JPS63218720A - Resin composition for laminated sheet - Google Patents

Abstract

PURPOSE:To obtain the titled composition suitable as a resin for metal-clad laminated sheet for electrical use, by compounding a specific curable prepolymer containing (meth)acryloyl group at terminal of side chain, a halogen-containing flame-retardant monomer and a vinyl monomer for crosslinking. CONSTITUTION:The objective composition is composed of (A) 10-60wt.% curable prepolymer of formula [A is main chain segment of random copolymer of a vinyl monomer and (meth)acryloyl monomer; R1-R3 are H or CH3; n is 0-5] and containing (meth)acryloyl group at the terminal of a side chain, (B) 5-50wt.% halogen-containing flame retardant monomer produced by addition reaction of (i) a monoglycidyl (meth)acrylate to (ii) an ester derived from a saturated polybasic acid and a polyhydric alcohol having 1-18C aliphatic or alicyclic saturated hydrocarbon group containing bromine or chlorine and (C) remaining part of a vinyl monomer for crosslinking.

Description

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

[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.

Flame retardancy is required in many cases for the above laminates, but the method of making unsaturated polyester resins and vinyl ester resins, which are typical radical curable resins, flame retardant is still a major issue. .

[Problems to be Solved by the Invention] The curable prepolymer represented by the general formula [I], which is a component of the present invention, can be used by itself or mixed with other vinyl monomers to produce metal foil-clad electrical laminates. However, there is currently a demand for further flame retardancy of the laminate.

An object of the present invention is to provide a resin composition for electrical laminates, which is made by effectively making flame retardant a curable resin mixture containing a curable prepolymer represented by the general formula CI) as a main component.

[Means for Solving the Problems] The object of the present invention is to solve the problem using the general formula: -R3 is hydrogen or a methyl group,
n represents an integer of 0 to 5] 10 to 60% by weight of a curable prepolymer containing an acryloyl group or a methacryloyl group (hereinafter both are referred to as (meth)acryloyl group) at the end of the side chain. On the other hand, monoglycidyl methacrylate or monoglycidyl acrylate is added to an esterified product of a polyhydric alcohol having an aliphatic or alicyclic saturated hydrocarbon group containing bromine or chlorine having 1 to 18 carbon atoms and a saturated polybasic acid. 5 to 5 halogen-containing flame-retardant monomers
This is achieved by a resin composition for electrical laminates whose main component is a flame-retardant resin compounded liquid in which the flame retardant resin is added in an amount of 50% by weight and the remainder is a crosslinking monomer.

[Function] In the general formula (I), A represents a random copolymer skeleton of a vinyl monomer and a (meth)acryloyl monomer, and the main chain polymer containing A has a weight average molecular weight of 1.
Approximately 200,000 to 200,000, preferably 20,000 to 200,000.

Furthermore, the density of vinyl side chains contained in the main chain polymer can be adjusted freely, but when used in a resin composition for a laminate, it is 0.1 to 2 mol/CI) LOOOg.

Further, as the vinyl monomer used to form the main chain portion containing A, any vinyl monomer that can be copolymerized with a (meth)acryloyl group can be used.

Among these are styrene, α-methylstyrene, vinyltoluene, chlorostyrene, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, and 2-acrylate. Ethylhexyl, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate,
cyclohexyl methacrylate, benzyl methacrylate,
Included are tetrahydrofurfuryl methacrylate, acrylonitrile, vinyl acetate, vinyl propionate, vinylidene chloride, vinyl chloride, and the like.

The properties of the prepolymer represented by general formula (I) can be changed by the combination of copolymerizable vinyl monomers used to form the main chain skeleton.

The method for producing a curable prepolymer having a (meth)acryloyl group at the end of a side chain according to the present invention is schematically shown as follows.

0) First, a desired amount of (meth)acrylic acid and an epoxy resin in an excess equivalent ratio to (meth)acryloyl groups are combined with a necessary reaction catalyst, such as a tertiary amine, amine salt, quaternary ammonium salt, metal A reaction is performed using a salt to produce an unsaturated epoxy resin (A) containing a (meth)acryloyl group and an epoxy group in one molecule.

(b) Next, after adding the required type and amount of vinyl monomer, the (meth)acryloyl group of the unsaturated epoxy resin (A) and the vinyl monomer are combined in the presence of an initiator such as azobisisobutyronitrile. By radical polymerization, a reaction mixture containing a polymer having an epoxy group in the side chain is obtained.

(c) Furthermore, add the required amount of (meth)acrylic acid, (
By reacting the epoxy groups remaining in the reaction mixture (b) with the carboxyl groups, it is possible to obtain the desired polymer having vinyl ester groups in the side chains.

The epoxy resin used in the present invention is a phenylglycidyl ether type polyaddition homolog synthesized from bisphenol and shrimp chlorohydrin. Its general formula is shown, for example, as follows: [where n-0 to 5, R1, R
2 is hydrogen or a hamethyl group] Types suitable for the present invention are old-style ones in which n is about 0 to 3.

When synthesizing an unsaturated epoxy resin, the ratio of (meth)acrylic acid to epoxy resin is 2 or 3 per mol of (meth)acrylic acid (i.e., per equivalent of carboxyl group) per molecule. If the number of epoxy groups is two, 1 mole or more of the epoxy resin having glycidyl ether type epoxy groups is used, and if the number of epoxy groups is more than 2, the amount of epoxy resin is 1 mole or more, and the epoxy group is less than 2 equivalents. It is also necessary to have a large number of

Still another method is to copolymerize a vinyl monomer and (meth)acrylic acid, and then to copolymerize the unsaturated epoxy resin (A
) is subjected to an esterification reaction with the side chain carboxyl group of a copolymer of a vinyl monomer and (meth)acrylic acid to obtain the curable prepolymer of the present invention having a (meth)acryloyl group at the end of the side chain. You can also do that.

It is known that aliphatic or alicyclic bromine compounds are not sufficiently thermally stable, and that they must be used in combination with a stabilizer such as an epoxy compound. On the other hand, it is said that chlorine provides about half the flame retardancy of bromine.

The present inventors attempted to introduce a stable halogen-containing substance into a resin composition, and found that a polyhydric alcohol having an aliphatic or alicyclic saturated hydrocarbon group containing bromine or chlorine and having 1 to 18 carbon atoms. It has been found that a halogen-containing flame-retardant monomer made by reacting an ester with a saturated polybasic acid with monoglycidyl methacrylate or monoglycidyl acrylate is effective.

The polyhydric alcohol is preferably an aliphatic or alicyclic alcohol having 1 to 12 carbon atoms, and an easily available example includes dibroneopentyl glycol, but is not limited thereto. .

The flame retardant effect value is 0.45 for chlorine when bromine is 1.
The value is ~0.50, which corresponds to the commonly said index.

For example, when producing a laminate using paper as a base material, 5b20
When 3 is used in combination, the resin mixture passes the UL-94-V-O test if the halogen content in terms of bromine is about 10% or more in the resin mixture.

Since this is a monomer, unlike additive-type flame retardants, it has the advantage that it does not migrate from the cured resin and that the viscosity of the resin mixture can be easily adjusted. It is effective in some cases.

Furthermore, as the vinyl monomer for crosslinking 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, 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, 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 (30 g, 0.41 mol), methyl ethyl ketone (400 g), styrene monomer (800 g,
g, 7.7 mol), azobisisobutyronitrile (5
, Og) and dodecyl mercaptan (12 g),
Polymerization was carried out at 75 to 80° C. for 10 hours under a nitrogen atmosphere.

Hydroquinone (0.5 g) was added to inhibit polymerization. The polymerization rate of styrene monomer was 76%, and the polymerization rate of methacrylic acid was 93%, and a polymer-containing liquid containing a styrene-methacrylic acid copolymer having a weight average molecular weight of about 50,000 was obtained.

In addition, in another reactor having the same configuration as above, [Epicote 82
7J (trade name, manufactured by Mitsubishi Yuka-Shell) (380g,
1 mol), methacrylic acid (138 g, L, S mol), benzyldimethylamine (1.2 g), and parabenzoquinone (0.12 g) were charged, and reacted at 120° C. for 3 hours under a nitrogen atmosphere. After the reaction, the acid value became almost zero, and a vinylation reagent containing an unsaturated epoxy resin 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 heat at the same temperature. The reaction was carried out for 5 hours.

After the reaction, the unsaturated epoxy resin was about 15% of the amount before the reaction. While adding styrene monomer (1000 g) intermittently, heating evaporation was continued at 30 to 50 mmt (g). Methyl ethyl ketone detected in the distillate was 0.1%.
The operation ended when the following conditions occurred. The thus obtained resin liquid containing the curable prepolymer was a yellowish brown liquid with a viscosity of 6.2 poise (25° C.) and a nonvolatile content of 52% by weight.

Production Example 2 Separable flask (5000ml) equipped with a stirrer, thermometer with gas inlet tube, reflux condenser, and dropping funnel.
Methacrylic acid (35 g, 0.41 mol), ethyl acrylate (600 g, 6 mol), methyl ethyl ketone (600 g), and dodecyl mercaptan (6 g) were charged into the mixture and heated to 75°C under a nitrogen atmosphere.

A solution of azobisisobutyronitrile (5 g) dissolved in 50 ml of methyl ethyl ketone was added from the dropping funnel so that the internal temperature was 80° C. or lower. It was made to react at 75-80 degreeC for 8 hours. Thereafter, the temperature was raised to 180°C, and methyl ethyl ketone and a very small amount of unreacted ethyl acrylate were distilled off. The obtained polymer weighed 631 g and had a weight average molecular weight of f170,000.

Another reactor (2000m1) with the same configuration as above
"Epicor" 827J (trade name, manufactured by Mitsubishi Yuka-Shell) (360r, 1 mol), methacrylic acid (13
8g.

1.6 mol), benzyldimethylamine (1.2 g),
Rose benzoquinone (0.12 g) was charged and reacted at 120° C. under a nitrogen atmosphere for 3 hours.

The acid value of the reaction solution became almost zero, and a vinylation reagent containing an unsaturated epoxy resin was obtained. Styrene monomer (1000 g) was added and dissolved in this vinylation reagent, and this was added to the flask containing the polymer prepared previously. Additionally, triphenylphosphine (5g) and rosebenzoquinone (
0.1 Og) was added thereto, heated, and reacted at 120'C for 4 hours. After the reaction, the unsaturated epoxy resin was reduced to about 13% of the amount before the reaction.

The thus obtained resin liquid containing the curable prepolymer has a non-volatile content of 53% by weight and a viscosity of 8.9 poise (at 25°C).
It was a yellowish brown liquid.

Production example 3 A separable flask (1) equipped with a dropping funnel and a stirrer
000 ml) dibromneopentyl glycol 36
After charging 0 g (1.37 mol) and melting at 110°C, 185 g (1.25 mol) of phthalic anhydride was added.
and 1.0 g of para-toluenesulfonic acid.

The reaction was carried out at 170° C. for 4 hours under a reduced pressure of 20 to 200 mo+Hg. As a result, the acid value of the product was 40.

Next, styrene monomer 140 [, glycidyl methacrylate] 54 g (0.38 mol), hydroquinone 0.1
After adding 1.2 g of 2rq triethylamine, the mixture was reacted at 80° C. for 4 hours. As a result, the reaction rate of glycidyl methacrylate was 95%, and a flame retardant monomer solution with an acid value of 9 was obtained.

Example Kraft paper with a basis weight of 135g/rf (10cm x 10
cm) was soaked in an aqueous solution of ``NicaResin S-305J (trade name, manufactured by Nippon Carbide Co., Ltd., methylolmelamine), squeezed with a roller, and dried at 120°C for 30 minutes. This paper was placed in a flat plate and floated on an impregnating resin mixture having the composition shown in Table 1 to be impregnated 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 kg weight was placed on top.

In this state, it was placed in an air oven at 120°C and 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 1.61 a+m. Table 2 shows the characteristic values of the laminate.

(The following is a blank space) Table 1 Resin compound liquid composition (The following is a blank space) Table 2 Laminated board characteristics*) Temperature at which defects no longer occur in a mold in which 4 1mmφ holes are arranged at a pitch of 1.78+++m [Effects of the invention] The resin composition for laminates has excellent flame retardancy, and also has good heat resistance, water resistance, and punching properties.

Claims (1)

[Claims] (1) General formula ▲ Numerical formulas, chemical formulas, tables, etc. methyl group, n is an integer of 0 to 5] Curable prepolymers 10 to 60 containing an acryloyl group or a methacryloyl group at the end of the side chain, represented by
Monoglycidyl methacrylate or monoglycidyl acrylate is added to the esterified product of a polyhydric alcohol having an aliphatic or alicyclic saturated hydrocarbon group containing bromine or chlorine having 1 to 18 carbon atoms and a saturated polybasic acid based on the weight%. A resin for electrical laminates, the main component of which is a flame-retardant resin mixture containing 5 to 50% by weight of a halogen-containing flame-retardant monomer resulting from an addition reaction, and the remainder being a cross-linking vinyl monomer. Composition.