JPH02283753A - Laminate resin composition - Google Patents

Abstract

PURPOSE:To prepare a laminate resin compsn. excellent in the heat resistance, mechanical strengths, and adhesive properties by compounding a resin mixture of a specific polyepoxy resin with a phenol resin having a linear polymer soluble in said resin mixture. CONSTITUTION:A polyepoxy resin with an mol.wt. of 1000-3000, obtd. by the glycidylation of a brominated bisphenol A of the formula (wherein (m)/(n) is 1-10 or (n)=0; and (a) is 1 or 2) and a polycondensate of bisphenol A or a brominated bisphenol A with formaldehyde, is mixed with a phenol resin with an mol.wt. of 1000-10000, obtd. by polycondensing bisphenol A with formalde hyde, in an equivalent ratio of the epoxy group of said polyepoxy resin to the hydroxyl group of said phenol resin of 0.7-1.2 to give a resin mixture. 100 pts.wt. said resin mixture is compounded with 1-60 pts.wt. linear polymer with an mol.wt. of 5000-100000 which is soluble in said resin mixture to give a lami nate resin compsn. The resin compsn. gives a cured product with an excellent heat resistance, mechanical strengths, and toughness when compared with a conventional one, and exhibits an excellent adhesion when used in producing a copper-clad laminate.

Description

[Detailed Description of the Invention] [Field of Industrial Application] This invention relates to a resin composition for laminates, and more specifically, a resin composition for laminates that has excellent heat resistance, mechanical strength, and crushability. This invention relates to a resin composition.

[Conventional technology]

The demand for laminates, especially copper-clad laminates, is increasing rapidly, and by combining a base material and a thermosetting resin, copper-clad laminates that are suitable for a variety of purposes are being obtained. μ paper-based phenolic resin copper-clad laminates are mainly used in the field of consumer electronic devices such as color televisions and audio equipment, as well as computers and controllers.

Glass-based epoxy resin steel-clad laminates are mainly used in the field of industrial electronic equipment such as measuring instruments.

However, as high-density wiring and multilayering progress,
The conventional glass-based epoxy resin copper-clad 8-unit board could not meet the required specifications in terms of one-dimensional stability, heat resistance, etc., and there was a demand for the development of a copper-clad laminate with excellent heat resistance.

As a copper-clad laminate with excellent heat resistance, for example, 1.
As shown in Publication No. 0-28423.

Those made of a polyimide resin (for example, polyaminobis!reimide resin) and a glass substrate are known, and have characteristics such as a high glass transition temperature and excellent dimensional stability when heated.

[Problem to be solved by the invention]

However, the above-mentioned polyimide resin has high hygroscopicity and has problems with dimensional stability under moist heat, and since a polar solvent with a high boiling point is used as a solvent during prepreg manufacturing, the solvent tends to remain during loading dock molding. .

It has drawbacks such as variations in quality.

The challenge was to resolve these issues.

This invention was made to solve this problem, and the cured product has superior heat resistance compared to conventional products, and
The object of the present invention is to provide a resin composition for a laminate that has excellent mechanical strength and toughness, and exhibits excellent adhesion when used in a copper-clad laminate, for example.

[Means to solve the problem]

The resin composition for laminates of this invention is:

(In the formula, m/n is expressed as an integer of H1 to lo or Hn: 0.aijl to 2. The molecular weight of the glycidylated polycondensate of prophylated bisphenol A, bisphenol A, or sepromated bisphenol A and formaldehyde is 10.
A polyfunctional epoxy resin (α) having a molecular weight of 1000 to 10,000, which is a polycondensate of bisphenol and formaldehyde, is added to a polyfunctional epoxy resin (α) having a molecular weight of 000 to 10,000, For 1 equivalent of terminal.

The hydroxyl group of the upper 6 piphenol resin 1β) is lLT~1.2
Based on 100 parts by weight of composition (1) blended in an equivalent ratio.

IQ with a molecular weight of 5ooo or more that is compatible with this composition (1)
G, Goo or less linear polymer (I)''Ikl-IO is blended in an amount by weight.

[Effect]

In this invention, by reacting a polyfunctional epoxy resin mainly with a phenolic resin, the crosslinking density is increased, the heat resistance is increased, and the heat resistance is improved.
By intervening a linear polymer as a near flexible component, a composition was created that provides toughness while maintaining heat resistance.

〔Example〕

The polyfunctional epoxy resin (α) according to the present invention is a glycidylated product of pro-hydrophorated bisphenol A, bisphenol A, or hafurophorated bisphenol A, formaldehyde, and a υ heavy complex, and has an atom molecular weight of too~3000.
It is. If the molecular weight is less than 1000, the final cured product will be brittle, and if the molecular weight exceeds goon, the curing reaction will not be carried out sufficiently, resulting in a decrease in heat resistance. In addition, since the manufactured prepreg needs to be flame retardant, the molar ratio of the essential components prophylated bisphenol A and bisphenol A must be set to 1 or more, and the viscosity of the pre-preg with a large molecular weight increases, making it difficult to mix. It needs to be 10 or less because it becomes a ding. In addition, the above-mentioned pro-chlorinated bisphenol A is 0, for example, motu-brominated, dibrominated tetra-pro-produced bisphenol A.
is used.

A phenolic resin (a polycondensate of bisphenol, bisphenol, and luminaldehyde) as a curing agent for the polyfunctional epoxy resin (α) according to this invention, and a cured product when other phenolic resins are used as the curing agent. The discoloration caused by heating can be prevented.Also, the molecular weight of this phenol resin is 1000 or more.
It is 0.000 or less. If it is less than this, it will not be possible to obtain sufficient reactivity, and the low molecular weight phenol resin will remain in the laminate, resulting in a decrease in mechanical properties, heat resistance, and moisture resistance. Also, the molecular weight is 10. If it exceeds Goo, the reactivity with epoxy groups will deteriorate. In order to obtain the composition (1), 1 total amount of the phenol resin is such that the hydroxyl group of the phenol resin is 0.7 to 1.2 equivalents per 1 equivalent of the terminal epoxy group of the above-mentioned polyfunctional epoxy resin. . If the amount is less than 0.7 equivalent, unreacted epoxy groups remain, resulting in poor heat resistance.
If the amount exceeds 1.2 equivalents, the phenol resin that does not participate in one reaction remains, resulting in poor moisture resistance and heat resistance.

As the linear polymer (1) according to the present invention, those that are compatible with polyfunctional epoxy resin (α) and phenol resin (β), such as polysulfone, polyethersulfone, polyester, and phenoxy resin, are preferably used. It will be done. The molecular weight is usually 5000 or more.

It is desirable that it is 100.000 or less, and if it is less than s, ooo, the effect of providing flexibility by the linear polymer will not be noticeable.

Also, if it exceeds 100.000, the resin viscosity will increase too much.
Impregnation into the base material becomes insufficient.

The blending amount is based on the composition (1) containing the polyfunctional epoxy resin (α) and the phenol resin (7?1t).

It is 1 to 60 parts. If the blending amount is less than 1 part by weight, the effect of imparting flexibility will not be sufficient, and the blending amount will be less than 60 parts by weight.
If the amount exceeds parts by weight, linear polymers may precipitate during curing. Furthermore, the viscosity of the resin increases too much, resulting in insufficient impregnation into the base material during the production of laminated prepregs.

The resin composition for a laminate according to an embodiment of the present invention may contain an imidazole compound, an imidacillin compound, etc. for the purpose of promoting the reaction.

Representative CDHs such as imidazole, 2-nitylimitasol, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecyl Imidazole, 4.5-diphenylimidazole, 2-methylimidacillin, 2-ethyl-4-methylimidacillin, 2-phenylimidacilline, 2-undecylimidacilline, 2-heptadecylimidacilline.

2-isopropylimidazole, 2.4-dimethylimidazole, 2-phenyl-4-methylimidazole, 2
-Ethylimidacillin, 2-isopropylimidacillin, 2,4-dimethylimidacillin.

Examples include 2-phenyl-4-methylimidacyline. These curing accelerators can be used in combination! #
is preferably polyfunctional epoxy resin (Q) 100 weight FI
The amount is 10.01 to 5 parts by weight based on BK. If it is less than 0.01 parts by weight, the effect will be small, and if it is more than 5 parts by weight, storage stability will be impaired.

The resin composition for a laminate thus obtained is dissolved in, for example, the following solvent, and applied as a resin liquid at a predetermined temperature of 11 degrees to prepreg production.

Solvents used here include acetone, methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, N,N-dimethylformamide.

N,N-dimethylacetamide, ethanol, etc. are available, and some of these may be mixed and used.

Further, as described above, a copper-clad laminate is impregnated with the above-described resin composition 1i for a predetermined base material, and then dried in a drying oven.
Prepreg is manufactured, copper mines are layered on top of this prepreg, and the process is carried out under heat and pressure.

The base material that can be used here is generally glass fiber, but aromatic polyamide fiber can also be used.
Matte glass, polyester.

Aromatic polyamides can also be used.

The resin for laminates is usually impregnated into the base material at room temperature and has a
It is dried for 1 to 20 minutes within the range of 'c' to form a prepreg.

A predetermined number of the obtained prepregs are stacked, and with the copper mine piled up on at least one side, the prepreg is heated and pressed at a pressure of 5 to 100 kg/d for 10 to 300 minutes to obtain a copper-clad laminate. Although the values are desirable for the conditions shown here, they are not limited to these.

The laminate obtained from the resin composition for laminates of this Example has excellent heat resistance, soldering heat resistance, and moisture resistance (1) and mechanical properties, and is suitable for use in high-density multilayer boards.

EXAMPLES The present invention will be specifically explained below with reference to Examples.

Example 1 Tetrabromobisphenol A and bisphenol At-
They were blended at a molar ratio of 2:1, and formalin No. 37 and oxalic acid were added thereto, heated and reacted, and then dehydrated and concentrated to obtain a pro-phthalated bisphenol A novolak resin. To this, add epichlorohydrin'Jt(fitetraethylammonium chloride).

After heating and reacting, Na0Hf was added and further reaction was carried out.1
A polyfunctional epoxy resin with a molecular weight of 2500 & J (m/n==2 in the formula) shown by the following formula A phenol resin (molecular weight 3500) 4B (molecular weight 3500) produced by polycondensation of the multifunctional epoxy resin 100F shown by the above formula, bisphenol A, and formaldehyde Equivalence ratio of phenolic hydroxyl group/epoxy group: o, 5s) t- The blended composition has a molecular weight of 1! SQ, OOG phenoxy resin (
PKHH, manufactured by Union Carbide) 46F, 2-ethyl-4-methylimidazole 0.1jFft was blended and dissolved in ethylene glycol monomethyl ether 125p,
A resin composition for a laminate according to one embodiment of this invention was prepared at a concentration of 60%.

This was impregnated into a crow woven fabric having a thickness of 0.18 fi and dried to obtain an O prepreg having a resin content of 4@wt%. and υ prepreg t-4 sheets were stacked and press-molded on both sides with 35 μm (D copper 16).The molding conditions were press temperature tso'c
, press pressure was 40 kg/d, and press time was 60 minutes.

The table shows the evaluation results for the mechanical properties of copper-clad laminates.

Example 2 Tetrabromobisphenol A and bisphenol Ai were blended at a molar ratio of 1:1, and the same reaction as in Example 1 was carried out to obtain a polyfunctional epoxy resin having a molecule of 1i11100 represented by the following formula.

(In the formula, m / n = 1) Phenol resin (molecular weight tsoo) produced by polycondensation of polyfunctional epoxy polar resin 10011 shown above, bisphenol A, and formaldehyde υ (molecular weight tsoo) ss p (phenolic water [4/epoxy group equivalent ratio : a, r) was blended with a polyester resin of molecular 1i15.00G (Vylon, 2., q,, o, Toyo IFj product name) 151.2-phenylimidazole Q, 2#, and methyl ethyl ketone toot. , dissolved in 81 t of ethylene glycol monomethyl ether.

A resin composition for a laminate according to another example of the present invention having an SSS concentration was obtained. This was impregnated into a glass woven fabric having a thickness of 0.18 fi and dried to obtain a prepreg having a resin content of 52 mm.

Four sheets of this prepreg were stacked and press-molded on both sides with 35 μm co copper brackets interposed therebetween. Press temperature 11 for molding conditions
10'c, press pressure aam/a1. The pressing time was 60 minutes. Physical properties of the resulting copper-clad laminates.

- The evaluation results for the physical properties are shown in the table.

Example 3 Tetrabromobisphenol A and bisphenol A were blended at a molar ratio of 5:10, and the following reaction was carried out in the same manner as in Example 1 to form the molecule 1i3. An oooυ polyfunctional epoxy resin was obtained.

(In the formula, m/n = 5) 43 g of phenolic resin (molecular weight 3.500) produced by combining 100 f of the polyfunctional epoxy resin shown above, bisphenol A, and formaldehyde (0 equivalents of phenolic hydroxyl group/epoxy group) Polysulfone resin (P-170AMOCOF
lfi product name) 13F, 0.12IQ of 2-ethyl-4-methylimidazole, acetone 301. Dissolved in methyl ethyl ketone 591 JF! −,63%m
Flv Kov departure 8Av other v5AI! We developed a resin composition for nrv stock N plates. This was impregnated into a 8.18 μm (Q) glass woven fabric and dried to obtain resin-containing J155!it% ribbed legs. Four sheets of this prepreg were stacked and press-molded with 35 μm copper foil interposed on both sides. The molding conditions were a press temperature of 200'c, a press pressure of 301qc/d, and a press time of 90 minutes.
The evaluation results for the physical properties are shown in the table.

Example 4 Tetrabrome and Suphenol A! : 37% formalin and Shu #R were heated and reacted, and then dehydrated and concentrated.

1 ton of brominated bisphenol A novolac resin.

The epoxidation reaction was carried out in the same manner as in Example 1.

A polyfunctional epoxy S resin having a molecular weight of 2.500 represented by the following formula was obtained.

(M frame 9 in the formula) A phenol resin (molecular weight s, ooo) produced by polycondensation of 100 g of a polyfunctional epoxy resin represented by the above formula, bisphenol A, and formaldehyde (molecular weight s, ooo) 33F (phenolic hydroxyl group/epoxy group equivalent ratio: O, A phenoxy resin (Y
P-50, manufactured by Toto Kasei) 29N.

Blend 0.231 of 2-ethylimidacillin, N.

30 g of N-dimethylacetamide, 87 fK bath ML of ethylene glycol monomethyl ether, and a 521% concentration resin composition were prepared. This prepreg was impregnated with 0.1111111 (7J) glass soft cloth and dried to give a resin content of 51% by weight. Four sheets of this prepreg were stacked and press-molded with 35 μm copper foil interposed on both sides.

Press molding conditions were the same as in Example 2. The results of the desired characteristics evaluation of the copper-clad laminate are shown in the table.

Comparative Example 1 A copper-clad laminate was prepared in the same manner as in Example 1, except that instead of the phenoxy resin with molecules J15G and OOO, 1 molecular weight 1.000v epoxy side fat (Epicoat 1001, manufactured by Yuka Shell) was used. Ta.

Comparative Example 2 A copper-clad laminate was obtained in the same manner as in Example 1, except that the phenoxy resin, which is a linear polymer, was not blended.

Comparative Example 3 A copper G1 ridge laminate was obtained in the same manner as in Example 2, except that 120ft- was used instead of the polyester resin '195jl.

The evaluation results of the copper-clad laminates of Comparative Examples 1 to 3 are shown in the table.

Polyfunctional epoxy 4 with a molecular weight of 1000 to 3000
Molecular weight of fatty acid (Al, polycondensate metal of bisphenol A and formaldehyde J)
The phenol resin (β) under oJ2 was added to the above Fe with respect to 1 equivalent of the epoxy group terminal of the above polyfunctional epoxy i-fat Cα1.

- Proportion of 0.7-1.2 equivalents of hydroxyl groups in 1M of the resin -i For 1001 parts by weight of the blended composition, this set is compatible with substance 1!
By using a laminate made by combining linear polymers 11) produced by 00 companies with 1 to 1 sol, the cured product has superior heat resistance as well as 9 mechanical strength and toughness compared to conventional laminates. can obtain a resin composition for use.

For example, when used in a zero-side laminate, it exhibits excellent adhesion.

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ Molecular weight 100 obtained by glycidylating a heavy complex of bisphenol A or brominated bisphenol A and formaldehyde
A polyfunctional epoxy resin (α) with a molecular weight of 0 to 3,000, and a phenol resin (β) with a molecular weight of 1,000 or more and 10,000 or less, which is a polycondensate of bisphenol A and formaldehyde.
, the epoxy group terminal 1 of the above polyfunctional epoxy resin (α)
The hydroxyl group of the phenol resin (β) is 0.
Composition (I) 10 blended at a ratio of 7 to 1.2 equivalents
0 parts by weight, a linear polymer (I
A resin composition for laminates containing 1 to 60 parts by weight of I).