JPS63120713A - Resin composition for electrical laminate - Google Patents

Abstract

PURPOSE:To obtain the title composition excellent in electrical properties, mechanical properties and punching quality, by mixing a specified curable prepolymer with a crosslinking vinyl monomer. CONSTITUTION:A polymer (a) having a hydroxyl group in the side chain is reacted with an unsaturated isocyanate (b) having a free isocyanate group and a (meth)acryloyl group in the molecule to obtain a curable prepolymer (A) in which the main chain is a polymer obtained by vinyl polymerization and the side chain has a (meth)acryloyl group bonded to the main chain through two urethane bonds, represented by the formula [wherein A is the main chain part of a random copolymer, MW of 10,000-100,000, of a vinyl monomer with a (meth)acryloyl monomer, R is H or methyl and X1-2 are 2-16C hydrocarbon groups which may be bonded together through an ether bond, provided that the carbon bonded to the oxygen in X1 and X2 is primary or secondaryl]. 10-60wt% component A is mixed with 90-40wt% crosslinking vinyl monomer (B) (e.g., styrene) to obtain a resin composition used to form a resin composition for electrical laminates.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a resin composition for metal foil-clad laminates used in electrical equipment, electronic equipment, communication equipment, and the like.

[Prior Art] Typical resins used in metal foil-clad electrical laminates are phenol resins, epoxy resins, and unsaturated polyester resins, and are used in combination with various base materials.

On the other hand, resins known as vinyl ester resins have excellent physical properties when cured, but are not widely used for the purposes of the present invention.

Existing vinyl ester resins have molecules between several hundred to 2000
When impregnating and heating paper or glass substrates, the resin flows out from the substrate to a large extent, and when other heptamers are added, the viscosity decreases significantly.

As a method of compensating for such drawbacks, measures such as adding silica or the like to impart chicken viscosity are taken. However, when impregnating paper or glass substrates, imparting chicken viscosity has the disadvantage that the rate of impregnation into the substrate decreases.

Furthermore, since it is mainly composed of epoxy acrylate, it is relatively expensive and has not been widely used.

[Problems to be solved by the invention] The present invention provides an electrical laminate that has balanced electrical properties and mechanical properties, has excellent miscibility with various blended monomers and additives, and is suitable for impregnation processing. The purpose is to provide a resin composition for plates.

[Means for Solving the Problems] The object of the present invention is to produce a curable prepolymer previously disclosed in JP-A-60-38403, that is, in the general formula C, A is a vinyl monomer and an acrylic monomer. [Represents the main chain portion of a random copolymer with 1-yl monomer or methacryloyl monomer, R is hydrogen or a methyl group, and X
and X2 are each the same or different and have 2 carbon atoms
~ 16 hydrocarbon groups or hydrocarbon groups connected by ether bonds, and the carbon atoms bonded to oxygen in x1 and x2 are primary or secondary], and the main chain is vinyl The polymer obtained by polymerization contains 10 to 60% by weight of a curable prepolymer whose side chain has an acryloyl group or a methacryloyl group r or less, both of which are referred to as a (meth)acryloyl group, through two urethane bonds. This can be achieved by using a resin composition for electrical laminates, the main component of which is a resin mixture, the remainder of which is a crosslinking vinyl monomer.

[Function] In the present invention, the molecular weight of the main chain polymer in general formula [I] is preferably from 10,000 to 100,000, and in general formula [I]
A curable prepolymer represented by 10
It has also been found that a preferable resin composition can be obtained by containing ~60ffiffi%.

The method for producing the curable prepolymer represented by the general formula [I] of the present invention includes (a) using a monomer containing a hydroxyl group as one component and copolymerizing it with a desired monomer to have a hydroxyl group in the side chain. Synthesize a polymer: (b) Diisocyanate and an unsaturated monoalcohol having a (meth)acryloyl group are reacted in a 1:1 (mole ratio) to form 111i11 isocyaners in one molecule of the reaction product. Synthesize an unsaturated isocyanate that shares a (meth)acryloyl group with a (meth)acryloyl group, (c) add a polymer having a hydroxyl group on the side chain in step (a) dissolved in a solvent or monomer, and add J to step (b): The unsaturated isocyanate is reacted with the unsaturated isocyanate in a solvent solution.

When a solvent is used, it is necessary to remove the solvent by any known method to obtain a monomer solution.

In order to synthesize a polymer having a hydroxyl group in the side chain, it is necessary to copolymerize a monomer having a hydroxyl group with a general heptamer.

Examples of hydroxyl group-containing sevenmers include 2- and droxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl acrylate.
Typical examples include hydroxypropyl methacrylate and methylol acrylamide.

Examples of monomers that can be copolymerized with monomers having hydroxyl groups to form polymers include the following types that are currently commercially available: styrene, α-methylstyrene, chlorostyrene, vinyltoluene, acrylic. Acid esters (methyl, ethyl)
, butyl-12-ethylhexyl, octyl, etc.),
Methacrylic acid esters (methyl, ethyl, propyl, butyl, isobutyl, tert-butyl, 2
(ethylhexyl, lauryl, benzyl, cyclohexyl, tetrahydrofurfuryl, etc.), vinyl acetate, vinyl propionate, vinyl versatate, vinyl chloride, vinyl bromide, acrylonitrile, ethylene, butadiene, etc. Acrylic acid and methacrylic acid can also be used for modification.

For the polymerization in step (a), solution polymerization is convenient and can proceed directly to the next step, but it is also practical to dissolve the polymer obtained by bar polymerization or bulk polymerization in monomer and use it for the next reaction. It is true.

The next step (step (a)) for obtaining a polymer having unsaturated bonds in the side chain is the reaction of the hydroxyl group in the polymer side chain with an unsaturated isocyanate.

Unsaturated isocyanates are synthesized by reacting diisocyanates with unsaturated monoalcohols having (meth)acryloyl groups such that the molar ratio of hydroxyl groups to isocyanate groups is substantially 1:1. Ru.

For unsaturated monoalcohols, the types listed above apply as is.

Typical commercially available diisocyanates include 2,4-tolylene diisocyanate,
2.4-Tolylene diisocyanate (80% by weight) and 2
．． 6-Tolylene diisocyanate (20wt 1'fi%)
mixed isocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, 1,5-naphthylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate Can be mentioned.

The reaction is carried out by dissolving the isocyanate in a solvent or monomer and adding the unsaturated alcohol dropwise.

When a solvent is used, it is usually necessary to replace the solvent with a monomer, which is accomplished by fractional distillation taking advantage of the difference in boiling points (the solvent has a lower boiling point). In the case of a monomer solution, it can be used as is.

In addition, as the crosslinking monomer used in the present invention, any known ones can be used, but among these, styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, p-vinyl Substituted styrenes such as styrene; various acrylic or methacrylic esters; ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, Vinyl polyfunctional acrylic acid or methacrylic acid esters such as methylolpropane triacrylate and trimethylolpropane trimethacrylate; vinyl polyfunctional oligoesters such as polyurethane acrylate, polyurethane methacrylate, polyether acrylate, and polyether methacrylate, etc. Included.

[Examples] 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, temperatures are only in °C, parts and %
are based on weight unless otherwise specified.

The resin components used in the formulation of the examples are as follows.

Ingredients (A) - Molecule m is approximately 40,000 and is composed of styrene, 2- and droxyethyl methacrylate, and the main chain (weight ratio 82%) and 2-
- Curable prepolymer consisting of a vinyl side chain (8% by weight) consisting of hydroxypropyl methacrylate and tolylene diisocyanate [R-methyl group in general formula [I], X 1 = -CH
2-CH2-1 X --CH2-CH- Corresponds to CH3] Example: Kraft paper (10cm
Cm) was immersed in an aqueous solution of Nikaledene S-305J (trade name, manufactured by Nippon Carbide Co., Ltd., methylolmelamine), squeezed with a wax comb, and dried at 120°C for 30 minutes. has developed.

This paper was placed in a flat plate and floated on an impregnating resin mixture having the composition shown in Table 1 to impregnate it with the liquid.

6 sheets of paper containing resin compound liquid and commercially available copper foil rMK with adhesive
-56J (trade name, manufactured by Mitsui Kinzoku Mining Co., Ltd.) was placed in a cellophane bag, sandwiched between two iron plates, and a 30 kO weight was placed on top.

It was cured at 120°C for 1 hour and then at 100°C for 10 hours. The resulting laminate had a thickness of 1.59 to 1661 mm.

l? Table 2 shows the characteristic values of the one-layer board.

Table 1 Resin compound composition Table 2 Physical properties of laminate *) Temperature at which no defects occur in a mold arranged in 1#φ hole x hole side 41.785 Il+pitch.

[Effect of the Invention 1 The resin composition for electrical laminates of the present invention has excellent electrical properties, mechanical properties, and punching properties.

Claims (1)

[Claims] (1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ [I] (In the formula, A represents the main chain portion of a random copolymer of vinyl monomer and acryloyl monomer or methacryloyl monomer, and R represents hydrogen or methyl group. and X_1
and X_2 are the same or different hydrocarbon groups having 2 to 16 carbon atoms, or hydrocarbon groups connected by an ether bond, and the carbon atoms bonded to oxygen in X_1 and X_2 are primary or secondary. ] Curable prepolymers 10 to 10 whose main chain is a polymer obtained by vinyl polymerization and whose side chain has an acryloyl group or a methacryloyl group via two urethane bonds.
A resin composition for electrical laminates, the main component of which is a resin compounded liquid containing 60% by weight and the remainder consisting of a crosslinking vinyl monomer.