JPH0280412A - Resin composition and laminated sheet - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. with excellent flame retardancy, heat resistance, water resistance, impact resistance, flexibility and electrical characteristics by incorporating a specified radical-polymerizable (co)polymer and a (mono)(meth)acrylate contg. a specified group as essential components. CONSTITUTION:A curable resin compsn. used for a laminated sheet for a printed wiring board is obtd. by incorporating a radical-polymerizable (co)polymer (A) consisting of a (meth)acrylate, fumarate or maleate of a (co)polymer of a conjugated diene monomer which may be hydrogenated [wherein the number of (meth)acrylates, fumarates or maleates in the (co)polymer is 1-5 and the number-average MW of the (co)polymer is 500-20,000] and a (mono)(meth) acrylate (B) contg. a halogen-substd. aryl group as essential components.

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a resin composition and a laminate.

[Conventional technology]

Epoxy resins, phenol resins, unsaturated polyester resins, and the like are known as curable resin compositions used for printed wiring board stacking boards.

Recently, there has been a strong demand for flame retardancy from the standpoint of safety, and aromatic halogen compounds (
For example, it is known to add decabromo diphenyl oxide, tetrabromo bisphenol A bis dibromopropyl ether, tetrabromo bisphenol A polycarbonate, etc.).

In addition, as laminates used for printed wiring boards become increasingly diverse, there is a demand for laminates that are bendable and have excellent flexibility. It is known to use rubber-modified vinyl esters to impart flexibility (e.g.
(Japanese Patent Application Laid-open No. 80-217232).

[Problem that the invention seeks to solve]

However, when aromatic halogen compounds are added to improve flame retardancy, visibility is lacking, and methods using rubber-modified vinyl esters do not provide sufficient flame retardancy.

[Means for solving problems]

The present inventors have conducted various studies in order to develop a resin composition with excellent flame retardancy, heat resistance, and visibility, and as a result, they have arrived at the present invention. In other words, the present invention provides a conjugated diene molecule,
A radically polymerizable (co)polymer consisting of an ester of (meth)acrylic acid, fumaric acid, or maleic acid as a (co)polymer with other ethylenically unsaturated monomers if necessary [However, radically polymerizable ( The average number of esters of (meth)acrylic acid, fumaric acid or maleic acid in the co)polymer is 1 to 5, and the number average molecular weight of the radically polymerizable (co)polymer is 500 to 20,000.] (A) and a halogen-substituted aryl group-containing (meth)acrylic acid monoester (B) as essential components, and a laminate obtained by impregnating and curing a synthetic resin into a base material, A laminate, wherein the synthetic resin is the curable resin composition according to any one of claims 1 to 6.

Examples of (co)polymers of conjugated diene monomers include polymers of conjugated diene monomers and copolymers of conjugated diene monomers and other ethylenic monomers.

Examples of the conjugated diene 6-unit include conjugated dienes having 4 or 5 carbon atoms, such as 1,3-butadiene, isoprene, and chloroprene, with 1 being preferred.

3-butadiene.

Examples of other ethylenically unsaturated monomers include aromatic vinyl monomers (styrene, a-methylstyrene, chlorostyrene, etc.); (meth)acrylic acid and its derivatives [acrylonitrile, methyl (meth)acrylate] , (meth)butyl acrylate, grindyl methacrylate, etc.];
Olefinic hydrocarbons (ethylene, propylene, isobutylene, etc.); vinyl diester single rJ forms (vinyl acetate, etc.); halogen-containing single 11 forms (vinyl chloride, vinylidene silide, etc.); vinyl ether single n1 forms (vinyl methyl ether, etc.) ; Allyl alcohol and its derivatives (allyl ethers, allyl esters), etc., and mixtures of two or more thereof.

Preferred among these are acrylonitrile, styrene, methyl methacrylate, ethylene and propylene, particularly preferred are acrylonitrile and styrene.

The unsaturated dim bonds based on the conjugated diene monomer of the (co)polymer may be partially or completely saturated by hydrogenation.

The structural unit based on the optionally hydrogenated conjugated diene or Lffi body of the copolymer (A) is usually 30% by weight.
2, preferably 00% by weight or more. If the amount of the structural unit based on the conjugated diene 11i1 is less than 30% by weight, the heat resistance and compatibility will be improved, but the compatibility will tend to decrease.

The number of (meth)acrylic acid, fumaric acid, or maleic acid (hereinafter also referred to as radically polymerizable unsaturated acid) esters in the radically polymerizable (co)polymer (A) is usually 1 to 1 on average.
The number is 5, preferably 1.5 to 3. Possible IA when the number of radically polymerizable unsaturated acid esters is more than 5
If there is less than one, the compatibility of the cured resin composition will deteriorate when the resin composition is cured.

The number average molecular weight of the radically polymerizable (co)polymer (A) is usually 500 to 10,000. Preferably 1000-10
It is 000.

When the molecule ■ is larger than 20000, (A) and (B)
The viscosity of the resin composition becomes too high, resulting in reduced workability. Moreover, if the molecular number is less than 500, the flexibility of the cured product of the composition of the present invention will decrease, which is not preferable.

The method for obtaining a radically polymerizable (co)polymer (A) from a (co)polymer is as follows: (1) In advance, a hydroxyl group-modified (co)polymer is created by introducing a hydroxyl group into the (co)polymer; A method of reacting this material with a radically polymerizable unsaturated acid or its acid anhydride, acid halide, lower alcohol ester, etc. (2) A hydroxyl group-modified (co)polymer in which a hydroxyl group is introduced into the (co)polymer in advance This product and a radically polymerizable unsaturated acid ester containing a hydroxyl group (e.g., 2-hyroxyethyl methacrylate, etc.) are combined with a diisocyanate compound (e.g., lylene diisocyanate, diphenylmethane diisonanate). (3) A method in which an epoxy-modified (co)polymer is prepared in advance by introducing an epoxy group into a (co)polymer and then reacted with a radically polymerizable unsaturated acid. etc.

As the (meth)acrylic acid monoester (b) containing halogen-substituted aryl J^, at least one
Examples include esters of a halogen-substituted aryl compound to which 1 halogen atoms are bonded and 1 acrylic acid or methacrylic acid.

Examples of halogen include chlorine and bromine, with bromine being preferred.

Examples of halogen-substituted aryl compounds include halogenated phenol compounds (dibromophenol, tribromophenol, pentabromophenol, polybromophenylene oxide, etc.), halogenated bisphenol compounds (tetrabromobisphenol A1, tetrabromobisphenol S, etc.), and these. Derivatives of the compounds, such as ethylene oxide and/or propylene oxide)' adducts, glycidyl ethers, and the like.

(8) Examples include di- or tribromophenol methacrylate, dibromophenol epoxy monomethacrylate, pentabromophenoxyethyl acrylate, tetrabromobisphenol A ethylene oxide adduct monoacrylate, and tetrabromobisphenol A dieboxide. Examples include monomethacrylic acid ester.

(B) is, for example, the halogen W lfi aryl compound and (meth)acrylic acid or a derivative thereof (for example,
1υ can be obtained by reaction with acid halides, lower alcohol esters, etc.).

In the composition of the present invention, the weight ratio of (A) and (n) is
(A):(B) is usually 10:9G to 410:10, preferably 20:8G to 80:20. (A)
If the ratio is smaller than this ratio, it will be difficult to obtain a resin with excellent flexibility, which is the object of the present invention.

Moreover, if (A) is larger than this ratio, the mechanical strength of the resin itself decreases, making it difficult to use it practically.

In addition, (B) has a halogen content formed from (B),
(B) is blended into the J1 composition of the present invention in an amount that is usually 5 to 50% by weight, preferably 10 to 30%. It is preferable that (B) be within this range in order to impart flame retardancy, which is one of the objects of the present invention.

The composition of the present invention can contain a radically polymerizable monomer. The radically polymerizable monomer is preferably heated at 25°C.
A compound with a viscosity of 1,000 centiboise or less, a molecular weight of 400 or less, and a boiling point of 50"C or more at normal pressure. For example, aromatic vinyl compounds (e.g., styrene, α-methylstyrene, halogenated styrene, divinylbenzene, etc.); (meth)acrylic acid or its derivatives [e.g. acrylonitrile, alkyl (CI)
CI2) (meth)acrylic acid ester, (
Glycidyl meth)acrylate, hydroxyalkyl(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, etc.); Vinyl ester monomers (vinyl acetate, etc.); Phthal Examples include diallyl acids and mixtures of two or more thereof.

Among these, preferred are acrylonitrile, styrene, alkyl (C+ to C4) (meth)acrylic acid esters and glycidyl (meth)acrylate, with styrene being particularly preferred.

Compositions of the invention can include additive flame retardants. Flame retardants include trioctyl phosphate, triphenyl phosphate, triethyl phosphite, triphenyl phosphite, tris (chloroethyl) phosphate, phosphorus flame retardants such as red phosphorus, decabrom diphenyl oxide, tetrabromo bisphenol A bis dibromopropyl Ether, tetrabromobisphenol A
polycarbonate, hexabromocyclododecane,
Examples include halogen compounds such as II-containing paraffin, antimony compounds such as antimony trioxide, antimony pentoxide, and sodium antimonate, zinc borate, aluminum hydroxide, and mixtures of two or more thereof.

The composition of the present invention includes a filling agent, an antioxidant 11 agent, a stabilizer,
Various additives such as inorganic pigments can be contained.

The resin composition of the present invention can be cured using a general-purpose radical polymerization initiator. Examples of radical polymerization initiators include benzoyl peroxide, dicumyl peroxide, methyl ethyl ketone peroxide, t-butyl peroxylauate, di-t-butyl peroxyphthalate, t-butylcumyl peroxide F1, t-butyl hydrobar Okisai 1! , di-t-butyl peroxide, cumene hydroperoxide, t-butyl peroxybenzoate, and other peroxides. The amount of radical polymerization 1''11 initiator used is usually 0.1 to 10% by weight based on the composition of the present invention.

Furthermore, amine compounds such as dimethylaniline, organic carboxylic acid metal salts such as cobalt naphthenate, etc. can also be used as radical reaction promoters.

When curing the composition of the present invention, the curing temperature is usually room temperature to 200°C, preferably 60 to 170°C.

When the composition of the present invention is cured, bending elasticity P1 of the cured product
The ratio is usually 3 to 80 kgf/lll112, preferably 5 to 30 kgf/llll2. When the flexural modulus is lower than this value, the mechanical strength is low, and a laminate made using the composition of the present invention requires a reinforcing material to hold the laminate. If the flexural modulus is higher than this, the laminate produced using the composition of the present invention will have a strong restoring force when bent, and a reinforcing material will be required to maintain the shape.

The laminate is manufactured by impregnating a base material with the composition of the present invention and curing it.

As the base material, those commonly used for laminated materials can be used. For example, tart of glass, silica, asbestos, etc.
Woven fabrics, non-woven fabrics, paper, or combinations of these are made of organic synthetic fibers such as machine fibers, polyamide-imide, polyester, nylon, acrylic fibers, and carbon fibers.

The amount of resin composition impregnated into the substrate is usually 30 to 95%, preferably 40 to 95%, based on the weight of the laminate.

A laminate is obtained by stacking one or several substrates impregnated with the resin composition and curing at room temperature or heating under no pressure or pressurized conditions.

〔Example〕

The present invention will be further explained below with reference to Production Examples, Examples, and Comparative Examples, but the present invention is not limited thereto.

The part in the real AI example is the fffffi part.

Production example 1 Polytail HE Mibokasei (1!1) in a four-roof flask
Polybutadiene glycol hydrogenated product, hydroxyl value 47.
3+ggK011/g12372 parts, maleic anhydride 1
96 copies were sold. The mixture was heated at 120° C. until the acid value reached 45.3 to obtain maleated hydrogenated polybutadiene glycol.

This product had a solid bark at room temperature.

Comparative Production Example l In a two-flask, polytetramethylene glycol [
Manufactured by Sanyo Chemical Co., Ltd., hydroxyl value 57.5mgKO1l/g]
1950 parts of maleic anhydride! ] 6 copies were added. 1
The mixture was heated at 20° C. until the acid value reached 52.4 to obtain maleated polytetramethylene glycol.

Example 1 poly bd R-45MA [manufactured by Idemitsu Petrochemical Co., Ltd.]
Liquid polybutadiene glycol maleate, number average molecular fi 290G, acid value 43mg KOII/g 1317 parts, tribromophenol methacrylate 383 parts, styrene 300gB were uniformly dissolved, 10 part of antimony trioxide, and Bark Mill H as a radical polymerization initiator. and Percure 0 [both Nippon Oil & Fats C! 12>] were added to the mixture to form a liquid resin composition of the present invention.

The resin composition was put into two glass plates /, 1E type, +21
Heat cure at 1'C for 30 minutes and at 170°C for 1 hour.
A flat plate was created. In addition, a nonwoven fabric made of glass/polyester is impregnated with a resin composition, and two sheets of this are laminated.
Heat cured at 120°C for 30 minutes and at 170°C for 1 hour to a thickness of 9.

Example 2 of creating a laminate of poly bd +? -Maleated hydrogenated polybutadiene glyco prepared by manufacturing example instead of 45MA-/
A resin composition was obtained in the same manner as in Example 1, except that L/W was used, and flat plates and laminates were further produced.

Example 3 +1ycar YTBNX 1300X 23[Goo
drlch cl+e+5lca1 (manufactured) butanene-acrylonitrile oligomer acrylic vinyl group 3
．． 8% containing] 429 parts, 428 parts of tribromophenol methacrylate, and 143 parts of styrene were uniformly dissolved, 10 parts of antimony trioxide, and 5 parts each of Percyl I (and Percure O) as radical polymerization initiators were added.
A resin composition was obtained. A flat plate and a laminate were produced in the same manner as in Example 1.

Example 4't44 A resin composition was obtained in the same manner as in Example 1, except that pentabromophenoxyethyl methacrylate was used instead of tribromophenol methacrylate,
Furthermore, flat plates and laminated plates were created.

Comparative example 1 poly b instead of poly bd R-4511
d R-45HT [manufactured by Idemitsu Petrochemical Co., Ltd., liquid polybutadiene glycol, number average molecule 12800, hydroxyl μ value 4
A resin composition was obtained in the same manner as in Example 1 using G, 6KgKO [/gCo], and flat plates and laminates were produced, and very brittle white cloudy solids were obtained. This product was not suitable for practical use.

Comparative Example 2 Comparative Production Example 1 instead of poly bd R-451A
Malein polytetramethylene glycol prepared with m
Except for the above, a resin composition was obtained in the same manner as in Example 1, and flat plates and laminates were also produced.

Comparison-Example 3 317 parts of poly bd R-45MA, tetrabromubi X7. /-ru A ethylene oxide adduct dimethacrylate) zss part, Decab σ modiphenyl oxyP
A resin composition was obtained by uniformly dissolving 128 parts of styrene and 300 parts of styrene, and adding 10 parts of anticeph dioxide and 5 parts each of Bark Mill H and Vercure 0 as radical polymerization initiators.

The resin composition was heated and cured in the same manner as in Example 1,
A flat plate and a laminated plate were created.

The main characteristics of P1 of the flat plates and laminates obtained in Examples and Comparative Examples are shown in the table. For flat plates, bending elastic modulus (JIS K-G!
S C-[1481 semi-m) and flame resistance test (DI, -9
4 method) was performed.

Table 1 Physical properties of flat plate Table 2 Physical properties of laminates 〔Effect of the invention〕 The resin composition and laminate of the present invention are ■Excellent flame retardancy.

2. Excellent heat resistance, solder heat resistance in laminates, and oven heat resistance.

3. Excellent flexibility.

4. Excellent electrical properties, particularly in high frequency electrical properties and dielectric properties in the case of laminated plates.

5. Resistance to IT? It has excellent tl properties and punching properties in laminates.

6. Excellent water resistance.

7. Excellent adhesion to copper foil.

By exhibiting the effects mentioned above, the resin composition and laminate of the present invention can be used as a copper-clad laminate for consumer appliances such as televisions,
Communication device? i. It is extremely suitable as a material for printed wiring boards such as audio equipment.

Claims (1)

[Claims] 1. A radically polymerizable (co)polymer consisting of an ester of (meth)acrylic acid, fumaric acid, or maleic acid of a (co)polymer of an optionally hydrogenated conjugated diene monomer Coalescence [However, the number of (meth)acrylic acid, fumaric acid, or maleic acid ester in the radically polymerizable (co)polymer is 1 to 5, and the number average molecular weight of the radically polymerizable (co)polymer is 500 to 500. 20,000] (A), and (meth)acrylic acid monoester containing a halogen-substituted aryl group (
A curable resin composition containing B) as an essential component. 2. The weight ratio of (A) and (B) is 10:90 to 90:10
The composition according to claim 1. 3. The composition according to claim 1 or 2, wherein the total weight of (A) and (B) is 50% or more in the curable resin composition. 4. The composition according to any one of claims 1 to 3, wherein the halogen content derived from (B) in the curable resin composition is 5 to 50% by weight. 5. Claim 1, wherein the structural unit based on the optionally hydrogenated conjugated diene monomer in (A) is 30% by weight or more.
4. The composition according to any one of 4 to 4. 6. The composition according to any one of claims 1 to 5, which provides a cured resin having a flexural modulus of 3 to 80 kgf/mm^2. 7. A laminate formed by impregnating and curing a synthetic resin into a base material, wherein the synthetic resin is the curable resin composition according to any one of claims 1 to 6.