JPS63218721A - Resin composition for laminated sheet - Google Patents

Abstract

PURPOSE:To obtain the titled composition suitable as a resin for metal-clad laminated sheet, by compounding a specific curable prepolymer, 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; R is H or CH3; X1 and X2 are 2-16C hydrocarbon group, etc.] having a main chain composed of a polymer produced by vinyl polymerization and containing (meth)acryloyl group via 2 urethane bonds on 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 Br or Cl and (C) remaining part of a vinyl monomer for crosslinking.

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, which are used in combination with various impregnated base materials. .

Although flame retardant performance is often required for the above-mentioned laminates, the method of making radical curable resins flame retardant is still a major issue.

[Problems to be Solved by the Invention] Like these resins, the main chain, which is one of the constituent components of the present invention, is a polymer obtained by vinyl polymerization, and the side chain has an acryloyl group via two urethane bonds. There is also a current demand for flame retardant metal foil-clad electrical laminates using the curable prepolymer disclosed in JP-A-60-38403 having a methacryloyl group.

An object of the present invention is to provide a flame-retardant resin composition suitable for manufacturing metal foil-clad electrical laminates.

[Means for Solving the Problems] The object of the present invention is to produce a curable prepolymer previously disclosed in JP-A No. 60-38403, that is, a curable prepolymer of the general formula [wherein A is a vinyl monomer and an acryloyl monomer or It shows the main chain part of a random copolymer with methacryloyl monomer, R is hydrogen or a methyl group, and X and X2 are each the same or different and have 2 to 2 carbon atoms.
16 hydrocarbon groups or hydrocarbon groups connected by ether bonds, and the carbon atoms bonded to oxygen in X and X2 are primary or secondary], and the main chain is vinyl polymerized. In the obtained polymer, carbon A halogen-containing product obtained by adding monoglycidyl methacrylate or monoglycidyl acrylate to an esterified product of a polyhydric alcohol having an aliphatic or alicyclic saturated hydrocarbon group containing 1 to 18 bromine or chlorine and a saturated polybasic acid. This is achieved by the resin composition for electrical laminates of the present invention, which contains as a main component a flame-retardant resin compounded liquid containing 5 to 50% by weight of a flame-retardant monomer and the remainder consisting of a crosslinking vinyl monomer.

[Function] The composition of the present invention has many properties suitable for metal foil-clad electrical laminates, but the preferred range of use as electrical laminates is impregnability into base materials, electrical properties, and mechanical properties. Selection is made taking into consideration physical properties, etc.

In the present invention, the molecular weight of the main chain polymer in general formula CI) is preferably 10,000 to 100,000, and the curable prepolymer represented by general formula (I) is contained in the resin composition. It has also been found that a preferable resin composition can be prepared by containing the compound in an amount by weight.

The method for producing the curable prepolymer represented by the general formula [E] of the present invention is as follows: 0) A monomer containing a hydroxyl group is used as one component and copolymerized with a desired monomer to produce a polymer having a hydroxyl group in the side chain. (b) By reacting diisocyanate and an unsaturated monoalcohol having a (meth)acryloyl group at a 1:1 (mole ratio), free isocyanate groups and ( meth) Synthesize an unsaturated isocyanate that shares an acryloyl group; (c) Combine the polymer having a hydroxyl group in the side chain from step 0) dissolved in a solvent or monomer and the unsaturated isocyanate from step (b). , react in monomer or solvent solution.

When a solvent is used, it is necessary to remove the solvent by any 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 monomer.

Examples of hexamers having hydroxyl groups include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate,
Typical examples include hydroxypropyl methacrylate and methylol acrylamide.

Vinyl monomers to be copolymerized with monomers having hydroxyl groups to form polymers include, for example, 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 0), solution polymerization is convenient and can proceed directly to the next step, but it is also practical to dissolve the polymer obtained by crowbar polymerization or bulk polymerization in monomer and use it for the next reaction. It is.

Step (c) for obtaining a polymer having an unsaturated bond in the side chain is a reaction between the hydroxyl group of the polymer side chain and 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.

The types of unsaturated monoalcohols described above are applicable as they are.

Typical commercially available diisocyanates include the curable diisocyanate of the present invention which has a (meth)acryloyl group at the end of the side chain by esterification reaction with 2.4-) lylene diivoxyl group; Prepolymers can also be obtained.

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. Esterified product with saturated polybasic acid 1
It has been found that a halogen-containing flame retardant monomer prepared by reacting nimonoglycidyl methacrylate or monoglycidyl acrylate is effective.

As the polyhydric alcohol, an aliphatic or alicyclic alcohol having 1' to 12 carbon atoms is preferable, and an easily available example includes dibroneopentyl glycol, but is not limited thereto. do not have.

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 the base material, 5bzO
When s 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 flame retardants, it does not migrate from the cured resin and has the advantage that the viscosity of the resin mixture can be easily adjusted.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-thalolstyrene, p-vinylstyrene Substituted styrenes such as various acrylic or methacrylic esters; ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, trimethylol Includes vinyl polyfunctional acrylic acid or methacrylic acid esters such as propane triacrylate and trimethylolpropane trimethacrylate; vinyl polyfunctional oligoesters such as polyurethane acrylate, polyurethane methacrylate, polyether acrylate, and polyether methacrylate. be done.

[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.

Further, the resin components used in the formulation in the examples were as follows.

Component (A) A main chain (weight ratio: 80%) consisting of styrene, acrylonitrile, and 2-hydroxyethyl methacrylate with a molecular weight of approximately 60,000, and a vinyl side chain (weight ratio: 80%) consisting of 2-hydroxylpropyl methacrylate and tolylene diisocyanate. 8%)) (contains 12% by weight of unreacted components) [R=methyl group in general formula (I), X -CH2
CH2- (1) A product obtained by reacting glycidyl methacrylate with a polyester oligomer derived from dibrome neopentyl glycol and phthalic anhydride. This product was synthesized using the following operational recipe.

A separable flask equipped with a dropping funnel and a stirrer (1
dibrome neopentyl glycol 38 in
After melting at 110° C., 185 g (1.25 mol) of phthalic anhydride and 1.0 g of p-toluenesulfonic acid were added.

It was made to react at 170 degreeC under reduced pressure of 20-200 mm11g for 4 hours. 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.
After adding 1.2 g of 2ys triethylamine, 4
Allowed time to react. 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 basis weight 135g/rr? kraft paper (10cm x 1
0 cm) 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 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 1.81 mm.

Table 2 shows the characteristic values of the laminate.

(Hereinafter in the margins) Table 1 Resin blend composition (hereinafter in the margins) Table 2 Laminate properties [Effects of the invention] The resin composition for electrical laminates of the present invention has excellent flame retardancy and heat resistance. It also has good hardness, 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. 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.
60% 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, the main component is a flame-retardant resin mixture containing 5 to 50% by weight of a halogen-containing flame-retardant monomer obtained by addition reaction with the remainder consisting of a cross-linking vinyl monomer. Resin composition.