JPH08239567A - New curable polyphenylene ether resin composition and composite material and laminated material produced by using the composition - Google Patents

Abstract

PURPOSE: To obtain the subject resin composition containing a reaction product of a polyphenylene ether with an unsaturated carboxylic acid or its acid anhydride, having excellent dielectric properties, free from evaporation loss of the components to keep stable compounding ratios and suitable as a prepreg for multi-layer printed circuit board. CONSTITUTION: This resin composition is composed of (A) a reaction product of a polyphenylene ether with an unsaturated carboxylic acid or its acid anhydride, (B) triallyl (iso)cyanurate, (C) an epoxy resin and (D) an inorganic filler. The amounts of the components A and B are 98-40 pts.wt. and 2-60 pts.wt. based on 100 pts.wt. of A+B, respectively, the amounts of A+B and C are 99-1 pt.wt. and 1-99 pts.wt. based on 100 pts.wt. of A+B+C, respectively and the amounts of A+B+C and D are 99-10 pts.wt. and 1-90 pts.wt. based on 100 pts.wt. of A+B+C+D, respectively. The composition is preferably further incorporated with (E) dicumyl peroxide and/or α,α'-bis(t-butylperoxy-m-isopropyl) benzene.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel curable polyphenylene ether resin composition and a cured product obtained by curing the same. Furthermore, the present invention relates to a composite material composed of the resin composition and a base material, a cured product thereof, and a laminate composed of the cured product and a metal foil.

[0002]

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. Further, the dimensional stability is poor, which causes a problem when designing a high frequency circuit.

As a new material for solving this problem, polyphenylene ether has attracted attention in recent years and its application to copper clad laminates has been attempted. However, control of specific permittivity and high dimensional stability are required for the design of high frequency circuits, and there is no material that satisfies all of these. Further, from the viewpoint of high density mounting of components, multilayering of printed wiring boards is becoming more important, and a material having high adhesive strength between prepregs is required.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, without impairing the excellent dielectric properties of polyphenylene ether,
Controls the dielectric constant, and shows excellent dimensional stability after curing, and excellent chemical resistance and heat resistance. Furthermore, in the case of a composite material, a curable polyphenylene ether resin composition having high interlayer adhesion strength is used. It is to be provided.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found a resin composition that meets the object of the present invention and completed the present invention. It was. That is, the present invention comprises the following six inventions.

The first aspect of the present invention is (a) a reaction product of a polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride, (b) a triallyl isocyanurate and / or a triallyl cyanurate, and (c) an epoxy resin. And (d) a curable polyphenylene ether resin composition comprising an inorganic filler, wherein the sum of the components (a) and (b) is 1
The component (a) is 98-40 parts by weight, the component (b) is 2-60 parts by weight, and (a)-
(A) + based on 100 parts by weight of the sum of components (c)
The component (b) is 99 to 1 parts by weight, the component (c) is 1 to 99 parts by weight, and the components (a) to (c) are based on 100 parts by weight of the sum of the components (a) to (d). 99-10 parts by weight,
A curable resin composition, wherein the component (d) is 1 to 90 parts by weight.

The second aspect of the present invention is (a) a reaction product of a polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride, (b) a triallyl isocyanurate and / or a triallyl cyanurate, and (c) an epoxy resin. , (D)
Inorganic filler, and (e) dicumyl peroxide and / or α, α′-bis (t-butylperoxy-m-
A curable polyphenylene ether resin composition composed of (isopropyl) benzene, wherein the component (a) is 98 to 40 based on 100 parts by weight of the sum of the components (a) and (b).
Parts by weight, 2 to 60 parts by weight of the component (b), and 99 to 1 parts by weight of the component (a) + (b) based on 100 parts by weight of the sum of the components (a) to (c), (c ) 1 component
To 99 parts by weight and the sum of components (a) to (d) 10
The components (a) to (c) are 99 to 10 based on 0 parts by weight.
Parts by weight, the component (d) is 1 to 90 parts by weight, and the component (e) is 0.1 to 10 parts by weight based on 100 parts by weight of the sum of the components (a) and (b). A characteristic curable resin composition.

The third aspect of the present invention is a cured resin composition obtained by curing the curable resin composition of the first or second aspect. A fourth aspect of the present invention is a curable composite material comprising the curable resin composition of the first or second aspect of the invention and a substrate. A fifth aspect of the present invention is a cured composite material obtained by curing the curable composite material of the fourth aspect. A sixth aspect of the present invention is a laminate comprising the cured composite material of the fifth aspect and a metal foil. 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).

Embedded image [In the formula, m is an integer of 1 to 6, J is a polyphenylene ether chain substantially composed of a unit represented by the following formula (A),

[0010]

Embedded image (Here, R _{1 to} R ₄ each independently represent a lower alkyl group, an aryl group, a haloalkyl group, a halogen atom, or a hydrogen atom.) Q represents a hydrogen atom when m is 1, and when m is 2 or more, It represents a residue of a polyfunctional phenol compound having 2 to 6 phenolic hydroxyl groups in one molecule and having a polymerization inactive substituent at the ortho and para positions of the phenolic hydroxyl group. ]

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. Typical examples of Q in the general paper (1) include the compounds represented by the following four general formulas.

[0012]

Embedded image

(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) Represents a derivative, oxygen, sulfur, a sulfonyl group, a carbonyl group, Y represents an aliphatic hydrocarbon residue and a substituted derivative thereof, an aromatic hydrocarbon residue and a substituted derivative thereof, an aralkyl group and a substituted derivative thereof, Z is oxygen, sulfur, sulfonyl group, a carbonyl group, two phenyl groups attached directly a _2, a ₂ and Y,
All the bonding positions of A ₂ and Z represent the ortho position and the para position of the phenolic hydroxyl group, r is 0 to 4, and s is an integer of 2 to 6. ) Specific examples include compounds having the following structural unit.

[0014]

[Chemical 4]

[0015]

Embedded image The polyphenylene ether chain represented by J in the general formula (1) contains a unit represented by the following general formula (B) in addition to the unit represented by the general formula (A). Good.

[0016]

[Chemical 6] [In the formula, R _{5 to} R ₉ each independently represent a hydrogen atom, a halogen atom, a lower alkyl group, an aryl group or a haloalkyl group, and R ₁₀ and R ₁₁ are not hydrogen at the same time. ]

As an example of the unit of the general formula (B),

[Chemical 7] Etc.

A preferred example of the polyphenylene ether resin of the general formula (1) used in the present invention is poly (2,6) obtained by homopolymerization of 2,6-dimethylphenol.
-Dimethyl-1,4-phenylene ether), styrene graft polymer of poly (2,6-dimethyl-1,4-phenylene ether), copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, 2,
Copolymer of 6-dimethylphenol and 2-methyl-6-phenylphenol, 2,6-dimethylphenol and polyfunctional phenol compound: compound represented by general formula (2)

[0019]

Embedded image (In the formula, m is an integer of 1 to 6, Q represents hydrogen when m is 1, and when m is 2 or more, it has 2 to 6 phenolic hydroxyl groups in one molecule and is phenolic. A polyfunctional polyphenylene ether resin obtained by polymerization in the presence of a polyfunctional phenol residue having a polymerization-inert substituent at the ortho-position and the para-position of the hydroxyl group.
Examples thereof include copolymers containing units of the general formulas (A) and (B) as disclosed in JP-A-3-301222 and JP-A-1-297428.

Regarding the molecular weight of the polyphenylene ether resin described above, the viscosity number ηsp / c measured at 30 ° C. in a chloroform solution of 0.5 g / dl is 0.1 to 1.0.
Those in the range can be used satisfactorily. 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-mentioned polyphenylene ether resin with an unsaturated carboxylic acid or an acid anhydride, and is substantially polymerizable due to the acid or the acid anhydride. It is a reaction product containing no double bond. The reaction product is probably a mixture of different products with different chemical structures,
Not all of their chemical structures have been elucidated. H. Glans, M .; K. Akka
peddi, Macromolecules, vol
The following chemical structures described in 1991, 24, 383 to 386 are given as examples.

[0022]

[Chemical 9]

Examples of suitable acids and acid anhydrides include acrylic acid, methacrylic acid, maleic anhydride, fumaric acid,
Examples thereof include itaconic acid, itaconic anhydride, glutaconic anhydride, citraconic anhydride and the like. Particularly, maleic anhydride and fumaric acid are most preferably used. The reaction was carried out by mixing the polyphenylene ether resin with an unsaturated carboxylic acid or acid anhydride 10 times.
It is performed by heating in the temperature range of 0 ° C to 390 ° C. At this time, a radical initiator may coexist. Although both a solution method and a melt mixing method can be used as the reaction method, the melt mixing method using an extruder or the like can be carried out more easily and is suitable for the purpose of the present invention.

The proportion of unsaturated carboxylic acid or acid anhydride is 100 parts by weight of polyphenylene ether resin.
It is 0.01 to 5.0 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 present invention is a trifunctional monomer represented by the following structural formula.

[0025]

[Chemical 10]

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 epoxy resin used as the component (c) of the present invention may be one having two or more epoxy groups in one molecule, and may be used alone or in combination of two or more. As a typical example, a glycidyl ether type epoxy resin obtained by the reaction of phenols or alcohols with epichlorohydrin, a glycidyl ester type epoxy resin obtained by the reaction of carboxylic acids with epichlorohydrin, amines or cyanuric acid with epichlorohydrin and Glycidyl amine type epoxy resin obtained by the reaction of, internal epoxy resin obtained by the oxidation of the double bond, etc. (For details of these, for example, Masaki Shinbo,
"Epoxy Resin Handbook" (Nikkan Kogyo Shimbun, 19
87)].

As the curing agent, usual epoxy resin curing agents such as polyamine type curing agents, acid anhydride type curing agents, polyphenol type curing agents, polymercaptan type curing agents, anionic polymerization type catalyst type curing agents, and cations are used. Polymerization type catalyst type curing agents, latent type curing agents and the like can be used [For details, for example, Masaki Shinbo, "Epoxy Resin Handbook" (published by Nikkan Kogyo Shimbun 1987), Soichi Muroi, Shuichi Ishimura,
"Introduction to Epoxy Resin" (Published by Japan Society of Polymer Publishing, 1988)
Etc.]].

The inorganic filler used as the component (d) of the present invention includes glass balloons, silica balloons, silica,
Alumina, titanium dioxide, aluminum oxide, talc,
Examples thereof include mica, glass beads, and barium titanate, which may be used alone or in combination of two or more, but are not limited thereto. Since the balloon-shaped inorganic filler is hollow, it has the effects of suppressing the dielectric constant to a low level, reducing the dielectric loss, and improving dimensional stability and heat resistance. The particle size is preferably 100 μm or less.

By using an inorganic filler having a high dielectric constant such as silica, alumina or titanium dioxide, the dielectric constant of a molded product made of a curable polyphenylene ether resin composition containing the same can be arbitrarily controlled over a wide range. . The peroxide used as the component (e) of the present invention is dicumyl peroxide and / or α, α′-.
Bis (t-butylperoxy-m-isopropyl) benzene.

Of the five components (a) to (e) described above, the compounding ratio of the component (a) and the component (b) is the sum of the two components.
98 to 40 parts by weight of the component (a) based on 0 parts by weight,
The component (b) is 2 to 60 parts by weight, more preferably the component (a) is 95 to 50 parts by weight, and the component (b) is 5 to 50 parts by weight.
The range is parts by weight.

When the amount of the component (b) is 2 parts by weight or less, the chemical resistance is insufficiently improved, which is not preferable. On the other hand, if the amount exceeds 60 parts by weight, the dielectric properties, flame retardancy, and moisture absorption properties deteriorate, and the material becomes extremely brittle after curing, which is not preferable. Further, when a resin composition is impregnated into glass cloth or the like to prepare a prepreg and a plurality of prepregs are laminated to form a cured composite material, the adhesive strength between the prepregs is significantly reduced, which is not preferable.

The mixing ratio of the component (c) is from (a) to
(A) + based on 100 parts by weight of the sum of components (c)
The component (b) is in the range of 99 to 1 part by weight, the component (c) is in the range of 1 to 99 parts by weight, more preferably (a) + (b) component is 90 to 10 parts by weight, and the component (c) is 10 to 10 parts by weight. It is in the range of 90 parts by weight. If the amount of the component (c) is less than 1 part by weight, the adhesiveness with the metal foil will not be improved. On the other hand, if the amount of component (c) exceeds 99 parts by weight, the dielectric properties will deteriorate, which is not preferable. In the present invention, when 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, and more preferably 10% by weight or more, based on the sum of components (a) to (c).

The mixing ratio of the component (d) is from (a) to
(A) -based on 100 parts by weight of the sum of the components (c)
Component (c) is 99 to 10 parts by weight, component (d) is 1 to 90.
Parts by weight, preferably 1 to 80 parts by weight, more preferably 1
˜70 parts by weight.

When the amount of the component (d) exceeds 90 parts by weight, the chemical resistance is insufficient, and when it is bonded to a metal foil as described later, the adhesive strength cannot be obtained, which is not preferable. further,
The use of a composite material is not preferable because the adhesive strength between the above prepregs is significantly reduced. On the other hand, when the amount of the component (d) is less than 1 part by weight, it is difficult to improve the dimensional stability or control the dielectric constant, which is not preferable.

The mixing ratio of the component (e) is 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the sum of the components (a) and (b). Parts by weight.
It is more preferably in the range of 1 to 6 parts by weight. If the amount of component (e) exceeds 10 parts by weight, the electrical characteristics will be poor and this is not preferred. On the contrary, when the amount of the component (e) is less than 0.1 parts by weight, the curing with the peroxide cannot be sufficiently effectively performed, which is not preferable.

A base material can be added to the curable resin composition of the present invention in order to enhance mechanical strength and dimensional stability. As the substrate used in the present invention, 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; polyvinyl alcohol fiber, polyester fiber, Woven or non-woven fabric obtained from synthetic fibers such as acrylic fiber, wholly aromatic polyamide fiber, polytetrafluoroethylene fiber; natural fiber cloth such as cotton cloth, linen cloth, felt; carbon fiber cloth; kraft paper, cotton paper, paper-glass blend Natural cellulose-based papers such as fine paper are 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% by weight, more preferably 10 to 80% by weight, further preferably 20 to 70% by weight, based on 100 parts by weight of the curable composite material. Is. 5% by weight of base material
When it is less, 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 in the range of 5 to 200 μm, more preferably 5 to 105 μm.

As a method for mixing the above-mentioned components (a) to (e), there are a solution mixing method in which the five components are uniformly dissolved or dispersed in a solvent, or a melt blending method in which heating is performed by an extruder or the like. Available. Solvents used for solution mixing include halogen-based solvents such as dichloromethane, chloroform and trichloroethylene; benzene, toluene,
Aromatic solvents such as 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, it is possible to obtain a sheet of the present resin composition by laminating several to several tens of films of the present resin composition prepared by a casting method and heating and melting the film by a heating and melting method, for example, using a press molding machine.

As the method for producing the curable composite material of the present invention, for example, the components (a) to (e) 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.

A coupling agent may be used in the curable composite material of the present invention, 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.

Other peroxides may be added to the peroxide of the present invention in addition to the above-mentioned peroxide of the component (e) as long as the original performance is not impaired. Representative examples are benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy). ) Hexin-3, di-t-butyl peroxide, t-butyl cumyl peroxide, 2,5-
Dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis (t-butylperoxy) butane, 2,2 There are peroxides such as -bis (t-butylperoxy) octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxide and trimethylsilyltriphenylsilylperoxide. It is not limited to these. Although not a peroxide, 2,3-dimethyl-2,3-diphenylbutane can also be used as a radical initiator.

The resin composition of the present invention may 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.
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. In the composite material including the base material, a combination of brominated diphenyl ethers and antimony oxide or a combination of brominated diphenylethanes and antimony oxide is preferably used. Furthermore, it is also possible to mix one or more kinds of other thermoplastic resins or thermosetting resins.

The curable resin composition of the present invention is obtained by curing the curable resin cured product described above. The curing method is arbitrary, and 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 120 to 250 ° C., although it varies depending on the presence or absence of the radical initiator and the curing agent and the type thereof. The time is in the range of 1 minute to 10 hours, more preferably 1 minute to 5 hours.

The resin composition of the obtained cured resin composition can be analyzed by a method 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 carried out simultaneously using a hot press or the like, but both may be carried out separately. 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. Laminates composed of a cured composite material and a metal plate, and metal-clad laminates composed of a metal foil, a cured composite material, and a metal plate can also be manufactured.

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.

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, and examples of the adhesive include epoxy-based, acrylic-based, phenol-based, and cyanoacrylate-based adhesives, 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.

[0052]

EXAMPLES The present invention will be described below 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. 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.
100 parts by weight of 6-dimethyl-1,4-phenylene ether), 1.5 parts by weight of maleic anhydride, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane [Perhexa 25B manufactured by NOF CORPORATION] ] After 1.0 part by weight was dry blended at room temperature, the cylinder temperature was 30.
It was extruded by a twin-screw extruder under the conditions of 0 ° C. and a screw rotation speed of 230 rpm. This reaction product is designated as A.

Reference Example 2 100 parts by weight of poly (2,6-dimethyl-1,4-phenylene ether) having a viscosity number ηsp / c of 0.40 measured by the same method as in Reference Example 1,
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. In the examples described below, the following components were used.

Epoxy resin: bisphenol A glycidyl ether epoxy resin (Asa 331 AER331 epoxy equivalent 18
9) ・ Low brominated bisphenol A glycidyl ether epoxy resin (Asahi Kasei AER711 epoxy equivalent 475 bromine content 20 wt%) ・ Highly brominated bisphenol A glycidyl ether epoxy resin (Asahi Kasei AER735 epoxy equivalent 350 bromine content 48 wt%) ・ Cresol novolac epoxy Resin (Asahi Kasei ECN
273 epoxy equivalent 217)

Initiator: -Dicumyl peroxide (NOF Park Mill D) -α, α'-bis (t-butylperoxy-m-isopropyl) benzene (NOF Perbutyl P) Curing agent: 2E4MZ: 2-Ethyl -4-Methylimidazole 2MZ: 2-Methylimidazole DDM: 4,4'-diaminodiphenylmethane

Example 1 The reaction product prepared in Reference Example 1, the triallyl isocyanurate, the epoxy resin, the silica balloon, the initiator, the flame retardant and the flame retardant auxiliary were dissolved in chloroform with the composition shown in Table 1. Alternatively, it was dispersed and poured onto a Teflon plate to form a film. The resulting film has a thickness of about 1
It was 00 μm. The film forming property was good.

After drying this film in an air oven, a plurality of films were laminated and then vacuum-pressed at 200 ° C. × 6.
It was molded and cured under the condition of 0 minutes to obtain a cured product having a thickness of about 1 mm. No change was observed in the appearance of this cured product after boiling in trichlorethylene for 5 minutes. The physical properties are shown in Table 2. Significant effects were seen on the dielectric constant and dimensional stability. Further, even when an inorganic filler was included, sufficient adhesive strength between the prepregs was obtained.

(Examples 2 and 3) The reaction products prepared in Reference Examples, triallyl isocyanurate, epoxy resin silica balloons, initiators, flame retardants and flame retardant auxiliaries were added to trichloroethylene in the compositions shown in Table 1. Dissolved or dispersed. A glass cloth was immersed in this solution for impregnation and dried in an air oven.

A plurality of the curable composite materials were superposed so that the thickness after molding was about 0.8 mm, and copper foil having a thickness of 35 μm was superposed on both surfaces of the curable composite material.
A laminate was obtained by molding at 0 ° C. × 40 kg / cm ² and curing. The physical properties of the thus obtained laminate were measured by the following methods, and as shown in Table 2, remarkable effects were observed in the dielectric constant and dimensional stability.

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. Linear expansion coefficient 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 rate of temperature increase of 20 ° C / min. 6. Adhesive strength between prepregs A test piece having a width of 20 mm and a length of 100 mm was cut out from the laminate, and after removing the copper foil, a parallel cut having a width of 10 mm was made on the substrate surface, and then 50 mm / min in the direction perpendicular to the surface. The prepreg in the surface layer portion was continuously peeled off at the speed of, and the stress at that time was measured by a tensile tester, and the minimum value of the stress was shown.

Example 4 A laminated body was obtained under the same conditions as in Examples 2 and 3 except that the silica balloon was replaced with alumina and the composition shown in Table 1 was used. Table 2 shows the physical properties of the obtained laminate. A laminate having a desired dielectric constant and excellent dimensional stability was obtained. (Example 5) Replacing the silica balloon with titanium dioxide,
A laminated body was obtained under the same conditions as in Examples 2 and 3 except that the composition shown in Table 1 was used. Table 2 shows the physical properties of the obtained laminate. A laminate having a desired dielectric constant and excellent dimensional stability was obtained.

Comparative Example 1 A film was prepared under the same conditions except that the silica balloon was not used in the composition shown in Example 1. Table 2 shows the physical properties of the obtained cured product.
Dielectric constant was higher than that with silica balloon. (Comparative Examples 2 and 3) A laminate was obtained under the same conditions as in Examples 2 to 5, except that the composition shown in Table 1 was used without using the inorganic filler. Table 2 shows the physical properties of the obtained laminate. From the comparison between Example 2 and Comparative Example 2 and the comparison between Example 3 and Comparative Example 3, those that did not use the inorganic filler had a large linear expansion coefficient.

[0065]

[Table 1]

[0066]

[Table 2]

[0067]

The curable polyphenylene ether resin composition of the present invention has excellent dielectric properties and can control the dielectric constant over a wide range. Further, since a peroxide that is solid at room temperature is used, there is little possibility of evaporation and the like, and it is possible to maintain the desired blending amount as it is. It also has excellent heat resistance and dimensional stability,
It is useful as a dielectric material, insulating material, and heat resistant material in the fields of space and aircraft industries. 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.
Especially when it is used as a printed circuit board, a material having a high adhesive strength between prepregs can be provided.

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Claims (6)

[Claims] 1. A reaction product of (a) a polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride, (b) a triallyl isocyanurate and / or a triallyl cyanurate, (c) an epoxy resin, and (d). A curable polyphenylene ether resin composition comprising an inorganic filler, wherein the component (a) is 98 to 40 parts by weight and the component (b) is 2 based on 100 parts by weight of the sum of the components (a) and (b).
To 60 parts by weight and the sum of components (a) to (c) 10
(A) + (b) component is 99 to 1 part by weight, (c) component is 1 to 99 parts by weight, and (a)
~ Based on 100 parts by weight of the sum of components (d) (a) ~
Component (c) is 99 to 10 parts by weight, component (d) is 1 to 90.
A curable resin composition, characterized in that it is part by weight. 2. A reaction product of (a) polyphenylene ether and an unsaturated carboxylic acid or acid anhydride, (b) triallyl isocyanurate and / or triallyl cyanurate, (c) epoxy resin, (d) inorganic. Filler, and (e) dicumyl peroxide and / or α,
A curable polyphenylene ether resin composition comprising α'-bis (t-butylperoxy-m-isopropyl) benzene, the sum of the components (a) and (b) being 10
98 to 40 parts by weight of the component (a) based on 0 parts by weight,
(B) component is 2 to 60 parts by weight, and (a) to
(A) + based on 100 parts by weight of the sum of components (c)
The component (b) is 99 to 1 parts by weight, the component (c) is 1 to 99 parts by weight, and the components (a) to (c) are based on 100 parts by weight of the sum of the components (a) to (d). 99-10 parts by weight,
The component (d) is 1 to 90 parts by weight, and the component (e) is 0.1 to 10 parts by weight based on 100 parts by weight of the sum of the components (a) and (b). Curable resin composition. 3. A cured polyphenylene ether resin composition obtained by curing the curable polyphenylene ether resin composition according to claim 1. 4. A curable composite material comprising the curable polyphenylene ether resin composition according to claim 1 or 2 and a base material, wherein the total amount of the curable polyphenylene ether resin composition and the base material is 100 parts by weight. A curable composite material, characterized in that the curable polyphenylene ether resin composition is 95 to 10 parts by weight and the base material is 5 to 90 parts by weight as a standard. 5. A cured composite material obtained by curing the curable composite material according to claim 4. 6. A laminate comprising the cured composite material according to claim 5 and a metal foil.