JPS63215711A - 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 water resistance, by mixing a radical-curable prepolymer having (meth)acryloyl-terminated side chains, a specified. halogenated flame-retarding 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.% radical-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 and R is H or methyl), 5-50wt.% halogenated flame-retarding monomer of formula II (wherein R is a 1-18C brominated chlorinated aliphatic or alicyclic hydrocarbon group, the carbon atom bonded to the oxygen atom is primary or secondary, and n is 0-15) and the balance of a crosslinking vinyl monomer.

Description

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

[Conventional technology]

Typical resins used in metal foil-clad electrical laminates include phenolic resins, epoxy resins, and unsaturated polyester resins, 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. .

[Problem that the invention seeks to solve]

Similar to these resins, the monomer type [
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 making the laminates flame retardant. 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 rendering flame retardant a resin liquid containing a radically curable prepolymer represented by general formula [I] as a main component.

[Means for solving problems]

The object of the present invention is represented by 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 is hydrogen or a methyl group]. Radical curable prepolymers 10 to 10 having an acryloyl group or methacryloyl group (hereinafter referred to as "f, (meth)acryloyl group") at the end of the side chain.
60% by weight, the general formula % formula % [wherein R is an aliphatic or alicyclic hydrocarbon group containing a bromine or chlorine atom having 1 to 18 carbon atoms, and is bonded to an oxygen atom] Carbon can be primary or secondary, n =
The electricity of the present invention is composed mainly of a flame-retardant resin compounded liquid in which 5 to 50 halogen-containing flame-retardant monomers shown in O~15 are added, and the remainder is a crosslinking vinyl monomer. This is achieved by a resin composition for laminates.

[For production]

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 A has a weight average molecular weight of 10,000 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 freely changed, but when used in a resin composition for laminates, it is preferably in the range of 0.1 to 2 mol/[■]1000F.

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, inbutyl acrylate, tert-butyl acrylate, and 2-acrylate. Ethylhexyl, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, inbutyl 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 shown in CD can be changed by 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 [1,1] of the present invention, a vinyl monomer and (meth)acrylic acid are copolymerized to produce a copolymer having a carboxyl group in the side chain. , then glycidyl (meth)
A method for obtaining the radically curable prepolymer of the present invention having a (meth)acryloyl group at the end of the side chain by adding acrylate and esterifying it with the carboxyl group in the side chain is mentioned.Similarly, first, vinyl monomer and glycidyl A copolymer having a glycidyl group as a base is obtained, and then (meta)
It is also possible to produce by adding acrylic acid to introduce a (meth)acryloyl group to the end of the side chain.

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 imparts flame retardancy comparable to that of bromine, and the inventors attempted to introduce a stable chlorine compound into a resin composition, and found that the general formula [■] It has been found that a flame retardant monomer containing no-rodan is effective.

This 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 3 is used in combination, the resin mixture passes the UL-94-V-O test if the halonic content in terms of bromine is about 10% or more in the resin mixture.

Another effect of this halodane-containing flame-retardant injection monomer was that, since it is a noriether derivative, it imparted flexibility to the feces of 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, 1,4-butanolnoacrylate, 1,4-butanediol dimethacrylate, Vinyl polyfunctional acrylic acid or methacrylic acid esters such as trimethylolpronocentriacrylate, trimethylolpropane trimethacrylate; polyurethane acrylate, polyurethane methacrylate, teriether acrylate, polyether methacrylate')L'-)4110' esters are included.

〔Example〕

Hereinafter, the present invention will be explained in detail with reference to examples, but the present invention is not limited to these examples without departing from the gist of the present invention.

Furthermore, this F! Throughout the A specification, all temperatures are in °C.
Parts and parts are by weight unless otherwise specified.

Yuzo Example 1 Acrylic acid (7211 g) was placed in a 5000 g.
, lmo#), ethyl acrylate (800J'.

8 mol), acrylonitrile (53JF, 1 mol), methyl ethyl ketone (700.9), and dodecyl mercaptan (log), and heated to 75°C under a nitrogen atmosphere.

Azobisisobutyronitrile (5 g) was dissolved in methyl ethyl ketone (50 JJ), and this solution was added dropwise through the dropping funnel over about 1 hour to bring the temperature inside the reactor to 75-80°C.
The mixture was added while being kept at ℃. After adding the catalyst, 8 hours at the same temperature.
The reaction continued for 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 polymer obtained in the reactor (flask) was 920I. The weight average molecular weight of this polymer was 40,000.

Glycidyl methacrylate (142 g
, 1 mol), and styrene (10100O),
After adding parabenzoquinone (0,2,9), )riphenylphosphine (1), the mixture was reacted at 110° C. for 5 hours. Glycidyl methacrylate underwent about 88 thiestylation reactions. The resulting resin solution containing radically curable pre-rimer T was a yellowish brown liquid with a non-volatile content of 53 cm and a viscosity of 7.1 poise (at 25 DEG C.).

Production example 2 A separable flask (1) equipped with a dropping funnel and a stirrer
0007d) in tribromeneopentyl alcohol (
68212 mol) and maleic anhydride (197Ii,
2 mol) t-heated and stirred.

Since it was uniformly dissolved at about 70°C, triethylamine Cl
l1) was added. The temperature was set to 80°C and the reaction was carried out for 6 hours.

Next, boron trifluoride ether catalyst (III) was added, and dehydrated epichlorohydrin (925, 9, 10 mol) was added from the dropping funnel into the stirring and cooling flask over 3 hours while maintaining the internal temperature at 60°C. The reaction was completed by standing for 1 hour.

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

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

Example Kraft paper with a basis weight of 13511/m (10 cIn
cIn) was soaked in an aqueous solution of "Nikaresin S-305" (trade name 1, manufactured by Nippon Carbide Co., Ltd., methylolmelamine), squeezed with a roller, and dried at 9,120°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 (product name, Mitsui Kinzoku Mining Co., Ltd.) 1 layered, put in a cellophane bag, sandwiched between 2 iron plates, 3
A weight of 0 kg was placed on it.

In this state, put it in an air oven at 120℃, and then put it in an air oven at -120℃.
It was cured for 1 hour at 100° C. and then for 10 hours at 100°C.

The resulting laminate had a thickness of 1.59 to 1.61 mm.

Table 2 shows the characteristic values of the laminate.

Table 1 Resin blend composition Table 2 Laminate physical properties *) 1 clear φ hole x 4 'e 1.78 [f Temperature at which mold defects arranged in y-chi do not occur [Effects of the invention]] For the laminate of the present invention The resin composition had excellent flame retardancy, and also had good heat resistance, water resistance, and punchability.

Patent applicant: Showa Kobunshi Co., Ltd. Representative: Sei Kikuchi - Yaguchi
flat

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
For 0 to 60% by weight, there are general formulas ▲ mathematical formulas, chemical formulas, tables, etc. The carbon bonded to the oxygen atom in the group is primary or secondary, and n=0
For electrical laminates, the main component is a flame-retardant resin compound containing 5 to 50% by weight of a halogen-containing flame-retardant monomer shown in Resin composition.