JPH06184213A - Curable resin composition and curable composite material - Google Patents

Abstract

PURPOSE:To provide a resin composition having the excellent dielectric characteristics of a polyphenylene ether and giving cured products excellent in chemical resistance and thermal resistance by compounding a specific grafted polyphenylene ether resin with a specified compound. CONSTITUTION:This resin composition comprises (A) 98-40 pts.wt. of a grafted polyphenylene ether resin produced by grafting the thermoplastic (co)polymer of an olefinic unsaturated double bond-containing compound (preferably an aromatic vinylic compound such as styrene) to a polyphenylene ether resin (preferably a homopolymer produced by oxidatively polymerizing 2,6- dimethylphenol) and (B) a compound selected from diallyl phthalate, divinyl benzene, triallyl (iso)cyanurate, a polyfunctional (meth)acryloyl compound, a polyfunctional isocyanate compound, an unsaturated polyester, an epoxy resin, a phenolic resin, a polybutadiene resin and/their prepolymers, the total amount of the components A and B being 100 pts.wt.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD 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 composed of the resin composition and a substrate, a cured product thereof, and a laminate composed of the 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 the fields of the electronic industry, the space / aircraft industry and the like.

[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. In addition, 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. Polyphenylene ether has attracted attention in recent years as a new material for solving this problem, and its application to copper-clad laminates has been attempted.

One of the methods of utilizing polyphenylene ether is a method of blending 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 obtain a material that takes advantage of the excellent dielectric properties of polyphenylene ether. Examples of curable polymers and monomers include epoxy resins (Japanese Patent Laid-Open No. 58-690).
46, etc.), 1,2-polybutadiene (Japanese Patent Laid-Open No. Sho 5
9-193929), polyfunctional maleimides (JP-A-56-133355, etc.), polyfunctional cyanates (JP-A-56-141349, etc.), polyfunctional acryloyl or methacroyl compounds ( JP-A-57-149317), triallyl isocyanurate and / or triallyl cyanurate (JP-A-61-218652), isocyanate compounds and the like.

However, since polyphenylene ether itself has no film-forming property, a film, sheet or prepreg having a good appearance could not be obtained even when mixed with these crosslinkable monomers and polymers. Furthermore, since polyphenylene ether originally has no chemical resistance,
Even if a curable polymer or monomer is used in combination, the improvement is naturally limited.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides polyphenylene ether with film-forming properties and at the same time retains the excellent dielectric properties of polyphenylene ether and after curing. The present invention aims to provide a novel curable resin composition exhibiting excellent chemical resistance and heat resistance.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, have found a novel resin composition in accordance with the object of the present invention and completed the present invention. Arrived That is, the present invention is as follows. 1. (A) a grafted polyphenylene ether resin obtained by grafting a polyphenylene ether resin with a thermoplastic polymer or copolymer of a compound containing one or more olefinic unsaturated double bonds in the molecule; and
(B) From diallyl phthalate, divinylbenzene, triallyl isocyanurate, triallyl cyanurate, polyfunctional acryloyl compound, polyfunctional methacryloyl compound, polyfunctional isocyanate, unsaturated polyester, epoxy resin, phenol resin, polybutadiene resin A curable resin composition comprising at least one compound selected from the group consisting of: and / or a prepolymer thereof, wherein the component (a) is 100 parts by weight based on the sum of the components (a) and (b). A curable resin composition comprising 98 to 40 parts by weight and 2 to 60 parts by weight of the component (b). 2. A cured resin composition obtained by curing the above curable resin composition. 3. (A) Graft polyphenylene ether resin in which a thermoplastic polymer or copolymer of a compound containing one or more olefinic unsaturated double bonds in the molecule is grafted onto the polyphenylene ether resin, (b) diallyl phthalate, divinyl Benzene, triallyl isocyanurate, triallyl cyanurate, polyfunctional acryloyl compound, polyfunctional methacryloyl compound, polyfunctional isocyanate, unsaturated polyester, epoxy resin, phenol resin, selected from the compound group consisting of polybutadiene resin A curable composite material comprising at least one compound and / or its prepolymer, and (c) a base material, wherein the component (a) is 98 to 40 wt% based on the sum of the components (a) and (b). Parts, 2 to 60 parts by weight of the component (b), One (a), (b), and (c), based on the sum 100 parts by weight of component (a) +
Component (b) is 95 to 10 parts by weight and component (c) is 5 to 90.
A curable composite material, characterized in that it is parts by weight. 4. A cured composite material obtained by curing the above curable composite material. 5. A laminate comprising the above-mentioned cured composite material and a metal foil.

The present invention will be described in detail below. The polyphenylene ether used in the present invention is represented by the following general formula (I).

[0008]

[Chemical 1]

Examples of the lower alkyl group represented by R _{1 to} R ₄ in the general formula A include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group. A phenyl group etc. are mentioned as an example of an aryl group. Examples of the haloalkyl group include a bromomethyl group and a chloromethyl group. Examples of halogen atoms include bromine and chlorine.

As a typical example of Q in the general formula (I),
The following chemical formula 2 includes a group of compounds represented by four general formulas.

[0011]

[Chemical 2]

Specific examples include the following chemical formulas 3-4.

[0013]

[Chemical 3]

[0014]

[Chemical 4]

In the polyphenylene ether chain represented by J in the general formula (I), in addition to the unit represented by the general formula A,
The unit represented by the general formula (B) may be included in the following chemical formula 5.

[0016]

[Chemical 5]

A particularly preferable example of the polyphenylene ether resin used in the present invention is a homopolymer obtained by oxidative polymerization of 2,6-dimethylphenol alone, 2,6.
A copolymer obtained by copolymerizing dimethylphenol and 2,3,6-trimethylphenol, and a bifunctional polyphenylene ether obtained by oxidatively polymerizing 2,6-dimethylphenol in the coexistence of the bifunctional phenol compound. .

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 one of unsaturated compounds having 2 to 18 carbon atoms, which contains one or more olefinic unsaturated double bonds in the molecule of the above polyphenylene ether resin. Alternatively, it is produced by graft polymerization of a mixture of two or more kinds using a radical polymerization initiator. Examples of the unsaturated compound include styrene,
Vinyltoluene, dimethylstyrene, chlorostyrene,
Aromatic vinyl compounds such as α-methylstyrene, tert-butylstyrene, vinylphenol, vinylpyridine; unsaturated nitrile compounds such as acrylonitrile, methacrylonitrile, ethacrylonitrile; methyl acrylate, butyl acrylate, methyl methacrylate, acetic acid Unsaturated ester compounds such as vinyl; conjugated diene compounds such as butadiene, isoprene, and 1,3-pentadiene; vinyl halide compounds such as vinyl chloride and vinylidene chloride; olefins such as ethylene and poropylene.
Among these compounds, aromatic vinyl compounds, unsaturated nitrile compounds and unsaturated ester compounds are particularly preferable.

Examples of radical polymerization initiators include di-t
ert-butyl peroxide, benzoyl peroxide, lauroyl peroxide, dicumyl oxide, potassium persulfate, ammonium persulfate, sodium perborate and the like, and one or more peroxides may be used in an amount of 100 parts by weight of the polyphenylene ether resin. For 0.3 to
Used in the range of 15 parts by weight. The reaction conditions are 70-300
The temperature is in the range of ° C, and usually depends on the method of reacting using an appropriate amount of an organic solvent.

The polyphenylene ether resin and the unsaturated compound are used in an amount of 60 to 99.9 wt% of the polyphenylene ether resin and 0.1 to 40 wt of the unsaturated compound.
Select from the range of% considering the application. The unsaturated compound is preferably 0.1 to 20 wt%, more preferably 0.2 to 10 wt%. 0.1 wt% of unsaturated compounds
If it is less than 40% by weight, the film formability is insufficient, and if it exceeds 40% by weight, the excellent dielectric properties of polyphenylene ether itself are impaired, which is not preferable.

As the component (b) of the curable resin composition of the present invention, diallylphthalate, divinylbenzene, triallyl isocyanurate, triallyl cyanurate, polyfunctional acryloyl compound, polyfunctional methacryloyl compound, polyfunctional Isocyanate, unsaturated polyester,
At least one compound selected from the group of compounds consisting of an epoxy resin, a phenol resin and a polybutadiene resin and / or a prepolymer thereof is used.

The diallyl phthalate and divinylbenzene used in the present invention are compounds represented by the following structural formulas.

[0023]

[Chemical 6]

Any of these ortho, meta and para isomers of these compounds can be used in the present invention. The triallyl isocyanurate and / or triallyl cyanurate used in the present invention are trifunctional monomers each represented by the following structural formula.

[0025]

[Chemical 7]

The polyfunctional acryloyl compound and polyfunctional methacryloyl compound used in the present invention are represented by the following two general formulas.

[0027]

[Chemical 8]

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 the following; residues of polyether polyols exemplified by diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol; a plurality of residues represented by xylene glycol and bisphenol A Aromatic polyol residues exemplified by aromatic polyols in which benzene rings are linked via a bridging portion and alkylene oxide adducts of these aromatic polyols; benzene polynuclear obtained by reacting phenol and formaldehyde Residues (preferably those having 10 or less nuclides are preferably used); residues derived from epoxy resins having two or more epoxy groups; residues derived from polyester resins having two or more hydroxyl groups at the ends There is a concrete The objects, ethylene glycol diacrylate, propylene glycol diacrylate,
1,3-propanediol acrylate, 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 triacryl
1,1,1-trimethylolpropane diacryle
1,1,1-trimethylolpropane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, sorbitol tetraacrylate, sorbitol hexaacrylate, sorbitol pentaacrylate, 1,4-hexanediol Diacrylate, 2,2-bis (acryloxycyclohexane)
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- (2-acryloxy-di- (ethyleneoxy) phenyl)) propane, 2,2-bis (4- (2-acryloxy-poly- (ethyleneoxy))
Phenyl)) propane; polyvalent acrylate of phenol resin initial condensation product; bisphenol A epoxy resin, novolac epoxy resin, alicyclic epoxy resin, phthalic acid diglycidyl ester, polycarboxylic acid, etc., and acrylic acid Obtained epoxy acrylates; polyester polyacrylates obtained by reacting a polyester having two or more hydroxyl groups at the end with acrylic acid; the above-mentioned acrylates converted to methacrylates; and hydrogen of these compounds Atoms are 2,
Examples thereof include 2-dibromomethyl-1,3-propanediol diacrylate, 2,2-dibromomethyl-1,3-propanediol dimethacrylate partially substituted with halogen, and the like.

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

[0030]

[Chemical 9]

Examples of polyfunctional isocyanates of the general formula (E) include 2,4-toluene diisocyanate, 2,
6-toluene diisocyanate, metaphenylene diisocyanate, paraphenylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, 4,4-diphenylmethane diisocyanate, tolidine diisocyanate, tetramethylxylene diisocyanate, isophorone diisocyanate, cyclohexane-1,4-diisocyane -To, lysine isocyanate, triphenylmethane triisocyanate, tris (isocyanatophenyl) thiophosphate,
1,6,11-Undecane triisocyanate, 1,8
-Diisocyanate-4-isocyanate methyl octane, 1,3,6-hexamethylene triisocyanate,
Examples thereof include bicycloheptane triisocyanate and polymethylene polyphenyl isocyanate.

These polyfunctional isocyanates can also be used by converting them into polyfunctional blocked isocyanates using various blocking agents. As examples of the blocking agent, known compounds such as alcohols, phenols, oximes, lactams, malonic acid esters, acetoacetic acid esters, acetylacetone, amides, imidazoles, and sulfites can be used.

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 an anhydride, ester or acid chloride thereof, and is generally used. What is used. Typical examples of glycols include ethylene glycol, propylene glycol, diethylene glycol, difluoropyrene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, hydrogenated bisphenol. A, bisphenol A propylene oxide adduct, dibromo neopentol 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,
Examples thereof include tetonic acid and tetrabromophthalic anhydride.

For details of the unsaturated polyester, see, for example, "Polyester Resin Handbook" by Eiichiro Takiyama.
See Nikkan Kogyo Shimbun (1988). The epoxy resin used in the present invention may be one having two or more epoxy groups in one molecule, and known ones may be used alone or in combination of two or more. Typical examples are glycidyl ether type epoxy resins obtained by reaction of phenols or alcohols with epichlorohydrin, glycidyl ester type epoxy resins obtained by reaction of carboxylic acids with epichlorohydrin, amines or cyanuric acid with epichlorohydrin, and Examples thereof include a glycidylamine type epoxy resin obtained by the reaction of the above, an internal epoxy resin obtained by oxidation of a double bond, etc. (For details of these, see, for example, Masaki Shinbo, "Epoxy Resin Handbook", Nikkan Kogyo Shimbun (1987). Shown).

The phenolic resin used in the present invention is
It has two or more phenolic hydroxyl groups in one molecule and is phenol, cresol, xylenol, propylphenol, amylphenol, bisphenol A.
The novolak resin and the resole resin, which are synthesized alone or in combination from the above, are shown. The polybutadiene resin used in the present invention is not particularly limited, but known ones may be used alone or in combination of two or more. Typical examples include 1,2-polybutadiene and 1,4-polybutadiene. It is also possible to use polybutadiene having a functional group at the terminal or side chain of the molecular chain. Representative examples of the functional group include a hydroxyl group, a carboxyl group, an epoxy group, a urethane group, an acryl group, a methacryl group, and an unsaturated acid anhydride group.

As the component (b) of the curable resin composition of the present invention, it is possible to use only one of the above-mentioned compound groups or a combination of two or more thereof. Further, a prepolymer obtained by prereacting these compounds with heat, light or the like in the presence or absence of known catalysts, initiators, curing agents and the like described later is also used as the component (b) of the present invention. You can

In addition to the above, the curable resin composition of the present invention comprises styrene, vinyltoluene, α-methylstyrene, methyl methacrylate, methyl acrylate, vinyl acetate, allyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate and the like. It is possible to blend one or more thermoplastic resins such as a hydrophilic monomer and polyphenylene ether.

Although the compounding ratio of both components (a) and (b) can be varied over a wide range, in the present invention, 98 to 40 parts by weight of component (a) is used based on the total amount of both components. 2 to 60 parts by weight of the component (b), more preferably 95 to 50 parts by weight of the component (a), and 5 to 50 parts of the component (b).
It is preferable to use parts by weight. When the amount of the component (b) is less than 2 parts by weight, the chemical resistance is not sufficiently improved, which is not preferable. Conversely, 60
It is not preferable that the amount is more than 100 parts by weight, because the dielectric properties deteriorate.

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 Natural cellulose-based cloths such as mixed fiber 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 laminate of 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. (A) above,
As a method for mixing the components (b), a solution mixing method in which the two are uniformly dissolved or dispersed in a solvent, or a melt blending method in which the two are heated by an extruder or the like can be used. As the solvent used for the solution mixture, 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 curable 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 curable resin composition is dissolved in the above-mentioned solvent and molded into a desired shape, or a heating and melting method in which the curable resin composition is heated and melted and molded into a desired shape is used. The above-mentioned casting method and heat melting method may be performed independently. Moreover, you may carry out combining each. For example, several to several tens of films of the curable resin composition of the present invention prepared by a casting method are laminated, and a film of the curable resin composition of the present invention is heated and melted by a heating and melting method, for example, a press molding machine. Can be obtained.

As the method for producing the curable composite material of the present invention, for example, the components (a) and (b) of the present invention and, if necessary, other components may be added to the above halogen-based, aromatic-based, ketone-based, etc. The method of uniformly dissolving or dispersing in the solvent or the mixed solvent thereof, impregnating the base material, and then drying. Impregnation is performed by dipping, coating, or the like. Impregnation can be repeated multiple times as needed, and in this case it is also possible to repeat impregnation using multiple solutions with different compositions and concentrations to finally adjust the desired resin composition and amount. Is.

In the curable composite material of the present invention, a coupling agent can be used if necessary for the purpose of improving the adhesiveness at the interface between the resin and the substrate. As the coupling agent, silane coupling agents, titanate coupling agents, aluminum-based coupling agents, zircoaluminate coupling agents and the like can be used. The curable resin composition of the present invention undergoes a crosslinking reaction by means of heating or the like to be cured as described below, and is a radical initiator for the purpose of lowering the reaction temperature at that time or promoting the crosslinking reaction of unsaturated groups. You may use by containing.

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, 2,5-dimethyl-2,5-di (t -Butylperoxy) 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-2, There are peroxides such as, but not limited to, 5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxide, and trimethylsilyltriphenylsilylperoxide. 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.

Further, an epoxy curing agent may be used. As the curing agent, an ordinary epoxy resin curing agent, for example, polyamine curing agent, acid anhydride curing agent, polyphenol curing agent, polymercaptan curing agent, anionic polymerization type catalyst curing agent, cationic polymerization type catalyst type A curing agent, a latent curing agent, or the like can be used (for details, see, for example, Masaki Shinbo, "Epoxy Resin Handbook", Nikkan Kogyo Shimbun (198).
7), Souichi Muroi, Shuichi Ishimura, "Introduced Epoxy Resin", published by Kobunshi Kobunkai (1988), etc.).

The curable 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 its use. The filler may be in the form of fibers or powder, carbon black, silica, alumina, talc,
Examples thereof include mica, glass beads, glass hollow spheres, and the like. Examples of the additives include antioxidants, heat stabilizers, antistatic agents, plasticizers, pigments, paints, colorants and the like. For the purpose of further improving the flame retardancy, chlorine-based, bromine-based, phosphorus-based flame retardants, Sb ₂ O ₃ , Sb ₂ O ₅ , NbSO ₃
-A flame retardant aid such as 1/4 H ₂ O can also be used in combination.
A combination of diphenyl ether bromide and antimony oxide is preferably used in the composite material including the base material. Furthermore, it is also possible to mix one or more kinds of other thermoplastic resins or thermosetting resins.

The cured 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., though it varies depending on the presence or absence of the radical initiator and the curing agent and the type thereof. The time 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 state nuclear magnetic resonance spectroscopy and pyrolysis gas chromatography. The cured composite material of the present invention can be used in the form of a film or a laminate composed of at least one type of metal foil and a cured resin composition obtained by laminating the above metal foil 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, 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 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 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. . In the present invention, the laminate is composed of the cured composite material of the present invention and a metal foil.
Examples of the metal foil used here include copper foil and aluminum foil as described above. The thickness is not particularly limited, but is 5 to 200 μm, more preferably 5 to
It is in the range of 105 μm.

The method for producing the laminate of the present invention includes:
For example, a method may be mentioned in which the curable composite material of the present invention and a metal foil are laminated in a layered structure according to the purpose, and each layer is adhered under heat and pressure and at the same time heat-cured. In the laminate, the curable composite material and the metal foil are laminated in any layer structure. The metal foil can be used as both the surface layer and the intermediate layer.

Further, a laminated plate composed of the cured composite material of the present invention and a metal plate, and a metal-clad laminated plate composed of a metal foil, a cured composite material, and a metal plate can also be manufactured. In the laminated plate, a curable composite material is laminated on one side or both sides of a metal plate as a base. In the metal-clad laminate, a metal foil is used as a base, and a metal foil is laminated on one or both surfaces of the metal foil via a curable composite material. At this time, the metal foil is used as the outermost layer, but may be used as an intermediate layer other than the outermost layer.

Besides the above, it is also possible to repeat lamination and curing a plurality of times to form a multilayer. An adhesive may be used to bond the metal foil and the metal plate. As an adhesive,
Examples thereof include epoxy type, acrylic type, phenol type and cyanoacrylate type, but are not particularly limited thereto. The above-mentioned lamination molding and curing can be performed under the same conditions as for the cured composite material of the present invention.

[0056]

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.

[0057]

[Synthesis Example 1] Poly (2,3) having a viscosity number ηsp / c of 0.54 measured at 30 ° C. in a chloroform solution of 0.5 g / dl.
6-dimethyl-1,4-phenylene ether) 100 parts by weight, styrene 60 parts by weight, ethylbenzene 110 parts by weight, and di-t-butyl peroxide 6 parts by weight 10 parts by weight.
After uniformly dissolving with stirring at 0 ° C., nitrogen gas was blown in to expel oxygen gas in the reaction system. Polymerization was carried out for 2.5 hours while controlling the temperature inside the reactor to be between 145 and 150 ° C, then the contents were taken out and dried at 180 ° C for 14 hours using a vacuum dryer to obtain ethylbenzene and unreacted. Was removed to obtain a graft polyphenylene ether resin.

The polystyrene content of this graft polyphenylene ether resin was 9 wt% as determined by infrared absorption spectrum analysis. This reaction product is designated as A.

[0059]

[Synthesis example 2] Viscosity number η measured by the same method as in synthesis example 1
Poly (2,6-dimethyl-1,4) with sp / c of 0.60
-Phenylene ether) 150 parts by weight, methyl acrylate 64 parts by weight, ethylbenzene 180 parts by weight and di-t-butyl peroxide 6 parts by weight were charged and 100 ° C.
After being uniformly dissolved with stirring at, nitrogen gas was blown in to expel oxygen gas in the reaction system. Reactor internal temperature is 15
2.5 while controlling to keep it around 0 ℃
After polymerization for a period of time, the contents were taken out and dried at 180 ° C. for 21 hours using a vacuum dryer to remove ethylbenzene and unreacted methyl methacrylate to obtain a graft polyphenylene ether resin. From the infrared absorption spectrum analysis, the polymethylmethacrylate content was 5 wt%. This reaction product is designated as B.

[0060]

Examples 1 to 2 Curable Resin Composition and Cured Resin Composition A and triallyl isocyanurate or orthodiallyl phthalate having the composition shown in Table 1 are melt cast using chloroform. Examples 1 and 2 are film-shaped. Therefore, make a 100 μm film and
Three sheets were piled up and molded by a press molding machine at 200 ° C. for 2 hours and cured. This cured product showed no warpage and no change in appearance even after boiling in trichlorethylene for 5 minutes, had good dimensional stability and chemical resistance.

[0061]

Comparative Example 1 Instead of A, poly (2,6-dimethyl-
1,4-phenylene ether) (ηsp / c = 0.5
Using 6), a curable compound and an initiator were used and cast by the same operation as in Examples 1 and 2 with the composition shown in Table 1, but no film was formed and a film could not be formed.

[0062]

Comparative Example 2 The same operation as in Examples 1 and 2 was repeated with the composition of Table 1 using only A and the initiator. Although a film was formed and a film was formed, when the molded and cured product was boiled in trichlorethylene for 5 minutes, swelling and warpage were observed, and there was no chemical resistance.

[0063]

Examples 3 to 8 Curable Composite Material Each component having the composition shown in Table 2 was dissolved or dispersed in trichlorethylene. A glass cloth was dipped in this solution for impregnation and dried in an air oven. A prepreg having a smooth surface and a good appearance was obtained.

Laminate A plurality of the above-mentioned curable composite materials are laminated so that the thickness after molding is about 0.8 mm, and the thickness is 35 μm on both sides.
The copper foil of was placed and cured by a press molding machine to obtain a laminate. The curing conditions of each example are shown in Table 3. The pressure was 40 kg / cm ^{2 in} all cases.

Various properties of the thus obtained laminate were measured by the following methods. 1. Trichloroethylene resistance The laminate from which the copper foil was removed was cut into 25 cm square pieces, boiled in trichlorethylene for 5 minutes, and the change in appearance was visually observed (based on JIS C 6481). 2. The measurement was performed at a dielectric constant and a dielectric loss tangent of 1 MHz (based on JIS C 6481). 3. Solder heat resistance Cut the laminate from which the copper foil was removed into 25 mm square pieces, 260
It was floated in a solder bath at a temperature of 120 ° C. for 120 seconds, and the change in appearance was visually observed (based on JIS C 6481). 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 (JIS C 6
481).

[0066]

[Comparative Examples 3 to 5] ηsp / c = in place of A or B
The same operation was performed using 0.56 of poly (2,6-dimethyl-1,4-phenylene ether) to produce a laminated plate. When the trichlorethylene resistance of this laminate was measured, significant whitening of the surface and exposure of glass cloth were observed.

[0067]

[Table 1]

[0068]

[Table 2]

[0069]

[Table 3]

[0070]

The curable resin composition of the present invention is a material exhibiting excellent film-forming properties, and at the same time, the cured product and the laminate have both good chemical resistance and excellent dielectric properties. In addition, it exhibits well-balanced properties in various physical properties such as heat resistance, adhesiveness with metals, dimensional stability, and heat dissipation.

Therefore, the material of the present invention can be used as a dielectric material, an insulating material, a heat-resistant material, etc. in the fields of electric industry, electronic industry, space / aircraft industry and the like. Particularly, it is suitably used as a single-sided, double-sided, multi-layer printed circuit board, semi-rigid substrate, metal base substrate, and prepreg for multi-layer printed circuit board. Further, the material of the present invention can be favorably used as an adhesive for a high-density circuit board having a line spacing of 100 μm or less, a multi-layer circuit board having a correlation insulating layer thickness of 200 μm or less, and a mounting circuit board because of its heat and moisture absorption resistance. .

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08L 61/06 LNB 8215-4J 63/00 NJN 8830-4J // C08F 299/02 MRS 7442-4J

Claims (5)

[Claims] 1. A graft polyphenylene ether resin comprising (a) a polyphenylene ether resin grafted with a thermoplastic polymer or copolymer of a compound containing one or more olefinic unsaturated double bonds in the molecule, and (B) diallyl phthalate, divinylbenzene,
At least one selected from the group consisting of triallyl isocyanurate, triallyl cyanurate, a polyfunctional acryloyl compound, a polyfunctional methacryloyl compound, a polyfunctional isocyanate, an unsaturated polyester, an epoxy resin, a phenol resin, and a polybutadiene resin. A curable resin composition comprising one compound and / or a prepolymer thereof, the sum of the components (a) and (b) being 10
98 to 40 parts by weight of the component (a) based on 0 parts by weight,
(B) Component is 2-60 weight part, The curable resin composition characterized by the above-mentioned. 2. A cured resin composition obtained by curing the curable resin composition according to claim 1. 3. A grafted polyphenylene ether resin obtained by grafting (a) a polyphenylene ether resin with a thermoplastic polymer or copolymer of a compound containing one or more olefinic unsaturated double bonds in the molecule,
(B) From diallyl phthalate, divinylbenzene, triallyl isocyanurate, triallyl cyanurate, polyfunctional acryloyl compound, polyfunctional methacryloyl compound, polyfunctional isocyanate, unsaturated polyester, epoxy resin, phenol resin, polybutadiene resin A curable composite material comprising at least one compound selected from the group consisting of the following compounds and / or a prepolymer thereof, and (c) a base material, wherein (a) and (b) are the sum of (a) ) Component is 98 to 40 parts by weight,
(B) component is 2 to 60 parts by weight, and (a),
Curing, characterized in that 95 to 10 parts by weight of (a) + (b) component and 5 to 90 parts by weight of (c) component are based on 100 parts by weight of the sum of components (b) and (c). Composite material. 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.