JP2000336261A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin compsn. (film) contg. no halogen in the compsn, i.e., enough flame-retardancy is given without halogen, a curable composite material formed with a substrate, its cured product, a laminate and a metal foil laminated with the resin comprising the cured product and a metal foil. SOLUTION: This curable resin compsn. (film) comprising a polyphenylene ether resin (A), a crosslinking agent (B), and a phosphorus compd. (C) whose 10% mass reduction temp. is not lower than 300 deg.C but not higher than 500 deg.C, and contg. as essential components 10-98 pts.wt. (A), 90-2 pts.wt. (B), and 10-80 pts.wt. (C) to 100 pts.wt. [(A)+(B)] is manufactured, and a curable composite material, its cured product, and a laminate and a metal foil laminated with the resin comprising the cured product and a metal foil is manufactured using the compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a halogen-free flame-retardant curable resin composition, a film thereof, and a cured product obtained by curing the film. Furthermore, the present invention
The present invention relates to a curable composite material comprising the curable resin composition and a substrate, a cured product thereof, a laminate comprising the cured product and a metal foil, and a metal foil with a resin. The curable resin composition of the present invention exhibits excellent chemical resistance, dielectric properties, heat resistance, and flame retardancy after curing, and is used in dielectrics, insulating materials, and heat-resistant materials in fields such as the electric industry, the space and aircraft industries. , Structural materials and the like. In particular, it can be used as a single-sided, double-sided, multilayer printed board, flexible printed board, build-up board, or the like.

[0002]

2. Description of the Related Art In recent years, there has been a remarkable trend toward miniaturization and high-density mounting methods in the field of electronic devices for communication, consumer use, industrial use, and the like, and accordingly, materials have become more excellent. Heat resistance, dimensional stability, and electrical properties are being demanded. For example, as a printed wiring board, a copper-clad laminate made of a thermosetting resin such as a phenol resin or an epoxy resin has been used. Although these have various performances in a well-balanced manner, they have a drawback that electrical characteristics, particularly, dielectric characteristics in a high frequency range are poor. As a new material for solving this problem, polyphenylene ether has recently attracted attention, and application to copper-clad laminates has been attempted.

For example, Japanese Unexamined Patent Publication (Kokai) No. 61-287739 discloses a laminated plate obtained by curing a resin composition containing polyphenylene ether and triallyl isocyanurate and / or triallyl cyanurate.
No. 7567 discloses a curable resin composition containing a polyphenylene ether modified by reaction with an unsaturated carboxylic acid or an acid anhydride and triallyl isocyanurate and / or triallyl cyanurate, and a laminate obtained using the same. Are disclosed in JP-A-64-69628 and JP-A-64-69628.
No. 69629, JP-A No. 1-113425, 1-11
No. 3426 discloses a curable resin composition containing a polyphenylene ether containing a triple bond or a double bond and triallyl isocyanurate and / or triallyl cyanurate.

As a material obtained by combining polyphenylene ether and epoxy, for example, Japanese Patent Publication No. 64-322
JP-A-2-13521 discloses a curable resin composition containing polyphenylene ether, various epoxy resins such as bisphenol A type epoxy resin and novolak type epoxy resin, and various curing agents such as phenols and amines.
Japanese Patent Application Laid-Open No. 2-166115 discloses a curable resin composition comprising a polyphenylene ether modified by a reaction with an unsaturated carboxylic acid or an acid anhydride, a polyepoxy compound, and a curing catalyst for epoxy. A curable resin composition comprising a processed polyphenylene ether, a polyepoxy compound, and a curing catalyst for epoxy is disclosed.

The above composition is used for various electronic materials such as a copper-clad laminate. In this case, the flame retardancy of the resin is an essential property from the viewpoint of product safety. Heretofore, organic halogen compounds such as aromatic bromides and brominated epoxies have been used as a method for making resins flame-retardant. However, organohalogen compounds may generate highly toxic dioxins during combustion, and their use has recently been restricted. In order to cope with such a situation, attempts have been made to impart halogen-free resin with flame retardancy. Until now, however, it has been difficult to provide halogen-free resin with sufficient flame retardancy. It was difficult.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and has a composition containing no halogen, that is, a curable composition which is halogen-free and has sufficient flame retardancy. The present invention provides a resin composition.

[0007]

The present invention firstly provides (A)
Polyphenylene ether resin, (B) crosslinking agent, (C)
10% to 98 parts by weight of (A) per 100 parts by weight of [(A) + (B)] and 90% by weight of (B) a crosslinking agent, A curable resin composition containing 2 parts by weight of a phosphorus compound (C) in a proportion of 10 to 80 parts by weight and a film thereof are provided. Here, (A) the polyphenylene ether resin is selected from i) a polyphenylene ether resin containing an unsaturated group, and / or ii) a reaction product of the polyphenylene ether resin with an unsaturated carboxylic acid and / or an acid anhydride. It is a preferred embodiment of the curable resin composition of the present invention that it is at least one kind. It is a preferred embodiment of the curable resin composition of the present invention that the crosslinking agent is a compound containing a polyfunctional unsaturated bond.

Further, (C) the phosphorus compound is melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, red phosphorus, aromatic dimer phosphate, phosphazene, phosphonate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- represented by the following formula (1)
A preferred embodiment of the present invention is one or more phosphorus compounds selected from the group consisting of oxide derivatives.

[0009]

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Second, a cured product obtained by curing the first curable resin composition (including its film) is provided. Third, a curable composite material comprising a first curable resin composition (including a film thereof) and a base material, wherein the base material is 5 to 90%.
A curable composite material characterized in that the curable composite material is contained in a percentage by weight. Fourth, a cured composite material obtained by curing the third curable composite material is provided. Fifth, a laminate comprising a fourth cured composite material and a metal foil is provided. Sixth
The present invention further provides a metal foil with resin, wherein a film of the first curable resin composition is formed on one surface of the metal foil.

Hereinafter, the present invention will be described in more detail. Examples of the polyphenylene ether resin (A) used in the present invention include poly (2,6-dimethyl-1,4-phenylene ether) obtained by homopolymerization of 2,6-dimethylphenol and poly (2,6- Dimethyl-1,4-phenylene ether) styrene graft copolymer, 2,6
-Copolymer of dimethylphenol and 2,3,6-trimethylphenol, copolymer of 2,6-dimethylphenol and 2-methyl-6-phenylphenol, presence of 2,6-dimethylphenol and polyfunctional phenol compound Polyfunctional polyphenylene ether resin obtained by polymerization under
For example, Japanese Patent Application Laid-Open No. 63-301222 and
2,6- as disclosed in JP-A-297428.
Examples include a nitrogen-containing polyphenylene ether resin obtained by polymerizing dimethylphenol in the presence of a substituted aniline or an aliphatic secondary amine.

With respect to the molecular weight of the polyphenylene ether resin described above, the viscosity number ηsp / C measured with a 0.5 g / dl chloroform solution at 30 ° C. is 0.1 to 1.
Those in the range of 0 can be preferably used. Further, the polyphenylene ether-based resin referred to in the present invention also includes a modified product. Examples of such a modified product include i) a polyphenylene ether resin containing an unsaturated group (Japanese Patent Application Laid-Open No. 64-69628).
JP-A-1-113425, JP-A-1-11342
No. 6) and ii) a reaction product of a polyphenylene ether resin and an unsaturated carboxylic acid and / or acid anhydride.

In the present invention, in order to improve the compatibility with the component (B), it is particularly preferable to use the modified product of the above i) and / or ii) as the polyphenylene ether resin (A). In the present invention, (A) the polyphenylene ether resin is based on 100 parts by weight of [(A) + (B)] based on the total amount of the components (A) and (B).
It is desirable to add 10 to 98 parts by weight, preferably 10 to 70 parts by weight, more preferably 30 to 70 parts by weight. When the amount of the component (A) is less than 10 parts by weight, there is a problem that the impact resistance of the cured product is reduced. When it exceeds 98 parts by weight, there is a problem that the chemical resistance of the cured product is reduced.

Examples of the crosslinking agent (B) used in the present invention include diallyl phthalate, divinyl benzene, polyfunctional acryloyl compound, polyfunctional methacryloyl compound, polyfunctional isocyanate, polyfunctional maleimide, unsaturated polyester, Examples include polyfunctional unsaturated bond-containing compounds such as triallyl isocyanurate, triallyl cyanurate, polybutadiene, styrene-butadiene, styrene-butadiene-styrene, and these may be used alone or in combination of two or more. .

As the crosslinking agent (B), an epoxy resin can also be used, and any epoxy resin may be used as long as it contains two or more epoxy groups in one molecule.
Known ones are used alone or in combination of two or more. Further, an epoxy resin and the above-mentioned compound having a polyfunctional unsaturated bond can be used in combination. Representative examples of such epoxy resins include glycidyl ether type epoxy resins obtained by reacting phenols or alcohols with epichlorohydrin, and reactions obtained by reacting amines or cyanuric acid with epichlorohydrin. Glycidyl-type epoxy resin, an internal epoxy resin obtained by oxidation of a double bond, etc. [For details, refer to “Epoxy Resin Handbook” edited by Masaki Shinbo (Nikkan Kogyo Shimbun, 1987)
checking)]. These epoxy resins can be used together with a curing agent.As the curing agent, as a compound usually used for curing the epoxy resin, for example, dicyandiamide, an aromatic amine or the like as an amine, a phenol novolak resin as a phenol curing system, Cresol novolak resin, bisphenol A, aniline modified
Examples thereof include nitrogen-modified phenol resins such as melamine-modified, guanidine-modified, and polyamide-modified, and these may be used alone or in combination of two or more.

(A) a polyphenylene ether-based resin,
(B) A curing accelerator can be used together with a curing agent for the crosslinking agent. Examples of the curing accelerator include curing accelerators and radical initiators usually used for epoxy resins, and the former includes, for example, imidazole The latter can be, for example, conventional peroxides such as perhexin 25B. In the present invention, a compound containing a polyfunctional unsaturated bond is preferably used as the crosslinking agent (B), and more preferably triallyl isocyanurate and / or triallyl cyanurate. By using such a polyfunctional unsaturated bond-containing compound, a cured product having excellent dielectric properties can be obtained. Further, by using triallyl isocyanurate and / or triallyl cyanurate, a cured product having excellent dielectric properties and heat resistance can be obtained.

The phosphorus compound (C) used in the present invention is a compound containing a phosphorus atom having a 10% mass reduction temperature of 300 ° C. or more and 500 ° C. or less. The 10% mass reduction temperature is a temperature at which the mass is reduced by 10% from the initial value due to thermal decomposition or evaporation when a phosphorus compound is heated under a nitrogen stream based on the method described in JIS K7120. is there. JIS K7120 is a standard for plastics, but can be similarly applied to phosphorus compounds.

In the present invention, if the 10% mass loss temperature of the phosphorus compound is less than 300 ° C., its thermal decomposition temperature or evaporation temperature is too low, and if the 10% mass loss temperature of the phosphorus compound exceeds 500 ° C., its thermal decomposition The temperature or evaporating temperature is too high, and the flame-retardant action is not sufficiently exhibited. Among such compounds containing a phosphorus atom having a 10% mass reduction temperature of 300 ° C. or more and 500 ° C. or less, those preferably used are melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, and ammonium polyphosphate. , Red phosphorus, aromatic dimer phosphate ester, phosphazene, phosphonate ester, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative represented by the following formula (1). One or more phosphorus compounds selected from the group.

[0019]

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The melamine phosphate among the components (C) generally refers to a compound in which phosphoric acid and melamine are bonded in various ratios. Also, when phosphoric acid does not bind to 100% melamine and binds to other nitrogen-containing compounds such as ammonia, amide, and ethylenediamine, or to metals such as aluminum, magnesium, and calcium, the majority of the parts that bind to melamine are also present. Is called melamine phosphate. Examples of the melamine phosphate that can be used in the present invention include P-7202 (manufactured by Sanwa Chemical Co., Ltd.), FyrolMP (registered trademark, manufactured by Akzo Nobel), and Antiblaze NH (registered trademark, Albright & Wilson) And melapurMP (registered trademark, manufactured by DSM) and the like, and these are used alone or in combination of two or more.

Melamine pyrophosphate generally refers to a compound in which pyrophosphate (a dehydration-condensed dimer of phosphoric acid) and melamine are bound in various ratios. Also, 100% of the phosphoric acid unit structure does not bind to melamine, but also binds to other nitrogen-containing compounds such as ammonia, amide, and ethylenediamine, or to metals such as aluminum, magnesium, and calcium.
When the portion that binds to melamine accounts for the majority, it is called melamine pyrophosphate. Examples of the melamine pyrophosphate that can be used in the present invention include, for example, Planelon NP (trade name, manufactured by Mitsui Chemicals, Inc.)
And the like.

Melamine polyphosphate generally refers to a compound in which polyphosphoric acid (a dehydration condensate of a trimer or more of phosphoric acid) and melamine are bound in various ratios. The degree of condensation of polyphosphoric acid and the primary structure of a molecule such as a chain or a ring can be used without any particular limitation. The unit structure of phosphoric acid is 100%
Is not bonded to melamine, and if a part is replaced with another nitrogen-containing compound such as ammonia, amide, ethylenediamine or a metal such as aluminum, magnesium, calcium, etc., the portion bonded to melamine occupies the majority. Is called melamine polyphosphate. Examples of the melamine polyphosphate that can be used in the present invention include MPP-A (manufactured by Sanwa Chemical Co., Ltd.) and P
MP-100 (manufactured by Nissan Chemical Industries, Ltd.), melapur200
(Registered trademark, manufactured by DSM) and the like, and these may be used alone or in combination of two or more.

[0023] Melam polyphosphate generally refers to a compound in which polyphosphoric acid and melam are combined in various ratios. Here, the degree of condensation of polyphosphoric acid and the primary structure of a molecule such as a chain or a ring can be used without any particular limitation. Even if 100% of the unit structure of phosphoric acid does not bind to melam and a part thereof is substituted by another nitrogen-containing compound such as melamine, amide, ammonia, ethylenediamine or a metal such as aluminum, magnesium, calcium, etc. In the case where the portion bonded to occupies the majority, it is referred to as melam polyphosphate. Examples of melam polyphosphate that can be used in the present invention include PMP as a trade name.
-200 (manufactured by Nissan Chemical Industries, Ltd.) and the like.

Ammonium polyphosphate generally refers to a compound in which polyphosphoric acid and ammonia are combined in various ratios. Regarding ammonium polyphosphate, the degree of condensation of polyphosphoric acid and the primary structure of a molecule such as a chain or a ring can be used without particular limitation. Unit structure of phosphoric acid 1
Even if 00% does not bind to ammonia and a part is substituted with another nitrogen-containing compound such as melamine, amide, or ethylenediamine, or a metal such as aluminum, magnesium, or calcium, a majority of the parts bind with ammonia. When it occupies, it is called ammonium polyphosphate. Examples of the ammonium polyphosphate that can be used in the present invention include Sumisafe P under the trade name.
(Registered trademark, manufactured by Sumitomo Chemical Co., Ltd.), Sumisafe PM (registered trademark, manufactured by Sumitomo Chemical Co., Ltd.), Terage C60 (registered trademark, manufactured by Chisso Co., Ltd.), FCP-700 (manufactured by Suzuyu Chemical Co., Ltd.), Taien S (Taira Chemical Industry Co., Ltd.) Nonnen PR-62 (manufactured by Marubishi Yuka Kogyo), ExolitAP422 (registered trademark,
ExolitAP462 (registered trademark, manufactured by Clariant), Phos-ChekP30
(Registered trademark, manufactured by Sorcia) and the like,
These may be used alone or in combination of two or more.

Red phosphorus is obtained by polymerizing a large number of phosphorus atoms, and the degree of polymerization and the primary structure of a molecule such as a chain or a ring can be used without any particular limitation. Examples of red phosphorus that can be used in the present invention include Nova Red 120 (registered trademark, manufactured by Rin Kagaku Kogyo), Nova Excel 140 (registered trademark, manufactured by Rin Kagaku Kogyo), and Hishigard CP-A15. (Registered trademark, manufactured by Nippon Chemical Industry Co., Ltd.), Hishigard TP-10 (registered trademark, manufactured by Nippon Chemical Industry Co., Ltd.), Hishigard White CP (registered trademark, manufactured by Nippon Chemical Industry Co., Ltd.), ExolitRP602 (registered trademark, manufactured by Clariant) These can be used alone or in combination of two or more.

The aromatic dimer type phosphoric ester has one or more substituents selected from vinyl, allyl, methallyl and 1-butenyl, preferably reactive allyls such as allyl. Those having no reactive substituent can be classified. Specific examples of those having a reactive substituent include, for example, resorcinol bis (di-2-allylphenylphosphate), resorcinol (di-2-methyl-4-allylphenylphosphate), hydroquinone bis (di-2-allyl) Phenyl phosphate), 2,2'-diallylbisphenol A bis (diphenyl phosphate) and the like, and these can be used alone or as a mixture of two or more.

Examples of those having no reactive substituent include chemical names of resorcinol bis (diphenyl phosphate), resorcinol bis (dicresyl phosphate), resorcinol bis (dicylenyl phosphate), and resorcinol bis (di-2,6). -Xylenyl phosphate), hydroquinone bis (diphenyl phosphate), hydroquinone bis (dicresyl phosphate), bisphenol A bis (diphenyl phosphate), bisphenol A bis (dicresyl phosphate), bisphenol A bis (dicylenyl phosphate), 4 CR-733S (manufactured by Daihachi Chemical Co., Ltd.) and CR-741 as trade names such as 4,4'-biphenylbis (diphenylphosphate) and 2,6-naphthalenediolbis (diphenylphosphate). (Manufactured by Daihachi Chemical Co., Ltd.), CR-7
47 (manufactured by Daihachi Chemical), PX-200 (manufactured by Daihachi Chemical), PX-201 (manufactured by Daihachi Chemical), PX-202
(Manufactured by Daihachi Chemical Co., Ltd.), Filol Flex RDP (registered trademark, manufactured by Akzo Nobel), Filol Flex BDP (registered trademark, manufactured by Akzo Nobel), Leofos RDP (registered trademark, manufactured by FMC), BPA-DP (Registered trademark, manufactured by FMC Corporation) and the like, and these may be used alone or as a mixture of two or more.

The phosphazene is a compound represented by the following formula (4).

[0029]

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R ₁ and R ₂ are not particularly limited, but at least one is preferably an aryl group. Further, the degree of polymerization n of the phosphazene may be arbitrary, and a copolymer of a different phosphazene may be used. In the present invention, the phosphazene used as the component (C) is also a vinyl group, an allyl group, a methallyl group,
It can be classified into those having one or more substituents selected from 1-butenyl groups, preferably allyl groups, and those having no reactive substituents.

Specific examples of those having a reactive substituent include, for example, bis (2-allylphenoxy) phosphazene and bis (2-methoxy-4-allylphenoxy)
Examples thereof include phosphazene and phenoxyallyl phosphazene, which are used alone or in combination of two or more. Examples of those having no reactive substituent include diphenoxyphosphazene and phenoxyisopropoxyphosphazene. These may be used alone or as a mixture of two or more.

The phosphonic acid ester also has one or more substituents selected from a vinyl group, an allyl group, a methallyl group, and a 1-butenyl group, preferably a reactive type substituent such as an allyl group. It can be divided into those that do not have. Specific examples of those having a reactive substituent include, for example, divinyl phenylphosphonate,
Diallyl phenylphosphonate, dimethallyl phenylphosphonate, bis (1-butenyl) phenylphosphonate, bis (2-allylphenyl) phenylphosphonate, bis (2-methoxy-4-allylphenyl) phenylphosphonate, bis (methylphosphonate) 2-allylphenyl),
Examples thereof include diphenyl allylphosphonate and dicresyl allylphosphonate, which may be used alone or as a mixture of two or more.

Examples of those having no reactive type substituent include diphenyl phenylphosphonate, dicresyl phenylphosphonate, dimethyl phenylphosphonate, diphenyl methylphosphonate, dicresyl methylphosphonate, and the like. These are used as a mixture. 9,10-dihydro-9-oxa-1
The 0-phosphaphenanthrene-10-oxide derivative is a compound represented by the following formula (1). The component (C) used is a substituent R ₁ bonded to a phosphorus atom.
Is a hydrogen atom, a hydroquinonyl group, a vinyl group, an allyl group,
A substituent such as methallyl group or butenyl, and the substituents R ₂ and R ₃ bonded to the aromatic ring are hydrogen atom or C ₁ -C ₆ such as methyl group, ethyl group, isopropyl group, tert-butyl group and cyclohexyl group. Of a hydrocarbon group.

[0034]

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Such a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative also includes a vinyl group, an allyl group, a methallyl group,
-Butenyl group, which has one or more substituents, preferably allyl group, having a reactive substituent and those having no reactive substituent.
Specific examples of those having a reactive substituent include, for example, 9,10-dihydro-9-oxa-10- (allylphospha) phenanthrene-10-oxide,
-Dihydro-9-oxa-10- (methallylphospha)
Phenanthrene-10-oxide, 9,10-dihydro-9-oxa-10- (1-butenylphospha) phenanthrene-10-oxide, 9,10-dihydro-9-
Oxa-10- (allylphospha) (2,7-dimethylphenanthrene) -10-oxide, 9,10-dihydro-9-oxa-10- (allylphospha) (1,3
6,8-tetramethylphenanthrene) -10-oxide, 9,10-dihydro-9-oxa-10- (allylphospha) (6,8-di-tert-butylphenanthrene) -10-oxide and the like. These may be used alone or as a mixture of two or more.

Examples of those having no reactive substituent include, for example, 9,10-dihydro-9-oxa-
10-phosphaphenanthrene-10-oxide, 9,
Examples of trade names such as 10-dihydro-9-oxa-10- (hydroquinonylphospha) phenanthrene-10-oxide include HCA (manufactured by Sanko) and HCA-HQ
(Manufactured by Sankosha Co., Ltd.), and these can be used alone or in combination of two or more.

Among the above components (C), those used as powders have a powder surface of, for example, melamine resin,
It may be coated with an epoxy resin or the like, or may be used as a paste by adding a carrier such as an unsaturated polyester resin or an epoxy resin to powder. Further in advance to these powders as a flame retardant aid, a foaming agent, a color tone adjusting agent, for example, melamine, benzoguanamine, acetoguanamine, ethylenediamine, melamine cyanurate, melam, melem, pentaerythritol, dipentaerythritol, talc, silica, carbonate Calcium, titanium oxide, aluminum hydroxide, magnesium hydroxide, low melting point glass and the like may be added to form composite particles.

In the present invention, the component (C) is more preferably used as melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, red phosphorus, or an aromatic system having a reactive substituent. Dimeric phosphate, phosphazene having reactive substituent, phosphonate having reactive substituent, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide having reactive substituent It is a derivative.

Melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, and red phosphorus are all incompatible with the component (A) and the component (B). Flame retardancy can be exhibited without lowering the transition temperature.
Aromatic dimer phosphate having a reactive substituent, phosphazene having a reactive substituent, phosphonic acid ester having a reactive substituent, 9,10-dihydro-9-oxa- having a reactive substituent When a compound having a polyfunctional unsaturated bond is used as the component (B), the 10-phosphaphenanthrene-10-oxide derivative can be obtained by using the compound (B)
Since it is copolymerized with the components, it is possible to exhibit flame retardancy without lowering the glass transition temperature after curing.

In the present invention, the component (C) is [(A) +
(B)] 10 to 80 parts by weight, preferably 15 to 60 parts by weight, more preferably 20 to 50 parts by weight, per 100 parts by weight. When the amount of the component (C) is [(A)
+ (B)] When the amount is less than 10 parts by weight with respect to 100 parts by weight, sufficient flame retardancy is not exhibited, and when it exceeds 80 parts by weight, the viscosity of the varnish becomes too high and the varnish cannot be impregnated with the base material. For these reasons, it becomes difficult to produce a composite material. When two or more types of the component (C) are combined, there is no particular limitation, and any combination can be used.

In addition to the above (A) to (C), the curable resin composition of the present invention may have an amount within a range that does not impair the original properties for the purpose of imparting desired performance according to its use. Fillers and additives can be compounded and used. Examples of such a filler include carbon black, silica, titanium oxide, barium titanate, glass beads, glass hollow spheres, and the like. In addition, as additives, antioxidants, heat stabilizers, antistatic agents, plasticizers, pigments, dyes,
Coloring agents and the like can be mentioned. Further, one or more thermoplastic resins and thermosetting resins other than the components (A) and (B) can be blended.

As a method of mixing the above components (A) to (C), a solution mixing method of uniformly dissolving or dispersing the three components in a solvent or a melt blending method of heating by an extruder or the like is used. Available. As a solvent used for the solution mixing, aromatic solvents such as benzene, toluene and xylene, and tetrahydrofuran alone or
Used in combination of more than one species. The curable resin composition of the present invention may be previously formed into a desired shape 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-described solvent and molded into a desired shape, or a heat melting method in which the resin composition is heated and melted to form a desired shape is used.

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

The curable resin composition of the present invention can be suitably used as a film. The method for producing such a film is not particularly limited. For example, the components (A) to (C) and, if necessary, other components are melted or uniformly dissolved or dispersed in a solvent.
There is a method of drying after applying to an ET film or the like. Further, this curable resin composition can be used by being bonded to a metal foil and / or a metal plate as in the case of a cured composite material described later.

Next, the curable composite material of the present invention and its cured product will be described. The curable composite material of the present invention comprises the curable resin composition of the present invention and a substrate.
Examples of the base material used here include various glass cloths such as roving cloths, cloths, chopped mats, and surfacing mats, asbestos cloths, metal fiber cloths and other synthetic or natural inorganic fiber cloths, wholly aromatic polyamide fibers, wholly aromatic fibers. Or non-woven fabric obtained from liquid crystal fiber such as aromatic polyester fiber or polybenzoxazole fiber, woven or non-woven fabric obtained from synthetic fiber such as polyvinyl alcohol fiber, polyester fiber or acrylic fiber, natural fiber such as cotton cloth, linen cloth, felt, etc. Natural cellulose-based cloths such as cloth, carbon fiber cloth, kraft paper, cotton paper, and paper-glass mixed fiber paper, and polytetrafluoroethylene porous films are used alone or in combination of two or more.

The proportion of such a base material is 5 to 90 parts by weight, preferably 10 to 80 parts by weight, more preferably 20 to 90 parts by weight based on 100 parts by weight of the curable composite material.
70 parts by weight. When the proportion of the base material is less than 5 parts by weight, the dimensional stability and strength after curing of the composite material are insufficient, and when the proportion of the base material is more than 90 parts by weight, the dielectric properties of the composite material are inferior, which is not preferable. . In the curable composite material of the present invention, a coupling agent can be used as needed for the purpose of improving the adhesiveness at the interface between the resin and the substrate. As such a coupling agent, general ones such as a silane coupling agent, a titanate coupling agent, an aluminum-based coupling agent, and a zircoaluminate coupling agent can be used.

As a method for producing the composite material of the present invention, for example, the components (A) to (C) of the present invention and, if necessary, other components are mixed with the above-mentioned aromatic or ketone solvent or the like. A method of uniformly dissolving or dispersing in a mixed solvent, impregnating the substrate, and then drying is used. Also (A) ~
The component (C) may be melted and impregnated into the substrate. The impregnation is performed by dipping (dipping), coating, or the like. The impregnation can be repeated multiple times as necessary, and in this case, the impregnation can be repeated using multiple solutions having different compositions and concentrations to finally adjust the desired resin composition and resin amount It is.

The cured composite material of the present invention is obtained by curing the curable composite material thus obtained by a method such as heating. The production method is not particularly limited. For example, a plurality of the curable composite materials are stacked, and the respective layers are adhered to each other under heat and pressure, and simultaneously heat-cured to obtain a cured composite material having a desired thickness. be able to. Moreover, it is also possible to obtain a cured composite material having a new layer configuration by combining the cured composite material once cured by adhesion and the curable composite material.

The lamination molding and curing are usually carried out simultaneously using a hot press or the like, but both may be carried out independently. That is, the uncured or semi-cured composite material obtained by lamination molding in advance can be cured by heat treatment or another method. Molding and curing are performed at a temperature of 80 to 300 ° C and a pressure of 0.1 to 1000k.
g / cm ² , time 1 minute to 10 hours, more preferably temperature 150 to 250 ° C., pressure 1 to 500 kg / cm
^{2. The} time can be from 1 minute to 5 hours.

The laminate of the present invention comprises the cured composite material of the present invention and a metal foil. Examples of the metal foil used here include a copper foil and an aluminum foil. The thickness is not particularly limited, but 3 to 20
0 μm, more preferably 3 to 105 μm.
As a method of manufacturing the laminate of the present invention, for example, the above-described curable composite material and a metal foil and / or a metal plate are laminated in a layer configuration according to the purpose, and the respective layers are bonded under heat and pressure. And a method of thermosetting at the same time. In the laminate of the present invention, the curable composite material and the metal foil are laminated in an arbitrary layer configuration. The metal foil can be used as both a surface layer and an intermediate layer. In addition to the above,
It is also possible to form a multilayer by repeating lamination and curing a plurality of times.

An adhesive can be used for bonding the metal foil. Examples of such an adhesive include, but are not particularly limited to, epoxy-based, acrylic-based, phenol-based, and cyanoacrylate-based adhesives. The above-mentioned lamination molding and curing can be performed under the same conditions as in the case of the curable composite material of the present invention. Further, the curable resin composition of the present invention can be used as a metal foil with resin.

The resin-attached metal foil of the present invention comprises the curable resin composition of the present invention and a metal foil. Examples of the metal foil used here include a copper foil and an aluminum foil. The thickness is not particularly limited,
It is in the range of 3-200 μm, more preferably 3-105 μm. The method for producing the resin-attached copper foil of the present invention is not particularly limited. For example, components (A) to (C) and, if necessary, other components may be an aromatic solvent, a ketone solvent or the like. Dissolve or disperse uniformly in the mixed solvent,
There is a method of drying after applying to a metal foil.

The application can be repeated a plurality of times as necessary. In this case, the application is repeated using a plurality of solutions having different compositions and concentrations to finally adjust the desired resin composition and resin amount. It is also possible.

[0054]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, embodiments of the present invention will be described based on examples. In the following Examples and Comparative Examples, “parts” means “parts by weight”.

[0055]

Example 1 Poly (2,500) having a viscosity number ηsp / C of 0.54 measured in a chloroform solution of 0.5 g / dl at 30 ° C.
6-dimethyl-1,4-phenylene ether) 50 parts,
46 parts of triallyl isocyanurate (Nippon Kasei)
GPPS (weight average molecular weight 270,000) 4 parts, PX-200
A varnish was prepared by dissolving or dispersing 30 parts (manufactured by Daihachi Chemical Co., Ltd.) and 6 parts of perhexin 25B (manufactured by NOF CORPORATION) in toluene, and dipped and impregnated with a glass cloth having a basis weight of 107 g / m ^2. And dried in an air oven to obtain a curable composite material.

Next, six pieces of the above-mentioned curable composite material are laminated so that the thickness after curing becomes about 0.8 mm, and a copper foil having a thickness of 35 μm is placed on both sides thereof at 180 ° C. and 40 kg / cm.
² were molded and cured using a press molding machine for 90 minutes.
The obtained laminate was subjected to a flammability test based on the UL94 standard, and the result was V-0. The PX-200 used as the phosphorus compound was heated at 10 ° C./TGA using a TGA (TGA-50, manufactured by Shimadzu Corporation) in a nitrogen stream.
10% mass loss temperature measured at a heating rate of 370 min
Met.

[0057]

Example 2 <Synthesis of maleic anhydride-modified polyphenylene ether> A maleic anhydride-modified polyphenylene ether was synthesized by the method described in Reference Example 3 of JP-B-7-37567. That is, using a drum blender,
100 parts by weight of the polyphenylene ether of Example 1, 2 parts by weight of maleic anhydride, and 1 part by weight of Perhexa 25B (manufactured by NOF Corporation) were dry-blended at room temperature, and then biaxially heated at a cylinder temperature of 300 ° C. and a screw rotation speed of 230 rpm. The mixture was extruded by an extruder to obtain maleic anhydride-modified polyphenylene ether.

<Production and evaluation of laminate> A laminate was prepared in the same manner as in Example 1 except that the above maleic anhydride-modified polyphenylene ether was used as the polyphenylene ether.
The flammability was measured to be V-0.

[0059]

Example 3 <Synthesis of allylated polyphenylene ether> An allylated polyphenylene ether was synthesized by the method described in Example 5 of JP-B-5-8931. That is, THF 100 obtained by dehydrating and distilling 20 g of the polyphenylene ether used in Example 1 in a 3 liter three-necked flask.
Then, 108 ml of n-butyllithium (1.55 mol / l, hexane solution) was added under a nitrogen stream, and the mixture was stirred at room temperature for 1 hour. After further adding 20 g of allyl bromide and stirring for 30 minutes, the contents of the flask were poured into a large amount of methanol to precipitate a polymer. ¹ HNM after isolation
The degree of substitution of the allyl group by R was 24%.

<Production and evaluation of laminate> 60 parts of the above allylated polyphenylene ether, 40 parts of triallyl isocyanurate, 4 parts of GPPS (weight average molecular weight 270,000), P
X-200 (manufactured by Daihachi Chemical Co., Ltd.) 30 parts, perhexin 25
A varnish was prepared by dissolving or dispersing 6 parts of B (manufactured by NOF Corporation) in toluene, and a laminate was prepared and subjected to a flammability test in the same manner as in Example 1 to obtain a V-0 result.

[0061]

Examples 4 to 17 Table 1 shows the number of parts of the curable resin composition.
A laminate was prepared and the flammability was measured in the same manner as in Example 1 except that the results were changed as in Examples 4 to 4, and the results shown in Tables 1 to 4 were obtained.
That is, as the component (C), the 10% mass reduction temperature is 30.
By using a phosphorus compound having a temperature of 0 ° C. or more and 500 ° C. or less, the flammability test result is V-0 in any composition.
It became.

[0062]

Example 18 A varnish was prepared in the same manner as in Example 1 and dried at 60 ° C. for 3 hours to dry toluene to obtain a curable composition. The curable composition was heated in an air oven at 180 ° C. for 90 minutes under a nitrogen stream to obtain a cured product. The flammability test result of this cured product was V-0.

[0063]

Example 19 A varnish was prepared in the same manner as in Example 1, applied to a PET film, and dried at 60 ° C. for 3 hours to dry toluene to obtain a curable film. This curable film was heated in an air oven at 180 ° C. for 90 minutes under a nitrogen stream to obtain a cured film.
The flammability test result of this cured film was V-0.

[0064]

Example 20 A varnish was prepared in the same manner as in Example 1 and applied to a copper foil having a thickness of 18 μm by a bar coater so that the resin layer had a thickness of 50 μm. After drying for a time, a copper foil with resin was produced. Next, two pieces of the resin-attached copper foil are laminated, and the temperature is set to 180 ° C. and 40 k.
It was molded and cured at 90 g / cm ² using a press molding machine. The flammability test result of the obtained laminate was V-
It was 0.

[0065]

Examples 21 to 35 A laminate was prepared in the same manner as in Example 1 except that the number of parts of the curable resin composition was changed as shown in Tables 5 to 7, and laminated by TMA (TMA-10 manufactured by Seiko Denshi). The measurement of the glass transition temperature of the body and the flammability test were performed, and the results shown in Tables 5 to 7 were obtained.

[0066]

Example 36 <Synthesis of bis (2-allylphenyl) phenylphosphonate> In a 500 ml three-necked flask, 21.1 g of dehydrated pyridine (manufactured by Wako Pure Chemical, special grade) and 2-allylphenol (manufactured by Wako Pure Chemical, 1 Grade) was added, and 26 g of phenylphosphonic dichloride (Wako Pure Chemical, first grade) was added using a dropping funnel while stirring under a nitrogen stream in an ice bath.
It was added dropwise over 2 hours. After stirring at room temperature for 1 hour, 100 ml of water was added. The oil layer was extracted therefrom using a separating funnel, and about 47 g of bis (2-allylphenyl) phenylphosphonate was obtained by distillation under reduced pressure (1 mmHg, 230 ° C). TGA (manufactured by Shimadzu Corporation, TGA-50
The 10% mass loss temperature of this product measured under a nitrogen stream using a mold was 330 ° C.

<Manufacture and evaluation of laminate> 30 ° C., 0.5 g
/ Dl viscosity measured in chloroform solution ηsp / C
Is 0.54, poly (2,6-dimethyl-1,4-phenylene ether) 50 parts, N, N '-(4,4'-methylenediphenylene) dimaleimide (manufactured by Wako Pure Chemical Industries) 30 parts,
Bis (2-allylphenyl) phenylphosphonate 4
0 parts and 6 parts of Perhexin 25B (manufactured by NOF CORPORATION) were dissolved or dispersed in toluene to prepare a varnish, and a laminate was prepared in the same manner as in Example 1, and TMA (TM, manufactured by Seiko Electronics Co., Ltd.)
(A-10 type), the glass transition temperature of the laminate was 170 ° C, and the flammability test result was V-0.

[0068]

Example 37 <9,10-Dihydro-9-oxa-1
Synthesis of 0- (allylphospha) phenanthrene-10-oxide (abbreviation: HCA-allyl)> 9,10-dihydro-9-oxide in a 500 ml three-necked flask equipped with a reflux condenser.
54.1 g of oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Co., trade name: HCA), 35 g of allyl bromide (manufactured by Wako Pure Chemical, special grade), 300 g of methanol (manufactured by Wako Pure Chemical, special grade), triethylamine (Wako Pure Chemical,
30 g of special grade) is added, and the mixture is heated to the extent that methanol is gently refluxed in the reflux condenser, and the reaction is allowed to proceed for 8 hours. Then, the flask was cooled to room temperature, methanol was distilled off under reduced pressure using a rotary evaporator, and the residue was distilled under reduced pressure (0.1 mmHg, 140 ° C) to obtain 9,10.
About 45 g of -dihydro-9-oxa-10- (allylphospha) phenanthrene-10-oxide (abbreviation: HCA-allyl) was obtained. TGA (manufactured by Shimadzu Corporation, TGA
-50) and measured under a nitrogen stream.
The 0% weight loss temperature was 350 ° C.

<Production and evaluation of laminate> 30 ° C., 0.5 g
/ Dl viscosity measured in chloroform solution ηsp / C
Is 0.54, poly (2,6-dimethyl-1,4-phenylene ether) 50 parts, triallyl isocyanurate 3
0 parts, the above-mentioned HCA-allyl 40 parts, perhexin 25B
A varnish was prepared by dissolving or dispersing 6 parts (produced by NOF Corporation) in toluene, and a laminate was prepared in the same manner as in Example 1.
The glass transition temperature of the laminate measured by TMA (TMA-10, manufactured by Seiko Denshi) was 175 ° C., and the result of the flammability test was V-0.

[0070]

Example 38 A varnish was prepared in the same manner as in Example 21, and dried at 60 ° C. for 3 hours to dry toluene to obtain a curable composition. The curable composition was heated in an air oven at 180 ° C. for 90 minutes under a nitrogen stream to obtain a cured product. The glass transition temperature of this cured product measured by TMA (TMA-10, manufactured by Seiko Instruments Inc.) was 178 ° C., and the flammability test result was V-0.

[0071]

Example 39 A varnish was prepared in the same manner as in Example 21, applied to a PET film, and dried at 60 ° C. for 3 hours to dry toluene to obtain a curable film. This curable film was heated in an air oven at 180 ° C. for 90 minutes under a nitrogen stream to obtain a cured film. The glass transition temperature of this cured film measured by TMA (TMA-10 manufactured by Seiko Denshi) is 18
At 2 ° C, the result of the flammability test was V-0.

[0072]

Example 40 A varnish was prepared in the same manner as in Example 21, and this was applied to a copper foil having a thickness of 18 μm with a bar coater so that the resin layer had a thickness of 50 μm. After drying for a time, a copper foil with resin was produced. Next, two pieces of the resin-attached copper foil are laminated,
It was molded and cured using a press molding machine at 90 kg / cm ² for 90 minutes. The obtained laminate had a glass transition temperature of 180 ° C. measured by TMA (TMA-10 manufactured by Seiko Denshi) and a flammability test result of V-0.

As described above, in Examples 21 to 40,
(C) Melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, red phosphorus, phosphonate having a reactive substituent (allyl group), reactive substituent (allyl group)
By using at least one member selected from the group consisting of 9,10-dihydro-9-oxa-10- (allylphospha) phenanthrene-10-oxide having
In any composition, the glass transition temperature (T
MA method) was reduced to 150 ° C. or lower, and V-0 in the flammability test. Tables 1 to 8 collectively show the results of Examples 1 to 40.

[0074]

[Table 1]

[0075]

[Table 2]

[0076]

[Table 3]

[0077]

[Table 4]

[0078]

[Table 5]

[0079]

[Table 6]

[0080]

[Table 7]

[0081]

[Table 8]

[0082]

Comparative Example 1 A laminate was prepared in the same manner as in Example 1 except that the same number of TPPs (manufactured by Daihachi Chemical Co., Ltd.) were used instead of PX-200 (manufactured by Daihachi Chemical Co., Ltd.), and a flammability test was performed. The result was V-1.

[0083]

Comparative Examples 2 to 7 The composition parts of the curable resin composition are shown in Tables 9 to
A laminate was prepared and subjected to a flammability test in the same manner as in Example 1 except that the results were changed as shown in Table 10, and the results shown in Tables 9 to 10 were obtained. That is, the 10% mass reduction temperature of the phosphorus compound is 30.
When the temperature was not higher than 0 ° C and not higher than 500 ° C, V-0 was not obtained with any composition (Comparative Examples 2 to 5). In addition, even when the 10% mass reduction temperature was 300 ° C. or more and 500 ° C. or less, V-0 was not attained unless the compound was a phosphorus compound (Comparative Example 6).
~ 7).

[0084]

Comparative Example 8 A cured product was prepared in the same manner as in Example 18 except that the same number of TPP (manufactured by Daihachi Chemical Co., Ltd.) was used instead of PX-200 (manufactured by Daihachi Chemical Co., Ltd.), and a flammability test was performed. Where I went,
V-1.

[0085]

Comparative Example 9 A cured film was prepared in the same manner as in Example 19 except that the same number of parts of TPP (manufactured by Daihachi Chemical Co., Ltd.) was used instead of PX-200 (manufactured by Daihachi Chemical Co., Ltd.), and a flammability test was performed. The result was V-1.

[0086]

Comparative Example 10 A laminate was prepared in the same manner as in Example 20 except that the same number of TPPs (manufactured by Daihachi Chemical Co., Ltd.) was used instead of PX-200 (manufactured by Daihachi Chemical Co., Ltd.), and a flammability test was performed. The result was V-1.

[0087]

Comparative Example 11 A laminate was prepared in the same manner as in Example 1 except that the number of PX-200 (manufactured by Daihachi Chemical Co., Ltd.) was changed to 5 parts, and a flammability test was performed.

[0088]

Comparative Examples 12 to 17 A laminate was prepared and subjected to a flammability test in the same manner as in Example 1 except that the number of parts of the curable resin composition was changed as shown in Tables 11 to 12. The results shown were obtained. That is, even if a phosphorus compound having a 10% mass reduction temperature of 300 ° C. or more and 500 ° C. or less is used, if the number of added parts is less than 10 parts with respect to 100 parts by weight of [(A) + (B)], V −0 was not obtained (Comparative Examples 12 to 15).

Similarly, when the amount exceeds 80 parts, the varnish viscosity becomes too high to impregnate the substrate (Comparative Example 1).
6-17).

[0090]

Comparative Example 18 A cured product was prepared in the same manner as in Example 18 except that the number of added PX-200 (manufactured by Daihachi Chemical Co., Ltd.) was changed to 5 parts.

[0091]

Comparative Example 19 A cured film was prepared and subjected to a flammability test in the same manner as in Example 19 except that the number of added PX-200 (manufactured by Daihachi Chemical Co., Ltd.) was changed to 5 parts.

[0092]

Comparative Example 20 A laminate was prepared and subjected to a flammability test in the same manner as in Example 20, except that the number of added PX-200 (manufactured by Daihachi Chemical Co., Ltd.) was changed to 5 parts. The results of Comparative Examples 1 to 20 are collectively shown in Tables 9 to 12.

[0093]

[Table 9]

[0094]

[Table 10]

[0095]

[Table 11]

[0096]

[Table 12]

[0097]

According to the present invention, it is possible to provide a curable resin composition free of halogen and having sufficient flame retardancy (for example, V-0 in UL94 test). Furthermore, by using a specific flame retardant, flame retardancy can be imparted without lowering the glass transition temperature of the cured product.

Claims (10)

[Claims] (A) a polyphenylene ether-based resin,
(B) a crosslinking agent, and (C) a 10% mass reduction temperature of 300
Containing a phosphorus compound of not less than 500 ° C and not more than 500 ° C,
[(A) + (B)] 100 parts by weight of (A)
A curable resin composition comprising 98 parts by weight, (B) 90 to 2 parts by weight of a crosslinking agent, and (C) 10 to 80 parts by weight of a phosphorus compound. 2. The curable resin composition according to claim 1, wherein the crosslinking agent (B) is a compound containing a polyfunctional unsaturated bond. (C) the phosphorus compound is melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, ammonium polyphosphate, red phosphorus, aromatic dimer phosphate, phosphazene, phosphonate; 9,10-dihydro-9- represented by the following formula (1)
The curable resin composition according to claim 1, wherein the composition is one or more phosphorus compounds selected from the group consisting of oxa-10-phosphaphenanthrene-10-oxide derivatives. Embedded image 4. A method according to claim 1, wherein (A) the polyphenylene ether-based resin comprises: i) a polyphenylene ether resin containing an unsaturated group;
4. The curable resin composition according to claim 1, wherein the curable resin composition is a reaction product of a polyphenylene ether resin and an unsaturated carboxylic acid and / or an acid anhydride. 5. The curable resin composition according to claim 1, which has a film shape. 6. A cured product obtained by curing the curable resin composition according to claim 1, 2, 3, or 4. 7. A curable composite material comprising the curable resin composition according to claim 1, and a base material, wherein the base material is contained in a ratio of 5 to 90% by weight. Curable composite material. 8. A cured composite material obtained by curing the curable composite material according to claim 6. 9. A laminate comprising the cured composite material according to claim 7 and a metal foil. 10. A resin-coated metal foil, wherein the film of the curable resin composition according to claim 1, 2, 3, or 4 is formed on one side of the metal foil.