JP2002308948A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable resin composition (film) endowed with flame retardance, water resistance, and heat resistance, a curable composite material composed of the same and a base material, is cured product, a laminate composed of its cured product and a metallic foil, and a metallic foil having a resin. SOLUTION: This curable resin composition (film) comprises (A) a polyphenylene ether based resin, (B) a curing agent, and (C) a diarylphosphine having a reactive type substituent represented by the formula (1): RP(O)Ar2 (wherein R is vinyl group, allyl group, methallyl group or 1-butenyl group; and Ar is a 6-30C aryl group or a hydrocarbon substituted aryl group) at a ratio of 10-98 pts.mass component (A), 90-2 pts.mass component (B); and 1-80 pts.mass component (C) based on 100 pts.mass sum of components (A) and (B) as the essential components, and by the use of this composition, the curable composite material, its cured product, the laminate composed of the cured product and the metallic foil, and the metallic foil having the resin are manufactured.

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. However, JP-A-64-69628, JP-A-64-69629, JP-A-1-113425 and JP-A-1-113426 disclose polyphenylene ethers containing a triple bond or a double bond and triallyl. A curable resin composition comprising isocyanurate and / or triallyl cyanurate is disclosed.

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 indispensable 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 flame retarding resins. However, organic halogen compounds may generate highly toxic dioxins during combustion, and their use has recently been restricted. To cope with such a situation, attempts have been made to impart flame retardancy to the polyphenylene ether-based curable resin using a halogen-free compound. That is, for example, metal hydroxides, phosphates, ammonium polyphosphate, and the like have been tried as halogen-free compounds. However, for example, when a metal hydroxide is used, the heat resistance characteristic of this resin is maintained, but it is difficult to provide sufficient flame retardancy, and when a phosphate ester is used, sufficient flame retardancy is provided. However, it is difficult to maintain the heat resistance. If ammonium polyphosphate is used, sufficient flame retardancy can be imparted while maintaining the heat resistance. However, when the cured product is immersed in water, the mass decreases and it cannot be put to practical use. That is, hitherto, it has been difficult to impart sufficient flame retardancy while maintaining the heat resistance and water resistance, which are features of a polyphenylene ether resin free of halogen.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made to solve the above problems, and does not contain a halogen in the composition. That is, the composition is halogen-free and has sufficient heat resistance and water resistance. An object of the present invention is to provide a curable resin composition having flame retardancy.

[0007]

The present invention firstly provides (A)
Polyphenylene ether resin, (B) crosslinking agent, (C)
Formula (1) RP (O) Ar 2 ········ (1) ( wherein R is a vinyl group, an allyl group, methallyl or 1-butenyl. The Ar is C ₆ ~ A C ₃₀ aryl group or a hydrocarbon-substituted aryl group, wherein the two aryl groups may be the same or different, and may be connected to each other via a covalent bond. It contains a diarylphosphine oxide derivative having a group, and (A) is 10 to 98 parts by mass, (B) is 90 to 2 parts by mass, and (C) is 1 part by mass with respect to 100 parts by mass of [(A) + (B)]. The present invention provides a curable resin composition and a film thereof in an amount of about 80 parts by mass. In addition, the curable resin composition of the present invention does not contain halogen as a whole.

Here, (A) the polyphenylene ether resin is 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. Is a preferred embodiment of the curable resin composition of the present invention. (B) The crosslinking agent must contain a polyfunctional unsaturated bond-containing compound. It is a preferred embodiment of the curable resin composition of the present invention that the crosslinking agent is a single compound containing a polyfunctional unsaturated bond.

Second, the present invention provides a cured product obtained by curing the first curable resin composition (including its film). Third, a curable composite material comprising a first curable resin composition (including the case of the film) and a base material, wherein the base material is contained in a ratio of 5 to 90% by mass. The present invention provides a curable composite material. 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, there is provided a metal foil with resin, wherein the 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-based 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. 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, JP-A 1-1113425, JP-A 1-11-1
No. 13426) and ii) a reaction product of a polyphenylene ether resin with an unsaturated carboxylic acid and / or acid anhydride.

In the present invention, in order to improve the compatibility with the component (B), a modified product of the above i) and / or ii), for example, an allylated polyphenylene ether, It is particularly preferable to use maleic acid-modified polyphenylene ether or the like. In the present invention, (A) the polyphenylene ether-based resin comprises a total amount of the components (A) and (B);
[(A) + (B)] 10 to 98 parts by mass, preferably 10 to 80 parts by mass, more preferably 2 to 100 parts by mass.
It is desirable to add in the range of 0 to 75 parts by mass. When the amount of the component (A) is less than 10 parts by mass, there is a problem that the impact resistance of the cured product is reduced. When it exceeds 98 parts by mass, 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 compounds, polyfunctional methacryloyl compounds, polyfunctional isocyanates, polyfunctional maleimides, unsaturated polyesters, Examples include polyfunctional unsaturated bond-containing compounds such as triallyl isocyanurate, triallyl cyanurate, polybutadiene, styrene-butadiene, styrene-butadiene-styrene, and these can be used alone or as a mixture of two or more. . (B)
An epoxy resin can also be used as the cross-linking agent, and any epoxy resin may be used as long as it contains two or more epoxy groups in one molecule, and 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 amines or cyanuric acid with epichlorohydrin. Examples thereof include a glycidyl-type epoxy resin obtained by a reaction and an internal epoxy resin obtained by oxidation of a double bond. [For details, refer to “Epoxy Resin Handbook” edited by Masaki Shinbo (Nikkan Kogyo Shimbun, 1987). See)). 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, nitrogen-modified phenolic resin such as aniline-modified, melamine-modified, guanidine-modified, polyamide-modified, and the like can be mentioned, and these can 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 As the compound, the latter includes, for example, ordinary peroxides such as perhexin 25B and perbutyl P. In the present invention,
(B) a polyfunctional unsaturated bond-containing compound as a crosslinking agent,
For example, by using triallyl isocyanurate and / or triallyl cyanurate, a cured product having excellent dielectric properties and heat resistance can be obtained. Also (B)
Epoxy resin such as bisphenol A as a crosslinking agent
By using the mold epoxy resin, a curable resin composition having excellent moldability during curing can be obtained.

In the present invention, the component (B) is used in an amount of 90 to 2 based on 100 parts by mass of the total of the components (A) and (B).
It is desirably contained in an amount of 90 parts by mass, preferably 90 to 20 parts by mass, more preferably 80 to 25 parts by mass. When the amount of the component (B) is less than 2 parts by mass, there is a problem that the chemical resistance of the cured resin composition is reduced. When the amount exceeds 90 parts by mass, the impact resistance of the cured resin composition is reduced. Is generated. In the present invention, the component (B) includes
A compound containing a polyfunctional unsaturated bond must be included.

In the present invention, the component (C) is represented by the following formula (1): RP (O) Ar ₂ (1) (where R is a vinyl group, an allyl group, methallyl, or 1-butenyl. the Ar is an aryl group or a hydrocarbon group substituted aryl group of C ₆ -C _30, 2 one aryl group may be identical or different from each other, via a covalent bond Or a diarylphosphine oxide derivative having a reactive substituent.

Specific examples of the diarylphosphine oxide derivatives having a reactive substituent represented by the above formula (1) include, for example, vinyl diphenyl phosphine oxide, allyl diphenyl phosphine oxide, methallyl diphenyl phosphine oxide, 1-butenyl diphenyl Phosphine oxide, vinyl ditolyl phosphine oxide, allyl ditolyl phosphine oxide, methallyl ditolyl phosphine oxide, 1-butenyl ditolyl phosphine oxide, allyl phenyl tolyl phosphine oxide, vinyl dixylenyl phosphine oxide, allyl dixylenyl phosphine oxide, Methallyl dixylenyl phosphine oxide, 1-butenyl dixylenyl phosphine oxide, vinyl dinaphthyl phosphine oxide,
Allyl dinaphthyl phosphine oxide, methallyl dinaphthyl phosphine oxide, 1-butenyl dinaphthyl phosphine oxide, allyl phenyl naphthyl phosphine oxide and the like can be mentioned, and these can be used alone or as a mixture of two or more.

In the present invention, the component (C) is [(A) +
(B)] 1 to 80 parts by mass, preferably 10 to 80 parts by mass, more preferably 15 to 60 parts by mass, still more preferably 20 to 50 parts by mass with respect to 100 parts by mass. When the addition amount of the component (C) is less than 1 part by mass relative to 100 parts by mass of [(A) + (B)], the addition of the component (C) has no effect on the combustion process. Addition of component (C) is 1
When the amount is not less than 10 parts by mass, for example, UL94V
Although sufficient flame retardancy that satisfies −0 is not exhibited, flame burning does not reach the clamp in the case of clamp combustion, and UL94V-2 is changed to UL94V-1. When the component (C) is at least 10 parts by mass, sufficient flame retardancy that satisfies, for example, UL94V-0 will be exhibited. When the component (C) exceeds 80 parts by mass, the production of a composite material becomes difficult because the viscosity of the curable resin composition as a varnish becomes too high and the varnish cannot be impregnated with the base material. .

The curable resin composition of the present invention may further comprise, in addition to the above (A) to (C), an amount of 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, other than the components (A) and (B), for example, polystyrene, ABS, S
It is also possible to mix one or two or more thermoplastic resins such as styrene resins such as BS, hydrogenated SBS and SEBS, and thermosetting resins.

As a method for mixing the above components (A) to (C), a solution mixing method in which the three components are uniformly dissolved or dispersed in a solvent, a melt blending method in which the components are heated by an extruder or the like, and the like are 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 curable resin composition described above. 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 favorably 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, and PET is used. A method of drying after applying to a film or the like may be used. Further, this curable resin composition can be used by being bonded to a metal foil and / or a metal plate, similarly to a cured composite material described later.

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. Cloth, carbon fiber cloth, kraft paper, cotton paper, natural cellulosic cloth such as paper-glass mixed fiber paper, polytetrafluoroethylene porous film, short fibers such as chopped strands composed of the above various fibers alone, or Two or more are used in combination.

The proportion occupied by such a base material is 5 to 90 parts by mass, preferably 10 to 80 parts by mass, more preferably 20 to 90 parts by mass based on 100 parts by mass of the curable composite material.
70 parts by mass. When the proportion of the base material is less than 5 parts by mass, 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 mass, 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 such as the above-mentioned coupling agent are mixed with an aromatic or ketone. Examples thereof include a method of uniformly dissolving or dispersing in a solvent such as a system or a mixed solvent thereof, impregnating the substrate, and then drying. Further, the components (A) to (C) may be melted and impregnated into the base material. 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. When the base material is a short fiber such as a chopped strand, it is uniformly dispersed in a solvent solution of the components (A) to (C) of the present invention and then molded by a casting method or the like, or
After being added to the component (C) and uniformly melt-kneaded, it is molded into a desired shape and manufactured.

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. Lamination molding and curing are usually performed simultaneously using a hot press or the like, but both may be performed independently. That is, the uncured or semi-cured composite material obtained by lamination molding in advance can be cured by heat treatment or another method.

When the lamination molding and curing are performed at the same time, the conditions are a temperature of 80 to 300 ° C. and a pressure of 0.009.
8 to 98 MPa, time 1 minute to 10 hours, more preferably temperature 150 to 250 ° C., pressure 0.098 to 49
MPa, time can be performed in the range 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. Examples of the metal foil used here include a copper foil and an aluminum foil.
The thickness is not particularly limited, but is in the range of 3 to 200 μm, more preferably 3 to 105 μm.

The method for producing the laminate of the present invention includes:
For example, a method in which 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 simultaneously heat-cured. . In the laminate of the present invention, the curable composite material and the metal foil are laminated in an arbitrary layer configuration. The metal foil can be used as both a surface layer and an intermediate layer. In addition to the above, lamination and curing may be repeated a plurality of times to form a multilayer. 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 and curing can be carried out 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 is obtained by forming a film of the curable resin composition of the present invention on one side of the metal foil. Examples of the metal foil used here include a copper foil and an aluminum foil. The thickness is not particularly limited, but is in the range of 3 to 200 μm, more preferably 3 to 105 μm.

The method for producing the resin-coated copper foil of the present invention is not particularly limited. For example, (A) to (C)
There may be mentioned a method of uniformly dissolving or dispersing the component and, if necessary, another component in an aromatic or ketone-based solvent or a mixed solvent thereof, applying the solution to a metal foil, and then drying. The application can be repeated multiple times as necessary, and in this case, the application can be repeated using multiple solutions with different compositions and concentrations to finally adjust the desired resin composition and resin amount It is.

[0031]

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 mass”.

Example 1 As the component (A), 30 ° C., 0.5 g / d
50 parts of poly (2,6-dimethyl-1,4-phenylene ether) having a viscosity number ηsp / C of 0.54 measured with a chloroform solution of l, triallyl isocyanurate (manufactured by Nippon Kasei Co., Ltd.) as the component (B) 46 parts, as the component (C), allyl diphenylphosphine oxide (Aldric)
h) 30 parts, Perhexin 25B as a curing accelerator
6 parts (manufactured by NOF Corporation) and polystyrene (GPPS,
A varnish was prepared by dissolving 4 parts of toluene having a weight average molecular weight of 270,000, and impregnated by dipping a glass cloth having a basis weight of 107 g / m ² , followed by drying in an air oven to obtain a curable composite material. .

Next, six pieces of the above-mentioned curable composite material are superposed 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 surfaces thereof at 90 ° C. at 180 ° C. and 3.9 MPa. It was molded and cured using a press molding machine for minutes. The obtained laminate was subjected to a flammability test based on the UL94 standard, and the result was V-0. In addition, the glass transition temperature of the laminated body determined by TMA (TMA-10, manufactured by Seiko Denshi) from the inflection point of the linear expansion coefficient per unit temperature was 177 ° C. Further, after immersion in water at 25 ° C. for 24 hours, the mass reduction of the laminate was 0.0%.

[0033]

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 mass of the polyphenylene ether of Example 1, 2 parts by mass of maleic anhydride, and 1 part by mass of Perhexa 25B (manufactured by NOF CORPORATION) as a denaturation accelerator were dry-blended at room temperature, and then the cylinder temperature was 300 ° C. The mixture was extruded with a twin-screw extruder at a screw rotation speed of 230 rpm to obtain maleic anhydride-modified polyphenylene ether. <Production and evaluation of laminate> A laminate was prepared and the flammability was measured in the same manner as in Example 1 except that the above-mentioned maleic anhydride-modified polyphenylene ether was used as the polyphenylene ether. Also, as in the first embodiment, the TM
The glass transition temperature determined by A was 174 ° C. Further, after immersion in water at 25 ° C. for 24 hours, the mass reduction of the laminate was 0.0%.

[0034]

Example 3 <Synthesis of Allylated Polyphenylene Ether> An allylated polyphenylene ether was synthesized by the method described in Example 2 of Japanese Patent Publication No. 5-8931.
That is, in a three-necked flask, 100 g of THF obtained by dehydrating and distilling 2 g of the polyphenylene ether used in Example 1 was used.
, And n-butyllithium (1.5
(5 mol / L, hexane solution) (2.2 ml) was added, and the mixture was heated under reflux in a nitrogen atmosphere for 1 hour. After cooling to room temperature,
0.40 g of allyl bromide was added, and the mixture was stirred at room temperature for 30 minutes. The contents of the flask were poured into a large amount of methanol to precipitate a polymer, and filtration and washing with methanol were repeated three times to obtain a white powdery product. ¹ H NMR
As a result, the substitution rate of the allyl group was determined to be 4%.

<Production and evaluation of laminate> 60 parts of the above allylated polyphenylene ether as component (A), 40 parts of triallyl isocyanurate as component (B), and allyl diphenylphosphine oxide (Ald) as component (C)
Rich) (30 parts), Perhexin 25B (Nippon Oil & Fats Co., Ltd.) 6 parts as a curing accelerator, and polystyrene (GP)
(PS, weight average molecular weight 270,000) 4 parts were dissolved in toluene to prepare a varnish, and a laminate was prepared in the same manner as in Example 1.
A flammability test was performed to obtain a result of V-0. The glass transition temperature determined from TMA in the same manner as in Example 1 was 176 ° C. Further, after immersion in water at 25 ° C. for 24 hours, the mass reduction of the laminate was 0.0%.

[0036]

Examples 4 and 5 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 Table 1, and the flammability, glass transition temperature, and The mass loss was measured. Table 1 shows the results of Examples 1 to 5 described above.

[0037]

[Table 1] That is, in Examples 1 to 5, the use of allyldiphenylphosphine oxide as the component (C) allows the polyphenylene ether-based resin / polyfunctional unsaturated bond-containing compound system of various compositions to maintain the water resistance and heat resistance while maintaining the water resistance and heat resistance.
It became -0.

[0038]

Examples 6 to 8 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 Table 2, and the flammability, the glass transition temperature, and the The mass loss was measured. Table 2 shows the results of Examples 6 to 8 described above.

[0039]

[Table 2] That is, in Examples 6 to 8, the use of allyldiphenylphosphine oxide as the component (C) provides water resistance and heat resistance even in polyphenylene ether-based resins / epoxy resins / polyfunctional unsaturated bond-containing compound systems having various compositions. Was maintained at V-0.

[0040]

Examples 9 and 10 Table 3 shows the number of parts of the curable resin composition.
A laminate was prepared in the same manner as in Example 1 except that
The flammability, glass transition temperature, and weight loss of the laminate after immersion in water were measured. Table 3 shows the results of Examples 9 and 10 described above.

[0041]

[Table 3] That is, the same allyl diphenylphosphine oxide as in Example 1 was used as the component (C), and the composition of the resin was greatly changed.
It became 0.

[0042]

Examples 11 and 12 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 Table 4, and the flammability, the glass transition temperature, and the The mass loss was measured. Table 4 shows the results of Examples 11 and 12 described above.

[0043]

[Table 4] That is, the amount of the component (C) added is [(A) + (B)] 10
When the amount is less than 10 parts by mass with respect to 0 parts by mass, HB and V did not reach V-0 while maintaining water resistance and heat resistance.
-1.

[0044]

Example 13 A varnish was prepared in the same manner as in Example 2, and dried at 60 ° C. for 3 hours to dry toluene to obtain a curable composition. This curable composition was heated in a vacuum press 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. The glass transition temperature determined from TMA in the same manner as in Example 1 was 176 ° C. Further, after immersion in water at 25 ° C. for 24 hours, the mass reduction of the laminate was 0.0%.

[0045]

Example 14 A varnish was prepared in the same manner as in Example 2, 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 a vacuum press 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. The glass transition temperature determined from TMA as in Example 1 was 1
75 ° C. Further, after immersion in water at 25 ° C. for 24 hours, the mass reduction of the laminate was 0.0%.

[0046]

Example 15 A varnish was prepared in the same manner as in Example 2, 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 were laminated, and the temperature was 180 ° C., 3.9.
Molding and curing were performed using a press molding machine at 90 MPa. The flammability test result of the obtained laminate was V-0. The glass transition temperature determined from TMA in the same manner as in Example 1 was 176 ° C. Further, after immersion in water at 25 ° C. for 24 hours, the mass reduction of the laminate was 0.0%. The results of Examples 13 to 15 are collectively shown in Table 5.

[0047]

[Table 5] That is, even in a cured body, a cured film, and a foil with a cured resin containing no glass cloth, V-0 was obtained while maintaining water resistance and heat resistance by using allyldiphenylphosphine oxide as the component (C).

[0048]

Comparative Examples 1 to 3 Instead of allyl diphenylphosphine oxide (manufactured by Aldrich) as the component (C),
A laminate was prepared in the same manner as in Examples 1 to 3, except that an aromatic dimer phosphate ester (PX-200, manufactured by Daihachi Chemical Co., Ltd.) was used, a flammability test, a glass transition temperature, and a laminate after water immersion. The body weight loss was evaluated. The results of Comparative Examples 1 to 3 are summarized in Table 6.

[0049]

[Table 6] That is, when the aromatic dimer phosphate ester was used as the component (C), the water resistance was maintained and V-0 was obtained, but the heat resistance was not maintained.

[0050]

Comparative Examples 4 to 6 Instead of allyl diphenylphosphine oxide (manufactured by Aldrich) as the component (C),
Except that aluminum hydroxide (Heidilite H43M, manufactured by Showa Denko KK) was used, a laminate was prepared in the same manner as in Examples 1 to 3, and a flammability test, a glass transition temperature, and a decrease in mass of the laminate after immersion in water. Was evaluated. Comparative Examples 4 to 6
Table 7 summarizes the results.

[0051]

[Table 7] That is, when aluminum hydroxide was used as the component (C), although water resistance and heat resistance were maintained, clamp combustion occurred and no flame retardancy was exhibited.

[0052]

Comparative Examples 7 to 9 Instead of allyl diphenylphosphine oxide (manufactured by Aldrich) as the component (C),
Ammonium polyphosphate (Terage C6, manufactured by Chisso)
Except that 0) was used, a laminate was prepared in the same manner as in Examples 1 to 3, and a flammability test, a glass transition temperature, and an evaluation of a decrease in mass of the laminate after immersion in water were performed. Table 8 summarizes the results of Comparative Examples 7 to 9 above.

[0053]

[Table 8] That is, when ammonium polyphosphate was used as the component (C), V-0 was obtained while maintaining heat resistance.
There is a 0.2% decrease in mass after immersion in water at 25 ° C for 24 hours,
It could not be put to practical use.

[0054]

Comparative Examples 10 to 12 Instead of allyl diphenylphosphine oxide (manufactured by Aldrich) as the component (C), an aromatic dimer phosphate ester (manufactured by Daihachi Chemical Co., Ltd., PX
A cured product, a cured film, and a laminate were prepared in the same manner as in Examples 13 to 15 except that -200) was used, and the flammability, the glass transition temperature, and the weight loss of the laminate after water immersion were evaluated. Was. The results of Comparative Examples 10 to 12 are summarized in Table 9 above.

[0055]

[Table 9] That is, even in a cured body, a cured film, and a foil with a cured resin that do not contain a glass cloth, the aromatic dimer phosphate ester maintains water resistance and becomes V-0, but does not maintain heat resistance. Was.

[0056]

Comparative Examples 13 to 15 Laminates were prepared in the same manner as in Examples 1 to 3, except that the number of parts of allyldiphenylphosphine oxide (manufactured by Aldrich) was changed to 85 parts as the component (C). However, in any case, the varnish viscosity of the curable resin composition was too high to be impregnated. The results of Comparative Examples 13 to 15 are summarized in Table 10.

[0057]

[Table 10] That is, even if allyldiphenylphosphine oxide (manufactured by Aldrich) is used as the component (C), the varnish viscosity is high when the number of added parts exceeds 80 parts with respect to [(A) + (B)] 100 parts by mass. Too much so that the substrate cannot be impregnated.

[0058]

According to the present invention, there is provided a curable resin composition having water resistance and flame retardancy without lowering the glass transition temperature of a cured product by using a halogen-free specific flame retardant. can do.

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Claims (9)

[Claims] (A) a polyphenylene ether-based resin,
(B) a crosslinking agent, (C) the following formula (1) RP (O) Ar ₂ ... (1) (where R is a vinyl group, an allyl group, a methallyl group, or a 1-butenyl group) Ar is a C ₆ -C ₃₀ aryl group or a hydrocarbon-substituted aryl group, and the two aryl groups may be the same or different from each other, or may be connected to each other via a covalent bond. ) Containing a diarylphosphine oxide derivative having a reactive substituent, wherein (A) is 10 to 98 parts by mass and (B) is 90 to 100 parts by mass of [(A) + (B)]. A curable resin composition in which 2 parts by mass and (C) are 1 to 80 parts by mass. 2. The curable resin composition according to claim 1, wherein (B) is a polyfunctional unsaturated bond compound. 3. The polyphenylene ether resin (A) comprising: i) a polyphenylene ether resin containing an unsaturated group;
And / or ii) at least one member selected from the reaction product of a polyphenylene ether resin and an unsaturated carboxylic acid and / or acid anhydride. Composition. 4. The curable resin composition according to claim 1, which has a film shape. 5. A cured resin composition obtained by curing the curable resin composition according to claim 1. 6. A curable composite material comprising the curable resin composition according to claim 1 and a base material, wherein the base material is contained at a ratio of 5 to 90% by mass. Curable composite material. 7. A cured composite material obtained by curing the curable composite material according to claim 6. 8. A laminate comprising the cured composite material according to claim 7 and a metal foil. 9. A metal foil with resin, wherein the film of the curable resin composition according to claim 1 is formed on one surface of the metal foil.