JPS63215712A - Resin composition for laminate - Google Patents

Abstract

PURPOSE:To make it possible to form a resin composition for laminates excellent in flame retardancy and good in heat resistance and punching quality, by mixing a specified prepolymer having (meth)acryloyl-terminated side chains with a halogenated flame-retardant monomer and a crosslinking vinyl monomer. CONSTITUTION:This resin composition for electrical laminates mainly consists of a flame-retarding liquid resin mixture comprising 10-60wt.% curable prepolymer having acryloyl or methacryloyl-terminated side chains, represented by formula I (wherein A is the main chain part of a random copolymer of a vinyl monomer with an acryloyl or methacryloyl monomer, R1-R3 are each H or methyl, and n is an integer of 0-5), 5-50wt.% halogenated flame-retarding monomer of formula II (wherein R is a 1-18C brominated or chlorinated aliphatic or alicyclic hydrocarbon, the carbon atoms bonded to the oxygen atoms are primary or secondary and n is 0-15) and the balance of a crosslinking vinyl monomer.

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.

[Conventional technology]

Conventionally, typical resins used in metal foil-clad electrical laminates include phenol resins, epoxy resins, and unsaturated polyester resins, which 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. .

[Problem that the invention seeks to solve]

The curable prepolymer represented by the general formula [11], which is a component of the present invention, can be used by itself or mixed with other vinyl monomers to produce a metal foil-clad laminate for stains. At present, there is a growing demand for plates to be more flame retardant.

The object of the present invention is to provide a resin composition for electrical laminates, which is made by effectively flame-retardating a curable resin compounded liquid containing a curable prepolymer represented by the general formula CI, l as a main component. .

[Means to solve all problems]

The object of the present invention is to satisfy the general formula % [wherein A represents a main chain portion of a random copolymer of a vinyl monomer and an acryloyl monomer or a methacryloyl monomer, and R, to R3 are hydrogen or methyl groups, and ,
n is an integer from O to 5], with an acryloyl group or methacryloyl group at the end of the side chain.
For 10 to 60% by weight of the curable polymer containing meth)acryloyl group, It is a hydrogen group, the carbon bonded to the oxygen atom is primary or secondary, and n = 0 to 15
] The electrical use of the present invention is composed mainly of a flame-retardant resin compounded liquid containing a halogen-containing flame-retardant monomer shown in 5 to 50 weight by weight, and the remainder being a crosslinking monomer. This is achieved by a resin composition for laminates.

[Effect]

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

Furthermore, the density of the vinyl side chains contained in the main chain polymer can be adjusted freely, but when used in a resin composition for laminates, it is in the range of 0.1 to 2 mol/ml 000 P, preferably 0.4 ~1.5 mol/I:I) 10001.

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, inbutyl 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.

It is possible to change the properties of the prepolymer represented by general formula (I) depending on the combination of copolymerizable vinyl monomers used to form the entire 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.

(b) First, a desired amount of (meth)acrylic acid and an epoxy resin in an excess equivalent ratio to the (meth)acryloyl group are mixed with a necessary reaction catalyst, such as a tertiary amine, an amine salt, a quaternary
An unsaturated epoxy resin (4) containing a (meth)acryloyl group and an epoxy group in one molecule is produced by reaction using a class ammonium salt and a metal salt.

(b) 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 azobisin butyronitrile. By radical polymerization, a reaction mixture containing a polymer having an epoxy group in the side chain is obtained.

C9 Furthermore, by adding the required amount of (meth)acrylic acid and causing the epoxy groups remaining in the reaction mixture in (b) to react with carboxyl groups, the desired polymer having vinyl ester groups in the side chains can be obtained. Obtainable.

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: [wherein n = 0-5, R1
, R2 is hydrogen or a methyl group] Types suitable for the present invention are those of both formulas in which n is about O 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. Epoxy resin having 2 or more glycidyl ether type epoxy groups If the total number of epoxy groups is 2, use 1 mole or more, and if there are more than 2 epoxy groups, use 1 mole or more. It is necessary to have a large equivalent amount.

Furthermore, as another method, a vinyl monomer and (meth)acrylic acid are copolymerized, and then 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 flame retardancy of about A compared to bromine, and the inventors tried to introduce a stable chlorine compound into the resin composition, and found that the general formula [■] It has been found that the halogen-containing flame-retardant monomer shown in is effective.

The monomer can be synthesized by polyetherifying epichlorohydrin to a reaction product of a brominated or chlorinated primary or secondary alcohol and maleic anhydride.

As the brominated or chlorinated alcohol, aliphatic or alicyclic alcohols having 1 to 12 carbon atoms are preferred, and readily available examples include 2,3-dibromopropanol and tribromeneopentyl alcohol. However, it is not limited to these.

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 used together with 5 and 5, if the halogen content in terms of bromine is about 10% or more in the resin mixture, it passes the UL-94-V-0 test.

Another effect of this halogen-containing flame-retardant monomer, since it is a polyether derivative, was also observed to be the effect of imparting flexibility to the cured product of the resin mixture.

This material is different from additive-type flame retardants because it is a monomer, and 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. This is effective when using

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-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.

〔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.

In addition, throughout this specification, all temperatures are in degrees Celsius, and parts and temperatures are based on ignition standards unless otherwise specified.

Production Example 1 Monomarable flask (3000 m
J), methacrylic acid (301,0,41 mol), methyl ethyl ketone (400p), styrene monomer (soo
5c, 7.7 mol), azobisinbutyronitrile (5
, OP) and dodecyl mercaptan (1254) were charged, and polymerization was carried out at 75 to 80° C. for 10 hours in a nitrogen atmosphere. Hydroquinone (0.5g-)? was added to inhibit polymerization. The polymerization rate of styrene monomer is 76! 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 with the same configuration as above, [Epicor-182
7j (product name, manufactured by Mitsubishi Yuka-Shell) (360L?,
1 mol), methacrylic acid (1385', 1.6 mol),
Benzyldimethylamine (1,25'), A'rapenzoquinone (0,12P)'! The mixture was reacted at 120° C. for 3 hours under a nitrogen atmosphere. After the reaction, the acid value was 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 (55') and parabenzoquinone (0,107), and heat to distill off the methyl ethyl ketone solvent at a boiling point of 110°C. 5 in temperature
Allowed time to react.

After the reaction, the unsaturated epoxy resin has about 15q6
Became. The styrene monomer (1000P) was heated and evaporated continuously at 30-5 Q tranfZg for 7 consecutive days while being added intermittently. The operation was terminated when the amount of methyl ethyl ketone detected in the distillate became 0.1 h or less. The thus obtained resin liquid containing the curable prepolymer has a nonvolatile content of 5
It was a yellow-brown liquid with a viscosity of 6.2 poise (25°C) and a weight of 1".

Production Example 2 Methacrylic acid (35p, 0.41 mol) and ethyl acrylate (600P, 6 mol) were placed in a 7-4 rubble flask (5000 g) equipped with a stirrer, a thermometer with a gas inlet tube, a reflux condenser, and a dropping funnel. , methyl ethyl ketone (
600, fi'), dodecyl mercaptan (6P) t-
The charge was heated to 75°C under a nitrogen atmosphere.

The solution in ketone was added through the dropping funnel.

It was made to react at 75-80 degreeC for 8 hours. After this, increase the temperature to 180
℃ to produce methyl ethyl ketone and a very small amount of unreacted ethyl acrylate? Distilled away. The obtained polymer is 6
311 and a weight average molecular weight of 70,000.

In addition, in another reaction apparatus (2000 ml) having the same configuration as above, "Epicote 827J (trade name, manufactured by Mitsubishi Yuka-Shell Co., Ltd.) (3605', 1 mol), methacrylic acid (138p,
1.6 mol), benzyldimethylamine (1.2 g-)
, add rosebenzoquinone (0.12p) and heat at 120°C.
The reaction was allowed to proceed for 3 hours under a nitrogen atmosphere.

The acid value of the reaction solution became almost zero, and a vinylation reagent containing an unsaturated epoxy resin was obtained. Styrene monomer (100OP) ffi was added and dissolved in this vinylation reagent, and this was added to the previously prepared polymer syringe flask. Further, triphenylphosphine (5P) and norR rapenzoquinone (0,10P) were added, heated, and reacted at 120° C. for 4 hours. After the reaction, the unsaturated epoxy resin was about 13% of the amount before the reaction.

The thus obtained resin liquid containing the curable prepolymer had a viscosity of 8.9 poise (25
) was a yellowish brown liquid.

Production Example 3 A separable flask (1) equipped with a dropping funnel and a stirrer
000 mJ) in tribromneo-ethyl alcohol (
682p, 2 mol) and arsenic maleic anhydride (197p,
2 mol) was heated and stirred.

Since it was uniformly dissolved at about 70°C, triethylamine (1
5') All added. The temperature was set to 80°C and the reaction was carried out for 6 hours.

Next, in addition to the boron trifluoride ether catalyst (IP)', dehydrated epichlorohydrin (925P, 10 mol) was added from the dropping funnel into the stirring and cooling flask over 3 hours while keeping the internal temperature at 60°C. The reaction was allowed to complete for some time.

Next, water was added to the liquid in the flask, and the upper layer of water and gold was decanted and washed.

The flask was heated again to distill off any remaining water.

Example Kraft paper with a basis weight of 135 f/m2 (10 crn
tM) was immersed in an aqueous solution of Nikaresin S-305J (trade name, manufactured by Nippon Carbide Co., Ltd., methylolmelamine), squeezed with a roller, and dried at 120° C. for 30 minutes.

11.4% by weight of melamine was spread in the obtained paper base material. 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 1'- of copper foil with commercially available adhesive
MK, -56J (trade name, manufactured by Mitsui Kinzoku Mining Co., Ltd.) were stacked one on top of the other, placed in a seven-piece bag, sandwiched between two iron plates, and placed on a weight of 30 to 9.

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 has a weight of 1.59 to 1.61w! It was n thick.

All characteristic values of the laminate are shown in Table 2.

[Effects of the invention]

The resin composition for laminates of the present invention has excellent flame retardancy (7), and also has good heat resistance, water resistance, and punching properties.

Patent applicant: Showa Kobunshi Co., Ltd. Chrysanthemum Earth Spirit - Arrow Mouth Flat

Claims (1)

[Claims] (1) General formula ▲ Numerical formulas, chemical formulas, tables, etc. is a methyl group, and n is an integer of 0 to 5.] General formula ▲ Formula Chemical formulas, tables, etc. are available ▼ [II] [In the formula, R is an aliphatic or alicyclic hydrocarbon group containing bromine or chlorine having 1 to 18 carbon atoms, and the carbon bonded to the oxygen atom is a primary or 2nd grade, n = 0 to 15
] An electrical laminate whose main component is a flame-retardant resin compounded liquid containing a halogen-containing flame-retardant monomer shown in 5 to 50% by weight, with the balance consisting of a cross-linking vinyl monomer. Resin composition for use.