JPH03739A - Heat-resistant resin composition - Google Patents

Abstract

PURPOSE:To provide a heat resistant resin compsn. for laminated sheet with excellent heat resistance, moisture resistance, solubility and storage stability by preparing an addition reaction product of an unsatd. dicarboxylic acid bisimide compd., an aminophenol and an arom. polyamine. CONSTITUTION:Addition reaction of an unsatd. dicarboxylic acid N,N'-bisimide compd. (A) of formula I (wherein R<1> is a 2C or higher divalent group; R<2> is a divalent group contg. a carbon-carbon double bond) (e.g. maleic acid N,N '-4,4'-(diphenyl methanebisimide), an aminophenol (B) of formula II (wherein R<3> is H, a halogen or an alkyl) (e.g. 2-amino-4-chlorophenol) and an arom. monoamine (C) of formula III (wherein R<4> is H or an alkyl, R<5> is an alkyl) (e.g. o-anisidine) is performed in such a way that 0.1-1.0 mole of the sum of the components B and C is reacted with 1 mole of the component A to prepare a heat-resistant resin compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to a heat-resistant a-phase acid having excellent heat resistance, moisture resistance, solubility, and storage stability.

(A branch of the conventional technique) With the development of electronic devices, the characteristics required for printed wiring boards used in these devices have become fairly strict, and polyimide resin is used especially when heat resistance is required. It has started to be done.

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 also types of addition reactions of bisimide and aminophenol, which have various drawbacks.

(Invention or problem to be solved a> That is, N of the former unsaturated dicarboxylic acid.

Although the reaction product of N'-bisimide and diaminodiphenylmethane has extremely high heat resistance, it has poor solubility in solvents and is only soluble in high-boiling polar solvents such as N-methylpyrrolidone, and the resulting varnish It also had poor storage stability and manufacturing defects.

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 unsaturated dicarboxylic acid and aminophenol has extremely good solubility and can be used in low boiling point solvents, and the varnish has good storage stability. Since the OH group in the skeleton is hydrophilic, it has the disadvantage of poor moisture resistance. in this way,
It has been difficult to obtain a heat-resistant resin composition for laminates that is excellent in terms of properties and production.

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

[Structure of the Invention (Means for Solving the Problem) As a result of extensive research aimed at achieving 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 provides: (A) General formula (wherein R1 represents a divalent group having at least two carbon atoms, R2 represents a divalent group containing a double bond between carbon atoms, ) of the unsaturated dicarboxylic acid represented by
-bisimide compound, (8) General formula N'-Bisimide compound has the following general formula.

(However, in the formula, R3 represents a hydrogen atom, a halogen atom, or an alkyl group.) General formula of aminophenol (C) (However, in the formula, R4 represents a hydrogen atom or an alkyl group, and R5 represents an alkyl group. ) is a heat-resistant resin composition characterized by being formed by addition-reacting an aromatic monoamine represented by:

The present invention will be explained in detail below.

N(D,
L, in which R1 represents a small group having at least 2 carbon atoms, and R2 represents a divalent group containing a double bond between carbon atoms, that is, R1 represents a linear or branched group. Alkylene group, cycloalkylene group having a ring of 5 to 6 carbon atoms, divalent heterocyclic group containing at least one oxygen, nitrogen or sulfur atom, phenylene group or 2#J polycyclic aromatic group Including -N HC0-5-NR' --
Examples include a plurality of aromatic groups and alicyclic groups bonded by 3iR'R'- or -SO□-. R', r(', R'' represent an alkyl group having 1 to 4 carbon atoms or a phenyl group.

Examples of R2, that is, a divalent group containing a double bond between carbon atoms, include maleic acid residues, citraconic acid residues, tetrahydrophthalic acid residues, etc., which may be used alone or in combination of two or more. can be used. Specific examples of these compounds include maleic acid N, N
'-4,4'-diphenylmethane bisimide, maleic acid N, N'-4,4'-diphenyl ether bisimide, maleic acid NN'-paraphenylene bisimide, maleic acid N.

N'-benzidine bisimide, N maleic acid, N'-metaxylene bisimide, N maleic acid, N'-1゜5-
Naphthalene bisimide, maleic acid N, N'-44'-
Diphenylsulfone bisimide, maleic acid N N'
-22'-4,4'-dimethylenecyclohexane bisimide, N maleic acid, N'-4,4'-dicyclohexylmethane bisimide, N maleic acid, N'-4,4'
-diphenylcyclohexane bisimide, maleic aN
, N'-4,4'-diphenylphenylamine bisimide, maleic acid N, N'-4,4'-diphenyldiphenylsilane bisimide, maleic acid NN'-4,4'
-Diphenyl sulfur bisimide, maleic acid N, N'-
2,2"-(4,4'-diphenyl)-propane bisimide, N maleic acid, N'-metaphenylene bisimide, N maleic acid, N'-3,3'-(NN'-metaphenylene bisbenz) (amide) bisimide, etc.

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. Specific compounds include, for example, 0-aminophenol, doaminophenol, p-aminophenol, 2-amino-4-talolophenol, 2-amino-
Examples include 4-methylphenol, and these can be used alone or in a mixture of two or more.

(C) Aromatic monoamine used in the present invention However, in the formula, R4 represents a hydrogen atom or an alkyl group, and R5 represents an alkyl group. Specific compounds include 0-anisidine (0-methoxyaniline) , p-anisidine (p-methoxyaniline), p-phenetidine (p-ethoxyaniline), p-cresidine (5-methyl-〇-anisidine), etc., which may be used alone or in combination of two or more. be able to.

The heat-resistant resin composition of the present invention contains the above-mentioned (A>N,N'-bisimide compound of unsaturated dicarboxylic acid, (B) aminophenol, (C) aromatic monoamine!! in a solvent or an inert solvent. The blending ratio of each of these components is (A) per mole of the N,N'-bisimide compound of the unsaturated dicarboxylic acid.
It is desirable that the total amount of fil[(F3)(C)] of B) aminophenol and (C) aromatic monoamine is blended from 0.1 to 1.0 mol. If the proportion is less than 0.1 mol, the reaction will not proceed and properties such as heat resistance and toughness will deteriorate, and if it exceeds 1.0 mol, unreacted amine will remain, which is not preferable since heat resistance will be significantly reduced. The mixing order of 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 aromatic monoamine are charged in a predetermined ratio, heated to 100 to 200°C to melt the contents, and achieve a predetermined viscosity. , proceed the addition reaction until cure time. A resin composition having properties suitable for use in laminates can be produced by dissolving this reactant in a solvent such as acetate, methyl ethyl ketone, dioxane, te)-rahydrofuran, or methyl cellosolve. Moreover, a solvent can also be used from the beginning of the eel. For example, an N,N'-bisimide compound of an unsaturated dicarboxylic acid, an aminophenol, and an aromatic monoamine are charged together with dioxane into a reaction vessel, and while the dioxane is refluxed, a predetermined viscosity is maintained.
A resin composition for a laminate can be produced by allowing the pressure section to proceed until the curing time, then adding a solvent and cooling.

The resin composition produced in this way may contain various additives and fillers, as necessary, within limits that do not contradict the purpose of the present invention.

Catalysts such as imidazole for adjusting the curing rate,
A coupling agent for imparting adhesive properties, a flame retardant for imparting flame retardance, an inorganic filler, etc. can be added as appropriate.

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

Actual example 1 In a flask equipped with a stirrer and a thermometer, malein fiN,
N'-4,4'-diphenylmethane bisimide 358
g and 2-amino-4-chlorophenol 71 (l and O-
Anisidine (O-methoxyaniline) 61i;],
Add 490 g of dioxane to it and heat while stirring.

When the temperature exceeds 100°C, it gradually begins to dissolve and becomes a brown liquid. This liquid was heated to 120° C. and stirred for 1 hour to obtain a heat-resistant resin composition. Dioxane was further added to this composition and stirred to produce a varnish.

Example 2 A flask equipped with a stirrer and a thermometer; malein IN, N'-4,4'-diphenylmethane bisimide 3
A heat-resistant resin composition and a varnish were prepared in the same manner as in Example 1 by adding 58 g of 0-amine phenol, 54 g of 0-amine phenol, 68 g of p-phenetidine (p-ethoxyaniline), and 4809 dioxane.

Example 3 In a flask equipped with a stirrer and a thermometer, maleiWN,
N'-4,4'-diphenylmethane bisimide 358
g and l-aminophenol 54Q and p-cresidine (
5-Methyl-0-anisidine) eag and 480 g of dioxane were added thereto, and a heat-resistant resin composition and varnish were produced in the same manner as in Example 1.

Comparative Example l 358 g of maleic acid N, N'-4,11'-diphenylmethane bisimide, 198 g of 4,4'-diaminodiphenylmethane, and 5509 N-methylpyrrolidone were charged into a flask, and 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 flask was charged with 358 maleic acid N, N'-4,4'-diphenylmethane bisimide, 109 g of ■-aminophenol and 460 g of dioxane, and Example 1 was prepared.
A heat-resistant resin composition and varnish were produced in the same manner as above.

Using the gM varnishes prepared in Examples 1 to 3 and Comparative Examples 1 to 2, a glass cloth with a thickness of 180 μm was coated and impregnated, and dried at a temperature of 150° C. to a resin content of 43! I! Get 8 sheets of this prepreg and 18 pieces of J7.
Using two pieces of μl copper foil at a temperature of 180°C.

It is heated and pressed into one piece for 120 minutes at a pressure of 40 kgf/cm', and has a heat resistance of 1.61+1 plate thickness. 4-layer laminate laminate. The obtained laminates were tested for jPI foil peel strength, water absorption, glass transition point, bending strength, soldering heat resistance, and varnish pot life and solubility, and the results are shown in Table 1. Na. The varnish of the present invention has excellent solubility and pot life, and also has good properties for laminates, 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
Represents a valence group. ) N,N'-bisimide compounds of unsaturated dicarboxylic acids, (B) General formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, R^3 is a hydrogen atom, a halogen atom, or an alkyl group. Aminophenol represented by (C) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, R^4 is a hydrogen atom or an alkyl group, R^
5 represents an alkyl group. ) A heat-resistant resin composition obtained by subjecting an aromatic monoamine represented by the following formula to an addition reaction.