JPH02311515A - Laminating resin composition - Google Patents

Abstract

PURPOSE:To obtain a laminating resin composition improve in heat resistance, mechanical strengths, toughness and adhesiveness by mixing a composition comprising an oligoepoxy resin and a phenolic resin with a specified linear polymer. CONSTITUTION:An oligoepoxy resin (a) of formula III is obtained by reacting a brominated bisphenol A (i) of formula I (wherein (a) is 1 to 4) with a polyfunctional epoxy resin (ii) of formula II in an amount to give 3 to 5 equivalents of the epoxy groups of component (ii) per equivalent of the hydroxyl groups of component (i). Component (a) is mixed with a phenol resin (b) of a mol.wt. of 1000 to 10000, which is a polycondensate of bisphenoal A with formaldehyde, in an amount to give 0.7 to 1.2 equivalents of the hydroxyl groups of component (b) per equivalent of the epoxy terminals of component (a). 100 pts.wt. component A is mixed with 1 to 60 pts.wt. linear polymer (B) of mol.wt. of 5000 to 100000 compatible with component A (e.g. phenoxy resin).

Description

[Detailed Description of the Invention] [Industrial Field of Application] This invention relates to a resin composition for laminated boards, and more specifically, a resin composition for laminate boards that has excellent heat resistance, mechanical strength, and adhesive properties. 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 can be used for 99 different purposes. In the field of consumer electronics such as color televisions and audio equipment, paper-based phenolic resin steel-clad laminates are mainly used, as well as computers and controllers.

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

However, as high-density wiring and multilayering progress,
Conventional glass-based epoxy resin copper-clad laminates cannot meet the required specifications in terms of dimensional stability, heat resistance, etc., and there has been a demand for the development of copper-clad laminates with excellent heat resistance.

As a copper-clad laminate with excellent heat resistance, for example, 1.
As shown in Publication No. 0-26423.

Materials made of a polyimide resin (eg, polyamino bismaleimide 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 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 production, the solvent tends to remain during lamination 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
A resin composition for laminates that has superior mechanical strength and toughness, and exhibits excellent adhesion when used in steel clad laminates, for example.
The purpose is to obtain.

[Means to solve the problem]

The resin composition for laminates of this invention is:

Brominated bisphenol A (β+) represented by the chemical formula (in the formula, a is an integer of 1 to 4) is added to the polyfunctional epoxy resin (α1) represented by , an oligoepoxy resin (α) expressed by (in the formula, is an integer from 1 to 4) obtained by blending and reacting the polyfunctional epoxy resin (α1) so that the epoxy groups are 3 equivalents or more and 5 or less. and 7 enol resin (β) t-for 1 equivalent of the epoxy group of the oligoepoxy resin (α), the above phenol resin (β)
For 100 parts by weight of composition (1) blended in such a proportion that the hydroxyl groups of are 0.7 to t2 equivalent, a linear chain having a molecular weight s, o o o or more, too, ooo or less, which is compatible with this composition (1), is added. 1 to 60 parts by weight of polymer (1).

[Effect]

In this invention, by reacting a phenol resin with an oligoepoxy resin obtained by reacting a polyfunctional epoxy resin and brominated bisphenol At in a predetermined ratio, the crosslinking density is increased and heat resistance is improved! , by interposing a linear polymer as a flexible component in the crosslinked network structure).

The composition provides toughness while maintaining heat resistance.

〔Example〕

The polyfunctional epoxy resin (α1) according to this invention is.

It is expressed as

Brominated bisphenol A (β1) for oricomerizing the polyfunctional epoxy resin (α1) according to this invention
For example, monobrominated, dibrominated, tetrabrominated bisphenol A is used.

(In the formula, a is an integer of 1 to 4) To obtain an oligoepoxy resin (α), brominated bisphenol A (
The polyfunctional epoxy resin (αI) is blended and reacted in such a manner that the amount of epoxy groups in the polyfunctional epoxy resin (αI) is 3 to 5 equivalents per 1 equivalent of hydroxyl groups in β1). When the amount of epoxy groups is less than 3 equivalents, the hydroxyl groups of the additional brominated bisphenol A (β1) are TA-produced, resulting in poor resin stability. If the amount is more than 5 equivalents, excess polyfunctional epoxy resin (α1) remains and the toughness of the cured product is impaired.

The phenol resin (β) according to the present invention is a polycondensate of bisphenol A and formaldehyde, and can prevent discoloration caused by heating of a cured product when other phenol resins are used as a curing agent. Moreover, the molecular weight of this phenol resin is 1,000 or more and 1G, Go.

It is as follows. If it is less than this, the phenolic resin with a low molecular weight will remain in the laminate instead of the resin that does not provide sufficient reactivity, and the mechanical properties, heat resistance, and moisture resistance will deteriorate. or,
If it exceeds 10.0 GO, the reaction with epoxy groups will deteriorate. To obtain composition (1).

The blending amount of phenol resin is the same as the above oligoepoxy resin (
For every equivalent of epoxy base of α), phenol resin (
The ratio is such that the hydroxyl group of β) is Q, T~1.2 equivalents.

If the weight is less than 0.7 equivalents, unreacted epoxy groups remain, resulting in poor heat resistance; if the weight exceeds 1.2 equivalents, phenol resin that does not participate in the reaction remains, resulting in poor moisture resistance and heat resistance.

The linear polymer according to this invention is as follows.

Multifunctional epoxies such as polysulfone, polyethersulfone, polyester and phenoxy resin
Those which are compatible with α1), brominated bisphenol A (β1), oligoepoxy resin (α) and phenol resin (β) are preferably used. Molecular weight is usually s, oo
Desirably, it is greater than or equal to o, 10G, and less than or equal to Goo.

If it is less than s, ooo, the effect of imparting flexibility by the linear polymer cannot be obtained. Moreover, if it exceeds too or ooo, the resin viscosity becomes too high and impregnation into the base material becomes insufficient. In addition, the blending amount is 1 to 60% with respect to the composition (1) containing the oligoepoxy resin (Suzuki and phenol resin (β)).
This is Shigebe. If the blending amount is less than 1 part of 11i, the effect of imparting flexibility will not be sufficient.

If the blending amount exceeds 60 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 side fat composition for a laminate according to an embodiment of the present invention may contain an imidazole compound, an imidapurine compound, etc. for the purpose of promoting the reaction.

Typical examples are imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole,
2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 4.5-diphenylimidazole, 2-methylimidacillin, 2-ethyl-4-methylimidacillin , 2-phenylimidacillin, 2-undecylimidacilline, 2-heptadecylimidacillin.

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

Examples include 2-phenyl-4-methylimidacyline. These curing accelerators may be used in combination, and the blending amount is preferably 1 lL01 to 5 parts by weight per 100 parts by weight of the polyfunctional epoxy resin (α). Q. If the amount is less than 1 part 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 of a predetermined concentration 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.

Examples include N, N-dimethylacetamide, ethanol, etc., and these may be used in combination.

Copper-clad laminates are produced by impregnating the resin composition for laminates into a predetermined base material and drying it in a drying oven to produce prepreg'f, as described above, and then overlaying copper foil on this prepreg. It is obtained by combining and heating and pressurizing.

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.

Laminate resins are usually impregnated into the substrate at room temperature and have an 80-20
Dry for 1 to 20 minutes at 0'C. A predetermined number of sheets of the obtained prepreg are stacked, and with copper foil layered on at least one side, the prepreg is usually heated for 80 to 250 r.
, and heat and press at a pressure of 5 to 100 kg/d for 10 to 300 minutes to form a copper-clad laminate. The conditions shown here are desirable values, but are not limited thereto.

The laminates obtained from the resin compositions for laminates of Examples of the present invention have excellent heat resistance, soldering heat resistance, moisture resistance, and mechanical properties, and are suitable for use in, for example, high-density multilayer boards.

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

ri2 \1 Multifunctional epoxy resin represented by the above formula (trade name: EPPN
-501 Nippon Kayakusabi) ssfI and tetrabromobisphenol A 35 y (Equivalent ratio of epoxy group of polyfunctional epoxy resin/hydroxyl group of brominated bisphenol A: λ0
) and oligoepoxy resin (α
) (a=2) is obtained. This oligoepoxy tree 1] 1
Phenol resin produced by polycondensation of 77N, bisphenol A, and formaldehyde (molecular weight & 50G)
23 y (equivalence ratio of phenolic hydroxyl group of phenol resin/epoxy group of oligoepoxy resin: Q, 9S)'
Phenoxy resin (PKHH.

461. 2-ethi h -
0.11 of 4-methylimidazole was blended and dissolved in 125f of ethylene glycol monomethyl ether.

A resin composition for a laminate according to an embodiment of the present invention having a concentration of 60% was obtained.

This was impregnated into a glass woven fabric having a thickness of 181 m+1 and dried to obtain a prepreg with a resin content of 48 layers. Four sheets of this prepreg were stacked and press-molded with 35 μm copper foil interposed on both sides. Molding conditions are press temperature 190'C
, press pressure was 40 kg/d, and press time was 60 minutes.

The table shows the evaluation results regarding the physical and electrical properties of the copper-clad laminate.

Example 2 The polyfunctional epoxy resin 691 used in Example 1 and tetrabromobisphenol ph 31 p (epoxy of polyfunctional epoxy resin: IE;/equivalent ratio of hydroxyl groups of brominated bisphenol A: 5) were blended and carried out. An oligoepoxy resin (α) is obtained in the same manner as in Example 1.

This oligoepoxy resin 821 was blended with phenol resin (molecular weight L500) 18f (equivalent ratio of phenolic hydroxyl group of phenol resin/epoxy group of oligoepoxy resin: 0.7) produced by polycondensation of bisphenol A and formaldehyde. The composition contains a polyester resin (Byron 200.
Toyobo product name)! 95F, 2-phenylimidazole 8.2 f t-& combined, methyl ethyl ketone 1 oot
The resin composition was dissolved in ethylene glycol monomethyl ether 87f to obtain a resin composition for a laminate having a concentration of 55%. A glass woven fabric having a thickness of 0.111 fl was impregnated with this material and dried to obtain a prepreg with a resin-containing lid of 52% by weight.

This prepreg was stacked 48 times and press-molded with 35 μm o steel foil interposed on both sides. The molding conditions are press temperature 18
The temperature was 0°C, the press pressure was 40 kg/d, and the press time was 60 minutes. Physical properties of the resulting copper-clad laminates.

The evaluation results for electrical properties are shown in the table.

Example 3 Polyfunctional epoxy resin 81F used in Example 1 and dibromobisphenol A19F (equivalent ratio of epoxy group of polyfunctional epoxy resin/hydroxyl group of bromobisphenol A is 210
) to obtain an oligoepoxy resin (α) in the same manner as in Example 1. Phenol resin (molecular weight 10G) produced by polycondensation of this oligoepoxy resin γL51, bisphenol A, and formaldehyde (molecular weight 10G) 27.5
f (phenolic hydroxyl group/epoxy group equivalent ratio: 1.
1)! j- Polysulfone resin (p-1) is added to the blended composition.
1raAMOCO brand name) 8jl, 2-ethyl-4-methylimidazole 0.12jF, acetone 30
m1゜Dissolved in methyl ethyl ketone 59f, 63%1
Resin composition t for laminates according to another example of this invention at 11 degrees
-I got it. This was impregnated into a 0.18 fl thick glass woven fabric and dried to obtain a prepreg with a 4!1 fat content of 55 inches.

Four sheets of this prepreg were stacked and press-molded with 35 μm copper foil interposed on both sides. What are the molding conditions?

The press temperature was 200°C, the press pressure was 30 kg/d, and the press time was 90 minutes. Physical properties of the resulting copper-clad laminates! The evaluation results regarding the physical properties are shown in the table.

Example 4 The polyfunctional epoxy resin 699 used in Example 1 and tetrabromobisphenol A3111 (equivalence ratio of epoxy group of polyfunctional Mu epoxy resin/hydroxyl group of bromobisphenol A: 3.5) were blended, and Example 1 and An oligoepoxy resin (α) is obtained in the same machine. A phenol resin (molecule II: 6,000
) 22 N (equivalent ratio of phenolic hydroxyl group/epoxy group: O, S) with a molecule of 3130.0
00 phenoxy resin (YP-50, Tobu Kasei g) 29
9.2-ethylimidacillin 0.231 is blended,
It was dissolved in 30 g of N,N-dimethylacetamide and 81 g of ethylene glycol monomethyl ether to obtain a resin composition for a laminate having a concentration of 58 weight by weight according to yet another example of the present invention. This was impregnated into a glass woven fabric having a thickness of 0.1 Bt1 g and dried to obtain a prepreg having a resin content of 51 weights. Four sheets of this prepreg 1c were stacked with 35 μm steel foil interposed on both sides.

Press molding was performed. Press molding conditions were the same as in Example 2. The results of characteristic evaluation of the obtained copper-clad laminate are shown in the table.

Comparative Example 1 A copper-clad laminate was made in the same manner as in Example 1 using an 9-molecular-weight 1.000 epoxy resin (Epicoat 1001. Yuka Shell Fragment) in place of the phenoxy resin with a molecular weight of so and ooo. Obtained.

Ratio 12 Example 2 A copper-clad laminate was obtained in the same manner as in Example 1 except that the phenoxy resin, which is a chain polymer, was not blended.

Comparison f113 A copper-clad laminate was obtained in the same manner as in Example 2 except that *120F was used instead of the polyester resin 'fr:959.

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

As is clear from the table, the cured products of the resin compositions for laminates of the Examples of the present invention have comparable heat resistance and excellent mechanical strength and toughness compared to the Comparative Examples.

For example, when this material is used in a T-copper clad laminate, it can be seen that it exhibits excellent NFC adhesion.

〔Effect of the invention〕

As explained above, this invention is.

A polyfunctional epoxy resin (α1) represented by t, brominated bisphenol A (βl) represented by the chemical formula (in the formula, a is an integer of 1 to 4), 1 equivalent of the hydroxyl group of the above brominated bisphenol A (β1) In contrast, the polyfunctional epoxy resin (αI) has a chemical formula (wherein aJdl~4
oligoepoxy at fat (α) and phenol resin (β) fc expressed by the above oligoepoxy side fat (α)
The above phenol resin (
This composition (1) was added to 100 parts by weight of the composition (1) in which the hydroxyl group of β) was blended in a proportion of O17 to 1.2 equivalents.
By using a linear polymer having a molecular weight of 5.000 or more and 10 (LOOQ or less) that is compatible with (1) t1 to 60 parts by weight.

The cured product has superior heat resistance compared to conventional products.

The resin composition for laminates can be expected to have excellent mechanical strength and toughness, and when used for example in copper-clad laminates, it is preferable because it shows excellent adhesiveness.

Claims (1)

[Claims] For the polyfunctional epoxy resin (α1) represented by the chemical formula ▲There are numerical formulas, chemical formulas, tables, etc.▼, there are chemical formulas ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, a is 1-4) brominated bisphenol A (β1) represented by an integer), such that the epoxy group of the polyfunctional epoxy resin (α1) is 3 or more and 5 or less per equivalent of hydroxyl group of the brominated bisphenol A (β1). The chemical formula obtained by blending and reacting ▲ There are mathematical formulas, chemical formulas, tables, etc. This composition ( I) Compatible with molecular weight 5,000 or more 100
A resin composition for a laminate, which contains 1 to 60 parts by weight of a linear polymer (II) having a molecular weight of 1 to 60 parts by weight.