JPH07258537A - Curable composite material containing polyphenylene ether resin - Google Patents

Abstract

PURPOSE:To obtain a composite material which gives a cured item excellent in flame retardance, dielectric characteristics, and heat resistance by combining a substrate with a resin compsn. comprising polyphenylene ether, a specific flame retardant, and a thermosetting monomer and/or a thermosetting resin. CONSTITUTION:A curable polyphenylene ether resin compsn. is prepd. by compounding 100 pts.wt. compsn. comprising polyphenylene ether and at least one thermosetting monomer and/or a thermosetting resin with 5-100 pts.wt. compd. of the formula (wherein m and n are each 3-5 provided m+n is 8 or higher; and Z is a 4C or lower optionally brominated alkylene group). The compsn. is used for preparing a curable composite material contg. 5-90wt.% substrate. The material is molded and cured at 80-300 deg.C under a pressure of 0.1-1000kg/cm<2> for 1min to 10hr to give a cured composite material, which is laminated to a metal foil to give a resin laminate.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a curable polyphenylene ether resin composite material comprising the curable polyphenylene ether resin composition and a substrate and having excellent flame retardancy, a cured composite material thereof, and a cured composite thereof. The present invention relates to a polyphenylene ether resin laminate including a material and a metal foil.

The curable polyphenylene ether resin composite material of the present invention exhibits excellent flame retardancy, chemical resistance, dielectric properties and heat resistance after curing, and is a dielectric material in the fields of the electronic industry, space and aircraft industry, etc. It can be used as an insulating material and a heat resistant 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 a problem that the electrical characteristics, particularly the dielectric characteristics in a high frequency region, are poor.

As a new material for solving this problem, polyphenylene ether has been attracting attention in recent years and its application to copper clad laminates has been attempted. However, polyphenylene ether does not have sufficient flame retardancy for use in electric parts such as copper-clad laminates. Although it is practically strongly demanded to impart flame retardancy without impairing the excellent dielectric properties and heat resistance of polyphenylene ether,
From the viewpoint of environmental protection, the addition of decabromodiphenyl ether analogs, which is one of the effective means, tends to be restricted or prohibited.

[0005]

In view of the above circumstances, the object of the present invention is to provide a novel curable polyphenylene which retains the excellent dielectric properties of polyphenylene ether and exhibits excellent flame retardancy after curing. It is intended to provide an ether resin composite material.

[0006]

The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, the present invention comprises the following three inventions. A first aspect of the present invention is a curable composite material comprising a curable polyphenylene ether resin composition and a substrate, wherein the curable polyphenylene ether resin composition is a compound represented by the following general formula (1) and polyphenylene. The weight of the compound represented by the general formula (1) in the curable polyphenylene ether resin composition contains ether and at least one thermosetting monomer and / or thermosetting resin, and 1)
It is 5 to 100 parts by weight based on 100 parts by weight of the components other than the compound represented by, and the base material is based on the total weight of the curable polyphenylene ether resin composition and the base material of 100 parts by weight. It is a curable polyphenylene ether resin composite material characterized by being 5 to 90 parts by weight.

[0007]

[Chemical 2]

A second aspect of the present invention is a polyphenylene ether resin-cured composite material obtained by curing the curable polyphenylene ether resin composite material according to claim 1. A third aspect of the present invention is a polyphenylene ether resin laminate comprising the polyphenylene ether resin cured composite material according to claim 2 and a metal foil. The present invention will be described in detail below.

The curable polyphenylene ether resin composition used in the present invention contains a compound represented by the general formula (1), polyphenylene ether and at least one thermosetting monomer and / or thermosetting resin. Is characterized by. The compound represented by the general formula (1) in the present invention is used as a flame retardant. In the general formula (1), m and n are each an integer 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. From the viewpoint of flame retardancy, m + n is preferably 9 or more, and most preferably 10. Z may have any number of hydrogens replaced by bromine. The number of carbon atoms may be any number as long as it is 4 or less, but --CH2 CH2-is mentioned as the most preferable structure.

The addition amount of the compound represented by the general formula (1) is 5 based on 100 parts by weight of the component other than the compound represented by the general formula (1) in the curable polyphenylene ether resin composition. To 100 parts by weight, preferably 5 to 80 parts by weight, more preferably 5 to 60 parts by weight, and most preferably 10 to 60 parts by weight. If it is less than 5 parts by weight, sufficient flame retardancy cannot be obtained. If it exceeds 100 parts by weight,
The adhesive force between the curable resin composite material and the metal decreases.

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

[0012]

[Chemical 3]

Examples of the lower alkyl group represented by R1 to R4 in the general formula (3) 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 typical examples of Q in the general formula (2), the following four general formulas (4), (5), (6),
The compound group represented by (7) is mentioned.

[0015]

[Chemical 4]

Specific examples include general formulas represented by the following formulas (8) to (12).

[0017]

[Chemical 5]

[0018]

[Chemical 6]

The polyphenylene ether chain represented by J in the above general formula (2) contains a unit represented by the following general formula (13) in addition to the unit represented by the general formula (3). May be.

[0020]

[Chemical 7]

Preferred examples of the polyphenylene ether of the general formula (2) used in the present invention include poly (2,6-dimethyl-1,4-phenylene ether) obtained by homopolymerization of 2,6-dimethylphenol, Poly (2,6
-Dimethyl-1,4-phenylene ether) styrene graft polymer, 2,6-dimethylphenol and 2,
A copolymer of 3,6-trimethylphenol, a copolymer of 2,6-dimethylphenol and 2-methyl-6-phenylphenol, a copolymer of 2,6-dimethylphenol and the following general formula (15) A polyfunctional polyphenylene ether resin obtained by polymerization in the presence of a polyfunctional phenol compound, for example, JP-A-63-301222.
Examples thereof include copolymers containing the units of the general formulas (3) and (13) as disclosed in JP-A-1-297428.

[0022]

[Chemical 8]

Regarding the molecular weight of the polyphenylene ether described above, one having a viscosity number η _sp / c measured in a chloroform solution of 30 g at 0.5 g / dl in the range of 0.1 to 1 can be preferably used. 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 viscosity number is preferably 0.8 or less, and most preferably 0.6 or less.

Specific examples of the thermosetting monomer and / or thermosetting resin used in the present invention include phenol resin, epoxy resin, diallyl phthalate, divinylbenzene, polyfunctional acryloyl compound and polyfunctional methacryloyl compound. , Polyfunctional maleimide, polyfunctional cyanate ester, polyfunctional isocyanate, unsaturated polyester, triallyl isocyanurate, triallyl cyanurate, polybutadiene, styrene-butadiene
Examples thereof include crosslinkable polymers such as styrene-butadiene-styrene.

In the present invention, examples of preferred combinations of polyphenylene ether and at least one thermosetting monomer and / or thermosetting resin include, but are not limited to, polyphenylene ether and triallyl isocyanurate and / or triary. Lucyanurate; Polyphenylene ether and epoxy resin;
Examples thereof include polyphenylene ether, epoxy resin and triallyl isocyanurate and / or triallyl cyanurate; polyphenylene ether, styrene butadiene block copolymer, and triallyl isocyanurate and / or triallyl cyanurate.

The compounding ratio of the polyphenylene ether and the thermosetting monomer and / or the thermosetting resin is determined according to the purpose. In the present invention, a thermoplastic resin may be blended in addition to the polyphenylene ether, the thermosetting monomer and / or the thermosetting resin. The resin to be mixed may be any resin as long as it does not impair the physical properties of the substrate as a material for a printed circuit board, which is the main application of the present invention.

Specific examples of thermoplastic resins include polyethylenes, polypropylenes, polybutenes, ethylene / propylene copolymers, polyolefins such as poly (4-methyl-pentene) and their derivatives, nylon 4, nylon 6 and nylon. Polyamides such as 6.6, nylon 6/10, nylon 12 and their derivatives, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate, polyethylene terephthalate / polyethylene glycol block copolymers and other polyesters and their derivatives, polyphenylene ether , Polycarbonate, polyacetal, polysulfone, polyvinyl chloride and its copolymer, polyvinylidene chloride and its copolymer, polymethylmethacrylates, acrylic acid (or Methacrylic acid) ester copolymers,
Polystyrenes, acrylonitrile styrene copolymer,
Polystyrenes such as acrylonitrile styrene butadiene-based copolymers and copolymers thereof, polyvinyl acetates, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, ethylene vinyl acetate copolymers and hydrolysates thereof, polyvinyl alcohols, Styrene-butadiene block copolymers, polybutadiene,
Rubbers of polyisoprenes, polyvinyl ethers such as polymethoxyethylene and polyethoxyethylene, polyacrylic amides, polyphosphazenes, polyether sulfones, polyether ketones, polyether imides,
Examples thereof include liquid crystal polymers such as polyphenylene sulphite, polyamide imide, thermoplastic polyimide and aromatic polyester, and side chain type liquid crystal polymers containing a liquid crystal component in their side chains.

The above-mentioned thermoplastic resins are blended for the purpose of improving the physical properties of a substrate, which is generally called a prepreg, and is produced by laminating a curable resin composite material.
The curable polyphenylene ether-based resin composition of the present invention may contain a radical initiator, a catalyst, a curing agent or the like for the purpose of lowering the reaction temperature of the thermosetting resin or promoting the crosslinking reaction. Good.

Typical examples of the radical initiator are:
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 curable polyphenylene ether resin composition in the present invention is not limited to these examples. Examples of the curing accelerator that causes the epoxy resin to react include amine compounds, imidazole compounds, nitrogen-containing heterocyclic compounds such as diazabicycloundecene, organic phosphine compounds, organic phosphine / organic boron complexes, and quaternary ammonium. Known compounds such as compounds and quaternary phosphonium compounds can be used. Details of the technique relating to the curing accelerator are described in, for example, Hiroki Kakiuchi, “Recent Advances in Epoxy Resins”, Shokoido (1990), Chapter 4, and references cited therein.

Other suitable curing agents for polyfunctional maleimides include polyamines. Suitable catalysts for the polyfunctional cyanate ester include mineral acids, Lewis acids, salts such as sodium carbonate or lithium chloride, and phosphoric acid esters such as tributylphosphine.

Suitable catalysts and curing agents for polyfunctional isocyanates are described in, for example, Keiji Iwata, "Polyurethane Resin Handbook", Nikkan Kogyo Shimbun (1987) P.
Amines as taught in pages 118-123,
Examples include organic metals and polyhydric alcohols. The above catalyst, initiator, curing agent, etc. are appropriately selected and used according to the type of the resin composition.

Further, for the purpose of further improving flame retardancy, Sb ₂ O ₃ , Sb ₂ O ₅ , NbSbO ₃ .1 / 4H ₂ O
It is also possible to use a flame retardant auxiliary such as Sb ₂ O ₃ is most preferable as the flame retardant aid. The amount of the flame retardant auxiliary compounded is preferably 10 to 50 parts by weight, more preferably 10 to 40 parts by weight, and most preferably 10 to 30 parts by weight, based on 100 parts by weight of the compound represented by the general formula (1). It is a department.

In the present invention, the curable polyphenylene ether resin composition is 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. You can The filler may be fibrous or powdered, silica, alumina,
Examples thereof include 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.

As a method for mixing the respective components of the curable polyphenylene ether resin composition in the present invention, a solution mixing method in which the respective components are uniformly dissolved or dispersed in a solvent, or melting by heating with an extruder or the like. A blending method or the like can be used. As the solvent used in the solution mixing method, 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 Alternatively, two or more kinds may be used in combination.

The base material used in the curable polyphenylene ether resin composite material of 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 materials. 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; natural fiber cloth such as cotton cloth, linen cloth, felt; carbon fiber Cloth: Natural cellulosic cloths 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.

The ratio of the base material in the curable polyphenylene ether resin composite material of the present invention is the sum of the weights of the curable polyphenylene ether resin composition and the base material.
The amount is 5 to 90 parts by weight, more preferably 10 to 80 parts by weight, further preferably 20 to 70 parts by weight, based on 0 part by weight. When the amount of the base material is less than 5 parts by weight, the dimensional stability and strength of the curable polyphenylene ether resin composite material after curing are insufficient, and when the amount of the base material is more than 90 parts by weight, the dielectric properties and flame retardancy of the resin composite material are increased. It is inferior in properties and is not preferable.

The method for producing the curable polyphenylene ether resin composite material of the present invention includes, for example, the curable polyphenylene ether resin composition used in the present invention and, if necessary, other components in addition to the above halogen-based and aromatic compounds. Tribe,
Examples include a method in which a solution is uniformly dissolved or dispersed in a solvent such as a ketone-based solvent or a mixed solvent thereof, a substrate is impregnated with this solution, and then the substrate is dried.

Impregnation is carried out by dipping, coating or the like. Impregnation can be repeated multiple times as needed, and in this case it is also possible to repeat impregnation using multiple solutions with different compositions and concentrations to finally adjust the desired resin composition and amount. Is. In the curable polyphenylene ether resin 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 composition and the substrate.

As the coupling agent, a general one such as a silane coupling agent, a titanate coupling agent, an aluminum type coupling agent and a zircoaluminate coupling agent can be used. The polyphenylene ether resin cured composite material of the present invention is obtained by curing the curable polyphenylene ether resin composite material obtained as described above by a method such as heating.
The manufacturing method is not particularly limited, for example, a plurality of the curable polyphenylene ether resin composite materials are stacked, and each layer is adhered under heat and pressure while being heat-cured at the same time to obtain a polyphenylene ether resin having a desired thickness. A cured composite material can be obtained.

It is also possible to obtain a polyphenylene ether resin-cured composite material having a new layer structure by combining the polyphenylene ether resin-cured composite material that has been adhesive-cured once and the curable polyphenylene ether resin composite material. The lamination molding and curing are usually performed simultaneously using a hot press or the like, but both may be performed independently. That is, the uncured or semi-cured resin composite material obtained by laminating in advance can be cured by heat treatment or by another method.

The molding and curing conditions are temperature 80 to 30.
0 ° C., pressure 0.1 to 1000 kg / cm ² , time 1 minute to
It is preferably in the range of 10 hours, more preferably a temperature of 120 to 250 ° C., a pressure of 1 to 100 kg / cm ² ,
The time is 1 minute to 5 hours. The polyphenylene ether resin laminated body of the present invention refers to a laminated body, a laminated plate or the like composed of the polyphenylene ether resin cured composite material of the present invention and a metal foil.

Examples of the metal foil used in the present invention include copper foil and aluminum foil. The thickness is not particularly limited, but is preferably 5 to 200 μm, more preferably 5 to 105 μm. As a method for producing the polyphenylene ether resin laminate of the present invention, for example, the polyphenylene ether resin cured composite material of the present invention and a metal foil are laminated in a layer structure according to the purpose, and each layer is adhered under heat and pressure. A method of heat curing at the same time can be mentioned.

In the polyphenylene ether resin laminate, the polyphenylene ether resin cured composite material and the metal foil are laminated in an arbitrary layered structure. The metal foil can be used as both the surface layer and the intermediate layer. Further, a polyphenylene ether resin laminated plate composed of the polyphenylene ether resin cured composite material of the present invention and a metal plate, and a metal-clad laminated plate composed of a metal foil, a polyphenylene ether resin cured composite material, and a metal plate are also produced. it can.

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 polyphenylene ether resin 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. Other than 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 the adhesive, epoxy-based, acrylic-based, phenol-based,
Examples thereof include cyanoacrylate type, but are not particularly limited thereto.

The lamination molding and curing of the above polyphenylene ether resin laminate can be carried out under the same conditions as in the case of the polyphenylene ether resin cured composite material of the present invention.

[0047]

EXAMPLES In order to further clarify the present invention, examples will be described below. The physical properties were measured as follows. (1). The dielectric constant was measured at 1 MHz (according to JIS C 6481). (2). Copper foil peeling strength A test piece with a width of 20 mm and a length of 100 mm was cut out from the polyphenylene ether resin laminate, and the width of the copper foil was 10 mm.
After making parallel cuts, the copper foil is continuously peeled off in a direction perpendicular to the surface at a speed of 50 mm / min with a tensile tester, and the stress at that time is measured. The value is shown (in accordance with JIS C 6481). (3). Flammability According to US UL-94 test standard.

[0048]

Examples 1 to 8 Viscosity numbers η _sp / c of 0.56 and 0.44 measured at 30 ° C. in a 0.5 g / dl chloroform solution.
Table 1 shows poly (2,6-dimethyl-1,4-phenylene ether) of 0.35 and 0.35 (abbreviated as A, B, and C, respectively), the compound represented by the general formula (1), and various components. The above composition was blended, and dissolved or dispersed in trichlorethylene to give a varnish.

Glass cloth (made of E glass) was immersed in these solutions for impregnation, and then dried in an air oven to prepare a curable resin composite material (prepreg). The weight of the base material in the prepreg was 40% with respect to the weight of the prepreg. Thickness after molding is about 0.05 mm ~
If necessary, a plurality of the above prepregs were superposed so as to have a thickness of 0.8 mm, and a copper foil having a thickness of 35 μm was placed on both surfaces of the prepreg, and the resin was molded and cured by a press molding machine to obtain a resin laminate.

The physical properties of the thus obtained polyphenylene ether resin laminate were measured. As a result, all the polyphenylene ether resin laminates had good dielectric properties,
The copper foil showed peeling strength, and the flame retardancy was V-0.

[0051]

Comparative Example 1 A cured product was obtained in the same manner as in Example 1 except that the amount of the flame retardant was changed to 3 parts. When a flammability test was conducted, it was equivalent to HB.

[0052]

Comparative Example 2 A resin laminate was obtained in the same manner as in Example 2 except that the amount of the flame retardant was changed to 120 parts. The peel strength of the copper foil was significantly reduced as compared with Example 2. Table 1 shows the results of Comparative Examples 1 and 2 together with Examples 1 to 8.

[0053]

[Table 1]

[0054]

The polyphenylene ether resin-cured composite material and the polyphenylene ether resin laminate obtained by using the curable polyphenylene ether resin composite material of the present invention are excellent in flame retardancy as compared with conventional ones, and moreover, copper foil. It is an excellent material that retains peel strength and dielectric properties and does not contain decabromodiphenyl ether.

The polyphenylene ether resin laminate of the invention has a V-thickness even in the case of an extremely thin plate (0.05 mm) which is easily burned.
It has outstanding flame retardancy of 0. Therefore, the above-mentioned material of the present invention can be used as a dielectric material, an insulating material, a heat-resistant material, etc. in the fields of electric industry, electronic industry, space / aircraft industry and the like. In particular, the curable polyphenylene ether resin composite material of the present invention is suitably used as a single-sided, double-sided, multi-layer printed circuit board, semi-rigid substrate, metal base substrate, prepreg for multi-layer printed circuit board.

Claims (3)

[Claims] 1. A curable composite material comprising a curable polyphenylene ether resin composition and a substrate, wherein the curable polyphenylene ether resin composition is a compound represented by the following general formula (1), polyphenylene ether, and At least one thermosetting monomer and / or thermosetting resin is contained, and the weight of the compound represented by the general formula (1) in the curable polyphenylene ether-based resin composition is represented by the general formula (1). It is 5 to 100 parts by weight based on 100 parts by weight of the components other than the compound represented by, and the base material is based on the total weight of the curable polyphenylene ether resin composition and the base material of 100 parts by weight. 5
A curable polyphenylene ether resin composite material, characterized in that it is from 90 to 90 parts by weight. [Chemical 1] 2. A polyphenylene ether resin cured composite material obtained by curing the curable polyphenylene ether resin composite material according to claim 1. 3. A polyphenylene ether resin laminate comprising the polyphenylene ether resin cured composite material according to claim 2 and a metal foil.