JPH0343420A - Heat-resistant resin composition - Google Patents

Abstract

PURPOSE:To obtain the title polyimide-based composition suitable for laminate, having excellent heat resistance, water-vapor resistance, solubility and shelf stability by subjecting an N,N'-bisimide compound of unsaturated dicarboxylic acid, aminophenol and a monocyclic aromatic diamine to addition reaction. CONSTITUTION:(A) An N,N'-bisimide compound of unsaturated dicarboxylic acid (e.g. maleic acid N,N'-4,4'-diphenylmethanebisimide) shown by formula I (R<1> is >=2C bifunctional group; R<2> is bifunctional group containing double bond between carbon and carbon), (B) an aminophenol (e.g. o-aminophenol) shown by formula II (R<3> is H, halogen or alkyl) and (C) a monocyclic aromatic diamine (e.g. o-phenylenediamine) shown by formula III (R<4> is H or alkyl) are subjected to addition reaction to give the aimed composition. Preferably 1mol component A is blended with 0.1-1.0mol components B+C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention provides a polyimide-based heat-resistant resin composition that has excellent heat resistance, moisture resistance, solubility, and storage stability.

(Prior art) With the development of electronic devices, the characteristics required of the printed wiring boards used in them are becoming increasingly strict, and polyimide resins are increasingly being used especially when heat resistance is required. It has become.

Polyimide resins used for these include reaction products of unsaturated dicarboxylic acid N,N'-bisimide and diaminodiphenylmethane, and unsaturated dicarboxylic acid N,N'-bisimide and diaminodiphenylmethane.
There are addition reaction types of bisimide and amine phenol reactants, which have various drawbacks.

(Problems to be Solved by the Invention) That is, the former reaction product of N,N'-bisimide of unsaturated dicarboxylic acid and diaminodiphenylmethane has extremely excellent heat resistance, but has poor solubility in solvents. N-
It is only soluble in high-boiling polar solvents such as methylpyrrolidone, and the resulting varnish has poor storage stability, which is a manufacturing drawback.

Furthermore, high boiling point solvents tend to remain in the prepreg, which has the disadvantage of deteriorating properties such as heat resistance when made into a laminate. On the other hand, the latter reaction product of N N'-bisimide of an unsaturated dicarboxylic acid and aminophenol has extremely good solubility, allows the use of low boiling point solvents, and has good storage stability of the varnish. Since the OH group is hydrophilic, it has the disadvantage of poor moisture resistance. As described above, it has been difficult to obtain a heat-resistant resin composition for laminates with excellent IJ in terms of properties and production.

The present invention has been made in view of the above circumstances, and provides a heat resistant laminate with excellent heat resistance, moisture resistance, solubility, and storage stability, or with excellent properties and manufacturing properties of the laminate. The present invention aims to provide a resin composition.

[Structure of the Invention] (Means for Solving the Problem) As a result of extensive research to achieve the above object, the present inventor discovered that the above object could be achieved by using the composition described below, This completes the present invention.

That is, the present invention has the following formula: (A>- formula (wherein R1 represents a divalent group having at least two carbon atoms, and R2 represents a divalent group containing a double bond between carbon atoms) N, N'- of the unsaturated dicarboxylic acid represented by
Bisimide compound, aminophenol represented by the formula (B) (wherein R' represents a hydrogen atom, a halogen atom, or an alkyl group), (C)-a formula (wherein R4 represents a hydrogen atom or an alkyl group) This is a heat-resistant resin composition characterized by being formed by addition-reacting monocyclic aromatic diamines represented by the following four R4 groups (representing the same or different groups).

The present invention will be explained in detail below.

As the NN'-bisimide compound of unsaturated dicarboxylic acid (A) used in the present invention, one having the following general formula is used.

However, in the formula, R1 is at least 2 (2 groups that accommodate the carbon atoms of Ill), and R2 is 2 groups containing a double bond between carbon atoms.
In other words, R1 represents a linear or branched alkylene group, a cycloalkylene group having a ring of 5 to 6 carbon atoms, or a divalent group containing at least one of oxygen, nitrogen, or sulfur atoms. including heterocyclic groups, phenylene groups or divalent polycyclic aromatic groups, -NHCO--NR'
Examples include a plurality of aromatic groups and alicyclic groups bonded by --3i R'R' --3o2- and the like. R', R', and R' represent an alkyl group having 1 to 4 carbon atoms or a phenyl group. R2, that is, a divalent group containing a double bond between carbon atoms, includes, for example, a maleic acid residue, Examples include citraconic acid residues and tetrahydrophthalic acid residues, and these can be used alone or in combination of two or more. Specific examples of these compounds include maleic GN, N'-4,4'-diphenylmethane bisimide, maleic acid N, N'-4,4
'-diphenyl ether bisimide, malein IN, N
'-Varaphenylene bisimide, maleic acid N, N'-
Benzidine bisimide, maleic acid N, N'-metaxylene bisimide, maleic acid N, N'-1,5-naphthalene bisimide, maleic MN, N'-4,4'-diphenylsulfone bisimide, maleic acid N .

N'-2,2'-4,4'-dimethylenecyclohexane bisimide, N maleic acid, N'-4,4'-dicyclohexylmethane bisimide, N maleic acid, N'-
4,4'-diphenylcyclohexane bisimide, maleic 9N, N'-4,4'-diphenylphenylamine bisimide, maleic acid N, N'-4,4'-diphenyldiphenylsilane bisimide, maleic acid N.

N'-4,4'-diphenyl sulfur 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.

Examples include N'-metaphenylenebisbenzamide)bisimide.

As the amine phenol (B) used in the present invention, those having the following general formula can be used.

However, in the formula, R3 represents a hydrogen atom, a halogen atom, or an alkyl group. Examples of specific compounds include 0-aminophenol, aminophenol, ρ-aminophenol, 2-amino-4-chlorophenol, and 2-aminophenol. −
Examples include 4-methylphenol, which can be used alone or in combination of two or more.

As the monocyclic aromatic diamine (C) used in the present invention, those having the following general formula can be used.

However, in the formula, R4 is a hydrogen atom or an alkyl group, and 4 R4
represent the same or different groups, and specific compounds include O-phenylenediamine, phenylenediamine, p-phenylenediamine, tolylenediamine, 4
, 6-dimethyl-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2,4-diaminomesitylene, 4-chloro-〇-phenylenediamine, 4-chloro-phenylenediamine, 2-chloro-p-phenylene Diamine, 2,5-dichloro-p-phenylenediamine, 2,6-dichloro-〇-phenylenediamine, 5
-chloro-2-methyl-p-phenylenediamine, etc., and these can be used alone or in a mixture of two or more.

The heat-resistant resin composition of the present invention contains the above-mentioned (A) N,N'-bisimide compound of unsaturated dicarboxylic acid, (B) aminophenol, and (C) monocyclic aromatic diamine in an inert solvent. It can be obtained by carrying out a heating addition reaction in a medium. The blending ratio of each of these components is (A) per mole of N,N'-bisimide compound of unsaturated dicarboxylic acid (
It is desirable to blend the total amount of B) amine phenol and (C) monocyclic aromatic diamine [(B) + (C)] from 0.1 to 1.0 mol. If the ratio is less than 0.1 mol, The reaction does not proceed and properties such as heat resistance and toughness deteriorate, and
．． If the amount exceeds 0 mole, unreacted amine will remain and the heat resistance will be significantly reduced, which is undesirable.The order of blending each component, reaction temperature, solvent, etc. can be selected as appropriate and are not particularly limited.

Next, a typical manufacturing method of the heat-resistant resin composition of the present invention will be explained.

Into a reaction vessel, an unsaturated dicarboxylic acid N,N'-bisimide compound, aminophenol, and monocyclic aromatic diamine were charged in a predetermined ratio (heated to 1 to 200°C to melt the contents, The addition reaction is allowed to proceed until a predetermined viscosity and cure time are reached. This reaction product is dissolved in a solvent such as acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, methyl cellosolve, etc. to produce a resin composition having properties suitable for use in laminates. Alternatively, a solvent can be used from the beginning. For example, an unsaturated dicarboxylic acid N,N'-bisimide compound, aminophenol, and monocyclic aromatic diamine are charged together with dioxane, and the dioxane is refluxed. However, the addition reaction is allowed to proceed until a predetermined viscosity and cure time are reached, and then a solvent is further added and cooled to produce a resin composition for a laminate.

The resin composition thus produced may contain various additives and fillers as necessary, within limits that do not contradict the purpose of the present invention. For example, a catalyst such as imidazole for adjusting the curing rate, a coupling agent for imparting adhesion, a flame retardant for imparting flame retardancy, an inorganic filler, etc. can be added as appropriate.

(Example) Next, the present invention will be explained by examples.

Example l In a flask equipped with a stirrer and a thermometer, maleic acid N,
N'-4,4''-diphenylmethane bisimide 358g
71 g of 2-amino-4-chlorophenol, 540 g of phenylenediamine, and 480 g of dioxane were charged and heated while stirring. When the temperature exceeds 100°C, it gradually begins to dissolve and becomes a brown liquid. 120% of this liquid
The temperature was raised to °C and stirred for 1 hour to obtain a heat-resistant resin composition. Dioxane was further added to this composition to produce a stirred-like varnish.

Example 2 In a flask equipped with a stirrer and a thermometer, maleic acid N,
N'-4,4'-diphenylmethane bisimide 358g
A heat-resistant resin composition and a varnish were prepared in the same manner as in Example 1 by charging 54 g of 0-aminophenol, 61 g of toluylene diamine, and 470 g of dioxane.

Example 3 In a flask equipped with a stirrer and a thermometer, maleic acid N,
N'-4,4'-diphenylmethane bisimide 358g
Example 1
A heat-resistant resin composition and varnish were produced in the same manner as above.

Comparative Example 1 358q of maleic acid N, N''-4,4'-diphenylmethane bisimide, 198 g of 4,4'-diaminodiphenylmethane, and 550 g of N-methylpyrrolidone were charged into a flask, and a heat-resistant resin was prepared in the same manner as in Example 1. A composition was obtained. N-methylpyrrolidone was further added to this composition and stirred to produce a --like varnish.

Comparative Example 2 A heat-resistant resin composition and varnish were prepared in the same manner as in Example 1 by charging 3589 g of malein 9N, N'-4,4'-diphenylmethane bisimide, 109 g of aminophenol, and 460 g of dioxane.

Using the varnishes produced in Examples 1 to 3 and Comparative Examples 1 to 2, a glass cloth with a thickness of 180 μm was coated and impregnated.
It was dried at a temperature of 50°C to obtain a prepreg with a resin content of 43% by weight. Using 8 sheets of this prepreg and 2 sheets of 18μ thick copper foil, the temperature was 180°C.

A heat-resistant copper-clad laminate having a thickness of 1.6 Ill was produced by heat-pressing and integrally bottom-shaping it at a pressure of 40 kgf/cn2 for 120 minutes. Regarding the obtained laminate, the copper foil peel strength,
The water absorption rate, glass transition point, bending strength, soldering heat resistance, and pot life and solubility of the varnish were tested, and the results are shown in Table 1. The varnish of the present invention has excellent solubility and pot life, and also has good properties for laminated plates, confirming the effects of the present invention.

[Effects of the Invention] As is clear from the above explanation and Table 1, the heat-resistant resin composition of the present invention has excellent heat resistance and moisture resistance, and also has good solubility and storage stability. It has excellent properties and manufacturing properties and is suitable for use in laminates.

Claims (1)

[Claims] 1 (A) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, R^1 represents a divalent group having at least 2 carbon atoms, and R^2 represents a carbon 2 containing double bonds between atoms
N,N'-bisimide compound of unsaturated dicarboxylic acid represented by (representing a valent group), (B) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, R^3 is a hydrogen atom, a halogen (C) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, R^4 is a hydrogen atom or an alkyl group, and four R^4 are the same or different groups) A heat-resistant resin composition characterized in that it is formed by addition-reacting a monocyclic aromatic diamine represented by the following: