JP3178958B2 - Novel toughening curable polyphenylene ether-based 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 after curing, dielectric properties, heat resistance, dimensional stability, and toughness,
It can be used as a dielectric material, an insulating material, and a heat-resistant material in the fields of the electronics industry, the space and aircraft industries, and the like.

[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, electrical properties, and moldability are being demanded. For example, as a printed wiring board, a conventional copper-clad laminate using a thermosetting resin such as a phenol resin or an epoxy resin as a base material has been used. 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.
193929), polyfunctional maleimides (JP-A-5
6-133355), polyfunctional cyanate esters (JP-A-56-141349, etc.), polyfunctional acryloyl or methacryloyl compounds (JP-A-57-14).
9317), triallyl isocyanurate and / or triallyl cyanurate (JP-A-61-218).
652) and isocyanate compounds.

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. In addition, polyphenylene ether has a higher coefficient of thermal expansion than conventional polyimide resins and the like, and is sometimes insufficient in terms of dimensional stability as a material for a laminated board or as a sealing material. Further, when cured, it becomes brittle, and in some cases, is weak to mechanical shock or thermal shock.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has excellent chemical resistance after curing without impairing the excellent dielectric and mechanical properties of polyphenylene ether resin. It is an object of the present invention to provide a novel curable polyphenylene ether-based resin composition having a low thermal expansion coefficient and toughness in addition to heat resistance and heat resistance.

Although the above description has been made with reference to a laminate for a printed wiring board and a sealing material as an example, a cured product having good dimensional stability and toughness can be obtained by the resin composition of the present invention. It goes without saying that the resin composition can be suitably used for the production of other molded articles.

[0007]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, (a) a reaction product of polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride; By mixing (b) triallyl isocyanurate and / or triallyl cyanurate, (c) silica, and (d) hydrogenated block copolymer, excellent after curing, in addition to chemical resistance and heat resistance. The inventors have found that a cured polyphenylene ether-based resin composition having low thermal expansion characteristics and toughness can be obtained, and completed the present invention. The present invention is constituted by the following five inventions.

That is, a first aspect of the present invention is that (a), (a)
98 parts by weight based on 100 parts by weight of the sum of the component and the component (b)
To 40 parts by weight of a reaction product of a polyphenylene ether and an unsaturated carboxylic acid or acid anhydride, and 2 to 6 parts by weight based on 100 parts by weight of the sum of the components (b), (a) and (b).
0 parts by weight of triallyl isocyanurate and / or triallyl cyanurate, components (c) and (a) and (b)
10 to 400 parts by weight of silica, based on 100 parts by weight of the sum of the components, the sum of the components (d), (a) and (b) 10
At least 1 to 50 parts by weight based on 0 parts by weight
Block A mainly composed of vinyl aromatic compounds
A curable polyphenylene ether-based resin composition comprising a hydrogenated block copolymer obtained by hydrogenating a block copolymer comprising a polymer block B mainly composed of at least one conjugated diene compound and at least one conjugated diene compound. Offer things.

A second aspect of the present invention provides a cured polyphenylene ether-based resin composition obtained by curing the curable polyphenylene ether-based resin composition of the first aspect.
A third aspect of the present invention is the reaction product of 98 to 40 parts by weight of polyphenylene ether and unsaturated carboxylic acid or acid anhydride based on 100 parts by weight of the sum of components (a), (a) and (b). The sum of the product, (b), component (a) and component (b) 1
2 to 60 parts by weight of triallyl isocyanurate and / or triallyl cyanurate, based on 100 parts by weight, and 10 to 100 parts by weight based on 100 parts by weight of the sum of components (c), (a) and (b). Parts by weight of silica, (d),
1 to 50 parts by weight of at least one vinyl aromatic compound-based polymer block A and at least 1 part by weight based on 100 parts by weight of the sum of the components (a) and (b)
Hydrogenated block copolymer obtained by hydrogenating a block copolymer composed of a polymer block B mainly composed of two conjugated diene compounds, and the sum of components (e) and (a) to (e) 100 A curable composite material comprising 5 to 90 parts by weight of a base material based on parts by weight.

[0010] 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. These inventions are described in detail below.

The polyphenylene ether used in the present invention is represented by the following formula 1.

[0012]

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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).

[0015]

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

[0017]

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[0018]

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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. .

[0020]

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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-dimethylphenol) obtained by homopolymerization of 2,6-dimethylphenol.
Dimethyl-1,4-phenylene ether), poly (2,4-phenylene ether)
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

[0022]

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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 an 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 of 100 ° C. to 390 ° C. At this time, a radical initiator may coexist. Although both the solution method and the melt mixing method can be used, the melt mixing method using an extruder or the like can be more easily performed and is suitable for the purpose of the present invention.

The proportion of the unsaturated carboxylic acid or acid anhydride is based on 100 parts by weight of the polyphenylene ether resin.
It is 0.01 to 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 polyphenylene ether-based resin composition of the present invention includes:
Each is a trifunctional monomer represented by the following structural formula.

[0027]

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In practicing the present invention, triallyl isocyanurate and triallyl cyanurate can be used not only singly, but also can be used as a mixture of both at an arbitrary ratio. In the present invention,
Triallyl isocyanurate and triallyl cyanurate exhibit effects as plasticizers and crosslinking agents. That is, the resin flow at the time of pressing and the crosslinking density are improved.

The silica used as the component (c) in the polyphenylene ether resin composition of the present invention is chemically silicon dioxide (SiO ₂ ). Hereinafter, silica, which is commonly used, is used. In the polyphenylene ether-based resin composition of the present invention, if necessary, the component (c) previously treated with a coupling agent can be used for the purpose of improving the adhesion at the interface between the component (c) and the resin. . 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. Further, the above-mentioned coupling agent may be added when mixing the components (a) to (d).

The particle shape and particle size of the component (c) are not particularly limited, but are preferably crushable particles having a wide particle size distribution with an average particle size of 4 to 10 μm. further,
You may mix and use a crushing type and a spherical type. The component (c) of the polyphenylene ether-based resin composition of the present invention has a feature that it contributes to improving the dimensional stability of the cured resin composition, and adversely affects the mechanical and dielectric properties of the cured composition. Do not give.

The hydrogenated block copolymer used as the component (d) of the polyphenylene ether resin composition of the present invention comprises at least one polymer block A mainly composed of a vinyl aromatic compound and at least one conjugated polymer block. It is obtained by hydrogenating a block copolymer composed of a polymer block B mainly composed of a diene compound and, for example,

[0032]

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This is a hydrogenated vinyl aromatic compound-conjugated diene compound block copolymer having the above structure. This hydrogenated block copolymer contains 5 to 85% by weight, preferably 10 to 70% by weight of a vinyl aromatic compound. Further referring to the block structure, a polymer block A mainly composed of a vinyl aromatic compound
Is a polymer block composed of only a vinyl aromatic compound or a copolymer block of a vinyl aromatic compound containing more than 50% by weight, preferably 70% by weight or more of a vinyl aromatic compound and a hydrogenated conjugated diene compound. And further, the polymer block B mainly composed of a hydrogenated conjugated diene compound is a polymer block composed of only a hydrogenated conjugated diene compound, or a hydrogenated conjugated diene compound. Is more than 50% by weight, preferably 70% by weight or more, and has a structure of a copolymer block of a hydrogenated conjugated diene compound and a vinyl aromatic compound. Further, these polymer blocks A mainly composed of a vinyl aromatic compound and the polymer blocks B mainly composed of a hydrogenated conjugated diene compound are each composed of a hydrogenated conjugated diene in the molecular chain of each polymer block. The distribution of the compound or the vinyl aromatic compound may be random, tapered (in which the monomer component increases or decreases along the molecular chain), partially block-like, or any combination thereof. When there are two or more polymer blocks mainly composed of a compound and two or more polymer blocks mainly composed of the hydrogenated conjugated diene compound, each of the polymer blocks may have the same structure. It may be.

Examples of the vinyl aromatic compound constituting the hydrogenated block copolymer include, for example, styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, p-tert.
One or more of butylstyrene and the like can be selected, and among them, styrene is preferable. Examples of the conjugated diene compound before hydrogenation that constitutes the hydrogenated conjugated diene compound include, for example, butadiene, isoprene, 1,3-
One or more kinds are selected from pentadiene, 1,3-dimethyl-1,3-butadiene and the like, and among them, butadiene, isoprene and a combination thereof are preferable.

Further, the number average molecular weight of the hydrogenated block copolymer having the above structure and used in the present invention is not particularly limited, but the number average molecular weight is 5,000 to 1,000,000, preferably 10,000 to 500,000, more preferably 300 to 500,000.
It can be used in the range of 00 to 300,000. Furthermore, the molecular structure of the hydrogenated block copolymer is linear, branched,
It may be radial or any combination of these.

As a method for producing these block copolymers, any production method having the above-mentioned structure may be used. For example, Japanese Patent Publication No. 40-23
No. 798, a vinyl aromatic compound-conjugated diene compound block copolymer is synthesized in an inert solvent using a lithium catalyst or the like, and then, for example, Japanese Patent Publication No. 42-8704 and Japanese Patent Publication No. 43-6636, particularly preferably JP-A-59-13.
According to the methods described in JP-A-3203 and JP-A-60-79005, hydrogenation is carried out in the presence of a hydrogenation catalyst in an inert solvent to synthesize a hydrogenated block copolymer to be used in the present invention. be able to. At this time, the aliphatic double bond based on the conjugated diene compound of the vinyl aromatic compound-conjugated diene compound block copolymer is at least 80%.
Can be hydrogenated to formally convert a polymer block mainly composed of a conjugated diene compound into an olefinic compound polymer block. Further, a polymer block A mainly composed of a vinyl aromatic compound and, if necessary,
The hydrogenation rate of the aromatic double bond based on the vinyl aromatic compound copolymerized with the polymer block B mainly composed of a conjugated diene compound is not particularly limited. Is preferred.

The block copolymer also includes a modified block copolymer to which a molecular unit containing a dicarboxylic acid group or a derivative thereof is bonded as long as its properties are not impaired. The molecular unit containing a dicarboxylic acid group or a derivative thereof can be used usually in a range of 0.05 to 5 parts by weight based on the block copolymer serving as a substrate. Examples of the modifier containing the dicarboxylic acid group or a derivative thereof include maleic acid, fumaric acid, chloromaleic acid, itaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, and anhydrides, esters, and esters of these dicarboxylic acids. Examples include amides and imides. Specific examples of preferred modifiers include maleic anhydride, maleic acid, and fumaric acid.

The method for producing the modified block copolymer is not particularly limited, but usually, the block copolymer and the modifier are reacted with or without a radical initiator in a state of being melted by an extruder or the like. A method is used. The component (d) of the polyphenylene ether-based resin composition of the present invention improves the toughness of the cured resin composition and does not adversely affect other mechanical and dielectric properties of the cured composition.

Of the four components (a) to (d) described above, the mixing ratio of the component (a) and the component (b) is such that the component (a) is 98 to 40 based on 100 parts by weight of the sum of both. Parts by weight, component (b) is 2 to 60 parts by weight, more preferably component (a) is 95 to 50 parts by weight, and component (b) is 5 to 5 parts by weight.
The range is 0 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 60
Exceeding the weight parts is not preferred because the dielectric properties and moisture absorption properties decrease and the material becomes very brittle after curing.

The proportion of the component (c) used in the resin composition of the present invention is 10 to 400 parts by weight, preferably 10 to 400 parts by weight, based on 100 parts by weight of the sum of the components (a) and (b).
0 to 300 parts by weight, more preferably 150 to 200 parts by weight. When the component (c) is less than 10 parts by weight, the thermal expansion characteristics of the cured resin composition are insufficiently improved, which is not preferable. If the amount exceeds 400 parts by weight, the fluidity of the resin at the time of melt molding and the adhesion to the metal foil when a laminate with the metal foil is formed are undesirably reduced.

The proportion of the component (d) is 1 to 50 parts by weight, preferably 1 to 30 parts by weight, more preferably 5 to 2 parts by weight based on 100 parts by weight of the sum of the components (a) and (b).
0 parts by weight. When the amount of the component (d) is less than 1 part by weight, the toughness of the cured product is insufficiently improved, which is not preferable. On the other hand, if it exceeds 50 parts by weight, the fluidity of the resin at the time of melt molding decreases, which is not preferable.

As a method for mixing the above components (a) to (d), a solution mixing method for uniformly dissolving or dispersing the four components in a solvent, or a melt blending method for heating by an extruder or the like is used. Available. As a solvent used for the solution mixing, a halogen-based solvent such as dichloromethane, chloroform, and trichloroethylene; an aromatic solvent such as benzene, toluene, and xylene; and tetrahydrofuran alone or in combination of two or more are used.

The resin composition of the present invention may be preliminarily formed into a desired shape depending on its use. The molding method is not particularly limited. Usually, a casting method in which the resin composition is dissolved in the above-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 present resin composition prepared by a casting method are laminated, and heated and melted by a heat melting method, for example, a press molding machine to obtain a sheet of the present resin composition.

The curable resin composition of the present invention and the curable composite material thereof are cured by causing a cross-linking reaction by means of heating or the like, as will be described later. A radical initiator may be used for the purpose of accelerating the reaction. The amount of the radical initiator used in the resin composition of the present invention is 0.1 to 10 parts by weight, preferably 0.1 to 8 parts by weight based on 100 parts of the sum of the components (a) and (b). Department.

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-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 There are peroxides such as, but not limited to, -2,5-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.

The resin composition of the present invention can be used by blending fillers and additives in an amount that does not impair the original properties for the purpose of imparting desired performance according to the use. The filler may be fibrous or powdery,
Examples include carbon black, alumina, talc, mica, glass beads, glass hollow spheres, and the like. Additives include antioxidants, heat stabilizers, antistatic agents, plasticizers,
Pigments, dyes, coloring agents, and the like are included. 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 , NbSbO ₃ .1 / 4H
A flame retardant aid such as ₂ O may be used in combination.

Further, one or two or more other thermoplastic resins or thermosetting resins can be blended. Examples of the thermoplastic resin include polyethylene, polypropylene, polybutene, ethylene / propylene copolymer, polyolefins such as poly (4-methyl-pentene) and derivatives thereof, nylon 4, nylon 6, nylon 6.
6, polyamides such as nylon 6,10 and nylon 12, and derivatives thereof, polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate / polyethylene glycol block copolymer and derivatives thereof, polyphenylene ether, modified polyphenylene Ether, polycarbonate, polyacetal, polysulfone, polyvinyl chloride and its copolymer, polyvinylidene chloride and its copolymer, polymethyl methacrylates, acrylic acid (or methacrylic acid) ester copolymers, polystyrenes, acrylonitrile styrene Copolymers, polystyrenes such as acrylonitrile styrene butadiene copolymers and their copolymers, polyvinyl acetates, Vinyl formal, polyvinyl acetal, polyvinyl butyral, ethylene vinyl acetate copolymer and its hydrolyzate, polyvinyl alcohol, styrene butadiene block copolymer, rubber such as polybutadiene, polyisoprene, polymethoxyethylene, polyethoxy Polyvinyl ethers such as ethylene, polyacrylamide, polyphosphazenes,
Examples thereof include liquid crystal polymers such as polyether sulfone, polyether ketone, polyether imide, polyphenylene sulfide, polyamide imide, thermoplastic polyimide, and aromatic polyester, and side chain type liquid crystal polymers having a liquid crystal component in a side chain. Examples of the thermosetting resin include an epoxy resin and a polyimide precursor.

The cured polyphenylene ether-based resin composition of the present invention is obtained by curing the above-described cured curable polyphenylene ether-based resin composition. The method of curing is arbitrary, and a method using heat, light, an electron beam, or the like can be employed. When curing by heating, the temperature varies depending on the type of radical initiator, but is preferably from 80 to 300 ° C., more preferably from 120 to 2 ° C.
It is selected in the range of 50 ° C. The time is about 1 minute to 10 hours, more preferably 1 minute to 5 hours.

The resin composition of the obtained cured polyphenylene ether resin composition can be analyzed by a method such as infrared absorption spectroscopy, high-resolution solid nuclear magnetic resonance spectroscopy, and pyrolysis gas chromatography. Further, this curable polyphenylene ether resin composition can be used by being bonded to a metal foil and / or a metal plate, similarly to a cured composite material described later as the fourth invention.

Next, the third and fourth curable composite materials of the present invention and their cured products will be described. Third of the present invention
The curable composite material is (a) a reaction product of polyphenylene ether and an unsaturated carboxylic acid or acid anhydride,
(B) triallyl isocyanurate and / or triallyl cyanurate, (c) silica, (d) hydrogenated block copolymer, and (e) base material.

As the base material of the component (e), various glass cloths such as roving cloth, cloth, chopped mat, surfacing mat, asbestos cloth, metal fiber cloth and other synthetic or natural inorganic fiber cloths; polyvinyl alcohol fiber, Woven or non-woven fabric obtained from synthetic fibers such as polyester fiber, acrylic fiber, wholly aromatic polyamide fiber, polytetrafluoroethylene fiber; cotton cloth;
Natural fiber cloths such as linen cloth and felt; carbon fiber cloths; natural cellulose-based cloths such as kraft paper, cotton paper, and paper-glass mixed paper are used alone or in combination of two or more.

The mixing ratio of component (a) and component (b) is 98 to 4 based on 100 parts by weight of the sum of the two.
0 parts by weight, 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 by weight of the component (b). 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 it exceeds 60 parts by weight, the dielectric properties and moisture absorption properties decrease,
It is also not preferable because it becomes a very brittle material after curing.

The mixing ratio of the component (c) is from 10 to 100 based on 100 parts by weight of the sum of the components (a) and (b).
Parts by weight, preferably 20 to 70 parts by weight, more preferably 30 to 50 parts by weight. When the component (c) is less than 10 parts by weight, the thermal expansion characteristics of the cured resin composition are insufficiently improved, which is not preferable. On the other hand, if it exceeds 100 parts by weight, the adhesive strength to metal decreases, which is not preferable.

The mixing ratio of the component (d) is 1 to 50 parts by weight, preferably 1 to 30 parts by weight, more preferably 5 to 2 parts by weight based on 100 parts by weight of the sum of the components (a) and (b).
0 parts by weight. When the amount of the component (d) is less than 1 part by weight, the toughness of the cured product is insufficiently improved, which is not preferable. On the other hand, if it exceeds 50 parts by weight, the fluidity of the resin at the time of melt molding decreases, which is not preferable.

The proportion of the component (e) is 5 to 90 parts by weight, preferably 10 to 80 parts by weight, more preferably 20 to 70 parts by weight based on 100 parts by weight of the curable composite material.
Parts by weight. When the amount of the component (e) is less than 5 parts by weight, the dimensional stability and strength after curing of the composite material are insufficient,
On the other hand, when the amount of the base material is more than 90 parts by weight, the dielectric properties of the composite material are inferior, which is not preferable.

In the 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 method for producing the composite material of the present invention includes, for example, the first method of the present invention.
The components (a) to (d) and other components, if necessary, are uniformly dissolved or dispersed in the above-mentioned halogen-based, aromatic-based, ketone-based solvents or their mixed solvents,
A method in which the substrate is impregnated and then dried is used.

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. The fourth 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 performed 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 150 to 250 ° C., a pressure of 1 to 500 kg / cm ² and a time of 1 minute to 5 hours. . Finally, the fifth laminate of the present invention will be described. The laminate of the present invention is constituted by the cured composite material described above as the fourth of the present invention and a metal foil. Examples of the metal foil used here include a copper foil and an aluminum foil. The thickness is not particularly limited, but is 5 to 200 μm, more preferably 5 to 1 μm.
It is in the range of 05 μm.

The method for producing the laminate of the present invention includes:
For example, a third method of the present invention is to laminate the curable composite material described above with a metal foil and / or a metal plate in a layer structure according to the purpose, to bond the layers under heat and pressure, and to simultaneously heat-cur. Can be mentioned. In the laminate of the present invention, 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.

In addition to the above, lamination and curing can be repeated a plurality of times to form a multilayer. An adhesive can be used for bonding the metal foil. Epoxy,
Acrylic-based, phenol-based, cyanoacrylate-based and the like can be mentioned, but not particularly limited thereto. The lamination and curing can be performed under the same conditions as in the fourth aspect of the invention.

[0061]

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. In the following examples, the following were used as each component. Polymerization initiator: 2,5-dimethyl-2,5-di (t-butylperoxy) hexine-3 (Nippon Oil & Fats Perhexin 25B; abbreviated as PH25B) Silica: Huze Rex E-2 (Tatsumori Corporation) FUZUREX silane coupling treatment E-2 (Tatsumori Co., Ltd.) Grassrain CUS-85K (Toshiba Ceramics Co., Ltd.) Hydrogenated block copolymer: H1041 (Asahi Chemical Industry Co., Ltd.)
H1051 (manufactured by Asahi Chemical Industry Co., Ltd.) Flame retardant: decabromodiphenyl ether (Asahi Glass A
FR-1021) Flame retardant auxiliary agent: Sb ₂ O ₃ (Nippon Seiko Steel PATOX-M) Glass cloth: E glass, basis weight 48 g / m ²

[0062]

Reference Example 1 Poly (2,6) having a viscosity number η _sp / c of 0.53 measured in a chloroform solution of 0.5 g / dl at 30 ° C.
-Dimethyl-1,4-phenylene ether), 100 parts by weight, 1.5 parts by weight of maleic anhydride, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (Nippon Oil & Fats Co., Ltd.) After dry blending 1.0 part by weight of Perhexa 25B) at room temperature, the cylinder temperature was 300.
The mixture was extruded with a twin screw extruder at a temperature of 230 ° C. and a screw rotation speed of 230 rpm. The viscosity number η _sp / c of the reaction product measured with a 0.5 g / dl chloroform solution at 30 ° C. was 0.48. This reaction product is designated as A.

[0063]

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 0.40
After 100 parts by weight of phenylene ether) and 1.5 parts by weight of maleic anhydride were dry-blended 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. 30 ° C, 0.5g /
The viscosity number η _sp / c of the reaction product measured with a dl chloroform solution was 0.43. This reaction product is designated B.

[0064]

Examples 1 to 10 Curable polyphenylene ether resin composition and curing
Polyphenylene ether resin composition Polyphenylene ether resin synthesized in Reference Examples 1 and 2, triallyl isocyanurate, silica and hydrogenated block copolymer were mixed with a composition shown in Table 1 using a Henschel mixer, and a press molding machine was used. 200 ° C, 30
It was molded and cured under the conditions of minutes to prepare a cured product having a thickness of about 1 mm.

The cured product was cut into a 7 mm square, and the coefficient of thermal expansion in the thickness direction was measured at a heating rate of 20 ° C./min by a thermomechanical analyzer. The coefficient of thermal expansion as used herein refers to the rate of increase in sample thickness when the temperature of the sample is raised from 30 ° C. to 150 ° C., which is a change in temperature of 120 ° C. (150 ° C.−30 ° C.).
° C). In any of the examples,
A cured product having a small coefficient of thermal expansion, toughness and resin fluidity was obtained. The results are shown in Table 1.

[0066]

Comparative Example 1 A cured product was prepared in the same manner as in Example 1, except that silica and the hydrogenated block copolymer were not added. The coefficient of thermal expansion was much larger than that of Example 1.

[0067]

Comparative Example 2 A cured product was prepared with the same composition as in Example 8 except that silica was not added. The coefficient of thermal expansion was much higher than that of Example 8.

[0068]

Comparative Example 3 A cured product was prepared with the same composition as in Example 6 except that no hydrogenated block copolymer was added. The cured product cracked when rubbed against a file.

[0069]

Comparative Example 4 A cured product was prepared with the same composition as in Example 8 except that 500 parts of silica was used. The cured product is brittle,
The surface was uneven.

[0070]

Comparative Example 5 A cured product was prepared with the same composition as in Example 9 except that the hydrogenated block copolymer was used in an amount of 60 parts. The coefficient of thermal expansion was much higher than that of Example 8. The results of the above comparative examples are shown in Table 1 together with Examples 1 to 10.

[0071]

[Table 1]

[0072]

EXAMPLES 11 to 20] In the composition of each shown in the curable composite material Table 2, the total amount 200g of Composition 8
It was dissolved or dispersed in 1000 ml of toluene at 0 ° C. The solution was cooled to 50 ° C. and impregnated by dipping a glass cloth at 50 ° C.
After drying for 0 minutes, a curable composite material was obtained.

A plurality of the above-mentioned curable composite materials are stacked so that the thickness after forming the laminate becomes 0.8 mm, and a copper foil having a thickness of 35 μm is placed on both surfaces thereof, and the resulting mixture is molded and cured by a press molding machine and laminated. I got a body. Table 3 shows the curing conditions of each example. The pressure was set to 20 kg / cm ² . See Table 3 for various physical properties
It was as follows.

The physical 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 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 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. 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. 5. Thermal Expansion Characteristics The laminate from which the copper foil had been removed was cut into 7 mm squares, and the amount of thermal expansion in the thickness direction was measured at a heating rate of 20 ° C./min using a thermomechanical analyzer. 6. Flame retardancy A flammability test corresponding to the UL94 standard was performed. 6. 3. Resin flowability Three curable composite materials are stacked and pressed at 170 ° C. for 10 minutes by a press molding machine at a surface pressure of 22 kg / cm ² , and the protruding resin composition is weighed to determine the volume of the resin composition. The value obtained by dividing this by the volume of only the resin composition in the curable composite material before pressing was shown. 7. Cracks In order to examine the toughness of the resin, a multilayer printed wiring board was prepared and subjected to 100 thermal shocks between −65 ° C. and 125 ° C. 100 times to determine whether resin cracks occur inside the wiring board.

In each of the examples, a cured product having a small coefficient of thermal expansion, being tough, having resin fluidity, and having excellent dielectric properties was obtained. Table 3 shows various physical properties.

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Comparative Example 6 A cured product was prepared in the same manner as in Example 11, except that silica and the hydrogenated block copolymer were not added. The coefficient of thermal expansion was larger than that of Example 11, and cracks occurred.

[0077]

Comparative Example 7 A cured product was prepared in the same manner as in Example 18 except that silica was not added, and in the same manner.
The coefficient of thermal expansion was larger than that of Example 18, and cracks occurred.

[0078]

Comparative Example 8 A cured product was prepared in the same manner as in Example 16 except that no hydrogenated block copolymer was added. A crack has occurred.

[0079]

Comparative Example 9 A cured product was prepared in the same manner as in Example 18 except that 125 parts of silica was used. The resin flowability was poor, and the copper foil peel strength decreased.

[0080]

Comparative Example 10 A cured product was prepared in the same manner as in Example 18 except that 60 parts of the hydrogenated block copolymer was used. The resin flowability was poor and the coefficient of thermal expansion was large. Various physical properties of the above comparative examples are shown in Table 3 together with Examples 11 to 20.

[0081]

[Table 2]

[0082]

[Table 3]

As is clear from the comparison between Examples 1 and 2 and Comparative Example 1, Example 8 and Comparative Example 2, and Example 6 and Comparative Example 3, the thermal expansion characteristics and toughness of the cured resin composition were as follows. The improvement was achieved by mixing 10 to 400 parts by weight of silica and 1 to 50 parts by weight of the hydrogenated block copolymer. Comparison between Example 8 and Comparative Example 4 and between Example 8 and Comparative Example 5 revealed that when the silica was added in an amount exceeding 400 parts by weight or the hydrogenated block copolymer was added in an amount exceeding 50 parts by weight, the fluidity of the resin was reduced. It is clear that this is undesirable.

The thermal expansion characteristics and toughness of the cured composite material were as shown in Example 11 and Comparative Example 6, Example 18 and Comparative Example 7,
As can be seen from the comparison between Example 16 and Comparative Example 8, it was improved by mixing 10 to 100 parts by weight of silica and 1 to 50 parts by weight of the hydrogenated block copolymer. Comparison between Example 18 and Comparative Example 9 shows that silica was 1
When added in excess of 00 parts by weight, the fluidity of the resin decreases,
It is clear that the copper foil peel strength is unfavorably reduced. By comparing Example 18 with Comparative Example 10,
When the hydrogenated block copolymer is added in excess of 50 parts by weight, it is apparent that the resin fluidity decreases and the linear expansion coefficient increases, which is not preferable. Further, from these Examples and Comparative Examples, it can be seen that even when silica is mixed, the chemical properties and electrical properties of the curable composite material and the cured composite material are equivalent to those of the conventional composition. This indicates that the laminate of the present invention is preferable as a material for a multilayer printed wiring board.

[0085]

As described above, the curable polyphenylene ether-based resin composition of the present invention has excellent dielectric properties, mechanical properties, chemical resistance and heat resistance, and has an unprecedented low coefficient of thermal expansion and toughness. A polyphenylene ether-based resin composition is obtained.

Continuation of the front page (51) Int.Cl. ⁷ identification code FI C08L 53/02 C08L 53/02 (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 1/00-101/16

Claims (5)

(57) [Claims] 1. The sum 1 of the components (a), (a) and (b)
The reaction product of 98 to 40 parts by weight of polyphenylene ether and unsaturated carboxylic acid or acid anhydride, based on 100 parts by weight, the sum of components (b), (a) and (b) 10
2 to 60 parts by weight of triallyl isocyanurate and / or triallyl cyanurate, based on 0 parts by weight, 10 to 400 parts by weight based on 100 parts by weight of the sum of components (c), (a) and (b) Parts by weight of silica, (d),
1 to 50 parts by weight of at least one vinyl aromatic compound-based polymer block A and at least 1 part by weight based on 100 parts by weight of the sum of the components (a) and (b)
A curable polyphenylene ether-based resin composition comprising a hydrogenated block copolymer obtained by hydrogenating a block copolymer comprising a polymer block B mainly composed of two conjugated diene compounds. 2. A cured polyphenylene ether-based resin composition obtained by curing the curable polyphenylene ether-based resin composition according to claim 1. 3. The sum 1 of the components (a), (a) and (b)
The reaction product of 98 to 40 parts by weight of polyphenylene ether and unsaturated carboxylic acid or acid anhydride based on 00 parts by weight, the sum of the components (b), (a) and (b) 10
2 to 60 parts by weight of triallyl isocyanurate and / or triallyl cyanurate, based on 0 parts by weight, 10 to 100 parts by weight based on 100 parts by weight of the sum of components (c), (a) and (b) Parts by weight of silica, (d),
1 to 50 parts by weight of at least one vinyl aromatic compound-based polymer block A and at least 1 part by weight based on 100 parts by weight of the sum of the components (a) and (b)
And a hydrogenated block copolymer obtained by hydrogenating a block copolymer composed of a polymer block B mainly composed of two conjugated diene compounds, and the sum of components (e) and (a) to (e) 100 A curable composite material comprising 5 to 90 parts by weight of a base material based on parts by weight. 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.