JPH0632876A - New curable polyphenylene ether-epoxy resin composition - Google Patents

Abstract

PURPOSE:To obtain a new curable polyphenylene ether-epoxy resin composition. CONSTITUTION:This resin composition consists of (a) a reactional product of a polyphenylene ether and an unsaturated carboxylic acid or acid anhydride, (b) triallylisocyanurate and/or triallylcyanurate, (c) a resin composition composed of (i) a brominated bisphenol polyglycidyl ether epoxy resin, (ii) a novolak epoxy resin and (iii) a phenol resin and (d) a compound having at least one epoxy resin and at least one unsaturated bond group. This compound is impregnated into a substrate to provide the objective 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. Further, the present invention relates to a curable composite material comprising the resin composition and a base material, 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 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, 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 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.

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 having poor chemical resistance because it easily swells and dissolves in an aromatic solvent or a halogen solvent. Various methods have been proposed for blending both of them 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 are 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 containing 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. 3-19
No. 03 and Japanese Patent Application No. 3-12582 proposed improvement of chemical resistance. In Japanese Patent Application No. 3-1903, (a)
A resin composition comprising a reaction product of a polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride, (b) triallyl isocyanurate and / or triallyl cyanurate, (c) an epoxy resin and a curing agent is also applied. No. 3-12582, (a) a reaction product of a polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride,
(B) triallyl isocyanurate and / or triallyl cyanurate, (c) (i) brominated bisphenol polyglycidyl ether epoxy resin, (ii) novolac epoxy resin, (iii) resin composition containing phenol resin as an essential component Is disclosed. However, although the composition satisfies the chemical resistance, the dimensional stability, that is, the thermal expansion property is still at an insufficient level, and further low thermal expansion property is desired.

[0008]

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, Further, it is intended to provide a novel curable polyphenylene ether / epoxy resin composition which exhibits low chemical expansion properties in addition to excellent chemical resistance, heat resistance and flame retardancy after curing.

[0009]

The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, (a) a reaction product of a polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride, (B) triallyl isocyanurate and / or triallyl cyanurate, (c) (i) brominated bisphenol polyglycidyl ether epoxy resin, (ii) novolac epoxy resin, (iii) phenol resin and at least 1 as component (d) Curable polyphenylene ether / epoxy resin composition having excellent storage stability, film-forming property, and melt flowability of resin by adding a compound having one epoxy group and at least one unsaturated bond group In addition to chemical resistance, heat resistance, and flame retardancy, it has a glass transition temperature after curing. And completed the present invention found that showing the linear expansion coefficient. The present invention consists of the following seven inventions.

That is, the first aspect of the present invention is (a), (a)
98-40% by weight based on the sum of the component and the component (b)
2 to 60% by weight of triallyl isocyanurate and / or, based on the reaction product of polyphenylene ether and unsaturated carboxylic acid or acid anhydride, (b), the sum of components (a) and (b). Triallyl cyanurate,
10-90% by weight of (i) brominated bisphenol polyglycidyl ether epoxy resin, based on the sum of (c), (a) component, (b) component and (c) component, (i
0 based on the sum of i) a novolac epoxy resin and (iii) a resin composition containing a phenol resin as an essential component, (d), (a) component, (b) component, (c) component and (d) component. A curable polyphenylene ether-epoxy resin composition comprising: 1 to 30% by weight of a compound having at least one epoxy group and at least one unsaturated bond group.

A second aspect of the present invention provides a cured polyphenylene ether / epoxy resin composition having a glass transition temperature 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 having one glass transition temperature obtained by curing the curable composite material of the third invention. 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 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]

Examples of the lower alkyl group represented by R _{1 to} R ₄ in the general formula (A) include methyl group, ethyl group, 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),
A compound group represented by the following four kinds of general formula (2) can be given.

[0017]

[Chemical 2]

As a specific example, 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 not only the unit represented by the general formula (A) but also the unit represented by the following general formula (5). 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 Coalescing,
Copolymer of 2,6-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.
No. 22, JP-A-1-297428, and copolymers containing the units of general formulas (A) and (B) are disclosed. 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 for a curable resin composition that places importance on molten resin flow, for example, a prepreg for a multilayer 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 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 and the like. Particularly, maleic anhydride and fumaric acid are most preferably used. The reaction is carried out by heating the polyphenylene ether resin and the unsaturated carboxylic acid or acid anhydride in the temperature range of 100 ° C to 390 ° 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 the unsaturated carboxylic acid or the acid anhydride is 0.01 to 5. With respect to 100 parts by weight of the polyphenylene ether resin.
It is 0 parts by weight, preferably 0.1 to 3.0 parts by weight.

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.

[0028]

[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 flow of resin 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).

[0031]

[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).

[0033]

[Chemical 9]

Among 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 phenolic resin used as one of the components (c) has two or more phenolic hydroxyl groups in one molecule, and includes phenol, cresol, xylenol, propylphenol, amylphenol, butylphenol, octylphenol and phenylphenol. , Novolac resin and resol resin which are synthesized from allylphenol, bisphenol A, etc. alone or in combination with them. Of these, novolak resins and resole resins synthesized from butylphenol or phenylphenol are (a), (b), and (c)-
Since it has excellent compatibility with each of the components (i) and (c)-(ii), it can be best used in the present invention.
Combinations of more than one species are used.

Of the above-mentioned component (c), the brominated bisphenol polyglycidyl ether epoxy resin is indispensable for imparting flame retardancy, and the novolac epoxy resin is indispensable for improving the chemical resistance and heat resistance by improving the crosslink density. Phenolic resin also acts as a curing agent for these epoxy resins,
Compared with other epoxy resin curing agents, it has the feature of being excellent in storage stability after resin blending.

In addition to the above, other epoxy resins may be blended in the component (c) as long as the properties such as flame resistance, 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 mixing ratio of the component (a) and the component (b) is based on the sum of the two components (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.

If the amount of the component (b) is less than 2% by weight, the chemical resistance is not sufficiently 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. Further, if the ratio of the component (a) to the component (b) is outside the above range, the film obtained by the casting method is very brittle and has a sticky surface, which is not preferable.

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 by 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 blending ratio of the novolac epoxy resin, but the content of bromine based on the sum of the components (a) to (d) should be 5% by weight or more and 20% by weight or less. It is preferable to use a brominated bisphenol polyglycidyl ether epoxy resin for imparting flame retardancy.

The proportion of the phenolic resin in the component (c) is such that the amount of phenolic hydroxyl groups in the resin is 0.5 to 1.5 equivalents, more preferably 0.6. It is advisable to adjust the concentration to be in the range of 1.2 equivalents. The mixing ratio of the component (d) is the component (a),
The amount is 0.1 to 30% by weight, preferably 0.1 to 20% by weight, 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 not sufficiently improved, which is not preferable. On the other hand, if it is less than 0.1% by weight, the linear expansion coefficient is not sufficiently reduced, 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 preferred halogen content for imparting flame retardancy is 5% by weight or more, more preferably 10% by weight or more, based on the sum of the components (a) to (d). 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. The base material used in the present invention includes "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 cellulosic 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. Component (e) in the curable composite material of the present invention The base material occupies 5 to 90% by weight, more preferably 10 to 80% by weight, based on 100 parts by weight of the curable composite material.
More preferably, it is 20 to 70% by weight. If the amount of the base material is less than 5% 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 retardancy of the composite material will be inferior.

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. Moreover, 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 ground 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 a method for mixing the four components (a) to (d) described 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 depending on 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 the 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. The method of 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. 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.

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 Ruperoxide, 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 such as 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 should be used by blending the filler and the additive in an amount within a range that achieves the purpose of imparting desired performance depending on the application and does not impair the original properties. You can The filler may be fibrous or powdery, and examples thereof include carbon black, silica, alumina, talc, mica, glass beads and glass hollow spheres. Examples of the additives include antioxidants, heat stabilizers, antistatic agents, plasticizers, pigments, dyes, colorants and the like. For the purpose of further improving flame retardancy, chlorine-based, bromine-based, phosphorus-based flame retardants, Sb ₂ O ₃ and Sb ₂ O
₅ , a flame retardant aid such as NbSbO ₃ .1 / 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 is performed by heating, the temperature is 80 to 30 though it varies depending on the presence or absence of a radical initiator or a curing agent and the type thereof.
It is selected in the range of 0 ° 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 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 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 performed simultaneously by using a hot press or the like, but both may be performed 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 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, and 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. The laminated plate is also composed of a cured composite material and a metal plate, and the 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 may be mentioned in which each layer is bonded 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.

Besides 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. In the following examples and comparative examples, the following components were used. Polyphenylene ether resin: Poly (2,6-dimethyl-1,4-phenylene ether) ηsp / c = 0.54 (30 ° C., 0.5 g / dl chloroform solution) Poly (2,6-dimethyl-1) , 4-phenylene ether) ηsp / c = 0.60 (chloroform solution at 30 ° C. and 0.5 g / dl) Epoxy resin: Highly brominated bisphenol A glycidyl ether epoxy resin Asahi Kasei Co., Ltd. AER735 epoxy equivalent
350 Bromine content 48% by weight-cresol novolac epoxy resin Asahi Kasei Corporation ECN273 epoxy equivalent
220 Initiator: 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 (NOF 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]

[Reference Example 1] Poly (2, having a viscosity number ηsp / c of 0/54 measured at 30 ° C. in a chloroform solution of 0.5 g / dl.
6-dimethyl-1,4-phenylene ether) 100 parts by weight, maleic anhydride 1.5 parts by weight, and 2,5-
After dry blending 1.0 part by weight of dimethyl-2,5-di (t-butylperoxy) hexane (Perhexa25B manufactured by NOF CORPORATION) at room temperature, the cylinder temperature was 30.
Extrusion was carried out by a twin-screw extruder under the conditions of 0 ° C. and screw rotation speed of 230 rpm. This reaction product is designated as A.

[0061]

[Reference Example 2] Reaction product, 100 parts by weight of poly (2,6-dimethyl-1,4-phenylene ether) having a viscosity number ηsp / c of 0.60 measured by the same method as in the measurement of A,
After dry blending 1.5 parts by weight of maleic anhydride at room temperature, the cylinder temperature was 300 ° C. and the screw rotation speed was 23.
It was extruded by a twin-screw extruder under the condition of 0 rpm. This reaction product is designated as B.

[0062]

Examples 1-4 Curable polyphenylene ether / epoxy resin composition and cured polyphenylene ether / epoxy resin composition: reaction product A or B, triallyl isocyanurate, epoxy resin, curing agent, allyl glycidyl ether, and initiation. The agents were mixed with the composition shown in Table 1 using a Henschel mixer, and the mixture was pressed at 200 ° C. for 2 hours.
It was molded and cured under the condition of time to prepare a cured product having a thickness of about 1 mm.

This cured product was added to trichloroethylene at 5
No warpage or change in appearance was observed even after boiling for a minute, and the dimensional stability was good.

[0064]

Example 5 A film composed of a curable polyphenylene ether / epoxy resin composition and a film obtained by curing: a reaction product A, triallyl isocyanurate, an epoxy resin, a curing agent, an allyl glycidyl ether, and an initiator. It was dissolved in chloroform with the same composition as in Example 1. This solution was cast on a Teflon dish to obtain a film. The obtained film had a thickness of about 100 μm, and the film had no stickiness and had excellent film forming properties.

After drying in an air oven, the obtained film was laminated and cured by a vacuum press molding machine to prepare a cured product having a thickness of 1 mm. This cured product showed good warpage and no change in appearance even after boiling with trichlorethylene for 5 minutes, and had good dimensional stability.

[0066]

Examples 6 to 17 Curable composite material: Each component having the composition shown in Table 2 and Table 3 was dissolved or dispersed in trichlorethylene. A glass cloth was immersed in this solution for impregnation and dried in an air oven.

Laminate: A plurality of the above-mentioned curable composite materials are superposed 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 for each example are shown in Tables 2 and 3. Pressure is 40 kg / cm ²
And Physical properties are shown in Tables 4 and 5.

[0068]

Comparative Examples 1 to 6 Each component was dissolved or dispersed in trichlorethylene with the composition shown in Tables 2 and 3 without using allyl glycyl ether. This solution was used in Examples 6-17.
Impregnation was performed in the same manner as in (1) and dried in an air oven. The obtained curable composite material was molded and cured in the same manner as in Examples 6 to 17 to obtain a laminate. Physical properties are shown in Tables 4 and 5.

The physical properties of the thus obtained laminate 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 having a width of 20 mm and a length of 100 mm was cut out from the laminate, and after making a parallel cut having 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, 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 laminated body 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. Resin flow 3 layers of curable composite material are stacked and pressed at 170 ° C. for 10 minutes by 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 The value divided by the weight of was shown.

The curable composite materials of Examples 6 to 17 and Comparative Examples 1 to 6 had good resin flowability even after being left at 23 ° C. for 3 months. Further, changes with time of physical properties of this curable composite material were not recognized. When the dynamic properties of the laminate were measured using a dynamic viscoelasticity spectrometer, the glass transition temperature was 1 in all cases and was 210 to 220 ° C. This means that the compatibility of each component is good, and as a result, it can be considered that a high glass transition temperature and good chemical resistance were achieved.

Further, by adding allyl glycidyl ether from Examples 6 to 8 and Comparative Examples 1 to 3, the chemical and electrical properties were not changed, but the linear expansion coefficient in the thickness direction was not added with allyl glycidyl ether. It can be seen that it is reduced compared to. This indicates that the laminate of the present invention is preferable as a material for a multilayer printed wiring board.

Further, it is understood from the comparison between Examples 12 to 14 and Comparative Example 1 or the comparison between Examples 15 to 17 and Comparative Example 5 that the resin flowability is increased by adding allyl glycidyl ether. These results indicate that the laminate of the present invention is preferable as a material for a multilayer printed wiring board.

[0075]

Example 18 Three pieces of the curable composite material obtained in Example 6 were laminated on an aluminum plate having a thickness of 1.0 mm which had been subjected to polishing, degreasing and etching treatment, and 220 ° C., 30 minutes, 40
A laminate was produced by press molding under the condition of kg / 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.

[0077]

Example 19 Three curable composite materials obtained in Example 10 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,
A metal-clad laminate was produced by press molding at 220 ° C. for 30 minutes under the conditions of 40 kg / cm ² .

The heat resistance of this laminate was measured by the same method as in Example 18 and found to be 23 ° C./W, which was excellent in heat dissipation.

[0079]

[Table 1]

[0080]

[Table 2]

[0081]

[Table 3]

[0082]

[Table 4]

[0083]

[Table 5]

[0084]

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 the acid anhydride can be produced inexpensively by using an extruder or the like, an economically excellent resin composition is provided. it can.

2. The above reaction products are excellent in solvent film-forming property, so that a film or curable composite material having excellent handleability without stickiness on the surface can be obtained. 3. 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.

4, excellent in storage stability, 3 at 23 ° C.
Good resin flow is retained even after storage for a month, and no deterioration in physical properties is observed after curing. 5. The components used in the resin composition have excellent compatibility with each other, and the glass transition temperature after curing becomes one, and excellent heat resistance, chemical resistance and low linear expansion coefficient can be realized.

The cured polyphenylene ether / epoxy resin composition of the present invention comprises (a) a reaction product of a polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride, (b)
Triallyl isocyanurate and / or triallyl cyanurate, (c)-(i) brominated bisphenol polyglycidyl ether epoxy resin, (c)-(ii)
A resin composition containing a novolac epoxy resin and a (c)-(iii) phenol resin as essential components, and (d)
Having at least one epoxy group and at least one
It is composed of a compound having an unsaturated bond group,
The composition is excellent in dimensional stability, particularly in the coefficient of linear expansion in the Z direction. That is, by adding the component (d), the components (a) to (c), which are compatible with each other at the molecular level, chemically bond through the component (d), so that a denser three-dimensional structure is formed. , And is considered to exhibit a single glass transition temperature.

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. Particularly, it is suitably used as a single-sided, double-sided, multi-layer printed circuit board, semi-rigid substrate, metal base substrate, and 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 resistance and moisture absorption resistance. .

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[Procedure amendment]

[Submission date] June 14, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0020

[Correction method] Change

[Correction content]

[0020]

[Chemical 4]

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display area C08L 63/00 NJY 8830-4J

Claims (11)

[Claims] 1. A reaction product of 98 to 40% by weight of polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride, based on (a), the sum of components (a) and (b), (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), component (a), component (b) and component (c). Brominated bisphenol polyglycidyl ether epoxy resin, (i
i) a resin composition containing a novolac epoxy resin and (iii) a phenol resin as essential components, and based on the sum of (d), (a) component, (b) component, (c) component and (d) component, 0 A curable polyphenylene ether-epoxy resin composition comprising 1 to 30% by weight of a compound having at least one epoxy group and at least 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 film comprising the resin composition according to claim 1 or 2. 4. A cured polyphenylene ether / epoxy resin composition having one glass transition temperature obtained by curing the curable polyphenylene ether / epoxy resin composition according to claim 1. 5. A film obtained by curing the film of claim 3. 6. A reaction product of 98 to 40% by weight of polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride, based on (a), the sum of (a) component and (b) component, (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), component (a), component (b) and component (c). Brominated bisphenol polyglycidyl ether epoxy resin, (i
i) a resin composition containing a novolac epoxy resin and (iii) a phenol resin as essential components, and based on the sum of (d), (a) component, (b) component, (c) component and (d) component, 0 1 to 30% by weight of a compound having at least one epoxy group and at least one unsaturated bond group, (e), component (a), component (b), component (c), (d) )
5 to 90% by weight based on the sum of the components and the component (e)
1. A curable composite material, comprising: 7. A component (a), a component (b), a component (c),
And the bromine content is 5 based on the sum of the components (d).
The curable composite material according to claim 6, which is 20% by weight. 8. A cured composite material having a glass transition temperature, which is obtained by curing the curable composite material according to claim 6. 9. A laminate comprising the cured composite material according to claim 8 and a metal foil. 10. A laminated board in which an insulator made of the cured composite material according to claim 8 is laminated on a metal base. 11. An insulating layer made of the cured composite material according to claim 8 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.