JPH02102262A - Heat-resistant copper-clad laminate - Google Patents

Abstract

PURPOSE:To obtain a heat-resistant copper-clad laminate of excellent humidity resistance and high reliability by using an addition type polyimide resin composition prepared from a specified aromatic diamine and a fluoro amino compound. CONSTITUTION:The title laminate is produced by laminating prepregs formed by impregnating a glass cloth with a heat-resistant resin composition comprising an N,N'-bisimide compound (A) of an usaturated dicarboxylic acid of formula I (wherein R<1> is a 2C or higher bivalent group; and R<2> is a bivalent group containing a C-C double bond) e.g., N,N'-4,4'-diphenylmethanebisimide, an amino compound (B) of formula II (wherein R<3> and R<4> are each H, an alkyl, a halogen, OH, OCH3 or the like) e.g., 2-amino-4-chlorophenol, an aromatic diamine (C) of formula III (wherein R<5>-R<8> are each an alkyl, a halogen or H) e.g., 4,4'- diaminodiphenylmethane, and a fluoro amino compound (D) which is a fluoro aromatic amine or diamine e.g., 2,2'-bis-4-aminophenylhexafluoropropane, and containing 0.01-0.5 equivalent of compound D per equivalent of compound A.

Description

DETAILED DESCRIPTION OF THE INVENTION [Object of the Invention] (Industrial Application Field) The present invention relates to a heat-resistant copper-clad laminate with excellent moisture resistance and high reliability.

(Prior Art) In recent years, the development of electronic devices has been remarkable, and accordingly, demands for high precision, high density, and high reliability of printed circuit boards have become stronger. For this reason, the resin materials for printed circuit boards are also changing from phenol resins, epoxy resins, etc. to highly heat-resistant epoxy resins, polyimide resins, etc. Among these, polyimide resin has excellent properties such as high heat resistance and almost no smearing during drilling for printed circuit boards. However, although polyimide resin has these excellent properties, it has strong hygroscopicity, so printed circuit boards have poor moisture resistance and insufficient reliability.

(Problems to be Solved by the Invention) The present invention has been made to eliminate the above-mentioned drawbacks, and aims to provide a heat-resistant steel clad laminate with excellent moisture resistance and high reliability.

[Structure of the Invention] (Means for Solving the Problems) As a result of intensive research to achieve the above object, the present inventors have discovered an addition method using a specific aromatic diamine in combination with a fluorine-containing amino compound. The present invention was completed by discovering that a highly reliable heat-resistant copper-clad laminate with excellent moisture resistance can be obtained by using a reactive polyimide resin composition.

That is, the present invention is based on (A) the general formula (wherein R1 is a divalent group having at least two carbon atoms, and R2 is 2 containing a double bond between carbon-carbon atoms).
N, N of the unsaturated dicarboxylic acid represented by (representing a valent group)
'-bisimide compound and (B) general formula (wherein R3, R' are hydrogen atoms, alkyl groups, halo'l'j atoms, -〇H1-0CH,, -QC2H,,
-COOCH3 or -COOC2H6), and (C) general formula (wherein R!I, R6, R7, and RB represent the same or different alkyl groups, halogen atoms, or hydrogen atoms)
and (D) an aromatic amine containing a fluorine atom or a fluorine-containing amino compound which is an aromatic diamine, with respect to 1 equivalent of the N,N'-bisimide compound of (A>), The fluorine-containing amino compound of (D) is 0
．． This heat-resistant copper-clad laminate is made by laminating a heat-resistant resin composition characterized by containing 0.01 to 0.5 equivalents, and a prepreg in which glass cloth is impregnated with this composition.

The present invention will be explained in detail below.

The (A) N,N'-bisimide compound used in the present invention has the following general formula.

However, in the formula, R1 is 2 having at least 2 carbon atoms.
a valent group, R2 is 2 containing a double bond between carbon-carbon atoms;
Represents a valence group. That is, R1 is a linear or branched alkyl 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, a benzene group, or Examples include polycyclic aromatic groups, a plurality of benzene groups bonded by -NHCO--NR9--8i R2H''--802-, and alicyclic groups.

However, R9 and R10 are alkyl groups having 1 to 4 carbon atoms,
Represents a cycloalkyl group or phenyl group having a ring having 5 to 6 carbon atoms.

Mana R2, that is, 2 containing a double bond between carbon-carbon atoms
Examples of the valent group include maleic acid residue, citraconic acid residue, and tetrahydrophthalic acid residue. Therefore, specific examples of unsaturated dicarboxylic acid N, N'- and simide compounds satisfying the above-mentioned conditions R1 and R2 include the following, and these can be used singly or in a mixed system of two or more. can do. maleic acid N,
N'-4,4'-diphenylmethane bisimide, N-maleic acid, N'-4,4'-diphenyl ether-bisimide, N maleic acid, N'-paraphenylene bisimide, N maleic acid, N'-benzidine Bisimide, maleic ilN, 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-cyclohexane-bisimide, maleic acid N, N'-4,4'-dicyclohexyl-methane bisimide, 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
'-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, N'
-metaphenylene-bisbenzamide) bisimide, and the like.

As the amino compound (B) used in the present invention, one having the following general formula is used.

However, in the formula, R2 and R4 represent a hydrogen atom, an alkyl group, a halogen atom, -OH, -0CH3, -〇〇2H,, -COOCH3 or -COOC2H. These compounds include aniline, 0-chloroaniline, totoluidine, methyl-
Examples include p-aminobenzoic acid ester and meta-aminophenol, and these may be used alone or in combination of two or more.

The aromatic diamine (C) used in the present invention has the following general formula.

However, in the formula, R5, R6, R', R8 represent the same or different alkyl group, halogen atom, hydrogen atom, and specific compounds include 4,4'-diamino-3,3'55'-
Tetrapropyldiphenylmethane, 4,4'-diamino-3,3'-diethyl-5,5'-dimethyldiphenylmethane, 4,4'-diethyl-5,5'-dimethyldiphenylmethane, 4,4'-diamino-3, 3', 5.
5'-tetraethyldiphenylmethane, 4,4'-diamino-3,3'-dichlorodiphenylmethane, 4,4'
-diaminodiphenylmethane, etc., and these may be used alone or in combination of two or more.

As the (D) fluorine-containing amino compound used in the present invention,
Aromatic amines or diamines containing fluorine atoms are used. Specific compounds include 4-aminobencitrifluorite, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4
-methylphenyl)hexafluoropropane, 2,2-bis[4-(aminophenoxy)phenyl]hexafluoropropane, etc., and these may be used alone or in combination of two or more.

The blending ratio of each component of the above-mentioned (A) N,N'-bisimide compound, (B) amino compound, (C) aromatic diamine, and (D) fluorine-containing amino compound is as follows.
For 1 equivalent of N,N'-bisimide compound (A),
(B) amino compound, (C) aromatic diamine, and (D
) Total amount of fluorine-containing amine compounds [(B)+ (C)+
(D)] is preferably blended in an amount of 0.1 to 1.0 equivalent. If the total amount is less than 0.1 equivalent, the reaction will not proceed and properties such as heat resistance and toughness will deteriorate, which is not preferable.

In addition, if the amount exceeds 1.0 equivalent, unreacted amine will remain,
It is not preferable because the heat resistance is significantly reduced. Also, (D)
The blending ratio of the fluorine-containing amine compound is (A) N, N'-
It is blended in an amount of 0.01 to 0.5 equivalent per equivalent of the bisimide compound. If the blending ratio is less than 0.01 equivalent, there is no effect on moisture resistance, and if it exceeds 0.5 equivalent, the cost will increase and it is not practical.

A heat-resistant resin composition is manufactured using the above components and blending ratios, or it is manufactured using a process similar to that used for ordinary clothing.

Each of the above-mentioned components is charged into a reaction vessel together with dioxane, and the reaction is allowed to proceed while refluxing the dioxane until a predetermined viscosity is achieved or until an appropriate cure time is obtained, and then a solvent such as diaminodimethylformamide is added to form a resin solution. Prepared. In the reaction of each component, the mixing order of the components, reaction temperature, and solvent can be appropriately selected, and are not particularly limited. The resin composition obtained in this way may contain an epoxy resin, various additives, curing accelerators, and fillers depending on the purpose, as long as it does not go against the spirit of the present invention.

A glass cloth is coated and impregnated with the thus produced heat-resistant resin composition, and then dried in a drying tower within a temperature range of 100 to 200°C to produce a prepreg.

A plurality of sheets of this prepreg are combined and laminated, silver foil is placed on at least one side of the prepreg, and the prepreg is heated and press-molded to produce a heat-resistant copper-clad laminate.

(Function) The heat-resistant copper-clad laminate of the present invention uses a specific aromatic diamine and a fluorine-containing amine compound in combination to obtain an addition reaction type polyimide resin composition, and by using this, it has particularly high heat resistance and moisture resistance. was able to be granted.

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

Example I N, N'-4,4'-diphenylmethane bisimide 3
58kg, 2-amino-4-chlorophenol 20k
g, 4,4'-diamino-3,3'-dimethyl-5,5
20 kg of '-diethyldiphenylmethane, and 2,2
20k of '-bis-4-aminophenyl-hexafluoropropane (] is charged into a reaction vessel and heated while stirring. Gradually starts to dissolve when the temperature exceeds 100°C and becomes a brown liquid. This liquid is further heated. The temperature was raised to 120° C. and stirred for 1 hour, and the amine compound was added to the bisimide compound to produce a heat-resistant resin composition.

This composition was dissolved in dioxane and stirred to prepare a 50% resin solution. A glass cloth treated with aminosilane was immersed in this resin solution, coated and impregnated with the resin solution, and dried by heating in a vertical drying tower to produce a prepreg. Layer several sheets of this prepreg, then layer silver foil on the front and back and apply pressure 4.
A heat-resistant copper-clad laminate was produced by heating and pressing at 0 kg/an' and a temperature of 170° C. for 2 hours. After curing this heat-resistant copper-clad laminate at 200°C for 1 hour, it was heated to 25°C.
The samples were allowed to cool for a while and their properties were tested, and the results are shown in Table 1. The copper-clad laminate of the present invention had a low water absorption rate, good measling resistance, and the effects of the present invention were recognized.

Examples 2 to 4 Heat-resistant steel clad laminates were manufactured in the same manner as in Example 1 using heat-resistant resin compositions having the compositions shown in Table 1. Also,
The test was conducted in the same manner as in Example 1, and the results are shown in Table 1. In all cases, the effects of the present invention could be confirmed.

Comparative Examples 1-2 Copper-clad laminates were manufactured in the same manner as in Example 1 using resin compositions having the compositions shown in Table 1. Further, tests were conducted in the same manner as in Example 1, and the results are shown in Table 1.

"Effects of the Invention" As is clear from the above explanation and Table 1, the heat-resistant copper-clad laminate of the present invention has a low water absorption rate and improved measling resistance by using a specific heat-resistant resin composition. Shina. Because of this, the present invention cannot provide a heat-resistant copper-clad laminate with excellent temperature resistance and extremely high reliability.

Claims (1)

[Claims] 1 (A) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, R^1 is a divalent group having at least two carbon atoms, and R^2 is a carbon- N of an unsaturated dicarboxylic acid represented by (representing a divalent group containing a double bond between carbon atoms)
, N'-bisimide compound, and (B) general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, R^3 and R^4 are hydrogen atoms, alkyl groups,
halogen atom, -OH, -OCH_3, -OC_2H_5, -COOCH_3 or -COOC_2H_5) and (C) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R^5 , R^6, R^7, R^8 represent the same or different alkyl group, halogen atom or hydrogen atom); and (D) aromatic amine or aromatic diamine containing a fluorine atom. and a certain fluorine-containing amino compound, and the amount of the fluorine-containing amino compound (D) is 0.0% per equivalent of the N,N'-bisimide compound (A).
1. A heat-resistant copper-clad laminate, characterized in that it is formed by laminating prepregs in which glass cloth is impregnated with a heat-resistant resin composition blended in an amount of 0.01 to 0.5 equivalents. 2 (A) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, R^1 is a divalent group having at least two carbon atoms, and R^2 is a double bond between carbon and carbon atoms. N of an unsaturated dicarboxylic acid represented by (representing a divalent group containing a bond)
, N'-bisimide compound, and (B) general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, R^3 and R^4 are hydrogen atoms, alkyl groups,
halogen atom, -OH, -OCH_3, -OC_2H_5, -COOCH_3 or -COOC_2H_5) and (C) General formula▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R^5 in the formula , R^6, R^7, R^8 are the same or different alkyl groups, halogen atoms or hydrogen atoms); and (D) an aromatic amine or aromatic diamine containing a fluorine atom. The fluorine-containing amino compound of (D) is 0.00% per equivalent of the N,N'-bisimide compound of (A).
A heat-resistant resin composition characterized in that it is blended in an amount of 0.01 to 0.5 equivalents.