JPH08253673A - Toughened flame retardant polyphenylene ethereal thermoplastic resin composition - Google Patents

Abstract

PURPOSE: To obtain the subject composition, comprising a polyphenylene ether, triallyl (iso)cyanurate, silica. a specific block copolymer and a specified flame retardant, excellent in moldability, flame retardance, toughness, heat resistance, dielectric properties, etc., and useful for insulating materials, heat-resistant materials, etc. CONSTITUTION: This resin composition comprises (A) a polyphenylene ether, (B) triallyl (iso)cyanurate, (C) silica, (D) a hydrogenated block copolymer prepared by hydrogenating a block copolymer consisting essentially of a vinyl aromatic compound and a polymer block consisting essentially of a conjugated diene compound and (E) a flame retardant which is decabromodiphenyl ether or selected from compounds of formula I Z is a (Br-substituted) 1-4C alkylene; (m) and (n) are each 3-5; [(m)+(n)] is >=8], formula II [(l) is 3-5] and formula III Z' is Z; (p) and (q) are each 2-4 and [(p)+(q)] is >=6}. The amount of the components based on 100 pts.wt. total amount of the components (A) and (B) is 75-40 pts.wt. component (A), 25-60 pts.wt. component (B), 10-400 pts.wt. component (C), 1-50 pts.wt. component (D) and 5-100 pts.wt. component (E).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable resin composition and a cured product obtained by curing the same. Furthermore, the present invention relates to a curable composite material composed of the resin composition and a substrate, a cured product thereof, and a laminate composed of the cured product and a metal foil. The resin composition of the present invention exhibits excellent chemical resistance, dielectric properties, heat resistance, and dimensional stability after curing, and further exhibits toughness and flame retardancy, and is used in the fields of the electronic industry, the space / aircraft industry, etc. In, it can be used as a dielectric material, an insulating material, and a heat resistant material.

[0002]

2. Description of the Related Art In recent years, there has been a remarkable trend toward miniaturization and high density of mounting methods in the field of electronic devices for communication, consumer use, industrial use, etc. Heat resistance, dimensional stability, electrical characteristics, and moldability are being demanded. For example, as a printed wiring board, a copper-clad laminate having a thermosetting resin such as a phenol resin or an epoxy resin as a base material has been used. These resins have various performances in good balance, but further improvement in electrical characteristics, particularly dielectric characteristics in a high frequency region, is desired.

Polyphenylene ether has recently attracted attention as a new material satisfying this demand, and its application to copper-clad laminates has been attempted. However, polyphenylene ether has a higher coefficient of thermal expansion than conventional polyimide resins and the like, and is required to have improved dimensional stability as a material for laminates and as an encapsulant, and if it becomes brittle when cured. First, it is desired to be strong against mechanical shock and thermal shock.

Further, since polyphenylene ether itself does not have sufficient flame retardancy for use in electric parts such as copper clad laminates, it is remarkably used as parts for consumer and industrial equipment. Applications have been limited.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and the object of the present invention is to:
It is intended to provide a curable resin composition having excellent toughness and flame retardancy in addition to excellent chemical resistance and heat resistance after curing without impairing the excellent dielectric properties of polyphenylene ether resin. is there.

Although the laminate for a printed wiring board has been described above as an example, it goes without saying that the resin composition can be suitably used as another molded article.

[0007]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found a novel resin composition that achieves the object of the present invention and completed the present invention. Came to. The present invention comprises the following five inventions. That is, the first aspect of the present invention is that (a) component polyphenylene ether, (b) component triallyl isocyanurate and / or triallyl cyanurate, (c) component silica, (d) hydrogenated block copolymer and ( A resin composition comprising a flame retardant of component e), wherein the composition ratio is 75 to 40 parts by weight of component (a), based on 100 parts by weight of the sum of components (a) and (b), and (b) above. )
25 to 60 parts by weight of the component, and 10 to 40 of the component (c).
0 parts by weight, 1 to 50 parts by weight of the component (d) from at least one vinyl aromatic compound-based polymer block A and at least one conjugated diene compound-based polymer block B The hydrogenated block copolymer obtained by hydrogenating the block copolymer, and the component (e) is represented by 5 to 100 parts by weight of decabromodiphenyl ether or the following general formulas (1) to (3). A curable polyphenylene ether resin composition comprising a flame retardant selected from the group of compounds.

[0008]

[Chemical 7]

[0009]

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[0010]

[Chemical 9]

A second aspect of the present invention is a cured polyphenylene ether resin composition obtained by curing the curable polyphenylene ether resin composition according to the first aspect of the present invention. The third aspect of the present invention is: (a) component polyphenylene ether, (b) component triallyl isocyanurate and / or triallyl cyanurate, (c) component silica, (d) component hydrogenated block copolymer and (e). A composite material comprising a component flame retardant, a component (f) antimony oxide and a component (g) base material, wherein the composition ratio is 100 parts by weight based on the sum of the components (a) and (b). 75 to 40 parts by weight of the component, 25 parts of the component (b)
-60 parts by weight, 10 to 100 parts by weight of the component (c),
The block copolymer of the component (d) comprises 1 to 50 parts by weight of a polymer block A containing at least one vinyl aromatic compound as a main component and a polymer block B containing at least one conjugated diene compound as a main component. The hydrogenated block copolymer obtained by hydrogenating the combined product, wherein the component (e) is 5 to
100 parts by weight of decabromodiphenyl ether or a flame retardant selected from compounds represented by the following general formulas (1) to (3), and (f) component are 10 to 10 parts by weight based on 100 parts by weight of (e) component. 50 parts by weight of antimony oxide and (g) component are composed of 5 to 90 parts by weight of a base material based on 100 parts by weight of the sum of components (a) to (g), and a curable composite material. ,.

[0012]

[Chemical 10]

[0013]

[Chemical 11]

[0014]

[Chemical 12]

A fourth aspect of the present invention is a cured composite material obtained by curing the curable composite material according to claim 3 of the third invention. 5th of this invention is the laminated body which consists of the hardening composite material of Claim 4 and metal foil of said 4th invention. Hereinafter, the present invention will be described in detail.

In the curable polyphenylene ether resin composition of the first aspect of the present invention, the component (a) is polyphenylene ether, the component (b) is triallyl isocyanurate and / or triallyl cyanurate, and (c). The component is silica, the component (d) is a hydrogenated block copolymer,
The component (e) is composed of decabromodiphenyl ether or a flame retardant selected from compounds represented by the structural formulas (1) to (3).

The polyphenylene ether used in the present invention is represented by the following general formula (4).

[0018]

[Chemical 13]

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. 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 (4),
A compound group represented by the following four kinds of general formula (5) can be given.

[0021]

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Specific examples include the following formulas (6) to (7).

[0023]

[Chemical 15]

[0024]

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The polyphenylene ether chain represented by J in the general formula (4) contains a unit represented by the following general formula (B) in addition to the unit represented by the general formula (A). It may be.

[0026]

[Chemical 17]

Preferred examples of the polyphenylene ether resin of the general formula (2) 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 polymer, 2,6-dimethylphenol and 2,3,6-trimethylphenol copolymerization Coalescing 2,
Copolymer of 6-dimethylphenol and 2-methyl-6-phenylphenol, 2,6-dimethylphenol and the following polyfunctional phenol compounds

[0028]

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A polyfunctional polyphenylene ether resin obtained by polymerization in the presence of, for example, JP-A-63-3012.
No. 22, JP-A-1-297428, and copolymers containing the units of general formulas (A) and (B) are disclosed. The molecular weight of the above-mentioned polyphenylene ether resin is 30 ° C., 0.5 g / dl
The viscosity number ηsp / c measured with the chloroform solution of 0.1 is 0.
Those in the range of 1 to 1.0 can be used favorably. A resin having a low viscosity number is preferable for a curable resin composition that places importance on molten resin flow, for example, a prepreg for a multilayer wiring board.

The triallyl isocyanurate and / or triallyl cyanurate used as the component (b) of the curable polyphenylene ether resin composition of the present invention is a trifunctional monomer represented by the following structural formula. is there.

[0031]

[Chemical 19]

In practicing the present invention, triallyl isocyanurate and triallyl cyanurate can be used not only individually but also as a mixture of both at an arbitrary ratio. In the present invention,
Triallyl isocyanurate and triallyl cyanurate act as a plasticizer and a crosslinking agent. That is, it improves the flow of resin during pressing and the crosslink density.

The silica used as the component (c) of the curable polyphenylene ether resin composition of the present invention is
Chemically it is silicon dioxide (SiO ₂ ). Hereinafter, it is referred to as silica, which is a commonly used name. The curable polyphenylene ether resin composition of the present invention,
If necessary, for the purpose of improving the adhesion at the interface between the component (c) component silica and the resin, it is possible to use the component (c) component silica which has been previously treated with a coupling agent. As the coupling agent, silane coupling agents, titanate coupling agents, aluminum-based coupling agents, zircoaluminate coupling agents and the like can be used. Further, the above coupling agent may be added when the components (a) to (d) are mixed.

The particle shape and particle size of the component (c) are not particularly specified, but preferably, a crush type particle shape having a wide particle size distribution with an average particle size of 4 to 10 μm is preferable. further,
You may mix and use a crushing type and a spherical type. The component (c) silica of the curable polyphenylene ether-based resin composition of the present invention is characterized in that it contributes to the improvement of the dimensional stability of the resin composition after curing, and the mechanical properties and dielectric properties of the cured composition. Does not adversely affect the characteristics.

The hydrogenated block copolymer used as the component (d) of the curable polyphenylene ether resin composition of the present invention comprises at least one polymer block A containing a vinyl aromatic compound as a main component and at least one polymer block A. Is obtained by hydrogenating a block copolymer consisting of a polymer block B containing the conjugated diene compound as a main component.

[0036]

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It is a hydrogenated product of a vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as. The hydrogenated block copolymer contains a vinyl aromatic compound in an amount of 5 to 85% by weight, preferably 10 to 70% by weight. Further referring to the block structure, a polymer block A mainly composed of a vinyl aromatic compound
Is a polymer block consisting of a vinyl aromatic compound alone 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 a polymer block B mainly composed of a hydrogenated conjugated diene compound, wherein the polymer block B is composed only of the hydrogenated conjugated diene compound, or a hydrogenated conjugated diene compound Of 50% by weight or more, preferably 70% by weight or more, has a structure of a copolymer block of a hydrogenated conjugated diene compound and a vinyl aromatic compound.

Further, the polymer block A mainly containing these vinyl aromatic compounds and the polymer block B mainly containing the hydrogenated conjugated diene compound are hydrogenated in the molecular chains of the respective polymer blocks. The distribution of the conjugated diene compound or vinyl aromatic compound may be random, tapered (in which the monomer component increases or decreases along the molecular chain), partially block-shaped, or any combination thereof. When there are two or more polymer blocks mainly containing a vinyl aromatic compound and polymer blocks mainly containing the hydrogenated conjugated diene compound, each polymer block may have the same structure. , May have different structures.

The vinyl aromatic compound constituting the hydrogenated block copolymer is, for example, styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, p-third.
One or more of butyl styrene and the like can be selected, and styrene is preferable among them. Examples of the conjugated diene compound before hydrogenation that constitutes the hydrogenated conjugated diene compound include, for example, butadiene, isoprene, and 1,3-
One kind or two 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.

The number average molecular weight of the hydrogenated block copolymer of the present invention having the above structure 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.
It can be used in the range of 00 to 300,000. Further, the molecular structure of the hydrogenated block copolymer is linear, branched,
It may be radial or any combination thereof.

Any method of producing these block copolymers may be used as long as it has the above-mentioned structure. For example, Japanese Patent Publication No. 40-23
A vinyl aromatic compound-conjugated diene compound block copolymer was synthesized in an inert solvent using a lithium catalyst or the like by the method described in JP-A-798-8. The method described in JP-A-43-6636, particularly preferably JP-A-59-13
Hydrogenation is carried out in the presence of a hydrogenation catalyst in an inert solvent by the method described in JP-A No. 3203 and JP-A No. 60-79005 to synthesize the hydrogenated block copolymer used in the present invention. be able to. At that 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 morphologically convert the polymer block mainly composed of the conjugated diene compound into the olefin compound polymer block.

An aromatic double compound based on a vinyl aromatic compound copolymerized with a polymer block A containing a vinyl aromatic compound as a main component and optionally a polymer block B containing a conjugated diene compound as a main component. The hydrogenation rate of the bond is not particularly limited, but the hydrogenation rate is preferably 20% or less. In addition, this block copolymer,
A modified block copolymer having a molecular unit containing a dicarboxylic acid group or a derivative thereof bound thereto is also included within a range that does not impair the characteristics. The molecular unit containing a dicarboxylic acid group or a derivative thereof can be used usually in the range of 0.05 to 5 parts by weight with respect to the block copolymer as the base.

Examples of the modifier containing the above dicarboxylic acid group or its derivative include maleic acid, fumaric acid, chloromaleic acid, itaconic acid, cis-4-cyclohexene-
1,2-dicarboxylic acids and their anhydrides, esters, amides, imides and the like. Specific examples of preferred modifiers include maleic anhydride, maleic acid,
Examples include fumaric acid.

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

Specific examples of the flame retardant (e) used in the curable polyphenylene ether resin composition of the present invention include decabromodiphenyl ether and the compounds represented by the general formulas (1) to (3). To be In the general formula (1), m + n is 9 from the viewpoint of the flame retardant effect.
The above is preferable and 10 is the most preferable. The number of carbon atoms of Z may be any number as long as it is 4 or less, but —CH ₂ CH ₂ — is mentioned as the most preferable structure. Also, Z may have any number of hydrogens replaced by bromine.

In the general formula (3), p + q is preferably 9 or more, and most preferably 10 from the viewpoint of the flame retardant effect. The number of carbons of Z ′ may be any number as long as it is 4 or less, but —CH ₂ CH ₂ — is mentioned as the most preferable structure. Further, Z ′ may have any number of hydrogens replaced by bromine. The above flame retardants can be used not only individually, but also in a mixture at an arbitrary ratio.

The component (f) antimony oxide used in the third invention of the present invention is used for the purpose of further improving the flame retardancy. Both Sb ₂ O ₃ and Sb ₂ O ₅ can be used, but Sb ₂ O ₃ is more preferable. The component (f) is third to
Although essential for obtaining flame retardancy in the fifth invention,
It is not essential for the cured (curable) resin composition of the first and second inventions. However, it is possible to improve flame retardancy by using this.

In the first and second aspects of the present invention, the mixing ratio of the components (a) and (b) among the components explained above is 7 parts by weight based on 100 parts by weight of the sum of both components.
5-40 parts by weight, component (b) is 25-60 parts by weight, preferably component (a) is 70-50 parts by weight, (b)
The components are in the range of 30 to 50 parts by weight. (B) component is 2
If it is less than 5 parts by weight, the chemical resistance is insufficiently improved, which is not preferable. On the other hand, if the amount exceeds 60 parts by weight, the dielectric properties deteriorate,
It is not preferable because it becomes a brittle material after curing.

The mixing ratio of the component (c) used in the curable polyphenylene ether resin composition of the present invention is
10 to 400 parts by weight, preferably 10 to 300 parts by weight, based on 100 parts by weight of the sum of the components (a) and (b),
It is more preferably 15 to 60 parts by weight. When the amount of the component (c) is less than 10 parts by weight, the thermal expansion characteristics of the resin composition after curing are insufficiently improved, which is not preferable. On the other hand, if it exceeds 400 parts by weight, the fluidity of the resin during melt molding and the adhesion to the metal foil when a laminate with the metal foil is produced are unfavorable.

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 component (d) is less than 1 part by weight, the toughness of the cured product is not sufficiently improved, which is not preferable. On the other hand, if the amount exceeds 50 parts by weight, the fluidity of the resin at the time of melt molding is lowered, which is not preferable. The mixing ratio of the component (e) is
It is 5 to 100 parts by weight, preferably 5 to 70 parts by weight, based on 100 parts by weight of the sum of the components (a) and (b).
It is more preferably 5 to 50 parts by weight. (E) component is 5
If the amount is less than 10 parts by weight, it is difficult to obtain sufficient flame retardancy.
If it exceeds 0 parts by weight, the fluidity of the resin during melt molding may be reduced, or the adhesive force to the metal foil may be reduced.

The above-mentioned components (a) to (e) can be mixed by a solution mixing method in which the respective components are uniformly dissolved or dispersed in a solvent, or a melt blending method in which the components are heated by an extruder or the like. Is available. Solvents used for solution mixing include dichloromethane, chloroform,
Halogen-based solvents such as trichlorethylene; benzene,
Aromatic solvents such as toluene and xylene; tetrahydrofuran and the like are used alone or in combination of two or more kinds.

The curable polyphenylene ether resin composition of the present invention may be molded into a desired shape in advance according to its use. The molding method is not particularly limited. Usually, a casting method in which the resin composition is dissolved in the above-mentioned solvent and molded into a desired shape, or a heating and melting method in which the resin composition is heated and melted and molded into a desired shape is used. The above-described casting method and heat melting method may be performed independently. Moreover, you may carry out combining each. For example, several to several tens of films of the resin composition of the present invention prepared by a casting method may be laminated and heated and melted by a heat melting method, for example, a press molding machine to obtain a sheet of the resin composition.

The curable polyphenylene ether resin composition of the present invention and the curable composite material thereof undergo a crosslinking reaction by means of heating or the like to be cured as described later, but the reaction temperature at that time is lowered or unsaturated. A radical initiator may be incorporated for use in order to accelerate the crosslinking reaction of the group. The amount of the radical initiator used in the curable polyphenylene ether-based resin composition of the present invention is 0.1 based on 100 parts of the sum of the components (a) and (b).
It is 1 to 10 parts by weight, preferably 0.1 to 8 parts by weight.

Typical examples of the radical initiator include:
Benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t-
Butyl peroxy) hexyne-3, di-t-butyl peroxide, t-butyl cumyl peroxide, α,
α'-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide,
Di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, 2,5-dimethyl There are peroxides such as, but not limited to, 2,2,5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxide, and trimethylsilyltriphenylsilylperoxide. Also, although not a peroxide, 2,3-dimethyl-2,
3-diphenylbutane can also be used as a radical initiator. However, the initiator used for curing the resin composition is not limited to these examples.

The curable polyphenylene ether resin composition of the present invention is used by blending an amount of a filler or an additive within a range that does not impair the original properties for the purpose of imparting desired performance depending on the application. You can The filler may be fibrous or powdery, and examples thereof include carbon black, alumina, talc, mica, glass beads, and glass hollow spheres. As additives, antioxidants,
Examples include heat stabilizers, antistatic agents, plasticizers, pigments, dyes, colorants and the like.

Further, it is possible to blend one or more kinds of other thermoplastic resins or thermosetting resins. Examples of thermoplastic resins include polyolefins such as polyethylene, polypropylene, polybutene, ethylene / propylene copolymer, poly (4-methyl-pentene), and their derivatives, nylon 4, nylon 6, nylon 6,
Polyamides such as 6, nylon 6/10, nylon 12 and their derivatives, polyesters such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate / polyethylene glycol block copolymers and their derivatives, modified polyphenylene ether, polycarbonate , Polyacetal, polysulfone, polyvinyl chloride and its copolymers, polyvinylidene chloride and its copolymers, polymethylmethacrylates, acrylic acid (or methacrylic acid) ester copolymers, polystyrenes, acrylonitrile styrene copolymers , Polystyrene such as acrylonitrile styrene butadiene-based copolymers and their copolymers, polyvinyl acetates, polyvinyl formal, poly Nyl acetals, polyvinyl butyral, ethylene vinyl acetate copolymers and their hydrolysates, polyvinyl alcohols, styrene butadiene block copolymers, rubbers such as polybutadiene and polyisoprene, polymethoxyethylene, polyethoxyethylene, etc. Liquid crystal components such as polyvinyl ethers, polyacrylic amides, polyphosphazenes, polyether sulfones, polyether ketones, polyetherimides, polyphenylene sulfides, polyamideimides, thermoplastic polyimides, aromatic polyesters, etc. Examples thereof include side chain type liquid crystal polymers. Examples of the thermosetting resin include epoxy resin and polyimide precursor.

The cured polyphenylene ether resin composition of the present invention is obtained by curing the above-mentioned curable polyphenylene ether resin composition. The curing method is arbitrary, and a method using heat, light, an electron beam or the like can be adopted. When curing is performed by heating, the temperature varies depending on the type of radical initiator, but is 80 to 300 ° C, and more preferably 120 to 250 ° C.
It is selected in the range of. Also, the time is about 1 minute to 10 hours,
More preferably, it is 1 minute to 5 hours.

The resin composition of the obtained cured polyphenylene ether resin composition can be analyzed by methods such as infrared absorption spectroscopy, high resolution solid state nuclear magnetic resonance spectroscopy and pyrolysis gas chromatography. Also, this curable polyphenylene ether resin composition can be used by laminating it with a metal foil and / or a metal plate, as in the case of the cured composite material described below as the fourth invention.

The curable resin composition according to the third aspect of the present invention comprises a polyphenylene ether as the component (a), triallyl isocyanurate (hereinafter, TAIC) and / or triallyl cyanurate (hereinafter as the component) (b). , TA
C), silica as the component (c), a hydrogenated block copolymer as the component (d), decabromodiphenyl ether as the component (e), or a compound represented by the structural formulas (1) to (3). The flame retardant, the antimony oxide as the component (f), and the base material as the component (g).

As the base material of the component (g), various kinds of glass cloth such as roving cloth, cloth, chopped mat, surfacing mat, asbestos cloth, metal fiber cloth and other synthetic or natural inorganic fiber cloth; polyvinyl alcohol fiber, 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 cellulosic cloths such as kraft paper, cotton paper, paper-glass mixed fiber paper, etc. may be used alone or in combination.

The mixing ratio of the component (a) and the component (b) is 75 to 4 for the component (a) based on 100 parts by weight of the sum of both.
0 parts by weight, component (b) is 25 to 60 parts by weight, and more preferably 70 to 50 parts by weight of component (a) and 30 to 50 parts by weight of component (b). If the amount of the component (b) is less than 25 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 and moisture absorption properties deteriorate, and the material becomes extremely brittle after curing, which is not preferable.

The mixing ratio of the component (c) is 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 amount of the component (c) is less than 10 parts by weight, the thermal expansion characteristics of the resin composition after curing are insufficiently improved, which is not preferable. Further, if it exceeds 100 parts by weight, the adhesive force with a 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, and 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 component (d) is less than 1 part by weight, the toughness of the cured product is not sufficiently improved, which is not preferable. On the other hand, if it exceeds 50 parts by weight, the heat resistance of the cured product decreases, which is not preferable. The mixing ratio of the component (e) is 5 to 100 parts by weight, preferably 5 to 70 parts by weight, based on 100 parts by weight of the sum of the components (a) and (b). It is more preferably 5 to 50 parts by weight. When the amount of the component (e) is less than 5 parts by weight, it is difficult to obtain sufficient flame retardancy, and when it exceeds 100 parts by weight, the fluidity of the resin at the time of melt molding is lowered and the adhesive force to the metal foil is lowered. I have something to do.

The mixing ratio of the component (f) is 100 (e).
10 to 50 parts by weight, preferably 10 based on parts by weight
-40 parts by weight, most preferably 10-30 parts by weight. When the amount of the component (f) is less than 10 parts by weight, the effect of improving the flame retardancy is insufficient as compared with the case where the component (e) alone is used as the flame retardant
If it exceeds 50 parts by weight, the fluidity at the time of melt molding may decrease, or the adhesive force to the metal foil may decrease.

The proportion of the component (g) is 5 based on 100 parts by weight of the sum of the components (a) to (g) of the curable composite material.
To 90 parts by weight, more preferably 10 to 80 parts by weight, still more preferably 20 to 70 parts by weight. (G) component is 5
If it is less than 100 parts by weight, the dimensional stability and strength of the composite material after curing will be insufficient, and if it is more than 90 parts by weight, the dielectric properties of the composite material will be poor, such being undesirable.

A coupling agent can be used in the curable composite material of the present invention, if necessary, for the purpose of improving the adhesiveness at the interface between the resin and the substrate. As the coupling agent, silane coupling agents, titanate coupling agents, aluminum-based coupling agents, zircoaluminate coupling agents and the like can be used. As the method for producing the curable composite material of the present invention, for example, the components (a) to (f) described in the section of the first invention of the present invention and, if necessary, other components as described above in the halogen system, Examples thereof include a method of uniformly dissolving or dispersing in an aromatic solvent, a ketone solvent, or a mixed solvent thereof, impregnating the base material of component g) 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 cured composite material of the fourth aspect of the present invention is obtained by curing the curable composite material thus obtained by a method such as heating. The manufacturing method is not particularly limited, and for example, a plurality of the curable composite materials are stacked, and each layer is adhered under heat and pressure, and at the same time heat cured to obtain a cured composite material having a desired thickness. You can It is also possible to obtain a cured composite material having a new layer structure by combining the cured composite material that has been adhesively cured once and the curable composite material. The lamination molding and curing are usually performed simultaneously by using a hot press or the like, but both may be performed independently. That is, an uncured or semi-cured composite material obtained by laminating in advance can be cured by heat treatment or another method.

Molding and curing are carried out at a temperature of 80 to 300 ° C.
It can be carried out at a pressure of 0.1 to 1000 Kg / cm ² , a time of 1 minute to 10 hours, more preferably a temperature of 150 to 250 ° C., a pressure of 1 to 500 Kg / cm ² , and a time of 1 minute to 5 hours. . Finally, the laminated body which is the fifth invention 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 fourth of the present invention. Examples of the metal foil used here include copper foil and aluminum foil. The thickness is not particularly limited, but is 5 to 200 μm, more preferably 5
Is in the range of up to 105 μm.

As the method for producing the laminate of the present invention,
For example, a method in which the curable composite material described above as the third aspect of the present invention and a metal foil and / or a metal plate are laminated in a layered structure according to the purpose, and each layer is adhered under heat and pressure and simultaneously heat-cured. Can be mentioned. In the laminate of the present invention, the curable composite material and the metal foil are laminated in any layer structure. The metal foil can be used as both the surface layer and the intermediate layer.

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. As an adhesive, epoxy type,
Examples thereof include acrylic type, phenol type, and cyanoacrylate type, but are not particularly limited thereto. The lamination molding and curing described above can be performed under the same conditions as in the fourth aspect of the present invention.

[0071]

EXAMPLES In order to further clarify the present invention, examples will be described below. The physical properties were measured by the following methods. (1) Trichlorethylene resistance The laminate from which the copper foil was removed was cut into 25 mm square pieces, boiled in trichlorethylene for 5 minutes, and visually observed for changes in appearance, and evaluated as ◯ or × by the presence or absence of swelling or warpage (JIS. According to C6481). (2) Dielectric constant and dielectric loss tangent were measured at 1 MHz (according to JIS C 6481). (3) Solder heat resistance The laminate from which the copper foil has been removed is cut into 25 mm square pieces and 260
Floating in a solder bath at ℃ for 120 seconds, visually observing the change of appearance, and the presence or absence of white smoke was evaluated by ○ and × (JIS.
According to C6481). (4) Copper foil peeling strength A test piece having a width of 20 mm and a length of 100 mm was cut out from the laminate, and a parallel cut having a width of 10 mm was made on the copper foil surface, and then 50 mm / min in the direction perpendicular to the surface. The copper foil was continuously peeled off at the speed of, and the stress at that time was measured by a tensile tester, and the minimum value of the stress was shown (JIS C 64
81). (5) Thermal expansion characteristics The laminate from which the copper foil was removed was cut into a 7 mm square, and the thermal expansion amount in the thickness direction was measured by a thermomechanical analyzer at a rate of temperature increase of 20 ° C / min. (6) Cracks To examine the toughness of the resin, a multilayer printed wiring board was prepared, and a thermal shock between −65 ° C. and 125 ° C. was applied 100 times to check whether resin cracks were generated inside the wiring board. It was evaluated by ○ and ×. (7) Flame retardance A flammability test corresponding to UL94 standard was conducted. (8) Appearance of Cured Product Visual observation of the cured composite material indicates that the resin flow is good and the appearance is good, and that the resin flow is poor and the appearance is bad, is x. (9) Toughness The cured composite material was rubbed against a file and evaluated as ◯ or X depending on the presence or absence of cracks or chips.

In the examples, the following components were used. Component (a) Polyphenylene ether: Polymer A: poly (2,6) having a viscosity number η _sp / c of 0.53 measured at 30 ° C. in a chloroform solution of 0.5 g / dl.
-Dimethyl-1,4-phenylene ether) Polymer B: Viscosity number η _sp / measured by the same method as above.
Poly (2,6-dimethyl-1,4-phenylene ether) in which c is 0.40 (b) component: TAIC or TAC (c) component Silica: Silane-coupling treated Hueslex E-2 (Tatsumori ( Ltd., trade name) (d) component hydrogenated block copolymer: H1041 (manufactured by Asahi Chemical Industry Co., Ltd., trade name) (e) component flame retardant: a): decabromodiphenyl ether (manufactured by Asahi Glass Co., Ltd. Name AFR1021) Saytex8010: Compound represented by general formula (1) (trade name of Ethyl Corporation) b): Phenylmaleimide compound with I = 3 in general formula (2) c): Z ′ in general formula (3) Is -CH ₂ CH _2- , and p
Phthalimide compound with + q = 8 (f) component Flame retardant aid: Sb ₂ O ₃ (Nippon Seiko Co., Ltd.)
(Product name: PATOX-M) (g) component glass cloth: E glass, fabric weight 48 g /
m ² Other polymerization initiator: 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 (NOF Perhexin 25B; abbreviated as PH25B)

[0073]

Examples 1 to 8 Curable resin composition and cured resin composition: Polymer A, polymer B of component (a), TAIC or TAC of component (b), silica of component (c), and component (d) The hydrogenated block copolymer, the flame retardant as the component (e), Sb ₂ O ₃ as the component (f), and the peroxide as the radical initiator were mixed in the composition shown in Table 1 using a Henschel mixer, It was 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.

The obtained cured products were all tough, and warped and changed in appearance were not observed even after boiling in trichlorethylene for 5 minutes, and the dimensional stability was good. Further, when a flammability test corresponding to the UL94 standard was conducted, it showed a flame retardancy equivalent to V-0. The results are shown in Table 1.
It was shown to.

[0075]

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

[0076]

Comparative Example 2 In Example 1, the amount of flame retardant added was 110.
A cured product was prepared in the same manner as in Example 1 except that the weight part was used. The appearance of the cured product was poor due to insufficient flowability of the resin.

[0077]

Comparative Examples 3 and 4 A cured product was prepared in the same manner as in Example 1 except that silica or hydrogenated block copolymer was not added. Comparative Example 3 in which silica was not added had a remarkably large coefficient of linear expansion as compared with Example 1. The cured product of Comparative Example 4 to which the hydrogenated block copolymer was not added was brittle.

Comparative Examples 1 to 1 are shown in Table 1 together with Examples 1 to 8.
4 shows the result.

[0079]

Examples 9 to 16 Curable composite material: Each component having each composition shown in Table 2 was dissolved or dispersed in toluene at 80 ° C. This solution was cooled to 50 ° C, glass cloth was immersed at 50 ° C for impregnation, and dried in an air oven.

Laminate: A plurality of the above-mentioned curable composite materials were superposed on each other, copper foil of 70 μm was placed on both sides, and the mixture was molded and cured by a press molding machine under the conditions shown in Table 3 to give a composition of 0.8 mm thickness. A laminated body was obtained. The curing conditions of each example are shown in Table 3. The molding pressure was 20 kg / cm ^{2 in} all cases. Table 3 shows the physical properties of the laminate thus obtained.

In any of the examples, trichloroethylene resistance, heat resistance (Tg and solder heat resistance), dielectric properties, adhesiveness to metal, and flame-retardant cured composite materials excellent in cracks and laminates were obtained. Was given.

[0082]

Comparative Example 5 A cured product was obtained in the same manner as in Example 9 except that the amount of the flame retardant added was 3 parts by weight. When a flammability test was conducted, it was equivalent to HB.

[0083]

Comparative Example 6 In Example 9, the amount of flame retardant added was 110.
A laminate was obtained in the same manner as in Example 9 except that the parts by weight were used. The peel strength of the copper foil was significantly reduced as compared with Example 9.

[0084]

Comparative Examples 7 and 8 Cured products were prepared in the same manner as in Example 9 except that silica or hydrogenated block copolymer was not added. In Comparative Examples 7 and 8, cracks occurred in the thermal shock test. Table 3 shows Examples 9 to 16
In addition, the results of Comparative Examples 5 to 8 are shown.

[0085]

[Table 1]

[0086]

[Table 2]

[0087]

[Table 3]

[0088]

Industrial Applicability The curable polyphenylene ether resin composition of the present invention is a resin composition which is particularly excellent in toughness and flame retardancy as compared with conventional ones. The curable polyphenylene ether resin composition of the present invention can be preformed into a film, sheet or curable composite material having a good appearance before curing.

The cured polyphenylene ether resin composition of the present invention is superior in toughness and flame retardancy to conventional ones, and has the same heat resistance, chemical resistance and excellent dielectric properties as in the conventional ones. It is an excellent material. The curable composite material of the present invention has excellent adhesion to metal. Further, the cured composite material and the laminate obtained by using the curable composite material of the present invention are particularly excellent in toughness and flame retardancy, and further have heat resistance, chemical resistance and excellent dielectric properties and cracks in a thermal shock test. It is an excellent material with no generation.

Therefore, the cured composite material and laminate of the present invention can be used as a dielectric material, an insulating material, a heat-resistant material, etc. in the fields of electric industry, electronic industry, space / aircraft industry and the like. In particular, the curable composite material of the present invention is suitably used as a single-sided, double-sided, multi-layer printed circuit board, semi-rigid substrate, metal base substrate, prepreg for multi-layer printed circuit board.

The material of the present invention is used as an adhesive for a high-density circuit board having a line spacing of 100 μm or less, a multi-layer circuit board having an interlayer insulating layer thickness of 200 μm or less, and a mounting circuit board because of its heat resistance and moisture absorption resistance. It can be used well.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 5/3415 C08K 5/3415 5/3477 5/3477 C08L 53/02 LLZ C08L 53/02 LLZ

Claims (5)

[Claims] 1. A component (a) polyphenylene ether,
A resin composition comprising component (b) triallyl isocyanurate and / or triallyl cyanurate, component (c) silica, component (d) hydrogenated block copolymer and component (e) flame retardant, wherein the composition ratio is Are components (a) and (b)
Based on 100 parts by weight of the sum of the components, the component (a) is 75 to 40 parts by weight, the component (b) is 25 to 60 parts by weight, the component (c) is 10 to 400 parts by weight, and the component (d) is )
1 to 50 parts by weight of a polymer block A mainly composed of at least one vinyl aromatic compound and a polymer block B mainly composed of at least one conjugated diene compound
A hydrogenated block copolymer obtained by hydrogenating a block copolymer consisting of
A curable polyphenylene ether-based resin composition comprising 0 parts by weight of decabromodiphenyl ether or a flame retardant selected from compounds represented by the following general formulas (1) to (3). Embedded image Embedded image Embedded image 2. A cured polyphenylene ether-based resin composition obtained by curing the curable polyphenylene ether-based resin composition according to claim 1. 3. A component (a) polyphenylene ether,
(B) triallyl isocyanurate and / or triallyl cyanurate, (c) silica, (d) hydrogenated block copolymer and (e) flame retardant,
A composite material comprising an antimony oxide component (f) and a base material of the component (g), wherein the composition ratio is 7 parts by weight based on 100 parts by weight of the sum of the components (a) and (b).
5 to 40 parts by weight, the component (b) is 25 to 60 parts by weight,
10 to 100 parts by weight of the component (c) and 1 to 50 parts by weight of the component (d) as a main component of a polymer block A mainly composed of at least one vinyl aromatic compound and at least one conjugated diene compound. Hydrogenated block copolymer obtained by hydrogenating a block copolymer consisting of polymer block B, decabromodiphenyl ether of 5 to 100 parts by weight of component (e) or the following general formula (1)
To the flame retardant selected from the compounds represented by (3), and the component (f) based on 100 parts by weight of the component (e),
Curable, characterized in that 10 to 50 parts by weight of antimony oxide and (g) component consist of 5 to 90 parts by weight of the base material, based on 100 parts by weight of the sum of components (a) to (g). Composite material. [Chemical 4] Embedded image [Chemical 6] 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.