JPH05287191A - Curable polyphenylene ether/epoxy resin composition - Google Patents

Abstract

PURPOSE:To provide the novel curable polyphenylene ether/epoxy resin composition excellent in dielectric characteristics, chemical resistance, heat resistance and flame retardance and exhibiting low thermal expansion characteristics. CONSTITUTION:A base material is impregnated with a resin composition comprising (a) polyphenylene ether resin, (b) triallylisocyanurate and/or triallylcyanurate, (c) (i) a brominated bisphenol polyglycidyl ether epoxy resin, (ii) a novolak resin and (iii) a phenolic resin, and (d) a compound having at least one epoxy group and at least one unsaturated bond to provide the composite material.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable polyphenylene ether / epoxy resin composition and a cured product obtained by curing the same. Furthermore, the present invention relates to a curable composite material comprising the resin composition and a substrate, a cured product thereof, a laminate comprising the cured product and a metal foil, and a laminate comprising the cured product and a metal base.

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, an insulating material and a heat-resistant material in the fields of the electronic industry, space / aircraft industry and the like. It can be used as a material.

[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. Although these have various performances in a well-balanced manner, they have the drawback of poor electrical characteristics, especially dielectric characteristics in the high frequency region. Polyphenylene ether has attracted attention in recent years as a new material for solving this problem, and its application to copper-clad laminates has been attempted.

Chemical resistance and heat resistance are usually required for the copper clad laminate material. Polyphenylene ether has a glass transition temperature of about 210 ° C., which is excellent in heat resistance, but is a material that is easily swelled and dissolved in an aromatic solvent or a halogen solvent and has poor chemical resistance. Various methods of blending both have been proposed for the purpose of improving the chemical resistance of polyphenylene ether and improving the heat resistance and dielectric properties of epoxy resins.

JP-B-64-3223 discloses a combination of polyphenylene ether and various epoxy resins. Examples of the epoxy resin include polyglycidyl ether of bisphenol A, 3,3 ′, 5 and
General-purpose materials such as polyglycidyl ether of 5'-tetrabromobisphenol A and epoxyphenol novolac resin are used, and various known curing agents such as amines have been used. However, this cured product is extremely inferior in chemical resistance and does not exhibit the trichlorethylene resistance required for printed circuit board materials at all.

Materials having improved chemical resistance and flame retardancy are disclosed in JP-A-2-55721 and JP-A-2-55721.
5722 discloses a resin composition comprising (1) a reaction product of bisphenol polyglycidyl ether, epoxy novolac and brominated bisphenol, (2) polyphenylene ether, (3) novolac resin, (4) imidazole and polyamines, (5) Zinc salt, (6) Sb
_A resin composition comprising ₂ O ₅ is disclosed. However, even this cured product is still insufficient for improving the trichlorethylene resistance, and after the boiling of trichlorethylene, remarkable changes such as roughness are observed.

On the other hand, European Patent Publication No. 315829
The publication discloses a resin composition comprising polyphenylene ether, a bisphenol A type epoxy resin, and an amine curing agent. However, the chemical resistance and thermal expansion characteristics of this cured product are not described in the above specification. The present inventors have filed Japanese Patent Application No. 2-20.
No. 7644 proposed improvement in chemical resistance. Japanese Patent Application No. 2-207644 discloses a resin composition comprising (a) polyphenylene ether, (b) triallyl isocyanurate and / or triallyl cyanurate, (c) epoxy resin and a curing agent. However, although the composition satisfies the chemical resistance, it still has an insufficient level of dimensional stability, that is, thermal expansion characteristics, and further low thermal expansion characteristics are desired.

[0008]

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

[0009]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that (a) polyphenylene ether, (b) triallyl isocyanurate and / or triallyl cyanurate. , (C)
(I) brominated bisphenol polyglycidyl ether epoxy resin, (ii) novolac epoxy resin, (ii
i) The addition of a compound having at least one epoxy group and at least one unsaturated bond group as the component (d) to the phenol resin, thereby improving the storage stability and the film-forming property and the melt flow of the resin. It has been found that a curable polyphenylene ether / epoxy resin composition having excellent properties is obtained, and that it exhibits a low coefficient of linear expansion in addition to chemical resistance, heat resistance and flame retardancy after curing, thus completing the present invention. The present invention consists of the following seven inventions.

That is, according to the first aspect of the present invention, based on (a), the sum of the components (a) and (b),
8 to 40% by weight of polyphenylene ether, (b), based on the sum of the components (a) and (b), 2
~ 60 wt% triallyl isocyanurate and / or triallyl cyanurate, 10-90 wt% (i), based on the sum of (c), (a) component, (b) component and (c) component. Brominated bisphenol polyglycidyl ether epoxy resin, (i
i) a resin composition containing a novolac epoxy resin and (iii) a phenol resin as essential components, based on the sum of (d), (a) component, (b) component, (c) component and (d) component, 0 1 to 30% by weight of at least one epoxy group, and at least 1
A curable polyphenylene ether-epoxy resin composition comprising: a compound having one unsaturated bond group.

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. The 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 according to 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 present invention will be described in detail below. The polyphenylene ether used in the present invention is represented by the following general formula (1).

[0014]

[Chemical 1]

R _{1 to} R ₄ in the above general formula (A)
Examples of the lower alkyl group of are a methyl group, an ethyl group,
Examples thereof include n-propyl group, isopropyl group, n-butyl group and isobutyl 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.

As a typical example of Q in the general formula (1),
The following four kinds of compounds represented by the general formula (2) can be mentioned.

[0017]

[Chemical 2]

As specific examples, the following general formulas (3) and (4)
Etc.

[0019]

[Chemical 3]

[0020]

[Chemical 4]

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

[0022]

[Chemical 5]

Preferred examples of the polyphenylene ether resin of 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 polymer, 2,6-dimethylphenol and 2,3,6-trimethylphenol copolymerization Coalescing 2,
Copolymer of 6-dimethylphenol and 2-methyl-6-phenylphenol, 2,6-dimethylphenol and polyfunctional phenol compound: general formula (6),

[0024]

[Chemical 6]

A polyfunctional polyphenylene ether resin obtained by polymerization in the presence of, for example, JP-A-63-3012.
For example, a copolymer containing the units of the general formulas (A) and (B) as disclosed in JP-A No. 22 and JP-A No. 1-297428 can be used. The molecular weight of the above-mentioned polyphenylene ether resin is 30 ° C., 0.5 g / dl
The viscosity number ηsp / c measured with the chloroform solution of 0.1 is 0.
Those in the range of 1 to 1.0 can be used favorably. A resin having a low viscosity number is preferable as a curable resin composition that places importance on molten resin flow, for example, a prepreg for a multilayer wiring board.

The triallyl isocyanurate and / or triallyl cyanurate used as the component (b) of the polyphenylene ether / epoxy resin composition of the present invention is a trifunctional compound represented by the following structural formula (7). It is a monomer.

[0027]

[Chemical 7]

In carrying out the present invention, triallyl isocyanurate and triallyl cyanurate can be used not only individually but also as a mixture of both at an arbitrary ratio. In the present invention,
Triallyl isocyanurate and triallyl cyanurate act as a plasticizer and a crosslinking agent. That is, it improves the resin flow during pressing and the crosslink density.

The brominated bisphenol polyglycidyl ether epoxy resin used as one of the components (c) of the polyphenylene ether / epoxy resin composition of the present invention is represented by the following general formula (8).

[0030]

[Chemical 8]

Of 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 novolac epoxy resin used as one of the components (c) is represented by the following general formula (9).

[0032]

[Chemical 9]

Of these, the average value of n is 0 to 5,
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. The phenol resin used as one of the components (c) is one having two or more phenolic hydroxyl groups in one molecule, and includes phenol, cresol, xylenol, propylphenol, amylphenol, butylphenol, octylphenol, and phenylphenol. , Novolac resin and resole resin synthesized from allylphenol, bisphenol A, etc., or in combination with them. Of these, novolak resins and resole resins synthesized from butylphenol or phenylphenol are (a), (b), and (c) (i),
Since it is excellent in compatibility with the components (c) and (ii), it can be used most effectively in the present invention, and one kind or a combination of two or more kinds is used.

Among the above-mentioned components (c), 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 improving crosslink density. Phenolic resin also acts as a curing agent for these epoxy resins,
Compared with other epoxy resin curing agents, it has a feature of being excellent in storage stability after compounding with a resin.

In addition to the above, other epoxy resins may be blended in the component (c) as long as various properties such as flame retardancy, chemical resistance and heat resistance are not deteriorated. The compound having at least one epoxy group and having at least one unsaturated bond group used as the component (d) of the curable polyphenylene ether / epoxy resin composition of the present invention,
Any compound having at least one epoxy group in one molecule and at least one unsaturated bond group may be used, and the unsaturated group may be a carbon-carbon double bond and / or Alternatively, a functional group containing a carbon-carbon triple bond is shown. Typical examples are allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate and the like.

The component (d) is characterized in that it contributes to the improvement of resin melt flow characteristics. Moreover, after curing, the cured composition can be imparted with low thermal expansion. Of the four components (a) to (d) described above, the blending ratio of the component (a) and the component (b) is based on the sum of the two (a).
98-40% by weight of component, 2-60% by weight of component (b)
More preferably, the component (a) is in the range of 95 to 50% by weight, and the component (b) is in the range of 5 to 50% by weight.

When the amount of the component (b) is less than 2% by weight, the chemical resistance is insufficiently improved, which is not preferable. On the other hand, if it exceeds 60% by weight, the dielectric properties, flame retardancy, and moisture absorption properties are deteriorated, and the material becomes extremely brittle after curing, which is not preferable. Furthermore, when the ratio of the component (a) and the component (c) is out of the above range, the film obtained by the casting method is very brittle,
Moreover, it is not preferable because it has a sticky surface.

The mixing ratio of the component (c) is the component (a),
10-9 based on the sum of the components (b) and (c)
0% by weight is preferred, more preferably 40-80% by weight
Is. When the content of the component (c) exceeds 90% by weight, the dielectric properties deteriorate, which is not preferable. On the other hand, if the content of the component (c) is less than 10% by weight, the improvement due to the epoxy resin, that is, the chemical resistance, flame retardancy and the like are insufficient, which is not preferable. Further, the adhesive strength with the metal foil is also lowered, which is not preferable.

The blending ratio of the brominated polyglycidyl ether epoxy resin and the novolac epoxy resin in the component (c) is determined by the balance between the chemical resistance and flame retardancy of the resin composition of the present invention. The chemical resistance is improved by increasing the compounding ratio of the novolac epoxy resin, but the content of bromine based on the sum of the components (a) to (d) is 5% by weight or more and 20% by weight or less. It is preferable to use brominated bisphenol polyglycidyl ether epoxy resin for the purpose of imparting flame retardancy.

The mixing ratio of the phenol resin in the component (c) is such that the amount of the phenolic hydroxyl group in the resin is 0.5 to 1.5 equivalents, more preferably 0.6. It is preferable to adjust the amount to be in the range of 1.2 equivalents. The mixing ratio of the component (d) is the component (a),
It is 0.1 to 30% by weight, preferably 0.1 to 20% by weight, and more preferably 0.2 to 6% by weight, based on the sum of the components (b), (c) and (d). (D)
When the content of the component exceeds 30% by weight, the chemical resistance is insufficiently improved, which is not preferable. On the other hand, if it is less than 0.1% by weight, the reduction of the linear expansion coefficient is insufficient, which is not preferable.

In the present invention, when a polyphenylene ether resin containing bromine or chlorine is used as the component (a) or a brominated epoxy resin is used as the component (c),
A flame-retardant resin composition can be obtained. The preferable halogen content for imparting flame retardancy is 5% by weight or more, more preferably 10% by weight based on the sum of the components (a) to (d).
It is more than weight%. When the bromine content exceeds 20% by weight, the thermal stability of the resin composition is deteriorated, which is not preferable.

The curable polyphenylene ether of the present invention
A base material of component (e) can be added to the epoxy resin composition in order to increase mechanical strength and dimensional stability. Examples of the base material used in the present invention include "various glass cloths such as roving cloth, cloth, chopped mat, surfacing mat", "asbestos cloth, metal fiber cloth and other synthetic or natural inorganic fiber cloth", "
Woven or non-woven fabric obtained from synthetic fibers such as polyvinyl alcohol fiber, polyester fiber, acrylic fiber, wholly aromatic polyamide fiber, polytetrafluoroethylene fiber, etc., "natural fiber cloth such as cotton cloth, linen cloth, felt", "carbon fiber" Cloth "," natural cellulose-based cloth such as kraft paper, cotton paper, paper-glass mixed fiber paper "and the like are used alone or in combination of two or more kinds.

In the curable composite material of the present invention, the ratio of the component (e) to the substrate is 100% by weight of the curable composite material.
Based on 5 to 90% by weight, more preferably 10 to 8
0% by weight, more preferably 20 to 70% by weight. When the amount of the base material is less than 5% 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.

Examples of the metal foil used in the present invention include copper foil and aluminum foil. The thickness is not particularly limited, but is 5 to 200 μm, more preferably 5
˜100 μm. Examples of the metal plate used in the present invention include an iron plate, an aluminum plate, a silicon steel plate, and a stainless plate. The thickness is not particularly limited, but is in the range of 0.2 mm to 5 mm. Prior to use, the metal plate is mechanically polished by sanding with a polishing paper or polishing cloth, wet blasting, dry blasting, etc. to improve its adhesiveness, and further subjected to degreasing, etching, alumite treatment, chemical conversion coating treatment, etc. Can be used. The aluminum plate is preferably degreased with sodium carbonate after polishing and etched with sodium hydroxide, but is not particularly limited to this method.

As the method for mixing the four components (a) to (d) above, a solution mixing method in which the four components are uniformly dissolved or dispersed in a solvent, or melting performed by heating with an extruder or the like. A blending method or the like can be used. Solvents used for solution mixing are "halogen solvents such as dichloromethane, chloroform, trichloroethylene", "aromatic solvents such as benzene, toluene, xylene", "ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone". , Tetrahydrofuran may be used alone or in combination of two or more kinds.

The resin composition of the present invention may be molded and cured in advance according to its use. The molding method is not particularly limited. Usually, a casting method in which the resin composition is dissolved in the above-mentioned solvent and molded into a desired shape, or a heating and melting method in which the resin composition is heated and melted and molded into a desired shape is used. The above-described casting method and heat melting method may be performed independently. Moreover, you may carry out combining each. For example, several to several tens of films of the present resin composition prepared by a casting method may be laminated and heated and melted by a heating and melting method, for example, a press molding machine to obtain a sheet of the present resin composition.

As a method for producing the curable composite material of the present invention, for example, the components (a) to (c) of the present invention and, if necessary, other components may be added to the above halogen-based, aromatic-based, ketone-based, etc. Examples of the method include uniformly dissolving or dispersing in the solvent or the mixed solvent thereof, impregnating the base material, and then drying. Impregnation is performed by dipping, coating, or the like. The impregnation can be repeated multiple times as necessary, and in this case, it is also possible to repeat the impregnation using multiple solutions having different compositions and concentrations to finally prepare the desired resin composition and resin amount. Is.

In the curable 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-based coupling agents, zircoaluminate coupling agents and the like can be used. The resin composition of the present invention undergoes a crosslinking reaction by means such as heating to be cured as described below, but contains a radical initiator for the purpose of lowering the reaction temperature at that time or accelerating the crosslinking reaction of the unsaturated group. You may use it.

The amount of the radical initiator used in the resin composition of the present invention is 0.1 to 10% by weight, preferably 0.1 to 8% by weight, based on the sum of the components (a) and (b). is there. Representative examples of radical initiators include benzoyl peroxide, cumene hydroperoxide,
2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, di-t-butylperoxide, t-butylcumi Luperoxide, α, α′-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, di-t -Butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis (t-butylperoxy)
Peroxides of butane, 2,2-bis (t-butylperoxy) octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxide, trimethylsilyltriphenylsilylperoxide, etc. Oxides include, but are not limited to. Although not a peroxide, 2,3-dimethyl-2,3-diphenylbutane can also be used as a radical initiator. However, the initiator used for curing the resin composition is not limited to these examples.

In addition to the above-mentioned radical initiator, a curing accelerator may be used for the purpose of reacting the component (c) and the component (d) of the present resin composition. Examples of the curing accelerator include amine compounds, imidazole compounds, nitrogen-containing heterocyclic compounds such as diazabicycloundecene, organic phosphine compounds, organic phosphine / organic boron complexes, and fourth compounds.
Known compounds such as a quaternary ammonium compound and a quaternary phosphonium compound can be used. Details of the technique relating to the curing accelerator are described in, for example, Hiroki Kakiuchi, "Recent Advances in Epoxy Resins" (Shokodo, 1990), Chapter 4, and references cited therein.

The resin composition of the present invention can be used by blending an amount of a filler or an additive within a range that does not impair the original properties for the purpose of imparting desired performance depending on the application. The filler may be fibrous or powdery,
Carbon black, silica, alumina, talc, mica,
Examples thereof include glass beads and glass hollow spheres.
As additives, antioxidants, heat stabilizers, antistatic agents,
Examples include plasticizers, pigments, dyes, colorants and the like. The chlorine in order to further improve the flame retardancy, bromine, and flame retardant _{phosphorus-based, Sb 2 O 3, Sb 2} O 5, NbSbO 3 · 1
A flame retardant aid such as / 4H ₂ O can also be used in combination. Furthermore, it is also possible to mix one or more kinds of other thermoplastic resins or thermosetting resins.

The cured polyphenylene ether / epoxy resin composition of the present invention is obtained by curing the curable polyphenylene ether / epoxy resin cured product described above. The method of curing is arbitrary, heat,
A method using light, an electron beam or the like can be adopted. When curing by heating, the temperature varies depending on the presence or absence of the radical initiator or the curing accelerator and the type thereof, but is 80 to
It is selected in the range of 300 ° C, more preferably 120 to 250 ° C. The time is about 1 minute to 10 hours, more preferably 1 minute to 5 hours.

The cured polyphenylene ether / epoxy resin composition thus obtained can be analyzed for resin composition by methods such as infrared absorption spectroscopy, high resolution solid state nuclear magnetic resonance spectroscopy and pyrolysis gas chromatography. .. The cured composite material of the present invention is in the form of a film, or as a laminate composed of at least one type of metal foil and / or metal plate and a cured resin composition obtained by laminating the above-mentioned metal foil and / or metal plate on at least one surface. Can be used.

The 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 overlapped, each layer is adhered under heat and pressure, and at the same time heat curing is performed to obtain a cured composite material with 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 performed simultaneously by using a hot press or the like, but both may be performed independently. That is, the uncured or semi-cured composite material obtained by laminating in advance can be cured by heat treatment or another method.

Molding and curing are carried out at a temperature of 80 to 300 ° C.
It can be carried out at a pressure of 0.1 to 1000 kg / cm ² , a time of 1 minute to 10 hours, more preferably a temperature of 120 to 250 ° C., a pressure of 1 to 100 kg / cm ² , and a time of 1 minute to 5 hours. .. The laminate of the present invention is composed of the cured composite material of the present invention and a metal foil. 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 metal foil, a cured composite material, and a metal plate.

As the method for producing the laminate, the laminate and the metal-clad laminate of the present invention, for example, the curable composite material of the present invention and a metal foil and / or a metal plate are laminated in a layered structure according to the purpose. Then, a method in which each layer is adhered under heat and pressure and at the same time heat curing is performed can be mentioned. 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 it 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 above-mentioned lamination molding and curing can be performed under the same conditions as for the cured composite material of the present invention.

[0059]

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. The following components were used in the following examples. Polyphenylene ether resin: ・ Poly (2,6-dimethyl-1,4-phenylene ether) ηsp / c = 0.54 (chloroform solution at 30 ° C., 0.5 g / dl) Epoxy resin: ・ Highly brominated bisphenol A glycidyl ether epoxy Resin Asahi Kasei Co., Ltd. AER735 Epoxy equivalent 350 350 Bromine content 48% by weight Cresol Novolac epoxy resin: Asahi Kasei Co. ECN273 Epoxy equivalent 220 Initiator: 2,5-dimethyl-2,5-di (t-butyl) Peroxy) Hexin-3 (Nippon Yushi Perhexin 25
B) Curing agent: 2E4MZ 2-Ethyl-4-methylimidazole BPR t-butylphenol resole resin (Gunei Kagaku PS2657) Glass cloth: E glass, basis weight 48 g / m ² or 1
05 g / m ²

[0060]

Examples 1 to 4 Curable polyphenylene ether / epoxy resin composition and cured polyphenylene ether / epoxy resin composition; polyphenylene ether, triallyl isocyanurate (TAIC), or triallyl cyanurate (TA)
C), the epoxy resin, the curing agent, the allyl glycidyl ether, and the initiator were mixed in the respective compositions shown in Table 1 by using a Henschel mixer, and the mixture was mixed with a press molding machine to obtain 200
It was molded and cured under conditions of 2 ° C. for 2 hours to prepare a cured product having a thickness of about 1 mm.

This cured product was treated with 5% in trichlorethylene.
No warpage or change in appearance was observed even after boiling for a minute, and dimensional stability was good.

[0062]

Examples 5 to 8 Curable composite materials: Each component was dissolved or dispersed in trichlorethylene with the respective compositions shown in Table 2. A glass cloth was immersed in this solution for impregnation and dried in an air oven to obtain a curable composite material.

Laminated body: A plurality of the above-mentioned curable composite materials are piled up so that the thickness after molding is about 0.8 mm, and a copper foil having a thickness of 35 μm is placed on both surfaces 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. The pressure was 40 kg / cm ^{2 in} all cases. Table 3 shows the physical properties.

[0064]

Comparative Examples 1 and 2 Each component was dissolved or dispersed in trichlorethylene with the respective composition shown in Table 2 without using allyl glycyl ether. This solution was impregnated in the same manner as in Examples 5 to 8 and dried in an air oven. Further, the obtained curable composite material was molded and cured in the same manner as in Examples 5 to 8 to obtain a laminate.

Various physical properties of the laminate thus obtained were measured by the following methods. 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. Dielectric constant and dielectric loss tangent were measured at 1 MHz.

3. Soldering heat resistance The laminate from which the copper foil has been removed is cut into 25 mm square pieces, and 280
Floating in a solder bath at ℃ for 120 seconds, the change in appearance was visually observed. 4. Copper foil peeling strength A test piece with a width of 20 mm and a length of 100 mm was cut out from the laminate, and after making a parallel cut with a width of 10 mm on the copper foil surface, 50 mm / min in the direction perpendicular to the surface. The copper foil was continuously peeled off at a speed, and the stress at that time was measured by a tensile tester, and the minimum value of the stress was shown.

5. Thermal expansion characteristics The laminate from which the copper foil was removed was cut into a 7 mm square, and the thermal expansion amount in the thickness direction was measured by a thermomechanical analyzer at a heating rate of 20 ° C./min. 6. Flow of resin Three curable composite materials are stacked and pressed at 170 ° C. for 10 minutes with a press molding machine at a surface pressure of 22 kg / cm ² , the protruding resin is weighed, and the curable composite material before pressing is pressed. The value divided by the weight of was shown.

All the curable composite materials had good resin flow even when left at 23 ° C. for 3 months. Further, changes with time of various physical properties of this curable composite material were not recognized. Further, the resin flowability was increased by adding allyl glycidyl ether, as is clear from the comparison between Example 5 and Comparative Example 1. Further, as is clear from the comparison between Example 5 and Comparative Example 1 and Example 6 and Comparative Example 2, by adding allyl glycidyl ether, the chemical properties and electrical properties do not change, but the linear expansion in the thickness direction. The coefficient was reduced as compared with that without allyl glycidyl ether. This indicates that the laminate of the present invention is preferable as a material for a multilayer printed wiring board.

[0069]

[Example 9] Three curable composite materials obtained in Example 5 were laminated on an aluminum plate having a thickness of 1.0 mm which had been subjected to polishing, degreasing and etching treatments, and 220 ° C, 30 minutes, 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 as compared with 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.

[0071]

[Embodiment 10] Three pieces of the curable composite material obtained in Embodiment 8 and a copper foil having a thickness of 35 μm were laminated on an aluminum plate having a thickness of 1.0 mm which had been subjected to polishing, degreasing and etching treatment, and 2
A metal-clad laminate was produced by press molding under the conditions of 20 ° C., 30 minutes and 40 kg / cm ² . When the thermal resistance of this laminate was measured by the same method as in Example 8, it was 23 ° C./W, and it was excellent in heat dissipation.

[0072]

[Table 1]

[0073]

[Table 2]

[0074]

[Table 3]

[0075]

The curable polyphenylene ether / epoxy resin composition of the present invention has the following features. 1. A specific epoxy resin and a phenol resin are used in combination, and since triallyl cyanurate and triallyl isocyanurate have an effect as a plasticizer, the resin flow at the time of pressing is good. Makes the resin flow even better.

2, excellent in storage stability, 3 at 23 ° C.
It retains a good resin flow even after storage for a month, and no deterioration in physical properties is observed after curing. 3. The components used in the resin composition have excellent compatibility with each other, and can achieve excellent heat resistance and chemical resistance after curing. The cured polyphenylene ether / epoxy resin composition of the present invention comprises (a) polyphenylene ether, (b) triallyl isocyanurate and / or triallyl cyanurate, (c) (i) brominated bisphenol polyglycidyl ether epoxy resin, ( ii) a novolak epoxy resin and (iii) a resin composition containing a phenol resin as an essential component, and (d) a compound having at least one epoxy group and having at least one unsaturated bond group. The composition is excellent in dimensional stability, and particularly in the coefficient of linear expansion in the Z direction. That is, it is considered that the addition of the component (d) causes the components (b) and (c) to chemically bond with each other via the component (d), so that a denser three-dimensional structure is formed.

Therefore, the material of the present invention can be used as a dielectric material, an insulating material, a heat-resistant material, etc. in the fields of electric industry, electronic industry, space / aircraft industry and the like. In particular, it is preferably used as a single-sided, double-sided, multi-layer printed circuit board, semi-rigid substrate, metal base substrate, prepreg for multi-layer printed circuit board. Further, the material of the present invention can be favorably 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 interphase insulating layer thickness of 200 μm or less, and a mounting circuit board because of its heat and moisture absorption resistance. ..

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display area C08L 63/02 NJW 8830-4J 63/04 NJY 8830-4J 71/12 LQM 9167-4J

Claims (9)

[Claims] 1. A polyphenylene ether of 98 to 40% by weight based on the sum of (a), (a) component and (b) component, and (b), the sum of (a) component and (b) component. As 2
~ 60 wt% triallyl isocyanurate and / or triallyl cyanurate, 10-90 wt% (i), based on the sum of (c), (a) component, (b) component and (c) component. Brominated bisphenol polyglycidyl ether epoxy resin, (i
i) a resin composition containing a novolac epoxy resin and (iii) a phenol resin as essential components, based on the sum of (d), (a) component, (b) component, (c) component and (d) component, 0 1 to 30% by weight of at least one epoxy group, and at least 1
A curable polyphenylene ether-epoxy resin composition comprising a compound having one unsaturated bond group. 2. The curable polyphenylene ether / epoxy resin composition according to claim 1, which has a bromine content of 5 to 20% by weight. 3. A cured polyphenylene ether / epoxy resin composition obtained by curing the curable polyphenylene ether / epoxy resin composition according to claim 1. 4. Based on the sum of (a), (a) component and (b) component, 98 to 40% by weight of polyphenylene ether, and (b), the sum of (a) component and (b) component. As 2
~ 60 wt% triallyl isocyanurate and / or triallyl cyanurate, 10-90 wt% (i), based on the sum of (c), (a) component, (b) component and (c) component. Brominated bisphenol polyglycidyl ether epoxy resin, (i
i) a resin composition containing a novolac epoxy resin and (iii) a phenol resin as essential components, based on the sum of (d), (a) component, (b) component, (c) component and (d) component, 0 1 to 30% by weight of at least one epoxy group, and at least 1
A compound having one unsaturated bond group, (e), (a) component, (b) component, (c) component, (d)
5 to 90% by weight based on the sum of the components and the component (e)
1. A curable composite material comprising: 5. A bromine content of 5 to 20 based on the sum of the components (a), (b), (c) and (d).
The curable composite material according to claim 4, wherein the curable composite material is wt%. 6. A cured composite material obtained by curing the curable composite material according to claim 4. 7. A laminate comprising the cured composite material according to claim 6 and a metal foil. 8. A laminated board in which an insulator 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.