JPH0352765B2 - - Google Patents

Description

[Detailed description of the invention]

BACKGROUND OF THE INVENTION The present invention relates to electrical laminates using a curable resin composition suitable for manufacturing electrical laminates. Here, the term "electrical laminate" refers to, for example, a single-sided or double-sided metal foil-covered laminate used as an insulating substrate for mounting various electrical and electronic components or a printed wiring board, and the thickness thereof is 0.5 to 5 mm.
A relatively rigid plate-like object. Recently, resin compositions used in electrical laminates are required to have increasingly high chemical, mechanical, and electrical performance. Until now, paper-based phenolic resin laminates have been used mainly in consumer equipment, and glass-based epoxy resins have been used mainly in the fields of office automation equipment and industrial equipment. Recently, unsaturated polyester resin has attracted attention as a resin for electrical laminates due to its electrical properties and its ability to be molded by a continuous process, and products using it are now on the market. However, unsaturated polyester resins generally have low adhesion strength between glass substrates such as glass cloth and glass paper, particularly between different types of glass substrates. In addition, in the processing process of printed wiring boards, there is a method that uses a solvent-developed dry film to form circuit patterns.
Since many solvents such as methylene chloride are used, chemical resistance, especially resistance to chlorinated solvents, has become a problem. Therefore, the present invention provides an electrical laminate that has excellent delamination strength of a base material, especially a glass fiber base material, and chemical resistance against chlorinated solvents, etc., while maintaining excellent flame retardancy, heat resistance, and water resistance. An object of the present invention is to provide an electrical laminate using a curable resin composition suitable for manufacturing the board. Solution According to the present invention, a plurality of substrates impregnated with a resin mixture containing (a) a halogenated bisphenolic unsaturated polyester resin and (b) an epoxy acrylate resin that may contain a halogen are used. An electrical laminate is provided which is laminated and cured. The halogenated bisphenol-based unsaturated polyester resin can be obtained by using an adduct of a halogenated bisphenol and an alkylene oxide as a glycol component and carrying out a condensation reaction with a polybasic acid component by a conventional method. Alkylene oxide adducts of bisphenol A are preferred and their amount should be at least 10 mole percent of the total glycol component. It is also preferable to include neopentyl glycol, which may contain a halogen, as the glycol component, and the amount thereof is at least 10 mol% of the remaining glycol component after removing the alkylene oxide adduct of bisphenol A from the total glycol component. preferable. Epoxy acrylate resin is obtained by ring-opening the terminal glycidyl group of a polyfunctional epoxy compound with (meth)acrylic acid, and examples of epoxy compounds include aromatic ring-containing epoxy compounds such as bisphenol type epoxy compounds, novolak or resol type epoxy compounds. is preferable from the viewpoint of chemical resistance, heat resistance, and water resistance. The resin composition of the present invention contains a crosslinking monomer such as styrene as a component of the unsaturated polyester resin, and the ratio of the unsaturated polyester resin (a) containing the crosslinking monomer to the epoxy acrylate resin (b) is preferably is 30-90:70-10, more preferably 50-70:50-30 by weight. The electrical laminate of the present invention is preferably manufactured by the continuous method disclosed in Japanese Patent Application Laid-Open No. 56-98136 of the present applicant. Preferred base materials are those made from glass fibers, such as glass cloth and glass paper. The present invention provides an electrical laminate that has superior peel strength between base layers and chemical resistance, as well as superior flame retardancy, heat resistance, and water resistance, compared to products using conventional unsaturated polyester resins. A board is obtained. Detailed Discussion Halogenated Bisphenolic Unsaturated Polyester Resins Generally, unsaturated polyester resins consist of an unsaturated polyester (alkyd) and a curing monomer. Unsaturated polyester (alkyd) consists of an acid component consisting of an unsaturated polycarboxylic acid alone or a mixture of an unsaturated polycarboxylic acid and a saturated polycarboxylic acid and/or an unsaturated monocarboxylic acid, and a glycol alone, or It is an oligomer obtained by dehydration condensation of a glycol component consisting of a mixture of glycol and monoalcohol. It is essential that the resin component (a) of the present invention contains an alkylene oxide adduct of a halogenated bisphenol, such as an ethylene oxide or propylene oxide adduct of tetrabromobisphenol A, as a glycol component. Preferably, the glycol component further includes neopentyl glycol or halogenated neopentyl glycol, such as dibrome neopentyl glycol, in order to improve water resistance. Glycol components other than those mentioned above may include, for example, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, hexanediol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like. Examples of the monoalcohol include hydroxylated disylclopentadiene, ethylene glycol monomethyl ether, etc. In some cases, stearyl alcohol, polyethylene glycol monomethyl ether, polypropylene glycol monomethyl ether, etc. can also be used in part. It is desirable that the alkylene oxide adduct of halogenated bisphenol accounts for at least 10 mol%, more preferably 20 mol% of the total glycol component from the viewpoint of chemical resistance. Neopentyl alcohol or its halide accounts for at least 10 mol%, preferably 20 mol% or more of the remaining glycol components after removing the alkylene oxide adduct of halogenated bisphenol from the total glycol components,
More preferably, it accounts for 40 mol%. As the acid component of the unsaturated polyester, usual ones can be used. Common unsaturated polycarboxylic acids include maleic anhydride, maleic acid, fumaric acid, etc., and saturated polycarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, enditic acid, trimellitic acid, Examples include pyromellitic acid, tetrabromophthalic acid, dibromoterephthalic acid, chlorendic acid, and acid anhydrides thereof, and in some cases, adipic acid, sebacic acid, and acid anhydrides thereof may also be used. Examples of unsaturated monocarboxylic acids include maleated dicyclopentadiene. Styrene is commonly used as a crosslinking monomer, but α-methylstyrene, vinyltoluene, p
- methylstyrene, chlorostyrene, divinylbenzene, _C1 - _C10 alkyl (meth)acrylate,
Hydroxyalkyl (meth)acrylates, diallyl phthalates, triallyl cyanurates, and the like can also be used. The blending amount of the crosslinking monomer is preferably 10 to 70% by weight, particularly 20 to 50% by weight of the entire unsaturated polyester resin (a). Epoxy acrylate resin Epoxy acrylate resin is obtained by reacting a polyfunctional epoxy compound with (meth)acrylic acid to open the oxirane ring. Examples of polyfunctional epoxy compounds include reaction products of bisphenols and epichlorohydrin;
Reaction products of novolac type or resol type phenol/formaldehyde condensates and epichlorohydrin, reaction products of polyols and epichlorohydrin, reaction products of polybasic acids and epichlorohydrin, reaction products of polyalkylene glycols and epichlorohydrin, etc. can be mentioned. An epoxy compound having an aromatic ring, particularly a reaction product of bisphenol A and epichlorohydrin, is preferred. The epoxy acrylate resin can be obtained by reacting the epoxy compound with an equivalent amount of acrylic acid or methacrylic acid. Curable Resin Composition The curable resin composition of the present invention contains the halogenated bisphenol unsaturated polyester resin of (a) above.
It should contain 30% by weight or more, preferably 50% by weight or more, and 10-70% by weight, preferably 30-50% by weight of the epoxy acrylate resin (b). Halogenated bisphenol which is a component in resin (a)/
Alkylene oxide adducts are effective in improving chemical resistance, especially against chlorinated solvents, and at the same time maintain heat resistance and good thermal stability while imparting flame retardancy. These effects cannot be expected if the amount of compounded is small. However, since resin (a) alone does not provide satisfactory adhesion strength, especially between glass substrates such as glass cloth and glass paper, this drawback can be compensated for by blending resin (b). The effect cannot be expected unless the amount of the resin (b) blended is 10% by weight or more of the entire mixture, and is preferably 30 to 50% by weight. Therefore, the weight ratio of (a) resin to (b) resin in the blend is 90:10.
to 30:70, preferably 70:30 to 50:50. The curable resin composition of the present invention can contain an oligomer that is cured by a radical polymerization reaction, such as a general unsaturated polyester resin other than the resin (a) and a diallyl phthalate resin. Other fillers,
Of course, it may contain colorants, flame retardants, etc. The resin composition of the present invention can contain an additive flame retardant. Flame retardants include trioctyl phosphate, triphenyl phosphate, tricresyl phosphate, triethyl phosphate, triphenyl phosphite, and tris(chlorethyl).
Phosphorus-based flame retardants such as phosphates and red phosphorus, chlorinated paraffins, tetrabromobisphenol A and its derivatives, halogen-based flame retardants such as brominated products of diphenyl ether, monoglycidyl ether of tribromophenol, antimony trioxide,
Examples include antimony compounds such as antimony pentoxide and sodium antimonate, zinc borate, and aluminum hydroxide. The resin composition of the present invention can be cured using a commonly used organic peroxide, such as benzoyl peroxide. More preferred examples of organic peroxides include 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane and 1,1-bis(t-butylperoxy)cyclohexane as peroxyketals. Examples of dialkyl peroxides include di-t-butyl peroxide, and examples of peroxyesters include t-butyl peroxybenzoate. These are used in an amount of about 0.5 to 2.0 parts based on the resin composition. Note that the curing catalyst is not limited to these, and known curing catalysts such as a curing catalyst that is sensitive to light or a curing catalyst that is sensitive to radiation and electron beams can also be used together with an organic peroxide or alone. Although there are no particular limitations on the use of the resin composition of the present invention, it can be suitably used in the production of electrical laminates according to known methods. That is, a base material is impregnated with a resin composition, a plurality of impregnated base materials are laminated, and in the case of a metal foil-clad laminate, metal foil is laminated on one or both sides.
An electrical laminate can be obtained by hardening and molding. As the base material, glass base materials such as glass cloth, glass mat, glass paper, cellulose base materials, or mixed base materials thereof can be used, but it is particularly preferable to use a different type of base material such as glass cloth or glass paper. This is the case when manufacturing composite laminates. In addition, in the case of laminating and curing the above-mentioned resin-impregnated base materials, as disclosed in JP-A No. 56-98136, there is a method of curing continuously under conditions where the molding pressure during curing is substantially no pressure. This is the best method. The present invention will be explained in detail below with reference to Examples. In the examples, "parts" and "%" are based on weight. Synthesis example 1 1 mol of ethylene glycol, 1 mol of neopentyl glycol, tetrabromo bisphenol A/
An unsaturated polyester is synthesized by dehydration condensation of 2 moles of ethylene oxide adduct, 1 mole of isophthalic acid, and 2 moles of maleic anhydride using a conventional method, and 30% by weight of styrene monomer based on the total resin is added to this to halogenate it. A bisphenolic unsaturated polyester resin was obtained. Synthesis Example 2 0.25 mol of ethylene glycol, 0.25 mol of neopentyl glycol, 2.5 mol of tetrabromobisphenol A/2 mol of ethylene oxide adduct, 1 mol of isophthalic acid, and 2 mol of maleic anhydride are dehydrated and condensed in a conventional manner to produce an unsaturated polyester. A halogenated bisphenol-based unsaturated polyester resin was obtained by adding 30% by weight of styrene monomer based on the total weight of the resin. Synthesis Example 3 2 moles of ethylene glycol, 2 moles of tetrabromobisphenol A/ethylene oxide adduct 1
1 mole of isophthalic acid, and 2 moles of maleic anhydride are dehydrated and condensed by a conventional method to synthesize an unsaturated polyester, and 30% by weight of the entire resin of styrene monomer is added to produce a halogenated bisphenol-based unsaturated polyester resin. I got it. Synthesis Example 4 3 moles of ethylene glycol, 1 mole of isophthalic acid, and 2 moles of maleic anhydride are dehydrated and condensed by a conventional method to synthesize an unsaturated polyester, and 30% by weight of styrene monomer based on the total resin is added to synthesize iso-unsaturated polyester. A saturated polyester resin was obtained. Synthesis Example 5 An unsaturated polyester was synthesized by dehydrating and condensing 2 moles of ethylene glycol, 2 moles of dibroneopentyl glycol, 1 mole of isophthalic acid, and 3 moles of maleic anhydride in a conventional manner, and 30% by weight of the total resin was added to this unsaturated polyester. Styrene monomer was added to obtain a halogenated aliphatic unsaturated polyester resin. Example 1 70 parts of unsaturated polyester resin obtained in Synthesis Example 1,
Bisphenol A-based epoxy acrylate resin (manufactured by Showa Kobunshi Co., Ltd., trade name Lipoxy R-806) 30
parts, antimony trioxide 3 parts, benzoyl peroxide 1 part
A resin composition was obtained by mixing the two parts. Example 2 50 parts of unsaturated polyester resin obtained in Synthesis Example 2,
Bisphenol A-based epoxy acrylate resin (Lipoxy R-806) 50 parts, antimony trioxide 3
1 part of benzoyl peroxide were mixed to obtain a resin composition. Example 3 In Example 1, the unsaturated polyester resin obtained in Synthesis Example 3 was used instead of the unsaturated polyester resin obtained in Synthesis Example 1 to obtain a resin composition. Comparative Example 1 70 parts of unsaturated polyester resin obtained in Synthesis Example 3,
Iso-unsaturated polyester resin 30 obtained in Synthesis Example 4
parts, antimony trioxide 3 parts, benzoyl peroxide 1 part
A resin composition was obtained by mixing the two parts. Comparative Example 2 A resin was prepared by mixing 30 parts of bisphenol A-based epoxy acrylate resin (Lipoxy R-806), 70 parts of the aliphatic unsaturated polyester resin obtained in Synthesis Example 5, 3 parts of antimony trioxide, and 1 part of benzoyl peroxide. A composition was obtained. Manufacture of laminates The resin compositions of Examples and Comparative Examples were
The base material layers each consisting of one layer of glass cloth on the outside and glass paper in the center are impregnated while being conveyed individually and continuously, five layers of impregnated base materials are laminated, and an epoxy adhesive is applied.
Electrolytic copper foil with a thickness of 35μ coated to a film thickness of 30μ is laminated, the laminate is cured at 100℃ for 20 minutes, and after cutting, it is further post-cured at 160℃ for 20 minutes to form a single-sided copper-clad sheet with a thickness of 1.6mm. A laminate was obtained. The performance is shown in the table below.

【table】

【table】

Claims (1)

[Scope of Claims] 1 (a) a halogenated bisphenol-based unsaturated polyester resin in which at least 10 mol% of the glycol component of the unsaturated polyester chain is an alkylene oxide adduct of halogenated bisphenol; and (b)
An electrical laminate made by laminating and curing a plurality of base materials impregnated with a resin mixture containing an epoxy acrylate resin that may contain halogen. 2. The electrical laminate according to item 1, wherein the halogenated bisphenolic unsaturated polyester resin contains neopentyl glycol, which may contain a halogen as a glycol component. 3 Neopentyl glycol, which may contain halogens, is at least 10 mol% of the remaining glycol component after removing alkylene oxide adducts of halogenated bisphenols from the total glycol component.
The second term, electrical laminates, accounts for the majority of the total. 4. The electrical laminate according to any one of Items 1 to 3, wherein the epoxy acrylate resin is an epoxy acrylate resin containing an aromatic ring. 5. The electrical laminate according to any one of Items 1 to 4, wherein the base material is glass fiber.