JPH04129737A - Electric laminated sheet - Google Patents

Abstract

PURPOSE:To prepare a copper clad laminated sheet improved in rigidity, strength, soldering heat resistance, the peel strength of a copper foil and tracking resistance by impregnating base materials with a resin solution prepared by compounding aluminum hydroxide with an allyl ester resin composition in a specific ratio and laminating the impregnated base materials to cure the same. CONSTITUTION:Base materials are impregnated with a resin solution prepared by compounding 5-100 pts.wt. of aluminum hydroxide with 100 pts.wt. of an allyl ester resin composition and laminated to be cured. The ally ester resin is a resin wherein an allyl ester group is provided to the terminal of saturated polyester formed from saturated polybasic acid and saturated polyhydric alcohol. In preparing a laminated sheet, a radical polymerizable crosslinkable monomer is used along with the allyl ester resin to prepare a resin composition.

Description

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

[Conventional technology]

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

[Invention or problem to be solved]

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 loss tangent, and tracking resistance. moreover,
When manufacturing paper-phenolic or glass-epoxy laminates, an intermediate called prepreg is usually produced by dissolving the resin in a solvent to form a solution, impregnating the base material with this solution, and removing the solvent from the impregnated base material. A laminate was manufactured by 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, or because unsaturated polyester resin has inherently poor heat resistance, the laminate also has poor rigidity when hot. There may be problems such as being small or lacking in strength.

The present invention has been made in view of the above circumstances, and can be manufactured without using the prepreg method, and has rigidity, strength, solder heat resistance, beer strength of copper foil, and torment resistance.

The purpose of this invention is to provide a copper-clad laminate with good kingability.

[Means to solve the problem]

As a result of various studies, the present inventors found that 5 to 100 parts of aluminum hydroxide per 100 parts by weight of the allyl ester resin composition.
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 containing the following parts by weight, laminating and curing the resin liquid, and have completed the present invention.

That is, we solved the problems in manufacturing paper-phenol laminates and Karasu-Epoquin laminates by using allyl ester resin, which allows laminates to be manufactured without using the prepreg method.
What's more, this resin is used to blend aluminum hydroxide,
By manufacturing a laminate, it has higher physical properties than a laminate manufactured using unsaturated polyester resin, and has better electrical properties than a laminate manufactured using fer/fer resin, It is possible to obtain a laminate with excellent soldering heat resistance, copper foil beer strength, and tracking resistance.

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

First, the allyl ester resin used in the present invention will be explained.

The allyl ester resin as used in the present invention 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.

Examples of saturated polybasic acids include dibasic acids such as orthophthalic acid, orthophthalic anhydride, isophthalic acid, phthalic acids such as terephthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetra human phthalic acid,
Hexahydrophthalic acid, methyl hexahydrophthalic acid,
and hydrophthalic acids such as their acid anhydrides, aliphatic dibasic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, tetrabromophthalic acid, tetrachlorophthalic acid, chlorendic acid, and acid anhydrides thereof, etc. Examples include halogenated dibasic acids. 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, ■
, 2-propylene glycol, 1,4 butanediol,
1,6-hexanediol, neopentyl glycol,
In addition to dihydric alcohols containing aliphatic, alicyclic or aromatic compounds such as 1,4-cyclohexane dimetatool and baraquinolengelicol, alcohols with the general formula HO(CHRCH,O)□H
(R is H or C@82 B*1+ m is 1-5
n is an integer of 2 to ]0), and n is an integer of 2 to 0). Examples of trihydric or higher polyhydric alcohols include aliphatic trihydric alcohols such as glycerin and trimethylolpropane, and tetrahydric or higher alcohols such as pentaerythritol and sorbitol. Further examples include aliphatic, alicyclic or aromatic halogenated polyhydric alcohols containing a halogen atom, such as dibromoneopentyl glycol and tetrabromobisphenol A ethylene oxide adduct. These can be used alone or in combination.

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 voluster 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 to form a resin composition. Any known resin composition can be used, but for example, diallyl Sialyl terephthalates such as orthophthalate, diallyl isophthalate, diallyl terephthalate, styrene,
Substituted styrenes such as α-methylstyrene, p-methylstyrene, p-chlorostyrene, flomstyrene, vinylhenseno, (methylmethaneacrylate, (meth)
Such as ethyl acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, hexyl (meth)acrylate, brominated phenyl (meth)acrylate, etc. Acrylic acid or methacrylic acid esters, ethylene glycolone (meth)acrylate), 1,4-butanediol/(meth)acrylate, trimethylolpropane tri(meth)acrylate, acrylated isocyanurate, pentaerythritol tri( Vinyl polyfunctional acrylic acids or methacrylic esters such as meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerine(meth)acrylate, a-opentyl glycol di(meth)acrylate, and bisphenol A(meth)acrylate; Vinyl polyfunctional oligoesters such as polyurethane (meth)acrylate, polyether (meth)acrylate, epichlorohydrin-modified bispher/-A di(meth)acrylate, polyethylene glycol/(meth)acrylate, polyethylene glycol di(meth)acrylate, etc. is 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 allyl ester resin in the present invention can be cured using a general-purpose organic peroxide, and may be used together with the organic peroxide or alone, such as a polymerization initiator that is sensitive to light, a polymerization initiator that is sensitive to radiation, or an electron beam. Known polymerization initiators can also be used.

Examples of organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide; 1. ] Bis(t-butyl peroxide/) 33.5-) dimethyl 7-dimethyl beef san, peroxyketals such as lobethyl-44-bis(t--1 tilburoxy/) valerate, t-butylhydrobao beef side , cumene hydroperoxide, p-menthane hydroperoxide and other hydroperoxides, di-t-butyl peroxide 7, tsucumyl peroxide, 2,5-dimethyl-25 di(t-butyl peroxide/
) Dialkyl peroxides such as hexane, shea/luperoxides such as lauroyl peroxide and hensyl peroxide, di-1so-propylene dicarbonate, cimilyl peroxide, bis(4-t-butyl) /Kurohegyu/ru) Baroki/Dicarbonate, etc.
Examples include peroxy/esters such as -butyl peroxy/pivalate, t-butyl peroxy-2-ethylhexanoate, and t-butyl peroxy dibenzoate. These are - types or a mixture of two or more types, types of resin,
It can be used depending on the curing conditions.

In the present invention, fillers, reinforcing materials, release agents, coloring agents, curing accelerators, stabilizers, etc. may be used in combination with the allyl ester resin to further enhance the performance of the laminate.

Next, the aluminum hydroxide used in the present invention is one having a kibutite crystal structure, one having a hemite crystal structure, and one having a hyarite crystal structure, all of which are industrially used as raw materials for aluminum. Manufactured in

In carrying out the present invention, it is preferable to use aluminum hydroxide having a bovine bushite crystal structure in consideration of its thermal decomposition temperature. Aluminum hydroxide with a kibsite crystal structure has a monoclinic crystal structure, and its crystal structure is a-8,62, b-5,480, c-9,70, and heta (β) angle. 85°82', and the refractive index is a
-1,568β-1588 and γ-] 567. Its thermal decomposition temperature is 160'C or higher. In addition, those with an average particle diameter of 100 microns or less are preferable, particularly 0.
A thickness of 5 to 60 microns is optimal. Commercially available product names include, for example, Hi/Lite H-32 and Hisilite H-42, which are aluminum hydroxide manufactured by Showa Denko K.K.
etc.

The amount of aluminum hydroxide used is 5 to 100 parts by weight per 100 parts by weight of the allyl ester resin composition! Quantity parts, 10
~80 parts by weight is preferred. If it is less than 5 parts by weight, no effect on tracking resistance will be exhibited, and if it exceeds 100 parts by weight, the viscosity of the resin liquid will increase, making it difficult to impregnate the base material.

A resin liquid prepared by blending aluminum hydroxide with an allyl ester resin or a resin composition mainly composed of the allyl ester resin can be used for manufacturing a laminate according to a known method. 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. Copper-clad laminates can be manufactured by: Of course,
- It is possible to form a laminate and then laminate it with copper foil coated with an adhesive.

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

When paper is used as the base material, from the viewpoint of impregnability and quality, it is preferable to use paper mainly composed of cellulose fibers, such as kraft paper, which has a density of 0.3 to 0.7 g/cm 3 when dried in air.

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 methylol (1 m, phenol resin, silane 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, and the application of adhesive to these copper foils is carried out using a normal roll-to-ter, flade coater, or wire bar. This may be done by appropriately selecting a coater or the like. The copper foil coated with the adhesive is preferably heat-treated to remove the solvent and to 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 0C, and parts and percentages are by weight unless otherwise specified.

〔Example〕

Production Example 1 Production of allyl ester resin (1) Diallyl terephthalate 60 was added to an IQ reactor equipped with a distillation device.
0g (2,44moρ), propylene glycol 95
．． 9 g (1,26 mo12) and 01 g of dibutyltin oxide were charged and heated to 180°C under a nitrogen stream to distill off the allyl alcohol produced. When 140 g (2.41 mog) of allyl alcohol had been distilled off, the pressure inside the reactor was reduced to 50 m+nHg to accelerate the distillation rate. After allyl alcohol in an amount equivalent to propylene glycol was distilled off, the reaction solution was distilled to 200 ml using a thin film distiller.
While maintaining the temperature at 1 mmHg, unreacted diallyl terephthalate was distilled off. Pour the reaction solution into a vat,
It was cooled and pulverized to obtain a powdery allyl ester resin (1).

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 at 120°C. It was dried for 30 minutes. The amount of melamine resin adhered to 100 parts by weight of kraft paper was 18 parts by weight. This paper base material is immersed in the blended solution of the resin composition shown in Table 2 to impregnate it with the resin solution,
Seven sheets were stacked, an adhesive-coated copper foil (MK-6 manufactured by Mitsui Mining and Mining Co., Ltd.) was stacked on one side, and a 50 μm polyester film was further stacked on both sides, followed by heating and pressure molding with a press machine. The conditions are 1/lO'c-]00 min-
It was 20 kg/cm'. After pressing, it was heated in a hot air drying oven at 150'C for 5 hours to a thickness of 1.6 mm.
A copper-clad laminate was obtained. Table 3 shows the results of measuring the physical properties of the copper-clad laminate.

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 tracking 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 tracking resistance. I can do it.

Claims (1)

[Claims] An electrical laminate is obtained by impregnating a base material with a resin liquid prepared by blending 5 to 100 parts by weight of aluminum hydroxide with 100 parts by weight of an allyl ester resin composition, then laminating and curing the resin liquid.