JPS6018341A - Flame-retarded epoxy resin copper lined laminated board - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] The present invention relates to a flame-retardant epoxy resin copper-clad laminate for industrial use, consumer use, and electric/electronic circuits, and its purpose is to provide heat resistance, copper foil and An object of the present invention is to provide a flame-retardant copper-clad laminate having high adhesive properties.

Next, the present invention will be explained in detail. The base material for the laminate used in the present invention may be glass, asbestos, etc., woven fabrics made of natural fibers such as fibers, polyester, polyamide, etc., natural fibers such as silk, cotton, etc., or paper. These combination base materials and other base materials for laminates in general. The copper foil is not particularly limited, and the copper foil used for the #i-clad ffi layer board is generally used.

Conventional flame retardant curing agents for epoxy resins include tetrabromophthalic anhydride, tetrachlorophthalic anhydride,
Dichloromaleic anhydride, chlorendic acid anhydride, etc. are used, but products using these have too strong reactivity with epoxy resins at room temperature, and mixtures of resin and acid anhydride have a short pot life. It is short and prone to loss of curing agent during pre-impregnation and generation of multiple harmful gases. Further, there are drawbacks such as the need to increase the amount of resin to be added to the resin by 50 parts or more in order to obtain a high degree of flammability, and at the same time, the contact strength with copper foil was not satisfactory.

As a result of a detailed study, the present inventors have found that by incorporating a specific halogenated benzophenone tetracarboxylic dianhydride into epoxy resin, the drawbacks of conventional flame-retardant curing agents can be overcome. , and the amount added is 1/2~
We have achieved an epoxy resin copper-clad laminate that costs only 1/4 of the weight and has excellent electrical insulation, heat resistance, and flame retardancy.

The halogenated benzophenone tetracarboxylic dianhydride used in the present invention is represented by the following general formula (1) (1) (where R1 is a halogen atom, Rz is a hydrogen atom or a halogen atom, and R3 is a hydrogen atom or a halogen atom. In addition, the above halogen atom C is chlorine or bromine.The highly halogenated form is effective for the flame retardant effect of this halogenated penzophenone de-1-lacarboxylic dianhydride; Often, benzophenonetetracarboxylic dianhydride with 4 to 6 halogen atoms bonded provides a better gas-burning effect.Also, this halogenated pencil 1nonte1-lacarboxylic dianhydride is used in epoxy resin. The blending amount is preferably 5 to 100 parts per 100 parts of resin.
If the amount is less than 5 parts, the effect of the flame-retardant curing agent tends to be reduced or reversed, and if it exceeds 100 parts, interlayer adhesion and adhesion to copper foil tend to decrease and "lead".

The epoxy resin used in the present invention is not particularly limited, but the following may be exemplified.

a. Difunctional or more polyfunctional epoxy resin, brominated difunctional or more polyfunctional Evo 4 Niji 461 resin.

C1 A mixture of the epoxy resins a and/or b above with non-substantive and/or organic flame retardant aids.

The present invention adds the above-mentioned cogenated benzophenone tetracarboxylic dianhydride (hereinafter simply abbreviated as X-BTDA) to any of these resin systems a, +1, and C as a flame-retardant curing agent. By blending, the object of the present invention can be effectively achieved.

To explain in more detail about the epoxy resin system, the polyfunctional epoxy resin having bifunctionality or higher is not particularly limited, but examples include bisphenol A type epoxy resin, bisphenol A type epoxy resin, phenol novolak type epoxy resin, alicyclic epoxy resin. , aliphatic epoxy resins such as propylene glycol diglycidyl ether, pentaerythryl 1-hel polyglycidyl ether, hydrogenated bisphenol A type epoxy resins, aliphatic epoxy resins, etc. Epoxy resin obtained by the reaction of the carboxylic acid of the formula with Ebichromehydrin, glycidyl l-almo 1-1-1 Bogi resin which is the reaction product of O-allylphenol novolac compound and epichlorohydrin, etc. Two or more types can be used arbitrarily in one scale.

Next, as the brominated tc bifunctional or higher polyfunctional epoxy resin, one or more of the above-mentioned difunctional or higher polyfunctional epoxy resins are brominated to a bromine-containing m2 to 50 parts. Two or more types can be used arbitrarily. Incidentally, in order to adjust the viscosity of the epoxy resin varnish, an organic solvent such as acetone, methane, Schiff[1-hexane, etc.] can be added as necessary. Next, the ff1ll flame auxiliary agent added to the above epoxy resin as needed is not particularly limited, but inorganic types include antimony trioxide, aluminum hydroxide, etc., and organic types include tricresyl phosphate, phenyl phosphate,
Phosphate esters such as tributyl sulfuric acid 1~, halogenated phosphate esters such as tris(β-chloro['edyl)bosphate and tris(dichloropropyl)phosphate, halogens such as chlorinated paraffin, dechlorambusis, hexabromobenzene, etc. The amount of the compound added to the epoxy resin is 1 to 30 parts in terms of 4.2 parts.

In addition, as a flexibilizing agent added to the epoxy resin as necessary (polyamide resin, polysepathic anhydride, boriapyraic anhydride, etc.), the additive to the epoxy resin (d is 1 to 30 parts) be.

Good effects can also be obtained when the above-mentioned flame retardant aids and flexibilizers are used in combination. The mixing ratio is not particularly limited.

Examples of reactive diluents that may be added to the epoxy resin as necessary include glycerol glycidyl ether, polyglycol diglycidyl di[--thyl], and tertiary fatty acid monoglycidyl ester. Furthermore, halides of these reactive diluents give good results as reactive diluents.

The present invention will be specifically explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 Bisphenol A epoxy resin (Ebi-1-10)
01, epoxy equivalent 480, manufactured by Yuka Ciel Evo Vshi) 1
00 parts and 30 parts of hexabrom-B TDA, which has 6 bromine atoms bonded in one molecule, and 5 methyl ethyl ketone.
5 parts were added to obtain an epoxy resin varnish.

This resin varnish was applied to a 0.18 m/m thick aminothicine-treated plain-woven glass cloth (base material for laminate) with a resin content of 4.
A prepreg was obtained by impregnation and drying to a concentration of 0%. Layer these 8 sheets of prepreg to a thickness of 0.03 mm below the 1st layer.
Layer 5 m/Tn of copper foil and press at 160°C.
Heat Ii molding was performed for 1 hour at 70 kg/crj to obtain a -C double-sided copper-clad glass-epoxy laminate.

Example 2 Bisphenol A epoxy resin (Epicote 1001
, epoxy equivalent: 480, manufactured by Yuka Shell Epoxy) and 20 parts of phenol novolak type epoxy (Al resin (Epicor 1" 154, epoxy equivalent: 180, manufactured by Yuka Shell Epoxy), containing 6 bromine atoms in one molecule. An epoxy resin varnish was obtained by blending 30 parts of the bonded Hegizabromo BTDA and adding 1 to 70 parts of Medillary Chiken.The following procedure was repeated in the same manner as in Example 1. .

Example 3 Talesol novolac type epoxy resin (Ebicor 1 to 1
54, Epoxy Todai 180, Yuka Shell Epoxy'Xj
) 5J'Jido bisphenol A type epoxy resin (
Epicor+-1ooi, epoxy equivalent 480, oil shell epoxy'! 'R) 50 parts, 20 parts of Hegisabromo BTDA with 6 bromine atoms bonded in one molecule and Tris(
Mix 5 parts of dichloropropyl (dichloropropyl) phosphate, add 1 to 70 parts of methane, and make a resin varnish.
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Hereinafter, Example 1 except that non-woven a was used as the base material for the laminate
A double-sided copper-clad glass-epoxy laminate was obtained in the same manner as above.

Example 4 Bisphenol A type epoxy resin (Shrimp”-1 to 828
, epoxy equivalent 190, manufactured by Yuka Shell Epoxy) 80 parts, and a reactive diluent added to this, 20 parts of tertiary fatty acid monoglycidyl ester (Kadular E1 manufactured by Yuka Shell Epoxy)
6 II! in one molecule. A resin varnish was obtained by blending 30 parts of hexabromo BTD A to which bromine atoms of 1 and 1 were bonded, and adding 55 parts of methyl ethyl ketone. Thereafter, a double-sided copper-clad glass-epoxy laminate was prepared in the same manner as in Example 1.

Example 5 Bisphenol A epoxy resin (Epicor)-100
1. Epoxy equivalent: 480, Yuka Shell Epoxy'PR>
Add 20 parts of phenol borac type epoxy resin (-F Pico-1 to 154, Epoxy Tosei 180, manufactured by Yuka Shell-L Boxy) to 80 parts, and add 20 parts of phenol borac type epoxy resin (-F Pico-1 to 154, Epoxy Tosei 180, manufactured by Yuka Shell-L Boxy), and add 6 chlorine Ill in one molecule.
A resin varnish was obtained by blending 45 parts of hexachloro-B T l)A to which r was bonded and adding 80 parts of methyl ethyl ketone. Thereafter, a double-sided copper-clad glass-epoxy laminate was obtained in the same manner as in Example 1.

Example 6 In place of 30 parts of hexabromo-BTDA in which 6 bromine atoms were bonded in 1 molecule in Example 1, 45 parts of tetrabromo-BTDA in which 4 bromine atoms were bonded in 1 molecule was used, and the other conditions were as in Example 1. In the same manner as above, a double-sided 11/11 glass poxy laminate was obtained.

[Comparative Example 1] Chlorendic acid was added to 100 parts of a bisphenol type epoxy resin (Epicoat 828, Ebogishi To Q 190, manufactured by Yuka Shell Epoxy). ! (Contains 117 parts of water,
Add 80 parts of methyl ethyl ketone to obtain a resin varnish.
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Thereafter, a double-sided copper-clad glass-epoxy laminate was obtained in the same manner as in Example 1.

Table 1 shows the performance of each laminate of Examples 1.2.3.4.5.6 and Comparative Example 1.

The insulation resistance values of the Examples containing X-I3 TDA were higher than those of the Comparative Examples. In addition, in terms of the amount used as a pH flammable curing agent, Examples 1, 2, and 4 showed equivalent heat resistance and flame retardancy, although the amount was 1/4 of that of the comparative example. Furthermore, Example 3, in which a flame retardant aid was blended, shows excellent flame retardant performance despite using about 1/6 of the amount of the comparative example. When X-B T I) Δ is blended into an epoxy resin, a laminate with excellent performance can be obtained with a significantly smaller amount than the conventional combustion type cured 1'ill.

``A small hand in a mountain τ1 mountain ii (self-said) [77 sum 5] ε
River ε) Moon:! 1til -1-1 Director General of the Patent Office Young 4, Sofurofu, 胛1, Indication of the incident 1981 Waiting i' [fall 12th (i6'J!: + No. 2, Name of the invention te fl IFA sex boxi + i + 111 1 point (・1■,
Aiichiso (N8 name (23/I) Sanyo [, ij sakupal/
') ; +, Shikiai stone 〒101 or Building L l lfi'1 Detailed explanation section of Hikari's specification

Claims (1)

[Claims] 1. Epoxy resin and halogenated benzophenone tetracarboxylic acid represented by general formula (1), which is a flame retardant curing agent.
Flame-retardant epoxy resin copper cladding (1) characterized by impregnating a base material for a laminate with an epoxy resin varnish mainly composed of anhydride (in the formula, R1 is a halogen atom, R2 is a hydrogen atom or a halogen 2. The flame-retardant epoxy resin copper-clad laminate according to claim 1, wherein the epoxy resin varnish contains a flame-retardant auxiliary agent. 3. The flame retardant epoxy resin copper-clad V4-layer board according to claim 1 or 2, wherein the epoxy resin varnish contains a flexibilizing agent. 4. Any one of claims 1 to 310, in which a reactive diluent is blended with the epoxy resin varnish.
Ill bamboo epoxy resin copper-clad laminate described in Section 1.