JPH07166049A - New curable polyphenylene ether resin composition and flame-retardant laminate - Google Patents

Abstract

PURPOSE:To obtain a resin compsn. having an improved flame retardancy by compounding a modified polyphenylene ether resin, triallyl cyanurate and/or triallyl isocyanurate, and an imidated arom. bromine compd. CONSTITUTION:This compsn. is obtd. by mixing 98-40 pts.wt. modified polyphenylene ether resin, 2-60 pts.wt. triallyl cyanurate or isocyanurate, 5-100 pts.wt. imidated arom. bromine compd. of formula III (wherein l is 3-5), Sb2O5 in an amt. of 10-50wt.% of the bromine compd., and if necessary a free-radical initiator. The modified polyphenylene ether resin is obtd. by reacting 100 pts.wt. polyphenylene ether of formula I [m is 1-6; J is a group of formula II (wherein R1 to R4 are each lower alkyl, aryl, etc.); and Q is H when m is 1 and Q is a polyhydric phenol residue when m is 2 or higher] with 0.01-5 pts.wt. unsatd. carboxylic acid (e.g. fumaric acid). A curable composite material is obtd. by laminating 95-10 pts.wt. the compsn. with 5-90 pts.wt. substrate.

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, and heat resistance after curing, and is a dielectric material, an insulating material, in the fields of the electronic industry, space / aircraft industry, etc.
It can be used as 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, and electrical characteristics are being demanded. For example, as a printed wiring board, a copper-clad laminate made of a thermosetting resin such as phenol resin or epoxy resin has been conventionally used. Although these have various performances in a well-balanced manner, they have the drawback of poor electrical properties, especially dielectric properties in the high frequency range. Polyphenylene ether has attracted attention in recent years as a new material for solving this problem, and its application to copper-clad laminates has been attempted.

One of the methods of utilizing polyphenylene ether is a method of blending a curable polymer or monomer. By combining it with a curable polymer or monomer, it is possible to obtain a material which improves the chemical resistance of polyphenylene ether and makes good use of the excellent dielectric properties of polyphenylene ether. Examples of curable polymers and monomers include epoxy resins (Japanese Patent Laid-Open No. 58-690).
46, etc.), 1,2-polybutadiene (JP-A-59-59)
193929), and polyfunctional maleimides (Japanese Patent Laid-Open No. Sho 5)
6-133355), polyfunctional cyanate ester (JP-A-56-141349, etc.), polyfunctional acryloyl or methacryloyl compound (JP-A-57-14).
9317), triallyl isocyanurate and / or triallyl cyanurate (JP-A-61-218).
No. 652) and isocyanate compounds.

However, polyphenylene ether is
Since it does not have chemical resistance at all, even if a curable polymer or monomer is used together, its improvement is naturally limited. This is because the polyphenylene ether was used without any modification. Further, polyphenylene ether does not have sufficient flame retardancy for use in electric parts such as copper-clad laminates. Although it is practically strongly demanded to impart flame retardancy without impairing the excellent dielectric properties and heat resistance of polyphenylene ether, the addition of decabromodiphenyl ether analogs, which is an effective means, is environmentally friendly. From the point of view of protection, it is restricted or prohibited.

[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. And a novel curable resin composition exhibiting heat resistance.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, have found a novel resin composition in accordance with the object of the present invention and completed the present invention. Arrived 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,
A curable resin composition comprising (b) triallyl cyanurate and / or triallyl isocyanurate, (c) a brominated aromatic compound containing at least one imide ring, and comprising (a) component and (b) component Of 100 parts by weight of the component (a) is 98 to 40 parts by weight, the component (b) is 2 to 60 parts by weight, and the component (c) is 5 to 100 parts by weight. It is a composition.

A second aspect of the present invention is a cured resin composition obtained by curing the curable resin composition of the first aspect. The third aspect of the present invention comprises (a) a reaction product of a polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride, (b) a triallyl cyanurate and / or a triallyl isocyanurate, and (c) at least one imide ring. A curable composite material comprising a brominated aromatic compound containing (d) a curable resin composition comprising antimony oxide and (e) a base material,
98 to 40 parts by weight of the component (a) and 2 to 60 parts by weight of the component (b) based on 100 parts by weight of the sum of the components (a) and (b).
Parts by weight, 5 to 100 parts by weight of component (c), component 1 of (c)
10 to 50 parts by weight of component (d) based on 00 parts by weight, and 95 to 10 parts by weight of components (a) to (d) based on 100 parts by weight of the sum of components (a) to (e), The curable composite material is characterized in that component (e) is 5 to 90 parts by weight.

A fourth aspect of the present invention is a cured composite material obtained by curing the curable composite material of the third aspect. The fifth aspect of the present invention is a laminate comprising the cured composite material of the fourth aspect and a metal foil. Hereinafter, the present invention will be described in detail. The polyphenylene ether used in the present invention is represented by the following general formula 1.

[0009]

[Chemical 1]

Examples of the lower alkyl group of R1 to R4 in the general formula A include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and the like. A phenyl group etc. are mentioned as an example of an aryl group. Examples of the haloalkyl group include a bromomethyl group and a chloromethyl group. Examples of halogen atoms include bromine and chlorine.

As a typical example of Q in Chemical formula 1, the following 4
The compound group represented by the general formula 2 of the species may be mentioned.

[0012]

[Chemical 2]

Specific examples include the following chemical formulas 3-4.

[0014]

[Chemical 3]

[0015]

[Chemical 4]

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. .

[0017]

[Chemical 5]

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

[0019]

[Chemical 6]

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 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 are most preferably used. The reaction is carried out by heating the polyphenylene ether resin and the unsaturated carboxylic acid or acid anhydride in the temperature range of 100 ° 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 ratio of the unsaturated carboxylic acid or the acid anhydride is 0.01 to 5. With respect to 100 parts by weight of the polyphenylene ether resin.
It is 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.

[0023]

[Chemical 7]

In carrying out 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 brominated aromatic compound containing at least one imide ring used as the component (c) of the polyphenylene ether resin composition of the present invention functions as a flame retardant. Specific examples of the flame retardant include compounds represented by the following structural formula 8 and compounds represented by the structural formula 9.

[0026]

[Chemical 8]

L is an integer of 3-5.

[0028]

[Chemical 9]

M and n are each an integer of 2 to 4 and m +
n is 6 or more and Z is an alkyl group having 4 or less carbon atoms or a bromine-substituted alkyl group. From the viewpoint of the flame retardant effect, m + n is preferably 9 or more, and most preferably 10. Z may have any number of hydrogens replaced by bromine. The number of carbon atoms may be any number as long as it is 4 or less, but —CH ₂ CH ₂ — is mentioned as the most preferable structure.

Oxidation of component (d) in the third invention of the present case
Antimony is used for the purpose of further improving flame retardancy.
It Sb₂O₃And Sb₂O_FiveEither of these can be used, but S
b₂O ₃Is more preferable. The component (d) is the third to fifth inventions.
In order to obtain higher flame retardancy, it is essential,
It is essential for the cured (curable) resin composition of the first and second inventions.
There is no. However, using it to improve flame retardancy
Is possible.

The mixing ratio of the components (a) and (b) described above is 98 to 40 parts by weight, preferably 98 to 40 parts by weight, based on 100 parts by weight of the sum of the components (a) and (b). Is 95 to 50 parts by weight, and the component (b) is 2 to 60 parts by weight, preferably 5 to 50 parts by weight. If the amount of component (b) is less than 2 parts by weight, the chemical resistance is not sufficiently improved, which is not preferable. On the other hand, if it exceeds 60 parts by weight, the dielectric properties, flame retardancy, and water absorption properties are deteriorated, and the resin becomes very brittle after curing, which is not preferable.

The mixing ratio of the component (c) is 5 to 100 parts by weight, preferably 5 to 70 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the sum of the components (a) and (b).
It is 50 parts by weight. If the blending ratio of the component (c) is less than 5 parts, it is difficult to obtain sufficient flame retardancy, and if it exceeds 100 parts by weight, fluidity is insufficient when the composition is heated and pressed, and the adhesive force to metal is insufficient. It may decrease.

The blending ratio of the component (d) is 10 parts of the component (c).
10 to 50 parts by weight, preferably 1 based on 0 parts by weight
It is 0 to 40 parts by weight, most preferably 10 to 30 parts by weight. The curable composite material of the present invention has increased mechanical strength,
Substrates can be used to increase dimensional stability. As the substrate used in the present invention, various glass cloths such as roving cloth, cloth, chopped mat, surfacing mat, asbestos cloth, metal fiber cloth and other synthetic or natural inorganic fiber cloth; polyvinyl alcohol fiber, polyester fiber, Woven or non-woven fabric obtained from synthetic fibers such as acrylic fiber, wholly aromatic polyamide fiber, polytetrafluoroethylene fiber; natural fiber cloth such as cotton cloth, linen cloth, felt; carbon fiber cloth; kraft paper, cotton paper, paper-glass Natural cellulose-based cloths such as mixed fiber paper are used alone or in combination of two or more kinds.

The proportion of the base material in the curable composite material of the present invention is 5 to 90 parts by weight, more preferably 10 to 80 parts by weight, further preferably 20 to 70 parts by weight, based on 100 parts by weight of the curable composite material. It is a department. If the amount of the base material is less than 5 parts by weight, the dimensional stability and strength of the composite material after curing will be insufficient, and if the amount of the base material is more than 90 parts by weight, the dielectric properties and flame retardancy of the composite material will be poor, such being undesirable.

Examples of the metal foil used in the present invention 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 a method for mixing the above components (a) to (c), a solution mixing method in which both are uniformly dissolved or dispersed in a solvent, or a melt blending method in which heating is performed by an extruder or the like can be used. As the 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; a ketone solvent such as acetone, methyl ethyl ketone and methyl isobutyl ketone; tetrahydrofuran alone or Used in combination of two or more.

The curable resin composition of the present invention may be molded and cured in advance depending on its use. The molding method is not particularly limited. Usually, a casting method in which the 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 curable resin composition of the present invention prepared by a casting method are laminated, and a heat melting method,
For example, a sheet of the curable resin composition of the present invention can be obtained by heating and melting with a press molding machine.

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

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

The amount of the radical initiator used in the curable resin composition of the present invention is 0.1 to 10% by weight, preferably 0.1 to 8% by weight, based on the sum of the components (a) and (b). %. Representative examples of the radical initiator include benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t -Butylperoxy) hexyne-3, di-t-butyl peroxide, t-butyl cumyl peroxide, α, α '
-Bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, dicumyl peroxide, di-t
-Butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis (t-butylperoxy) butane, 2,2-bis (t-butylperoxy) octane, 2,5-dimethyl-2, There are peroxides such as, but not limited to, 5-di (benzoylperoxy) hexane, di (trimethylsilyl) peroxide, and trimethylsilyltriphenylsilylperoxide. Although not a peroxide, 2,3-dimethyl-2,3-diphenylbutane can also be used as a radical initiator. However, the initiator used for curing the resin composition is not limited to these examples.

The curable resin composition of the present invention can be used by blending an amount of a filler or an additive within a range that does not impair the original properties for the purpose of imparting desired performance depending on its use. The filler may be fibrous or powdery, and examples thereof include silica, alumina, talc, mica, glass beads, and glass hollow spheres. Examples of the additives include antioxidants, heat stabilizers, antistatic agents, plasticizers, pigments, dyes, colorants and the like. Furthermore, it is also possible to mix one or more kinds of other thermoplastic resins or thermosetting resins. Specifically, phenol resin, epoxy resin, diallyl phthalate, divinylbenzene, polyfunctional acryloyl compound, polyfunctional methacryloyl compound, polyfunctional maleimide, polyfunctional cyanate ester, polyfunctional isocyanate, unsaturated polyester, Thermosetting resins such as triallyl isocyanurate, triallyl cyanurate, polybutadiene, cross-linkable polymers such as styrene-butadiene / styrene-butadiene-styrene, polyethylene, polypropylene,
Polybutene, ethylene-propylene copolymer, poly (4
-Methyl-pentene) and other polyolefins and their derivatives, nylon 4, nylon 6, nylon 6.6, nylon 6,10, nylon 12, and other polyamides and their derivatives, polyethylene terephthalate, polybutylene terephthalate, polyethylene phthalate. Polyesters such as polyethylene terephthalate / polyethylene glycol block copolymers and their derivatives, polyphenylene ethers, polycarbonates, polyacetals, polysulfones, polyvinyl chlorides and their copolymers, polyvinylidene chlorides and their copolymers, polymethylmethacrylates , Acrylic acid (or methacrylic acid) ester copolymers, polystyrenes, acrylonitrile styrene copolymers, acrylonitrile styrene butadiene copolymers And other polystyrenes and copolymers thereof, polyvinyl acetates, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, ethylene vinyl acetate copolymers and hydrolysates thereof, polyvinyl alcohols, styrene butadiene block copolymers , Polybutadiene, polyisoprene rubbers, polyvinyl ethers such as polymethoxyethylene, polyethoxyethylene, polyacrylic amide, polyphosphazenes, polyether sulfone, polyether ketone, polyetherimide, polyphenylene sulfite, polyamide Examples of the thermoplastic resin include liquid crystal polymers such as imide, thermoplastic polyimide and aromatic polyester, and side chain type liquid crystal polymers containing a liquid crystal component in the side chain.

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

The resin composition of the obtained cured resin composition can be analyzed by methods such as infrared absorption spectroscopy, high resolution solid state nuclear magnetic resonance spectroscopy and pyrolysis gas chromatography. The cured composite material of the present invention can be used as a film-like material or a laminate in which at least one kind of metal foil is laminated on at least one surface.

The 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.
The pressure may be in the range of 0.1 to 1000 kg / cm2, the time of 1 minute to 10 hours, and more preferably, the temperature of 120 to 250 ° C, the pressure of 1 to 100 kg / cm2, and the time of 1 minute to 5 hours. The laminate of the present invention is composed of the cured composite material of the present invention and a metal foil.

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

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

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

[0048]

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.

[0049]

Reference Example 1 Poly (2,6) having a viscosity number ηsp / c of 0.53 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.
Extrusion was carried out by a twin-screw extruder under the conditions of ℃ and screw rotation speed of 230 rpm. The viscosity number ηsp / c of the reaction product measured with a chloroform solution of 30 g at 0.5 g / dl was 0.48. This reaction product is designated as A.

[0050]

Reference Example 2 Viscosity number η measured by the same method as in Reference Example 1
Poly (2,6-dimethyl-1,4-) with sp / c of 0.40
100 parts by weight of phenylene ether) and 1.5 parts by weight of maleic anhydride were 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. 30 ° C, 0.5g /
The viscosity number ηsp / c of the reaction product measured with a dl chloroform solution was 0.43. This reaction product is designated as B.

[0051]

Examples 1 to 3 Curable Resin Composition and Cured Resin Composition A or B, a phenylmaleimide compound in which 1 = 3 in Chemical formula 8 and Sb2O3 were mixed with a composition shown in Table 1 using a Henschel mixer. Then, it is molded and cured by a press molding machine at 200 ° C for 30 minutes, and the thickness is about 1 m.
A cured product of m was prepared.

This cured product was treated with 5% in trichlorethylene.
No warpage or change in appearance was observed even after boiling for a minute, 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. When the glass transition temperature (Tg) was measured by a thermomechanical property analyzer (TMA), a good value of 150 to 170 ° C. was obtained.

[0053]

[Examples 4 to 6] Films made of curable resin compositions and cured resin compositions A and B obtained by laminating films, a phenylmaleimide compound with l = 3 in Chemical formula 8 and Sb2O3 in toluene The mixture was stirred at 80 ° C for 1 hour. Thereafter, triallyl isocyanurate or triallyl cyanurate was dissolved in the above-mentioned solution in the amounts shown in Table 1. This solution was cast on a Teflon dish to obtain a film. The film obtained is about 10
Since the film had a thickness of 0 μm, the film had no stickiness and had excellent film-forming properties.

After drying in an air oven, the obtained film was laminated and cured by a vacuum press molding machine to prepare a cured product having a thickness of 1 mm. The cured product had good dimensional stability without any warpage or change in appearance even after boiling with trichlorethylene for 5 minutes. Further, when a flammability test corresponding to the UL94 standard was conducted, it showed a flame retardancy equivalent to V-0. When the glass transition temperature (Tg) was measured using TMA, a good value of 150 to 170 ° C. was obtained.

[0055]

Comparative Example 1 Instead of A in Example 1, poly (2,6-dimethyl-1,4-phenylene ether) (ηsp / c =
The same operation as in Example 1 was repeated except that 0.53) was used. When the obtained cured product was boiled in trichlorethylene for 5 minutes, swelling and warpage were observed.

[0056]

Comparative Example 2 A cured product was obtained in the same manner as in Example 3 except that the amount of the flame retardant was changed to 3 parts. When a flammability test was conducted, it was equivalent to HB.

[0057]

Comparative Example 3 A cured product was obtained in the same manner as in Example 3, except that the amount of the flame retardant was changed to 120 parts. The appearance of the cured product was poor due to insufficient flowability of the resin. The results of Examples 1 to 6 and Comparative Examples 1 to 3 are shown in Table 1.

[0058]

Examples 7 to 9 Curable Resin Composition and Cured Resin Composition A or B, Z in Chemical Formula 9 is —CH 2 CH 2 — and m +
Phthalimide compound with n = 6 to 8 and Sb2
O3 having the composition shown in Table 3 was mixed using a Henschel mixer, and molded and cured by a press molding machine at 200 ° C. for 30 minutes to prepare a cured product having a thickness of about 1 mm.

This cured product was mixed with trichlorethylene in 5
No warpage or change in appearance was observed even after boiling for a minute, and 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. When the glass transition temperature (Tg) was measured using TMA, a good value of 150 to 170 ° C. was obtained.

[0060]

[Examples 10 to 12] Films made of curable resin compositions and cured resin compositions A and B obtained by laminating films, wherein Z in Chemical formula 9 is -CH2CH2- and m +.
Phthalimide compound with n = 6 to 8 and Sb2
O3 was stirred in toluene at 80 ° C for 1 hour. Thereafter, triallyl isocyanurate or triallyl cyanurate was dissolved in the above-mentioned solution in the amounts shown in Table 1. This solution was cast on a Teflon dish to obtain a film. The obtained film had a thickness of about 100 μm, and the film had no stickiness and had excellent film forming properties.

After drying in an air oven, the obtained film was laminated and cured by a vacuum press molding machine to prepare a cured product having a thickness of 1 mm. The cured product had good dimensional stability without any warpage or change in appearance even after boiling with trichlorethylene for 5 minutes. Further, when a flammability test corresponding to the UL94 standard was conducted, it showed a flame retardancy equivalent to V-0. When the glass transition temperature (Tg) was measured using TMA, a good value of 150 to 170 ° C. was obtained.

[0062]

Comparative Example 4 Instead of A, poly (2,6-dimethyl-
1,4-phenylene ether) (ηsp / c = 0.5
The same operation as in Example 7 was repeated except that 3) was used.
When the obtained cured product was boiled in trichlorethylene for 5 minutes, swelling and warpage were observed.

[0063]

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

[0064]

Comparative Example 6 A cured product was obtained in the same manner as in Example 9 except that the amount of the flame retardant was changed to 120 parts. The appearance of the cured product was poor due to insufficient flowability of the resin. The results of Examples 7-12 and Comparative Examples 4-6 are shown in Table 2.

[0065]

Examples 13 to 18 Curable composite material A phenylmaleimide compound with l = 3 in Chemical formula 8 was used as a flame retardant, and 80 parts of each component were prepared in the composition shown in Table 3.
Dissolved or dispersed in toluene at 0 ° C. A glass cloth was immersed in this solution for impregnation and dried in an air oven.

Laminated body A plurality of the above-mentioned curable composite materials are superposed if necessary so that the thickness after molding is about 0.05 mm to 0.8 mm, and a copper foil with a thickness of 35 μm is placed on both sides thereof. A laminate was obtained by molding and curing with a press molding machine. The curing conditions of each example are shown in Table 3. The pressure is 30 kg / cm2
And

Various physical properties of the thus obtained laminate were measured by the following methods. 1. Trichloroethylene resistance The laminate from which the copper foil was removed was cut into 25 mm square pieces, boiled in trichlorethylene for 5 minutes, and the change in appearance was visually observed (in accordance with JIS C 6481). 2. The dielectric constant and the dielectric loss tangent were measured at 1 MHz (according to JIS C 6481). 3. 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). 4. Copper foil peeling strength A test piece having a width of 20 mm and a length of 100 mm was cut out from the laminate, and a parallel cut having a width of 10 mm was made on the copper foil surface, and then a speed of 50 mm / min in a direction perpendicular to the surface. Then, the copper foil was continuously peeled off, and the stress at that time was measured by a tensile tester, and the minimum value of the stress was shown (JIS C 6
481). 5. Glass transition temperature (Tg) A sample cut out from the laminate was measured by TMA.

The results are shown in Table 4. In each of the examples, a cured composite material and a laminate having excellent trichlorethylene resistance, heat resistance (Tg and solder heat resistance), dielectric properties, adhesion to metal, and flame retardancy were obtained.

[0069]

Comparative Example 7 In Example 13, ηsp instead of A
The same operation was performed using poly (2,6-dimethyl-1,4-phenylene ether) with /c=0.53 to prepare a laminated plate. When the trichlorethylene resistance of this laminate was measured, significant whitening of the surface and exposure of glass cloth were observed.

[0070]

Comparative Example 8 A cured product was obtained in the same manner as in Example 14, except that the amount of the flame retardant was changed to 3 parts. When a flammability test was conducted, it was equivalent to HB.

[0071]

[Comparative Example 9] A laminate was obtained in the same manner as in Example 14, except that the amount of the flame retardant was changed to 120 parts. The peel strength of the copper foil was significantly reduced as compared with Example 14. In Table 4, Comparative Examples 7 to 9 in combination with Examples 13 to 18
The result is shown.

[0072]

Examples 19 to 24 Z in the chemical formula 9 was used as a flame retardant.
The same operation as in Examples 13 to 18 was carried out except that a phthalimide compound having CH2CH2- and m + n = 8 was used, and an experiment was conducted with the composition shown in Table 5 to obtain the results shown in Table 6.
In each of the examples, a cured composite material and a laminate having excellent trichlorethylene resistance, heat resistance (Tg and solder heat resistance), dielectric properties, adhesion to metal, and flame retardancy were obtained.

[0073]

Comparative Example 10 In Example 19, ηs instead of A
Poly (2,6-dimethyl-1,4-p / c = 0.53)
The same operation was performed using phenylene ether) to produce a laminated board. When the trichlorethylene resistance of this laminate was measured, significant whitening of the surface and exposure of glass cloth were observed.

[0074]

Comparative Example 11 A cured product was obtained in the same manner as in Example 20, except that the amount of the flame retardant was changed to 3 parts.
When a flammability test was conducted, it was equivalent to HB.

[0075]

Comparative Example 12 The amount of the flame retardant in Example 20 was 120.
A laminate was obtained in the same manner as in Example 20 except that the parts were used. The peel strength of the copper foil was significantly reduced as compared with Example 20. In Table 6, Comparative Examples 10 to 10 are combined with Examples 19 to 24.
12 results are shown.

[0076]

[Table 1]

[0077]

[Table 2]

[0078]

[Table 3]

[0079]

[Table 4]

[0080]

[Table 5]

[0081]

[Table 6]

[0082]

EFFECTS OF THE INVENTION The curable resin composition of the present invention has a good solvent film-forming property and is free from stickiness on the surface, and a film and a curable composite material having excellent handleability can be obtained. The cured resin composition of the present invention has flame retardancy, heat resistance, chemical resistance and excellent dielectric properties, and is an excellent material containing no decabromodiphenyl ether.

The curable composite material of the present invention has excellent adhesion to metal. Further, the cured composite material and laminate obtained by using the curable composite material of the present invention have flame retardancy, heat resistance, chemical resistance, and excellent dielectric properties, and are excellent in that they do not contain decabromodiphenyl ether. It is a material. In the laminated body of the present invention, even if it is an extremely thin plate that easily burns, the outstanding combustibility of V-0 was obtained.

Therefore, the material of the present invention can be used as a dielectric material, an insulating material, a heat resistant material, etc. in the fields of electric industry, electronic industry, space / aircraft industry and the like. In particular, the curable composite material of the present invention is a single-sided, double-sided, multilayer printed circuit board,
It is preferably used as a prepreg for semi-rigid boards, metal base boards, and multilayer printed boards. Further, the material of the present invention can be favorably used as an adhesive for a high-density circuit board having a line spacing of 100 μm or less, a multilayer 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. .

Claims (5)

[Claims] 1. Containing (a) a reaction product of a polyphenylene ether and an unsaturated carboxylic acid or an acid anhydride, (b) triallyl cyanurate and / or triallyl isocyanurate, and (c) at least one imide ring. A curable resin composition comprising a brominated aromatic compound,
98 to 40 parts by weight of the component (a) and 2 to 60 parts by weight of the component (b) based on 100 parts by weight of the sum of the components (a) and (b).
A curable resin composition, characterized in that 5 parts by weight of the component (c) is 5 to 100 parts by weight. 2. A cured resin composition obtained by curing the curable resin composition according to claim 1. 3. Containing (a) a reaction product of polyphenylene ether and an unsaturated carboxylic acid or acid anhydride, (b) triallyl cyanurate and / or triallyl isocyanurate, and (c) at least one imide ring. A flame retardant which is a brominated aromatic compound, (d) a curable resin composition comprising antimony oxide, and (e) a curable composite material comprising a substrate, wherein the sum of the components (a) and (b) is 100. 98 to 40 parts by weight of the component (a) based on parts by weight,
2 to 60 parts by weight of component (b) and 5 to 100 of component (c)
1 to 50 parts by weight of the component (d) based on 100 parts by weight of the component (c), and 1 of the components (a) to (e).
95 parts by weight of components (a) to (d) based on 00 parts by weight
0 parts by weight, component (e) is 5 to 90 parts by weight, a curable 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.