JP2002030211A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition having excellent chemical resistance, dielectric characteristic, low water absorptivity, heat resistance, flame retardant property and mechanical characteristic after curing. SOLUTION: The curable resin composition is produced by including (C) a silicate having an average particle diameter of 10 μm or less in a composition consisting of (A) a functionalized polyphenylene ether based resin obtained by reacting a mixture containing a polyphenylene ether based resin (a) and at least one kind of a functionalized compound (b) having in its molecular structure (1) at least one of carbon-carbon double bond or triple bond and (2) at least one group selected from a group consisting of a carboxylic acid, an acid anhydride, an acid amide, an imide, an amino, a hydroxyl and a glycidyl group, and (B) a crosslinking component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a curable resin composition containing a functionalized polyphenylene ether resin and a crosslinkable component, a film made of the curable resin composition, and a cured product obtained by curing the same. Furthermore, the present invention
The present invention relates to a curable composite material comprising the resin composition and a substrate, a cured product thereof, a laminate comprising a cured product and a metal foil, and a copper foil with a resin.

[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, a copper-clad laminate made of a thermosetting resin such as a phenol resin or an epoxy resin has been used as a printed wiring board. 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 laminate obtained by curing a curable resin composition containing polyphenylene ether and triallyl isocyanurate and / or triallyl cyanurate. JP-A-37567 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. The plates are disclosed in JP-A-64-69628, JP-A-64-69629, JP-A-1-113425,
JP-A-113426 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. 64-3223
Patent Publication No. discloses polyphenylene ether and bisphenol A
Curable resin compositions containing various epoxy resins such as epoxy resins and novolak epoxy resins and various curing agents such as phenols and amines are disclosed in JP-A-2-135216.
Japanese Patent Application Laid-Open No. 2-166115 discloses a curable resin composition comprising a polyphenylene ether modified by 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 polyphenylene ether, a polyepoxy compound, and a curing catalyst for epoxy is disclosed.

The above compositions are used for various electronic materials such as copper-clad laminates. In this case, the mechanical properties of the resin composition are indispensable from the viewpoint of handling stability accompanying the reduction in size and weight of products. It is a characteristic. However, it has been difficult to improve the polyphenylene ether-based resin because its mechanical properties are equivalent to those of ordinary thermosetting resins.

[0006]

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems, and has excellent chemical resistance, dielectric properties, low water absorption, heat resistance, flame retardancy, and mechanical properties after curing. And vice versa.

[0007]

That is, the present application provides the following inventions. (1) (A) With respect to 100 parts by weight of a polyphenylene ether-based resin (a) comprising a structural unit of the following formula (I), i) at least one carbon-carbon double bond or triple bond is present in the molecular structure. And (ii) at least one functionalized compound having at least one group selected from the group consisting of carboxylic acids, acid anhydrides, acid amides, imides, aminos, hydroxyl groups, and glycidyl groups (b) 0.1-1
(C) Silicic acid having an average particle diameter of 10 μm or less with respect to 100 parts by weight of a functionalized polyphenylene ether-based resin obtained by reacting a mixture containing 0.0 parts by weight and (B) a crosslinkable component. A curable resin composition containing 1 to 90 parts by weight of a salt.

[0008]

Embedded image [R ₁ and R ₄ are each independently halogen, primary or secondary lower alkyl, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy (provided that at least two carbon atoms Atoms separate a halogen atom and an oxygen atom), and R ₂ and R ₃ are each independently halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy, or halo. Hydrocarbon oxy, provided that at least two carbon atoms separate the halogen and oxygen atoms. ]

(2) A film comprising the curable resin composition according to (1). (3) A curable composite material comprising the curable resin composition according to the above (1) and a base material, wherein the base material is contained at a ratio of 5 to 90% by weight. (4) A cured composite material obtained by curing the film and the curable composite material according to (3). (5) A laminate comprising the cured composite material according to (4) and a metal foil. (6) A metal foil with resin, wherein the film of the curable resin composition according to the above (1) is formed on one surface of the metal foil.

Hereinafter, the present invention will be described in more detail. The polyphenylene ether-based resin (a) used in the present invention has a structure represented by the following formula (I) and can produce a product / part having a desired shape by a molding method such as a melt injection molding method or a melt extrusion molding method. It is a plastic material that is widely used as a material for products and parts in the fields of electricity and electronics, the field of automobiles, and various other industrial materials.

[0011]

Embedded image

In the polyphenylene ether resin (a) used in the present invention, R ₁ and R ₄ are each independently halogen, a primary or secondary lower alkyl,
Phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy (provided that at least two carbon atoms separate a halogen atom and an oxygen atom), and R ₂ and R ₃ are each independently , Halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy, or halohydrocarbonoxy, provided that at least two carbon atoms separate the halogen atom from the oxygen atom.

The polyphenylene ether resin (a) used in the present invention has a reduced viscosity of 0.15 to 0.7 as measured at 30 ° C. using a chloroform solution of 0.5 g / dl.
0 dl / g, more preferably 0.20 to 0.60
Polymer or copolymer in the range of dl / g. Polyphenylene ether resin (a) used in the present invention
Are specifically poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-
1,4-phenylene ether), poly (2-methyl-6)
-Phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like.

Specific examples of the polyphenylene ether resin (a) used in the present invention include 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol and 2-methyl-6-methylphenol). Polybutylene ether copolymer such as a copolymer with butylphenol). The polyphenylene ether-based resin (a) used in the present invention is a poly (2,6-dimethyl-
1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol can be preferably used.

The most preferred polyphenylene ether resin (a) used in the present invention is poly (2,6-dimethyl-1,4-phenylene ether). The method for producing the polyphenylene ether-based resin (a) used in the present invention is not limited. As an example of the method for producing the polyphenylene ether-based resin (a) used in the present invention, there is disclosed a method of oxidatively polymerizing 2,6-xylenol using a complex of a cuprous salt and an amine as a catalyst described in US Pat. No. 3,308,874. is there.

US Pat. Nos. 3,306,875 and 325
Nos. 7357 and 3257358;
The methods described in US Pat. No. 17,880, JP-A-50-51197, JP-A-63-152628 and the like are also preferable as the method for producing the polyphenylene ether-based resin (a).

The terminal structure of the polyphenylene ether resin (a) used in the present invention is preferably a structure of the formula (II).

Embedded imageHowever, R of the formula (II)₁, R_Two, R_Three, R_FourAre
In the formula (I), R ₁, R_Two, R_Three, R_FourDefined as
It is.

The terminal structure of the polyphenylene ether resin (a) of the present invention is more preferably a structure of the formula (III).

Embedded image However, R ₁ in the formula (III) is defined in the same manner as R ₁ in the formula (I), and R ₅ and R ₅ ′ are alkyl groups.

The functionalized compound (b) used in the present invention
Has at least one carbon-carbon double bond or triple bond and at least one carboxylic acid, acid anhydride, acid amide, imide, amino, hydroxyl group or glycidyl group in the molecular structure Organic compounds.

The functionalized compound (b) used in the present invention
Is preferably a compound having, in its molecular structure, at least one kind having a double bond and at least one carboxylic acid, acid anhydride, acid amide, imide, amino, hydroxyl group or glycidyl group. The functionalized compound (b) used in the present invention is more preferably a compound having at least one compound having a double bond and at least one carboxylic acid or acid anhydride in a molecular structure.

The functionalized compound (b) used in the present invention
Is very preferably maleic anhydride, maleic acid, fumaric acid or itaconic acid. In the method for producing a functionalized polyphenylene ether-based resin of the present invention, 0.1 to 10.0 parts by weight of a functionalized compound (b) is mixed with 100 parts by weight of a polyphenylene ether-based resin (a) and reacted. . When the amount of the functionalized compound (b) is less than 0.1 part by weight, the amount of the functional group is insufficient. When the amount of the functionalized compound (b) exceeds 10.0 parts by weight, the unreacted functionalized compound (b) is contained in the functionalized polyphenylene ether-based resin.
Remains in a large amount and causes silver streaks at the time of molding.

Next, as the crosslinkable component used in the present invention, any material may be used as long as it does not impair the physical properties of the substrate as a material for a printed circuit board which is the object of the present invention. Specific examples of such a crosslinkable component include a phenol resin, an epoxy resin, diallyl phthalate, divinylbenzene, a polyfunctional acryloyl compound, a polyfunctional methacryloyl compound, a polyfunctional maleimide, a polyfunctional methacryloyl compound, and a polyfunctional methacryloyl compound. Crosslinkable polymers such as functional maleimide, polyfunctional cyanate ester, polyfunctional isocyanate, unsaturated polyester, triallyl isocyanurate, triallyl cyanurate, butadiene, styrene-butadiene / styrene-butadiene-styrene, various heats Curable resins and the like can be mentioned. These are generally blended for the purpose of improving the physical properties of a substrate produced by laminating and molding a prepreg.

Preferred examples of the crosslinkable component used in the present invention include a functionalized polyphenylene ether-based resin and triallyl isocyanurate and / or triallyl cyanurate, a functionalized polyphenylene ether-based resin and epoxy resin, and a functionalized polyphenylene ether. And a styrene-butadiene block copolymer and triallyl isocyanurate and / or triallyl cyanurate. The amount of each component in these systems is selected according to the purpose.

In order to accelerate the curing reaction, the crosslinking component used in the present invention may contain an ordinary radical initiator or an ordinary epoxy resin curing agent. Furthermore, fillers and additives can be blended and used in an amount that does not impair the original properties for the purpose of imparting desired performance depending on the application. Examples of the filler include carbon black, alumina, silica and the like. I can give it. Additives include antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, fluorescent agents, plasticizers, pigments, dyes (including fluorescent agents),
Coloring agents and the like can be mentioned.

For the purpose of further improving the flame retardancy, a bromine-based, chlorine-based, phosphorus-based, or silicon-based flame retardant, or a flame retardant auxiliary such as antimony trioxide or antimony pentoxide can be used in combination. . Examples of the silicate used in the present invention include:
Examples thereof include talc, clay, and mica, which can be used alone or in combination of two or more. In the present invention, it is preferable to use a silicate having an average particle size of 10 μm or less.

The average particle size is a weight average particle size. When a silicate having an average particle size of more than 10 μm is contained, the composition loses uniformity. In this case, the physical properties of the substrate are reduced, for example, the reliability of the wiring is reduced. More preferably, it contains a silicate having an average particle size of 2 μm or less. When a silicate having an average particle size of more than 2 μm is contained, for example, when fine holes are formed on a printed circuit board by a laser or the like, the physical properties of the substrate are deteriorated such that the reliability of the hole shape or the like is lowered.

The silicate used in the present invention is preferably used in an amount of 1 to 90 parts by weight based on the composition. If the amount is less than 1 part by weight, the mechanical properties are insufficiently improved, and if it exceeds 90 parts by weight, the fluidity of the composition is significantly reduced. The composition of the present invention may contain desired additives according to the purpose. Examples of such additives include a heat stabilizer, an antioxidant, a UV absorber, a surfactant, a lubricant, and a filler. Polymer additives, dialkyl peroxides, diacyl peroxides, peroxy, peroxycarbonates, hydroperoxides, peroxyketals and the like.

In producing the above composition, the components may be mixed by a solution mixing method of uniformly dissolving or dispersing the components in a solvent, or a blending method of stirring and mixing with a Henschel mixer or the like. Etc. are available.
As the solvent used for the solution mixing, aromatic solvents such as benzene, toluene, and xylene, and tetrahydrofuran are used alone or in combination of two or more.
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 product of the curable resin composition of the present invention is obtained by curing the above-described polyphenylene ether-based 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,
More preferably, it is selected in the range of 120 to 250 ° C. The time is about 1 minute to 10 hours, more preferably 1 minute to
5 hours.

The curable resin composition can be used by bonding it 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 curable resin composition of the present invention and the cured product thereof will be described.
The curable composite material of the curable resin composition of the present invention is characterized by comprising the curable resin composition of the present invention and a substrate.

Examples of such a base material include various glass cloths such as roving cloth, cloth, chopped mat and surfacing mat, asbestos cloth, metal fiber cloth and other synthetic or natural inorganic fiber cloths, wholly aromatic polyamide fibers, Woven or non-woven fabric obtained from liquid crystal fiber such as wholly aromatic polyester fiber, polybenzozar fiber, woven or non-woven fabric obtained from synthetic fiber such as polyvinyl alcohol fiber, polyester fiber, acrylic fiber, cotton cloth, linen, felt, etc. Natural cellulosic cloth such as natural fiber cloth, carbon fiber cloth, kraft paper, cotton paper, paper-glass mixed fiber paper, etc. alone or 2
Used in combination of more than one species.

The proportion occupied by the substrate is determined by the curable composite material 10
The amount is 5 to 90 parts by weight, more preferably 10 to 80 parts by weight, even more preferably 20 to 70 parts by weight based on 0 parts by weight. If the base material is less than 5 parts by weight, the dimensional stability and strength of the composite material after curing are insufficient, and
When the amount is more than 0 parts by weight, the dielectric properties of the composite material are inferior and are not preferable. In the curable composite material of the curable resin composition of the present invention, a coupling agent can be used, if necessary, for the purpose of improving the adhesion at the interface between the resin and the substrate.
As the 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 curable composite material of the present invention, for example, the curable resin composition of the present invention and, if necessary, other components are mixed with the aforementioned aromatic or ketone-based solvent or a mixture thereof. A method of uniformly dissolving or dispersing in a solvent, impregnating the substrate, and then drying is used. 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 product of the curable resin composition of the present invention is obtained by curing the curable composite material thus obtained by a method such as heating. The manufacturing method is not particularly limited.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. Can be. Further, 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.

The molding and curing are performed at a temperature of 80 to 300.
° C, pressure: 0.1 to 1000 kg / cm ² , time: 1 minute to 10 hours, more preferably temperature: 150 to 2
50 ° C., pressure 1 to 500 kg / cm ² , time: 1 minute to 5
Can be done in a time range. The laminate of the curable resin composition of the present invention is composed of the cured composite material of 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, but is 3 to 2
It is in the range of 00 μm, more preferably 3 to 105 μm.

As a method for producing a laminate of the curable resin composition of the present invention, for example, a curable composite material of the curable resin composition of the present invention described above, a metal foil and / or a metal plate may be used. And bonding the layers under heating and pressurization and simultaneously thermosetting. In the laminate of the curable resin composition of the present invention, the curable composite material and the metal foil are laminated in any 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 the adhesive include an epoxy-based, acrylic-based, phenol-based, and cyanoacrylate-based adhesive, but are not particularly limited thereto. The lamination molding and curing can be performed under the same conditions as for the cured composite material of the curable resin composition of the present invention. The film of the present invention is obtained by molding the curable resin composition of the present invention into a film. The thickness is not particularly limited, but is in the range of 3 to 200 μm, more preferably 5 to 105 μm.

The method for producing the film of the present invention is not particularly limited. For example, the curable resin composition and, if necessary, other components may be mixed with an aromatic or ketone-based solvent or a mixed solvent thereof. Dissolved or dispersed uniformly in P
A method of drying after applying to a resin film such as an ET film may be used. 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.

Finally, the resin-attached metal foil of the curable resin composition of the present invention will be described. The metal foil with resin of the present invention is constituted by 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, but is preferably 3 to 200 μm, more preferably 5 to 1 μm.
It is in the range of 05 μm.

The method for producing the resin-attached metal foil of the present invention is not particularly limited. For example, the curable resin composition and, if necessary, other components may be an aromatic or ketone solvent or the like. A method of uniformly dissolving or dispersing in a mixed solvent, applying to a metal foil, and then drying is used. 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.

[0041]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, examples of specific embodiments of the present invention will be described based on examples.

[0042]

[Example 1] In a pressure-resistant container having a capacity of 50 liters, 30
Poly (2,6-dimethyl-) having a viscosity number ηsp / c of 0.41 as measured with a chloroform solution of 0.5 g / dl at 0.5 ° C.
(1,4-phenylene ether) 12 Kg of polyphenylene ether and 48 g of maleic anhydride were charged and degassed. Then, the mixture was stirred and heated at a stirring speed of 60 rpm and a heating rate of 5 ° C./min. After reaching 150 ° C,
After stirring for 10 minutes, the mixture was cooled to 30 ° C. or lower. Thereafter, 5.5% of triallyl isocyanurate manufactured by Nippon Kasei was added.
Kg, 0.3 g of Perhexa peroxide 25B made by NOF Corporation
6 kg, 7 kg of talc with an average particle size of 6 μm
After the addition, the mixture was stirred at 30 ° C. or lower for 15 minutes.

This composition is dissolved or dispersed in toluene.
To produce a varnish, and the weight of the varnish was 107 g / m2.^TwoMoth
Impregnate by immersing lath cloth, and in an air oven
After drying, a curable composite material was obtained. Next, the thickness after curing is about
6 sheets are stacked so that the thickness is 0.8mm, and both sides are thick
180 ° C., 40 kg / cm with 35 μm copper foil ^Two
For 90 minutes using a press molding machine. This
The flexural modulus of the obtained laminate was measured.
The result was 20 GPa.

[0044]

[Example 2] In a pressure-resistant container having a capacity of 50 liters, 30
Poly (2,6-dimethyl-) having a viscosity number ηsp / c of 0.41 as measured with a chloroform solution of 0.5 g / dl at 0.5 ° C.
(1,4-phenylene ether) 12 Kg of polyphenylene ether and 48 g of maleic anhydride were charged and degassed. Then, the mixture was stirred and heated at a stirring speed of 60 rpm and a heating rate of 5 ° C./min. After reaching 150 ° C,
After stirring for 10 minutes, the mixture was cooled to 30 ° C. or lower.

Thereafter, 5.5 kg of triallyl isocyanurate manufactured by Nippon Kasei, 0.36 kg of peroxide perhexa 25B manufactured by NOF Corporation, and 14 kg of talc having an average particle diameter of 6 μm were added. Stirring was performed for minutes. This composition was dissolved or dispersed in toluene to prepare a varnish, applied to a copper foil, and dried to obtain a resin-coated copper foil. This material can be suitably used as a build-up material.

[0046]

Example 3 A pressure-resistant container having a capacity of 50 liters contains 30 liters.
Poly (2,6-dimethyl-) having a viscosity number ηsp / c of 0.41 as measured with a chloroform solution of 0.5 g / dl at 0.5 ° C.
(1,4-phenylene ether) 12 Kg of polyphenylene ether and 48 g of maleic anhydride were charged and degassed. Then, the mixture was stirred and heated at a stirring speed of 60 rpm and a heating rate of 5 ° C./min. After reaching 150 ° C,
After stirring for 10 minutes, the mixture was cooled to 30 ° C. or lower.

Thereafter, triallyl isocyanate manufactured by Nippon Kasei
5.3 kg of nurate, a peroxide perhex made by NOF
0.35Kg of 25B, average particle diameter 6 microns
Talc 21 kg, flame retardant SAY manufactured by Albemarle
4.4 kg of TEX8010 and 0.7 K of polystyrene
g was added and the mixture was stirred at 30 ° C. or lower for 15 minutes. This group
Make a varnish by dissolving or dispersing the product in toluene
And the basis weight is 107 g / m^TwoSoak the glass cloth
Impregnated, dried in an air oven and cured
The material was obtained. Next, the thickness after curing will be about 0.8mm
6 sheets are piled up and copper foil of 35μm thickness is put on both sides
180 ℃, 40kg / cm ^TwoPress for 90 minutes
It was molded and cured using a molding machine.

[0048] The laminate obtained here is 290 ° C.
Was subjected to a heat resistance test by immersion in a solder bath for 2 minutes, and no abnormality was found on the surface of the laminate. This laminate has a dielectric constant of 3.50 (1 MHz) and a dielectric loss tangent of 0.0021.
(1 MHz), moisture absorption 0.2%, glass transition temperature 160
C. (measured by TMA), flexural modulus 25 GPa, and excellent dielectric properties, low moisture absorption, heat resistance, and mechanical properties.

[0049]

Example 4 A pressure-resistant container having a capacity of 50 liters contained 30 liters.
Poly (2,6-dimethyl-) having a viscosity number ηsp / c of 0.41 as measured with a chloroform solution of 0.5 g / dl at 0.5 ° C.
(1,4-phenylene ether) 12 Kg of polyphenylene ether and 48 g of maleic anhydride were charged and degassed. Then, the mixture was stirred and heated at a stirring speed of 60 rpm and a heating rate of 5 ° C./min. After reaching 150 ° C,
After stirring for 10 minutes, the mixture was cooled to 30 ° C. or lower.

Thereafter, 5.3 kg of triallyl isocyanurate manufactured by Nippon Kasei, 0.35 kg of peroxide perhexa 25B manufactured by NOF Corporation, 21 kg of talc having an average particle diameter of 6 μm, and a flame retardant SAY manufactured by Albemarle Co., Ltd.
4.4 kg of TEX8010 and 0.7 K of polystyrene
g was added and the mixture was stirred at 30 ° C. or lower for 15 minutes. This composition was dissolved or dispersed in toluene to produce a varnish, which was applied to a PET film and dried in an air oven to obtain a film. Next, the thickness after curing is about 0.
Ten sheets were stacked so as to have a thickness of 6 mm, and a copper foil having a thickness of 35 μm was formed on both surfaces thereof, and was molded and cured using a press molding machine at 180 ° C. and 10 kg / cm ² for 90 minutes. The flexural modulus of the laminate obtained here was 7 GPa.

[0051]

[Comparative Example 1] In a pressure-resistant container having a capacity of 50 liters, 30
Poly (2,6-dimethyl-) having a viscosity number ηsp / c of 0.41 as measured with a chloroform solution of 0.5 g / dl at 0.5 ° C.
(1,4-phenylene ether) 12 Kg of polyphenylene ether and 48 g of maleic anhydride were charged and degassed. Then, the mixture was stirred and heated at a stirring speed of 60 rpm and a heating rate of 5 ° C./min. After reaching 150 ° C,
After stirring for 10 minutes, the mixture was cooled to 30 ° C. or lower.

Thereafter, triallyl isocyanate manufactured by Nippon Kasei
5.5 kg of nurate, a peroxide perhex made by NOF Corporation
Add 0.36Kg of 25B for 30 minutes at 30 ° C or less
Stirring was performed. Dissolve or dissolve this composition in toluene
A varnish was prepared by scattering the varnish, and the^Twoof
Impregnate the glass cloth by immersing it in an air oven.
To obtain a curable composite material. Next, the thickness after curing
6 sheets are stacked so as to be about 0.8mm, and on both sides
180 ° C, 40 kg / cm with a copper foil of 35 μm thickness
^TwoFor 90 minutes using a press molding machine.
The flexural modulus of the laminate obtained here was 17 GPa.
Was.

[0053]

[Comparative Example 2] In a pressure-resistant container having a capacity of 50 liters, 30
Poly (2,6-dimethyl-) having a viscosity number ηsp / c of 0.41 as measured with a chloroform solution of 0.5 g / dl at 0.5 ° C.
(1,4-phenylene ether) 12 Kg of polyphenylene ether and 48 g of maleic anhydride were charged and degassed. Then, the mixture was stirred and heated at a stirring speed of 60 rpm and a heating rate of 5 ° C./min. After reaching 150 ° C,
After stirring for 10 minutes, the mixture was cooled to 30 ° C. or lower.

Then, 5.3 kg of triallyl isocyanurate manufactured by Nippon Kasei, 0.35 kg of peroxide hexahexa 25B manufactured by NOF Corporation, and a flame retardant S manufactured by Albemarle Co., Ltd.
4.4 kg of AYTEX8010 and 0.1 kg of polystyrene.
7 kg was added, and the mixture was stirred at 30 ° C. or lower for 15 minutes. This composition was dissolved or dispersed in toluene to produce a varnish, which was applied to a PET film and dried in an air oven to obtain a film. Next, 10 sheets are laminated so that the thickness after curing becomes about 0.6 mm, and a copper foil having a thickness of 35 μm is placed on both sides thereof at 180 ° C. and 10 kg / cm.
² were molded and cured using a press molding machine for 90 minutes.
The flexural modulus of the laminate obtained here was 2 GPa.

[0055]

The curable resin composition of the present invention has excellent chemical resistance after curing, dielectric properties, low water absorption, heat resistance,
It exhibits flame retardancy and mechanical properties, and can be used as a dielectric material, an insulating material, a heat-resistant material, a structural material, and the like in fields such as the electric industry, the space and aircraft industries. In particular, it can be used as a single-sided, double-sided, multilayer printed board, flexible printed board, build-up board, or the like.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08J 5/24 CEZ C08J 5/24 CEZ C08K 3/34 C08K 3/34 F term (reference) 4F071 AA51 AB26 AH13 BB02 BC01 BC02 4F072 AA04 AB03 AB05 AB09 AB11 AB28 AB29 AD42 AD53 AF06 AH31 AK05 AL13 4F100 AA03A AA03H AB01B AB33B AG00 AK21A AK24A AK26A AK35A AK49A AK51 CD02 EJ53 EJ53 EJ08 EJ08 EJ08 EJ08 EJ08 EJ11 DG08 CF212 CH071 DJ006 EA047 EH147 ER007 EU197 FD130 FD142 FD147 GQ00 4J005 AA23 BD02 BD05

Claims (6)

[Claims] (A) per 100 parts by weight of a polyphenylene ether-based resin (a) comprising a structural unit represented by the following formula (I): i) at least one carbon-carbon double bond or triple At least one functionalized compound having a bond and ii) having at least one group selected from the group consisting of a carboxylic acid, an acid anhydride, an acid amide, an imide, an amino, a hydroxyl group, and a glycidyl group ( b)
A functionalized polyphenylene ether-based resin obtained by reacting a mixture containing 0.1 to 10.0 parts by weight, and (B)
With respect to 100 parts by weight of the composition comprising the crosslinkable component, (C)
A curable resin composition containing 1 to 90 parts by weight of a silicate having an average particle size of 10 μm or less. Embedded image [R ₁ and R ₄ are each independently halogen, primary or secondary lower alkyl, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy (provided that at least two carbon atoms Atoms separate a halogen atom and an oxygen atom), and R ₂ and R ₃ are each independently halogen, primary or secondary lower alkyl, phenyl, haloalkyl, hydrocarbonoxy, or halo. Hydrocarbon oxy, provided that at least two carbon atoms separate the halogen and oxygen atoms. ] 2. A film comprising the curable resin composition according to claim 1. 3. 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 weight. . 4. A cured composite material obtained by curing the curable composite material according to claim 3. 5. A laminate comprising the cured composite material according to claim 4 and a metal foil. 6. 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.