JPH0737567B2 - Curable resin composition and composite material and laminate using the same - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a curable resin composition using a reaction product of a polyphenylene ether resin and an unsaturated carboxylic acid or an acid anhydride, and a cured product obtained by curing the same. Furthermore, the present invention relates to a composite material composed of the resin composition and a substrate, a cured product thereof, a laminate composed of the cured product and a metal foil, and a laminated plate composed of the cured product and a metal plate.

The resin composition of the present invention exhibits excellent chemical resistance, dielectric properties, heat resistance and flame retardancy after curing, and is used as a dielectric material and an insulating material in the fields of electric industry, electronic industry, space / aircraft industry and the like. It can be used as a material, a heat resistant material, a structural material and the like. In particular, it can be used as a single-sided or double-sided, multi-layered printed board, flexible printed board, semi-rigid board, board having excellent heat dissipation characteristics, and the like.

[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 the drawback of poor electrical characteristics, especially dielectric characteristics in the high frequency region. Polyphenylene ether has recently attracted attention as a new material for solving this problem, and its application to copper-clad laminates has been attempted.

Japanese Patent Laid-Open No. 61-287739 discloses a laminate obtained by curing a resin composition containing polyphenylene ether and triallyl isocyanurate and / or triallyl cyanurate. The polyphenylene ether used here is not chemically modified at all and does not show any chemical resistance. Therefore, chemical resistance when the laminated plate is used as a printed wiring board, that is, boiling trichloroethylene property is Is insufficient. Further, since polyphenylene ether itself has extremely poor solvent film-forming property, it has a drawback that it is difficult to obtain a film having a smooth surface when producing the laminated plate.

In order to solve the above-mentioned drawbacks, the present inventors previously invented a polyphenylene ether substituted with a propargyl group or an allyl group, and a polyphenylene ether containing a triple bond or a double bond (Japanese Patent Laid-Open Publication No. Sho. 64-69628, 64-69629, JP-A-1-113425 and JP-A-11-134426), resins made of these polyphenylene ethers and triallyl isocyanurate and / or triallyl cyanurate. It has been found that the composition is excellent in various properties such as solvent film-forming property, chemical resistance after curing, and dielectric property, and is suitable as a printed circuit board material (see JP-A-2-208355). . However, the production of these polyphenylene ethers requires a process of substitution reaction with an organic metal, and further requires a solvent removal and a polymer purification step, which requires expensive equipment and a large amount of energy, and is industrially carried out. It was a disadvantage to me.

On the other hand, Japanese Examined Patent Publication No. 64-3223 discloses that
Combinations of polyphenylene ether and various epoxy resins are disclosed. As this epoxy resin, general ones such as polyglycidyl ether of bisphenol A, 3,3 ′, 5,5′-tetrabromobisphenol A, and epoxyphenol novolac resin are used, and various publicly known amines and the like are used. Curing is performed by using the curing agent of. However, here too, the polyphenylene ether itself has not been modified at all, so this cured product is extremely inferior in chemical resistance and does not exhibit the trichlorethylene resistance required for printed circuit board materials at all.

As materials having improved chemical resistance, US Pat. No. 4,912,172 discloses (i) polyphenylene ether, (ii) bisphenol polyglycidyl ether, (i)
ii) A resin composition comprising an aluminum or zinc salt is disclosed. Further, as a material to which flame retardancy is imparted, JP-A-2-55521, JP-A-2-55522 and JP-A-2-2
No. 22412 discloses (i) polyphenylene ether,
(ii) bromine-containing epoxy resin composition, (iii) novolac resin, (iv) imidazole and polyamines, (v)
A resin composition comprising a zinc salt and (vi) Sb ₂ O ₅ is disclosed.

Japanese Unexamined Patent Publication (Kokai) No. 2-269732 discloses a composition for improving the water flow of a resin at the time of molding (i)
A resin composition comprising low molecular weight polyphenylene ether, (ii) bromine-containing epoxy resin composition, (iii) imidazole and polyamines, and (iv) aluminum or zinc salt is disclosed.

As a material obtained by treating polyphenylene ether itself, Japanese Patent Laid-Open No. 135216/1990 discloses:
(i) a reaction product of a polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride, (ii) a polyepoxy compound, (i)
ii) A resin composition comprising a curing catalyst for epoxy is disclosed in JP-A-2-166115, (i) melt-processed polyphenylene ether, (ii) polyepoxy compound, (iii)
A resin composition comprising a curing catalyst for epoxy is disclosed.

However, even in the above series of resin compositions, the improvement of the resistance to trichlorethylene after curing was still insufficient, and it was found that after the boiling of trichlorethylene, a remarkable change in appearance such as roughness was observed.
Further, as shown in Example 6 in JP-A-2-55721, the dielectric constant is 4.19, even though polyphenylene ether is used in an amount of about 1/2 of the total resin composition.
And not sufficiently improved. This is a commercially available glass /
Epoxy resin copper-clad laminate dielectric constant 4.5 (resin amount about 4
0%) and almost the same level.

European Patent No. 315829 discloses a resin composition comprising polyphenylene ether, a bisphenol A type epoxy resin, and an amine curing agent. However, the chemical resistance of this cured product is not described in this specification, and the required properties are becoming more and more stringent in recent years.
Similar to -3223, further improvement in chemical resistance is awaited.

[0012]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, retains excellent dielectric properties of polyphenylene ether, is inexpensive, and has excellent chemical resistance after curing. And a novel curable resin composition exhibiting heat resistance.

[0013]

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 The present invention consists of the following nine inventions.

That is, the first aspect of the present invention is to cure (a) a reaction product of a polyphenylene ether resin and an unsaturated carboxylic acid or an acid anhydride, and (b) a triallyl isocyanurate and / or a triallyl cyanurate. Resin composition, wherein the amount of the component (a) is 98 to 40 parts by weight and the amount of the component (b) is 2 to 60 parts by weight, based on 100 parts by weight of the sum of the components (a) and (b). A characteristic curable resin composition is provided.

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

A third aspect of the present invention is the first aspect or the second aspect.
A cured resin composition obtained by curing the curable resin composition of the invention is provided. A fourth aspect of the present invention provides a curable composite material comprising the curable resin composition of the first aspect and a substrate. A fifth aspect of the present invention provides a curable composite material comprising the curable resin composition of the second aspect and a substrate. A sixth aspect of the present invention provides a cured composite material obtained by curing the curable composite material of the fourth to fifth inventions.

A seventh aspect of the present invention provides a laminate comprising the cured composite material of the sixth aspect and a metal foil. 8th of this invention
Provides a laminated plate in which an insulating layer made of the cured composite material of the sixth invention is laminated on a metal base. 9th of this invention
Provides a metal-clad laminate in which an insulating layer made of the cured composite material of the sixth invention is laminated on at least one surface of a metal base, and a metal foil is laminated on at least the outermost layer of the insulating layer.

The above nine inventions will be described in detail below. The polyphenylene ether resin used for producing the component (a) of the first and second curable resin compositions of the present invention is represented by the following general formula (I).

[0019]

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

[0020]

[Chemical 2] (Here, R _{1 to} R ₄ each independently represent a lower alkyl group, an aryl group, a haloalkyl group, a halogen atom or a hydrogen atom.) Q represents a hydrogen atom when m is 1 and m is 2
In the above case, it represents a residue of a polyfunctional phenol compound having 2 to 6 phenolic hydroxyl groups in one molecule and having a polymerization inactive substituent at the ortho position and the para position of the phenolic hydroxyl group. Examples of the lower alkyl group represented by R _{1 to} R ₄ in the general formula (II) include a methyl group, an ethyl group, and n.
-Propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and the like. 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 compound group represented by the following four kinds of general formulas can be mentioned.

[0022]

[Chemical 3] [Wherein A ₁ and A ₂ represent the same or different linear alkyl groups having 1 to 4 carbon atoms, X represents an aliphatic hydrocarbon residue and a substituted derivative thereof, an aralkyl group and a substituted derivative thereof, oxygen Represents a sulfur, a sulfonyl group, a carbonyl group, Y represents an aliphatic hydrocarbon residue and a substituted derivative thereof, an aromatic hydrocarbon residue and a substituted derivative thereof, an aralkyl group and a substituted derivative thereof,
Z is oxygen, sulfur, sulfonyl group, a carbonyl group, two phenyl groups attached directly A _2, A ₂ and X,
All the bonding positions of A ₂ and Z represent the ortho position and the para position of the phenolic hydroxyl group, r is 0 to 4 and s is an integer of 2 to 6. ] As a specific example,

[0023]

[Chemical 4]

[0024]

[Chemical 5] Etc. The polyphenylene ether chain represented by J in the general formula (I) may contain a unit represented by the following general formula (III) in addition to the unit represented by the general formula (II).

[0025]

[Chemical 6] [In the formula, R _{5 to} R ₉ each independently represent a hydrogen atom, a halogen atom, a lower alkyl group, an aryl group or a haloalkyl group, and R ₁₀ and R ₁₁ each independently represent a hydrogen atom, an alkyl group,
It represents a substituted alkyl group, an aryl group or a substituted aryl group, and R ₁₀ and R ₁₁ are not hydrogen at the same time. ] As an example of the unit of the general formula (III),

[0026]

[Chemical 7] Etc. In addition, units obtained by graft-polymerizing a polymerizable monomer having an unsaturated bond such as styrene or methyl methacrylate to the units of the above formulas (II) and (III) may be included.

Preferred examples of the polyphenylene ether resin of the general formula (I) used in the present invention include 2,6-
Poly (2,6) obtained by homopolymerization of dimethylphenol
-Dimethyl-1,4-phenylene ether), poly (2,6-dimethyl-1,4-phenylene ether) styrene graft copolymer, copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol Polymer,
2,6-dimethylphenol and 2,6-dimethyl-3-
Copolymer of phenylphenol, polyfunctional polyphenylene ether resin obtained by polymerizing 2,6-dimethylphenol in the presence of polyfunctional phenol compound Q- (H) _m (m is an integer of 2 to 6) , For example, JP-A-63-301
222, and copolymers containing the units of the general formulas (II) and (III) as disclosed in JP-A-1-297428.

The molecular weight of the polyphenylene ether resin described above is not particularly limited, but is 30 ° C., 0.5
Those having a viscosity number η _sp / C measured with a chloroform solution of g / dl in the range of 0.1 to 1.0 can be favorably used.
A resin having a low viscosity number is preferable for a composition that places importance on molten resin flow, for example, a prepreg for a multilayer printed wiring board.

The component (a) used in the present invention is produced by reacting the above polyphenylene ether resin with an unsaturated carboxylic acid or acid anhydride. The reaction
The product is a polymerizable double bond due to acid or acid anhydride.
The product is substantially free of Polymerizable double bond
The presence or absence of can be analyzed by infrared absorption spectroscopy.
Examples of suitable acids and acid anhydrides include acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, itaconic acid,
Examples thereof include itaconic anhydride, glutaconic anhydride, citraconic anhydride, and the like. The reaction is performed by mixing the polyphenylene ether resin and the unsaturated carboxylic acid or acid anhydride at 100 ° C to 390 ° C.
It is carried out by heating in the temperature range of. At this time, a radical initiator may coexist. Both the solution method and the melt-mixing method can be used, but the melt-mixing method using an extruder or the like is simpler and more suitable for the purpose of the present invention. The ratio of unsaturated carboxylic acid or acid anhydride is 0.01 to 100 parts by weight of the polyphenylene ether resin.
The amount is 5.0 parts by weight, preferably 0.1 to 3.0 parts by weight.

The triallyl isocyanurate and / or triallyl cyanurate used as the component (b) of the first and second curable resin compositions of the present invention are trifunctional compounds represented by the following structural formulas. It is a monomer.

[0031]

[Chemical 8] In carrying out, the triallyl isocyanurate and the triallyl cyanurate can be used not only individually, but also both can be mixed and used at an arbitrary ratio. In the present invention, triallyl isocyanurate and triallyl cyanurate exert their effects as a plasticizer and a crosslinking agent. That is, it improves the resin flow during molding and the crosslink density.

In the second curable resin composition of the present invention, an epoxy resin is further used as the component (c). By adding the epoxy resin, the adhesiveness to the metal foil is improved and flame retardancy can be easily imparted as described later. Further, the resin flow at the time of molding is improved, and the resin cost becomes lower.

The epoxy resin used here 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. As typical examples, 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 glycidyl type epoxy resin obtained by reaction of cyanuric acid and epichlorohydrin, internal epoxy resin obtained by oxidation of double bond, etc. (For details of these, see, for example, Masaki Shinbo, “Epoxy Resin Handbook”. (See Nikkan Kogyo Shimbun, 1987).

The first curable resin composition of the present invention comprises the two components (a) and (b) among the above, and the mixing ratio of both is (a) based on 100 parts by weight of the sum of the two components. Component) is 98-40 parts by weight, component (b) is 2-60 parts by weight, more preferably component (a) is 95-50 parts by weight,
The component (b) is in the range of 5 to 50 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. On the other hand, if the amount exceeds 60 parts by weight, the dielectric properties, flame retardancy and moisture absorption properties deteriorate, and the material becomes extremely brittle after curing, which is not preferable.

The second curable resin composition of the present invention comprises the above-mentioned three components (a) to (c), and the mixing ratio of the components (a) and (b) among them is the first invention. As in the case of the curable resin composition, the component (a) is 98-40 parts by weight and the component (b) is 2-60, based on 100 parts by weight of the sum of the two.
Parts by weight, more preferably 95 to 50 parts by weight of component (a) and 5 to 50 parts by weight of component (b).

The mixing ratio of the component (c) is from (a) to
(A) + based on 100 parts by weight of the sum of components (c)
The component (b) is 99 to 1 parts by weight, the component (c) is 1 to 99 parts by weight, and more preferably (a) + (b) component 90 to
It is in the range of 10 parts by weight and 10 to 90 parts by weight of the component (c). When the amount of the component (c) is less than 1 part by weight, no remarkable improvement effect is exhibited in the adhesiveness to the metal foil, and when imparting flame retardancy, the effect is insufficient, which is not preferable. On the other hand, if the amount of component (c) exceeds 99 parts by weight, the dielectric properties will deteriorate, which is not preferable. In the second curable resin composition of the present invention, when a brominated epoxy resin is used as the component (c), a flame-retardant resin composition can be obtained. The preferred halogen content for imparting flame retardancy is from (a) to
It is 5% by weight or more, more preferably 10% by weight or more, based on the sum of the components (c). In addition to bromine in the epoxy resin, halogen in the polyphenylene ether resin used for producing the component (a) can be included in the halogen.

As a method for mixing the above-mentioned respective components, a solution mixture in which they are uniformly dissolved or dispersed in a solvent, or a melt blending method in which they are heated by an extruder or the like can be used.

Solvents used for mixing the solutions 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. Or a combination of two or more.

The first and second curable resin compositions of the present invention can be favorably used as a film.
As a manufacturing method thereof, for example, an ordinary solvent film forming method (casting method) or the like can be used, and one having an arbitrary thickness can be manufactured. The composition suitable for producing the film is not particularly limited, but 98 to 50 parts by weight of the component (a) based on 100 parts by weight of the sum of the components (a) and (b),
The component (b) is in the range of 2 to 50 parts by weight, and when the component (c) is used, the sum of the components (a) to (c) is 1
90 to 2 parts by weight of (a) + (b) components based on 00 parts by weight
0 parts by weight, and the component (c) is in the range of 10 to 80 parts by weight. When the component (b) or the component (c) is less than the above range, the chemical resistance and the adhesiveness to the metal foil are insufficient as described above, which is not preferable. On the other hand, if the amount exceeds the above range, the film becomes brittle or sticky, resulting in poor handleability, which is not preferable.

The first and second curable resin compositions of the present invention undergo a crosslinking reaction by means of heating or the like to be cured as described later, but the temperature at that time is lowered or the crosslinking reaction is promoted. A radical initiator or a curing agent may be contained for use for the purpose. A usual peroxide can be used as the radical initiator.

As the curing agent, usual epoxy resin curing agents such as polyamine type curing agents, acid anhydride type curing agents, polyphenol type curing agents, polymercaptan type curing agents, anionic polymerization type catalyst type curing agents, and cations are used. Polymerization type catalyst type curing agents, latent type curing agents and the like can be used (for details, for example, Masaki Shinbo, "Epoxy Resin Handbook" (Nikkan Kogyo Shimbun, 1987), Soichi Muroi, Shuichi Ishimura, "Introduction Epoxy Resin" (Polymer Publishing, 1988) and the like). Each of the radical initiator and the curing agent may be used alone or in combination of two or more.

The first and second curable resin compositions of the present invention do not impair the original properties for the purpose of imparting desired performance in addition to the above-mentioned radical initiator and curing agent, depending on the application. Fillers and additives in an amount within the range can be blended and used. Examples of the filler include carbon black, silica, alumina, barium titanate, talc, mica, glass beads, glass hollow spheres and the like. Examples of the additive include an antioxidant, a heat stabilizer, an antistatic agent, a plasticizer, a pigment, a dye and a coloring material. Also, for the purpose of further improving flame retardancy, chlorine-based, bromine-based, phosphorus-based flame retardants,
Sb ₂ O ₃ , Sb ₂ O ₅ , NaSbO ₃ .1 / 4H ₂ O
It is also possible to use a flame retardant auxiliary such as Further, for example, a crosslinkable monomer such as allyl glycidyl ether, glycidyl methacrylate, or glycidyl acrylate, a thermoplastic resin such as polyphenylene ether, or another thermosetting resin may be blended alone or in combination. .

The third curable resin composition of the present invention is obtained by curing the curable resin composition of the first invention or the second invention described above. The curing method is arbitrary, and a method using heat, light, an electron beam or the like can be adopted.

When the curing is carried out by heating, the temperature varies depending on the presence or absence of the radical initiator and the curing agent and the type thereof, but is 80 to 300 ° C. in the curable resin composition of both the first invention and the second invention. More preferably 150-25
It is selected in the range of 0 ° C. The time is 1 minute to 10 hours, more preferably 1 minute to 5 hours. The resin composition of the obtained cured resin composition can be analyzed by methods such as infrared absorption spectroscopy, high resolution solid state nuclear magnetic resonance spectroscopy, and thermal decomposition gas chromatography.

The cured resin composition of the present invention can be favorably used as a film. Further, this cured resin composition, like the cured composite material described below as the sixth invention,
It can be used by laminating it with a metal foil and / or a metal plate.

Next, the fourth and fifth curable composite materials of the present invention will be described. The fourth curable composite material of the present invention is composed of the curable resin composition and the substrate described above as the first of the present invention. The fifth curable composite material of the present invention is composed of the curable resin composition of the second invention and a substrate. As the substrate used here, various kinds of glass cloth or glass non-woven cloth such as roving cloth, cloth, chopped mat, surfacing mat; ceramic fiber cloth, asbestos cloth, metal fiber cloth and other synthetic or natural inorganic fiber cloth; polyvinyl Woven or non-woven fabric obtained from synthetic fibers such as alcohol fiber, polyester fiber, acrylic fiber, wholly aromatic polyamide fiber; natural fiber cloth such as cotton cloth, linen cloth and felt; carbon fiber cloth; kraft paper, cotton paper, paper-glass Natural cellulosic cloths such as mixed woven paper may be 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 parts by weight, more preferably 10 to 80 parts by weight, further preferably 20 to 70 parts by weight, based on 100 parts by weight of the curable composite material. It is a range of parts. When the amount of the base material is less than 5 parts by weight, 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.

In the 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 coupling agents, zircoaluminate coupling agents and the like can be used.

As a method for producing the composite material of the present invention, for example, the components (a) to (c) described in the first and second aspects of the present invention and, if necessary, other components may be added to the above halogen. Examples thereof include a method of uniformly dissolving or dispersing in a solvent such as a solvent, an aromatic solvent, a ketone solvent, or a mixed solvent thereof, impregnating the base material, and then drying.

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.

The sixth curable composite material of the present invention is obtained by curing the curable composite material of the fourth or fifth invention described above by a method such as heating. The production method is not limited to obtaining, and for example, a plurality of the curable composite materials are overlapped, each layer is adhered under heat and pressure, and at the same time, heat curing is performed to obtain a cured composite material having a desired thickness. be able to. It is also possible to obtain a cured composite material having a new layer structure by combining the cured composite material that has been adhesively cured once and the curable composite material.

The lamination molding and curing are usually carried out simultaneously using a hot press or the like, but both may be carried out 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. in any of the curable composite materials of the fourth and fifth inventions.
Pressure 0.1 to 500 kg / cm ² , time 1 minute to 10 hours, more preferably temperature 150 to 250 ° C., pressure 1 to
It can be performed at 100 kg / cm ² for 1 minute to 5 hours. Finally, the seventh, eighth, and ninth laminated bodies, laminated plates, and metal-clad laminated plates of the present invention will be described.

The laminate of the present invention is composed of the cured composite material and the metal foil described above as the sixth of the present invention. A laminated plate is also composed of a cured composite material and a metal plate, and a metal-clad laminated plate is composed of a cured composite material, a metal foil, and a metal plate. Examples of the metal foil used here include copper foil,
Aluminum foil etc. are mentioned. The thickness is not particularly limited, but 5-200 μm, more preferably 5-100.
It is in the range of μm.

Examples of the metal plate include iron plate, aluminum plate, silicon steel plate and stainless plate.
The thickness is not particularly limited, but is in the range of 0.2 mm to 10 mm, more preferably 0.2 mm to 5 mm. Prior to use, the metal plate is mechanically ground by sanding with a polishing paper or polishing cloth, wet blasting, dry blasting, etc. to improve its adhesiveness, and further subjected to degreasing, etching, alumite treatment, chemical conversion coating treatment, etc. Can be used.
For aluminum plates, degrease with sodium carbonate after polishing,
Etching with sodium hydroxide is preferred, but not limited to this method.

The method for producing the laminate, the laminate and the metal-clad laminate of the present invention includes, for example, the curable composite material described above as the fourth and fifth of the present invention, a metal foil and / or a metal. Laminate the plates in a layered structure according to the purpose,
Examples include a method in which each layer is adhered under heat and pressure and at the same time, thermosetting is performed.

For example, in the laminated body, the curable composite material and the metal foil are laminated in an arbitrary layer structure. The metal foil can be used as both the surface layer and the intermediate layer. In the laminated plate, a curable composite material is laminated on one side or both sides of a metal plate as a base. For metal-clad laminates,
A metal plate is used as a base, and a metal foil is laminated on one or both surfaces of the metal plate with a curable composite material interposed therebetween. At this time, the metal foil is used as the outermost layer, but may be used as an intermediate layer other than the outermost layer. In addition to the above, it is also possible to repeat lamination and curing a plurality of times to form a multilayer.

An adhesive may be used to bond the metal foil and the metal plate. Examples of the adhesive include epoxy-based, acrylic-based, phenol-based, and cyanoacrylate-based adhesives, but are not particularly limited thereto. The above-mentioned lamination molding and curing can be performed under the same conditions as in the sixth aspect of the present invention.

[0059]

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

Reference Example 1 Poly (2,6-dimethyl-) having a viscosity number η _sp / C of 0.54 measured at 30 ° C. in a chloroform solution of 0.5 g / dl.
1,4-phenylene ether) 100 parts by weight, maleic anhydride 1.5 parts by weight, and 2,5-dimethyl-2,5
After dry blending 1.0 part by weight of di (t-butylperoxy) hexane (Perhexa 25B manufactured by NOF CORPORATION) at room temperature, a twin screw extruder was used under the conditions of a cylinder temperature of 300 ° C. and a screw rotation speed of 230 rpm. Extruded. This polymer is designated as A.

Reference Example 2 Bifunctional polyphenylene ether obtained by oxidative polymerization of 2,6-dimethylphenol in the presence of 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane (30 ° C., 100 parts by weight of a viscosity number η _sp / C measured with a 0.5 g / dl chloroform solution (0.40) and 2 parts by weight of maleic anhydride were dry blended, and then Reference Example 1
Extrusion was carried out under the same conditions as above. Let the polymer obtained here be B.

Reference Example 3 Poly (2,6-dimethyl-) having a viscosity number η _sp / C measured with a chloroform solution of 0.5 g / dl at 30 ° C. of 0.31.
1,4-phenylene ether) 100 parts by weight, maleic anhydride 1.5 parts by weight, and 2,5-dimethyl-2,5
After 1.0 part by weight of -di (t-butylperoxy) hexane (Peroxa 25B manufactured by NOF CORPORATION) was dry blended at room temperature, extrusion was performed under the same conditions as in Reference Example 1. Let the polymer obtained here be C.

In the examples described below, the following components were used. Epoxy resin: ・ Bisphenol A glycidyl ether epoxy resin Asahi Kasei AER331 epoxy equivalent 189 ・ Low brominated bisphenol A glycidyl ether epoxy resin Asahi Kasei AER711 epoxy equivalent 475 Bromine content 20 wt% ・ Highly brominated bisphenol A glycidyl ether epoxy resin Asahi Kasei AER735 epoxy equivalent 350 Bromine content 48% by weight Cresol novolac epoxy resin Asahi Kasei ELN273 Epoxy equivalent 217 Initiator: 2,5-Dimethyl-2,5-di (t-butylperoxy) hexyne-3 (NOF Perhexin 25B) Curing agent: 2E4MZ 2 -Methyl-4-methylimidazole 2MZ 2-Methylimidazole DDM 4.4'-diaminodiphenylmethane Flame retardant: decabromodiphenylace Tell (Asahi Glass AFR 1
021) Flame retardant aid: Sb ₂ O ₃ (Nippon concentrate PATOX-M) Sb ₂ O ₅ (Nissan Kagaku NA-4800) Glass cloth: E glass, basis weight 48 g / m ² or 105 g / m ² D glass , polymer a, and B obtained by the basis weight 87 g / m ² examples 1-7 reference examples 1 and 2, triallyl isocyanurate or triallyl cyanurate, epoxy resin, initiator, curing agent, and Table 1 of glycidyl methacrylate It was dissolved in chloroform with the composition shown in (1) and poured onto a Teflon plate to form a film. The resulting film had a thickness of about 100 μm. The film forming properties are good,
No stickiness on the surface was observed.

After drying this film in an air oven, it was molded and cured in a vacuum press to obtain a cured product having a thickness of about 1 mm. The curing conditions are as follows:
30 minutes, 180 ° C. in Examples 5 to 7 and 2 hours. No change was observed in the appearance of these cured products after boiling in trichlorethylene for 5 minutes.

Comparative Examples 1 and 2 Polymer A. Table 1 shows polyphenylene ether used as a raw material for producing B, triallyl isocyanurate or triallyl cyanurate, and an initiator.
The composition shown in (1) was mixed using a Henschel mixer, and molded and cured by a press molding machine at 200 ° C. for 30 minutes to prepare a cured product having a thickness of about 1 mm. When this cured product was boiled in trichlorethylene for 5 minutes, swelling and warpage were observed.

Comparative Example 3 The same operation as in Example 7 was carried out without using triallyl isocyanurate and the initiator. When the obtained cured product was boiled in trichlorethylene for 5 minutes, swelling and warpage were observed.

Examples 8 to 13 Components having the compositions shown in Tables 2 and 3 were dissolved or dispersed in trichlorethylene. A glass cloth was immersed in this solution for impregnation and dried in an air oven. E glass cloth having a basis weight of 48 g / m ^{2 was used in} Example 8, D glass cloth having a basis weight of 87 g / m ² was used in Examples 10 and 12, and E glass cloth having a basis weight of 105 g / m ² was used in all the other examples. Using. Each of the obtained curable composite materials had no stickiness on the surface and was excellent in handleability.

Next, a plurality of the above-mentioned curable composite materials were superposed so that the thickness after curing would be about 0.8 mm, and copper foil with a thickness of 35 μm was placed on both sides thereof and molded and cured by a press molding machine. To obtain a laminate. Table 3 shows the curing conditions of each example.
It was shown to. All pressures were 40 kg / cm ² . In all of the examples, the resin flow during pressing was good.

The physical properties of the laminate thus obtained were measured by the following methods, and good results as shown in Table 3 were obtained. 1. Trichloroethylene resistance The laminate from which the copper foil was removed was cut into 25 mm square pieces, boiled in trichlorethylene for 5 minutes, and the change in appearance was visually observed. 2. The dielectric constant and the dielectric loss tangent were measured at 1 MHz. 3. Solder heat resistance Cut the laminated body from which the copper foil has been removed into 25 mm squares, 260 ° C
It was floated for 120 seconds in the solder bath and the change in appearance was visually observed. 4. Copper foil peeling strength A test piece with a width of 20 mm and a length of 100 mm was cut out from the laminate, and after making a parallel cut with a width of 10 mm on the copper foil surface, the speed was 50 mm / min in the direction perpendicular to the surface. Then, the copper foil was continuously peeled off, and the stress at that time was measured by a tensile tester, and the minimum value of the stress was shown. 5. Flame-retardant From the laminate without copper foil, length 127mm, width 12.7mm
The test piece was cut out, and the test was performed according to the UL-94 test method.

Comparative Examples 4 and 5 The same operations as in Examples 11 and 13 were carried out without using triallyl isocyanurate, triallyl cyanurate and an initiator to prepare laminates. When the trichlorethylene resistance of this laminate was measured, whitening of the surface and exposure of glass cloth were observed.

Example 14 Three pieces of the curable composite material obtained in Example 10 were laminated on an aluminum plate having a thickness of 1.0 mm which had been subjected to polishing, degreasing and etching treatments, and the temperature was 180 ° C. for 2 hours and 40 kg. A laminate was produced by press molding under the condition of / cm ² . The thermal resistance of this laminated plate was 24 ° C./W, which was excellent in heat dissipation as compared with the case where no aluminum plate was used (60 ° C./W). The thermal resistance was measured by forming a circuit on a sample of 35 mm × 50 mm, soldering a 100 Ω chip resistor, and measuring the temperature rise after voltage application.

Example 15 Three pieces of the curable composite material obtained in Example 11 and a copper foil having a thickness of 35 μm were laminated on an aluminum plate having a thickness of 1.0 mm which had been subjected to polishing, degreasing and etching treatment, and 220 ℃, 30
Min, 40 kg / cm ² was press-molded to produce a metal-clad laminate.

The heat resistance of this metal plate-clad laminate was measured in Example 1.
When measured by the same method as in Example 4, it was 24 ° C./W, and was excellent in heat dissipation.

[0074]

[Table 1]

[0075]

[Table 2]

[0076]

[Table 3]

[0077]

[Table 4]

[0078]

EFFECTS OF THE INVENTION The curable resin composition of the present invention has a good solvent film-forming property, has a surface without stickiness even when a liquid epoxy resin is used as a main component, and has excellent handleability and a curable composite material. Is obtained. The resin flow during pressing is also good. Further, the reaction product of the polyphenylene ether resin and the unsaturated carboxylic acid or acid anhydride used in the curable resin composition of the present invention can be produced at low cost using an extruder or the like, and thus the curability is excellent in economic efficiency. A resin composition can be provided.

The laminate, laminate and 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. That is,
It has sufficient resistance to boiling trichlorethylene and shows a dielectric constant of approximately 4.0 or less even when an epoxy resin is used as a main component. Chemical resistance is particularly excellent by using triallyl isocyanurate and / or triallyl cyanurate in combination. In addition, they also have an effect as a plasticizer and contribute to the improvement of resin flow during pressing.

The laminate, laminate, and metal-clad laminate of the present invention are well balanced in various physical properties such as heat resistance, flame retardancy, adhesion to metal, dimensional stability, hygroscopicity and heat dissipation. It exhibits excellent characteristics. Therefore, the material of the present invention can be used as a dielectric material, an insulating material, a heat-resistant material, a structural material, etc. in the fields of electric industry, electronic industry, space / aircraft industry and the like. In particular, it is suitably used as a single-sided or double-sided, multi-layer printed circuit board, flexible printed circuit board, semi-rigid substrate, metal base board, prepreg for multi-layer printed circuit board, and the like. Further, the material of the present invention, due to its heat and moisture absorption resistance, is well used as a high-density circuit board with a line spacing of 100 μm or less, a multilayer circuit board with an interlayer insulating layer thickness of 200 μm or less, an adhesive for a mounting circuit board, etc. it can.

Claims (18)

[Claims] 1. A (a) the reaction product of a polyphenylene ether resin and an unsaturated carboxylic acid or acid anhydride met
A reaction product containing substantially no polymerizable double bond ,
And (b) a curable resin composition comprising triallyl isocyanurate and / or triallyl cyanurate, wherein the component (a) is 98 to 100 parts by weight based on the total of 100 parts by weight of the component (a) and the component (b). 40 parts by weight and 2 to 60 parts by weight of component (b), a curable resin composition. Wherein (a) the reaction product of a polyphenylene ether resin and an unsaturated carboxylic acid or acid anhydride met
A reaction product containing substantially no polymerizable double bond ,
A curable resin composition comprising (b) triallyl isocyanurate and / or triallyl cyanurate and (c) an epoxy resin, based on 100 parts by weight of the sum of the components (a) and (b) ( a) component is 98-40
Parts by weight, 2 to 60 parts by weight of the component (b), and 99 to 1 parts by weight of the component (a) + (b) based on 100 parts by weight of the sum of the components (a) to (c), (c ) 1 component
~ 99 parts by weight of a curable resin composition. 3. A comprising a curable resin composition according to claim 1 Symbol mounting film. 4. The curable resin composition according to claim 2.
Film. 5. The curable resin composition obtained by curing the curable resin composition of claim 1 Symbol placement. 6. Curing the curable resin composition according to claim 2.
The cured resin composition thus obtained. 7. A film comprising the cured resin composition according to claim 5 . 8. A cured resin composition according to claim 6.
the film. 9. (a) the reaction product of a polyphenylene ether resin and an unsaturated carboxylic acid or acid anhydride met
A reaction product containing substantially no polymerizable double bond ,
A curable composite material comprising (b) triallyl isocyanurate and / or triallyl cyanurate, and (d) a base material, wherein the sum of (a) component and (b) component is 100.
98 to 40 parts by weight of the component (a) based on parts by weight,
(B) component is 2 to 60 parts by weight, and (a),
Curable, wherein (a) + (b) component is 95 to 10 parts by weight and (d) component is 5 to 90 parts by weight, based on 100 parts by weight of the sum of components (b) and (d). Composite material. 10. (a) the reaction product of a polyphenylene ether resin and an unsaturated carboxylic acid or acid anhydride met
A reaction product containing substantially no polymerizable double bond ,
A curable composite material comprising (b) triallyl isocyanurate and / or triallyl cyanurate, (c) epoxy resin, and (d) base material, wherein the sum of (a) component and (b) component is 100% by weight. The component (a) is 98 to 40 parts by weight, the component (b) is 2 to 60 parts by weight based on parts, and the total of 100 parts by weight of the components (a) to (c) is (a) + ( The component (b) is 99 to 1 parts by weight, the component (c) is 1 to 99 parts by weight, and the components (a) to (c) are 95 parts by weight based on 100 parts by weight of the sum of the components (a) to (d).
-10 parts by weight, and component (d) is 5 to 90 parts by weight, a curable composite material. 11. The cured composite material obtained by curing the curable composite material of claim 9 Symbol mounting. 12. A curable composite material according to claim 10 is hardened.
Cured composite material obtained by liquefaction. 13. A laminate comprising the cured composite material according to claim 11 and a metal foil. 14. A cured composite material according to claim 12 and a metal.
A laminate made of foil. 15. A laminated board in which an insulating layer made of the cured composite material according to claim 11 is laminated on a metal base. 16. Curing according to claim 12 on a metal base.
A laminated plate in which insulating layers made of a composite material are laminated. 17. An insulating layer made of the cured composite material according to claim 11 is laminated on at least one surface of a metal base, and a metal foil is laminated on at least the outermost layer of the insulating layer. A characteristic metal-clad laminate. 18. Claim on at least one side of a metal base
Item 12. An insulating layer made of the cured composite material is laminated.
And a metal foil is laminated on at least the outermost layer of the insulating layer.
A metal-clad laminate characterized by being provided.