JPH0742345B2 - Thermosetting resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Field of Industrial Application) The present invention relates to a thermosetting resin composition having excellent heat resistance, moisture resistance, mechanical properties, processability and the like.

(Prior Art) As a heat resistant resin, an addition reaction type polyimide resin having excellent processability is widely used as a laminated plate, a molded product, an adhesive, and the like. There are various types of this resin, and there are various problems.

That is, firstly, a product obtained by reacting an unsaturated dicarboxylic acid N, N′-bisimide with a diamine has a suitable use as a laminated plate, but on the other hand, it has a property of being hardly soluble in a solvent. For example, it has a property that it is difficult to dissolve unless it is a polar solvent having a high boiling point such as dimethylformamide, so that it has a problem in processability and has a drawback that the life of the resin solution is short. Second, the unsaturated dicarboxylic acid N,
Some use N'-bisimide and aminophenol as reaction components. This resin shows well-balanced properties for laminates, is soluble in low boiling point solvents and has good processability, but has a drawback in moisture resistance.For example, for long-term storage of the obtained copper clad laminates, etc. Must pay particular attention to moisture absorption. Furthermore, those having a third unsaturated dicarboxylic acid N, N'-bisimide and aminobenzoic acid as reaction components are also suitable for laminates, but have poor solubility in low boiling point solvents, such as glass cloth. However, there is a drawback in that the storability of the resin solution before making the prepreg must be taken into consideration.

In addition, addition reaction type polyimide resins are generally excellent in thermal properties, but due to their molecular structure, they are inferior in mechanical strength. Therefore, even if the thermal properties are sacrificed to some extent by copolymerization with other materials. The current situation is to improve the mechanical strength.

(Problems to be Solved by the Invention) The present invention has been made in view of these drawbacks, has improved heat resistance, mechanical properties, and moisture resistance, and has good solubility in low boiling point solvents, It is an object of the present invention to provide a thermosetting resin composition which is excellent in processability and can exhibit excellent practicality in the fields of laminated products, molded products, adhesives and the like.

[Structure of the Invention] (Means and Actions for Solving Problems) The inventors of the present invention have earnestly studied to achieve the above object, and as a result, if poly-p-vinylphenols are blended, The present invention has been completed by finding out that the object is achieved.

That is, the present invention relates to (A) poly-p-vinylphenols, (B) (a) N, N′-bisimide compound of unsaturated dicarboxylic acid, (b) aminophenol, and (c) aniline or an aniline derivative. A thermosetting resin composition comprising the reaction product of (1), the epoxy compound (C), and the curing accelerator (D) as essential components.

Hereinafter, the present invention will be described in detail.

The poly-p-vinylphenols (A) used in the present invention have the general formula (However, n represents an integer of 10 to 40 in the formula), and specific examples of the compound include Marzene resin M and Marzene resin MB, which may be used alone or in combination of two or more kinds.

The reaction product (B) used in the present invention is obtained by reacting (a) an N, N'-bisimide compound of an unsaturated dicarboxylic acid, (b) aminophenol and (c) aniline or an aniline derivative.

(A) The N, N′-bisimide compound of unsaturated dicarboxylic acid has a general formula However, in the formula, R ¹ represents a divalent group having at least 2 carbon atoms, and R ² represents a divalent group containing a double bond between carbon atoms. That is, R ¹ is a linear or branched alkylene group, a cycloalkylene group having a ring of 5 to 6 carbon atoms, a heterocyclic group containing at least one of oxygen, nitrogen or sulfur atoms, benzene group or polycyclic aromatic Introduction ^{-NHCO -, - NR 6 -,} SiR 6 R 7 - or -SO ₂ - and the like plurality of benzene groups or alicyclic groups bonded by such (However, R ⁶ and R ⁷ represent an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having a ring having 5 to 6 carbon atoms, and a benzene group). Examples of the latter R ² , that is, a divalent group containing a carbon-carbon double bond include a maleic acid residue, a citraconic acid residue, and a tetrahydrophthalic acid residue. Therefore, specific examples of the N, N′-bisimide compound of unsaturated dicarboxylic acid satisfying the above-mentioned conditions of R ¹ and R ² include the following, and each of them is one kind or two or more kinds. It is possible to use it in a mixed system. For example, maleic acid N, N'-4,4'-diphenylmethane bisimide, maleic acid N, N'-4,4'-diphenyl ether bisimide, maleic acid N, N'-paraphenylene bisimide, maleic acid N, N ′ -Benzidine bisimide, maleic acid N, N′-metaxylene bisimide, maleic acid N, N′-1,5-naphthalene-bisimide,
Maleic acid N, N'-4,4'-diphenylsulfone-bisimide, maleic acid N, N'-2,2'-4,4'-dimethylene-
Cyclohesane-bisimide, maleic acid N, N'-4,4'-
Dicyclohexyl-methanebisimide, maleic acid N,
N'-4,4'-diphenylcyclohexane-bisimide,
Maleic acid N, N'-4,4'-diphenyl-phenylamine-bisimide, maleic acid N, N'-4,4'-diphenyl-
Diphenylsilane-bisimide, maleic acid N, N'-4,
4'diphenylsulfur-bisimide, maleic acid N, N'-2,
2 '-(4,4'-diphenyl) -propane-bisimide,
Maleic acid N, N'-metaphenylene-bisimide, maleic acid N, N'-3,3 '-(N, N'-metaphenylene-bisbenzamido) bisimide, and the like.

As the aminophenol (b), those having the following general formula can be used.

However, in the formula, R ³ represents a hydrogen atom, a halogen atom or an alkyl group.

Specific compounds include the following, and these are used as one type or as a mixed system of two or more types. For example o
-Aminophenol, m-aminophenol, p-aminophenol, 2-amino-4-chloroferrol, 2
-Amino-4-methylphenol and the like.

As (c) aniline or an aniline derivative, one having the following general formula is used.

However, in the formula, R ⁴ and R ⁵ are a hydrogen atom, an alkyl group, a halogen atom, -OCH ₃ , -OC ₂ H ₅ , -COOCH ₃ , or a group such as -COOC ₂ H ₅ , which does not contain active hydrogen. Specific compounds are, for example, aniline, o-chloroaniline, m-toluidine, methyl-p-aminobenzoic acid ester and the like, and any compounds that do not contain active hydrogen in the nuclear substituent of aniline Can be used. These may be used alone or in admixture of two or more.

The (C) epoxy compound used in the present invention is a low molecular weight compound or a high molecular weight compound having at least two epoxy groups in the molecule. For example, Epicoat 828 (trade name, manufactured by Shell Chemical Co., Ltd.), which is an epibis type compound based on bisphenol A, and alkyl-modified type Epiclon 80
0, Epiglycon 4050 (manufactured by Dainippon Ink and Chemicals, Inc., trade name), Shodyne (Showa Denko KK, trade name), Araldite CY-183 (Ciba Geigy, trade name) and other glycidyl ester compounds, novolak type Epicote
154 (Shell Chemical Company, trade name), DEN431, DEN438 (Dow Chemical Company, trade name), cresol novolac type EC
N1280, ECN1235 (Ciba-Geigy, trade name), urethane modified EPU-6, EPU-10 (Asahi Denka Kogyo, trade name)
and so on. Further, epoxy resins represented by the following formulas (1) to (3) can also be used.

In addition to the above epoxy resins, various epoxy resins can be used, and in short, all kinds of epoxy resins can be used if the conditions are appropriately selected. These epoxy resins may be used alone or in combination of two or more.

Examples of the (D) curing accelerator used in the present invention include disiamide, Epicure YPH-2011 (trade name of Yuka Shell Epoxy Co., Ltd.), and BF ₃ imidazole chain AC-4B series (trade name of Maruzen Petroleum Co., Ltd.). ), Imidazole derivative, 4,
Aromatic amines such as 4'-diaminodiphenyl sulfone can be mentioned, and these can be used alone or in admixture of two or more.

The thermosetting resin composition of the present invention contains poly-p-vinylphenols, addition reaction products, and epoxy compounds as essential components, and the blending ratios of these will be described.

An N, N'-bisimide compound of an unsaturated dicarboxylic acid is reacted with aminophenol and aniline or an aniline derivative in the absence of solvent or in an inert solvent, and then an epoxy compound is reacted with poly-p-vinylphenol. It is a thermosetting resin composition. In this case, (a) the total amount of (b) aminophenol and (c) aniline or an aniline derivative [(b) + (c)] with respect to 1 mol of the N, N'-bisimide compound of unsaturated dicarboxylic acid. Is 0.1 to 1.0 mol, and the epoxy compound is preferably 0.2 to 2.0 equivalents. When the total amount of (b) aminophenol and (c) aniline or an aniline derivative exceeds 1.0 mol, an epoxy compound corresponding to the excess must be blended, and as a result, the most characteristic feature of the resin composition is This is because some heat resistance is impaired. On the other hand, if it is less than 0.1 mol, the softening temperature is high, the solubility is deteriorated, and it is insoluble in the low boiling point solvent, which is not preferable. This is because when the epoxy compound is less than 0.2 equivalent, the moisture resistance becomes poor, and when it exceeds 2.0 equivalent, the heat resistance (bending strength and hardness at a high temperature of 200 ° C.) is impaired. (A) Poly-
Resin component [(A) + (B), which is the total amount of p-vinylphenols, (B) reaction product, and (C) epoxy compound.
+ (C)] is 5 to 50 of poly-p-vinylphenols.
It is desirable that the composition comprises 50% by weight and 50 to 95% by weight of the total amount [(B) + (C)] of the reaction product and the epoxy compound.

This is because if the blending amount of [(B) + (C)] is less than 50% by weight, sufficient heat resistance cannot be obtained, and if it exceeds 95% by weight, the mechanical strength is lowered, which is not preferable. The (D) curing accelerator is used to accelerate the curing of the epoxy compound and is preferably added in an amount of 0.01 to 5% by weight based on the epoxy compound. If the blending amount is less than 0.01% by weight, there is no effect in promoting curing,
Further, if it exceeds 5% by weight, storage stability and workability are deteriorated, which is not preferable.

The active hydrogen of the reaction product of N, N′-bisimide compound and aminophenol and / or aniline or aniline derivative can be sufficiently reacted with the epoxy compound, and the moisture resistance can be improved without impairing the heat resistance. it can. Further, by introducing poly-p-vinylphenols into the resin system, the mechanical strength can be improved and the conventional excellent workability can be maintained.

Next, the method for producing the thermosetting resin composition of the present invention will be described. The mixing order and reaction temperature of the poly-p-vinylphenols, reaction products, epoxy compounds, and curing accelerators that are the above-mentioned components. The solvent can be appropriately selected and is not particularly limited.

In the reaction vessel, N, N'-bisimide compound of unsaturated dicarboxylic acid, aminophenol and aniline or aniline derivative are charged at a predetermined ratio, and the temperature is raised to 100 to 200 ° C to melt the contents, After advancing the reaction until the viscosity of 1 is reached, the temperature is lowered to 80 to 150 ° C., a predetermined amount of epoxy compound and poly-p-vinylphenol are added, and the reaction is continued while stirring at the same temperature. As the reaction progresses, the reaction system gradually becomes viscous, so the cure time is measured and the reaction proceeds to an appropriate point. This reaction product can be dissolved in a solvent such as acetone, methyl ethyl ketone, dioxane, or tetrahydrofuran to obtain a resin solution suitable for lamination or adhesion. Further, by pulverizing the solid content of the reaction product, a powder suitable for molding can be obtained.

On the other hand, when preparing a resin solution for a laminate or an adhesive, a solvent can be used from the beginning. For example, in a reaction vessel, N, N'-bisimide compound of unsaturated dicarboxylic acid, aminophenol and aniline or aniline derivative are charged together with dioxane, and the reaction is allowed to proceed while refluxing dioxane until a predetermined viscosity is reached. Add a quantity of epoxy compound and poly-p-vinylphenols. Then, by allowing the reaction to continue while refluxing dioxane until an appropriate cure time is exhibited, a resin solution for a laminate or an adhesive can be obtained.

The resin composition thus prepared may contain various additives and fillers depending on the intended use. For example, to obtain a composition suitable for molding, a curing rate is adjusted by adding a curing agent for epoxy resins such as amines and imidazole to this resin composition. Further, in order to obtain a composition suitable for a laminate or an adhesive, a filler such as a tackifier or a flame retardant can be appropriately blended in addition to the above-mentioned curing agent.

(Examples) Next, the present invention will be specifically described with reference to Examples. In the following Examples and Comparative Examples, "parts" and "%" mean "parts by weight" and "% by weight", respectively.

Example 1 Maleic acid N, N ′ was placed in a flask equipped with a stirrer and a thermometer.
36.03 parts of -4,4'-diphenyl ether bisimide, p
-Aminophenol (6.0 parts), aniline (4.15 parts) and dioxane (26.0 parts) were charged, and the reaction was allowed to proceed for 12 hours while the dioxane was refluxed until it reached 57 seconds (50 ° C) with a bubble viscometer.
Next, 30.0 parts of Epikote 828 (trade name, manufactured by Shell Chemical Co., Ltd.), 75.0 parts of Marzene resin MB and 75 parts of dioxane were mixed, and the mixture was further heated and stirred for 30 minutes and cooled. An adhesive was prepared by adding 0.1 part of 2-ethyl-4-methyl-imidazole to this solution. The adhesive strength of this adhesive was measured by the tracker method, and the result was 71 kg / mm ² . next
125 μm Nomex paper (made by DuPont, polyamide paper) is coated with an adhesive of about 50 μm, air-dried, and further dried at 50 ° C. for 5 minutes, 80 ° C. for 10 minutes, and 105 ° C. for 10 minutes.
Two Nomex papers with a width of 0 mm were sandwiched between Teflon glass cloths and pressed at 170 ° C., 10 kg / cm ² for 30 minutes to bond them. The bonded product was subjected to after-curing at 200 ° C for 15 hours. Nomex paper in vacuum degassed silicone oil The above bonded product was subjected to a deterioration test at 220 ° C for 300 hours. The adhesive strength was retained at 80%, and no deterioration of the silicone oil was observed, indicating excellent heat resistance. showed that.

Example 2 Maleic acid N, N'-4,4'-diphenylmethanebisimide
35.83 parts, o-aminophenol 1.64 parts and p-aminobenzoic acid ethyl ester 0.84 parts were charged and heated with occasional stirring. The contents melted at about 130 ° C. Stir this liquid strongly, raise the temperature to 150 ° C and proceed the reaction for about 15 minutes, lower the temperature to 120 ° C and proceed the reaction for another 15 minutes, and when the temperature is lowered to 80 ° C, epoxy resin Epicoat 1001
20 parts (trade name, manufactured by Shell Chemical Co., Ltd.) was added, and heating and stirring was continued for another hour. Next, 0.08 part of 2-ethyl-4-methyl-imidazole, 23 parts of graphite, and Marzene range M
After 3.2 parts were added and uniformly dispersed, the contents were poured into an enameled bat and cooled, and then pulverized with a mixer.
Place this powder in a mold and press at a temperature of 200 ° C and a pressure of 50 kg / cm ² , 30
It was compression molded for a minute to obtain a molded product. This molded product at 200 ℃ 1
After after-curing for 5 hours, the bending strength was measured and found to be 9.5 kg / mm ^{2 at} room temperature and 9.0 kg / mm ² at 220 ° C. After heating the molded product at 230 ° C. for 200 hours, the bending strength at room temperature was measured and found to be 9.2 kg / mm ² . Furthermore, the coefficient of friction of the same molded product at a load of 100 kg and a linear velocity of 1 m / sec was calculated to be 0.03. Although the temperature of the friction surface had risen to 220 ° C, almost no deterioration due to wear was observed, indicating excellent heat resistance.

Example 3 Maleic acid N, N'-4,4'-diphenylmethane-bisimide 358.0 parts, 2-amino-4-chlorophenol 72.31
And 27.03 parts of m-toluidine are mixed and stirred, and when the temperature exceeds 100 ° C., the solution gradually begins to dissolve and becomes a brown liquid. This liquid was heated to 120 ° C. and stirred for 1 hour. In this way, bismaleimide was added with aminophenol and aniline derivative, and dissolved in dioxane to give 50
% Solution, 100 parts of this solution (50 parts of resin content), epoxy novolac resin DEN438 (trade name, manufactured by Dow Chemical Co.)
49.0 parts, Marzene resin MB51.4 parts, and methyl cellosolve acetate 100 parts were blended. Further, 0.5 part of AC-4B50 (manufactured by Maruzen Petrochemical Co., Ltd.) was added and stirred to obtain a uniform mixed solution. Dip aminosilane-treated glass cloth, air-dry for 30 minutes, and then dry in a dryer kept at 100 ° C for 10 minutes.
After that, it was dried for 7 minutes at 150 ° C. to prepare a prepreg.

Stacking several prepregs, pressure 40kg / cm ² , temperature 170
The laminate was molded by heating and pressing at ℃ for 1 hour. Also, thickness 35
A copper clad laminate was also prepared in the same manner by bonding with a copper foil of μm. After this laminate was after-cured at 200 ° C for 1 hour, 25
When the bending strength was measured when it was left to cool to ℃, it was 57 kg.
/ mm ² , and the bending strength in an atmosphere of 200 ° C is 20 kg / mm ² ,
The surface hardness at 200 ° C. was 55 as a Barcol hardness. As a hygroscopicity accelerating test, it was floated in a solder bath at 300 ° C. after boiling and tested, but there was no abnormality for 2 minutes even 6 hours after boiling. In addition, a measling test (2
Even after 8 hours of boiling, there was no abnormality.

Examples 4 to 6 and Comparative Examples 1 to 2 A resin composition having the composition shown in Table 1 was prepared in the same manner as in Example 3, a prepreg and a laminated board were prepared, and various properties were similarly tested. The results are shown in Table 1.

[Effects of the Invention] As is clear from the above description and Table 1, the thermosetting resin composition of the present invention has excellent heat resistance, mechanical properties, and moisture resistance, and has good solubility in low boiling point solvents, It has excellent workability, and when it is used for laminated plates, molded products, adhesives, etc., the B stage can be easily achieved, which is very useful in practice.

Continuation of front page (56) Reference JP-A-51-77698 (JP, A) JP-A-53-30700 (JP, A) JP-A-53-41397 (JP, A) JP-A-55-48216 (JP , A) JP 56-125423 (JP, A) JP 56-151726 (JP, A) JP 62-62880 (JP, A)

Claims (5)

[Claims] 1. A general formula (A) (Wherein, n represents an integer of 10 to 40), poly-p-vinylphenol, (B) (a) general formula (In the formula, R ¹ represents a divalent group having at least 2 carbon atoms, and R ² represents a divalent group containing a double bond between carbon atoms.) N of the unsaturated dicarboxylic acid represented by , N'-bisimide compound and (b) general formula (Wherein R ³ represents a hydrogen atom, a halogen atom or an alkyl group) and (c) the general formula (In the formula, R ⁴ and R ⁵ represent a hydrogen atom, an alkyl group, a halogen atom, -OCH ₃ , or a group of -OC ₂ H ₅ that does not contain active hydrogen) and an aniline or an aniline derivative. A thermosetting resin composition comprising the reaction product (1), (C) an epoxy compound having two or more epoxy groups in the molecule, and (D) a curing accelerator as essential components. 2. The resin component [(A) + (B) + (C)] is
5 to 50% by weight of poly-p-vinylphenol, and the total amount of reaction product and epoxy compound [(B) + (C)]
The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition comprises 50 to 95% by weight. 3. The total amount [(b) + (c)] of aminophenol (b) and aniline or aniline derivative (c) is 0.1 to 1.0 with respect to 1 mol of N, N'-bisimide compound (a).
The thermosetting resin composition according to claim 1 or 2, which is in a molar amount. 4. The thermosetting composition according to claim 1, wherein 0.2 to 2.0 equivalents of the epoxy compound (C) is added to 1 mol of the N, N'-bisimide compound (a). Resin composition. 5. The thermosetting resin composition according to any one of claims 1 to 4, wherein the curing accelerator (D) is blended in an amount of 0.01 to 5% by weight with respect to the epoxy compound (C).