JP2000290490A - Flame retardant curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a halogen free curable resin composition having sufficient flame retandancy. SOLUTION: (F) A polyphosphate melamine or (D) a phenolic resin including nitrogen atom or phosphorus atom and nitrogen atom including phenolic resin as a component of a curing agent is added to a curable resin composition including (A) a polyphenylene ether based resin, (B) a bisphenol A type epoxy resin, (C) a novolac type epoxy resin, (D) the curing agent and (E) an inorganic filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a halogen-free curable resin composition and a cured product obtained by curing the same. Furthermore, the present invention relates to a curable composite material comprising the resin composition and a substrate, a cured product thereof (cured composite material), a laminate comprising the cured product and a metal foil, and a copper foil with resin.

[0002] The halogen-free resin composition of the present invention exhibits excellent chemical resistance, dielectric properties, heat resistance, and flame retardancy after curing, and is used in the fields of electric industry, space and aircraft industry, etc. , Heat-resistant materials, 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.

[0003]

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 conventionally 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.

Further, 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 can 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, but until now, halogen-free resin has sufficient flame retardancy (for example, UL94 standard). V
−0) was difficult to impart.

[0007]

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. A resin composition, a cured product thereof, a curable composite material comprising the curable resin composition and a base material, a cured product thereof (cured composite material), a laminate comprising the cured product and a metal foil, and a resin-attached metal foil. To provide.

[0008]

The present invention firstly comprises (A) a polyphenylene ether-based resin, (B) a bisphenol A type epoxy resin, (C) a novolak type epoxy resin, (D) a curing agent, A) a curable resin composition characterized by comprising an inorganic filler and (F) melamine polyphosphate as essential components, and containing (F) melamine polyphosphate in a proportion of 1 to 70% by weight based on the whole resin composition. Offer things.

Second, (A) polyphenylene ether resin, (B) bisphenol A type epoxy resin, (C) novolak type epoxy resin, (D-1) (i) phenol compound, (ii) melamine compound and / or A curable resin composition comprising: a guanamine compound; and (iii) a nitrogen-containing phenol resin which is a cocondensation resin with an aldehyde compound; and (E) an inorganic filler.

Third, (A) polyphenylene ether resin, (B) bisphenol A type epoxy resin, (C)
Novolak type epoxy resin, (D-2) (i) reactive phosphate ester, (ii) phenol compound, (iii)
A melamine compound and / or a guanamine compound, (i
v) A curable resin composition characterized by containing a phenolic resin containing a phosphorus atom and a nitrogen atom, which is a reaction product with an aldehyde compound, and (E) an inorganic filler.

Fourth, (A) polyphenylene ether resin, (B) bisphenol A type epoxy resin, (C)
A novolak-type epoxy resin, (D-1) a phenol compound, (ii) a melamine compound and / or a guanamine compound, and (iii) a nitrogen-containing phenol resin which is a co-condensation resin with an aldehyde compound, (D-3) )
Provided is a curable resin composition comprising a reactive phosphate ester and (E) an inorganic filler.

Fifthly, a cured product obtained by curing the first to fourth flame-retardant curable resin compositions is provided. Sixth, a curable composite material comprising the first to fourth curable resin compositions and a base material, wherein the base material is contained at a ratio of 5 to 90% by weight. I will provide a.

Seventh, there is provided a cured composite material obtained by curing the sixth curable composite material. Eighth, there is provided a laminate comprising the seventh cured composite material and a metal foil.
Ninth, the present invention provides a resin-attached metal foil, wherein the first to fourth curable resin composition films are formed on one surface of the metal foil. Hereinafter, the present invention will be described in more detail.

Preferred examples of the polyphenylene ether resin (A) used in the present invention include poly (2,6-dimethyl-phenol) obtained by homopolymerization of 2,6-dimethylphenol.
1,4-phenylene ether), styrene graft copolymer of poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol and 2,3,6-
Copolymer of trimethylphenol, copolymer of 2,6-dimethylphenol and 2-methyl-6-phenylphenol, polyfunctional obtained by polymerization in the presence of 2,6-dimethylphenol and polyfunctional phenol compound Polyphenylene ether resins include, for example, copolymers containing units of the general formulas (A) and (B) as disclosed in JP-A-63-301222 and JP-A-1-297428.

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 includes a modified product. Such a modified product is specifically a polyphenylene ether resin containing an unsaturated group (Japanese Patent Application Laid-Open No. 64-69).
No. 628, JP-A-1-113425, JP-A-1-11
No. 3426), and a reaction product of a polyphenylene ether resin with an unsaturated carboxylic acid and / or acid anhydride.

The above (A) polyphenylene ether resin is used in an amount of 1 part per 100 parts by weight of [(A) + (B) + (C)].
It is preferable to mix in a ratio of 0 to 70 parts by weight. The bisphenol A type epoxy resin (B) used in the present invention is a reaction product of bisphenol A and epichlorohydrin. The bisphenol A type epoxy resin used in the present invention usually has an epoxy equivalent of 170 to 1,000. When the epoxy equivalent exceeds 1000, the impregnating property of the obtained composition into the glass cloth decreases, which is not preferable. Such bisphenol A type epoxy resins are commercially available, for example, from Yuka Shell Co., Ltd. as Epicoat series and from Ciba Geigy Co., Ltd. as Araldite series. Bisphenol A
The epoxy resins can be used alone or in combination of two or more.

The bisphenol A type epoxy resin (B) is not particularly limited when (F) melamine polyphosphate is used, but is not used when melamine polyphosphate is not used.
[(B) + (C)] is blended in an amount of 60 to 95 parts by weight with respect to 100 parts by weight. The (C) novolak epoxy resin used in the present invention is an epoxy resin obtained by reacting epichlorohydrin with the novolak resin, and the novolak resin is a resin obtained by condensing phenols and formaldehyde with an acidic catalyst. is there. As phenols that form a novolak resin by reaction with formaldehyde, phenol, cresol, bisphenol A and the like can be used. The novolak-type epoxy resin used in the present invention preferably has a softening point of 70 to 130 ° C, more preferably 80 to 100 ° C. Such novolak type epoxy resins are commercially available, for example, from Toto Kasei Co., Ltd. or Dainippon Ink. Novolak type epoxy resin can be used alone or
It can be used in combination of more than one kind.

The (D) curing agent used in the present invention comprises:
(F) The use of melamine polyphosphate is not particularly limited, and may be any compound that is usually used for curing epoxy resins. Such compounds include dicyandiamide, aromatic amines and the like as amine curing systems. Examples of the phenol curing system include a phenol novolak resin, a cresol novolak resin, a bisphenol A type novolak resin, and the like, and these can be used alone or in combination of two or more.

In the present invention, when (F) melamine polyphosphate is not used, a phenol resin having a nitrogen atom in the molecule (nitrogen atom-containing phenol resin) must be contained as a curing agent (D) component. . A phenol resin is a condensation product of phenols and formaldehyde, and the nitrogen atoms contained in the nitrogen-containing phenol resin may be present in the resin in any form. The nitrogen atom-containing phenol resin preferably used in the present invention is a co-condensation resin with (D-1) (i) a phenol compound, (ii) a melamine compound and / or a guanamine compound, and (iii) an aldehyde compound.

[0020] Such a curing agent (D-1) is prepared by using (i) a phenol compound, (ii) a melamine compound and / or a guanamine compound, and (iii) an aldehyde compound as an acid catalyst (eg, oxalic acid, p-toluene sulfone). (Acid). In that case, the molar ratio of the aldehyde compound and the phenol compound is less than 1.0, preferably 0.5 or more and less than 1.0, and 1 mole relative to one primary amino group of the melamine compound and / or the guanamine compound. Aldehyde compound (for example, formaldehyde 3 per mole of melamine)
Mol) is preferably used.

Examples of the phenol compound used here include phenol, resorcin, and alkylphenol (cresol, xylenol, etc.). Formaldehyde is particularly preferred as the aldehyde compound. Further, as the melamine compound, melamine, phenylmelamine, butylmelamine and the like, and as the guanamine compound, benzoguanamine, acetoguanamine, formguanamine and the like can be mentioned. There is no particular limitation.

In the present invention, when melamine polyphosphate is not used, flame retardancy can be obtained even by using the above-mentioned nitrogen-containing phenol resin. However, in order to further improve flame retardancy, a curing agent in the molecule is used. Phenolic resin containing nitrogen and phosphorus atoms, preferably (D-2) (i)
Reactive phosphate ester, (ii) phenol compound,
It is possible to use (iii) a melamine compound and / or a guanamine compound, and (iv) a phenol resin containing a phosphorus atom and a nitrogen atom, which is a reaction product with an aldehyde compound. Such a curing agent (D-2) can be produced by further reacting the above-mentioned phenol compound, melamine compound and / or guanamine compound, aldehyde compound with a reactive phosphate ester.

In this reaction, a phenol compound, a melamine compound and / or a guanamine compound and an aldehyde compound are used in the same ratio as in the case of producing the above-mentioned co-condensation resin, and the reactive phosphate ester is used in an amount of 2 per free hydroxyl group. Preferably, it is used in such a ratio as to give a molar aldehyde. For example, a phosphorus atom and a nitrogen atom-containing phenol resin may be a phenol compound, a melamine compound and / or a guanamine compound, an aldehyde compound,
It can be obtained in one step by reacting a reactive phosphate ester. Alternatively, for the phenol resin containing a phosphorus atom and a nitrogen atom, a phenol compound, a melamine compound and / or a guanamine compound, and a co-condensation resin of an aldehyde compound are prepared in advance, and the aldehyde compound and the reactive phosphoric acid ester are reacted therewith. Can also be obtained by In any case, the phenol compound, the melamine compound and / or the guanamine compound, the aldehyde compound, and the reactive phosphate ester are used in the above ratio. Therefore, when the above-mentioned co-condensation resin is manufactured in advance, the sum of the amount of the aldehyde compound used at that time and the amount of the aldehyde compound to be subsequently reacted with the co-condensation resin is set to be the above ratio.

The reactive phosphoric acid ester used is obtained by reacting three molecules of a phenol compound with one molecule of phosphorus oxychloride, and at least one of the three molecules of the phenol compound has at least two phenol compounds. It has a hydroxyl group. Examples of such a phenol compound having two or more hydroxyl groups include resorcinol and pyrogallol.

This reactive phosphate ester can be represented by the following formula.

[0026]

Embedded image

(Where a + b + c = 3, a is 1, 2 or 3, b is 0, 1 or 2, c is 0, 1 or 2, n is 1 or 2, each of R1 to R5 is a hydrogen atom or An alkyl group, at least one of which is an alkyl group) Among such reactive phosphate esters, for example, resorcil diphenyl phosphate is commercially available from Ajinomoto Co. under the trade name of RDP.

The co-condensation resin of the phenol compound and the melamine compound and / or the guanamine compound and the aldehyde compound and the reactive phosphoric acid ester are not reacted with each other in advance and blended with the resin, but they are formed as separate components into the resin. Can be blended. That is, as a curing agent,
In addition to the above (D-1), a reactive phosphate ester (D-3) can be further blended into the resin as an independent component.

In this case, the compounding ratio of the components (D-1) and (D-3) is such that (D-3) is 5 to 100 parts by weight of [(D-1) + (D-3)]. Used in a proportion of 30 parts by weight. If (D-3) is less than 5 parts by weight, sufficient flame retardancy cannot be obtained, and if it exceeds 30 parts by weight, moisture resistance and other physical properties deteriorate. In addition, as the curing agent, in addition to those described above, further, a crosslinkable compound such as diallyl phthalate, divinylbenzene, a polyfunctional acryloyl compound,
Polyfunctional methacryloyl compounds, polyfunctional isocyanates, unsaturated polyesters, triallyl isocyanurate, triallyl cyanurate, polybutadiene, styrene-butadiene, styrene-butadiene-styrene and the like can also be mentioned, and these can be used alone or in combination of two or more. Used as a mixture.

The curing agents (D) and (D-
1), (D-2) or [(D-1) + (D-3)]
Is not particularly limited when melamine polyphosphate is used, but when melamine polyphosphate is not used, nitrogen atoms are 1 to 10 with respect to the entire resin composition of (A) to (E). % By weight, preferably 4 to 10% by weight, more preferably 7 to 10% by weight,
% By weight, preferably 1 to 6% by weight, more preferably 3 to
It is preferable to mix them so as to be contained at a ratio of 6% by weight in order to impart flame retardancy.

In the present invention, a curing accelerator can be used together with the curing agent.
Curing accelerators and radical initiators usually used for epoxy resins are mentioned. As the former, for example, 2-ethyl-4-
Imidazole compounds such as methylimidazole and 1-benzyl-2-methylimidazole, and the latter include, for example, ordinary peroxides such as perhexin 25B. Each of these can be used alone or in combination of two or more, and a curing accelerator and a radical initiator which are usually used for an epoxy resin can also be used in combination.

The (E) inorganic filler used in the present invention comprises:
This is for imparting additional flame retardancy, heat resistance, and moisture resistance to the resin composition. These fillers include talc, silica, alumina, aluminum hydroxide, magnesium hydroxide, titanium oxide and the like, and can be used alone or as a mixture of two or more. These inorganic fillers are preferably blended at a ratio of 5 to 50% by weight based on the entire resin composition (A) to (E) or (A) to (F). If the amount is less than 5%, sufficient flame retardancy cannot be obtained, and if it exceeds 50% by weight, the viscosity of the composition increases and coating unevenness tends to occur on the substrate.

The melamine polyphosphate (F) used in the present invention is a phosphate of melamine with polyphosphoric acid such as pyrophosphoric acid, triphosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid and the like. There is no. The amount of the melamine polyphosphate is 1 to 70% by weight, preferably 10% by weight, based on the entire resin composition (A) to (F).
７０70% by weight, more preferably 50-70% by weight. If the amount is less than 1% by weight, sufficient flame retardancy cannot be obtained, and if it exceeds 70% by weight, the moisture resistance decreases.

The curable resin composition of the present invention may further contain, in addition to the above-mentioned ones, an amount within a range not impairing the original properties for the purpose of imparting desired performance according to the application. Fillers and additives can be compounded and used.
Examples of such a filler include carbon black, barium titanate, glass beads, and hollow glass spheres. In addition, examples of the additive include an antioxidant, a heat stabilizer, an antistatic agent, a plasticizer, a pigment, a dye, and a colorant. Furthermore, one or two types of thermoplastic resins and thermosetting resins other than the components (A), (B) and (C) are used.
More than one kind can be blended.

The above (A) to (E) or (A) to
As the method of mixing the components (F), a solution mixing method in which each component is uniformly dissolved or dispersed in a solvent, a melt blending method in which the components are heated by an extruder or the like can be used. Solvents used for solution mixing include benzene,
Aromatic solvents such as 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 formed into a desired shape in advance according to its use. The molding method is not particularly limited, but 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 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 is as follows:
Depending on the type of radical initiator, 80-30
0 ° C, more preferably in the range of 120 to 250 ° C. The time is about 1 minute to 10 hours, more preferably 1 minute to 5 hours. In addition, this curable resin composition,
Like the cured composite material described below, it can be used by bonding it to a metal foil and / or metal plate.

Next, the sixth and seventh curable composite materials of the present invention and their cured products will be described. Sixth Embodiment
Is characterized by comprising the first to fourth curable resin compositions of the present invention and a substrate. Examples of the base material used in the present invention include various glass cloths such as roving cloths, cloths, chopped mats, surfacing mats, asbestos cloths, metal fiber cloths and other synthetic or natural inorganic fiber cloths, wholly aromatic polyamide fibers, Woven or non-woven fabric obtained from liquid crystal fiber such as aromatic polyester fiber and polybenzozar fiber, woven or non-woven fabric obtained from synthetic fiber such as polyvinyl alcohol fiber, polyester fiber and acrylic fiber, cotton cloth, linen, felt and other natural materials Fiber cloth, carbon fiber cloth, kraft paper,
Natural cellulosic fabrics such as cotton paper and paper-glass mixed fiber paper may be used alone or in combination of two or more.

In the present invention, the proportion of the base material is 5 to 90 parts by weight based on 100 parts by weight of the curable composite material.
More preferably 10 to 80 parts by weight, even more preferably 2
0 to 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, if necessary, a coupling agent can be used for the purpose of improving the adhesion 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.

The method for producing the composite material of the present invention includes, for example, the methods (A) to (A) described in the first to fourth aspects of the present invention.
The component (E) or the components (A) to (F) and, if necessary, other components are uniformly dissolved or dispersed in the above-mentioned aromatic or ketone-based solvent or a mixed solvent thereof, and the base material is impregnated. And then drying. The impregnation is performed by dipping (dipping), coating, or the like. Further, the impregnation can be repeated a plurality of times as necessary.In this case, the impregnation is repeated using a plurality of solutions having different compositions and concentrations, and finally the desired resin composition and the desired resin amount can be adjusted. It is possible.

The seventh 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.

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
The reaction can be performed at 50 ° C., pressure: 1 to 500 kg / cm ² , time: 1 minute to 5 hours. The eighth laminate of the present invention is constituted by the seventh 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 5 to 200 μm, more preferably 5 to 105 μm.

The method for producing the laminate of the present invention includes:
For example, a method of laminating the curable composite material described above as the sixth of the present invention and a metal foil and / or a metal plate in a layer constitution according to the purpose, bonding the respective layers under heat and pressure, and simultaneously thermosetting. Can be mentioned. 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 may be used for bonding the metal foil, and examples of such an adhesive include, but are not limited to, epoxy, acrylic, phenol, and cyanoacrylate. The lamination molding and curing can be performed under the same conditions as in the seventh aspect of the present invention.
Finally, the ninth metal foil with resin of the present invention will be described.

The resin-coated metal foil of the present invention is the first of the present invention.
-4 and curable resin compositions and metal foils. Examples of the metal foil used here include a copper foil and an aluminum foil. The thickness is not particularly limited, but is 5 to 200 μm, more preferably 5 to 1 μm.
It is in the range of 05 μm. The method for producing the metal foil with a resin of the present invention is not particularly limited, for example,
A metal foil is prepared by uniformly dissolving or dispersing the components (A) to (E) or the components (A) to (F) and other components as necessary in an aromatic or ketone-based solvent or a mixture thereof. And then drying.

The application can be repeated a plurality of times, if 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.

[0048]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, the present invention will be described with reference to embodiments. In the following Examples and Comparative Examples, “parts” means “parts by weight”. (Reference Example 1) 100 parts of phenylmelamine, 218 parts of a 37% formalin aqueous solution, 212 parts of phenol, and RDP
(Resorsil diphenyl phosphate manufactured by Ajinomoto Co., Inc.)
To a mixture of 115 parts was added 0.1 part of oxalic acid.
After reacting the reaction mixture at 80 ° C. for 2 hours, the mixture was dehydrated under reduced pressure to obtain a phenylmelamine phosphate / phenol / formaldehyde co-condensation resin. The resulting co-condensation resin contained 10% by weight of nitrogen and 2% by weight of phosphorus.

Reference Example 2 60 parts of phenylmelamine, 3
Oxalic acid (0.1 part) was added to a mixture of 300 parts of a 7% formalin aqueous solution and 367 parts of phenol. After the obtained mixture was reacted at 80 ° C. for 2 hours, it was dehydrated under reduced pressure to obtain a phenol / phenylmelamine / formaldehyde co-condensation resin. The resulting co-condensation resin contained 5% by weight of nitrogen.

[0050]

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) 100
Part, bisphenol A type epoxy resin epicoat 100
260 parts of 1 (product of Yuka Shell Co., epoxy equivalent 456, resin solid content 70% by weight), 65 parts of cresol novolac epoxy resin YDCN-704P (product of Toto Kasei Co., epoxy equivalent 210, solid content 70% by weight), Reference Example 250 parts of the phenolic resin containing a nitrogen atom and a phosphorus atom obtained in 1 above, 100 parts of aluminum hydroxide, 20 parts of triallyl isocyanurate, 0.1 part of imidazole, and Perhexin 25B
A varnish was prepared by dissolving or dispersing 0.5 part in toluene, a glass cloth having a basis weight of 107 g / m ² was immersed in the varnish, and dried in an air oven to obtain a curable composite material. Next, six sheets 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 surfaces thereof at 180 ° C. and 40 kg / cm ² using a press molding machine for 90 minutes. Molded and cured.

The laminated body obtained here was subjected to UL94
When a flammability test was performed based on the standard, it was V-0.

[0052]

Examples 2 to 11 Except that the number of parts of each component of the curable resin composition was changed as shown in Table 1, a laminated body was prepared and flammability was measured in the same manner as in Example 1, and all were measured according to UL94 standard. V-
It became 0.

[0053]

Example 12 A varnish was prepared in the same manner as in Example 1 and 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. A copper foil was produced. Next, two pieces of the resin-attached copper foil are superimposed, and heated at 180 ° C. and 40 kg / cm ² for 9 hours.
It was molded and cured using a press molding machine for 0 minutes.

With respect to the laminate obtained here, UL94
When a flammability test was performed based on the standard, it was V-0. Table 1 summarizes the results of Examples 1 to 12.

[0055]

[Table 1]

[0056]

Comparative Example 1 Except that the number of parts of the phenolic resin containing a nitrogen atom and a phosphorus atom obtained in Reference Example 1 was changed to 100 parts,
A laminate was prepared and flammability was measured in the same manner as in Example 1,
V-1 according to UL94 standard.

[0057]

Comparative Examples 2 to 6 A laminated body was prepared and flammability was measured in the same manner as in Comparative Example 1 except that the number of parts of each component of the curable resin composition was changed as shown in Table 2. The result was obtained.

[0058]

Comparative Example 7 Except that the number of parts of the phenolic resin containing a nitrogen atom and a phosphorus atom obtained in Reference Example 1 was changed to 100 parts,
A resin-coated copper foil was prepared and flammability was measured in the same manner as in Example 12, and the result was V-1 according to UL94 standard. Comparative Example 1
Tables 2 to 7 summarize the results.

[0059]

[Table 2]

[0060]

According to the present invention, a curable resin composition which is halogen-free and has sufficient flame retardancy (V-0 according to UL94 standard), a cured product thereof, a curable resin composition and a substrate A curable composite material, a cured product thereof (cured composite material), a laminate comprising the cured product and a metal foil, and a metal foil with a resin can be provided.

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Claims (9)

[Claims] (A) a polyphenylene ether-based resin,
(B) bisphenol A type epoxy resin, (C) novolak type epoxy resin, (D) curing agent, (E) inorganic filler, and (F) melamine polyphosphate as essential components,
(F) 1 part of melamine polyphosphate to the whole resin composition
A curable resin composition, which is contained in a proportion of about 70% by weight. (A) a polyphenylene ether-based resin,
(B) bisphenol A type epoxy resin, (C) novolak type epoxy resin, (D-1) (i) a phenol compound, (ii) a melamine compound and / or a guanamine compound, and (iii) a co-condensation resin with an aldehyde compound. A curable resin composition comprising: a nitrogen-containing phenolic resin, and (E) an inorganic filler. (A) a polyphenylene ether-based resin,
(B) bisphenol A type epoxy resin, (C) novolak type epoxy resin, (D-2) (i) reactive phosphate ester, (ii) phenol compound, (iii) melamine compound and / or guanamine compound, (iv) A curable resin composition comprising: (a) a phenol resin containing a phosphorus atom and a nitrogen atom which is a reaction product with an aldehyde compound; and (E) an inorganic filler. (A) a polyphenylene ether-based resin,
(B) bisphenol A type epoxy resin, (C) novolak type epoxy resin, (D-1) (i) a phenol compound, (ii) a melamine compound and / or a guanamine compound, and (iii) a co-condensation resin with an aldehyde compound. A curable resin composition comprising a nitrogen-containing phenolic resin, (D-3) a reactive phosphate ester, and (E) an inorganic filler. 5. A cured product 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 5 to 90%.
A curable composite material, characterized in that it is contained in a proportion by weight. 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.