JPH08245872A - Polyphenylene ether resin composition with low permittivity and low loss tangent - Google Patents

Abstract

PURPOSE: To obtain excellent dielectric characteristics by compounding a reaction product of polyphenylene ether with an unsatd. carboxylic acid, etc., with triallyl cyanurate, a peroxie, decabromodiphenyl ether, and a flame retardant represented by a specific formula. CONSTITUTION: 100 pts.wt. mixture comprising 65-75wt.% reaction product of 100 pts.wt. polyphenylene ether with 0.1-3 pts.wt. unsatd. carboxylic acid, etc., and 35-25wt.% triallyl cyanurate is compounded with 1-3 pts.wt. peroxide (e.g. di-t-butyl peroxide), 5-100 pts.wt. flame retardant component comprising decabromodiphenyl ether and at least one flame retardant selected from among compds. represented by formulas I, II, and III (wherein m and n are each 3-5 provided m+n>8; l is 3-5; p and q are each 2-4 provided p+q>6; and Z and Z' are each 4C or lower alkylene, brominated alkylene, etc.), Sb2 O3 in an amt. of 10-50wt.% of the flame retardant, etc., and kneaded on an extruder to give a curable resin compsn. A substrate such as a metal foil is immersed in and impregnated with a soln. contg. the compsn. and thermally pressed to give a cured composite material.

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 flame retardancy, chemical resistance, dielectric properties, heat resistance and adhesiveness with a metal foil after curing, and a dielectric material in the fields of the electric / electronic industry, etc.
It can be used as an insulating material and a heat resistant material.

[0002]

2. Description of the Related Art In recent years, there has been a remarkable increase in the speed of computers and the widespread use of high-frequency equipment, and along with this, excellent heat resistance, dimensional stability, and especially electrical characteristics are being demanded in terms of materials. For example, as a printed wiring board, an epoxy resin has been conventionally used as a general-purpose thermosetting resin for a copper-clad laminate, but it has a drawback that the electrical characteristics, particularly the dielectric characteristics in a high frequency region, are poor. On the other hand, although the fluororesin has excellent electric characteristics, it is inferior in heat resistance and workability and is currently limited to special applications.

As a new material for solving this problem, polyphenylene ether has attracted attention in recent years and its application to copper clad laminates has been attempted. However, since polyphenylene ether itself has no chemical resistance, one method of utilizing it has been considered to improve the chemical resistance by blending a curable polymer or monomer. Examples of curable polymers and monomers include epoxy resins (JP-A-58-69046 and the like), 1,2-polybutadiene (JP-A-59-193929 and the like), and polyfunctional maleimides (JP-A-56-133355). Etc.), polyfunctional cyanate ester (JP-A-56-141349, etc.),
Many examples are known, such as polyfunctional acryloyl or methacryloyl compounds (JP-A-57-149317 and the like), triallyl isocyanurate and / or triallyl cyanurate (JP-A-61-218652 and the like), isocyanate compounds and the like. ing.

However, although the addition of a curable monomer or polymer can certainly improve the chemical resistance, it often greatly lowers the excellent heat resistance or dielectric properties originally possessed by polyphenylene ether. There were many difficulties in terms of flame retardancy. In addition, when sheets of cured products are laminated to form a laminate and this is used as an electric / electronic material, it is required that the adhesive force between the laminate and the metal foil or the laminate is large. When a large amount of the compound is added, the adhesive force tends to be lowered due to the reason that the resin becomes brittle and the like, and there is a problem that the reliability is lowered when it is used as a part of industrial equipment.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and retains the excellent dielectric properties of polyphenylene ether, and has excellent flame retardancy and chemical resistance after curing. Another object of the present invention is to provide a novel curable resin composition exhibiting heat resistance and excellent adhesiveness to a metal foil.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, have found a novel resin composition in accordance with the object of the present invention and completed the present invention. Arrived The present invention comprises the following five inventions. The first of the present invention is (a) a reaction product of a polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride,
(B) triallyl cyanurate and / or triallyl isocyanurate, (c) peroxide, and (d) decabromodiphenyl ether and the general formulas (1) to (3).
A curable resin composition comprising at least one flame retardant selected from the group consisting of compounds represented by:
(A) based on 100 parts by weight of the sum of the component and the component (b)
65-75 parts by weight of component, 25-35 parts by weight of component (b), 1-3 parts by weight of component (c), 5-10 parts of component (d).
There is provided a curable resin composition characterized by being 0 part by weight.

A second aspect of the present invention provides a cured resin composition obtained by curing the curable resin composition of the first aspect.
The third aspect of the present invention is (a) a reaction product of a polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride, (b) triallyl cyanurate and / or triallyl isocyanurate, (c) peroxide, (d) ) At least one flame retardant selected from the group consisting of decabromodiphenyl ether and compounds represented by the general formulas (1) to (3),
A curable composite material comprising (e) antimony oxide and (f) a base material, the sum of the components (a) and (b) being 10
65 to 75 parts by weight of the component (a) based on 0 parts by weight,
Component (b) is 25 to 35 parts by weight, component (c) is 1 to 3 parts by weight, component (d) is 5 to 100 parts by weight, component (d) 10
10 to 50 parts by weight of component (e) based on 0 parts by weight,
And curing based on 100 parts by weight of the sum of the components (a) to (f) being 95 to 35 parts by weight of the components (a) to (e) and 5 to 65 parts by weight of the component (f). Provide a composite material.

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. The present invention will be described in detail below.

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

[0010]

[Chemical 4]

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

As a typical example of Q in the general formula (4),
A compound group represented by the following four kinds of general formula (5) can be given.

[0013]

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

[0015]

[Chemical 6]

[0016]

[Chemical 7]

In the polyphenylene ether chain represented by J in the general formula (4), in addition to the unit represented by the general formula A,
The unit represented by the following general formula 8 may be included.

[0018]

Embedded image

As a preferred example of the polyphenylene ether resin of the general formula 1 used in the present invention, poly (2,6-) obtained by homopolymerization of 2,6-dimethylphenol is preferred.
Dimethyl-1,4-phenylene ether), poly (2,
6-dimethyl-1,4-phenylene ether) styrene graft polymer, 2,6-dimethylphenol and 2,
3,6-Trimethylphenol copolymer, 2,6-Dimethylphenol and 2-methyl-6-phenylphenol copolymer, 2,6-Dimethylphenol and polyfunctional phenol compound

[0020]

[Chemical 9]

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 the general formulas A and B, and the like. Regarding the molecular weight of the polyphenylene ether resin described above, the viscosity number ηsp / c measured with a chloroform solution of 0.5 g / dl at 30 ° C. is 0.1 to 1.
Those in the range of 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 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, and is substantially polymerizable due to the acid or the acid anhydride. Is a reaction product containing no double bond. The reaction product is probably a mixture of various products having various chemical structures, and the chemical structures thereof are not all elucidated. H. Glans, M .; K. A
kkapeddi, Macromolecules, 1
The following chemical structures described in 991, vol 24, 383 to 386 are mentioned as examples.

[0023]

[Chemical 10]

Examples of suitable acids and acid anhydrides include acrylic acid, methacrylic acid, maleic anhydride, fumaric acid,
Examples thereof include itaconic acid, itaconic anhydride, glutaconic anhydride, citraconic anhydride and the like. Particularly, maleic anhydride and fumaric acid are most preferably used. The reaction was carried out by mixing the polyphenylene ether resin with an unsaturated carboxylic acid or acid anhydride 10 times.
It is performed by heating in the temperature range of 0 ° C to 390 ° C. At this time, a radical initiator may coexist. Both the solution method and the melt-mixing method can be used, but the melt-mixing method using an extruder or the like is simpler and more suitable for the purpose of the present invention.

The proportion of unsaturated carboxylic acid or acid anhydride is 100 parts by weight of 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 resin composition of the present invention is a trifunctional monomer represented by the following structural formula.

[0026]

[Chemical 11]

In carrying out the present invention, triallyl isocyanurate and triallyl cyanurate may be used alone, or both may be mixed in an arbitrary ratio and used. 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.

Typical examples of the peroxide used as the component (c) of the polyphenylene ether resin composition of the present invention are benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,
5-dihydroperoxide, 2,5-dimethyl-
2,5-di (t-butylperoxy) hexyne-3 (P
H25B), di-t-butyl peroxide, t-butyl cumyl peroxide, α, α′-bis (t-butylperoxy-m-isopropyl) benzene (PBP),
2,5-Dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis (t- Butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxide, trimethylsilyltriphenylsilylper There are oxides and the like.

Particularly preferably 2,5-dimethyl-2,5
-Di (t-butylperoxy) hexyne-3, di-t-
Butyl peroxide or α, α′-bis (t-butylperoxy-m-isopropyl) benzene.
(D) of the polyphenylene ether resin composition of the present invention
The component functions as a flame retardant.

Specific examples of the flame retardant include decabromodiphenyl ether and compounds represented by the general formulas (1) to (3). In the general formula (1), m
From the viewpoint of flame retardancy, + n is preferably 9 or more, and most preferably 10. 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. Further, flame retardants other than these may be added to the extent that the original properties are not impaired.

The antimony oxide as the component (e) in the third aspect of the present invention is used for the purpose of further improving flame retardancy. Both Sb ₂ O ₃ and Sb ₂ O ₅ can be used, but S
b ₂ O ₃ is more preferred. The component (e) is essential for obtaining flame retardancy in the third to fifth inventions, but is not essential in the cured (sexual) resin composition of the first and second inventions, but flame retardancy is obtained by using it. It is possible to improve the property.

In the resin composition of the first invention of the present case,
Among the components described above, the mixing ratio of the component (a) and the component (b) is 65 to 75 parts by weight of the component (a) and 25 to 35 parts by weight of the component (b), based on 100 parts by weight of the sum of both. Is. If the amount of component (b) is less than 25 parts by weight, the resin flowability during molding is insufficiently improved, which is not preferable. On the other hand, if it exceeds 35 parts by weight, the dielectric properties will deteriorate.

The mixing ratio of the component (c) is 1 to 3 parts by weight, preferably 1.5 to 2.5 parts by weight, based on 100 parts by weight of the sum of the components (a) and (b). If the blending ratio of the component (c) is less than 1 part, it is difficult to obtain sufficient hardness and heat resistance. The mixing ratio of the component (d) is 5 to 100 parts by weight, preferably 5 to 70 parts by weight, and more preferably 5 to 50 parts by weight, based on 100 parts by weight of the sum of the components (a) and (b). . When the amount of the component (d) 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.

As a method for mixing the above components (a) to (d), there may be mentioned 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 ingredients are heated by an extruder or the like. Available. As the solvent used for the solution mixing, halogen-based solvents such as dichloromethane, chloroform and trichloroethylene; aromatic solvents such as benzene, toluene and xylene; tetrahydrofuran and the like are used alone or in combination of two or more kinds.

The resin composition of the present invention may be preliminarily molded 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-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, it is possible to obtain a sheet of the present resin composition by laminating several to several tens of films of the present resin composition prepared by a casting method and heating and melting the film by a heating and melting method, for example, using a press molding machine.

The resin composition of the present invention can be used by blending an amount of a filler or an additive in a range that does not impair the original properties for the purpose of imparting desired performance depending on the application. The filler may be fibrous or powdery,
Examples thereof include carbon black, alumina, talc, mica, glass beads and glass hollow spheres. As additives, antioxidants, heat stabilizers, antistatic agents, plasticizers,
Examples include 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 and nylon 12 and their derivatives, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyesters such as polyethylene terephthalate / polyethylene glycol block copolymers and their derivatives, polyphenylene ether, modified polyphenylene Ether, polycarbonate, polyacetal, polysulfone, polyvinyl chloride and its copolymer, polyvinylidene chloride and its copolymer, polymethylmethacrylates, acrylic acid (or methacrylic acid) ester copolymers, polystyrenes, acrylonitrile styrene Polystyrenes such as copolymers, acrylonitrile styrene butadiene-based copolymers and their copolymers, polyvinyl acetates, polyethylene Vinyl formal, polyvinyl acetal, polyvinyl butyral, ethylene vinyl acetate copolymers and hydrolysates thereof, polyvinyl alcohols, styrene butadiene block copolymers, rubbers such as polybutadiene and polyisoprene, polymethoxyethylene, polyethoxy Polyvinyl ethers such as ethylene, polyacrylic amide, 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 containing a liquid crystal component in the side chain. Examples of the thermosetting resin include epoxy resin and polyimide precursor.

The second cured polyphenylene ether resin composition of the present invention is obtained by curing the curable polyphenylene ether resin cured composition described above. The temperature for curing by heating varies depending on the type of radical initiator, but is 80 to 300.
℃, more preferably selected in the range of 120 ~ 250 ℃. 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 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 third curable composite material of the present invention is
(A) a reaction product of a polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride, (b) triallyl isocyanurate and / or triallyl cyanurate,
It is characterized by comprising (c) peroxide, (d) flame retardant, (e) antimony oxide and (f) base material. As the base material of the component (e), 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, polyester fiber, Woven or non-woven fabric obtained from synthetic fibers such as acrylic fiber, wholly aromatic polyamide fiber, polytetrafluoroethylene fiber; natural fiber cloth such as cotton cloth, linen cloth, felt; carbon fiber cloth; kraft paper, cotton paper, paper-glass blend Natural cellulose-based cloths such as fine paper are used alone or in combination of two or more kinds.

The blending ratio of the component (a) and the component (b) is 65 to 7 for the component (a) based on 100 parts by weight of the sum of both.
5 parts by weight, and the component (b) is 25 to 35 parts by weight.
When the amount of component (b) is less than 25 parts by weight, the resin flowability during molding is insufficient, which is not preferable. On the other hand, if it exceeds 35 parts by weight, the dielectric properties will deteriorate. The mixing ratio of the component (c) is (a)
1 to 3 based on 100 parts by weight of the sum of the component and the component (b)
Parts by weight, preferably 1.5 to 2.5 parts by weight.
When the amount of the component (c) is less than 1 part by weight, sufficient hardness and heat resistance cannot be obtained, and when it exceeds 3 parts by weight, the dielectric properties are slightly deteriorated.

The mixing ratio of the component (c) is 1 to 3 parts by weight, preferably 1.5 to 2.5 parts by weight, based on 100 parts by weight of the sum of the components (a) and (b). When the amount of the component (c) is less than 1 part by weight, sufficient heat resistance and chemical resistance cannot be obtained, and when it exceeds 3 parts by weight, the dielectric properties are slightly deteriorated. The mixing ratio of the component (d) is 5 to 100 parts by weight, preferably 5 to 70 parts by weight, and most preferably 5 to 50 parts by weight, based on 100 parts by weight of the sum of the components (a) and (b). If the amount of component (d) is less than 5 parts by weight, the flame retardant is insufficient, and if it exceeds 100 parts by weight, the fluidity during melt molding may be reduced, or the adhesive strength to the metal foil may be reduced.

The mixing ratio of the component (e) is 100 for the component (d).
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 (e) is less than 10 parts by weight, the effect of improving the flame retardancy is insufficient as compared with the case where the component (d) 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 (f) is from (a) to
The amount is 5 to 65 parts by weight, more preferably 10 to 60 parts by weight, further preferably 30 to 50 parts by weight, based on 100 parts by weight of the sum of the components (f). When the amount of the component (g) is less than 5 parts by weight, the dimensional stability and strength of the composite material after curing are insufficient, and when the amount of the base material is more than 65 parts by weight, the dielectric properties of the composite material are poor, which is not preferable.

In the composite material of the present invention, a coupling agent can be used if necessary for the purpose of improving the adhesiveness at the interface between the resin and the substrate. As the coupling agent, silane coupling agents, titanate coupling agents, aluminum-based coupling agents, zircoaluminate coupling agents and the like can be used. The method for producing the composite material of the present invention includes, for example, the first method of the present invention.
Component (a) to (e) and other components as required in the section (1) are uniformly dissolved or dispersed in the above-mentioned halogen-based, aromatic-based, ketone-based solvent or a mixed solvent thereof,
A method of impregnating the base material and then drying the base material may be mentioned.

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 fourth curable composite material of the present invention is obtained by curing the curable composite material thus obtained by a method such as heating. The manufacturing method is not particularly limited, and for example, a plurality of the curable composite materials are stacked, and each layer is adhered under heat and pressure, and at the same time heat cured to obtain a cured composite material having a desired thickness. You can It is also possible to obtain a cured composite material having a new layer structure by combining the cured composite material that has been adhesively cured once and the curable composite material. The lamination molding and curing are usually performed simultaneously 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 fifth embodiment 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 to 1
It is in the range of 05 μm.

As the method for producing the laminate of the present invention,
For example, the curable composite material described above as the third aspect of the present invention,
There may be mentioned a method in which 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 at the same time heat-cured. 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.

[0051]

EXAMPLES Hereinafter, the present invention will be described with reference to examples in order to further clarify the present invention, but the scope of the present invention is not limited to these examples. In the examples below, the following components were used. Polymerization initiator: α, α′-bis (t-butylperoxy-
Meta - isopropyl) benzene (NOF Perbutyl P; referred to as PBP) a flame retardant aid: Sb ₂ O ₃ (Nippon Seiko PATOX-M) Glass cloth: E glass, weight per unit area 48 g / m ²

[0052]

[Reference Example 1] Product obtained by modifying polyphenylene ether with an unsaturated acid anhydride: poly (2,6) having a viscosity number ηsp / c of 0.54 measured at 30 ° C. in a chloroform solution of 0.5 g / dl.
-Dimethyl-1,4-phenylene ether) 100 parts by weight, maleic anhydride 1.5 parts by weight, and 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (NOF Corporation). Perhexa 25B) 1.0 part by weight is dry blended at room temperature, and then the cylinder temperature is set to 300.
The reaction product was obtained by extrusion with a twin-screw extruder under the conditions of ℃ and screw rotation speed of 230 rpm. The ηsp / c of this reaction product was 0.48. Hereinafter, this reaction product is abbreviated as polymer A.

[0053]

[Reference Example 2] Product obtained by subjecting polyphenylene ether to modification reaction with an unsaturated acid anhydride: poly (2,6) having a viscosity number ηsp / c of 0.40 measured with a chloroform solution of 30 g at 0.5 g / dl.
-Dimethyl-1,4-phenylene ether) 100 parts by weight and maleic anhydride 1.5 parts by weight are dry-blended at room temperature, and then extruded by a twin-screw extruder under the conditions of a cylinder temperature of 300 ° C and a screw rotation speed of 230 rpm. A reaction product was obtained. The ηsp / c of this reaction product is 0.
It was 43. Hereinafter, this reaction product is abbreviated as polymer B.

[0054]

Examples 1 to 10 Curable resin composition and cured resin composition Polymer A or B, TAIC or TAC, peroxide
Objects, flame retardants, and Sb ₂O₃With the composition shown in Table 1
Mix using a shell mixer, and press the 2
Molded and cured at 00 ° C for 30 minutes, thickness about 1mm
A cured product of

This cured product showed a flame retardancy equivalent to V-0 when subjected to a flammability test corresponding to UL94 standard. When the glass transition temperature (Tg) was measured with a thermomechanical property analyzer (TMA), a good value of 150 ° C. or higher was obtained.

[0056]

Comparative Example 1 Example 1 except that the ratio of polymer A to TAIC in Example 1 was changed from 75:25 to 85:15.
A cured product was obtained by the same procedure as described above. Due to insufficient flowability of the resin, the surface of the cured product was uneven.

[0057]

Comparative Example 2 A cured product was obtained in the same manner as in Example 1, except that the amount of peroxide was changed to 0.5 part.
Since the TAIC was uncured, the surface was sticky.

[0058]

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

[0059]

Comparative Example 4 A cured product was obtained in the same manner as in Example 1 except that the amount of the flame retardant was changed to 110 parts. The appearance of the cured product was poor due to insufficient flowability of the resin. The results of Examples 1 to 10 and Comparative Examples 1 to 4 are shown in Table 1.

[0060]

[Table 1]

[0061]

Examples 11 to 18 Curable composite material Each component having the composition shown in Table 2 was dissolved or dispersed in toluene at 80 ° C. A glass cloth was immersed in this solution for impregnation and dried in an air oven. Laminated body If necessary, a plurality of the above-mentioned curable composite materials are laminated so that the thickness after molding is about 0.8 mm, and a copper foil with a thickness of 35 μm is placed on both sides of the laminate and molded and cured by a press molding machine. To obtain a laminate. The curing conditions of each example are shown in Table 3. The pressure was 30 kg / cm ^{2 in} all cases.

Various physical properties of the laminate thus obtained were measured by the following methods. 1. The dielectric constant and the dielectric loss tangent were measured at 1 MHz (according to JIS C 6481). 2. Solder heat resistance Cut the laminate from which the copper foil was removed into 25 mm square pieces, 260
Floating in a solder bath at ℃ for 120 seconds, the change in appearance was visually observed (in accordance with JIS C 6481). 3. Glass transition temperature (Tg), linear expansion coefficient A sample cut out from the laminate was measured by TMA. 4. Copper foil peeling strength (interlayer peeling strength) A test piece having a width of 20 mm and a length of 100 mm was cut out from the laminate, and after making parallel cuts having a width of 10 mm on the copper foil surface, a direction perpendicular to the surface The copper foil was continuously peeled off at a speed of 50 mm / min, and the stress at that time was measured by a tensile tester, and the minimum value of the stress was shown (JIS C 6
481). The interlayer peeling strength of the laminate was measured in the same manner as the copper foil peeling strength by peeling off the surface sheet from the laminate obtained by stacking a plurality of sheet-shaped curable composite materials and press-molding them.

The results are shown in Table 3. In any of the examples, heat resistance (Tg and solder heat resistance), dielectric properties,
A cured composite material and a laminate having excellent adhesion to metal and flame retardancy were obtained.

[0064]

Comparative Example 5 Polymer A and TAIC in Example 11
A cured product was obtained in the same manner except that the ratio was changed from 75:25 to 85:15. The laminate had uneven surface due to poor flow during molding.

[0065]

Comparative Example 6 In Example 13, the amount of peroxide was 0.5.
A cured product was obtained in the same manner as in Example 13 except that the parts were used. The heat resistance was inferior.

[0066]

Comparative Example 7 A cured product was obtained in the same manner as in Example 13 except that the amount of peroxide was changed to 5 parts.
The dielectric loss tangent was large.

[0067]

Comparative Example 8 A cured product was obtained in the same manner as in Example 13, except that the amount of the flame retardant was changed to 3 parts. When a flammability test was conducted, it was equivalent to HB.

[0068]

[Comparative Example 9] A laminate was obtained in the same manner as in Example 13 except that the amount of the flame retardant was changed to 110 parts. The laminate has uneven surface due to poor flow during molding,
The copper foil peeling strength was significantly reduced as compared with Example 13. Table 3 shows the results of Comparative Examples 5 to 9 together with Examples 11 to 18.

[0069]

[Table 2]

[0070]

[Table 3]

[0071]

EFFECTS OF THE INVENTION The curable resin composition of the present invention has a good solvent film-forming property, and a film and a curable composite material which are free from surface stickiness and have excellent handleability can be obtained. The cured resin composition of the present invention is an excellent material having flame retardancy, heat resistance and excellent dielectric properties.

The curable composite material of the present invention is excellent in adhesion to metal and adhesion between layers. Further, the cured composite material and the laminate obtained by using the curable composite material of the present invention are excellent materials having both flame retardancy, heat resistance and excellent dielectric properties. Therefore, the material of the present invention is a dielectric material in the fields of electric industry, electronic industry, space and aircraft industry, etc.
It can be used as an insulating material, a heat resistant material, or the like.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 5/06 C08K 5/06 5/14 5/14 5/3415 5/3415 5/3477 5 / 3477

Claims (5)

[Claims] 1. A reaction product of (a) a polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride, (b) a triallyl cyanurate and / or a triallyl isocyanurate, (c) a peroxide, and (d). ) A curable resin composition comprising at least one flame retardant selected from the group consisting of decabromodiphenyl ether and compounds represented by the following formulas (1) to (3), wherein the component (a) and the component (b) 65 to 75 parts by weight of the component (a), 25 to 35 parts by weight of the component (b), based on 100 parts by weight of the sum of the components,
A curable polyphenylene ether-based resin composition, wherein the component (c) is 1 to 3 parts by weight and the component (d) is 5 to 100 parts by weight. Embedded image Embedded image Embedded image 2. A cured resin composition obtained by curing the curable resin composition according to claim 1. 3. A reaction product of (a) a polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride, (b) a triallyl cyanurate and / or a triallyl isocyanurate, (c) a peroxide, (d). At least one flame retardant selected from the group consisting of decabromodiphenyl ether and compounds represented by general formulas (1) to (3),
A curable composite material comprising (e) antimony oxide and (f) a base material, the sum of the components (a) and (b) being 10
65 to 75 parts by weight of the component (a) based on 0 parts by weight,
Component (b) is 25 to 35 parts by weight, component (c) is 1 to 3 parts by weight, component (d) is 5 to 100 parts by weight, component (d) 10
10 to 50 parts by weight of component (e) based on 0 parts by weight,
And curing based on 100 parts by weight of the sum of the components (a) to (f) being 95 to 35 parts by weight of the components (a) to (e) and 5 to 65 parts by weight of the component (f). Composite material. 4. A cured composite material obtained by curing the curable composite material according to claim 3. 5. A laminate comprising the cured composite material according to claim 4 and a metal foil.