JPH04239019A - Curable polyphenylene ether/epoxy resin composition, and composite material and laminate prepared by using same - Google Patents

Abstract

PURPOSE:To provide a new curable polyphenylene ether/epoxy resin composition which has the excellent dielectric properties of polyphenylene ether and the well-balanced properties and economical profitability of epoxy resin and can develop excellent chemical resistance, heat resistance and flame retardancy when cured. CONSTITUTION:A reaction product (a) of a polyphenylene ether resin with an unsaturated carboxylic acid or anhydride is mixed with an epoxy resin composition (b) essentially consisting of a brominated bisphenol polyglycidyl ether epoxy resin and a novolac epoxy resin and optionally a curing agent. The obtained mixture is formed into a film or infiltrated into a base to obtain a composite material. The obtained film or composite material is optionally laminated with a metallic foil or sheet, and then heated and cured. The mixing ratio between components (a) and (b) is such that 90-10 pts.wt. component (a) is used per 10-90 pts.wt. component (b).

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a curable polyphenylene ether epoxy resin composition using a reaction product of a polyphenylene ether resin and an unsaturated carboxylic acid or an acid anhydride, and a hardened polyphenylene ether epoxy resin composition obtained by curing the same. Regarding the body. Furthermore, the present invention relates to a composite material made of the resin composition and a base material, a cured product thereof, a laminate made of the cured product and metal foil, and a laminate made of the cured product and a metal plate.

The resin composition of the present invention exhibits excellent chemical resistance, dielectric properties, heat resistance, and flame retardancy after curing, and is used as a dielectric material and insulation material in fields such as the electrical industry, electronic industry, and space/aircraft industry. It can be used for materials, heat-resistant materials, structural materials, etc. In particular, it can be used as single-sided, double-sided, multilayer printed circuit boards, flexible printed circuit boards, semi-rigid boards, and boards with excellent heat dissipation properties.

0003

[Prior Art] In recent years, there has been a remarkable trend toward smaller packaging methods and higher density mounting methods in the field of electronic equipment for communications, consumer use, industrial use, etc. Heat resistance, dimensional stability, and electrical properties are increasingly required. For example, as printed wiring boards, copper-clad laminates made of thermosetting resins such as phenol resins and epoxy resins have traditionally been used. Although these have a good balance of various performances, they have the disadvantage of poor electrical properties, particularly poor dielectric properties in the high frequency range. Polyphenylene ether has recently attracted attention as a new material that can solve this problem, and attempts are being made to apply it to copper-clad laminates.

[0004] Japanese Patent Publication No. 64-3223 discloses combinations of polyphenylene ether and various epoxy resins. Commonly used epoxy resins include polyglycidyl ethers of bisphenol A, 3,3',5,5'-tetrabromobisphenol A, and epoxyphenol novolac resins, and various resins including amines are used. Curing is performed using known curing agents. However, the polyphenylene ether used here has not undergone any chemical modification and exhibits no chemical resistance, so the cured product is significantly inferior to the boiling trichlorethylene properties required for printed circuit board materials. .

As a material with improved chemical resistance, US Pat. No. 4,912,172 discloses a resin composition comprising (i) polyphenylene ether, (ii) bisphenol polyglycidyl ether, and (iii) aluminum or zinc salt. ing. Furthermore, as a material imparted with flame retardancy, JP-A Nos. 2-55721 and 2-55722
No. 2-222412 discloses (i) polyphenylene ether, (ii) epoxy resin composition containing bromine, (iii) novolak resin, (iv) imidazole and polyamines, (v) zinc salt, ( vi) S
A resin composition comprising b2 O5 is disclosed.

JP-A-2-269732 discloses (i) as a composition for improving the flowability of resin during molding.
) a low molecular weight polyphenylene ether, (ii) an epoxy resin composition containing bromine, (iii) an imidazole and polyamines, and (iv) an aluminum or zinc salt. Furthermore, as materials obtained by treating polyphenylene ether itself, JP-A-2-135216 describes (i) a reaction product of polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride, (ii) a polyepoxy compound, (iii)
A resin composition comprising a curing catalyst for epoxy has been disclosed
No. 166115 discloses (i) melt-processed polyphenylene ether, (ii) polyepoxy compound, (i)
ii) A resin composition comprising a curing catalyst for epoxy is disclosed.

However, it has been found that even in the above series of resin compositions, the improvement in trichlorethylene resistance after curing is still insufficient, and significant changes in appearance such as roughness are observed after boiling trichlorethylene. Furthermore, as shown in Example 6 of JP-A No. 2-55721, although polyphenylene ether is used in about 1/2 of the total resin composition, the dielectric constant is 4.19.
and sufficient improvements have not been made. This is commercially available glass/
Dielectric constant of epoxy resin copper-clad laminate: 4.5 (resin amount approx. 4
0%).

[0008] European Patent No. 315,829 discloses a resin composition comprising polyphenylene ether, bisphenol A type epoxy resin, and an amine curing agent. However, there is no explanation in the specification regarding the chemical resistance of this cured product, and since the required properties have become increasingly strict recently,
Similar to No. 3223, further improvement in chemical resistance is awaited.

[0009]

[Problems to be Solved by the Invention] The present invention has been made in view of the above circumstances, and combines the excellent dielectric properties of polyphenylene ether with the well-balanced performance and economic efficiency of epoxy resin. The present invention also aims to provide a novel curable polyphenylene ether epoxy resin composition that exhibits excellent chemical resistance, heat resistance, and flame retardancy after curing.

0010

[Means for Solving the Problems] As a result of extensive studies in order to solve the above-mentioned problems, the present inventors have discovered a novel resin composition that meets the purpose of the present invention, and have completed the present invention. It has arrived. By using a polyphenylene ether resin modified with an unsaturated carboxylic acid or an acid anhydride and a specific epoxy resin, the present invention not only solves the above-mentioned problems, but also provides a resin composition that has excellent solvent film formability. This was based on the discovery that . To describe the present invention in more detail, the present invention is comprised of the following seven inventions.

That is, the first aspect of the present invention is (a) a reaction product of a polyphenylene ether resin and an unsaturated carboxylic acid or an acid anhydride, and (b) (i) a brominated bisphenol polyglycidyl ether epoxy resin, (ii) ) A curable polyphenylene ether epoxy resin composition consisting of an epoxy resin composition containing a novolak epoxy resin as an essential component, wherein component (a) is based on 100 parts by weight of the sum of components (a) and (b). 90-10 parts by weight, (b
A curable polyphenylene ether epoxy resin composition is provided, characterized in that the component (1) is contained in an amount of 10 to 90 parts by weight.

A second aspect of the present invention provides a cured polyphenylene ether/epoxy resin composition obtained by curing the curable polyphenylene ether/epoxy resin composition of the first invention. A third aspect of the present invention provides a curable composite material comprising the curable polyphenylene ether epoxy resin composition of the first aspect and a base material.

A fourth aspect of the present invention provides a cured composite material obtained by curing the curable composite material of the third aspect of the present invention. A fifth aspect of the present invention provides a laminate comprising the cured composite material of the fourth aspect and metal foil. A sixth aspect of the present invention provides a laminate in which an insulating layer made of the cured composite material of the fourth aspect is laminated on a metal base.

Finally, the seventh aspect of the present invention is that an insulating layer made of the cured composite material of the fourth aspect is laminated on at least one side of the metal base, and a metal foil is laminated on at least the outermost layer of the insulating layer. Provides metal-clad laminates made of The above seven inventions will be explained in detail below. First, the curable polyphenylene ether epoxy resin composition and its cured product, which are the first and second aspects of the present invention, will be explained.

The polyphenylene ether resin used in the production of component (a) of the first curable polyphenylene ether/epoxy resin composition of the present invention is represented by the following general formula 1.
It is expressed as

[0016]

[Chemical formula 1]

Examples of lower alkyl groups for R1 to R4 in general formula A include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and see-butyl groups. Examples of aryl groups include phenyl groups. Examples of haloalkyl groups include bromomethyl group, chloromethyl group, and the like. Examples of halogen atoms include bromine, chlorine, and the like.

Representative examples of Q in general formula 1 include the following four groups of compounds represented by general formula 2.

[0019]

[Case 2]

[In the formula, A1 and A2 represent the same or different linear alkyl groups having 1 to 4 carbon atoms, and X represents an aliphatic hydrocarbon residue and substituted derivatives thereof, an aralkyl group and substituted derivatives thereof, represents oxygen, sulfur, sulfonyl group, carbonyl group, Y represents aliphatic hydrocarbon residues and substituted derivatives thereof, aromatic hydrocarbon residues and substituted derivatives thereof, aralkyl and substituted derivatives thereof, Z represents oxygen , sulfur, sulfonyl group, carbonyl group, two phenyl groups directly bonded to A2, the bonding positions of A2 and X, A2 and Z all indicate the ortho and para positions of the phenolic hydroxyl group, and r is 0 to 4. ,
s and an integer from 2 to 6. ] As a specific example, the following formula 3
~ Chemical 4 etc. can be mentioned.

[0021]

[Chemical formula 3]

[0022]

[C4] etc.

The polyphenylene ether chain represented by J in the general formula 1 may contain a unit represented by the following general formula 5 in addition to the unit represented by the general formula (A).

[0024]

[C5] etc.

In addition, units obtained by graft polymerizing a polymerizable monomer having an unsaturated bond, such as styrene or methyl methacrylate, to the units of formulas A and B above may be included. Preferred examples of the polyphenylene ether resin of general formula 1 used in the present invention include 2,6-
Poly(2,6) obtained by homopolymerization of dimethylphenol
-dimethyl-1,4-phenylene ether), poly(2
, 6-dimethyl-1,4-phenylene ether) styrene graft copolymer, 2,6-dimethylphenol and 2,3,6-trimethylphenol copolymer, 2,6-dimethylphenol and 2,3,6-trimethylphenol copolymer
- Copolymer of dimethylphenol and 2,6-dimethyl-3-phenylphenol, 2,6-dimethylphenol is converted into a polyfunctional phenol compound Q (H)m (m is 2 to
Polyfunctional polyphenylene ether resin obtained by polymerization in the presence of (an integer of 6), for example, JP-A-63-30122
Copolymers containing units of general formulas A and B as disclosed in No. 2 and JP-A-1-297428 can be mentioned.

The molecular weight of the polyphenylene ether resin described above is not particularly limited, but it is 0.5 at 30°C.
Viscosity number ηsp/ measured in chloroform solution in g/dl
Those having c in the range of 0.1 to 1.0 can be used satisfactorily. For compositions in which molten resin flow is important, such as prepregs for multilayer printed wiring boards, resins with a low viscosity number are preferred.

Component (a) used in the present invention is produced by reacting the above polyphenylene ether resin with an unsaturated carboxylic acid or acid anhydride. Examples of suitable acids and acid anhydrides include acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, glutaconic anhydride, citraconic anhydride, etc., of which maleic anhydride, Fumaric acid is best used. The reaction is carried out by heating the polyphenylene ether resin and the unsaturated carboxylic acid or acid anhydride in a temperature range of 100°C to 390°C. At this time, a radical initiator may be present. Although both the solution method and the melt mixing method can be used, the melt mixing method using an extruder or the like can be carried out more easily and is suitable for the purpose of the present invention. The proportion of unsaturated carboxylic acid or acid anhydride is 0.01 to 5 parts by weight per 100 parts by weight of polyphenylene ether resin.
．． 0 parts by weight, preferably 0.1 to 3.0 parts by weight.

In the present invention, the role played by the unsaturated carboxylic acid or acid anhydride in the polyphenylene ether resin is not known in detail so far. However, it is presumed that it plays an important role in increasing the compatibility between the polyphenylene ether resin and the epoxy resin, improving chemical resistance and heat resistance, and at the same time imparting film-forming properties to the resin composition.

Curable polyphenylene ether of the present invention
The brominated bisphenol polyglycidyl ether epoxy resin used as one of the components (b) of the epoxy resin composition is represented by the following general formula 6.

[0030]

[C6]

Among these, those in which all p's are 2, q is substantially 0, and A3 is an isopropylidene group can best be used in the present invention. Similarly, the novolak epoxy resin used as one of the components (b) is represented by the following general formula 7.

[0032]

[C7]

Among these, the average value of n is 0 to 5, and A
Those in which 4 is a hydrogen atom or a methyl group can best be used in the present invention, and one type or a combination of two or more types can be used. Of the above components (b), the brominated bisphenol polyglycidyl ether epoxy resin is essential for imparting flame retardancy, and the novolac epoxy resin is essential for improving chemical resistance and heat resistance by increasing crosslink density.

In addition to the above, component (b) may contain other epoxy resins as long as they do not reduce properties such as flame retardancy, chemical resistance, and heat resistance. The blending ratio of component (a) and component (b) explained above is the sum of 100
Based on parts by weight, component (a) is 90 to 10 parts by weight, (
Component b) is 10 to 90 parts by weight, more preferably (
70 to 10 parts by weight of component a), 30 to 90 parts by weight of component (b), more preferably 60 to 20 parts by weight of component (a), (
Component b) is in the range of 40 to 80 parts by weight.

If the amount of component (b) is less than 10 parts by weight, chemical resistance and flame retardance may be insufficient, or adhesive strength may not be obtained when bonded to metal foil or the like as described later, which is not preferable. On the other hand, if component (b) exceeds 90 parts by weight, the dielectric properties deteriorate, which is not preferable. The blending ratio of brominated bisphenol polyglycidyl ether epoxy resin and novolac epoxy resin in component (b) is determined by the balance between chemical resistance and flame retardance of the resin composition of the present invention as a whole. Chemical resistance improves by increasing the blending ratio of epoxy resin, but (a) + (b)
) The bromine content based on the sum of the components is 5% by weight or more2
It is preferable to use a brominated bisphenol polyglycidyl ether epoxy resin so that the amount is 0% by weight or less. If the bromine content exceeds 20% by weight, the thermal stability of the resin composition will decrease, which is not preferred.

Methods for mixing the above two components (a) and (b) include a solution mixing method in which both are uniformly dissolved or dispersed in a solvent, a melt blending method in which they are heated using an extruder, etc. is available. Solvents used for solution mixing include dichloromethane, chloroform,
Halogenated solvents such as trichlorethylene; benzene,
Aromatic solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone are used alone or in combination of two or more.

The resin composition of the present invention can be conveniently used in the form of a film. The manufacturing method is as follows:
For example, a normal solvent film forming method (casting method) can be used, and a film having an arbitrary thickness can be manufactured. Compositions suitable for film production are not particularly limited, but include (a)
(a) based on the sum of 100 parts by weight of component and (b) component
The preferred range is 90 to 20 parts by weight of component and 10 to 80 parts by weight of component (b). If component (b) is less than 10 parts by weight, as described above, chemical resistance and adhesion to metal foil will be insufficient, which is not preferable. On the other hand, if the amount of component (b) exceeds 80 parts by weight, the film becomes brittle and sticky, resulting in poor handling properties, which is not preferable.

The resin composition of the present invention is cured by causing a crosslinking reaction by heating or other means as described below, but a curing agent may be contained in order to lower the temperature at that time or to promote the crosslinking reaction. May be used. As a curing agent, a normal epoxy resin curing agent such as a polyamine curing agent, an acid anhydride curing agent, a polyphenol curing agent, a polymercaptan curing agent, an anionic polymerization type catalyst type curing agent, a cationic polymerization type catalyst type curing agent can be used. Hardening agents, latent hardening agents, etc. can be used (
For details, see, for example, "Epoxy Resin Handbook" edited by Masaki Shinbo (Nikkan Kogyo Shimbun, 1987), "Introductory Epoxy Resin" (Kobunshi Publishing Co., Ltd., 1988), written by Soichi Muroi and Shuichi Ishimura.
) etc.).

[0039] The curing agent may be used alone or in combination of two or more. In addition to the above-mentioned curing agent, the resin composition of the present invention may be used by blending fillers and additives in an amount within a range that does not impair the original properties, in order to impart desired performance depending on the intended use. I can do it. Examples of fillers include carbon black, silica, alumina, barium titanate, talc, mica, glass beads, glass hollow spheres, and the like. Examples of additives include antioxidants, heat stabilizers, antistatic agents, plasticizers, pigments, dyes, and colorants. In addition, in order to further improve flame retardancy, chlorine-based, bromine-based, and phosphorus-based flame retardants, as well as Sb2O3
, Sb2 O5 , NaSbO3 ・1/4H2 O
It is also possible to use flame retardant aids such as: Furthermore, it is also possible to blend one or more crosslinkable monomers such as allyl glycidyl ether, glycidyl methacrylate, and glycidyl acrylate, thermoplastic resins such as polyphenylene ether, or other thermosetting resins. .

The second cured polyphenylene ether/epoxy resin composition of the present invention is obtained by curing the above-mentioned curable polyphenylene ether/epoxy resin composition. The method of curing is arbitrary;
Methods using heat, light, electron beams, etc. can be employed. When curing is performed by heating, the temperature is selected in the range of 80 to 300°C, more preferably 150 to 250°C, although it varies depending on the presence or absence of a curing agent and its type. Moreover, the time is about 1 minute to 10 hours, more preferably 1 minute to 5 hours.

The resin composition of the obtained cured polyphenylene ether/epoxy resin composition can be analyzed using methods such as infrared absorption spectroscopy, high-resolution solid-state nuclear magnetic resonance spectroscopy, and pyrolysis gas chromatography. . The cured polyphenylene ether epoxy resin composition of the present invention can be satisfactorily used in the form of a film.

[0042] Also, this cured polyphenylene ether/epoxy resin composition can be used by laminating it with a metal foil and/or a metal plate, similar to the cured composite material described later as the fourth aspect of the invention. Next, the third and fourth curable composite materials of the present invention and their cured products will be explained.

The curable composite material of the present invention is the first curable composite material of the present invention.
It is composed of the curable polyphenylene ether epoxy resin composition described above and a base material. Substrates used in the present invention include various glass cloths or nonwoven glass cloths such as roving cloths, cloths, chopped mats, and surfacing mats; ceramic fiber cloths, asbestos cloths, metal fiber cloths, and other synthetic or natural inorganic fiber cloths; Woven or nonwoven fabrics obtained from synthetic fibers such as polyvinyl alcohol fibers, polyester fibers, acrylic fibers, and fully aromatic polyamide fibers; Natural fiber fabrics such as cotton fabrics, linen fabrics, and felt; Carbon fiber fabrics; Kraft paper, cotton paper, and paper. Natural cellulose cloth such as glass wet woven paper can be used alone or in combination of two or more.

The proportion of the base material in the curable composite material of the present invention is 5 to 90 parts by weight, more preferably 10 to 80 parts by weight, even more preferably 20 to 70 parts by weight, based on 100 parts by weight of the curable composite material. This is within the scope of the department. If the amount of the base material is less than 5 parts by weight, the dimensional stability and strength of the composite material after curing will be insufficient, and if the amount of the base material is more than 90% by weight, the dielectric properties and flame retardance of the composite material will be poor.

[0045] If necessary, a coupling agent may be used in the composite material of the present invention for the purpose of improving adhesion at the interface between the resin and the base material. As the coupling agent, common ones such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, a zircoaluminate coupling agent, etc. can be used. As a method for producing the composite material of the present invention, for example, the components (a) and (b) explained in the first section of the present invention, and other components as necessary, may be combined with the above-mentioned halogen-based, aromatic-based, Uniformly dissolved or dispersed in a ketone-based solvent or a mixed solvent thereof,
An example is a method of impregnating a base material and then drying it.

[0046] Impregnation is carried out by dipping, coating, or the like. Impregnation can be repeated multiple times if necessary, and it is also possible to repeat impregnation using multiple solutions with different compositions and concentrations to finally adjust the desired resin composition and resin amount. It is. The fourth cured composite material of the present invention is obtained by curing the curable composite material thus obtained by a method such as heating. The manufacturing method thereof is not particularly limited, and for example, a plurality of sheets of the curable composite material may be stacked, each layer may be bonded under heat and pressure, and at the same time, heat curing may be performed to obtain a cured composite material with a desired thickness. I can do it. It is also possible to obtain a cured composite material with a new layer configuration by combining a cured composite material that has been once adhesively cured and a curable composite material.

[0047] Laminate molding and curing are usually carried out simultaneously using a hot press or the like, but both may be carried out independently. That is, an uncured or semi-cured composite material obtained by lamination molding in advance can be cured by heat treatment or another method. Molding and curing are performed at a temperature of 80 to 300°C and a pressure of 0.1 to 500 kg/
cm2, time range of 1 minute to 10 hours, more preferably temperature 150 to 250°C, pressure 1 to 100 kg/cm2
, can be carried out for a time ranging from 1 minute to 5 hours.

Finally, the fifth, sixth, and seventh aspects of the present invention, which are laminates, laminates, and metal-clad laminates, will be explained. The laminate of the present invention is composed of the cured composite material and metal foil described above as the fourth aspect of the present invention. A laminate is also composed of a cured composite material and a metal plate, and a metal-clad laminate is composed of a cured composite material, metal foil, and a metal plate.

[0049] Examples of the metal foil used here include copper foil and aluminum foil. The thickness is not particularly limited, but is 5 to 200 μm, more preferably 5 to 200 μm.
The range is 100 μm. Further, examples of the metal plate include an iron plate, an aluminum plate, a silicon steel plate, and a stainless steel plate. The thickness is not particularly limited, but is 0.2m
m to 10 mm, more preferably 0.2 mm to 5 mm. Before use, metal plates are mechanically polished by sanding with abrasive paper or abrasive cloth, wet blasting, dry blasting, etc. to improve their adhesion, and then degreased and polished.
It can be used after being subjected to etching, alumite treatment, chemical conversion coating treatment, etc. For aluminum plates, it is preferable to degrease with sodium carbonate and etch with sodium hydroxide after polishing, but the method is not particularly limited.

[0050] As a method for manufacturing the laminate, laminate, and metal-clad laminate of the present invention, for example, the curable composite material described above as the third aspect of the present invention and a metal foil and/or metal plate may be used. Examples include a method in which the layers are laminated in a layer configuration corresponding to the above, and the layers are bonded together under heat and pressure, and at the same time, the layers are thermally cured. For example, in a laminate, a curable composite material and metal foil are laminated in an arbitrary layer configuration. Metal foil can be used both as a surface layer and as an intermediate layer.

[0051] In the laminate plate, a curable composite material is laminated on one or both sides of a metal plate as a base. In a metal-clad laminate, a metal plate is used as a base, and metal foil is laminated on one or both sides of the base with a curable composite material interposed therebetween. In this case, the metal foil is used as the outermost layer, but it may be used as an intermediate layer in addition to the outermost layer.

In addition to the above, it is also possible to repeat lamination and curing several times to form a multilayer structure. An adhesive can also be used to bond the metal foil and metal plate. As an adhesive,
Examples include epoxy type, acrylic type, phenol type, cyanoacrylate type, etc., but are not particularly limited to these. The above lamination molding and curing can be performed under the same conditions as in the fourth aspect of the present invention.

[0053]

[Examples] The present invention will be explained below with reference to examples in order to make it more clear, but the scope of the present invention is not limited to these examples.

[0054]

[Reference Example 1] Poly(2,
6-dimethyl-1,4-phenylene ether) 100 parts by weight, maleic anhydride 1.5 parts by weight, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (NOF Corporation) After dry blending 1.0 part by weight of Perhexa 25B) at room temperature, the cylinder temperature was 300°C.
The mixture was extruded using a twin-screw extruder at a screw rotation speed of 230 rpm. This polymer is designated as A.

[0055]

[Reference Example 2] Bifunctional polyphenylene ether obtained by oxidative polymerization of 2,6-dimethylphenol in the coexistence of 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane (30°C, 0 Viscosity number η sp/c of 0.40 measured with chloroform solution of .5 g/dl)
After dry blending 0 parts by weight and 2 parts by weight of maleic anhydride, extrusion was performed under the same conditions as in Reference Example 1. The polymer obtained by troweling is designated as B.

[0056]

[Reference Example 3] Poly(2,
6-dimethyl-1,4-phenylene ether) 100 parts by weight, maleic anhydride 1.5 parts by weight, and 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (NOF Corporation) After dry blending 1.0 part by weight of Peroxa 25B) at room temperature, extrusion was performed under the same conditions as in Reference Example 1. The polymer obtained here is designated as C.

In the examples described below, the following components were used. Brominated bisphenol A diglycidyl ether epoxy resin: Asahi Kasei AER735 Epoxy equivalent 35
0 Bromine content 48% by weight Cresol novolak epoxy resin: Asahi Kasei ECN273 Epoxy equivalent 21
7 Phenol novolac epoxy resin: Ciba Geigy EPN1138 Epoxy equivalent weight 180 Curing agent: 4,4'-diaminodiphenylmethane (DDM)2
-ethyl-4-methylimidazole (2E4MZ)
Flame retardant aid: Sb2 O5 (Nissan Chemical NA-4800) Glass cloth: Made by E glass, basis weight 105 g/m2 Made by D glass, basis weight 87 g/m2 The following components were also used as comparative examples. Bisphenol A diglycidyl ether epoxy resin:
Asahi Kasei AER331 Epoxy equivalent 18
9 Low brominated bisphenol A polyglycidyl ether epoxy resin: Asahi Kasei AER711 Epoxy equivalent 47
5 Bromine content 20% by weight

[0058]

Examples 1 to 3 Polymers A and B obtained in Reference Examples 1 and 2 and each of the above components were dissolved in chloroform with the composition shown in Table 1, and the solution was poured onto a Teflon plate to form a film. The resulting film had a thickness of about 100 μm. Film formability was good in all cases, and no stickiness or the like on the surface was observed.

After drying this film in an air oven, it was formed and cured in a vacuum press to a thickness of about 1 mm.
A cured product was obtained. All curing conditions were 220°C for 30 minutes. No change in appearance was observed in these cured products even after boiling them in trichlorethylene for 5 minutes.

[0060]

[Comparative Example 1] The polyphenylene ether, epoxy resin, and curing agent used as raw materials for producing Polymer A in Reference Example 1 were mixed using a Henschel mixer with the composition shown in Table 1, and then heated at 180°C for 2 hours using a press molding machine. It was molded and cured under the following conditions to produce a cured product with a thickness of about 1 mm. When this cured product was boiled in trichlorethylene for 5 minutes, swelling and warping were observed.

[0061]

[Comparative Example 2] As shown in Table 1, the same operations as in Examples 1 to 3 were carried out using Polymer A, AER331 as the epoxy resin, and 2E4MZ as the curing agent. When the obtained cured product was boiled in trichlorethylene for 5 minutes,
Swelling and warping were observed.

[0062]

Examples 4 to 6 Each component was dissolved or dispersed in trichlorethylene according to the composition shown in Table 2. A glass cloth was dipped in this solution for impregnation and dried in an air oven. In Examples 4 and 6, E with a basis weight of 105 g/m2
In Example 5, the glass cloth was D with a basis weight of 87 g/m2.
Glass cloth was used for each. All of the obtained curable composite materials had no stickiness on the surface and were excellent in handleability.

[0063] Next, a plurality of sheets of the above-mentioned curable composite material were stacked together so that the thickness after curing was approximately 0.8 mm, and copper foil with a thickness of 35 μm was placed on both sides of the composite material, which was then molded and hardened using a press molding machine. A laminate was obtained. Table 3 shows the curing conditions for each example. The pressure was 40 kg/cm2 in all cases. In all Examples, the resin flowed well during pressing. Various physical properties of the thus obtained laminate were measured by the following methods, and good results as shown in Table 3 were obtained. 1. The laminate from which the trichlorethylene-resistant copper foil had been removed was cut into 25 mm square pieces, boiled in trichlorethylene for 5 minutes, and changes in appearance were visually observed. 2. The dielectric constant and dielectric loss tangent were measured at 1 MHz. 3. The laminate from which the solder heat-resistant copper foil has been removed is cut into 25 mm square pieces.
It was floated for 120 seconds in a solder bath at 0.degree. C., and changes in appearance were visually observed. 4. Copper foil peel strength A test piece with a width of 20 mm and a length of 100 mm was cut from the laminate, and a parallel cut of 10 mm in width was made on the copper foil surface, and then the peel strength was peeled off at a speed of 50 mm/min in a direction perpendicular to the surface. The copper foil was continuously peeled off, and the stress at that time was measured using a tensile tester, and the lowest stress value was shown. 5. Length 127mm, width 12.7mm from the laminate with flame retardant copper foil removed
A test piece of mm was cut out and tested according to the UL-94 test method.

[0064]

[Comparative Example 3] Using the polyphenylene ether used as the raw material for producing Polymer A in Reference Example 1, a laminate was produced with the composition shown in Table 2. All operations were performed in the same manner as in Examples 4-6. When the trichlorethylene resistance of this laminate was measured, whitening of the surface and exposure of the glass cloth were observed. Also, during the solder heat resistance test, blistering occurred in the copper foil part.

[0065]

[Comparative Example 4] As shown in Table 2, a laminate was produced in the same manner as in Examples 4 to 6 using Polymer A, AER711 as the epoxy resin, and 2E4MZ as the curing agent. When the trichlorethylene resistance of this laminate was measured, whitening of the surface and exposure of the glass cloth were observed.

[0066]

[Example 7] Three sheets of the curable composite material obtained in Example 4 were laminated on a 1.0 mm thick aluminum plate that had been subjected to polishing, degreasing, and etching treatment, and was heated at 180°C for 2 hours for 40k.
A laminate was produced by press molding under the condition of g/cm2. The thermal resistance of this laminate was 25° C./W, which was superior in heat dissipation compared to the case where no aluminum plate was used (60° C./W).

Thermal resistance was determined by forming a circuit on a 35 mm x 50 mm sample, soldering a 100 Ω chip resistor, and measuring the temperature rise after voltage application.

[0068]

[Example 8] Three sheets of the curable composite material obtained in Example 6 and a 35 μm thick copper foil were laminated on a 1.0 mm thick aluminum plate that had been subjected to polishing, degreasing, and etching.
A metal-clad laminate was produced by press forming at 0° C. and 40 kg/cm 2 for 2 hours. The thermal resistance of this metal plate clad laminate was measured in the same manner as in Example 7 and found to be 24°C.
/W, and had excellent heat dissipation properties.

[0069]

[Table 1]

[0070]

[Table 2]

[0071]

[Table 3]

[0072]

Effects of the Invention The curable polyphenylene ether epoxy resin composition of the present invention has the following characteristics. 1. Since the reaction product of the polyphenylene ether resin and the unsaturated carboxylic acid or acid anhydride used in the resin composition can be produced at low cost using an extruder or the like, a resin composition with excellent economic efficiency can be provided. 2. The above-mentioned reaction product has excellent solvent film-forming properties, and therefore, films and curable composite materials with excellent handling properties and no stickiness on the surface can be obtained. 3. The above reaction product has excellent compatibility with the epoxy resin, and can achieve excellent heat resistance and chemical resistance after curing. 4. The use of epoxy resin allows for good resin flow during pressing.

[0073] Furthermore, the curable polyphenylene ether
A laminate, a laminate obtained using an epoxy resin composition,
Metal-clad laminates have the following characteristics. 1. This material has both flame retardancy and chemical resistance due to the use of brominated bisphenol polyglycidyl ether epoxy resin and novolac epoxy resin. 2. Even when epoxy resin is used as the main component, it exhibits a dielectric constant of approximately 4.0 or less, and is a material with excellent dielectric properties. 3. Heat resistance, adhesion with metal foil, dimensional stability, moisture absorption,
It also exhibits well-balanced physical properties such as heat dissipation. Due to the above characteristics, the material of the present invention can be used as a dielectric material, an insulating material, a heat-resistant material, a structural material, etc. in fields such as the electrical industry, electronic industry, space industry, and aircraft industry. In particular, it is suitably used as single-sided, double-sided, multilayer printed circuit boards, flexible printed circuit boards, semi-rigid circuit boards, metal base boards, prepregs for multilayer printed circuit boards, and the like.

Furthermore, because of its heat-resistant, moisture-absorbing, and insulating properties, the material of the present invention can be used as an adhesive for high-density circuit boards with a line spacing of 100 μm or less, multilayer circuit boards with an interlayer insulation layer thickness of 200 μm or less, and circuit boards for mounting. Can be used in good condition.

Claims (9)

[Claims] Claim 1: (a) a reaction product of a polyphenylene ether resin and an unsaturated carboxylic acid or acid anhydride; and (b) (i) a brominated bisphenol polyglycidyl ether epoxy resin and (ii) a novolak epoxy resin. A curable polyphenylene ether epoxy resin composition consisting of an epoxy resin composition as a component, wherein the component (a) is 90 to 10 parts by weight, based on 100 parts by weight of the sum of the components (a) and (b), (b) component is 1
A curable polyphenylene ether epoxy resin composition, characterized in that it contains 0 to 90 parts by weight. 2. A film comprising the curable polyphenylene ether epoxy resin composition of claim 1. 3. A cured polyphenylene ether/epoxy resin composition obtained by curing the curable polyphenylene ether/epoxy resin composition according to claim 1. 4. A film comprising the curable polyphenylene ether epoxy resin composition according to claim 3. 5. (a) a reaction product of a polyphenylene ether resin and an unsaturated carboxylic acid or acid anhydride; (b)
) (i) a brominated bisphenol polyglycidyl ether epoxy resin; (ii) an epoxy resin composition containing a novolak epoxy resin as an essential component; and (c) a base material. (b
) component (a) is 90 parts by weight based on the sum of 100 parts by weight of the components
~10 parts by weight, component (b) is 10 to 90 parts by weight,
Curing characterized in that the components (a) + (b) are 95 to 10 parts by weight and the component (c) is 5 to 90 parts by weight, based on the sum of 100 parts by weight of components (a) to (c). Composite material. 6. A cured composite material obtained by curing the curable composite material according to claim 5. 7. A laminate comprising the cured composite material according to claim 6 and metal foil. 8. A laminate comprising an insulating layer made of the cured composite material according to claim 6 laminated on a metal base. 9. An insulating layer made of the cured composite material according to claim 6 is laminated on at least one side of the metal base, and a metal foil is laminated on at least the outermost layer of the insulating layer. metal-clad laminate.