JPS63218722A - Resin composition for laminated sheet - Google Patents

Abstract

PURPOSE:To provide the titled composition having excellent flame-retardance, heat-resistance, water-resistance and punchability and composed mainly of a compounded liquid of a flame-retardant resin consisting of a specific radially curable prepolymer, a specific halogen-containing flame-retardant monomer and a crosslinking monomer. CONSTITUTION:The objective composition is composed mainly of a compounded liquid of a flame-retardant resin consisting of (A) 10-60wt.% radically curable prepolymer expressed by formula [A is main chain segment of random copolymer of a vinyl monomer and a (meth)acryloyl monomer; R is H or methyl] and having (meth)acryloyl group at the terminal of side chain, (B) 5-50wt.% halogen-containing flame-retardant monomer produced by the addition reaction of a monoglycidyl (meth)acrylate to an esterified product 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 monomer for crosslinking (e.g. styrene).

Description

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

[Prior art] Typical resins used for metal foil-clad electrical laminates include phenolic resin, epoxy resin, and unsaturated polyester resin, which are used in combination with various impregnated base materials. . Flame-retardant performance is often required for the above-mentioned 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] Similar to these resins, the general formula C which is a constituent component of the present invention
The radically curable prepolymer represented by I) can be used by itself or mixed with other vinyl monomers to produce metal foil-clad electrical laminates, but there is a further demand for flame retardancy of the laminates. The current situation is that

An object of the present invention is to provide a resin composition for electrical laminates, which is made by effectively flame-retardating a resin liquid containing a radically curable prepolymer represented by general formula (1) as a main component.

[Means for Solving the Problems] The object of the present invention is to achieve the following: General formula () [In the formula, A represents a main chain portion of a random copolymer of a vinyl monomer and an acryloyl monomer or a methacryloyl monomer, and R represents hydrogen. or a methyl group] and has an acryloyl group or a methacryloyl group at the end of the side chain (hereinafter, both are referred to as (meth)acryloyl group) 10 to 6
0% by weight, 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. For electrical laminates of the present invention, the main component is a flame-retardant resin compounded liquid containing 5 to 50% by weight of a halogen-containing flame-retardant monomer obtained by addition reaction with the remainder being a cross-linking vinyl monomer. This is achieved by a resin composition.

[Function] In the general formula CI), 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 10,000 to 200,000, It is preferably 20,000 to 200,000.

Furthermore, the density of the vinyl side chains contained in the main chain polymer can be freely changed, but when used in a resin composition for laminates, it is preferably in the range of 0.1 to 2 mol/[I]1000 g.

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

Representative examples of these include 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,
Examples include 2-ethylhexyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, tetrahydrofurfuryl methacrylate, acrylonitrile, vinyl acetate, vinyl propionate, vinylidene chloride, and vinyl chloride.

The properties of the radically curable prepolymer represented by CI] can be changed depending on the combination of vinyl monomers used to form the main chain skeleton.

As a method for producing the radically curable prepolymer represented by the general formula CI) of the present invention, a copolymer having a carboxyl group in the side chain is produced by copolymerizing a nyl monomer and (meth)acrylic acid, and then A method for obtaining the radical curable prepolymer of the present invention having a (meth)acryloyl group at the end of the side chain by adding glycidyl (meth)acrylate and esterifying it with the carboxyl group in the side chain. Similarly, first, vinyl monomer and glycidyl (
It can also be produced by copolymerizing with meth)acrylate to obtain a copolymer having a glycidyl group in the side chain, and then adding (meth)acrylic acid to introduce a (meth)acryloyl group at the end of the side chain. It is.

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 is dibroneopentyl glycol, but it 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 material is a monomer, unlike additive-type flame retardants, it has the advantage that it does not migrate from the cured resin and that it is easy to adjust the viscosity of the resin mixture.When using a curable prepolymer shown by CI) It is effective for

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, 1.4-
Vinyl polyfunctional acrylic acid or methacrylic acid esters such as butanediol diacrylate, 1,4-butanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate; polyurethane acrylate, polyurethane methacrylate, polyether Vinyl polyfunctional oligoesters such as acrylate and polyether methacrylate are included.

[Examples] Hereinafter, the present invention will be explained 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 Acrylic acid (72g) was placed in a separable flask (5000ml) equipped with a stirrer, cooling tube, dropping funnel, and thermometer.
, 1 mol), ethyl acrylate (800 g, 8
mol), acrylonitrile (53g, 1 mol), methyl ethyl ketone (700r), dodecyl mercaptan (
10 g) and heated to 75° C. under nitrogen atmosphere.

Azobisisobutyronitrile (5 g) was dissolved in methyl ethyl ketone (50 g), and this solution was added dropwise from the dropping funnel over about 1 hour to bring the temperature inside the reactor to 75-80°C.
It was added while maintaining the After the addition of the catalyst was completed, the reaction was continued at the same temperature for 8 hours.

Next, the inside of the reactor was heated to 180° C., and methyl ethyl ketone was distilled off along with a small amount of unreacted monomer.

The amount of polymer obtained in the reactor (flask) was 920 g. The weight average molecular weight of this polymer was 40,000.

Glycidyl methacrylate (142 g
, 1 mol) and styrene (LOOOg), and after adding rosebenzoquinone (0.2 g) and triphenylphosphine (4 g), the mixture was reacted at 110° C. for 5 hours. Approximately 88% of glycidyl methacrylate was esterified. The resulting resin liquid containing the radically curable prepolymer was a yellowish brown liquid with a nonvolatile content of 53% and a viscosity of 7.1 poise (25°C).

Production example 2 A separable flask (1) equipped with a dropping funnel and a stirrer
dibrome neopentyl glycol 38 in 000 ml)
After charging 0 g (1.37 mol) and melting at 110°C, 185 g (1.25 mol) of phthalic anhydride was added.
and para-toluenesulfonic acid i,o g were added.

The reaction was carried out at 170° C. for 4 hours under a reduced pressure of 20 to 200 mo+1 g. As a result, the acid value of the product was 40.

Next, 140 g of styrene monomer, 54 g (0.38 mol) of glycidyl methacrylate, and 0.1 mol of hydroquinone.
2g.

After adding 1.2 g of 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 (10cm x l) with a basis weight of 135g/rrr
Ocm) was immersed in an aqueous solution of Nikaresin S-3054 (trade name, manufactured by Nippon Carbide Co., Ltd., methylolmelamine), squeezed with a roller, and dried at 120°C for 30 minutes. The melamine was spread.This paper was placed in a flat plate and floated on an impregnating resin mixture having the composition shown in Table 1, and impregnated with the liquid.

6 sheets of paper containing resin compound liquid and commercially available copper foil rMK with adhesive
-58J (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 mm.

Table 2 shows the characteristic values of the laminate.

(Left below) Table 1 Resin blend composition (Left below) Table 2 Laminate properties*) Temperature at which mold defects do not occur when 4 1mmφ holes are arranged at a pitch of 1.78+am [Effects of the invention] Lamination of the present invention The resin composition for plates had excellent flame retardancy, and also had good heat resistance, water resistance, and punchability.

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. Radically curable prepolymer 1 having an acryloyl group or a methacryloyl group at the end of the side chain, represented by
0 to 60% by weight, monoglycidyl methacrylate or monoglycidyl methacrylate 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. A halogen-containing flame retardant monomer obtained by addition reaction of glycidyl acrylate is added in a range of 5 to 50% by weight,
A resin composition for electrical laminates, the main component of which is a flame-retardant resin compounded liquid, the remainder of which is a crosslinking monomer.