JP2000248170A - Flame-retardant, curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition which is halogen-free and imparted with sufficient flame-retardancy. SOLUTION: This curable resin composition comprises, as essential components, a polyphenylene ether-based resin (A), a halogen-free epoxy resin (B) and an inorganic filler (C), the inorganic filler (C) being contained in an amount of 20-500 pts.wt., based on 100 pts.wt. of the total of (A) and (B), and is free from a halogen-containing flame-retardant.

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. Further, the present invention relates to a curable composite material comprising the resin composition and a substrate, a cured product thereof, a laminate comprising the cured product (cured composite material) 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 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. However, hitherto, halogen-free resin has sufficient flame retardancy (for example, It is difficult to give V-0) according to UL94 standard.

[0008]

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

[0009]

The present invention firstly provides:
(A) a polyphenylene ether resin, (B) an epoxy resin containing no halogen, and (C) an inorganic filler as essential components, and (C) based on 100 parts by weight of the total of the components (A) and (B). A curable resin composition comprising an inorganic filler in a proportion of 20 to 500 parts by weight and containing no halogen-based flame retardant.

Here, the proportion of (C) the inorganic filler is as follows:
For the total of 100 parts by weight of the components (A) and (B),
Preferably 50 to 500 parts by weight, more preferably 2 to 500 parts by weight
It is 00 to 500 parts by weight. Second, (A) a polyphenylene ether-based resin, (B) an epoxy resin, and (D) red phosphorus as essential components, and a total of component (A) and component (B) of 1
A curable resin composition characterized by containing (D) 1 to 100 parts by weight of red phosphorus with respect to 00 parts by weight and containing no halogen-based flame retardant.

Here, the proportion of (D) red phosphorus is preferably 5 to 70 parts by weight, more preferably 10 to 50 parts by weight. Third, (A) a polyphenylene ether-based resin, (B) an epoxy resin containing no halogen, (C) an inorganic filler, and (D) red phosphorus as essential components, and a total of components (A) and (B) A curable resin composition containing 10 to 50 parts by weight of the total of the component (C) and the component (D) based on 100 parts by weight and containing no halogen-based flame retardant. provide.

Fourthly, the present invention provides a cured product obtained by curing the first to third curable resin compositions. Fifth, a curable composite material comprising the first to third 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.

Sixth, a cured composite material obtained by curing the fifth curable composite material is provided. Seventh, the sixth
And a laminate comprising a cured composite material and a metal foil. Eighth, the present invention provides a resin-attached metal foil, wherein the first to third 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 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 10 to 70 parts by weight based on 100 parts by weight of [(A) + (B)].
It is preferable to mix them in parts by weight. Examples of the (B) halogen-free epoxy resin used in the present invention include:
What is necessary is just to contain two or more epoxy groups in one molecule, and known ones are used alone or in combination of two or more. Representative examples include glycidyl ether type epoxy resins obtained by reacting phenols or alcohols with epichlorohydrin, glycidyl type epoxy resins obtained by reacting amines or cyanuric acid with epichlorohydrin, An internal epoxy resin obtained by oxidation of a double bond may be mentioned (for details, refer to “Epoxy Resin Handbook” edited by Masaki Shinbo, Nikkan Kogyo Shimbun, 1987).
checking).

The (A) polyphenylene ether-based resin and (B) a halogen-free epoxy resin can be used together with a curing agent.
Examples of compounds usually used for curing epoxy resins include, for example, dicyandiamide and aromatic amines as amines, phenol novolak resins, cresol novolak resins, bisphenol A, aniline modification, melamine modification, guanidine modification, and phenol curing systems. Nitrogen-modified phenolic resins such as polyamide-modified resins may be used, and these may be used alone or in combination of two or more.
Further, as a curing agent, a crosslinkable compound such as diallyl phthalate, divinylbenzene, a polyfunctional acryloyl compound, a polyfunctional methacryloyl compound, a polyfunctional isocyanate, an unsaturated polyester, triallyl isocyanurate, triallyl cyanurate, polybutadiene, styrene -Butadiene, styrene-butadiene-styrene, and the like, and these can be used alone or in combination of two or more. It is also possible to use a mixture of two or more compounds which are usually used for curing an epoxy resin and a crosslinkable compound.

A curing accelerator can be used together with a curing agent for the (A) polyphenylene ether-based resin and (B) a halogen-free epoxy resin. The former includes, for example, an imidazole-based compound, and the latter includes, for example, perhexin 2
Usual peroxides such as 5B are mentioned.

Examples of the inorganic filler (C) used in the present invention include talc, silica, alumina, aluminum hydroxide, magnesium hydroxide, titanium oxide, antimony trioxide and the like. These may be used alone or in combination of two or more. Can be used. As the red phosphorus (D) used in the present invention, generally known red phosphorus can be used, and red phosphorus dispersed or coated with an inorganic substance such as aluminum hydroxide, magnesium hydroxide, or titanium oxide. Or those coated with a resin such as a phenolic resin, and these can be used alone or as a mixture of two or more thereof.

In addition, the halogen-free curable resin composition of the present invention, in addition to the above (A) to (D), has a range in which the original properties are not impaired for the purpose of imparting desired performance according to its use. Of fillers and additives. Examples of the filler include carbon black, barium titanate, glass beads, and hollow glass spheres. Examples of the additive include an antioxidant, a heat stabilizer, an antistatic agent, a plasticizer, a pigment, a dye, and a colorant. Further, it is also possible to mix one or more thermoplastic resins and thermosetting resins other than (A) and (B).

(C) When the inorganic filler is used alone, it is 20 to 500 parts by weight, preferably 50 to 500 parts by weight, more preferably 200 to 500 parts by weight per 100 parts by weight of [(A) + (B)]. Parts are blended. If the blending ratio of the inorganic filler is less than 20 parts by weight, sufficient flame retardancy cannot be obtained, and if the blending ratio exceeds 500 parts by weight, the viscosity increases, coating unevenness occurs on the base material, and voids and plate thickness defects occur. Is not preferred.

When (D) red phosphorus is used alone, 1 to 100 parts by weight, preferably 5 to 70 parts by weight, more preferably 10 to 100 parts by weight per 100 parts by weight of ((A) + (B)).
It is blended in the range of 50 parts by weight. Red phosphorus is 1
If the amount is less than 10 parts by weight, sufficient flame retardancy cannot be obtained.
If the amount exceeds 00 parts by weight, the electric characteristics are deteriorated. When (C) the inorganic filler and (D) red phosphorus are used together, [(C) +
(D)] is 1 to 100 parts by weight of [(A) + (B)].
It is blended in a ratio of 0 to 50 parts by weight.

As a method for mixing the above components (A) to (D), a solution mixing method for uniformly dissolving or dispersing the respective components in a solvent or a melt blending method in which the components are heated by an extruder or the like are used. 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 formed into a desired shape in advance depending on its use. The molding method is not particularly limited. Usually, a casting method in which the resin composition is dissolved in the above-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. Further, this cured product 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 fifth and sixth curable composite materials of the present invention and the cured composite materials will be described. The fifth curable composite material of the present invention is characterized by comprising the first to third 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 or polybenzozar fiber, woven or non-woven fabric obtained from synthetic fiber such as polyvinyl alcohol fiber, polyester fiber, acrylic fiber, natural such as cotton cloth, linen cloth and felt Natural cellulosic cloths such as fiber cloth, carbon fiber cloth, kraft paper, 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 occupied by the substrate is 5 to 90 parts by weight, more preferably 10 to 80 parts by weight, and further preferably 20 to 70 parts by weight, based on 100 parts by weight of the curable composite material. 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 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 components (A) to (D) described in the first section of the present invention and, if necessary, other components may be mixed with the aforementioned 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.

The impregnation is performed by dipping (dipping), coating or the like. The impregnation can be repeated a plurality of times as necessary.In this case, the impregnation can be repeated using a plurality of solutions having different compositions and concentrations to finally adjust the resin composition and the amount of the desired resin. It is possible. The sixth 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 carried out at a temperature of from 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 seventh laminate of the present invention is constituted by the sixth 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, the curable composite material described above as the fifth of the present invention and a metal foil and / or a metal plate are laminated in a layer constitution according to the purpose, and the respective layers are adhered under heat and pressure and simultaneously thermoset. Methods 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. 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 in the sixth aspect of the present invention. Finally, the eighth resin-attached copper foil of the present invention will be described. The resin-coated copper foil of the present invention comprises the first to third curable resin compositions of the present invention and a metal foil. Examples of the metal foil used here include a copper foil and an aluminum foil. Although its thickness is not particularly limited, it is 5 to 200 μm.
m, more preferably in the range of 5 to 105 μm.

The method for producing the resin-coated copper foil of the present invention is not particularly limited.
A method of uniformly dissolving or dispersing the component (D) and, if necessary, other components in an aromatic or ketone-based solvent or a mixed solvent thereof, applying the mixture to a metal foil, and then drying the mixture. 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.

[0034]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, specific examples of the present invention will be described with reference to examples. In the following Examples and Comparative Examples, “parts” means “parts by weight”.

[0035]

Example 1 Chloroform solution of 0.5 g / dl at 30 ° C.
Poly (2) having a viscosity number ηsp / C of 0.54
6-dimethyl-1,4-phenylene ether) 100
Part, bisphenol A type epoxy resin (epoxy equivalent 1
87) 173 parts, cresol novolak epoxy resin
(Epoxy equivalent 210, solid content 70% by weight) 23 parts,
41 parts of Sphenol A, bisphenol A type novolak
108 parts of resin (hydroxyl value 118, solid content 70% by weight)
0.1 parts of imidazole and 80 parts of aluminum hydroxide
Dissolve or disperse in Ruen to make varnish,
107g / m2 ^TwoImpregnation by immersing the glass cloth
And dried in an air oven to obtain a curable composite material
Was.

Next, six pieces of the above-mentioned curable composite material are superimposed 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 / c.
It was molded and cured using a press molding machine at m ² for 90 minutes. The obtained laminate was subjected to a flammability test based on the UL94 standard, and the result was V-0.

[0037]

Examples 2 to 9 A laminate was prepared and flammability was measured in the same manner as in Example 1, except that the number of parts of each component of the curable resin composition was changed as shown in Table 1. V-0
It became.

[0038]

Example 10 A varnish was prepared in the same manner as in Example 1, and the varnish was applied to a copper foil having a thickness of 18 μm using a bar coater so that the thickness of the resin layer was 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 10.

[0040]

[Table 1]

[0041]

Comparative Example 1 A laminate was prepared and the flammability was measured in the same manner as in Example 1, except that the number of parts of aluminum hydroxide was changed to 40 parts.

[0042]

Comparative Examples 2 to 5 Except that the number of parts of each component of the curable resin composition was changed as shown in Table 2, a laminate was prepared and flammability was measured in the same manner as in Comparative Example 1, and the results are shown in Table 2. The result was obtained.

[0043]

Comparative Example 6 A copper foil with a resin was prepared and flammability was measured in the same manner as in Example 10, except that the number of parts of aluminum hydroxide was changed to 40 parts. The results of Comparative Examples 1 to 6 are collectively shown in Table 2.

[0044]

[Table 2]

[0045]

According to the present invention, a curable resin composition free of halogen and having sufficient flame retardancy (V-0 according to UL94 standard) can be provided.

Claims (8)

[Claims] (A) a polyphenylene ether-based resin,
(B) an epoxy resin containing no halogen, (C) an inorganic filler as an essential component, and (C) an inorganic filler in an amount of from 20 to 100 parts by weight in total of the components (A) and (B).
A curable resin composition containing 500 parts by weight and containing no halogen-based flame retardant. (A) a polyphenylene ether-based resin,
(B) Epoxy resin containing no halogen, (D) red phosphorus as an essential component, and a total of 10 components (A) and (B).
A curable resin composition comprising (D) 1 to 100 parts by weight of red phosphorus based on 0 parts by weight and containing no halogen-based flame retardant. (A) a polyphenylene ether-based resin,
(B) an epoxy resin containing no halogen, (C) an inorganic filler, and (D) red phosphorus as essential components, and (C) component and (C) component with respect to a total of 100 parts by weight of components (A) and (B). (D) containing a total of 10 to 50 parts by weight of the total components,
A curable resin composition containing no halogen-based flame retardant. 4. A cured product obtained by curing the curable resin composition according to claim 1. 5. A curable composite material comprising the curable resin composition according to claim 1 and a substrate, wherein the substrate is 5-90.
A curable composite material, characterized in that it is contained in a proportion by weight. 6. A cured composite material obtained by curing the curable composite material according to claim 5. 7. A laminate comprising the cured composite material according to claim 6 and a metal foil. 8. 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.