JPH08239566A - Curable polyphenylene ether resin composition and composite material and laminated material produced by using the composition - Google Patents

Abstract

PURPOSE: To obtain the subject composition containing a reaction product of a polyphenylene ether with an unsaturated carboxylic acid or its acid anhydride, having excellent dielectric properties, a dielectric constant controllable over a wide range and excellent heat-resistance and dimensional stability and useful for a multi-layer printed circuit board, etc. 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 inorganic filler and preferably further (D) a compound of the formula ((m) and (n) are each 3-5; m+n>=8; Z is a >=4C (bromine-substituted)alkyl]. 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 99-10 pts. wt. and 1-90 pts.wt. based on 100 pts.wt. of A+B+C, respectively and the amounts of A+B+C and D are 95-50 pts.wt. and 5-50 pts.wt. based on 100 pts.wt. of A+B+C+D, respectively.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a 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. Also,
Dimensional stability is poor, causing problems when designing high-frequency circuits.

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 As a result of intensive studies to solve the above-mentioned problems, the present inventors have succeeded in controlling the dielectric constant without impairing the excellent dielectric properties of polyphenylene ether, and An object of the present invention is to provide a curable polyphenylene ether resin composition that exhibits excellent dimensional stability, chemical resistance, and heat resistance after curing and, when used as a composite material, has high interlayer adhesion strength.

[0005]

The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, have found a resin composition in accordance with 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) triallyl isocyanurate and / or triallyl cyanurate, and (c) an inorganic material. A curable polyphenylene ether resin composition comprising a filler, wherein the component (a) is 98 to 40 parts by weight and the component (b) is 2 to 2 parts by weight based on 100 parts by weight of the sum of the components (a) and (b).
60 parts by weight and the sum of components (a) to (c) 100
A curable resin composition, characterized in that (a) + (b) component is 99 to 10 parts by weight and (c) component is 1 to 90 parts by weight based on parts by weight.

The second aspect of the present invention is (a) a reaction product of a polyphenylene ether with an unsaturated carboxylic acid or an acid anhydride, (b) a triallyl isocyanurate and / or a triallyl cyanurate, and (c) an inorganic filler. And (d) a curable polyphenylene ether resin composition comprising a compound represented by the following general formula (1):
(A) based on 100 parts by weight of the sum of the component and the component (b)
The components are 98 to 40 parts by weight, the (b) component is 2 to 60 parts by weight, and the (a) + (b) component is 99 to 10 parts based on 100 parts by weight of the sum of the (a) to (c) components. Parts by weight,
Component (c) is 1 to 90 parts by weight, and (a) to
Based on 100 parts by weight of the sum of components (d), (a)-
(C) is 95 to 50 parts by weight, and component (d) is 5 to 50 parts by weight, which is a curable resin composition.

[0008]

Embedded image [In the formula, m and n are integers of 3 to 5 and m + n is 8 or more,
Z is an alkyl group having 4 or less carbon atoms or a bromine-substituted alkyl group. ]

A 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 more detail below. The polyphenylene ether used in the present invention is represented by the following general formula (2).

[0011]

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),

[0012]

[Chemical 4] (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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an 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. Representative examples of Q in the general formula (2) include compounds represented by the following four general formulas.

[0014]

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 represented by the following general formula.

[0016]

[Chemical 6]

[0017]

[Chemical 7] In the polyphenylene ether chain represented by J in the general formula (2), in addition to the unit represented by the general formula (A), a unit represented by the following general formula (B) is contained. Good.

[0018]

Embedded image [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 9] Etc.

Preferred examples of the polyphenylene ether resin of the general formula (2) used in the present invention include 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: the following general formula (3)

[0021]

[Chemical 10] (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 with a chloroform solution of 30 g at 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 polyphenylene ether resin with an unsaturated carboxylic acid or an acid anhydride, and is substantially polymerizable due to the acid or the acid anhydride. Is a reaction product containing no double bond. The reaction product is probably a mixture of various products having various chemical structures, and the chemical structures thereof are not all elucidated. H. Glans, M .; K. Ak
capeddi, Macromolecules, vo
The following chemical structures described in 1991, 24, 383 to 386 are given as examples.

[0024]

[Chemical 11]

Examples of suitable acids and acid anhydrides are 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 the solution method and the melt-mixing method can be used, the melt-mixing method using an extruder or the like is simpler and more suitable for the purpose of the present invention. The proportion of unsaturated carboxylic acid or acid anhydride is 0.01 to 5.0 parts by weight, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the polyphenylene ether resin.
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.

[0026]

[Chemical 12]

In carrying out the present invention, triallyl isocyanurate and triallyl cyanurate may be used alone, or both may be mixed in an arbitrary ratio and used. 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 inorganic filler used as the component (c) 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 a low dielectric constant and a low dielectric loss.
It has the effect of 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 flame retardant used as the component (d) of the present invention is represented by the structural formula (1). m and n are each an integer of 3 to 5, m + n is 8 or more, and Z is 4 carbon atoms.
The following alkyl groups or bromine-substituted alkyl groups are used. m
From the viewpoint of flame retardancy, + n is preferably 9 or more, and most preferably 10. Z may have any number of hydrogens replaced by bromine, and may have any number of carbons as long as it has 4 or less, but —CH ₂ CH ₂ — is most preferable.

Of the four components (a) to (d) described above, the mixing ratio of the component (a) and the component (b) is 10 in total.
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, and when it exceeds 60 parts by weight, the dielectric properties, flame retardancy and moisture absorption properties are deteriorated.
Further, it is not preferable because it becomes a very brittle material after curing.

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 remarkably reduced, which is not preferable. The mixing ratio of the component (c) is
99 to 10 parts by weight of (a) + (b) component, 1 to 90 parts by weight of (c) component, preferably 1 to 80 parts by weight, based on 100 parts by weight of the sum of components (a) to (c). More preferably, it is in the range of 1 to 70 parts by weight.

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

The mixing ratio of the component (d) is from (a) to
Based on 100 parts by weight of the sum of components (d), (a)-
Component (c) is 95-50 parts by weight, component (d) is 5-50.
Parts by weight, preferably 5 to 40 parts by weight, more preferably 5
-30 parts by weight. When the amount of the component (d) is less than 5 parts by weight, it is difficult to obtain sufficient flame retardancy, and when it exceeds 50 parts by weight, the fluidity is lowered, the adhesive force to the metal foil, or the adhesive strength between the prepregs described above. Is significantly reduced, 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 (d), there are a solution mixing method in which the four 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. As the solvent used for the solution mixing, a halogen-based solvent such as dichloromethane, chloroform and trichloroethylene; an aromatic solvent such as benzene, toluene and xylene; a ketone solvent such as acetone, methyl ethyl ketone and methyl isobutyl ketone; tetrahydrofuran alone or Used in combination of two or more.

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 (d) 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.

As will be described later, the resin composition of the present invention undergoes a crosslinking reaction by means of heating or the like to be cured, but radical initiation is carried out for the purpose of lowering the reaction temperature at that time or accelerating the crosslinking reaction of unsaturated groups. You may use it, including an agent. The amount of radical initiator used in the resin composition of the present invention,
0.1 to 1 based on the sum of the components (a) and (b)
It is 0% by weight, preferably 0.1 to 8% by weight.

Typical examples of the radical initiator will be given below.
Benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-
Butyl peroxy) hexyne-3, di-t-butyl peroxide, t-butyl cumyl peroxide, 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) butane, 2,2-bis (t-butylperoxy) octane, 2,5-dimethyl There are peroxides such as, but not limited to, 2,2,5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxide, and trimethylsilyltriphenylsilylperoxide. Also, 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.

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.
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. Also time is
It is about 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 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 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, more preferably at 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. 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.

[0051]

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. 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) ) Cylinder temperature 3 after dry blending with 1.0 part by weight at room temperature
Extrusion was carried out by a twin-screw extruder under the conditions of 00 ° C. and 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.

Example 1 The reaction product prepared in Reference Example 1, the triallyl isocyanurate, the silica balloon, the initiator, the flame retardant and the flame retardant auxiliary were dissolved or dispersed in chloroform with the composition shown in Table 1. A film was formed by pouring on a Teflon plate. The resulting film had a thickness of about 100 μm. The film forming property was good.

After drying this film in an air oven, it was molded and cured in a vacuum press at 200 ° C. for 60 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.

Examples 2 to 4 The reaction product prepared in Reference Example, triallyl isocyanurate, silica balloon,
The initiator, flame retardant, and flame retardant aid were dissolved or dispersed in trichlorethylene in the composition shown in Table 1. 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 thereof.
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. Further, even when an inorganic filler was included, sufficient adhesive strength between the prepregs was obtained.

1. Trichloroethylene resistance The laminate from which the copper foil was removed was cut into 25 mm square pieces, boiled in trichlorethylene for 5 minutes, and the change in appearance was visually observed. 2. The dielectric constant and the dielectric loss tangent were measured at 1 MHz. 3. Solder heat resistance Cut the laminate from which the copper foil was removed into 25 mm square pieces, 260
Floating in a solder bath at ℃ for 120 seconds, the change in appearance was visually observed.

4. Copper foil peeling strength A test piece having a width of 20 mm and a length of 100 mm was cut out from the laminate, and a parallel cut having a width of 10 mm was made on the copper foil surface, and then a speed of 50 mm / min in a direction perpendicular to the surface. Then, the copper foil was continuously peeled off, and the stress at that time was measured by a tensile tester, and the minimum value of the stress was shown. 5. Flame-retardant From the laminate without copper foil, length 127mm, width 12.7
mm test pieces were cut out, and the test was performed according to the UL-94 test method.

6. 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. 7. Adhesive strength between prepregs A test piece with 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 with 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 of 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.

(Examples 5 and 6) Examples 2 to 6 except that the silica balloon was changed to alumina and the composition shown in Table 1 was used.
A laminated body was obtained under the same conditions as in 4. The physical properties of the obtained laminate are as shown in Table 2, and a laminate having a desired dielectric constant and excellent dimensional stability was obtained. (Example 7) The silica balloon was replaced with titanium dioxide,
Laminated bodies were obtained under the same conditions as in Examples 2 to 5, except that the composition shown in Table 1 was used. The physical properties of the obtained laminate are as shown in Table 2, and 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 of Example 1 shown in Table 1. The physical properties of the obtained laminate are as shown in Table 2, and the dielectric constant was larger than that of the product containing silica balloons. (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. The physical properties of the obtained laminate are as shown in Table 2. Compared with Comparative Example 2 and Example 3, and compared with Comparative Example 3 and Example 6, those not using an inorganic filler have a large linear expansion coefficient and cannot obtain a desired dielectric constant. It was

[0062]

[Table 1]

[0063]

[Table 2]

[0064]

The curable polyphenylene ether resin composition of the present invention has excellent dielectric properties and can control the dielectric constant over a wide range. It also has excellent heat resistance and dimensional stability, and is useful as a dielectric material, an insulating material, and a heat resistant material 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 a multi-layer printed circuit board. Furthermore, since no decabromodiphenyl ether analogue is used as a flame retardant, it is an excellent material from the viewpoint of environmental protection.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location C08K 5/3477 C08K 5/3477 C08L 39/00 LJY C08L 39/00 LJY // C08F 290/06 MRS C08F 290 / 06 MRS

Claims (6)

[Claims] 1. Curing comprising (a) a reaction product of a polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride, (b) triallyl isocyanurate and / or triallyl cyanurate, and (c) an inorganic filler. A polyphenylene ether resin composition, wherein the component (a) is 98 to 40 parts by weight and the component (b) is 2 to 60 parts by weight based on 100 parts by weight of the sum of the components (a) and (b). And, based on 100 parts by weight of the sum of the components (a) to (c), (a) + (b) component is 99 to 10 parts by weight, and (c) component is 1 to 90 parts by weight. Curable resin composition. 2. 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 inorganic filler, and (d). ) A curable polyphenylene ether resin composition comprising a compound represented by the following general formula (1), 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 10 parts by weight of the component (a) + (b) based on 100 parts by weight of the sum of the components (a) to (c), (c ) Component is 1 to 90 parts by weight and the sum of components (a) to (d) is 1
95 to 50 of (a) to (c) based on 00 parts by weight
A curable resin composition, characterized in that 5 parts by weight of component (d) is 5 parts by weight. Embedded image [In the formula, m and n are integers of 3 to 5 and m + n is 8 or more,
Z is an alkyl group having 4 or less carbon atoms or a bromine-substituted alkyl group. ] 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 a curable polyphenylene ether resin composition according to claim 1 or 2 and a substrate, wherein the curable polyphenylene ether ether resin composition is based on 100 parts by weight of the sum of both components. Is 95-
10 parts by weight, and the base material is 5 to 90 parts by weight, a curable composite material. 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.