JPH01287173A - Resin composition for flame retardant electrical laminated board - Google Patents

Abstract

PURPOSE:To obtain the subject composition, excellent in heat resistance and flame retardance and suitable as electrical and electronic devices, etc., by blending a side-chain double bond type resin with a specific bromine compound. CONSTITUTION:A compound obtained by blending a side-chain double bond type resin which is a backbone polymer constituted of a backbone chain which is a backbone polymer containing vinyl monomer units having functional group and 5,000-400,000 weight-average molecular weight and side chain which is a polymer having radically polymerizable carbon-carbon double bond with an aliphatic bromine compound (e.g. alkyl bromide) and/or an alicyclic bromide compound (e.g. monobromocyclohexane) and an aromatic bromine compound (e.g. monobromobenzene).

Description

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

[Prior Art] Conventionally, typical resins used for electrical laminates include phenol resins, epoxy resins, and unsaturated polyester resins, which are used in combination with various base materials.

However, phenolic resins have problems with the generation of reaction by-products during curing and removal of solvents, and epoxy resins have the same problems with solvent removal as described above. Unsaturated polyester resin does not have these problems and is a radical curing type that is easy to use, but on the other hand,
It is difficult to obtain a laminate that is excellent in both heat resistance and flame retardancy and has a well-balanced performance in both, and is currently a major issue.

For example, as shown in JP-A-57-93140, an unsaturated polyester resin laminate containing aliphatic bromine and/or alicyclic bromine and aromatic bromine in an unsaturated polyester resin has been proposed. However, the problem cannot be said to have been fully resolved.

[Problems to be Solved by the Invention] The purpose of the present invention is to provide a radical-curable resin composition for electrical laminates that has high flame retardancy and excellent heat resistance. As a result of efforts made by the present inventors to achieve these objectives, the present inventors have achieved excellent heat resistance and flame retardancy by using a resin composition in which a specific bromine compound is blended with a side chain double bond type resin. The present invention was completed based on the discovery that it is possible to make an electrical laminate. That is, the gist of the present invention is to provide a flame-retardant electrical laminate resin composition comprising a side chain double bond type resin mixed with an aliphatic bromine compound and/or an alicyclic bromine compound and an aromatic bromine compound. be.

The present invention will be explained in detail below.

The side chain double bond type resin referred to in the present invention is a polymer composed of a main chain and a side chain, where the main chain is a backbone polymer containing a vinyl monomer unit having a functional group, and the side chain is a backbone polymer containing a vinyl monomer unit having a functional group. It refers to a polymer that is a branch having a radically reactive carbon-carbon double bond formed through a functional group in the main chain. It is an essential unit and contains a vinyl monomer unit in the i-position, which does not have a functional group, depending on the number of units, and these are polymerized to form the main chain.

Monomers constituting the essential units listed in item 1 include vinyl monomers having a carboxyl group as a functional group such as acrylic acid, methacrylic acid, maleic anhydride, and maleic acid monoester; glycidyl as a functional group such as glycidyl methacrylate and glycidyl acrylate; Vinyl monomers having groups, allyl alcohol, 2-hydroxyethyl methacrylate-1, 2-hydroxyethyl acrylate, 2
-Hydroxypropyl methacrylate-1, 2-hydroxypropyl acrylate-1, N-methylol acrylamide, and other vinyl monomers having a hydroxyl group as a functional group are typical, and in particular, acrylic acid and methacrylic acid are most preferably used.

In the present invention, the vinyl monomer unit having a functional group may be present as an active functional group when the main chain is formed by polymerization, or may be polymerized by reacting the side chain described below with the functional group of the monomer in advance. Refers to a type of vinyl monomer unit with a functional group that functions to form a side chain into the main chain, regardless of whether the side chain is formed into the main chain.

As a vinyl monomer without a functional group, S = 3
- Styrene, α-methylstyrene, chlorostyrene, vinyltoluene, vinyl chloride, vinylidene chloride, vinyl bromide,
Examples include acrylonitrile, ethylene, propylene, butadiene, acrylic ester, methacrylic ester, vinyl acetate, vinyl propionate, maleic diester, ethylvinylbenzene, and the like.

The weight average molecular weight of the main chain composed of these vinyl monomer units is from 5,000 to 400,000, preferably from 10,000 to 200,000. This value is appropriately selected depending on the type of side chain. This molecular weight affects the physical properties and impregnation properties of electrical laminates,
If it is less than 5,000, the mechanical properties of the cured laminate will be insufficient, and if it exceeds 400,000, the resin impregnation into flies (paper, etc.) will be poor, and both are not preferred.

The amount of monomer units having functional groups in the main chain is related to the density of the side chains and affects the curing reactivity between the side chains, so an appropriate ratio is selected. The side chain density is preferably 0.1 to 2 moles, more preferably 0.4 to 1.5 moles.

The side chain referred to in the present invention refers to a chain having a double bond of >C=C at the end or in the middle, and refers to a chain forming a branch on the main chain via its functional group. As for things, (below the margin) 1 to 匡工0□Q 1 0
l 1 etc. can be exemplified as a general formula.

(I) In the formula, R1 to R3 are hydrogen or a methyl group, n represents an integer of 0 to 5, and in the (n) formula, R4 is hydrogen or a methyl group, Ll and L2 are -0- or -NH - indicates,
X and X2 represent a C2 to C1B hydrocarbon group or a hydrocarbon group connected by an ether bond, and X in parentheses
The carbon atoms bonded to the oxygen adjacent to X1 and X2 in l and X2 are primary or secondary carbons, and B is C2
is an aliphatic, alicyclic or aromatic hydrocarbon group up to o.

(III) In the formula, R5 is hydrogen or a methyl group.

Note that the side chains of the side chain double bond type resin according to the present invention are not limited to these, and any type that can form a crosslink between side chains by a radical reaction using a crosslinking vinyl monomer may be used.

In the present invention, various methods can be employed to introduce a side chain having a double bond at the end of the side chain into the polymer constituting the main chain. Some examples are as follows.

(1) For the carboxyl group of the main chain functional group, =
7 - An unsaturated group-containing epoxy compound prepared by reacting one epoxy group of a compound having a jepoxy group such as a bisphenol-type diglycidyl ether-type epoxyhexy group with (meth)acrylic acid is added and reacted.

(ji) React the carboxyl group of the functional group of the main chain with glycidyl (meth)acrylate.

(iii) Reacting the epoxy group of the side chain with (meth)acrylic acid.

(iv) Hydroxyethyl (
A reaction product containing monoisocyanate as a main component and almost no diisocyanate compound is prepared by reacting meth)acrylate, and the isocyanate contained in this reaction product is reacted with the hydroxyl group of the main chain polymer.

In the exemplified method, the main chain was copolymerized first, but of course in the present invention, the reaction to form the side chain is performed first, and such monomers are copolymerized last to form the side chain terminal. A side chain double bond type resin containing a (meth)acryloyl group may also be produced.

The aliphatic bromine compound in the present invention refers to an aliphatic hydrocarbon group in which hydrogen is replaced with bromine.

The aliphatic bromine compounds include alkyl bromides, polybrominated alkanes, bromocarboxylic acids, bromocarboxylic esters, bromine alcohols, bromine polyols, alkyl bromide group-containing compounds, and derivatives thereof. etc. are included.

The alicyclic bromine compound in the present invention refers to an alicyclic hydrocarbon group in which hydrogen has been replaced with bromine.

The alicyclic bromine compounds include monobromocyclohexane, polybromocyclohexane, hexabromocyclododecane, tetrabromophthalic anhydride, and derivatives thereof.

The aromatic bromine compound in the present invention refers to one in which hydrogen in an aromatic group is replaced with bromine.

The aromatic bromine compounds include monobromobenzene, polybromobenzene, monobromophenol, polybromophenol, bromophenyl derivatives, polybromophenyl derivatives, bromopyridine, polybromopyridine, monobromonaphthalene, polybromonaphthalene, and tetrabromobisphenol. Derivatives and derivatives of these compounds, etc. are included.

Aliphatic bromine and alicyclic bromine compounds generally have a large flame retardant effect or poor heat resistance, making it difficult to obtain a good 1111 layer plate. By combining it with an aliphatic bromine and/or alicyclic bromine compound and blending it with a side chain double bond type resin, a flame retardant resin composition for electrical laminates with significantly improved heat resistance can be obtained. .

The bromine content contained in the resin composition in the present invention can be appropriately selected depending on the performance of the laminate, but the bromine content of aliphatic bromine and/or alicyclic bromine is 2 to 15% by weight, It is also preferable that the bromine content of the aromatic bromine is 5 to 25% by weight, and that the total bromine content does not exceed 30% by weight.

Crosslinking vinyl monomers can be used in the resin composition of the present invention, and any known ones can be used, but among these, styrene, α-methylstyrene, p-methylstyrene, p- Substituted styrenes such as chlorstyrene and p-vinylstyrene; various acrylic or methacrylic esters; ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1.4
-butanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, diacrylated isocyanurate,
Vinyl polyfunctional acrylic acid or methacrylic acid such as pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, glycerin di(meth)acrylate, neopentyl glycol di(meth)acrylate, bisphenol A di(meth)acrylate, etc. Esters: polyurethane (meth)acrylate, polyether (meth)acrylate-1-, epichlorohydrin-modified bisphenol A di(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, propylene oxide-modified bisphenol A
Di(meth)acrylate, polyethylene glycol di(
Vinyl polyfunctional oligoesters such as meth)acrylate, polypropylene glycol di(meth)acrylate, and the like are included.

Also, diene compounds such as dibutyl maleate, dioctyl maleate, phenylmaleimide, vinyl acetate, vinyl propionate, cyclopentadiene, butadiene, diallylisocyanure-1, triallylisocyanure-1.
1., etc. can also be used.

There is no problem in using two or more types of crosslinking vinyl monomers in combination depending on the purpose.

The resin composition of the present invention can contain an additive plasticizer. As plasticizers, commercially available ester plasticizers,
Examples include tung oil, soybean oil, linseed oil, and derivatives thereof.

Other plasticizers include thermoplastics such as saturated polyesters, polystyrene, polyvinyl chloride, polyvinyl acetate, polymethacrylates, polyacrylates, and terpolymer copolymers such as acrylonitrile-styrene-butadiene. Polymers can be used.

It is also possible to add flame retardants other than the above-mentioned aliphatic bromine compounds, alicyclic bromine compounds, and aromatic bromine compounds to the resin composition of the present invention, such as trioctyl phosphate, triphenyl phosphate, and trichloride. Examples include phosphorus flame retardants such as diyl phosphate, triphenyl phosphite, and tris(chloroethyl) phosphate, antimony compounds such as antimony trioxide, antimony pentoxide, and sodium antimonate, zinc borate, and aluminum hydroxide.

Furthermore, in the present invention, fillers, reinforcing materials, mold release agents, colorants, curing agents, accelerators, stabilizers, etc. can be used in combination with the resin composition as necessary to further enhance its performance.

The resin composition of the present invention can be used for manufacturing electrical laminates according to known methods. That is, an electrical laminate is obtained by laminating a plurality of base materials impregnated with a resin composition, and in the case of a metal foil-clad laminate, layering metal foil on one or both sides, and hardening and molding. I can do it.

The base material can usually be a cellulose base material, or more preferably, for example, kraft paper or linter paper. may be pre-impregnated.

Furthermore, the resin composition of the present invention is applicable not only to cellulose-based substrates, but also to glass-based substrates such as glass cloth and glass mats, or to mixed substrates of these and cellulose substrates. A molded product with no residual residue can be obtained.

The resin composition of the present invention can be cured using a general-purpose organic peroxide, and can be cured using a known curing catalyst such as a curing catalyst that is sensitive to light or a curing catalyst that is sensitive to radiation and electron beams, together with the organic peroxide or alone. Catalysts can also be used.

[Example] 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.

Production Example 1 A separable flask (3000 ml) equipped with a stirrer, a thermometer with a gas inlet tube, a reflux condenser, and a dropping funnel.
), methacrylic acid (35 g, 0.41 mol), methyl ethyl ketone (400 g), styrene monomer (800 g)
g, 7.7 mol), azobisisobutyronitrile (
5.0 g) and dodecyl mercaptan (1'2 g) were charged, and polymerization was carried out at 75 to 80° C. for 10 hours in a nitrogen atmosphere. Hydroquinone (0.5 g) was added to inhibit polymerization. The polymerization rate of styrene monomer is 76%, the polymerization rate of methacrylic acid is 93%, and the weight! 1! - A polymer-containing liquid containing a styrene-methacrylic acid copolymer having an average molecular weight of about 50,000 was obtained.

In addition, another reactor with the same configuration as above was equipped with "Epicor" 827.
J (trade name, manufactured by Yuka Shell Epokin Co., Ltd.) (360g,
1 mol), methacrylic acid (138 g, 1.8 mol), benzyldimethylamine (1.2 g), and parabenzoquinone (0.12 g) were charged, and the mixture was reacted at 120° C. under a nitrogen atmosphere for 3 hours. After the reaction, the acid value became almost zero, and a vinylation reagent containing an epoxy resin containing an unsaturated group was obtained.

Add the entire amount of the previously prepared polymer-containing liquid to the vinylation reagent, add triphenylphosphine (5 g) and parabenzoquinone (0.1 Og) and heat, distill the methyl ethyl ketone solvent at a boiling point of 110 °C, and 5 in temperature
Allowed time to react.

After the reaction, the unsaturated group-containing epoxy resin is about 1
It became 5%. Heat evaporation was continued at 30-50+ nmHg with intermittent addition of styrene monomer (iooog). Methyl ethyl ketone detected in distillate is 0
．． The operation was terminated when it became 1% or less. The thus obtained resin liquid containing the curable prepolymer was a yellowish brown liquid containing a polymer having side chains of type (1) and having a non-volatile content of 52% by weight and a viscosity of 6.2 poise (at 25°C). .

Example Kraft paper with a basis weight of 135g/r+f (10cm x 1
0 cm) in an aqueous solution of Nikaledin S-305J (methylolmelamine manufactured by Nippon Carbide Co., Ltd.) at 120°C.
and dried for 30 minutes. 15% by weight in the obtained paper base material,
−′ Adhered. This base material was impregnated with a resin compound solution for impregnation having the composition shown in Table 1, and commercially available adhesive-coated copper foil rMK-58J (three pieces) was prepared using six sheets of paper containing the resin compound solution and a phenolic adhesive. (manufactured by Kinzoku Mining Co., Ltd.) were stacked, a 100 tlr II polyester film was used as a release paper, and it was sandwiched between two stainless steel plates.
Apply a pressure of 5 kg/c-, 100°C for 30 minutes, 120°C
It was allowed to cure for 2 hours.

Table 2 shows the performance of the obtained laminate.

Comparative Example A laminate was produced using the impregnating resin mixture shown in Table 1 in the same manner as in the Example.

Table 2 shows the performance of the obtained laminate.

[Effects] The flame-retardant electrical laminate resin composition of the present invention can provide a laminate having excellent heat resistance and flame retardancy.

Claims (1)

[Claims] A flame-retardant resin composition for electrical laminates comprising a side chain double bond type resin, an aliphatic bromine compound and/or an alicyclic bromine compound, and an aromatic bromine compound.