JPH02218750A - Composition for laminating material - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent heat-resistance and suitable as a laminated board for printed circuit board by compounding a compound having a specific structure with an aromatic polycarbodiimide compound and, as necessary, a polyvalent epoxy compound. CONSTITUTION:The objective composition is produced by compounding (A) a compound containing >=2 groups having the structure of formula I (R is H or hydrocarbon group) with (B) an aromatic polycarbodiimide compound which is a linear polymeric compound having a polymerization degree of >=5 and containing the recurring unit of formula II (Y is residue having aromatic ring) at a weight ratio (A:B) of 10:90-90:10, preferably 20:80-80:20 and, as necessary, (C) 0-100wt.% (based on A+B) of a polyvalent epoxy compound (e.g. a reaction product of bisphenol A and an epihalohydrin).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a heat-resistant fiber-reinforced laminate material, particularly to a composition for a laminate material suitable as a laminate substrate for a printed wiring board.

[Prior art] Laminated materials made of reinforcing fibers such as glass fibers and thermosetting resins have been widely used as printed wiring boards and structural composite materials. The composition has been most widely used as a thermosetting resin component.

However, multilayer wiring in the field of printed wiring boards,
Due to the expanding use of structural composite materials for aircraft, etc., there is a high demand for heat resistance (and attempts are being made to use polyimide resins, cyanate ester resins, etc. instead of epoxy resins.

Although the cured product of polyimide resin has excellent heat resistance, its poor solubility in organic solvents makes it inconvenient for impregnating glass cloth, etc., and it is difficult to perform a sufficient curing reaction. However, they require heat treatment at high temperatures and have many problems in terms of processability for obtaining laminates.

On the other hand, cyanate ester resin is
As disclosed in No. 2, it has good heat resistance and has improved processability, which is considered a defect of polyimide resins, but it has high hygroscopicity and has poor heat resistance after moisture absorption, such as heat distortion temperature. The downside is that it goes down.

In order to solve this problem, a method of using the above-mentioned polyimide resin and cyanate ester resin in combination was proposed in Japanese Patent Application Laid-Open No.
-129700, etc., and attempts have been made to put it into practical use, but the above-mentioned problems have not necessarily been fully solved.

[Problems to be Solved by the Present Invention] The purpose of the present invention is to develop a novel laminate material as described above, which has excellent processability during the production of the laminate material and which exhibits excellent heat resistance in any storage environment. An object of the present invention is to provide a composition.

[Means to solve problems]

The present invention is directed to a laminated material comprising (A) a compound containing two or more groups in one molecule having the structure of the general formula (wherein R is hydrogen or a hydrocarbon group) and (B) an aromatic polycarposiimide compound. A composition, a compound containing two or more groups in one molecule having the structure (wherein R is hydrogen or a hydrocarbon group), (B) an aromatic polycarposiimide compound, and CC)
This is a composition for laminated materials made of a polyvalent epoxy compound.

The above-mentioned (A)-catalytic structure (in the formula, R is hydrogen or a hydrocarbon group, and the hydrocarbon group preferably has about 1 to 16 carbon atoms, preferably about 1 to 8 carbon atoms) structure Compounds containing two or more groups in one molecule are usually compounds containing two or more groups in one molecule, where n is an integer of 1 or more, (wherein R is hydrogen or a hydrocarbon group), ° Namely, the above-mentioned aromatic compound is obtained by the reaction of a primary or secondary polyvalent amine compound with cyanogen halide, and the above-described polyvalent amine compound is preferably an aromatic polyvalent amine compound. As the ring skeleton, a compound having the following structure is used.Also, the hydrogen of the aromatic ring described above may be substituted with an inert hydrocarbon group such as a methyl group, an ethyl group, or a tertiary-butyl group. Moreover, the above-mentioned exemplary structures may of course be any of ortho, meta, and rose isomers or isomer mixtures.

The above-mentioned aromatic polycarposiimide compound (B) has a structure of the general formula, +Y-N-C-N→1-o-, -s--301--CO-, etc. (in the formula, Y is a linear polymer compound having a repeating unit (residue having an aromatic ring), and the degree of polymerization, that is, the value of n, is preferably 5 or more, more preferably 10 or more, and usually has a general formula of Y(NGO)g. It can be obtained by decarboxylating and polymerizing the diisocyanate represented by, for example, in the presence of a known carbodiimidization catalyst such as phosphorene oxides. Specifically Y (Nco)
Examples of the raw material diisocyanate represented by the general formula t include tolylene diisocyanate, diphenylmethane diisocyanate, naphthylene diisocyanate, biphenylene diisocyanate, dimethylphenylmethane diisocyanate, xylylene diisocyanate, α,
Examples include α, α 2 , α-tetramethylxylylene diisocyanate.

In addition, when producing the aromatic polycarposiimide compound (B) from diisocyanate, for example, monofunctional active hydrogen compounds such as monoalcohols, monocarboxylic acids, and secondary monoamines are used in combination to inert the molecular terminals. The compound of the present invention may include a compound blocked by a group, and may also include a compound in which a dihydric alcohol or a dibasic acid is coexisting and a part of the carposiimide bond is replaced with a urethane bond or an amide bond. In order to achieve the objective, substitution should be limited to 20 mol% or less, preferably 10 mol% or less of the carposiimide groups forming the main chain of the molecule.

Examples of the polyepoxy compound (C) mentioned above include bisphenol A, bisphenol F, novolak phenol resin, Talesol novolak phenol resin, and polyepoxy compounds obtained by reacting polyhydric phenols such as biphenol with shrimp helohydrin. Polyvalent epoxy resins, such as glycidyl compounds of polyvalent amines such as diaminodiphenylmethane, diaminodiphenylsulfone, xylylene diamine, diaminodiphenyl ether, and diaminobenzophenone, polyvalent carboxylates such as triglycidyl isocyanurate, phthalic acid, isophthalic acid, and terephthalic acid. Glycidyl esters of acids, glycidyl esters/ethers of oxybenzoic acid, glycidyl compounds of aminophenols, etc. are used.

A compound containing two or more groups in one molecule having the structure of general formula (A) (in which R is a hydrogen or hydrocarbon group) will undergo a crosslinking reaction when heated alone, and its cured product will have poor heat resistance. However, the cured product has the disadvantage that the heat distortion temperature decreases due to moisture absorption and the like.

Further, although the above-mentioned aromatic polycarposiimide compound (B) also undergoes a crosslinking reaction when heated, its cured product cannot achieve the desired heat resistance.

However, in the present invention, the above (^) and (B)
By using these compounds in combination, it is possible to overcome the drawbacks of both and achieve remarkable action curing that achieves good heat resistance even in a moisture-absorbing environment.

In addition, as a more preferred embodiment of the present invention, by using the above-mentioned (C) polyvalent epoxy compound in combination, this is thought to undergo a crosslinking reaction with the above-mentioned (A) and (B) compounds during heating, and the heat resistance is improved. It has been found that this method improves hygroscopicity and also improves the adhesion of metals to copper foil and the like without impairing properties.

The compounding ratio of the compounds (A) and CB) of the present invention is useful in a wide range of weight ratios from 10:90 to 90:10, but more preferably from 20:80 to 80:2.
It is preferably in the range of 0.

In addition, the blending ratio of the polyvalent epoxy compound (C) above is 0 to 10 oI with respect to the total amount of (A) and (B) 17).
It can be used in an amount of i%, but if heat resistance is important, it is preferably used in an amount of 0 to 50% by weight, and li!
For the purpose of improving adhesion to metals such as fi, it is preferable to use 10 to 50% by weight.

In order to put the composition of the present invention into practical use as a laminated material, the compounds (A) and (B) above, or the polyvalent epoxy resin (C), are usually dissolved in an organic solvent in which they can be dissolved. A reinforcing fiber such as glass cloth is impregnated into it, and the solvent is removed by drying at an appropriate temperature.
First, so-called brev regs are manufactured. Next, the brev regs thus obtained are laminated, and the laminated prepregs are heated and pressed to harden the resin component to obtain a laminated material with excellent heat resistance. The heating temperature at this time is usually 15
Approximately 0 to 250℃, pressurization conditions are usually 5 to 100 kg/
If necessary, post-curing may be further performed at about 200 to 250° C. after decompression.

Therefore, in the case of manufacturing printed wiring boards, copper foil is placed on one or both sides of the laminated Bleiprig during the above process, heated and pressurized as described above, and multilayer printed wiring boards are manufactured. In this case, the above-mentioned bleb ring is inserted between the laminated plates on which circuits have already been formed, or between the laminated plates and the w4M, and heat and pressure are applied in the same manner.

In addition, when putting the above-mentioned composition of the present invention into practical use, auxiliary agents such as a curing accelerator, an adhesion imparting agent, an antifoaming agent, a flame retardant, a mold release agent, an inorganic filler, a coloring agent, etc. are mixed and used. It's okay to do that.

Hereinafter, embodiments of the present invention will be specifically described with reference to Examples.

〔Example〕

(Example 1) 3. A 40% by weight solution of the compound (A) having the structural formula obtained by the reaction of 3'-diaminobenzophenone and chlorocyan in toluene/methyl ethyl ketone; 2.4-) Lylene diisocyanate in toluene/methyl ethyl ketone In the mixed solution, 3
- 40% by weight solution of polycarposiimide compound (B) obtained by polymerization in the presence of a methyl-1-phenyl-phosphorene oxide catalyst (number average molecular weight in terms of polystyrene in GPC: 8500) shown in Table 1. Experiment number (1
) to (5) were mixed in the weight proportions shown.

Next, the glass fiber woven fabric was immersed in the solutions of each experiment number (1) to (5), and the excess resin solution was removed with a squeezing roll.
The organic solvent was volatilized and removed by passing through a hot air drying oven at ℃ to obtain prepregs corresponding to each experiment number.

The resin content in each prepreg was measured by a pyrolysis method and found to be in the range of 45 to 47% by weight.

Next, 8 laminates of each of the above prepregs were formed and hot-press molded at 180°C for 60 minutes at a pressure of 40kg/cj to form laminates (1) to (5) with a thickness of about 1.6M corresponding to each experiment number. Obtained.

Experiment numbers (2) to (4) are examples of the present invention, and experiment numbers (1) and (5) are comparative examples.

Table 1 also lists the measurement results of the heat deformation temperature, water absorption rate, heat deformation temperature after water absorption, and thermal expansion coefficient of the laminate for each experiment number.

(Example 2) Bisphenol A diglycidyl ether, which is a type of polyvalent epoxy compound, was added to a 40% by weight solution of compound (A) and a 40% by weight solution of compound (B) used in Example 1.
Blended at the weight ratio shown in Table 2, experiment numbers (6) to (9)
Each solution was prepared, impregnated into glass fiber cloth under the same conditions as in Example 1, and further hot-press molded to obtain experimental numbers (6) to (9).
) The same evaluation as in Example 1 was performed on each of the laminates produced, and the measurement results are also listed in Table 2.

In addition, the measurement results of epoxy resin-based laminates used for printed wiring boards are also listed in Table 2 as experiment number Oω.

(Example 3) Experiment numbers (2), (3), created in Examples 1 and 2
Use prepregs corresponding to (6), (7), (8) and (9) respectively, and place 1 oz electrolytic copper foil on both sides of the prepreg as shown in Figure 1. and the other side was stacked so that the electrolytic copper foil surface-treated side was in contact with the prepreg, hot-press molded in the same manner as in Example 1, and the copper foil was laminated with experiment numbers 00 to 0ω in Table 3. After obtaining the laminate test pieces, a 5 m thick resist ink film with etching resistance was formed by screen printing on the copper foil of each test piece, and then unnecessary parts of the copper foil were coated with a cupric chloride hydrochloric acid solution. was removed by etching, and the resist ink film was further removed with an aqueous sodium carbonate solution to form a copper conductor with a width of 5 m+1 on both sides. Using an Instron, the adhesive strength between the copper foil and the laminate was measured on the non-treated side and the surface treated side of the electrolytic copper foil, and the results are also listed in Table 3.

figure surface Figure 1 ↓ ↓ ↓ Pressure/heating Copper foil surface treatment surface Preg Copper foil non-treated side ↑ ↑ ↑

Claims (1)

[Claims] 1. (A) Compounds containing two or more groups in one molecule having the structure of the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (wherein R is hydrogen or a hydrocarbon group) (B) A composition for laminated materials comprising an aromatic polycarbodiimide compound. 2. (A) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R is hydrogen or a hydrocarbon group) Compounds containing two or more groups in one molecule and (B) aromatic polycarbonate a diimide compound, and (C)
A composition for laminated materials comprising a polyvalent epoxy compound.