JP3178925B2 - Curable resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable resin composition and a cured product obtained by curing the same. Furthermore, the present invention relates to a curable composite material comprising the resin composition and a substrate, a cured product thereof, and a laminate comprising a cured product and a metal foil. The resin composition of the present invention exhibits excellent chemical resistance, dielectric properties, and heat resistance after curing, and can be used as a dielectric material, an insulating material, and a heat-resistant material in fields such as the electronics industry, the space and aircraft industries.

[0002]

2. Description of the Related Art In recent years, there has been a remarkable trend toward miniaturization and high-density mounting methods in the field of electronic devices for communication, consumer use, industrial use, and the like, and accordingly, materials have become more excellent. Heat resistance, dimensional stability, and electrical properties are being demanded. For example, a copper-clad laminate made of a thermosetting resin such as a phenol resin or an epoxy resin has been used as a printed wiring board. Although these have various performances in a well-balanced manner, they have a drawback that electric characteristics, particularly dielectric characteristics in a high frequency range, are poor. As a new material for solving this problem, polyphenylene ether has recently attracted attention and is being applied to copper-clad laminates.

[0003] One of the methods using polyphenylene ether is to use a curable polymer or monomer. By combining it with a curable polymer or monomer, it is possible to improve the chemical resistance of polyphenylene ether and to obtain a material utilizing the excellent dielectric properties of polyphenylene ether. As the curable polymer or monomer, epoxy resin (JP-A-58-690)
46, etc.), 1,2-polybutadiene (Japanese Unexamined Patent Publication No.
9-193929), polyfunctional maleimide (JP-A-56-133355), polyfunctional cyanate ester (JP-A-56-141349, etc.),
Many examples include polyfunctional acryloyl or methacryloyl compounds (JP-A-57-149317, etc.), triallyl isocyanurate and / or triallyl cyanurate (JP-A-61-218652, etc.), isocyanate compounds and the like. Are known.

However, polyphenylene ether is
Since there is no inherent chemical resistance, even if a curable polymer or monomer is used in combination, there is naturally a limit to the improvement. This is because polyphenylene ether was used without any modification. Further, since PPE itself does not have a film-forming property, a film cannot be formed, and a composition having a good appearance cannot be obtained.

[0005]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and retains the excellent dielectric properties of polyphenylene ether, and provides excellent chemical resistance and heat resistance after curing. It is an object of the present invention to provide a novel curable resin composition as shown below.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, have found a novel resin composition that meets the object of the present invention, and have completed the present invention. It has arrived. The present invention is constituted by the following five inventions. That is, a first aspect of the present invention is (a) a reaction product of a polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride; and (b) diallyl phthalate, divinylbenzene, a polyfunctional acryloyl compound, or a polyfunctional methacryloyl compound. , Polyfunctional maleimide, polyfunctional cyanate ester, polyfunctional isocyanate, unsaturated poly
A curable resin composition comprising at least one compound selected from the group consisting of esters and / or a prepolymer thereof, and (c) a thermoplastic resin,
Component (a) is 98 to 40 parts by weight, component (b) is 2 to 60 parts by weight, and component (c) is 2 based on 100 parts by weight of the sum of components (a), (b) and (c). The present invention provides a curable resin composition characterized in that the amount is from 60 to 60 parts by weight.

A second aspect of the present invention provides a cured resin composition obtained by curing the curable resin composition of the first aspect. A third aspect of the present invention provides a curable composite material comprising the curable resin composition of the first aspect and a substrate. A fourth aspect of the present invention provides a cured composite material obtained by curing the curable composite material of the third aspect.

A fifth aspect of the present invention provides a laminate comprising the cured composite material of the fourth aspect and a metal foil. Hereinafter, the present invention will be described in detail. The polyphenylene ether used in the present invention is represented by the following general formula 1.

[0009]

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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. Examples of the aryl group include a phenyl group. Examples of the haloalkyl group include a bromomethyl group and a chloromethyl group. Examples of the halogen atom include bromine and chlorine.

As a typical example of Q in Chemical Formula 1, the following 4
And a group of compounds represented by the general formula (2).

[0012]

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Specific examples include the following chemical formulas (3) to (4).

[0014]

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[0015]

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In the polyphenylene ether chain represented by J in the general formula 1, in addition to the unit represented by the general formula A, a unit represented by the following general formula 5 may be contained. .

[0017]

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Preferred examples of the polyphenylene ether resin represented by the general formula 1 used in the present invention include poly (2,6-dimethyl-1,4-phenylene ether) and poly (2,6-dimethyl-1,4-phenylene ether) obtained by homopolymerization of 2,6-dimethylphenol. 2,
Styrene graft polymer of 6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol and 2,6-dimethylphenol
3,6-trimethylphenol copolymer, 2,6-dimethylphenol and 2-methyl-6-phenylphenol copolymer, 2,6-dimethylphenol and polyfunctional phenol compound: general formula (6),

[0019]

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A polyfunctional polyphenylene ether resin obtained by polymerization in the presence of, for example, JP-A-63-3012
And copolymers containing the units of the general formulas A and B as disclosed in JP-A No. 22-294 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. and a 0.5 g / dl chloroform solution is 0.1 to 1.
Those in the range of 0 can be used favorably. As a curable resin composition that emphasizes the flow of molten resin, for example, a prepreg for a multilayer wiring board, a resin having a small viscosity number is preferable.

The component (a) used in the present invention is produced by reacting the above polyphenylene ether resin with an unsaturated carboxylic acid or acid anhydride. Examples of suitable acids and acid anhydrides include acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, glutaconic anhydride, citraconic anhydride and the like. Particularly, maleic anhydride and fumaric acid can be used most preferably. The reaction is carried out by heating the polyphenylene ether resin and the unsaturated carboxylic acid or acid anhydride in a temperature range from 100C to 390C. 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 can be more easily performed and is suitable for the purpose of the present invention.
The ratio of the unsaturated carboxylic acid or acid anhydride is 0.01 to 5.0 parts by weight based on 100 parts by weight of the polyphenylene ether resin.
0 parts by weight, preferably 0.1 to 3.0 parts by weight.

The component (b) of the curable resin composition of the present invention includes diallyl phthalate, divinylbenzene, a polyfunctional acryloyl compound, a polyfunctional methacryloyl compound, a polyfunctional maleimide, a polyfunctional cyanate ester,
At least one compound selected from the group consisting of polyfunctional isocyanates and unsaturated polyesters, and / or
Alternatively, a prepolymer thereof is used.

The diallyl phthalate and divinyl benzene used in the present invention are compounds represented by the following structural formulas, respectively.

[0024]

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Any of the ortho, meta and para isomers of these compounds can be used in the present invention. The polyfunctional acryloyl compound and the polyfunctional methacryloyl compound used in the present invention are compounds represented by the following two general formulas.

[0026]

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Examples of the polyfunctional acryloyl or methacryloyl compound R ₁₂ of the general formula (C) include ethylene glycol, propylene glycol, butanediol,
Neopentyl glycol, hexanediol, glycerin, trimethylolethane, trimethylolpropane,
Pentaerythritol, sorbitol, bis (hydroxymethyl) cyclohexane, hydrogenated bisphenol A
Residues of alkane polyols exemplified by, for example, etc .; Residues of polyether polyols exemplified by, for example, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol polypropylene glycol; and a plurality of benzenes represented by xylene glycol and bisphenol A Aromatic polyols whose rings are linked via a bridge and aromatic polyol residues exemplified by alkylene oxide adducts of these aromatic polyols; polynuclear benzenes obtained by reacting phenol with formaldehyde A residue derived from an epoxy resin having two or more epoxy groups; a residue derived from a polyester resin having two or more hydroxyl groups at a terminal; Yes, specific compound The ethylene glycol diacrylate, propylene glycol diacrylate,
1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,3-butanediol diacrylate, 1,5-pentanediol diacrylate, neopentyl glycol diacrylate, 1,6
-Hexanediol diacrylate, glycerin triacrylate, 1,1,1-methylolethane diacrylate, 1,1,1-trimethylolethane triacrylate, 1,1,1-trimethylolpropane acrylate, 1,1,1- Trimethylolpropane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, sorbitol tetraacrylate, sorbitol hexaacrylate, sorbitol pentaacrylate, 1,4-hexanediol diacrylate, 2,2-bis (acryloxy Cyclohexane)
Propane, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, bisphenol A-diacrylate, 2,2-bis (4- (2-acryloxyethoxy) phenyl ) Propane, 2,2-bis (4- (acryloxy-di- (ethyleneoxy) phenyl)) propane, 2,2-bis (4-
(Acryloxy-poly- (ethyleneoxy) phenyl)) propane; polyhydric acrylate of a phenol resin precondensate; bisphenol A epoxy resin, novolak epoxy resin, alicyclic epoxy resin, diglycidyl phthalate and polycarboxylic acid Epoxy acrylates obtained by reacting the above with acrylic acid; polyester polyacrylates obtained by reacting a polyester having two or more hydroxyl groups at the terminals with acrylic acid; those obtained by converting the above acrylate into methacrylates; Further, there may be mentioned those in which the hydrogen atoms of these compounds are partially substituted with halogen such as 2,2-dibromomethyl-1,3-propanediol dimethacrylate.

Representative examples of the polyfunctional acryloyl or methacryloyl compound of the formula (D) include hexahydro-1,3,5-triacryloyl-s-triazine, hexahydro-1,3,5-trimethacryloyl- s-triazines. The polyfunctional maleimide used in the present invention is represented by the following general formula.

[0029]

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The polyfunctional maleimide of the general formula (E) is obtained by reacting maleic anhydride with a polyamine having 2 to 10 amino groups in the molecule to form maleamic acid, and then subjecting this maleamic acid to dehydration cyclization. It is manufactured by Suitable amines include metaphenylenediamine, paraphenylenediamine, metaxylylenediamine, paraxylylenediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, hexahydroxylylenediamine, 4,4-diaminobiphenyl , Bis (4-aminophenyl) methane, bis (4-aminophenyl) ether, bis (4-aminophenyl)
Sulfone, bis (4-amino-3-methylphenyl) methane, bis (4-aminophenyl) cyclohexane,
2,2-bis (4-aminophenyl) propane, 2,2
-Bis (4-amino-3-methylphenyl) propane,
Bis (4-amino-3-chlorophenyl) methane, 2,
2-bis (3,5-dibromo-4-aminophenyl) methane, 3,4-diaminophenyl-4′-aminophenylmethane, 1,1-bis (4-aminophenyl) -1-
Examples thereof include phenylethane, melanins having an s-triazine ring, and polyamines obtained by reacting aniline with formaldehyde (usually those having 10 or less benzene nuclei are preferably used).

The polyfunctional cyanate ester used in the present invention is represented by the following general formula.

[0032]

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Examples of the polyfunctional cyanate of the general formula (E) include 1,3-dicyanatebenzene, 1,4-
Dicyanate benzene, 1,3,5-tricyanate benzene 1,3-dicyanate naphthalene, 1,4-dicyanate naphthalene, 1,6-dicyanate naphthalene, 1,8-dicyanate naphthalene, 2,6-di Cyanate naphthalene, 2,7-dicyanate naphthalene,
1,3,6-tricyanate naphthalene, 4,4-dicyanate biphenyl, bis (4-cyanate phenyl)
Methane, 2,2-bis (4-cyanatephenyl) propane, 2,2-bis (3,5-dicyclo-4-cyanatephenyl) propane, 2,2-bis (3,5-dibromo-4-cyanatephenyl) ) Propane, bis (4-cyanatephenyl) ether, bis (4-cyanatephenyl) thioether, bis (4-cyanatephenyl) sulfone, tris (4-cyanatephenyl) phosphite, tris (4-cyanatephenyl) phosphate, and A polynuclear benzene polycyanate compound obtained by reacting a phenol resin with a cyanogen halide is exemplified.

The polyfunctional isocyanate used in the present invention is represented by the following general formula.

[0035]

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Examples of the polyfunctional isocyanate of the general formula (F) include 2,4-toluene diisocyanate,
6-toluene diisocyanate, metaphenylene diisocyanate, paraphenylene diisocyanate, meta-xylylene diisocyanate, 1,5-naphthalene diisocyanate, 4,4-diphenylmethane diisocyanate, tolidine diisocyanate, tetramethyl xylene diisocyanate, isophorone diisocyanate, cyclohexane-1,4-diisocyanate , Lysine isocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate,
1,6,11-undecane triisocyanate, 1,8
-Diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate,
Bicycloheptane triisocyanate, polymethylene polyphenyl isocyanate and the like can be mentioned.

These polyfunctional isocyanates can also be used after being converted into polyfunctional blocked isocyanates using various blocking agents. Examples of the blocking agent include known compounds such as alcohols, phenols, oximes, lactams, malonic esters, acetoacetates, acetylacetones, amides, imidazoles, and sulfites.

The unsaturated polyester used in the present invention is obtained by reacting a glycol with an unsaturated polybasic acid and a saturated polybasic acid, or anhydrides, esters and acid chlorides thereof. Is used. Representative examples of glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, hydrogenated bisphenol A, bisphenol A propylene oxide adduct, dibromoneopentol glycol and the like.

Representative examples of unsaturated polybasic acids include maleic anhydride, fumaric acid, itaconic acid and the like.
Representative examples of saturated polybasic acids include phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, adipic acid, sebacic acid,
Tetonic acid, tetrabromophthalic anhydride and the like.

For details of unsaturated polyester, see, for example, "Polyester Resin Handbook" by Eiichiro Takiyama.
(Nikkan Kogyo Shimbun, 1988). As the component (b) of the curable resin composition of the present invention, only one of the above-described compounds may be used alone, or two or more may be used in combination. Further, a prepolymer obtained by preliminarily reacting these compounds with heat, light, or the like in the presence or absence of known catalysts, initiators, curing agents, and the like described below may also be used as the component (b) of the present invention. Can be.

The thermoplastic resin used as the component (c) of the curable resin composition of the present invention includes polyolefins such as polyethylene, polypropylene, polybutene, ethylene / propylene copolymer and poly (4-methyl-pentene). And its derivatives, polyamides such as nylon 4, nylon 6, nylon 6.6, nylon 6.6 and nylon 12, and their derivatives, polyethylene terephthalate, polybutylene terephthalate, pottyethylene naphthalate, polyethylene terephthalate and polyethylene glycol block copolymer. Polyesters and their derivatives such as coalesce, polyphenylene ether, polycarbonate, polyacetal, polysulfone, polyvinyl chloride and its copolymer, polyvinylidene chloride and its copolymer, polymethyl Polystyrenes such as acrylates, acrylic acid (or methacrylic acid) ester copolymers, polystyrenes, acrylonitrile styrene copolymers, acrylonitrile styrene butadiene copolymers and copolymers thereof, polyvinyl acetates, polyvinyl formal , Polyvinyl acetal, polyvinyl butyral, ethylene vinyl acetate copolymer and its hydrolysates, polyvinyl alcohols, styrene butadiene block copolymers, polybutadiene, rubbers of polyisoprenes, polymethoxyethylene, polyethoxyethylene, etc. Polyvinyl ethers, polyacrylamides, polyphosphazenes, polyether sulfones, polyether ketones, polyether imides, polyphenylene sulfites, polyamide imides, heat Plastic polyimide, liquid crystal polymers such as aromatic polyesters, side chain type liquid crystal polymer or the like that includes the liquid crystal component in the side chain.

The mixing ratio of the above components (a), (b) and (c) can be varied in a wide range, but in the present invention, the total of both components (a) and (b) is based on 100 parts by weight. Component (a) is 98 to 40 parts by weight, component (b) is 2 to 60 parts by weight, more preferably component (a) is 95 to 5 parts by weight.
0 parts by weight and the component (b) are preferably 5 to 50 parts by weight. If the amount of the component (b) is less than 2 parts by weight, the improvement of the chemical resistance is insufficient, which is not preferable. Conversely, if the amount exceeds 60 parts by weight, the dielectric properties deteriorate, which is not preferable. Further, in the present invention, the compounding ratio of the component (c) is 100% for the component (a) + (b).
2 to 60 parts by weight, more preferably 5 to 5 parts by weight based on parts by weight
It is preferable to use 0 parts by weight. If the amount of the component (c) is less than 2 parts by weight, the film-forming property is insufficiently improved, which is not preferable. Conversely 6
Exceeding 0 parts by weight is not preferred because chemical resistance is reduced.

A substrate can be added to the curable resin composition of the present invention in order to increase mechanical strength and increase dimensional stability. Examples of the base material used in the present invention include various glass cloths such as roving cloth, cloth, chopped mat, and surfacing mat, asbestos cloth, metal fiber cloth and other synthetic or natural inorganic fiber cloths; polyvinyl alcohol fiber, polyester fiber, Woven or non-woven fabric obtained from synthetic fiber 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 cellulosic cloths such as fine paper may be used alone or in combination of two or more.

The ratio of the substrate in the curable composite material of the present invention is 5 to 90% by weight, more preferably 10 to 80% by weight, and still more preferably 20 to 70% by weight, based on 100 parts by weight of the curable composite material. It is. Base material is 5% by weight
If the amount is less than the above, the dimensional stability and strength after curing of the composite material are insufficient, and if the amount is more than 90% by weight, the dielectric properties and the flame retardancy of the composite material are inferior.

Examples of the metal foil used in the present invention include a copper foil and an aluminum foil. Although the thickness is not particularly limited, it is 5 to 200 μm, more preferably 5 to 200 μm.
１０５105 μm. The above (a), (b),
As the method for mixing the components (c), a solution mixing method in which the three components are uniformly dissolved or dispersed in a solvent, a melt blending method in which the components are heated by an extruder or the like can be used. Examples of the solvent used for the solution mixing include halogen solvents such as dichloromethane, chloroform and trichloroethylene; aromatic solvents such as benzene, toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; and tetrahydrofuran alone or Two or more types are used in combination.

The curable resin composition of the present invention may be molded and cured in advance according to its use. The molding method is not particularly limited. Usually, a casting method in which the resin composition is dissolved in the above-described solvent and molded into a desired shape, or a heat melting method in which the resin composition is heated and melted to form a desired shape is used. The above-described casting method and heat melting method may be performed alone. Moreover, you may combine and perform each. For example, several to several tens of films of the curable resin composition of the present invention created by a casting method are laminated, and then heated and melted,
For example, a sheet of the present resin composition can be obtained by heating and melting with a press molding machine.

As a method for producing the curable composite material of the present invention, for example, the components (a), (b) and (c) of the present invention and, if necessary, other components may be mixed with the aforementioned halogen-based or aromatic-based materials. ,
Examples thereof include a method of uniformly dissolving or dispersing in a solvent such as a ketone-based solvent or a mixed solvent thereof, impregnating the substrate, and then drying. The impregnation is performed by dipping (dipping), coating, or the like. The impregnation can be repeated multiple times as necessary, and in this case, the impregnation can be repeated using multiple solutions having different compositions and concentrations to finally adjust the desired resin composition and resin amount It is.

In the curable composite material of the present invention, if necessary, a coupling agent can be used for the purpose of improving the adhesion at the interface between the resin and the substrate. As the coupling agent, general ones such as a silane coupling agent, a titanate coupling agent, an aluminum-based coupling agent, and a zircoaluminate coupling agent can be used. The resin composition of the present invention is cured by causing a crosslinking reaction by means of heating or the like as described later, and contains a radical initiator for the purpose of lowering the reaction temperature or promoting the crosslinking reaction of the unsaturated group. You may use it.

The amount of the radical initiator used in the curable resin composition of the present invention is 0.1 to 10% by weight, preferably 0.1 to 8% by weight based on the sum of the components (a) and (b). %. Representative examples of the radical initiator include benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, and 2,5-dimethyl-2,5-di (t -Butylperoxy) hexyne-3, di-t-butyl peroxide, t-butylcumyl 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-2, There are peroxides such as, but not limited to, 5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxide, and trimethylsilyltriphenylsilyl peroxide. 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 present resin composition is not limited to these examples.

In addition, a suitable curing agent for the polyfunctional maleimide is polyamine, and a suitable catalyst for the polyfunctional cyanate ester is mineral acid, Lewis acid, salts such as sodium carbonate or lithium chloride, and tributylphosphine. Phosphates and the like, catalysts and curing agents suitable for polyfunctional isocyanates, for example, edited by Keiji Iwata,
"Polyurethane resin handbook" (Nikkan Kogyo Shimbun,
1987), pages 118-123, amines, organometallics, polyhydric alcohols, and the like, respectively.

The above catalyst, initiator, curing agent and the like are (b)
It is appropriately selected and used according to the type of the component. The resin composition of the present invention can be used by blending a filler or an additive in an amount that does not impair the original properties for the purpose of imparting desired performance according to its use. The filler may be in the form of fiber or powder, and examples thereof include carbon black, silica, alumina, talc, mica, glass beads, and hollow glass spheres. Additives include antioxidants, heat stabilizers, antistatic agents, plasticizers, pigments, dyes,
Coloring agents and the like. For the purpose of further improving the flame retardancy, chlorine-based, bromine-based, phosphorus-based flame retardants, Sb
Flame retardant aids such as ₂ O ₃ , Sb ₂ O ₅ and NbSbO ₃ １ ／ H ₂ O can be used in combination. In a composite material including a base material, a combination of brominated diphenyl ether and antimony oxide is preferably used.

Further, styrene, vinyl toluene, α-methylstyrene, methyl methacrylate, methyl acrylate, vinyl acetate, triallyl isocyanurate, triallyl cyanurate, allyl Crosslinkable monomers such as glycidyl ether, glycidyl methacrylate, glycidyl acrylate,
Thermoplastic resins, including polyphenylene ether,
Alternatively, one or more thermosetting resins such as an epoxy resin and a phenol resin can be blended.

The cured resin composition of the present invention is obtained by curing the above-described cured resin. The method of curing is arbitrary, and a method using heat, light, an electron beam, or the like can be employed. In the case of curing by heating, the temperature is selected in the range of 80 to 300 ° C, more preferably 120 to 250 ° C, depending on the presence or absence and type of the radical initiator and the curing agent. The 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 a method such as infrared absorption spectroscopy, high-resolution solid nuclear magnetic resonance spectroscopy, and pyrolysis gas chromatography. The cured composite material of the present invention can be used as a film or as a laminate composed of at least one kind of metal foil and a cured resin composition in which the above-mentioned metal foil is laminated on at least one surface.

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.For example, a plurality of the curable composite materials are stacked, and the respective layers are adhered to each other under heat and pressure, and simultaneously heat-cured to obtain a cured composite material having a desired thickness. Can be. Further, it is also possible to obtain a cured composite material having a new layer configuration by combining the cured composite material once cured by adhesion and the curable composite material. 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 composite material obtained by lamination molding in advance can be cured by heat treatment or another method.

The molding and curing are performed at a temperature of 80 to 300 ° C.
The reaction can be carried out at a pressure of 0.1 to 1000 kg / cm 2 and 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.

The method for producing the laminate of the present invention includes:
For example, there is a method in which the curable composite material of the present invention and a metal foil are laminated in a layer configuration according to the purpose, and the respective layers are adhered to each other under heating and pressurization and, at the same time, thermally cured. In the laminate, the curable composite material and the metal foil are laminated in an arbitrary layer configuration. The metal foil can be used as both a surface layer and an intermediate layer.

Also, a laminate composed of the curable composite material of the present invention and a metal plate, and a metal-clad laminate composed of a metal foil, a cured composite material, and a metal plate can be manufactured.
In a laminate, a curable composite material is laminated on one or both sides of a metal plate as a base. In a metal-clad laminate, a metal foil is laminated on one or both sides of a metal plate 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, the lamination and curing may be repeated a plurality of times to form a multilayer. An adhesive can be used for bonding the metal foil and the metal plate. As an adhesive,
Examples include epoxy-based, acrylic-based, phenol-based, and cyanoacrylate-based, but are not particularly limited thereto. The above-mentioned lamination molding and curing can be performed under the same conditions as the cured composite material of the present invention.

[0060]

EXAMPLES Hereinafter, the present invention will be described with reference to examples to further clarify the present invention, but the scope of the present invention is not limited to these examples.

[0061]

Reference Example 1 Poly (2,500) having a viscosity number ηsp / c of 0.54 measured in a chloroform solution of 0.5 g / dl at 30 ° C.
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 dry blending 1.0 part by weight at room temperature, cylinder temperature 30
Extrusion was performed 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.

[0062]

REFERENCE EXAMPLE 2 Viscosity number η measured by the same method as in Reference example 1.
poly (2,6-dimethyl-1,4 having an sp / c of 0.60
After dry-blending 100 parts by weight of (phenylene ether) and 1.5 parts by weight of maleic anhydride at room temperature, the mixture was extruded by a twin-screw extruder at a cylinder temperature of 300 ° C. and a screw rotation speed of 230 rpm. This reaction product is designated B.

[0063]

Examples 1 to 3 The curable resin composition and the cured resin composition A or B were mixed with various compounds in the composition shown in Table 1 using a Henschel mixer, and mixed with a press molding machine.
Molding and curing were performed at 0 ° C. for 2 hours to prepare a cured product having a thickness of about 1 mm.

This cured product is prepared in trichloroethylene for 5 hours.
No warping or change in appearance was observed even after boiling for 1 minute, and dimensional stability was good.

[0065]

[Table 1]

In Table 1, note 1) a: polystyrene b: polycarbonate c: 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 d: t-butylperoxybenzoate e: Dibutyltin laurate Note 2) ○: Appearance was good.

X: Swelling and warpage were observed. Note 3) A film could not be formed.

[0068]

Examples 4 to 7 A film composed of a curable resin composition and a film A or B obtained by curing and various compounds were dissolved in chloroform with the compositions shown in Table 1. This solution was cast on a Teflon dish to obtain a film. The obtained film is about 100
The film had a thickness of μm, and had no stickiness or the like, and was excellent in film-forming properties.

After drying in an air oven, the obtained film was laminated and cured by a vacuum press molding machine to prepare a cured product having a thickness of 1 mm. This cured product did not show any warpage or change in appearance even after boiling for 5 minutes in trichloroethylene, and had good dimensional stability.

[0070]

Comparative Example 1 Instead of A or B, poly (2,6-dimethyl-1,4-phenylene ether) (ηsp / c =
0.56), the same operations as in Examples 1 to 3 were repeated with the compositions shown in Table 1. When the obtained cured product was boiled in trichlorethylene for 5 minutes, swelling and warpage were observed.

[0071]

Comparative Example 2 When the same operation was performed with the compositions shown in Table 1, film formation was poor, so that many cracks occurred and no film was obtained.

[0072]

Examples 8 to 12 Curable Composite Materials Each component having the composition shown in Table 2 was dissolved or dispersed in trichlorethylene. A glass cloth was immersed in this solution for impregnation, and dried in an air oven. A prepreg having a smooth surface and good appearance was obtained.

[0073]

[Table 2]

In Table 2, note 1) a: polystyrene b: polycarbonate c: nylon 66 d: polyethylene terephthalate e: 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 f: Zinc octylate g: Dicumyl peroxide Note 2) BT2100, BT2170: Bismaleimide
Triazine resin laminate A plurality of the above-mentioned curable composite materials are laminated so that the thickness after molding becomes about 0.8 mm, and a thickness of 35 μm is formed on both surfaces thereof.
Was placed and molded and cured by a press molding machine to obtain a laminate. Table 3 shows the curing conditions of each example. The pressure was 40 kg / cm ^{2 in} each case.

[0075]

[Table 3]

Note that in Table 3, Note 1) ○: Appearance was good. ×: The surface was whitened, and exposure of the glass cloth was observed. Various properties of the thus obtained laminate were measured by the following methods. 1. Trichlorethylene resistance The laminate from which the copper foil had been removed was cut into 25 mm squares, boiled in trichlorethylene for 5 minutes, and visually observed for changes in appearance (according to JIS C6481). 2. The dielectric constant and the dielectric loss tangent were measured at 1 MHz (based on JIS C6481). 3. Solder heat resistance The laminate from which the copper foil has been removed is cut into 25 mm squares,
The sample was floated in a solder bath at 120 ° C. for 120 seconds, and the change in appearance was visually observed (according to JIS C6481). 4. Copper foil peeling strength A test piece having a width of 20 mm and a length of 100 mm is cut out from the laminate, and a parallel cut having a width of 10 mm is formed in the copper foil surface, and then a speed of 50 mm / min is perpendicular to the surface. , The copper foil was continuously peeled off, and the stress at that time was measured with a tensile tester, and the lowest value of the stress was shown (JIS C6).
481).

[0077]

Comparative Examples 3 and 4 In Examples 7 and 10, poly (2,6) having ηsp / c = 0.56 was substituted for A or B.
-Dimethyl-1,4-phenylene ether) to produce a laminate. When the trichlorethylene resistance of the laminate was measured, significant whitening of the surface and exposure of the glass cloth were observed.

[0078]

According to the curable resin composition of the present invention, a film or a curable composite material having good solvent film formability and excellent handleability without stickiness on the surface can be obtained. A laminate, a laminate, and a metal-clad laminate obtained by using the curable resin composition of the present invention are materials having both good chemical resistance and excellent dielectric properties.

In addition, it exhibits well-balanced properties in various physical properties such as heat resistance, adhesiveness to metal, dimensional stability, and heat dissipation. Therefore, the material of the present invention is
It can be used as a dielectric material, an insulating material, a heat-resistant material, and the like in fields such as the electronics industry, the space and aircraft industries.
In particular, it is suitably used as a prepreg for single-sided, double-sided, multi-layer printed boards, semi-rigid boards, metal base boards, and multi-layer printed boards.

Further, the material of the present invention is excellent as an adhesive for a high-density circuit board having a line spacing of 100 μm or less, a multilayer circuit board having a phase insulating layer thickness of 200 μm or less, and a circuit board for mounting because of its heat-resistant, moisture-absorbing and insulating properties. Can be used for

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 1/00-101/16

Claims (5)

(57) [Claims] 1. A reaction product of (a) a polyphenylene ether and an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride, and (b) diallyl phthalate, divinylbenzene, a polyfunctional acryloyl compound, or a polyfunctional methacryloyl compound. , Polyfunctional maleimide, polyfunctional cyanate ester, polyfunctional isocyanate, unsaturated polyester
A curable resin composition comprising at least one compound selected from the group consisting of compounds and / or a prepolymer thereof, and (c) a thermoplastic resin, wherein (a)
(A) based on 100 parts by weight of the sum of component (b) and component (b)
The component is 98 to 40 parts by weight, the component (b) is 2 to 60 parts by weight, and 100 parts by weight of the component (a) + (b)
(C) A curable resin composition comprising 2 to 60 parts by weight of a component. 2. A cured resin composition obtained by curing the curable resin composition according to claim 1. 3. A reaction product of (a) a polyphenylene ether and an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride, (b) diallyl phthalate, divinylbenzene, a polyfunctional acryloyl compound, a polyfunctional methacryloyl compound, From functional maleimide, polyfunctional cyanate ester, polyfunctional isocyanate, unsaturated polyester
A curable composite material comprising at least one compound selected from the group of compounds and / or a prepolymer thereof, (c) a thermoplastic resin, and (d) a base material, wherein the component (a) and the component (b) Component (a) is 98 to 40 parts by weight, component (b) is 2 to 60 parts by weight, and component (c) is 100 parts by weight of component (a) + (b) based on the sum of components. 2 to 60 parts by weight, and (a) to
(D) +
(B) + (c) Component is (d) based on 95 to 10 parts by weight.
A curable composite material comprising 5 to 90 parts by weight of a component. 4. A cured composite material obtained by curing the curable composite material according to claim 3. 5. A laminate comprising the cured composite material according to claim 4 and a metal foil.