purity of B ₁ by GPC was 96.1%, the composition ratio of the isomers of B ₁ by GC was Y component / Z component 0.17 / 0.88, and the melting point was 208 to 210 ° C.

Reference Example-3 [Synthesis of Raw Material B ₁ ] In a 500 ml four-necked flask equipped with a stirrer, a thermometer, and a cooling condenser, 98.1 g (1 mol) of maleic anhydride and N-
Phenyl-N'-isopropyl-1,4-phenylenediamine 4.51 g, toluene 120 g and methyl isobutyl ketone 3
Charge 0g. Subsequently, the temperature was raised to 120 ° C., and while maintaining the same temperature, 59.1 g of α-methylstyrene was taken over 2 hours.
(0.5 mol) was added dropwise, and after the completion of the addition, the temperature was kept at the same temperature for 8 hours. After the reaction, 60 g of toluene and 15 g of methyl isobutyl ketone were added and cooled to precipitate crystals. The crystals were separated, washed with toluene several times, and then dried to obtain 67.2 g of powder crystals close to white.

In this product, the purity of B ₁ by GPC was 97.8%, the composition ratio of the isomers of B ₁ by GC was Y component / Z component 0.66 / 0.34, and the melting point was 181-183 ° C.

Reference Example-4 A flask equipped with a stirrer, a thermometer, a cooling liquid separator, 2,
4-Toluenediamine (26.2 g, 0.215 mol) and m-cresol (117 g) were charged and the temperature was raised to 70 ° C. to dissolve 2,4-toluenediamine, and then the raw material 45.0 obtained in Reference Example-1 was used.
Charge g (0.143 mol) to form the polyamic acid.
Then, 25.2 g of toluene was charged, the temperature was raised to 150 ° C., and the dehydration reaction was continued at the same temperature for 10 hours.

After the reaction, the obtained resin solution was precipitated in 750 g of isopropanol, washed twice and dried under reduced pressure to obtain an imide compound.
This had an amine equivalent of 498 g / eq and a melting point of about 260 ° C.

Reference Example-5 44.8 g (0.143 mol) of the raw material obtained in Reference Example-1, 161 g of m-cresol, and 8.68 g of 2,4-toluenediamine (0.0714) were placed in a flask equipped with a stirrer, a thermometer, and a cooling separator. Mol), and the reaction is carried out at 70 ° C. for 1 hour. Further, 15.5 g (0.143 mol) of m-aminophenol is charged and the reaction is carried out at the same temperature for 1 hour.
React for time. After that, 32.2 g of xylene was charged and 170 ° C
The dehydration reaction was continued for 6 hours.

After the reaction, the obtained resin liquid was precipitated in 550 g of isopropanol, washed twice and dried under reduced pressure to obtain an imide compound.
The hydroxyl equivalent of this product was 473 g / eq, and the melting point was about 270 ° C.

Reference Example-6 In Reference Example-5, 44.8 g of the raw material obtained in Reference Example-1
30.1 g (0.10 mol) of the raw material obtained in Reference Example-2
2 moles of 2,4-toluenediamine 8.68 g (0.0714 moles) 4,4'-diaminodiphenylethane 12.9 g (0.0639
Mol) and 8.30 g (0.0761) of m-aminophenol.
Mol) and other conditions were the same as in Reference Example 5 to obtain an imide compound. The hydroxyl equivalent of this product is 702 g / eq,
The melting point was about 270 ° C.

Reference Example-7 In Reference Example-4, the raw material obtained in Reference Example-1 was replaced with the raw material obtained in Reference Example-3, and other conditions were set in Reference Example-4.
An imide compound was obtained in the same manner as in. This had an amine equivalent of 506 g / eq and a melting point of about 260 ° C.

Example-1,2 Sumiepoxy ELA-128 (bisphenol A type epoxy resin, epoxy equivalent 187 g / eq, Sumitomo Chemical Co., Ltd. product)
And the imide compounds obtained in Reference Examples 4 and 7 were mixed at a ratio shown in Table 1 and uniformly dissolved in dimethylformamide, and the solution was mixed with a glass cloth (Nitobo Co., Ltd. WE18K, BZ-).
2) was impregnated and treated in an oven at 180 ° C for 5 minutes to obtain a prepreg. Six pieces of prepreg and copper foil (TAI treated by Furukawa Circuit Foil Co., Ltd., 35μ) were layered and press-molded at 180 ° C. under a pressure of 50 kg / cm ² for 5 hours to obtain a 1 mm-thick copper-clad laminate. The physical properties of this laminated plate were measured according to JIS-C-6481 and the results shown in Table 1 were obtained.

Comparative Example-1 Sumiepoxy ESA-011 (Bisphenol A type epoxy resin, epoxy equivalent 489 g / eq, Sumitomo Chemical Co., Ltd. product) 2
40 g, Sumiepoxy ESCN-220 (o-cresol novolac type epoxy resin, epoxy equivalent 210 g / eq, Sumitomo Chemical Co., Ltd. product) 20 g, dicyandiamide 9 g, 2-phenyl-4-methyl-5-hydroxymethylimidazole 1 g
Was dissolved in a mixed solvent of 40 g of dimethylformamide, 60 g of ethylene glycol monomethyl ether and 60 g of methyl ethyl ketone, glass cloth was impregnated with this solution in the same manner as in Example-1, and treated for 5 minutes in an oven at 160 ° C. to obtain a prepreg. A laminate was produced by press molding under the same conditions as in Example-1. The physical properties of the laminate are shown in Table-1.

Example-3,4 Sumiepoxy ESCN-195XL (o-cresol novolac type epoxy resin, epoxy equivalent 197 g / eq, product of Sumitomo Chemical Co., Ltd.) 100 g, imide compound 25 g obtained in Reference Examples 5 and 6, phenol novolac Resin 51 g, 2,4,6-tris (dimethylaminomethyl) phenol 1 g, carnauba wax 1 g, silane coupling agent (Toray Silicon SH-
6040) 2 g and silica 420 g were kneaded with a two-roll mill at 100 ° C. for 5 minutes, cooled and pulverized to produce a molding material. The molding material is 170
It was press molded at 70 ° C. and 70 kg / cm ² for 5 minutes, and then post-cured in an oven at 180 ° C. for 5 hours. The physical properties of the cured product are shown in Table 2.

Comparative Example-4 A cured product was obtained in the same manner as in Example-3, except that 56 g of phenol novolac was used alone as the curing agent in Example-3 and 364 g of silica was used as the filler.

The physical properties of the cured product are summarized in Table-2.

As shown in Tables 1 and 2, it is clear that the composition according to the present invention has excellent heat resistance and gives a molded product with high dimensional accuracy.

Continuation of the front page (56) References JP-A-59-166531 (JP, A) JP-A-59-46266 (JP, A) JP-A-62-212419 (JP, A) JP-A-63-165427 (JP , A) JP-A-63-264631 (JP, A)

Claims (4)

[Claims] 1. An epoxy resin composition comprising an epoxy resin and an imide compound represented by the following general formula (I) as essential components. [In the formula, X represents an —NH ₂ group and / or an —OH group, and
r ₁ and Ar ₂ each independently represent an aromatic residue, R ₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R ₂ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group or a hydroxyl group. , M and n represent numbers from 0 to 30. ] 2. The epoxy resin composition according to claim 1, wherein m and n represent a number of 0 to 4. 3. The epoxy resin composition according to claim 1, wherein R ₁ is an alkyl group having 1 to 3 carbon atoms. 4. The epoxy resin composition according to claim 1, wherein R ₂ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.