JPH04129738A - Fire retardant electric laminated sheet - Google Patents

Abstract

PURPOSE:To enhance rigidity, strength, soldering heat resistance, the peel strength of a copper foil and resistance to thermal aging by impregnating base materials with resin solution prepared by compounding an organotin compound with a fire retardant allyl ester resin composition in a specific ratio and laminating the impregnated ones to cure the same. CONSTITUTION:Base materials are impregnated with a resin solution prepared by compounding 0.1-5 pts.wt. of an orgnaotin compound with 100 pts.wt. of a fire retardant allyl ester resin composition and laminated to be cured. The fire retardant allyl ester resin composition is based on a fire retardant allyl ester resin and prepared by adding an allyl ester resin and crosslinkable monomer to said resin. The organotin compound is one kind of an organometal compound and means a compound wherein a tin atom is directly bonded to a carbon atom and there is di-n-butyltin bismaleate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a flame-retardant electrical laminate used in electrical equipment, electronic equipment, communication equipment, etc.

[Conventional technology]

Conventionally, paper-phenol laminates, glass-epoxy laminates, and the like have been commonly used as electrical laminates. Here, the electrical laminate refers to a laminate having a wall thickness of 0.15 to 5++1I11, which is used, for example, as a substrate for various electronic components.

[Problem to be solved by the invention]

However, when manufacturing paper-phenol laminates,
As the phenolic resin hardens, reaction by-products such as water are generated, and this reaction by-product has a negative effect on the physical properties of the laminate. It becomes necessary to apply pressure. moreover,
Paper-phenol laminates have the disadvantage of poor electrical properties such as dielectric constant, dielectric voltage contact, and tracking resistance.

Furthermore, when manufacturing paper-phenolic laminates or glass-epoxy laminates, the resin is usually dissolved in a solvent to form a solution, the solution is impregnated into the substrate, and the solvent is removed from the impregnated substrate. Laminated plates have been manufactured by forming an intermediate called prepreg and laminating the prepregs under high temperature and pressure.

However, when a laminate is manufactured using such a prepreg method, there are problems in that raw material costs and equipment costs are high, and the process is complicated.

In order to solve these problems, a paper-based laminate made of unsaturated polyester resin was proposed, but since unsaturated polyester resin inherently has poor heat resistance, the laminate also has poor heat resistance. There are problems such as low rigidity and insufficient strength.

The present invention has been made in view of the above circumstances, and provides a flame-retardant electrical laminate that can be manufactured without using the prepreg method and has good rigidity, strength, soldering heat resistance, beer strength of copper foil, and heat aging resistance. The purpose is to provide boards.

[Means to solve the problem]

As a result of various studies, the present inventors found that 0.1 to 0.1 to
5f! It has been discovered that the above object can be achieved by an electrical laminate made by impregnating a base material with a resin liquid of a certain amount, laminating and curing the resin liquid, and has completed the present invention.

That is, we solved the problems in manufacturing paper-phenol laminates and glass-epoxy laminates by using allyl ester resin, which allows laminates to be manufactured without using the prepreg method.
Moreover, by manufacturing a laminate using a resin liquid containing this resin and an organic tin compound, it has higher physical properties than a laminate manufactured using an unsaturated polyester resin, and it also has higher physical properties than a laminate manufactured using an unsaturated polyester resin. This makes it possible to obtain a laminate that has better electrical properties than other laminates, and has excellent solder heat resistance, copper foil peel strength, and heat aging resistance.

Hereinafter, the content of the present invention will be explained in detail.

First, the flame-retardant allyl ester resin composition in the present invention refers to a composition mainly composed of a flame-retardant allyl ester resin, to which an allyl ester resin, a crosslinking monomer, etc. are added as necessary.

The above-mentioned allyl ester resin refers to a resin having an allyl ester group at the end of a saturated polyester formed from a saturated polybasic acid and a saturated polyhydric alcohol.

Saturated polybasic acids include, for example, dibasic acids such as orthophthalic acid, orthophthalic anhydride, isophthalic acid, phthalic acids such as terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalate. acid,
Hexahydrophthalic acid, methyl hexahydrophthalic acid,
Examples include hydrophthalic acids such as and their acid anhydrides, and aliphatic dibasic acids such as malonic acid, succinic acid, glutaric acid, and adipic acid. Examples of trifunctional or higher-functional polybasic acids include trimellitic acid, pyromellitic acid, and acid anhydrides thereof. These can be used alone or in combination.

Saturated polyhydric alcohols include ethylene glycol, 1
, 2-propylene glyfur, 1,4-butanediol, 1,6-hebosanediol, neopentyl glycol, 1,4-cyclohexane dimetatool, paraxylene glycol, etc., aliphatic, alicyclic or aromatic In addition to dihydric alcohols containing the general formula HO(CHRCH, O)r
Dihydric alcohol obtained by the addition reaction of alkylene oxide such as ethylene oxide or propylene oxide, which is expressed as lH (R is H or C@H2@*11m is an integer of 1 to 5, n is an integer of 2 to 10) can be given. Examples of the trihydric or higher polyhydric alcohol include aliphatic trihydric alcohols such as glycerin and trimethylolpropane, and tetrahydric or higher alcohols such as pentaerythritol and sorbitol. These can be used alone or in combination.

Further, the flame-retardant allyl ester resin refers to an allyl ester resin containing as a constituent a saturated polybasic acid containing bromine or chlorine, and/or a saturated polyhydric alcohol containing bromine or chlorine. A saturated polybasic acid containing bromine or chlorine refers to a compound in which the above saturated polybasic acid is substituted with one or more bromine or chlorine, such as tetrabromophthalic acid, tetrachlorophthalic acid, chlorendoic acid. , and their acid anhydrides, but are not limited to these. A saturated polyhydric alcohol containing bromine or chlorine refers to a compound in which the above saturated polyhydric alcohol is substituted with one or more bromine or chlorine, such as dibrome neopentyl glycol, tetrabromo bisphenol A, ethylene, etc. Examples include, but are not limited to, oxide and propylene oxide adducts. Such flame-retardant allyl ester resins are composed of one or more saturated polybasic acids containing bromine or chlorine, and/or one or more saturated polyhydric alcohols containing bromine or chlorine. It is also possible to use bromine- or chlorine-free saturated polybasic acids and/or bromine- or chlorine-free saturated polyhydric alcohols.

In the present invention, the flame-retardant allyl ester resin may be used alone or in a mixture of two or more types. Depending on the required level of flame retardancy, a flame-retardant allyl ester resin may be mixed and used. By various combinations, it is possible to obtain electrical laminates with good electrical properties, flame retardance, etc. while maintaining heat resistance.

The method for producing allyl ester resins is already known and is described, for example, in Japanese Patent Application No. 63-262217. For example, an allyl ester resin is produced by charging a diallyl ester of a saturated dibasic acid such as diallyl terephthalate and a saturated polyhydric alcohol together with a transesterification catalyst into a reactor and reacting the allyl alcohol while distilling off the allyl alcohol. A more industrially effective method is to charge a dialkyl ester of a saturated dibasic acid, such as dimethyl terephthalate, in place of diallyl terephthalate, together with allyl alcohol, polyhydric alcohol, and a transesterification catalyst, to remove by-produced alcohols such as methanol. It can be obtained by reacting while distilling off.

Further, depending on the reaction temperature, a polymerization inhibitor such as hydroquinone may be allowed to coexist in the reaction solution. In this way, an allyl ester resin having an allyl ester group at the end of a saturated polyester can be produced.

The types of allyl ester resins that can be used in the present invention may be one type or a mixture of two or more types. By selecting various types of saturated polybasic acid and saturated polyhydric alcohol, a laminate with a good balance of heat resistance, electrical properties, etc. can be obtained.

In producing the laminate in the present invention, a radically polymerizable crosslinking monomer can be used together with the allyl ester resin, and any known ones can be used, but for example, diallyl orthophthalate, diallyl isophthalate, etc. (
Methyl acrylate, ethyl (meth)acrylate,
Butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, (meth)acrylate
Acrylic acid or methacrylic esters such as benzyl acrylate, brominated phenyl (meth)acrylate, ethylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate,
Trimethylolpropane tri(meth)acrylate, diacrylated incyanurate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerin di(meth)acrylate, neobentyl glycol di(meth)acrylate, bisphenol A Vinyl polyfunctional acrylic acid or methacrylic acid esters such as di(meth)acrylate,
Vinyl polyfunctional oligoesters such as polyurethane (meth)acrylate, polyether (meth)acrylate, epichlorohydrin-modified bisphenol A di(meth)acrylate, polyethylene glycol di(meth)acrylate, polybrobylene glycol di(meth)acrylate, etc. included.

There is no problem in using two or more types of crosslinking monomers in combination depending on the purpose. In the present invention, by blending a crosslinking monomer, the viscosity of the allyl ester resin, which is originally a solid or viscous liquid, can be lowered, and the manufacturing process of the laminate can be simplified without going through the prepreg state using a solvent etc. can be converted into

The flame-retardant allyl ester resin composition of the present invention can be cured using a general-purpose organic peroxide, and can be cured by a polymerization initiator, radiation, or electron beam, which is first sensitized, together with or alone with the organic peroxide. Known polymerization initiators such as polymerization initiators can also be used.

Examples of organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, 1,1 bis(t-butylperoxy) 3,3,5-trimethylcyclohexane, and n-butyl- Peroxy ketals such as 4,4-bis(1-butylperoxy)valerate, hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide 7. Dicumyl peroxide, 2,5-dimethyl-2,5 di(t-butylperoxy), dialkyl peroxides such as beef san, diacyl peroxides such as lauroyl peroxide and benzoyl peroxide, di-1so - Peroxydicarbonates such as propyl peroxydicarbonate, cimilistyl peroxydicarbonate, bis(4-1-butylcyclohexyl)peroxydicarbonate, t-butylperoquine piperate, t-butylperoquine-2 Examples include peroxy esters such as -ethyl hexa/ate and t-butylbaquine benzoate. These can be used in one type or in a mixture of two or more types depending on the type of resin and curing conditions.

In the present invention, fillers, reinforcing materials, mold release agents, colorants, curing accelerators, stabilizers, etc. may be used in combination with the flame-retardant allyl ester resin composition to further enhance the performance of the laminate. It is possible.

Next, the organotin compound used in the present invention is a type of organometallic compound, and refers to a compound in which a tin atom is directly bonded to a carbon atom, and examples thereof include the following.

In the n-butyltin series, di-n-butyltin bismaleate salt, di-n-butyltin bismaleate polymer, di-n-butyltin bisoctylthioglycol ester salt, di-n-butyltin β- Mercaptopropionate polymer di-butyltin diurarate, polythiobis-n-butyltin sulfide, di-n-butylsumarate ester-carboxylate, di-n
-Butyltin maleate ester-mercaptide, di-lobyltin oxide, mono-lobyltin oxide, n-octyltin series, di-n-octyltin bis(isooctylthioglycolic acid ester), di-n-octyl Tin maleate polymer, di-n-octyltin dilaurate, di-n-octyltin maleate salt, di-n-octyl-tin oxide, monooctyltin tris(in-octylthioglycolic acid ester), methyl Examples of tin-based materials include dimethyltin bis(in-octylmercaptoacetate), but are not limited thereto.

These may be used alone (or may be used in combination).

Furthermore, some of these organic tin compounds exhibit a synergistic effect when used in combination with calcium-based, barium-based, zinc-based, cadmium-based metal soaps, and epoxy compounds, and are used in combination with these compounds as appropriate. The amount of organotin compound used is 100% of the flame retardant allyl ester resin composition.
The amount is 0.1 to 5 parts by weight.

If it is less than 0.1 part by weight, no effect on heat aging resistance will be exhibited, and if it exceeds 5 parts by weight, printability, adhesion, etc. will be impaired due to blooming, and the appearance will also be unfavorable.

A resin solution prepared by blending an organic tin compound with a flame-retardant allyl ester resin or a resin composition mainly composed of the flame-retardant allyl ester resin can be used in the production of electrical laminates such as copper-clad laminates according to known methods. That is, a base material is impregnated with the above-mentioned resin liquid, a plurality of impregnated base materials are laminated, a copper foil coated with an adhesive is layered on one or both sides, and then heated, cured, and molded without pressure or under pressure. A copper clad laminate can be manufactured by the following method. Of course - the laminate has been formed;
This can be laminated with copper foil coated with adhesive.

The above-mentioned base material can be the same as the base material used for conventional laminates. For example, glass-based base materials such as glass fiber cloth and glass non-woven fabric, cellulose-based base materials such as kraft paper, linter paper, cotton paper, etc. Refers to paper base materials, inorganic fiber-based sheet-like or band-like base materials, etc.

When paper is used as the base material, from the viewpoint of impregnability and quality, paper mainly composed of cellulose fibers, such as kraft paper, having an air-dried density of 0.3 to 0.7 g/c+e' is preferable.

Before impregnating these base materials with the impregnating resin composition, N
- It is also possible to improve the electrical properties by impregnating and drying with a methylol compound, phenol resin, 7-run coupling agent, etc.

Copper foil generally refers to copper foil commonly used for copper-clad laminates for electrical circuits, such as electrolytic copper foil and rolled copper foil. Adhesives can be applied to these copper foils using a normal roll coater, blade coater, or wire coater. It may be done by selecting a bar tweeter or the like as appropriate. It is preferable that the copper foil coated with the adhesive be heat treated to remove the solvent and be used in a partially cured state.

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples unless it departs from the gist of the present invention. Throughout this specification, all temperatures are in degrees Celsius, and parts and percentages are by weight unless otherwise specified.

〔Example〕

Production Example 1 Production of Allyl Ester Resin (1) Into a 112 reactor equipped with a distillation apparatus, 00 g (2,44 +++ of) of diallyl fref 9 and 9 g of propylene glycol 95 (1,261 o(2 ),
0.1 g of dibutyltin oxide was charged and heated to 180°C under a nitrogen stream, and allyl alcohol produced was distilled off. Allyl alcohol 140g (2,41mo
12) After distillation, the pressure inside the reactor was reduced to 50 mmHg to accelerate the distillation rate. After allyl alcohol equivalent to propylene glycol was distilled off, the reaction solution was heated to 1 mff1Hg while maintaining it at 200°C using a thin film distiller.
Unreacted diallyl terephthalate was distilled off.

The reaction solution was poured into a vat, cooled and pulverized to obtain powdered allyl ester resin 0).

Production Example 2 Production of allyl ester resin (2) containing bromine Except for the conditions shown in Table 1, allyl ester resin (1
) to obtain a bromine-containing allyl ester resin (2).

Examples 1 to 5 and Comparative Examples 1 to 2 Kraft paper with a basis weight of 155 g/m'' and a thickness of 300 μm was soaked in a water-methanol solution of melamine resin (S-305 manufactured by Nippon Carbide Co., Ltd.) and air-dried. The amount of melamine resin adhered to 100 parts by weight of kraft paper was 18 parts by weight.This paper base material was immersed in the blended solution of the resin composition shown in Table 2 to impregnate it with the resin solution. , seven sheets were stacked together, an adhesive-coated copper foil (MK-61 manufactured by Mitsui Mining and Mining Co., Ltd.) was superimposed on one side, and a 50 μm polyester film was superimposed on both sides, followed by heating and pressure molding with a press. The conditions are 140'C-10 minutes-2
0 kg/cra". After pressing, heating was performed at 150°C for 5 hours in a hot air drying oven to obtain a copper clad laminate with a thickness of 1.61. The physical property measurement results of the copper clad laminate were It is shown in Table 3.

As is clear from the results in Table 3, the electrical laminate of the present invention has excellent solder heat resistance, high copper foil peel strength, and good heat aging resistance.

〔Effect of the invention〕

The electrical laminate of the present invention can be manufactured without using the prepreg method, and has advantages such as good rigidity, strength, soldering heat resistance, copper foil peel strength, and heat aging resistance. I can do it.

Claims (1)

[Claims] For 100 parts by weight of the flame-retardant allyl ester resin composition,
A flame-retardant electrical laminate made by impregnating a base material with a resin liquid containing 0.1 to 5 parts by weight of an organic tin compound, laminating and curing the base material.