JPH0764915B2 - Curable polyphenylene ether / epoxy resin composition, and composite material and laminate using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION 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 curing obtained by curing the same. Regarding the body Furthermore, the present invention relates to a composite material composed of the resin composition and a substrate, a cured product thereof, a laminate composed of the cured product and a metal foil, and a laminated plate composed 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 an insulating material in the fields of electric industry, electronic industry, space / aircraft industry and the like. It can be used as a material, a heat resistant material, a structural material and the like. In particular, it can be used as a single-sided or double-sided, multi-layered printed board, flexible printed board, semi-rigid board, board having excellent heat dissipation characteristics, and the like.

[0003]

2. Description of the Related Art In recent years, there has been a remarkable trend toward miniaturization and high density of mounting methods in the field of electronic devices for communication, consumer use, industrial use, etc. Heat resistance, dimensional stability, and electrical characteristics are being demanded. For example, as a printed wiring board, a copper-clad laminate made of a thermosetting resin such as phenol resin or epoxy resin has been conventionally used. These have various types of performance in a well-balanced manner, but have the drawback of poor electrical properties, especially dielectric properties in the high frequency range. Polyphenylene ether has recently attracted attention as a new material for solving this problem, and its application to copper-clad laminates has been attempted.

JP-B-64-3223 discloses a combination of polyphenylene ether and various epoxy resins. As the epoxy resin, general ones such as polyglycidyl ether of bisphenol A, 3,3 ′, 5,5′-tetrabromobisphenol A, and epoxyphenol novolac resin are used, and various epoxy resins such as amines are used. Curing is performed by using a known curing agent. However, the polyphenylene ether used here is not chemically modified at all and does not exhibit chemical resistance at all, so that the cured product is significantly inferior to the boiling trichlorethylene property required for printed circuit board materials. .

As a material having 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. Further, as a material to which flame retardancy is imparted, JP-A-2-55521, JP-A-2-55522, and JP-A-2-222224 disclose (i) polyphenylene ether, (ii) bromine-containing epoxy resin composition,
A resin composition comprising (iii) novolac resin, (iv) imidazole and polyamines, (v) zinc salt, and (vi) Sb ₂ O ₅ is disclosed.

Japanese Unexamined Patent Publication (Kokai) No. 2-269732 discloses a composition for improving the flowability of a resin at the time of molding.
A resin composition comprising (i) low molecular weight polyphenylene ether, (ii) bromine-containing epoxy resin composition, (iii) imidazole and polyamines, and (iv) aluminum or zinc salt is disclosed. Further, as a material obtained by subjecting polyphenylene ether itself to treatment, JP-A-2-
135216, (i) a reaction product of a polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride,
(Ii) Polyepoxy compound, (iii) A resin composition comprising a curing catalyst for epoxy is disclosed in JP-A-2-166115, (i) melt-processed polyphenylene ether, (ii) polyepoxy compound, (iii). ) Each discloses a resin composition comprising an epoxy curing catalyst.

However, even in the above series of resin compositions, the improvement of the resistance to trichlorethylene after curing was still insufficient, and it was found that a remarkable change in appearance such as roughness was observed after boiling of trichlorethylene.
Further, as shown in Example 6 in JP-A-2-55721, the dielectric constant is 4.19, even though polyphenylene ether is used in an amount of about 1/2 of the total resin composition.
And not sufficiently improved. This is a commercially available glass /
Epoxy resin copper-clad laminate dielectric constant 4.5 (resin amount about 4
0%) and almost the same level.

European Patent No. 315829 discloses a resin composition comprising polyphenylene ether, a bisphenol A type epoxy resin, and an amine curing agent. However, the chemical resistance of this cured product is not described in this specification, and the required properties are becoming more and more stringent in recent years.
Similar to -3223, further improvement in chemical resistance is awaited.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has both excellent dielectric properties of polyphenylene ether and various performances and economical efficiency balanced with epoxy resin, Moreover, it is intended to provide a novel curable polyphenylene ether / epoxy resin composition which exhibits excellent chemical resistance, heat resistance and flame retardancy after curing.

[0010]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, have found a novel resin composition in accordance with the object of the present invention and completed the present invention. Arrived The present invention, by using a polyphenylene ether resin modified with an unsaturated carboxylic acid or an acid anhydride and a specific epoxy resin, not only the above problems can be solved, but also a resin composition excellent in solvent film forming property It was made based on the discovery that To describe the present invention in more detail, the present invention consists 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 comprising an epoxy resin composition containing a novolac epoxy resin as an essential component, wherein the component (a) is based on 100 parts by weight of the sum of the components (a) and (b). 90 to 10 parts by weight,
Provided is a curable polyphenylene ether / epoxy resin composition, wherein the component (b) is 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 aspect. 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 substrate.

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

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

The polyphenylene ether resin used for producing the component (a) of the first curable polyphenylene ether / epoxy resin composition of the present invention is represented by the following general formula 1
Is represented by.

[0016]

[Chemical 1]

Examples of the lower alkyl group represented by R _{1 to} R ₄ in the general formula A are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and s.
Examples thereof include ee-butyl group. A phenyl group etc. are mentioned as an example of an aryl group. Examples of the haloalkyl group include a bromomethyl group and a chloromethyl group. Examples of halogen atoms include bromine and chlorine.

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

[0019]

[Chemical 2]

[Wherein A ₁ and A ₂ represent the same or different linear alkyl groups having 1 to 4 carbon atoms, X represents an aliphatic hydrocarbon residue and a substituted derivative thereof, an aralkyl group and a substituted thereof. Derivative, oxygen, sulfur, sulfonyl group,
Represents a carbonyl group, Y represents an aliphatic hydrocarbon residue and a substituted derivative thereof, an aromatic hydrocarbon residue and a substituted derivative thereof, aralkyl and a substituted derivative thereof, Z represents oxygen, sulfur, a sulfonyl group, a carbonyl group. represents a group, two phenyl groups attached directly a _2, a ₂
And X, A ₂ and Z are all at the ortho and para positions of the phenolic hydroxyl group, r is 0 to 4, s and 2 are
Represents an integer of 6. ] Specific examples include the following Chemical Formulas 3 to 4 and the like.

[0021]

[Chemical 3]

[0022]

[Chemical 4] 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]

[Chemical 5] Etc.

In addition to the above, units obtained by graft-polymerizing a polymerizable monomer having an unsaturated bond such as styrene and methyl methacrylate to the units of the above formulas A and B may be included. Preferred examples of the polyphenylene ether resin represented by the 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, copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol Polymer,
2,6-dimethylphenol and 2,6-dimethyl-3-
A copolymer of phenylphenol, 2,6-dimethylphenol, is used as a polyfunctional phenol compound Q (H) _m (m is 2
To an integer of 6) to obtain a polyfunctional polyphenylene ether resin obtained by polymerization in the presence of, for example, JP-A-63-3012.
No. 22, and copolymers containing the units of the general formulas A and B as disclosed in JP-A-1-297428.

The molecular weight of the polyphenylene ether resin described above is not particularly limited, but is 30 ° C., 0.5.
Viscosity number η sp / measured with g / dl chloroform solution
Those having c in the range of 0.1 to 1.0 can be favorably used. A resin having a low viscosity number is preferable for a composition that places importance on molten resin flow, for example, a prepreg for a multilayer printed wiring board.

The component (a) used in the present invention is produced by reacting the above polyphenylene ether resin with an unsaturated carboxylic acid or an acid anhydride, and is substantially polymerizable due to the acid or the acid anhydride. Is a reaction product containing no double bond. The reaction product is probably a mixture of various products having various chemical structures, and the chemical structures thereof are not all elucidated. H. Glans, M .; K. A
kkapeddi, Macromolecules, v
The following chemical structures described in ol 1991, 24, 383 to 386 are given as examples.

[Chemical 8] Examples of suitable acids and acid anhydrides include acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, itaconic acid,
Examples thereof include itaconic anhydride, glutaconic anhydride, citraconic anhydride, and of these, maleic anhydride and fumaric acid are most preferably used. The reaction is performed by mixing the polyphenylene ether resin and the unsaturated carboxylic acid or acid anhydride at 100 ° C to 39 ° C.
It is carried out by heating in the temperature range of 0 ° C. At this time, a radical initiator may coexist. Both the solution method and the melt-mixing method can be used, but the melt-mixing method using an extruder or the like is simpler and more suitable for the purpose of the present invention. The ratio of unsaturated carboxylic acid or acid anhydride is 0.0 with respect to 100 parts by weight of the polyphenylene ether resin.
The amount is 1 to 5.0 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 has not been known so far. However, it is presumed that it plays an important role in enhancing compatibility between the polyphenylene ether resin and the epoxy resin, improving chemical resistance and heat resistance, and at the same time imparting film-forming property to the resin composition.

The 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]

[Chemical 6]

Among these, those in which p is all 2, q is substantially 0, and A ₃ is an isopropylidene group can be best 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]

[Chemical 7]

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

In addition to the above, other epoxy resins may be blended in the component (b) within a range not deteriorating various characteristics such as flame retardancy, chemical resistance and heat resistance. The mixing ratio of the component (a) and the component (b) described above is 100, the sum of the two.
90 to 10 parts by weight of the component (a) based on 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), and even more preferably 60 to 20 parts by weight of component (a),
Component (b) is in the range of 40 to 80 parts by weight.

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

As a method for mixing the above two components (a) and (b), a solution mixing method of uniformly dissolving or dispersing them in a solvent, or a melt blending method of heating with an extruder or the like. Is available. Solvents used for solution mixing include dichloromethane, chloroform,
Halogen-based 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 favorably used as a film. As its manufacturing method,
For example, an ordinary solvent film forming method (casting method) or the like can be used, and one having an arbitrary thickness can be manufactured. The composition suitable for producing the film is not particularly limited, but (a)
(A) based on 100 parts by weight of the sum of the component and the component (b)
The range of 90 to 20 parts by weight of the component and 10 to 80 parts by weight of the component (b) are preferable. When the amount of the component (b) is less than 10 parts by weight, the chemical resistance and the adhesiveness to the metal foil are insufficient as described above, which is not preferable. On the other hand, if the amount of the component (b) exceeds 80 parts by weight, the film becomes brittle and sticky, resulting in poor handleability, which is not preferable.

As will be described later, the resin composition of the present invention undergoes a crosslinking reaction by means of heating or the like to be cured, but it contains a curing agent for the purpose of lowering the temperature or promoting the crosslinking reaction. May be used. As the curing agent, an ordinary epoxy resin curing agent, for example, polyamine curing agent, acid anhydride curing agent, polyphenol curing agent, polymercaptan curing agent, anionic polymerization type catalyst curing agent, cationic polymerization type catalyst type A curing agent, a latent curing agent or the like can be used (for details, see, for example, Masaki Shinbo, "Epoxy Resin Handbook" (Nikkan Kogyo Shimbun, 1987), Soichi Muroi, Shuichi Ishimura, "Introduction Epoxy Resin" (Polymer) Press, 198
8) etc.).

The curing agents may be used alone or in combination of two or more. The resin composition of the present invention, in addition to the above-mentioned curing agent, to be used by blending an amount of fillers and additives in a range that does not impair the original properties for the purpose of imparting desired performance depending on the application You can Examples of the filler include carbon black, silica, alumina, barium titanate, talc, mica, glass beads, glass hollow spheres and the like. As additives, antioxidants, heat stabilizers, antistatic agents, plasticizers, pigments, dyes,
Colorants and the like can be mentioned. For the purpose of further improving flame retardancy, chlorine-based, bromine-based, phosphorus-based flame retardants, Sb
A flame retardant aid such as ₂ O ₃ , Sb ₂ O ₅ , NaSbO ₃ ¼H ₂ O or the like can be used in combination. Furthermore, for example, allyl glycidyl ether, glycidyl methacrylate,
It is also possible to blend one or more kinds of crosslinkable monomers such as glycidyl acrylate, thermoplastic resins such as polyphenylene ether, and 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,
A method using heat, light, an electron beam or the like can be adopted.
When curing is performed by heating, the temperature is selected in the range of 80 to 300 ° C., and more preferably 150 to 250 ° C., though it varies depending on the presence or absence of the curing agent and the type thereof. 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 by 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 favorably used as a film.

The cured polyphenylene ether / epoxy resin composition can be used by laminating it with a metal foil and / or a metal plate as in the case of the cured composite material described below as the fourth invention. Next, the third and fourth curable composite materials of the present invention and their cured products will be described.

The curable composite material of the present invention is the first invention of the present invention.
The curable polyphenylene ether / epoxy resin composition described above as above and a substrate. As the substrate used in the present invention, various glass cloths or glass non-woven cloths such as roving cloth, cloth, chopped mat, surfacing mat; ceramic fiber cloth, asbestos cloth, metal fiber cloth and other synthetic or natural inorganic fiber cloth; Polyvinyl alcohol fiber, polyester fiber,
Woven or non-woven fabric obtained from synthetic fibers such as acrylic fiber and wholly aromatic polyamide fiber; natural fiber cloth such as cotton cloth, linen cloth and felt; carbon fiber cloth; natural paper such as kraft paper, cotton paper, paper-glass wet woven paper Cellulosic cloth or the like may be used alone or in combination of two or more kinds.

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, further preferably 20 to 70 parts by weight, based on 100 parts by weight of the curable composite material. It is a range of parts. When the amount of the base material is less than 5 parts by weight, the dimensional stability and strength of the composite material after curing are insufficient, and when the amount of the base material is more than 90% by weight, the dielectric properties and flame retardancy of the composite material are poor, which is not preferable.

In the composite material of the present invention, a coupling agent can be used if necessary for the purpose of improving the adhesiveness at the interface between the resin and the substrate. As the coupling agent, silane coupling agents, titanate coupling agents, aluminum coupling agents, zircoaluminate coupling agents and the like can be used. The method for producing the composite material of the present invention includes, for example, the first method of the present invention.
The components (a) and (b) described in the section 1) and, if necessary, other components are uniformly dissolved or dispersed in the above-mentioned halogen-based, aromatic-based, ketone-based solvent or a mixed solvent thereof, A method of impregnating the base material and then drying the base material may be mentioned.

Impregnation is carried out by dipping, coating or the like. Impregnation can be repeated multiple times as needed, and in this case it is also possible to repeat impregnation using multiple solutions with different compositions and concentrations to finally adjust the desired resin composition and amount. Is. The fourth curable 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 is not particularly limited, and for example, a plurality of the curable composite materials are stacked, and each layer is adhered under heat and pressure, and at the same time heat cured to obtain a cured composite material having a desired thickness. You can It is also possible to obtain a cured composite material having a new layer structure by combining the cured composite material that has been adhesively cured once and the curable composite material.

The lamination 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 laminating in advance can be cured by heat treatment or another method. Molding and curing are performed at a temperature of 80-300 ° C and pressure of 0.1-500 kg.
/ Cm ² , time range of 1 minute to 10 hours, more preferably temperature 150 to 250 ° C., pressure 1 to 100 kg / cm 2.
^{2. The} time can be 1 minute to 5 hours.

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

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, and more preferably 5 to
It is in the range of 100 μm. Examples of the metal plate include an iron plate, an aluminum plate, a silicon steel plate, and a stainless plate. The thickness is not particularly limited, but 0.2 m
The range is m to 10 mm, more preferably 0.2 mm to 5 mm. Prior to use, the metal plate is mechanically ground by sanding with a polishing paper or polishing cloth, wet blasting, dry blasting, etc. to improve its adhesiveness, and further degreasing,
It can be used after being subjected to etching, alumite treatment, chemical conversion film treatment and the like. The aluminum plate is preferably degreased with sodium carbonate after polishing and etched with sodium hydroxide, but is not particularly limited to this method.

The method for producing the laminate, the laminate and the metal-clad laminate of the present invention is, for example, the curable composite material described above as the third of the present invention and the metal foil and / or the metal plate. There may be mentioned a method in which the layers are laminated according to the above, and each layer is adhered under heat and pressure and at the same time heat-cured. For example, in the laminated body, the curable composite material and the metal foil are laminated in an arbitrary layer structure. The metal foil can be used as both the surface layer and the intermediate layer.

In the laminated plate, a curable composite material is laminated on one side or both sides of a metal plate as a base. In the metal-clad laminate, a metal foil is used as a base, and a metal foil is laminated on one or both surfaces of the metal foil via a curable composite material. At this time, the metal foil is used as the outermost layer, but may be used as an intermediate layer other than the outermost layer.

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

[0053]

EXAMPLES Hereinafter, the present invention will be described with reference to examples in order to further clarify the present invention, but the scope of the present invention is not limited to these examples.

[0054]

Reference Example 1 Poly (2,6) having a viscosity number ηsp / c of 0.54 measured at 30 ° C. in a chloroform solution of 0.5 g / dl.
-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 (manufactured by NOF Corporation). Perhexa 25B) 1.0 part by weight is dry blended at room temperature, and then the cylinder temperature is set to 300.
It was extruded by a twin-screw extruder under the conditions of ℃ and screw rotation speed of 230 rpm. This polymer is designated as A.

[0055]

Reference Example 2 Bifunctional polyphenylene ether (30 ° C., 0 ° C.) obtained by oxidative polymerization of 2,6-dimethylphenol in the coexistence of 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane. Viscosity number ηsp / c measured with chloroform solution of 0.5 g / dl is 0.40) 10
After 0 parts by weight and 2 parts by weight of maleic anhydride were dry-blended, extrusion was performed under the same conditions as in Reference Example 1. The polymer obtained from the iron is designated as B.

[0056]

Reference Example 3 Poly (2,6) having a viscosity number ηsp / c of 0.31 measured at 30 ° C. in a chloroform solution of 0.5 g / dl.
-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 (manufactured by 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. Let the polymer obtained here be C.

In the examples described below, the following components were used. Brominated bisphenol A diglycidyl ether epoxy resin: Asahi Kasei AER735 epoxy equivalent 350 bromine content 48 wt% cresol novolac epoxy resin: Asahi Kasei ECN273 epoxy equivalent 217 phenol novolac epoxy resin: Ciba Geigy EPN1138 epoxy equivalent 180 Curing agent: 4,4'-diaminodiphenylmethane (DDM) 2-ethyl-4-methylimidazole (2E4MZ) flame retardant aid: Sb ₂ O ₅ (Nissan chemical NA-4800) glass cloth: E glass, weight per unit area 105 g / m ² D glass basis weight 87 g / m ² The following components were also used as comparative examples. Bisphenol A diglycidyl ether epoxy resin: Asahi Kasei AER331 epoxy equivalent 189 Low brominated bisphenol A polyglycidyl ether epoxy resin: Asahi Kasei AER711 epoxy equivalent 475 Bromine content 20% by weight

[0058]

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

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

[0060]

Comparative Example 1 The polyphenylene ether used as the raw material for producing the polymer A in Reference Example 1, the epoxy resin and the curing agent were mixed in the composition shown in Table 1 using a Henschel mixer, and the mixture was pressed at 180 ° C. for 2 hours. Was molded and cured under the conditions described above to prepare a cured product having a thickness of about 1 mm. When this cured product was boiled in trichlorethylene for 5 minutes, swelling and warpage were observed.

[0061]

COMPARATIVE EXAMPLE 2 As shown in Table 1, the same operations as in Examples 1 to 3 were performed using polymer A, AER331 as an epoxy resin, and 2E4MZ as a curing agent. When the obtained cured product was boiled in trichlorethylene for 5 minutes,
Swelling and warpage were noted.

[0062]

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

Next, a plurality of the above-mentioned curable composite materials were superposed so that the thickness after curing would be about 0.8 mm, and copper foil with a thickness of 35 μm was placed on both sides thereof and molded and cured by a press molding machine. To obtain a laminate. The curing conditions of each example are shown in Table 3. All pressures were 40 kg / cm ² . In all of the examples, the resin flow during pressing was good. The physical properties of the thus obtained laminate were measured by the following methods, and good results as shown in Table 3 were obtained. 1. Trichloroethylene resistance The laminate from which the copper foil was removed was cut into 25 mm square pieces, boiled in trichlorethylene for 5 minutes, and the change in appearance was visually observed. 2. The dielectric constant and the dielectric loss tangent were measured at 1 MHz. 3. Solder heat resistance Cut the laminate from which the copper foil was removed into 25 mm square pieces, 260
Floating in a solder bath at ℃ for 120 seconds, the change in appearance was visually observed. 4. Copper foil peeling strength A test piece having a width of 20 mm and a length of 100 mm was cut out from the laminate, and a parallel cut having a width of 10 mm was made on the copper foil surface, and then a speed of 50 mm / min in a direction perpendicular to the surface. Then, the copper foil was continuously peeled off, and the stress at that time was measured by a tensile tester, and the minimum value of the stress was shown. 5. Flame-retardant From the laminate without copper foil, length 127mm, width 12.7
mm test pieces were cut out, and the test was performed according to the UL-94 test method.

[0064]

Comparative Example 3 Using the polyphenylene ether used as the starting material for polymer A in Reference Example 1, a laminate was prepared 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 glass cloth were observed. In the solder heat resistance test, blistering occurred on the copper foil part.

[0065]

[Comparative Example 4] As shown in Table 2, a laminate was prepared 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 glass cloth were observed.

[0066]

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

The thermal resistance was measured by forming a circuit on a sample of 35 mm × 50 mm, soldering a chip resistor of 100Ω, and measuring the temperature rise after voltage application.

[0068]

Example 8 Three curable composite materials obtained in Example 6 and a copper foil having a thickness of 35 μm were laminated on an aluminum plate having a thickness of 1.0 mm that had been subjected to polishing, degreasing, and etching, and 18
A metal-clad laminate was produced by press molding at 0 ° C. for 2 hours under the condition of 40 kg / cm ² . When the thermal resistance of this metal plate-clad laminate was measured by the same method as in Example 7, it was 24 ° C. /
W, which was excellent in heat dissipation.

[0069]

[Table 1]

[0070]

[Table 2]

[0071]

[Table 3]

[0072]

The curable polyphenylene ether / epoxy resin composition of the present invention has the following features. 1. Since the reaction product of the polyphenylene ether resin used in the resin composition and the unsaturated carboxylic acid or acid anhydride can be produced at low cost using an extruder or the like, it is possible to provide the economical resin composition. 2. The above-mentioned reaction product is excellent in solvent film-forming property, so that a film or curable composite material having no stickiness on the surface and excellent handleability can be obtained. 3. The above reaction product has excellent compatibility with the epoxy resin and can realize excellent heat resistance and chemical resistance after curing. 4. Good resin flow during pressing due to the use of epoxy resin.

The curable polyphenylene ether
Laminate obtained by using the epoxy resin composition, a laminate,
The metal-clad laminate has the following features. 1. It is a material that has both flame resistance and chemical resistance by using brominated bisphenol polyglycidyl ether epoxy resin and novolac epoxy resin. 2. Even if an epoxy resin is used as a main component, it has a dielectric constant of approximately 4.0 or less, and is a material having excellent dielectric properties. 3. Heat resistance, adhesion to metal foil, dimensional stability, moisture absorption,
It also shows well-balanced properties in terms of physical properties such as heat dissipation. From 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 the fields of electric industry, electronic industry, space, aircraft industry and the like. In particular, it is suitably used as a single-sided or double-sided, multi-layer printed circuit board, flexible printed circuit board, semi-rigid substrate, metal base board, prepreg for multi-layer printed circuit board, and the like.

The material of the present invention is used as an adhesive for a high-density circuit board having a line spacing of 100 μm or less, a multi-layer circuit board having an interlayer insulating layer thickness of 200 μm or less, and a mounting circuit board because of its heat and moisture absorption resistance. It can be used well.

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Claims (9)

[Claims] 1. An essential component of (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 and (ii) a novolac epoxy resin. A curable polyphenylene ether / epoxy resin composition comprising an epoxy resin composition as a component,
90 to 10 parts by weight of the component (a) and 10 to 9 parts by weight of the component (b) based on 100 parts by weight of the sum of the components (a) and (b).
A curable polyphenylene ether / epoxy resin composition, characterized in that it is 0 part by weight. 2. A film comprising the curable polyphenylene ether / epoxy resin composition according to 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. An essential component comprising (a) a reaction product of a polyphenylene ether resin and an unsaturated carboxylic acid or an acid anhydride, (b) (i) a brominated bisphenol polyglycidyl ether epoxy resin and (ii) a novolac epoxy resin. Which is a curable composite material comprising an epoxy resin composition and (c) a base material, wherein (a) component is 90 to 10 parts by weight based on 100 parts by weight of the sum of (a) component and (b) component. , (B) component is 10 to 90 parts by weight, and (a) + (b) component is 95 to 10 parts by weight based on 100 parts by weight of the sum of components (a) to (c).
A curable composite material, wherein the component (c) is 5 to 90 parts by weight. 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 a metal foil. 8. A laminated board in which an insulating layer made of the cured composite material according to claim 6 is 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 surface of a metal base, and a metal foil is laminated on at least the outermost layer of the insulating layer. A metal-clad laminate.