JPH01271236A - Heat-resistant copper plated laminated sheet - Google Patents

Abstract

PURPOSE:To obtain a heat-resistant copper plated laminated sheet which is superior in dielectric constant and dielectric loss tangent and possesses favorable processability, by making use of a polyimide resin composition whose amount of resin is increased and prepreg obtained by impregnating glass nonwoven fabric with the resin composition. CONSTITUTION:An N, N'-bisimide compound of unsaturated dicalboxylic acid of a formula I (R<1> is a bivalent group having at least two carbon atoms and R<2> is a bivalent group containing carbon double bond) is used. Then a reaction product between aminophenol of a formula II (R<3> is H and a halogen atom) and aniline of a formula III (R<4> and R<5> are the H and alkyl) and further an epoxy compound having at least two epoxy groups within its molecule are added to the N, N'-bisimide compound. Prepreg obtained by impregnating glass nonwoven fabric with at least the 70wt.% heat-resistant resin composition is laminated. The heat-resistant copper plated laminated sheet is superior in dielectric constant and dielectric loss tangent properties and favorable in processability and becomes a low cost.

Description

Detailed Description of the Invention [Objective of the Invention] (Industrial Application Field) The present invention relates to a heat-resistant resin composition with excellent dielectric constant and dielectric loss tangent properties, and a heat-resistant @stretched laminate using the same. .

(Conventional technology) In recent years, the development of electronic devices has been remarkable, and satellite broadcasting,
2. Description of the Related Art Applications using high-frequency technology and fields that require high-speed calculations, such as mobile radio and high-speed computers, are increasing. For this reason, printed circuit boards are now required to have excellent dielectric constant and dielectric 7 [contact] in addition to the conventionally required properties. Teflon substrates and the like are known as substrates with excellent dielectric constants, etc., but they have many practical drawbacks because they have poor workability and are expensive.

(Problems to be Solved by the Invention) The present invention has been made in order to eliminate the above-mentioned drawbacks. The present invention aims to provide a fat composition.

[Structure of the Invention] (Means for Solving the Problems) As a result of intensive research aimed at achieving the above object, the present inventors have developed a polyimide resin composition described below and a glass nonwoven fabric impregnated with the same. The present invention has been completed by discovering that the above object can be achieved by using prepreg.

That is, the present invention relates to (A) (a)--formula (ffl L, where R' is only two groups having at least two carbon atoms, and R2 represents a double bond between carbon-carbon atoms. A N,N'-bisimide compound of an unsaturated dicarboxylic acid represented by the formula (representing a divalent group containing aminophenol, (C)-formula (wherein R4 and R5 are hydrogen atoms, alkyl groups, halogen atoms, -00H,, -QC2H,, -COOCI-
(, or -〇〇, an OC2H5 group representing a group not containing active hydrogen) and (B) a reaction product with a 7'niline group having two or more epoxy groups in the molecule. This is a heat-resistant copper-clad laminate comprising 81 layers of prepreg in which glass nonwoven fabric is impregnated with 70% by weight or more of a heat-resistant resin composition containing a boxy compound as an essential component.

The present invention will be explained in detail below.

[I] About essential ingredients N,N'-bisimide compounds of O-unsaturated dicarboxylic acids: One having the following general formula is used.

However, in the formula, R1 is 2 having at least 2 carbon atoms.
A few groups, R2, represent a divalent group containing a diffi bond between carbon atoms, i.e., R' is a linear or branched alkylene group, a cycloalkylene having a ring of 5 to 6 carbon atoms; group, a heterocyclic group containing at least one oxygen, nitrogen or sulfur atom, a benzene group or a polycyclic aromatic group, including -NHCO+, -NR'+, -5lR
Examples include multiple benzene groups and alicyclic groups bonded by 'R'-, -5O7-, etc. (R5 and R7 are alkyl groups having 1 to 4 carbon atoms, carbon 1
1! Indicates a cycloalkyl group having 5 to 6 rings, a benzene group).

In addition, the latter R2, that is, 2 containing a double bond between carbon atoms.
Examples of the valent group include maleic acid residue, citraconic acid residue, and tetrahydrophthalic acid residue.
Therefore, N of the unsaturated dicarboxylic acid satisfies the above-mentioned conditions of R1 and R2.

Specifically, the N'-bisimide compounds include the following, and each of these can be used alone or in a mixed system of two or more.

Maleic acid N, N'-4,4'-diphenylmethane bisimide, maleic UN, N'-4,4'-diphenyl ether bisimide, maleic aN, N-paraphenylene bisimide, maleic acid N, N'- Benzidine bisimide, maleic aN, 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, N maleic acid, N'-4,4'-dicyclohexyl-methane bisimide, N maleic acid.

N''-4,4'-diphenylcyclohexane-bisimide, malein fiN, N'-4,4'-diphenyl-
Phenylamine-bisimide, malein'MN, N'
-4,4'-diphenyl-diphenylsilane-bisimide, N maleic acid, N'-4,4''-diphenylsulfur-bisimide, N maleic acid, N'-2,2'-(4
,4'-diphenyl)-10pan-bisimide, Male 4
Examples include phosphoric acid N,N'3.3'-(N,N'-metaphenylene-bisbenzamide)bisimide.

0 aminophenol: One having the following general formula is used.

-Maximum However, in the formula, R3 represents a hydrogen atom, a halogen atom, or an alkyl group. Specific compounds include the following, which may be used singly or as a mixture of two or more. 0-aminophenol, 1-7 minophenol,
Examples include p-aminophenol, 2-amino-4-tritetraphenol, and 2-amino-4-methylphenol.

0 Anilines: One having the following general formula is used.

- In the formula, R4 and R@ are hydrogen atoms, alkyl groups, /'
110 Gen atoms, -0CH, , -〇〇2H. ,C0
0CHz, -COOC2 R5, etc., which do not contain active hydrogen; specific examples include aniline, 0-chloroaniline, totoluidine, methyl-9-aminobenzoic acid ester, etc.; in short, it is a nuclear substituent of aniline. Any substance that does not contain active hydrogen can be used.

Zero-engineered poxy compound: Low molecule i having at least two Evo-N groups in the molecule
It is explosive or high molecular weight. For example, Ebiko, an Ebibis-type compound based on bisphenol A, etc. -828
(manufactured by Shell Chemical Co., Ltd., trade name), alkyl-modified Nogo-type Ebikuron 800, Ebikuron 4050 (manufactured by Dainippon Ink Chemical Co., Ltd., trade name), Shodyne (manufactured by Showa Denko Co., Ltd., trade name), Araldai)-CY Glycidyl ester compounds such as -1133 (manufactured by Ciba Chemical Co., Ltd., trade name), Novosic type shrimp w-1=154 (manufactured by Shell Chemical Co., Ltd., trade name), DEN43 i, DEN438 (Dauk')
Manufactured by Michal, product name), Cresol Novosic type E
CN1280, ) ECN1235 (manufactured by Jiba Chemical Co., Ltd., trade name), urethane modified EPU-6, EPU-10 (
Manufactured by Asahi Denka Kogyo Co., Ltd., product name).

Furthermore, in the compounds represented by the following formulas (1) to (3), oxyresin etc. can be used.

In addition to the epoxy resins listed above, other types of epoxy resins can be used, and in short, all kinds of epoxy resins can be used as long as the material is selected appropriately. ] Heat-resistant resin composition! ! ! About the production method To produce the heat-resistant resin composition of the present invention, the above-mentioned N,N'-bisimide compound of unsaturated dicarboxylic acid is reacted with aminophenol, aniline, etc. without a solvent or in an inert solvent. After that, a doxy compound is added and reacted to produce the product. The molar ratio of the above four components is N of the unsaturated dicarboxylic acid.

The reason for this is that it is preferable that the combined J1 of aminophenol and aniline is 0.1 to 1.0 mol and the epoxy compound is 0.62 to 2.0 equivalent per 1 mol of N'-bisimide compound. If the total amount of aminophenol and aniline exceeds 0.1 mole, remove the excess epoxy compound! 7. However, as a result, the heat resistance, which is the most important feature of the resin composition, is impaired.If it is less than 0.071 mol, the softening temperature is high and the solubility is poor. It will not dissolve and is not desirable.

If the epoxy compound is less than 0.2 equivalents, the moisture resistance will deteriorate, and if it exceeds 2.0 equivalents, the heat resistance (flexural strength and hardness at a high temperature of 200°C) will be impaired. The explanation is as follows.

According to the present invention, aminophenol and/or aniline are added to the bisimide compound; 1. ! (4), (
5) A reaction product of the formula is produced. Therefore CR1
By selecting substituents that do not contain active water crabs for 4 and R2', the amount of epoxy compound to be reacted can be reduced compared to reacting a bisimide compound with a8:7 nophenol alone. ! V# It is possible to improve moisture resistance without compromising thermal properties, i.e.
From the experimental results, it was confirmed that moisture resistance can be improved by sufficiently reacting active hydrogen (hydrogen atoms such as -.NH++, -o)r, etc. with J and boxy groups2.

In the present invention, the order of blending the four components, the reaction temperature, and the solvent can be appropriately selected and are not particularly limited. For example, in the reaction vessel, N,N'' of the unsaturated dicarboxylic acid mentioned above.
- A bisimide compound, an aminophenol, and an aniline are charged together with dioxane, and the reaction is allowed to proceed until a predetermined viscosity is exhibited while refluxing the dioxane, and then a predetermined amount of an epoxy compound is added. A resin solution can then be obtained by continuing the reaction while refluxing dioxane until a suitable curing time is achieved.

The resin composition prepared in this way may be added with various additives and fillers depending on the purpose, such as catalysts such as imidazole for adjusting the curing speed, adhesion, and moisture resistance, depending on the purpose. Coupling agents for this purpose, various fillers for increasing volume and improving mechanical strength, etc. can be blended.

[II[] Manufacturing method of copper-clad laminate After coating and impregnating the resin composition manufactured as above on a glass nonwoven fabric base material, drying within a temperature range of 100 to 200 ° C. in a dry bee tower, Prepreg was manufactured. The amount of resin in this prepreg is 70% by weight or more. This is because if the resin amount is less than 70% by weight, desired dielectric properties cannot be obtained, which is not preferable. In addition, a prepreg is prepared by impregnating glass cloth with a resin amount of 30 to 70% by weight in a similar manner, and is combined with the above-mentioned 1 repreg or alone in combination with copper foil and molded under heat and pressure. M combination is a method of stacking 2 to 8 sheets of glass nonwoven fabric prepreg and stacking copper foil on at least one side, and a method of stacking 0.05 to 0.18 on the front and back.
There is a method in which copper foil is hung and formed using nn glass cloth prepreg. 0.181 in terms of cost and physical characteristics
Although it is advantageous to use n glass cloth prepregs on the front and back sides, it is better to use thin glass cloth to lower the dielectric constant.

(Function) The heat-resistant copper-clad laminate of the present invention uses a prepreg using a polyimide resin containing a large amount of resin 1 and a glass nonwoven fabric, which prevents slipping during molding compared to a glass cloth with an increased amount of resin. Furthermore, by increasing the amount of resin, the dielectric constant and dielectric loss tangent can be lowered.

(Example) Next, embodiments of the present invention will be specifically described.

Example I 358 kg of N, N'-4,4'-diphenylmethane-bisimide and 85 kg of meta-aminophenol 33 kQ aniline are mixed and when the temperature exceeds 100° C. while stirring, they gradually begin to dissolve and turn into a brown liquid. 1 of this liquid
The temperature was raised to 20°C and stirred for 1 hour. In this way, the complete addition reaction of aminophenol and aniline to bismaleimide was dissolved in dioxane to make a 50% solution, and this was mixed with 2 epoxy novolak resin (DEN438 manufactured by Dow Chemical Company, trade name) in 50 kg of 10 kgt resin.
4.5k! II was added. Furthermore, 25 kg of dimethylbenzylamine O was added to form a stirred mixture. This solution was impregnated into glass nonwoven fabric EPM4050 (manufactured by Nippon Vilene Co., Ltd., trade name) and heated and dried in a vertical drying tower to produce prepreg (A). The amount of resin in this prepreg was determined by adjusting the solution viscosity. The content was 85% by weight. In addition, a glass loss 216 with a thickness of 0.11 was obtained using the same method.
/ AS450 (manufactured by Asahi Siebel Co., Ltd., trade name) was impregnated with resin to make prepreg (B) with a resin content of 55% by weight. Six sheets of prepreg A and prepreg B were stacked on the front and back, and a layer of 18 μI thick was placed above and below them. Layer electrolytic copper foil and sandwich with stainless steel plates to create a pressure of 40! 11/CP, temperature 178
A heat-resistant copper-clad laminate was manufactured by heating and pressing at °C for 2 hours. This laminate was after-cured at 200°C for 1 hour, then left to cool to 25°C, and various properties were tested. The results are shown in Table 1, and the heat-resistant copper 81 laminate of the present invention has excellent dielectric properties, confirming the effects of the present invention.

Examples 2 to 4 Heat-resistant copper-clad laminates were manufactured in the same manner as in Example 1 using the compositions shown in Table 1. The laminate was tested in the same manner as in Example 1, and the results are shown in Table 1.

In all cases, the excellent effects of the present invention were confirmed.

Comparative Examples 1-2 Heat resistance @
Zhang! ? An i-layer board was manufactured.゛ The laminate was tested 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 excellent dielectric constant and dielectric loss tangent characteristics, good workability, low cost, and reliability. Satellite broadcasting is expensive! It is suitable for wireless, high-speed converters.

Claims (1)

[Claims] 1(A) (a) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, R^1 is a divalent group having at least 2 carbon atoms, R^2 (represents a divalent group containing a double bond between carbon-carbon atoms) is an N,N'-bisimide compound of an unsaturated dicarboxylic acid, and (b) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, R^3 in the formula represents a hydrogen atom, a halogen atom, or an alkyl group) and (c) General formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (However, R^3 in the formula 4, R^5 is a hydrogen atom, an alkyl group,
a reaction product with an aniline represented by a halogen atom, -OCH_3, -OC_2H_5, -COOCH_3, or -COOC_2H_5 (representing a group not containing active hydrogen); and (B) two or more epoxy groups in the molecule. 1. A heat-resistant copper-clad laminate, characterized in that it is formed by laminating prepregs in which glass nonwoven fabric is impregnated with 70% by weight or more of a heat-resistant resin composition containing an epoxy compound having the following as an essential component. 2 (A) (a) General formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, R^1 is a divalent group having at least 2 carbon atoms, and R^2 is a carbon-carbon (represents a divalent group containing a double bond) and (b) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, in the formula (R^3 represents a hydrogen atom, a halogen atom, or an alkyl group), and (c) General formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, R^4 and R^5 are hydrogen atom, alkyl group,
a reaction product with an aniline represented by a halogen atom, -OCH_3, -OC_2H_5, -COOCH_3, or -COOC_2H_5 (representing a group not containing active hydrogen); and (B) two or more epoxy groups in the molecule. A heat-resistant resin composition comprising an epoxy compound having the following as an essential component.