JP2006070136A - Curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a material which yields a cured product which is excellent in chemical resistance, dielectric property, heat resistance, flame retardance and mechanical characteristics and a low water absorptivity and can be used as a dielectric material, an insulating material, a heat-resistance material, a structural material, a packaging material, an adhesive material, etc. <P>SOLUTION: The curable resin composition comprises (A) a polyfunctional vinyl aromatic copolymer and (B) sheet silicate, wherein the component (A) has a structural unit derived from a monomer comprising (a) a divinyl aromatic compound and (b) an ethyl vinyl aromatic compound and contains ≥20 mol% repeating unit derived from (a) the divinyl aromatic compound, wherein the molar ratio of a structural unit of formula (a1) in the figure to the total of the structural units of formula (a1) and (a2) (wherein R<SP>1</SP>and R<SP>2</SP>are each a 6-30C aromatic hydrocarbon group) in the figure is ≥0.5. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a curable resin composition containing a soluble polyfunctional vinyl aromatic copolymer and a layered silicate, and a film formed therefrom. Furthermore, this invention relates to the curable composite material which consists of this resin composition and a base material, its hardening body, the laminated body which consists of a hardening body and metal foil, and copper foil with resin.

  2. Description of the Related Art In recent years, along with rapid progress in IT technology, electronic devices such as portable terminal devices, computers, displays, and the like that have been used are rapidly increasing in performance, functionality, and size. Accordingly, higher density and higher performance electronic components such as semiconductor elements used in electronic devices and substrates on which they are mounted have been demanded. With the increase in frequency of electronic devices, there has been a strong demand for a low dielectric loss tangent of an insulating layer adjacent to a circuit board, particularly a metal forming a circuit. Conventionally, an epoxy resin or an epoxy resin film excellent in adhesiveness with a metal forming a circuit has been widely used for such an insulating layer. However, the dielectric loss tangent is as large as 0.01 or more and the frequency is increased. It has become difficult to respond. As a new material for solving this problem, thermosetting polyphenylene ether has attracted attention in recent years, and its application to copper-clad laminates has been attempted.

  On the other hand, in recent years, with the increase in density and thickness of multilayer printed boards, it has been desired to make the interlayer extremely thin, and there is a need for an interlayer insulating substrate that uses a thin glass cloth or no glass cloth at all. Yes. However, the thermosetting polyphenylene ether used by introducing a crosslinkable functional group into the chain of the conventional polyphenylene ether and further curing it is a satisfactory solution so far in terms of molding processability in thinning. Is not obtained.

  For example, U.S. Pat. Nos. 3,321,393 and 3,420,262 produce polyphenylene ethers containing allyl groups by copolymerization of 2-allyl-6-methylphenol and 2,6-dimethylphenol, and cure them. Thus, a cured polyphenylene ether is obtained. However, since the polyphenylene ether containing allyl groups has a melting temperature higher than the curing temperature, it is impossible to perform thermoforming including vacuum lamination. In this method for improving moldability, a large amount of plasticizer is used in combination, which not only impairs the excellent electrical properties (low dielectric constant and low dielectric loss tangent) of polyphenylene ether, but also heat resistance after curing. It has also led to a decrease in chemical and chemical resistance.

  On the other hand, in US Pat. No. 4,463,472, a polymer of 2,6-dimethylphenol is used, and it is curable by converting a methyl group into a vinyl group or introducing a vinyl group at the 3,5-position of a phenyl group. The polyphenylene ether is heat-cured. In this case, the vinyl group is directly bonded to the aromatic ring of the polyphenylene ether without via a flexible carbon chain or an ether bond, so that it becomes insufficient in flexibility after curing and becomes a very brittle material.

JP-A-6-179734 Japanese Patent Laid-Open No. 2003-261743 JP 2003-292570 A JP 2000-128908 A Japanese Patent Laid-Open No. 2003-292787 Japanese Patent Laid-Open No. 2004-59918

  Another method using polyphenylene ether is a method in which a polyphenylene ether resin is mixed with a curable polymer or monomer. By combining with a curable polymer or monomer, the chemical resistance of polyphenylene ether can be improved, and a material that makes use of the excellent dielectric properties of polyphenylene ether can be obtained. Patent Document 1 introduces the following technique as a conventional technique. A method using an epoxy resin as a curable polymer or monomer (JP-A-58-69046, etc.), a method using 1,2-polybutadiene (JP-A-59-193929, etc.), a polyfunctional maleimide (Japanese Patent Laid-Open No. 56-133355), a method using a polyfunctional cyanate ester (Japanese Patent Laid-Open No. 56-141349, etc.), a method using a polyfunctional acryloyl compound, etc. (Japanese Patent Laid-Open No. 57-149317) And the like, triallyl isocyanurate and the like (JP-A-61-218652).

  Patent Document 1 discloses (a) a reaction product of polyphenylene ether and unsaturated carboxylic acid, (b) diallyl phthalate, divinylbenzene, polyfunctional acryloyl compound, polyfunctional methacryloyl compound, polyfunctional maleimide, A curable composite material comprising (c) a thermoplastic resin and (d) a base material such as a polyfunctional cyanate ester, a polyfunctional isocyanate, and an unsaturated polyester is disclosed. Patent Document 1 discloses that divinylbenzene or a prepolymer thereof can be used as component (b). However, in the examples, polyphenylene ether and unsaturated are used as component (a). A reaction product with a carboxylic acid or an unsaturated carboxylic acid anhydride, only divinylbenzene is used as the component (b). And since the curable composition manufactured by this method has low compatibility between the component (a) and the component (b), the cured product obtained from this composition has heat resistance, appearance, and chemical resistance. In addition to having the disadvantage that the properties and mechanical properties are not sufficient, there is a problem that the mechanical properties of the product are likely to vary. Also in the molding process, there is a problem in industrial implementation that a special process is required for film production and the processing conditions are narrow.

Patent Documents 2 and 3 describe reactive polyphenylene ether oligomers having a cyanate group or an epoxy group at the end, but nothing teaches those having a vinyl group.
On the other hand, when trying to use a vinyl-based thermosetting resin material as an extremely thin interlayer insulating substrate, there is a problem that the inherent properties of the resin cannot be exhibited due to a decrease in curing speed or insufficient curing. It was. Patent Document 4 describes a method for obtaining a styrenic polymer from a polyfunctional vinyl compound, a polyfunctional chain transfer agent and a styrenic monomer, but teaches that it is used by mixing with a layered silicate. There was no.

  Patent Document 5 discloses a resin composition in which a layered silicate is dispersed in a thermosetting resin or a mixture of a thermosetting resin and a thermoplastic resin. The thermosetting resin is an epoxy resin. At least selected from the group consisting of thermosetting modified polyphenylene ether resins, thermosetting polyimide resins, urea resins, allyl resins, silicon resins, benzoxazine resins, phenol resins, unsaturated polyester resins, and bismaleimide triazine resins. It is described that it is 1 type. However, the thermosetting resin used exclusively in the examples of Patent Document 5 is an epoxy resin, and the thickness of the molded product is as thick as 100 μm to 2 mm. Further, it is disclosed that a thermosetting modified polyphenylene ether resin can be used as the thermosetting resin. However, the thermosetting modified polyphenylene ether resin must be molded by a heating process and has a thickness of The resin was not suitable for forming a thin film of less than 20 μm. In addition, although it is described that an unsaturated polyester resin is also used, since the unsaturated polyester resin has a low heat hydrolysis property, it is used in a field where a high heat hydrolysis property is required such as an extremely thin insulating layer. The resin was problematic in practical use.

  Patent Document 6 discloses a resin molded product containing a layered silicate in a thermosetting resin or a thermoplastic resin. In this document, the purpose of adding a layered silicate in a thermosetting resin or a thermoplastic resin is to reduce the linear expansion coefficient and to improve the flame retardancy without using a halogen-containing flame retardant. there were. In the prior art described therein, it is described that the multilayer printed circuit board used for the electronic device is thinned. However, in this case, the thinned substrate is exclusively used by reducing the linear expansion coefficient. The purpose was to prevent product defects and reliability degradation. Therefore, the technique disclosed in the literature suggests that the curable resin composition containing the soluble polyfunctional vinyl aromatic copolymer and the layered silicate synergistically improves the curing characteristics in the thin-walled molded article. I can't find it. On the other hand, specific examples of thermosetting resins disclosed in the literature are epoxy resins, thermosetting modified polyphenylene ether resins, thermosetting polyimide resins, urea resins, allyl resins, silicon resins, benzoxazine resins. , Phenol resin, unsaturated polyester resin, bismaleimide triazine resin, alkyd resin, furan resin, melamine resin, polyurethane resin, aniline resin, etc., but the thermosetting resin used in the examples is only epoxy resin The thickness of the molded product is also as thick as 150 μm to 2 mm. Therefore, the technique disclosed in this example does not suggest that an insulating material in a high functional field that requires high dielectric properties, heat hydrolysis resistance, and curability is required. On the other hand, this document discloses that a thermosetting modified polyphenylene ether resin can be used as a thermosetting resin. However, what is specifically described as a thermosetting modified polyphenylene ether resin is a resin obtained by modifying a polyphenylene ether resin with a thermosetting functional group such as a glycidyl group, an isocyanate group, or an amino group. The thermosetting modified polyphenylene ether resin must be molded by a heating process and is not suitable for forming a thin film having a thickness of less than 20 μm. There is no suggestion of a synergistic effect with salt. In addition, although it is described that an unsaturated polyester resin is also used, since the unsaturated polyester resin has a low heat hydrolysis property, it is used in a field where a high heat hydrolysis property is required such as an extremely thin insulating layer. As a resin, there is a possibility of causing a problem in actual use.

  As described above, from the conventionally disclosed technique, when the curable resin composition containing the soluble polyfunctional vinyl aromatic copolymer and the layered silicate is cured, the vinyl group of the soluble polyfunctional vinyl aromatic copolymer is reduced. The synergistic effect of reactivity and multifunctionality and the interfacial effect of layered silicate solves various problems of the prior art, and it has high dielectric properties, heat hydrolysis resistance and curability like an extremely thin interlayer insulating substrate. It could not be imagined that a material that can be used as an insulating material in a high-functional field required is obtained.

  The present invention shows excellent curing characteristics, dielectric characteristics, heat resistance, and heat hydrolysis resistance after thinning the film. In advanced technology fields such as the electronics industry, the space and aircraft industries, etc. It aims at providing the resin composition which can be used for a material, a heat resistant material, a packaging material, an adhesive material, etc., hardened | cured material, or a material containing this.

（式中、Ｒ¹及びＲ²は独立に、炭素数６〜３０の芳香族炭化水素基を示す。）で表されるジビニル芳香族化合物（ａ）由来のビニル基を含有する構造単位のモル分率が、（a1）／[（a1）＋（a2）]≧０．５を満足し、かつ多官能ビニル芳香族共重合体のゲル浸透クロナトグラフィー（ＧＰＣ）で測定されるポリスチレン換算の数平均分子量（Ｍｎ）が６００〜３０，０００であり、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）が２０．０以下である溶剤可溶性の多官能ビニル芳香族共重合体と
（Ｂ）成分：層状珪酸塩、
を含んでなる硬化性樹脂組成物であり、（Ａ）成分及び（Ｂ）成分の合計に対する（Ａ）成分の配合量が２〜９９．９wt％、（Ｂ）成分の配合量が０．１〜９８wt％であることを特徴とする硬化性樹脂組成物である。 The present invention relates to a polyfunctional vinyl aromatic copolymer having a structural unit derived from a monomer comprising component (A): divinyl aromatic compound (a) and ethyl vinyl aromatic compound (b), It contains 20 mol% or more of repeating units derived from the compound (a), and the following formulas (a1) and (a2)

(In the formula, R ¹ and R ² independently represent an aromatic hydrocarbon group having 6 to 30 carbon atoms.) The mole of the structural unit containing a vinyl group derived from the divinyl aromatic compound (a) represented by The fraction satisfies (a1) / [(a1) + (a2)] ≧ 0.5 and is calculated in terms of polystyrene as measured by gel permeation chromatography (GPC) of a polyfunctional vinyl aromatic copolymer. Solvent-soluble polyfunctional vinyl aromatic having a number average molecular weight (Mn) of 600 to 30,000 and a weight average molecular weight (Mw) to number average molecular weight (Mn) ratio (Mw / Mn) of 20.0 or less Copolymer and component (B): layered silicate,
The blending amount of the component (A) with respect to the sum of the components (A) and (B) is 2 to 99.9 wt%, and the blending amount of the component (B) is 0.1. It is -98 wt%, It is curable resin composition characterized by the above-mentioned.

（但し、Ｑは飽和若しくは不飽和の脂肪族炭化水素基、芳香族炭化水素基又はベンゼン環に縮合した芳香族環若しくは置換芳香族環を示し、ｎは０〜４の整数である。）で表されるインダン構造を有すること。
2） （Ａ）成分がジビニル芳香族化合物（ａ）及びエチルビニル芳香族化合物（ｂ）からなる単量体由来の構造単位を有する多官能ビニル芳香族共重合体中に、エチルビニル芳香族化合物（ｂ）以外のモノビニル芳香族化合物（ｃ）に由来する構造単位を含有すること。
3） （Ｂ）成分が、有機溶媒に親和性のある膨潤性層状珪酸塩であること。
4） （Ａ）成分及び（Ｂ）成分の他に、（Ｃ）成分としての熱可塑性樹脂、（Ｄ）成分としての熱硬化性樹脂及び（Ｅ）成分としての充填剤から選ばれる１種以上の成分を含み、（Ａ）〜（Ｅ）成分の合計に対し、（Ｃ）成分の配合量は１〜８０wt％、（D）成分の配合量は１〜８０wt％、（Ｅ）成分の配合量は２〜９０wt％であること。
5）（Ａ）成分、（Ｂ）成分及び（Ｃ）成分の合計に対する（Ｃ）成分の配合量が１〜８０wt％であること。
6） （Ｃ）成分が、ガラス転移温度が２０℃以下の重合体セグメントを有するブロック共重合体及びポリフェニレンエーテルからなる群から選ばれる１種類以上の熱可塑性樹脂であること。
7） （Ａ）成分、（Ｂ）成分、（Ｃ）成分及び（Ｄ）成分の合計に対する（Ｄ）成分の配合量が１〜８０wt％であること。
8） （Ｄ）成分が、熱硬化性ポリフェニレンエーテル、両末端に官能基を有するポリフェニレンエーテルオリゴマー及び多官能性エポキシ化合物からなる群から選ばれる１種類以上の熱硬化性樹脂であること。
9） （Ａ）成分、（Ｂ）成分、（Ｃ）成分、（Ｄ）成分及び（Ｅ）成分の合計に対する（Ｅ）成分の配合量が２〜９０wt％であること。 Here, that the curable resin composition satisfies one or more of the following requirements 1) to 9) gives a better curable resin composition.
1) In the main chain skeleton of the polyfunctional vinyl aromatic copolymer, the component (A) has a structural unit derived from a monomer composed of a divinyl aromatic compound (a) and an ethyl vinyl aromatic compound (b). Formula (1)

(Wherein Q represents a saturated or unsaturated aliphatic hydrocarbon group, an aromatic hydrocarbon group or an aromatic ring or a substituted aromatic ring condensed with a benzene ring, and n is an integer of 0 to 4). Have the indan structure represented.
2) In the polyfunctional vinyl aromatic copolymer in which the component (A) has a structural unit derived from a monomer comprising the divinyl aromatic compound (a) and the ethyl vinyl aromatic compound (b), the ethyl vinyl aromatic compound (b And a structural unit derived from the monovinyl aromatic compound (c) other than).
3) The component (B) is a swellable layered silicate having an affinity for an organic solvent.
4) In addition to the component (A) and the component (B), one or more selected from a thermoplastic resin as the component (C), a thermosetting resin as the component (D), and a filler as the component (E) The amount of component (C) is 1 to 80 wt%, the amount of component (D) is 1 to 80 wt%, and the amount of component (E) is the total of components (A) to (E) The amount should be 2 to 90 wt%.
5) The blending amount of the component (C) with respect to the sum of the components (A), (B) and (C) is 1 to 80 wt%.
6) The component (C) is at least one thermoplastic resin selected from the group consisting of a block copolymer having a polymer segment with a glass transition temperature of 20 ° C. or lower and polyphenylene ether.
7) The blending amount of the component (D) with respect to the sum of the components (A), (B), (C) and (D) is 1 to 80 wt%.
8) The component (D) is one or more thermosetting resins selected from the group consisting of thermosetting polyphenylene ether, polyphenylene ether oligomers having functional groups at both ends, and polyfunctional epoxy compounds.
9) The blending amount of the component (E) with respect to the sum of the component (A), the component (B), the component (C), the component (D) and the component (E) is 2 to 90 wt%.

Furthermore, this invention is a film formed by shape | molding said curable resin composition in a film form. Moreover, this invention is also a metal foil with a resin which has the film | membrane formed from the said curable resin composition on the single side | surface of metal foil.
Further, the present invention is a curable composite material comprising the curable resin composition and a base material, wherein the base material is contained at a ratio of 5 to 90 wt%, or a curable composite material comprising the base material. It is a cured composite material obtained by curing. Furthermore, the present invention is a laminate characterized by having a layer of the cured composite material and a metal foil layer.

  Hereinafter, the curable resin composition of the present invention will be further described.

The curable resin composition of the present invention comprises the above component (A) and component (B) as essential components.
(A) Solvent-soluble polyfunctional vinyl aromatic copolymer used as component (hereinafter referred to as soluble polyfunctional vinyl aromatic copolymer) is not only derived from its molecular structure but has good dielectric properties. The thin film film solves the problems related to moldability, such as the low reactivity of general thermosetting vinyl resins, and is effective as a component to further improve heat resistance by synergistic effects with the component (B) of the present invention. It is.

The component (A) includes an ethyl vinyl aromatic compound in a polyfunctional vinyl aromatic copolymer having a structural unit derived from a monomer composed of a divinyl aromatic compound (a) and an ethyl vinyl aromatic compound (b). Soluble polyfunctional vinyl containing a structural unit derived from a monovinyl aromatic compound other than (b) (hereinafter, a monovinyl aromatic compound not corresponding to ethylvinyl aromatic compound (b) is referred to as monovinyl aromatic compound (c)) Aromatic copolymers are also preferable from the viewpoint of improving compatibility with other thermoplastic resins such as polyphenylene ether resins and thermosetting resins.
This copolymer preferably contains a structural unit represented by the general formula (1) in addition to the above formulas (a1) and (a2) as a repeating unit derived from the divinyl aromatic compound (a). R ¹ , R ² and Q and n in the structural units represented by the above formulas (a1), (a2) and (1) have the above-mentioned meanings, but the proportion of each structural unit present in the copolymer Is determined by the reaction conditions such as the type of divinyl aromatic compound (a) and ethyl vinyl aromatic compound (b) used, the reaction catalyst, and the reaction temperature. The structural unit represented by the general formula (1) is divinyl aromatic compound, ethyl vinyl aromatic compound (b) and other monovinyl aromatic compound (c) when cationic polymerization is performed using a Lewis acid catalyst. From this, the carbocation at the growth end attacks the aromatic ring of the repeating unit at the front end and cyclizes to produce an indane structure.

  Examples of the divinyl aromatic compound (a) used include m-divinylbenzene, p-divinylbenzene, 1,2-diisopropenylbenzene, 1,3-diisopropenylbenzene, and 1,4-diisopropenyl. Benzene, 1,3-divinylnaphthalene, 1,8-divinylnaphthalene, 1,4-divinylnaphthalene, 1,5-divinylnaphthalene, 2,3-divinylnaphthalene, 2,7-divinylnaphthalene, 2,6-divinylnaphthalene 4,4′-divinylbiphenyl, 4,3′-divinylbiphenyl, 4,2′-divinylbiphenyl, 3,2′-divinylbiphenyl, 3,3′-divinylbiphenyl, 2,2′-divinylbiphenyl, 2, 1,4-divinylbiphenyl, 1,2-divinyl-3,4-dimethylbenzene, 1,3-divinyl-4,5,8-tributy Lunaphthalene, 2,2'-divinyl-4-ethyl-4'-propylbiphenyl, and the like can be used, but are not limited thereto. These can be used alone or in combination of two or more.

  Preferable specific examples of the divinyl aromatic compound (a) include divinylbenzene (both m- and p-isomers) and divinylbiphenyl (including each isomer) in terms of cost and heat resistance of the obtained polymer. And divinylnaphthalene (including the respective isomers) are preferred. More preferred are divinylbenzene (both m- and p-isomers) and divinylbiphenyl (including each isomer). In particular, divinylbenzene (both m- and p-isomers) is most preferably used. Furthermore, divinylbiphenyl (including each isomer) and divinylnaphthalene (including each isomer) are preferably used in a field where high heat resistance is required.

  Examples of the ethyl vinyl aromatic compound (b) include o-ethyl vinyl benzene, m-ethyl vinyl benzene, p-ethyl vinyl benzene, 2-vinyl-2′-ethyl biphenyl, 2-vinyl-3′-ethyl biphenyl, 2- Vinyl-4′-ethylbiphenyl, 3-vinyl-2′-ethylbiphenyl, 3-vinyl-3′-ethylbiphenyl, 3-vinyl-4′-ethylbiphenyl, 4-vinyl-2′-ethylbiphenyl, 4- Vinyl-3′-ethylbiphenyl, 4-vinyl-4′-ethylbiphenyl, 1-vinyl-2-ethylnaphthalene, 1-vinyl-3-ethylnaphthalene, 1-vinyl-4-ethylnaphthalene, 1-vinyl-5 -Ethylnaphthalene, 1-vinyl-6-ethylnaphthalene, 1-vinyl-7-ethylnaphthalene, 1-vinyl-8-ethylnaphthalene, 2-bi 1-ethylnaphthalene, 2-vinyl-3-ethylnaphthalene, 2-vinyl-4-ethylnaphthalene, 2-vinyl-5-ethylnaphthalene, 2-vinyl-6-ethylnaphthalene, 2-vinyl-7-ethyl Naphthalene, 2-vinyl-8-ethylnaphthalene, and the like can be used, but are not limited thereto. These can be used alone or in combination of two or more.

  In the polyfunctional vinyl aromatic copolymer, the ethyl vinyl aromatic compound (b) is adjusted for compatibility with the thermoplastic resin (C) and the thermosetting resin (D), solvent solubility and processing Gives structural units that improve sex. Moreover, the structural unit derived from the ethyl vinyl aromatic compound (b) is introduced into the polyfunctional vinyl aromatic copolymer, thereby preventing the copolymer from gelling and increasing the solubility in a solvent. Not only can it be improved, but mechanical properties such as tensile elongation at break of the cured product of the curable resin composition of the present invention can be improved. Preferable specific examples include ethyl vinyl benzene (both m- and p-isomers) and ethyl vinyl biphenyl (including each isomer) in terms of cost, prevention of gelation and heat resistance of the obtained polymer. Can be mentioned.

As the monovinyl aromatic compound (c) other than the ethyl vinyl aromatic compound (b), an aromatic compound having one polymerizable double bond is used. Here, the carbon atom which comprises the vinyl group of a monovinyl aromatic compound (c) may be substituted by the alkyl group etc.
Examples of the monovinyl aromatic compound (c) include unsubstituted monovinyl aromatic compounds such as styrene and vinylnaphthalene, nuclear alkyl-substituted aromatic vinyl compounds such as nuclear alkyl-substituted styrene, α-alkyl-substituted styrene, and α-alkyl-substituted aromatics. An aromatic vinyl compound substituted with a vinyl group such as an aromatic vinyl compound, β-alkyl-substituted styrene and alkoxy-substituted styrene, and a cyclic olefin such as indene and acenaphthylene.

  As the unsubstituted monovinyl aromatic compound, for example, styrene, 2-vinylbiphenyl, 3-vinylbiphenyl, 4-vinylbiphenyl, 1-vinylnaphthalene, 2-vinylnaphthalene and the like can be used.

  Examples of the core alkyl-substituted aromatic vinyl compound include o-methyl styrene, m-methyl styrene, p-methyl styrene, o-propyl styrene, m-propyl styrene, p-propyl styrene, on-butyl styrene, mn-butyl styrene. , Pn-butyl styrene, o-isobutyl styrene, m-isobutyl styrene, p-isobutyl styrene, ot-butyl styrene, mt-butyl styrene, pt-butyl styrene, on-pentyl styrene, mn-pentyl styrene, pn-pentyl styrene , O-2-methylbutyl styrene, m-2-methylbutyl styrene, p-2-methylbutyl styrene, o-3-methylbutyl styrene, m-3-methylbutyl styrene, p-3-methylbutyl styrene, ot -Butyl styrene, mt-butyl styrene, pt-butyl styrene, ot-butyl styrene, mt-butyl styrene, pt-butyl styrene, on-pliers Styrene, mn-pentylstyrene, pn-pentylstyrene, o-2-methylbutylstyrene, m-2-methylbutylstyrene, p-2-methylbutylstyrene, o-3-methylbutylstyrene, m-3-methylbutyl Styrene, p-3-methylbutylstyrene, ot-pentylstyrene, mt-pentylstyrene, pt-pentylstyrene, on-hexylstyrene, mn-hexylstyrene, pn-hexylstyrene, o-2-methylpentylstyrene, m- 2-methylpentylstyrene, p-2-methylpentylstyrene, o-3-methylpentylstyrene, m-3-methylpentylstyrene, p-3-methylpentylstyrene, o-1-methylpentylstyrene, m-1- Methylpentylstyrene, p-1-methylpentylstyrene, o-2,2-dimethylbutylstyrene, m-2,2-dimethylbutylstyrene, p-2,2-dimethylbutylstyrene, o-2,3-dimethylbutyl Styrene, m-2,3-dimethylbutylstyrene, p-2,3-dimethylbutylstyrene, o-2,4-dimethylbutylstyrene, m-2,4-dimethylbutylstyrene, p-2,4-dimethylbutyl Styrene, o-3,3-dimethylbutylstyrene, m-3,3-dimethylbutylstyrene, p-3,3-dimethylbutylstyrene, o-3,4-dimethylbutylstyrene, m-3,4-dimethylbutyl Styrene, p-3,4-dimethylbutylstyrene, o-4,4-dimethylbutylstyrene, m-4,4-dimethylbutylstyrene, p-4,4-dimethylbutylstyrene, o-2-ethylbutylstyrene, m-2-ethylbutylstyrene, p-2-ethylbutylstyrene, o-1-ethylbutylstyrene, m-1-ethylbutylstyrene, p-1-ethylbutylstyrene, o-cyclohexylstyrene, m-cyclohexylstyrene, p-cyclohexylstyrene, o-cyclohexylstyrene, m-cyclohexyl Nuclear alkyl-substituted styrenes such as styrene and p-cyclohexylstyrene can be used.

  Examples of the core alkyl-substituted aromatic vinyl compound other than the core alkyl-substituted styrene include 2-vinyl-2′-propylbiphenyl, 2-vinyl-3′-propylbiphenyl, 2-vinyl-4′-propylbiphenyl, 3- Vinyl-2′-propylbiphenyl, 3-vinyl-3′-propylbiphenyl, 3-vinyl-4′-propylbiphenyl, 4-vinyl-2′-propylbiphenyl, 4-vinyl-3′-propylbiphenyl, 4- Vinyl-4′-propylbiphenyl, 1-vinyl-2-propylnaphthalene, 1-vinyl-3-propylnaphthalene, 1-vinyl-4-propylnaphthalene, 1-vinyl-5-propylnaphthalene, 1-vinyl-6 Propylnaphthalene, 1-vinyl-7-propylnaphthalene, 1-vinyl-8-propylnaphthalene, 2-bi 1-propylnaphthalene, 2-vinyl-3-propylnaphthalene, 2-vinyl-4-propylnaphthalene, 2-vinyl-5-propylnaphthalene, 2-vinyl-6-propylnaphthalene, 2-vinyl-7-propyl Naphthalene, 2-vinyl-8-propylnaphthalene, or the like can be used.

  Alkoxy-substituted styrenes include o-ethoxystyrene, m-ethoxystyrene, p-ethoxystyrene, o-propoxystyrene, m-propoxystyrene, p-propoxystyrene, on-butoxystyrene, mn-butoxystyrene, pn- Butoxystyrene, o-isobutoxystyrene, m-isobutoxystyrene, p-isobutoxystyrene, ot-butoxystyrene, mt-butoxystyrene, pt-butoxystyrene, on-pentoxystyrene, mn-pentoxystyrene, pn- Pentoxystyrene, α-methyl-o-butoxystyrene, α-methyl-m-butoxystyrene, α-methyl-p-butoxystyrene, ot-pentoxystyrene, mt-pentoxystyrene, pt-pentoxystyrene, on -Hexoxystyrene, mn-hexoxystyrene, pn-hexoxystyrene, α-methyl-o-pentoxystyrene Len, α-methyl-m-pentoxystyrene, α-methyl-p-pentoxystyrene, o-cyclohexoxystyrene, m-cyclohexoxystyrene, p-cyclohexoxystyrene and the like can be used. In addition, o-phenoxystyrene, m-phenoxystyrene, p-phenoxystyrene, and the like can be used.

  Examples of the α-alkyl-substituted styrene include α-methyl styrene, α-ethyl styrene, α-propyl styrene, α-n-butyl styrene, α-isobutyl styrene, α-t-butyl styrene, α-n- Pentyl styrene, α-2-methylbutyl styrene, α-3-methylbutyl 2-styrene, α-t-butyl styrene, α-t-butyl styrene, α-n-pentyl styrene, α-2-methylbutyl styrene, α- 3-methylbutylstyrene, α-t-pentylstyrene, α-n-hexylstyrene, α-2-methylpentylstyrene, α-3-methylpentylstyrene, α-1-methylpentylstyrene, α-2,2- Dimethylbutylstyrene, α-2,3-dimethylbutylstyrene, α-2,4-dimethylbutylstyrene, α-3,3-dimethylbutylstyrene, α-3,4-dimethylbutylstyrene, α-4,4- Dimethylbutylstyrene, α-2-ethylbutylstyrene alpha-1-ethyl-butylstyrene, alpha-cyclohexyl styrene, it can be used alpha-cyclohexyl styrene.

  Examples of indenes include indene, methylindene, ethylindene, propylindene, butylindene, t-butylindene, sec-butylindene, n-pentylindene, 2-methyl-butylindene, 3-methyl-butylindene, Alkyl-substituted indenes such as n-hexylindene, 2-methyl-pentylindene, 3-methyl-pentylindene, 4-methyl-pentylindene and the like can be used. Further, methoxyindene, ethoxyindene, ptoxyindene, butoxyindene, t-butoxyindene, sec-butoxyindene, n-pentoxyindene, 2-methyl-butoxyindene, 3-methyl-butoxyindene, n-hexoxyindene, 2-methyl Alkicosiindene such as -pentoxyindene, 3-methyl-pentoxyindene, 4-methyl-pentoxyindene, and the like can be used.

  As acenaphthylenes, for example, in addition to acenaphthylene, 1-methylacenaphthylene, 3-methylacenaphthylene, 4-methylacenaphthylene, 5-methylacenaphthylene, 1-ethylacenaphthylene, 3-ethylacena Alkyl acenaphthylenes such as butylene, 4-ethylacenaphthylene, 5-ethylacenaphthylene, 1-chloroacenaphthylene, 3-chloroacenaphthylene, 4-chloroacenaphthylene, 5-chloroacena Halogenated acenaphthylenes such as butylene, 1-bromoacenaphthylene, 3-bromoacenaphthylene, 4-bromoacenaphthylene, 5-bromoacenaphthylene, 1-phenylacenaphthylene, 3-phenylacenaphthylene Phenylacenaphthyl such as len, 4-phenylacenaphthylene, 5-phenylacenaphthylene, etc. Kind, and the like.

  The monovinyl aromatic compound (c) is not limited to these. These can be used alone or in combination of two or more. Of these monovinyl aromatic compounds, styrene, α-alkyl-substituted styrene, and α-alkyl-substituted aromatic vinyl compounds are preferred in that the amount of indane structure produced in the skeleton of the copolymer during polymerization is large. . As most preferred specific examples, styrene, α-methylstyrene and 4-isopropenylbiphenyl can be mentioned in terms of cost and heat resistance of the obtained polymer. The monovinyl aromatic compound (c) is added for the purpose of increasing the heat resistance of the cured product of the curable resin composition of the present invention or for improving the compatibility with other resins.

  The polyfunctional vinyl aromatic copolymer of component (A) contains a divinyl aromatic compound (a) and an ethyl vinyl aromatic compound (b), and if necessary, a monomer containing a monovinyl aromatic compound (c) is polymerized. Obtained. If the amount of each monomer used is (a), (b), and (c), the divinyl aromatic compound (a) is 20 with respect to the total of (a), (b), and (c). ˜99.5 mol%, preferably 30 to 99 mol%, more preferably 40 to 95 mol%, particularly preferably 50 to 85 mol%. When the content of the divinyl aromatic compound (a) is less than 20 mol%, when the produced soluble polyfunctional vinyl aromatic copolymer is cured, the curability tends to decrease and the heat resistance tends to decrease. Is not preferable.

  The ethyl vinyl aromatic compound (b) is 0.5 to 80 mol%, preferably 1 to 70 mol%, more preferably 5 to 60 mol%, and particularly preferably 15 to 50 mol%. When the content of the ethyl vinyl aromatic compound (b) is 80 mol% or more, when the produced soluble polyfunctional vinyl aromatic copolymer is cured, the heat resistance tends to decrease, which is not preferable.

  The monovinyl aromatic compound (c) is 0 to 40 mol%, preferably 0 to 30 mol%, more preferably 0 to 25 mol%, particularly preferably 0 to 20 mol%. When the content of the monovinyl aromatic compound (c) is 40 mol% or more, when the produced soluble polyfunctional vinyl aromatic copolymer is cured, the heat resistance tends to decrease, which is not preferable.

By the way, in addition to the divinyl aromatic compound (a), the ethyl vinyl aromatic compound (b), and the monovinyl aromatic compound (c), the monomer that forms the polyfunctional vinyl aromatic copolymer of the component (A) A small amount of other monomers (d) such as a trivinyl aromatic compound, other divinyl compounds, and monovinyl compounds can be contained within a range not impairing the effects of the present invention.
Specific examples of the trivinyl aromatic compound include, for example, 1,2,4-trivinylbenzene, 1,3,5-trivinylbenzene, 1,2,4-triisopropenylbenzene, 1,3,5-triiso Examples include propenylbenzene, 1,3,5-trivinylnaphthalene, 3,5,4'-trivinylbiphenyl, and the like. In addition, examples of other divinyl compounds include diene compounds such as butadiene and isoprene. Examples of other monovinyl compounds include alkyl vinyl ether, aromatic vinyl ether, isobutene, diisobutylene and the like. These can be used alone or in combination of two or more. These other monomers (d) are less than 30 mol%, preferably less than 30 mol% based on the total amount of monomers including divinyl aromatic compound (a), ethyl vinyl aromatic compound (b) and monovinyl aromatic compound (c). Is used in the range of 0 to 10 mol%.

  Even when other monomer (d) is included, the amount of divinyl aromatic compound (a), ethyl vinyl aromatic compound (b) and monovinyl aromatic compound (c) used in the total amount of monomers is It is preferable to satisfy the above mol%, and the preferable range is the same.

  In the soluble polyfunctional vinyl aromatic copolymer used in the curable resin composition of the present invention, a structural unit containing a vinyl group derived from the divinyl aromatic compound represented by the above formulas (a1) and (a2) is used. The molar fraction (a1) / [(a1) + (a2)] needs to satisfy ≧ 0.5. The molar fraction is preferably 0.7 or more, particularly preferably 0.9 or more. If it is less than 0.5, the heat resistance of the cured product of the copolymer is lowered, and it takes a long time for curing, which is not preferable.

  The soluble polyfunctional vinyl aromatic copolymer preferably has an indane structure represented by the general formula (1) in the main chain skeleton thereof. In the general formula (1), Q includes an unsaturated aliphatic hydrocarbon group such as a vinyl group, an aromatic hydrocarbon group such as a phenyl group, a substituted hydrocarbon group thereof, and the like. be able to. Q may also be a divalent hydrocarbon group that forms a condensed ring with a benzene ring having an indane structure to form a naphthalene ring or the like, and this divalent hydrocarbon group may have a substituent. .

  The indane structure represented by the general formula (1) is a structural unit that further improves the heat resistance and solubility in a solvent of the soluble polyfunctional vinyl aromatic copolymer used in the curable resin composition of the present invention. When producing a functional vinyl aromatic copolymer, the active site at the end of the growing polymer chain is derived from a divinyl aromatic compound and a monovinyl aromatic compound by producing it under production conditions such as a specific solvent, catalyst, and temperature. It is generated by attacking the aromatic ring of the structural unit. The indane structure is preferably present in an amount of 0.01 mol% or more, more preferably 0.1 mol% or more, still more preferably 1 mol% or more, particularly preferably 3 mol%, based on all structural units. Above, most preferably 5 mol% or more. Although there is no restriction | limiting in an upper limit, it is good that it is 20 mol%, Preferably it is 10 mol%. If the above indane structure is not present in the main chain skeleton of the polyfunctional vinyl aromatic copolymer of the present invention, heat resistance and solubility in a solvent are insufficient, and the affinity with the component (B) is decreased. Absent.

  The number average molecular weight Mn (based on standard polystyrene obtained using gel permeation chromatography) of the soluble polyfunctional vinyl aromatic copolymer is 600 to 30,000, preferably 600 to 10,000, more preferably 700. ~ 5,000. If the Mn is less than 600, the viscosity of the soluble polyfunctional vinyl aromatic copolymer is too low, so that it is difficult to form a thick film and the workability is lowered. Further, when a thin thin film of 20 μm or less is formed, the curability is insufficient, and the heat resistance after curing is not preferable. Further, if Mn is 30,000 or more, gel is formed or compatibility with other resin components is liable to be lowered, and when formed into a film or the like, appearance deterioration and physical property deterioration are caused, which is preferable. Absent.

  The soluble polyfunctional vinyl aromatic copolymer has a molecular weight distribution (Mw / Mn) determined from Mn and a weight average molecular weight (referred to as Mw) of 20 or less, preferably 15 or less, more preferably 10 or less. Particularly preferably, it is 5 or less. The lower limit is not limited, but is preferably 1.5 or more from the viewpoint of polymerization. When Mw / Mn exceeds 20, problems such as deterioration in processing characteristics accompanying an increase in the viscosity of the curable resin composition of the present invention and deterioration in appearance and physical properties due to a decrease in compatibility with other resin components. This is not preferable.

  The metal ion content of the soluble polyfunctional vinyl aromatic copolymer is preferably 100 ppm or less, more preferably 50 ppm or less for each metal ion. If it is 20 ppm or less, it is more preferable, and if it is 10 ppm or less, it is especially preferable. 1 ppm or less is most preferable. When the metal ion content is 100 ppm or more, the electrical characteristics of the polymer deteriorate.

（式中、Ｒ³は水素原子又は炭素数１〜６の１価の炭化水素基を示し、Ｒ⁴はｐ価の芳香族炭化水素基又は脂肪族炭化水素基を示し、Ｚはハロゲン原子、炭素数１〜６のアルコキシル基又はアシルオキシ基を示し、ｐは１〜６の整数を示す。一分子中に、複数のＲ³及びＺがある場合、それぞれは同一であって、異なってもよい。）
重合反応停止後、共重合体を回収する方法は特に限定されず、例えば、スチームストリッピング法、貧溶媒での析出などの通常用いられる方法を用いればよい。 The soluble polyfunctional vinyl aromatic copolymer (A) component is, for example, a monomer component containing a divinyl aromatic compound (a), an ethyl vinyl aromatic compound (b) and a monovinyl aromatic compound (c). It can be obtained by polymerizing in one or more organic solvents having a dielectric constant of 2 to 15 at a temperature of 20 to 100 ° C. in the presence of a Lewis acid catalyst and an initiator represented by the following general formula (2). it can.

(Wherein R ³ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, R ⁴ represents a p-valent aromatic hydrocarbon group or aliphatic hydrocarbon group, Z represents a halogen atom, An alkoxyl group having 1 to 6 carbon atoms or an acyloxy group, and p represents an integer of 1 to 6. When a plurality of R ³ and Z are present in one molecule, they may be the same or different. .)
The method for recovering the copolymer after the termination of the polymerization reaction is not particularly limited. For example, a commonly used method such as a steam stripping method or precipitation with a poor solvent may be used.

  The layered silicate of the component (B) used in the present invention means a layered silicate mineral having an exchangeable metal cation between layers, and may be a natural product or a synthetic product. The layered silicate is not particularly limited, and examples thereof include smectite clay minerals such as montmorillonite, hectorite, saponite, beidellite, stevensite, and nontronite, swelling mica, vermiculite, and halloysite. Among these, at least one selected from the group consisting of montmorillonite, hectorite, and swellable mica is preferably used. These layered silicates may be used alone or in combination of two or more.

  The crystal shape of the layered silicate is not particularly limited, but the preferable lower limit of the average length is 0.005 μm, the upper limit is 3 μm, the preferable lower limit of the thickness is 0.001 μm, the upper limit is 1 μm, and the preferable lower limit of the aspect ratio is 20 The upper limit is 500, the more preferred lower limit of the average length is 0.01 μm, the upper limit is 2 μm, the more preferred lower limit of the thickness is 0.005 μm, the upper limit is 0.5 μm, the more preferred lower limit of the aspect ratio is 50, the upper limit Is 200.

The layered silicate preferably has a large shape anisotropy effect defined by the following formula (3). By using a layered silicate having a large shape anisotropy effect (E), the cured resin obtained from the resin composition has excellent mechanical properties. S1 represents the surface area of the laminated surface of the flaky crystals, and S2 represents the surface area of the laminated side surface of the flaky crystals.
(E) = S1 / S2 (3)

  The exchangeable metal cation existing between the layers of the layered silicate means a metal ion such as sodium or calcium existing on the surface of the lamellar crystal of the layered silicate, and these metal ions are cations with the cationic substance. Since it has exchangeability, various substances having cationic properties can be inserted (intercalated) between the crystal layers of the layered silicate.

  Although it does not specifically limit as a cation exchange capacity | capacitance of the said layered silicate, A preferable minimum is 50 milliequivalent / 100g, and an upper limit is 200 milliequivalent / 100g. When the amount is less than 50 milliequivalents / 100 g, the amount of the cationic substance intercalated between the crystal layers of the layered silicate is reduced by cation exchange, so that the crystal layers are not sufficiently depolarized (hydrophobized). Sometimes. If it exceeds 200 milliequivalents / 100 g, the bonding strength between the crystal layers of the layered silicate becomes too strong, and the crystal flakes may be difficult to peel off.

  As the layered silicate, those having improved dispersibility in the resin by chemical treatment are preferable. Hereinafter, such a layered silicate is also referred to as an organic layered silicate. As said chemical treatment, it can implement by the chemical modification method (1)-(6) shown below, for example. These chemical modification methods may be used alone or in combination of two or more.

  The chemical modification method (1) is also referred to as a cation exchange method using a cationic surfactant, and specifically, is a method in which cation exchange is performed between the layers of the layered silicate with a cationic surfactant to make it hydrophobic. By making the layers of the layered silicate hydrophobic in advance, the affinity between the layered silicate and the low polarity resin is increased, and the layered silicate can be finely dispersed in the low polarity resin more uniformly.

  The cationic surfactant is not particularly limited, and examples thereof include quaternary ammonium salts and quaternary phosphonium salts. Especially, since the crystal | crystallization layer of layered silicate can fully be hydrophobized, the quaternary ammonium salt which has a C6 or more alkyl chain containing the C6 or more alkylammonium ion is used suitably.

  The quaternary ammonium salt is not particularly limited, and examples thereof include trimethyl alkyl ammonium salt, triethyl alkyl ammonium salt, tributyl alkyl ammonium salt, trihexyl alkyl ammonium salt, trioctyl alkyl ammonium salt, dimethyl dialkyl ammonium salt, and dibutyl dialkyl ammonium salt. Derived from aromatic amines such as methylbenzyldialkylammonium salt, dibenzyldialkylammonium salt, trialkylmethylammonium salt, trialkylethylammonium salt, trialkylbutylammonium salt, quaternary ammonium salt having an aromatic ring, trimethylphenylammonium Quaternary ammonium salt, dialkyl quaternary ammonium salt having two polyethylene glycol chains, polypropylene glycol Dialkyl quaternary ammonium salt having two Le chains, trialkyl quaternary ammonium salt having one polyethylene glycol chain, a trialkyl quaternary ammonium salt having one polypropylene glycol chain. Among them, lauryl trimethyl ammonium salt, stearyl trimethyl ammonium salt, trioctyl methyl ammonium salt, distearyl dimethyl ammonium salt, di-cured tallow dimethyl ammonium salt, distearyl dibenzyl ammonium salt, N-polyoxyethylene-N-lauryl-N N-dimethylammonium salt and the like are preferred. These quaternary ammonium salts may be used alone or in combination of two or more.

  The quaternary phosphonium salt is not particularly limited. For example, dodecyl triphenyl phosphonium salt, methyl triphenyl phosphonium salt, lauryl trimethyl phosphonium salt, stearyl trimethyl phosphonium salt, trioctyl phosphonium salt, distearyl dimethyl phosphonium salt, distearyl di Examples thereof include benzylphosphonium salts. These quaternary phosphonium salts may be used alone or in combination of two or more.

  The chemical modification method (2) is a functional group capable of chemically bonding a hydroxyl group present on the crystal surface of the organically modified layered silicate chemically treated by the chemical modification method (1) or a chemical affinity for the hydroxyl group. This is a method of chemical treatment with a compound having one or more large functional groups at the molecular end.

  The functional group capable of chemically bonding to the hydroxyl group or the functional group having a large chemical affinity with the hydroxyl group is not particularly limited, and examples thereof include an alkoxy group, a glycidyl group, a carboxyl group (including dibasic acid anhydrides), A hydroxyl group, an isocyanate group, an aldehyde group, etc. are mentioned. The compound having a functional group capable of chemically bonding to the hydroxyl group or the compound having a functional group having a large chemical affinity with the hydroxyl group is not particularly limited. For example, a silane compound, titanate compound, or glycidyl compound having the functional group. , Carboxylic acids, alcohols and the like. These compounds may be used independently and 2 or more types may be used together.

  The silane compound is not particularly limited, and examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-amino. Propyldimethylmethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyldimethylethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, hexyltrimethoxysilane, hexyltri Ethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropyltriethoxysilane, N-β- (aminoethyl) γ- Minopropylmethyldimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltri An ethoxysilane etc. are mentioned. These silane compounds may be used independently and 2 or more types may be used together.

  The chemical modification method (3) has a large chemical affinity with a functional group or a hydroxyl group that can chemically bond a hydroxyl group present on the crystal surface of the organically modified layered silicate chemically treated by the chemical modification method (1). In this method, chemical treatment is performed with a compound having at least one functional group and one reactive functional group at the molecular end.

  The chemical modification method (4) is a method in which the crystal surface of the organically modified layered silicate chemically treated by the chemical modification method (1) is chemically treated with a compound having an anionic surface activity.

  The compound having an anionic surface activity is not particularly limited as long as the layered silicate can be chemically treated by ionic interaction. For example, sodium laurate, sodium stearate, sodium oleate, higher alcohol sulfate ester salt , Secondary higher alcohol sulfates, unsaturated alcohol sulfates and the like. These compounds may be used independently and 2 or more types may be used together.

  The chemical modification method (5) is a method of chemically treating a compound having one or more reactive functional groups in addition to the anionic site in the molecular chain among the compounds having anionic surface activity.

  In the chemical modification method (6), the organically modified layered silicate chemically treated by any one of the chemical modification methods (1) to (5) is further layered, for example, a maleic anhydride-modified polyphenylene ether resin. It is a method of chemically treating with a resin having a functional group capable of reacting with silicate.

The blending ratio of the above components (A) and (B) for making the curable resin composition of the present invention can be varied over a wide range, but the blending amount of the components (A) and (B) (wt %) Must satisfy the following formula.
(A) Component blending amount = 2-99.9 (wt%)
(B) Component blending amount = 0.1 to 98 (wt%)
Preferably, the amount of component (A) is 3 to 99.5 wt%, more preferably 30 to 99.0 wt%, and the amount of component (B) is 0.5 to 97 wt%, more preferably 1.0 to 70 (wt). %). When the blending amount of the component (B) is less than 0.1 wt%, the hardening accelerating action which is an effect of the layered silicate is lowered, and when it exceeds 98 wt%, the mechanical properties are lowered. Furthermore, since the polyfunctional vinyl aromatic copolymer (A) used in the present invention is a material having low dielectric properties, a cured product having a low dielectric constant can be formed.

  Although the curable resin composition of this invention contains (A) and (B) component as an essential component, it is good to contain any 1 or more types of (C)-(E) component demonstrated below. The component (C) is a thermoplastic resin, the component (D) is a thermosetting resin, and the component (E) is a filler. And these compounding ratios are calculated on the basis of the sum total of the compounding quantity of (A) and (B) component as an essential component, and (C)-(E) component as an arbitrary component. Hereinafter, when it is referred to as a reference amount, it means an amount obtained by summing the components (A) and (B) and the components (C) to (E).

  As the component (C), one kind or two or more kinds of thermoplastic resins can be blended. The blending amount (weight ratio) of the component (C) relative to the total amount of the component (C) or the sum of the components (A), (B) and (C) is preferably 1 to 80 wt%. , Preferably 5 to 70 wt%. When the amount of component (C) is less than 1 wt%, the mechanical properties are lowered, and when it exceeds 80 wt%, chemical resistance and heat-resistant dimensional stability are lowered.

  As the thermoplastic resin of component (C), polyolefins such as polyethylene, polypropylene, polybutene, ethylene / propylene copolymer, poly (4-methyl-pentene) and derivatives thereof, nylon 4, nylon 6, nylon 6,6, Polyamides such as nylon 6, 10 and nylon 12 and derivatives thereof, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyesters such as polyethylene terephthalate / polyethylene glycol block copolymer and derivatives thereof, polyphenylene ether, modified polyphenylene ether, Polycarbonate, polyacetal, polysulfone, polyvinyl chloride and copolymers thereof, polyvinylidene chloride and copolymers thereof, polymethyl methacrylates, acrylic acid ( Is methacrylic acid) ester copolymers, polystyrenes, acrylonitrile styrene copolymers, polystyrenes such as acrylonitrile styrene butadiene copolymers and their copolymers, polyvinyl acetates, polyvinyl formal, polyvinyl acetal, polyvinyl Butyrals, ethylene vinyl acetate copolymers and hydrolysates thereof, polyvinyl alcohols, rubbers such as styrene conjugated diene block copolymers, rubbers such as hydrogenated styrene conjugated diene block copolymers, polybutadiene, polyisoprene Rubbers such as polymethoxyethylene, polyethoxyethylene, polyacrylamide, polyphosphazenes, polyethersulfone, polyetherketone, polyetherimide, polyphenylenesulfide , At least one selected from liquid crystal polymers such as polyamideimide, thermoplastic polyimide, aromatic polyester, side chain type liquid crystal polymer containing a liquid crystal component in the side chain, or epoxy group, carboxylic acid group, and maleic anhydride group And thermoplastic block copolymer having two functional groups introduced therein.

Among these thermoplastic resins, from the viewpoint of improving toughness, it is preferable to use a block copolymer or a polyphenylene ether having a polymer segment having a glass transition temperature of 20 ° C. or lower. It is more preferable to use a block copolymer or polyphenylene ether having a polymer segment having a glass transition temperature of 0 ° C. or lower. The block copolymer having a polymer segment having a glass transition temperature of 20 ° C. or less mentioned here is a rubber such as a styrene conjugated diene block copolymer or a rubber such as a hydrogenated styrene conjugated diene block copolymer. Preferably there is. From the viewpoint of thermal oxidation deterioration resistance of the curable resin composition of the present invention, hydrogenated rubbers such as hydrogenated styrene conjugated diene block copolymers are most preferable. The structure of the hydrogenated block copolymer is a block copolymer comprising a polymer block A mainly composed of at least one vinyl aromatic compound and a polymer block B mainly composed of at least one conjugated diene compound. For example, it can be obtained by hydrogenating a vinyl aromatic compound-conjugated diene compound block copolymer having the following structural formula. In the structural formula, A represents a polymer block mainly composed of vinyl aromatic compound units, and B represents a polymer block mainly composed of conjugated diene compound units.
A-B,
A-B-A,
B-A-B-A,
[A-B-] ₄ -Si,
[B-A-B-] ₄ -Si,
This hydrogenated block copolymer contains 5 to 85 wt%, preferably 10 to 70 wt% of a vinyl aromatic compound. More preferably, it contains 15 to 40 wt%.

  Referring to the block structure obtained by hydrogenation, the polymer block A ′ mainly composed of a vinyl aromatic compound is a polymer block consisting only of a vinyl aromatic compound, or a vinyl aromatic compound is 50% by weight or more, preferably Has a copolymer block structure of a vinyl aromatic compound containing 70% by weight or more and a hydrogenated conjugated diene compound, and a polymer block B ′ mainly composed of a hydrogenated conjugated diene compound. A hydrogenated conjugated diene compound containing only 50% by weight, preferably 70% by weight or more of a hydrogenated conjugated diene compound and a vinyl aromatic compound. It has the structure of a copolymer block.

  In addition, the polymer block A ′ and the polymer block B ′ have random, tapered (along the molecular chain) distribution of hydrogenated conjugated diene compound or vinyl aromatic compound in the molecular chain in each polymer block. The monomer component may be increased or decreased), partially in the form of a block, or any combination thereof. When there are two or more of these polymer blocks, each polymer block has the same structure. There may be different structures.

  As the vinyl aromatic compound constituting the hydrogenated block copolymer, one or more kinds selected from, for example, styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, p-tert-butylstyrene, etc. Among them, styrene is preferable. Examples of the conjugated diene compound before hydrogenation constituting the hydrogenated conjugated diene compound include 1 from butadiene, isoprene, 1,3-pentadiene, 1,3-dimethyl-1,3-butadiene and the like. A seed | species or 2 or more types is selected, and a butadiene, isoprene, and these combination are especially preferable. From the viewpoint of compatibility with the component (A) and the component (B) of the present invention, butadiene is most preferable.

  The number average molecular weight of the hydrogenated block copolymer having the above structure is not particularly limited, but the number average molecular weight is in the range of 5,000 to 1,000,000, preferably 10,000 to 500,000, more preferably 30,000 to 300,000. Can be used. Furthermore, the molecular structure of the hydrogenated block copolymer may be linear, branched, radial, or any combination thereof.

  On the other hand, as polyphenylene ether which is a thermoplastic resin suitably used as the component (C), the reduced viscosity measured at 30 ° C. using a 0.5 g / dl chloroform solution is 0.15 to 0.70 dl / g. It is preferable that the polymer or the copolymer be in the range of 0.20 to 0.60 dl / g. Specific examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2-methyl- 6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like.

  Specific examples of polyphenylene ether resins include polyphenylene ether copolymers such as copolymers of 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol and 2-methyl-6-butylphenol). A polymer is also mentioned. Poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol can be preferably used. Most preferred is poly (2,6-dimethyl-1,4-phenylene ether).

  The method for producing the polyphenylene ether-based resin is not limited, and there is a method of oxidative polymerization of 2,6-xylenol using a complex of cuprous salt and amine described in US Pat. No. 3,306,874 as a catalyst. Also, the methods described in U.S. Pat. Nos. 3,306,875, 3,257,357 and 3,257,358, JP-B-52-17880, JP-A-50-51197 and JP-A-63-152628 are also disclosed in Japanese Patent Publication No. It is preferable as a manufacturing method.

  The curable resin composition of this invention can mix | blend a thermosetting resin as (D) component other than (A) and (B) component. (D) When component (B), (B), (C) component and (D) component are combined, the blending amount of (D) component with respect to the reference amount is 1 to 80 wt%. It is preferably 5 to 70 wt%. If the amount of component (D) is less than 1 wt%, the degree of improvement in curability, adhesion and chemical resistance due to the addition of the thermosetting resin is insufficient, and if it exceeds 80 wt%, the composition The mechanical properties of the are significantly reduced.

As component (D), thermosetting polyphenylene ether, polyphenylene ether oligomer having functional groups at both ends, polyfunctional epoxy compound, polyfunctional oxetane compound, diallyl phthalate, polyfunctional acryloyl compound, polyfunctional methacryloyl compound, The compound which consists of polyfunctional maleimide, polyfunctional cyanate ester, polyfunctional isocyanate, unsaturated polyester, and these prepolymers are mentioned. These are used alone or in combination of two or more.
Hereinafter, some thermosetting resins of the component (D) that can be suitably used will be described.

  First, the thermosetting polyphenylene ether will be described. In this thermosetting polyphenylene ether, a reactive functional group is introduced so that part of the structural unit improves properties such as heat resistance and adhesiveness. Examples of reactive functional groups include acids, acid anhydrides, alkenyls, alkynyls, amines, imides, epoxies, oxazolines, esters, hydroxyls, phosphates, phosphonates, and the like.

  Typical examples of the structural unit into which the reactive functional group of the thermosetting polyphenylene ether resin having a reactive functional group is introduced or the terminal structural unit are represented by the following general formulas (4) to (6). Can be mentioned.

（但し、Ｒ⁵及びＲ⁸は、それぞれ独立して、水素、アリル基及びプロパギル基からなる群から選ばれ、かつ、Ｒ⁵及びＲ⁸のいずれか一つはアリル基又はプロパギル基である。Ｒ⁶及びＲ⁷は、それぞれ独立して、水素、ハロゲン、第一級若しくは第二級の低級アルキル、ハロアルキル、炭化水素オキシ、芳香族炭化水素基又は少なくとも２個の炭素原子がハロゲン原子と酸素原子を隔てているハロ炭化水素オキシである。）

(However, R ⁵ and R ⁸ are each independently selected from the group consisting of hydrogen, an allyl group, and a propargyl group, and any one of R ⁵ and R ⁸ is an allyl group or a propargyl group. R ⁶ and R ⁷ are each independently hydrogen, halogen, primary or secondary lower alkyl, haloalkyl, hydrocarbonoxy, aromatic hydrocarbon group, or at least two carbon atoms are halogen atoms and oxygen Halohydrocarbon oxy separating atoms.)

  The structural unit represented by the general formula (4) is “Polyfile Vol. 30, No. 3, p55 to 57, 1993”, “Polymer Papers Vol.54, No. 4, p171 to 182, 1997”. As disclosed in Japanese Patent Publication No. 5-8930 and Japanese Patent Publication No. 5-8931, after polyphenylene ether resin is metallized with an organometallic compound such as butyl lithium, allyl halide or propargyl is used. Allyl groups or propargyl groups can be introduced by reaction with halides.

  Examples of the organometallic compound used for metalation include methyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, and the like, and phenyl lithium and alkyl sodium can also be used. The allyl halide is selected from allyl chloride, allyl bromide, and allyl iodide, and the propargyl halide is selected from propargyl chloride, propargyl bromide, and propargyl iodide.

  The reaction can be carried out in an ether solvent such as tetrahydrofuran (hereinafter abbreviated as THF), 1,4-dioxane, dimethoxyethane, etc., and N, N, N ′, N′-tetramethylethylenediamine (hereinafter abbreviated as TMEDA). ) In the presence of hydrocarbon solvents such as cyclohexane, benzene, toluene and xylene. In the actual reaction, these solvents are preferably used after being subjected to pretreatment such as purification and dehydration. These solvents may be mixed in an appropriate ratio, and the first and second other than the above which do not inhibit the reaction. The solvent may be present. The reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon.

There are no particular limitations on the temperature and time of the reaction of metalation and subsequent allylation and propargylation. For example, in the case of metalation, the reaction is carried out in the range of −78 ° C. to the boiling point (in the case where the reaction system solidifies, the freezing point to the boiling point), particularly preferably in the range of 5 ° C. to the boiling point, and the time is from 1 second to 50 The time is preferably about 1 minute to 10 hours. Regarding the reaction of allylation and propargylation, the reaction is carried out in the range of −78 ° C. to the boiling point (in the case where the reaction system solidifies, the freezing point to the boiling point), and the time is about 1 second to 50 hours, preferably 1 minute. About 10 hours is preferable.
The preferable introduction amount of allyl group and propargyl group is the substitution rate of allyl group and propargyl group calculated by the percentage of the total number of moles of allyl group and propargyl group introduced to the total number of moles of phenyl group constituting the polyphenylene ether resin. This substitution rate is preferably 0.1 mol% or more and 100 mol% or less.

  On the other hand, the reaction product of the polyphenylene ether resin represented by the above formulas (4) to (5) and the unsaturated carboxylic acid or acid anhydride causes the polyphenylene ether resin to react with the unsaturated carboxylic acid or acid anhydride. Manufactured by. It is a reaction product substantially free of polymerizable double bonds resulting from an acid or an acid anhydride. The reaction product is probably a mixture of different products with different chemical structures, not all of which have been elucidated. H. Grans, M.M. K. Examples include the chemical structures of the above formulas (5) to (6) described in Akkapeddi, Macromolecules, 1991, vol 24, 383 to 386.

Examples of suitable acids and acid anhydrides include acrylic acid, methacrylic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, glutaconic anhydride, citraconic anhydride, and the like. In particular, maleic anhydride and fumaric acid can be most preferably used. The reaction is carried out by heating the polyphenylene ether resin and the unsaturated carboxylic acid or acid anhydride in a temperature range of 100 ° C to 390 ° C. At this time, a radical initiator may coexist. Although both the solution method and the melt mixing method can be used, the melt mixing method using an extruder or the like can be performed more easily and is suitable for the purpose of the present invention.
The ratio of unsaturated carboxylic acid or acid anhydride is 0.01 to 5.0 parts by weight, preferably 0.1 to 3.0 parts by weight, based on 100 parts by weight of the polyphenylene ether resin.

Next, a polyphenylene ether oligomer having a vinyl group at both ends (hereinafter referred to as bifunctional OPE-2Vn) will be described. This bifunctional OPE-2Vn is obtained by introducing a reactive functional group at the end of its molecular chain in order to improve the properties such as moldability, heat resistance and adhesiveness. This bifunctional OPE-2Vn is a polyphenylene ether oligomer (hereinafter referred to as bifunctional OPE) represented by the structural formula (7) obtained by oxidative copolymerization of divalent phenol and monovalent phenol. It can be obtained by reacting with chloromethylstyrene, glycidyl methacrylate, glycidyl acrylate and the like.

In the bifunctional OPE represented by the structural formula (7),-(OXO)-is represented by the following structural formula (8), and-(YO)-is defined by the following structural formula (9). More than one type of structure is randomly arranged.

In the formula, R ⁹ , R ¹⁰ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ may be the same or different, and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁹ and R ²⁰ may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. A is a linear, branched or cyclic hydrocarbon group having 20 or less carbon atoms. a and b each represents an integer of 0 to 20 in which at least one of them is not 0. Preferably, R ⁹ , R ¹⁰ , R ¹⁵ , and R ¹⁶ are methyl groups, R ¹¹ , R ¹² , R ¹³ , and R ¹⁴ are hydrogen atoms,-(YO)-is the structural formula (10), It is desirable to have a structure in which Formula (11) or Structural Formula (10) and Structural Formula (11) are randomly arranged.

ここで、構造式（１２）及び（１３）のA及びR⁹〜R²⁰は上記と同じ意味を有する。 The bifunctional OPE represented by the structural formula (7) is obtained by converting a divalent phenol represented by the structural formula (12) and a monovalent phenol represented by the structural formula (13) alone or in a mixture of toluene It can be efficiently produced by oxidative polymerization in an alcohol or ketone solvent.

Here, A and R ^{9 to} R ²⁰ in the structural formulas (12) and (13) have the same meaning as described above.

The divalent phenol represented by the structural formula (12) is a divalent phenol in which R ⁹ , R ¹⁰ , R ¹⁵ , and R ¹⁶ are not necessarily hydrogen atoms, and 4,4′-methylenebis (2, 6-dimethylphenol), 4,4 '-(1-methylethylidene) bis (2,6-dimethylphenol), 4,4'-methylenebis (2,3,6-trimethylphenol), 4,4'-cyclohex Silidenebis (2,6-dimethylphenol), 4,4 '-(phenylmethylene) bis (2,3,6-trimethylphenol), 4,4'-[1,4-phenylenebis (1-methylethylidene) )] Bis (2,6-dimethylphenol), 4,4'-methylenebis [2,6-bis (1,1-dimethylethyl) phenol], 4,4'-cyclopentylidenebis (2,6-dimethyl) Phenol), 4,4 '-(2-furylmethylene) bis (2,6-dimethylphenol), 4,4'-(1,4-phenylenebismethylene) bis (2,6-dimethylphenol), 4 '-(3,3,5-trimethylcyclohexylene) bis (2,6-dimethyl) Tilphenol), 4,4 '-[4- (1-methylethyl) cyclohexylidene] bis (2,6-dimethylphenol), 4,4'-(4-methylphenylethylene) bis (2,3, 6-trimethylphenol), 4,4 '-(1,4-phenylenebismethylene) bis (2,3,6-trimethylphenol), 4- [1- [4- (4-hydroxy-3,5-dimethyl) Phenyl) -4-methylcyclohexyl] -1-methylethyl] -2,6-dimethylphenol, 4,4 '-(4-methoxyphenylmethylene) bis (2,3,6-trimethylphenol), 4,4' -[4- (1-methylethyl) phenylmethylene] bis (2,3,6-trimethylphenol), 4,4 '-(9H-fluorene-9-ylidene) bis (2,6-dimethylphenol), 4 , 4 '-[1,3-phenylenebis (1-methylethylidene)] bis (2,3,6-trimethylphenol), 4,4'-(1,2-ethanediyl) bis [2,6-di- (1,1-dimethylethyl) phenol], 5,5 '-(1-methylethylidene) bis [3- (1,1-dimethylethyl) -1,1- Phenyl-2-ol], and the like, but not limited thereto.

  Next, as the monovalent phenol represented by the structural formula (13), those having a substituent at the 2,6 position alone or those having a substituent at the 3 position or 3, 5 position may be used in combination. It is preferable. More preferably, 2,6-dimethylphenol and 2,3,6-trimethylphenol are used alone, and 2,6-dimethylphenol and 2,3,5-trimethylphenol are used together.

  As the oxidation method, there is a method of directly using oxygen gas or air. There is also an electrode oxidation method. Any method may be used and is not particularly limited. Air oxidation is preferred because safety and capital investment are inexpensive.

As a catalyst for oxidative polymerization using oxygen gas or air, one or more of copper salts such as CuCl, CuBr, Cu ₂ SO ₄ , CuCl ₂ , CuBr ₂ , CuSO ₄ and CuI are used. In addition to the above catalysts, mono and dimethylamine, mono and diethylamine, mono and dipropylamine, mono- and di-n-butylamine, mono- and di-sec-dipropylamine, mono and dibenzylamine, mono And dicyclohexylamine, mono- and diethanolamine, ethylmethylamine, methylpropylamine, butyldimethylamine, allylethylamine, methylcyclohexylamine, morpholine, methyl-n-butylamine, ethylisopropylamine, benzylmethylamine, octylbenzylamine, octylchlorobenzyl Amine, methyl (phenylethyl) amine, ben Ruethylamine, Nn-butyldimethylamine, N, N'-di-tert-butylethylenediamine, di (chlorophenylethyl) amine, 1-methylamino-4-pentene, pyridine, methylpyridine, 4-dimethylaminopyridine, piperidine, etc. Are used in combination with one or more amines. If it is a copper salt and an amine, it will not specifically limit to these.

  As a reaction solvent, in addition to aromatic hydrocarbon solvents such as toluene, benzene and xylene, halogenated hydrocarbon solvents such as methylene chloride, chloroform and carbon tetrachloride, etc., together with alcohol solvents or ketone solvents can do. Examples of alcohol solvents include methanol, ethanol, butanol, propanol, methyl propylene diglycol, diethylene glycol ethyl ether, butyl propylene glycol, and propyl propylene glycol. Ketone solvents include acetone, methyl ethyl ketone, diethyl ketone, and methyl butyl. Examples include ketones and methyl isobutyl ketone, and others include tetrahydrofuran and dioxane, but are not limited thereto.

  Although it does not specifically limit about reaction temperature, 25-50 degreeC is preferable. Since oxidation polymerization is an exothermic reaction, temperature control is difficult and molecular weight control is difficult at 50 ° C. or higher. Below 25 ° C., the reaction rate becomes extremely slow, so that efficient production cannot be performed.

で表される。すなわち、-(O-X-O)-は構造式（８）で表され、-(Y-O)-は構造式（９）で表される。 The above-mentioned bifunctional OPE-2Vn has the following structural formula (14)

It is represented by That is,-(OXO)-is represented by structural formula (8), and-(YO)-is represented by structural formula (9).

Z is an organic group having 1 or more carbon atoms and may contain an oxygen atom. Illustrative examples include — (— CH ₂ —) —, — (— CH ₂ —CH ₂ —) —, — (— CH ₂ —Ar —) — and the like, but are not limited thereto. Examples of the addition method include, but are not limited to, a method of directly adding to the bifunctional OPE represented by the structural formula (7) and a method of using a halide having a long carbon chain during the synthesis of the derivative.

  Hereinafter, for the sake of convenience, a derivative from the bifunctional OPE represented by the structural formula (7), which is the simplest structure, will be described. In order to produce bifunctional OPE-2Vn, bifunctional OPE represented by the above structural formula (7) is used, but either a powder separated from the reaction solution or a form dissolved in the reaction solution can be used.

  The production method of bifunctional OPE-2Vn is illustrated. It can be synthesized by reacting a compound having a phenolic hydroxyl group at both ends represented by the structural formula (7) with chloromethylstyrene, glycidyl methacrylate, glycidyl acrylate or the like. The reaction temperature is preferably between -10 ° C and 110 ° C.

  The number average molecular weight Mn of the bifunctional OPE-2Vn is limited to a range of 700 to 4000. When the number average molecular weight exceeds 4000, the melt viscosity of the resin composition increases and not only the moldability decreases, but also the compatibility with other resin components such as the component (A) decreases, and the appearance of the fill deteriorates. This is not preferable because it causes a decrease in physical properties. On the other hand, if Mn is less than 700, mechanical strength and heat resistance are lowered. The above bifunctional OPE-2Vn has low melt viscosity, good fluidity, excellent compatibility with polyfunctional vinyl aromatic copolymers, and has vinyl groups at both ends, so the strength and heat resistance of the resin composition The cured product is more excellent in hot strength. As a result, generation of cracks can be prevented when exposed to high temperatures such as solder.

Subsequently, the thermosetting resin used as the component (D) will be described.
The polyfunctional epoxy compound may be an epoxy resin having two or more epoxy groups in the molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydantoin type epoxy resin, fat Examples include cyclic epoxy resins, biphenyl type epoxy resins, and epoxy resins obtained by halogenating these resins, triphenylmethane type epoxy resins, tetraphenyl glycidyl ether ethane (tetrafunctional epoxy resins), and various novolac type epoxy resins. Two or more types may be used in combination. In addition, the epoxy resin which has one epoxy group in a molecule | numerator within the range which does not impair the effect of this invention can also be used together.

  When using a polyfunctional epoxy compound, the curable resin composition of the present invention can contain a curing agent. Examples of curing agents for polyfunctional epoxy compounds include amide curing agents such as dicyandiamide and aliphatic polyamide, amine curing agents such as diaminodiphenylmethane, metaphenylenediamine, ammonia, triethylamine, and diethylamine, bisphenol A, and bisphenol F. Phenolic curing agents such as phenol novolac resin, cresol novolak resin, p-xylene-novolak resin, and acid anhydrides may be used, and these may be used in combination as long as the effects of the present invention are not impaired.

  In addition, when using a polyfunctional epoxy compound, in order to accelerate | stimulate hardening reaction, addition of a hardening accelerator can also be performed within the range which does not impair the effect of this invention. Examples of the curing accelerator include imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole, 1,8-diaza-bicyclo [5.4.0] undecene-7, Examples include tertiary amines such as ethylenediamine and benzyldimethylamine, organic phosphines such as tributylphosphine and triphenylphosphine, and tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphinetetraphenylborate. You may use the above together.

  The polyfunctional oxetane compound may be an oxetane resin having two or more oxetane groups in the molecule. For example, 1,4-bis [{(3-ethyl-3-oxetanyl) methoxy} methyl] benzene (XDO ), Di [1-ethyl (3-oxetanyl)] methyl ether (DOX), 9,9-bis [2-methyl-4- {2- (3-oxetanyl)} butoxyphenyl] fluorene, 9,9-bis Bifunctional oxetane compounds such as [4- [2- {2- (3-oxetanyl)} butoxy] ethoxyphenyl] fluorene, and polyfunctional oxetane compounds such as oxetated novolak resins can be mentioned. These compounds are readily available on the market. Moreover, these may use together 2 or more types. In addition, the oxetane resin which has one oxetane group in a molecule | numerator within the range which does not impair the effect of this invention can also be used together.

  Furthermore, when using a polyfunctional oxetane compound, a hardening | curing agent can be mix | blended. The curing agent is selected from the group consisting of a compound having two or more carboxyl groups in the molecule and a compound having one or more acid anhydride groups in the molecule. As such a compound, conventionally known compounds can be used, and specifically, dibasic acids such as maleic acid, fumaric acid, hexahydrophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, adipic acid, and oxalic acid. , Tribasic acids such as trimellitic acid, tetrabasic acids such as pyromellitic acid, polycarboxylic acids having 5 or more carboxylic acid groups in one molecule, such as polyacrylic acid derivatives, and anhydrides thereof. Although not limited to these, there is no limitation on the type as long as it is a compound having a carboxyl group or a carboxylic anhydride group having reactivity with an oxetane compound.

  When a carboxylic acid anhydride is used, the formulation and composition are determined on the assumption that one acid anhydride group corresponds to two carboxyl groups. It is preferable that two or more carboxyl groups in the curing agent are contained in one molecule, and three or more carboxyl groups are contained in order to improve the crosslinking density. As a combination of these polyfunctional oxetane compounds and a curing agent, in consideration of availability, a combination of a bifunctional oxetane compound and a curing agent having three or more carboxyl groups in one molecule is optimal.

  The blending ratio of the polyfunctional oxetane compound and the curing agent is preferably blended so that the number of carboxyl groups of the curing agent is 1.5 to 2.5 per oxetane ring of the polyfunctional oxetane compound. It is more preferable to mix | blend so that it may become 8-2.2 pieces. When the amount of the carboxyl group is below this range, a dense cross-linked structure cannot be obtained, and the heat resistance of the cured resin product may be reduced. Further, if the amount exceeds this range, unreacted groups are generated, which may adversely affect properties such as the water absorption rate of the resin.

（式中、Ｒ²¹〜Ｒ²³は、アルキル基、アリール基、アラルキル基、アルコキシ基、アリーロキシ基、カルボキシル基、ハロゲン及び水素から選ばれる１価の基であり、互いに同一であっても異なっていてもよい。） In order for the polyfunctional oxetane compound to exhibit excellent rapid curability, it is essential to use a curing catalyst. The curing catalyst is a compound that accelerates the reaction between the polyfunctional oxetane compound and the curing agent, and is selected from a Lewis acid or an organic boron compound represented by the general formula (15). Here, Lewis acid is a compound as defined by GN Lewis, and includes all acids included in this definition. Examples of the organic boron compound represented by the general formula (15) include boron chelate compounds such as diglycerin borate and di (2,3-dihydroxynaphthalene) borate.

(Wherein R ^{21 to} R ²³ are monovalent groups selected from an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, a carboxyl group, halogen and hydrogen, and they may be the same or different from each other. May be.)

  As the diallyl phthalate used as the component (D), any isomer of ortho, meta and para can be used as the component (D).

（式中、ｍは２〜１０の整数であり、Ｒ²⁴及びＲ²⁶は水素又はメチル基を示し、Ｒ²⁵は多価ヒドロキシ基化合物の残基を示す） (D) As a polyfunctional (meth) acryloyl compound used as a component, there exists a compound represented by a following formula.

(In the formula, m is an integer of 2 to 10, R ²⁴ and R ²⁶ represent hydrogen or a methyl group, and R ²⁵ represents a residue of a polyvalent hydroxy group compound)

In the above formula, as the residue R ²⁵ of the polyvalent hydroxy compound, ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hexanediol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, bis (hydroxy Residues of alkane polyols exemplified by methyl) cyclohexane and hydrogenated bisphenol A; Residues of polyether polyols exemplified by diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol polypropylene glycol, etc .; xylene glycol, bisphenol A An aromatic polyol in which a plurality of benzene rings represented by Aromatic polyol residues exemplified by oxide adducts, etc .; residues of benzene polynuclear products obtained by reacting phenol with formaldehyde (usually those having 10 nuclei or less are preferably used); 2 epoxy groups Residues derived from epoxy resins having at least one group; residues derived from polyester resins having two or more hydroxyl groups at the terminals.

Specific examples of the polyfunctional (meth) acryloyl compound include ethylene glycol diacrylate, propylene glycol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, and 1,3-butanediol diacrylate. 1,5-pentanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, glycerol triacrylate, 1,1,1-methylolethane diacrylate, 1,1,1-trimethylolethanetri Acrylate, 1,1,1-trimethylolpropane acrylate, 1,1,1-trimethylolpropane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, sorbitol tetraacrylate, sorbitol hexaacrylate, sorbitol pentaacrylate, 1,4-hexanediol diacrylate, 2,2-bis (acryloxycyclohexane) propane, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene Glycol diacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, bisphenol A-diacrylate, 2,2-bis (4- (2-acryloxyethoxy) phenyl) propane, 2,2-bis (4- (acryloxy- Di- (ethyleneoxy) phenyl)) propane, 2,2-bis (4- (acryloxy-poly- (ethyleneoxy) phenyl)) propane; Polyhydric acrylate of diol resin initial condensate; bisphenol A epoxy resin, novolac epoxy resin, alicyclic epoxy resin, epoxy acrylates obtained by reacting phthalic acid diglycidyl ester, polycarboxylic acid, etc. with acrylic acid Polyester polyesters obtained by reacting a polyester having two or more hydroxyl groups at the end with acrylic acid; those obtained by converting the above acrylates into methacrylates; Examples thereof include those partially substituted with halogen such as dibromomethyl-1,3-propanediol dimethacrylate.
Furthermore, hexahydro-1,3,5-triacryloyl-s-triazine and hexahydro-1,3,5-trimethacryloyl-s-triazine can be mentioned.

（式中、ｎは２〜１０の整数であり、Ｒ²⁷、Ｒ²⁸は水素、ハロゲン又は低級アルキル基を表し、Ｒ²⁹は２〜１０価の芳香族又は脂肪族有機基を示す） As the polyfunctional maleimide, there is one represented by the following formula.

(In the formula, n is an integer of 2 to 10, R ²⁷ and R ²⁸ represent hydrogen, halogen, or a lower alkyl group, and R ²⁹ represents a 2 to 10-valent aromatic or aliphatic organic group)

This polyfunctional maleimide is produced by reacting maleic anhydrides with a polyamine having 2 to 10 amino groups in the molecule to form maleamic acid, and then dehydrating and cyclizing the maleamic acid.
Suitable polyamines include metaphenylenediamine, paraphenylenediamine, metaxylylenediamine, paraxylylenediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, hexahydroxylylenediamine, 4,4-diaminobiphenyl. Bis (4-aminophenyl) methane, bis (4-aminophenyl) ether, bis (4-aminophenyl) sulfone, bis (4-amino-3-methylphenyl) methane, bis (4-aminophenyl) cyclohexane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (4-amino-3-methylphenyl) propane, bis (4-amino-3-chlorophenyl) methane, 2,2-bis (3 5-Dibromo-4-aminophenyl) methane, 3,4-diaminofe -4'-aminophenylmethane, 1,1-bis (4-aminophenyl) -1-phenylethane, melanins having an s-triazine ring, polyamines obtained by reacting aniline and formaldehyde (usually benzene) And those having a nucleus of 10 or less nuclei are preferably used).

（式中、ｐは２〜１０の整数であり、Ｒ³⁰は２〜１０価の芳香族有機基を表し、シアン酸エステル基は有機基Ｒ³⁰の芳香環に直接結合している） As the polyfunctional cyanate ester, there is one represented by the following formula.

(In the formula, p is an integer of 2 to 10, R ³⁰ represents a 2 to 10 valent aromatic organic group, and the cyanate ester group is directly bonded to the aromatic ring of the organic group R ³⁰ )

  Examples of such polyfunctional cyanate esters include 1,3-dicyanate benzene, 1,4-dicyanate benzene, 1,3,5-tricyanate benzene 1,3-dicyanate naphthalene, 1,4- Dicyanate naphthalene, 1,6-dicyanate naphthalene, 1,8-dicyanate naphthalene, 2,6-dicyanate naphthalene, 2,7-dicyanate naphthalene, 1,3,6-tricyanate naphthalene, 4,4- Dicyanate biphenyl, bis (4-cyanatephenyl) methane, 2,2-bis (4-cyanatephenyl) propane, 2,2-bis (3,5-dicyclo-4-cyanatephenyl) propane, 2,2-bis (3,5-dibromo-4-cyanatephenyl) propane, bis (4-cyanatephenyl) ether, bis ( 4-Cyanatephenyl) thioether, bis (4-cyanatephenyl) sulfone, tris (4-cyanatephenyl) phosphite, tris (4-cyanatephenyl) phosphate, and benzene polynuclear obtained by reaction of phenolic resin with cyanogen halide Body polycyanate compounds and the like.

（式中、ｑは２〜１０の整数であり、Ｒ³¹は２〜１０価の芳香族又は脂肪族有機基を示す） As polyfunctional isocyanate, there exists what is represented by a following formula.

(Wherein q is an integer of 2 to 10 and R ³¹ represents a 2 to 10 valent aromatic or aliphatic organic group)

  Examples of such polyfunctional isocyanates include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, metaphenylene diisocyanate, paraphenylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, 4,4-diphenylmethane diisocyanate. , Tolidine diisocyanate, tetramethylxylene diisocyanate, isophorone diisocyanate, cyclohexane-1,4-diisocyanate, lysine isocyanate, triphenylmethane triisocyanate, tris (isocyanatephenyl) thiophosphate, 1,6,11-undecane triisocyanate, 1,8 -Diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylenetriiso Aneto, bicycloheptane triisocyanate, polymethylene polyphenyl isocyanate.

  These polyfunctional isocyanates can also be used after being converted into polyfunctional blocked isocyanates using various blocking agents. Examples of the blocking agent include known ones such as alcohols, phenols, oximes, lactams, malonic esters, acetoacetic esters, acetylacetone, amides, imidazoles, and sulfites.

Examples of the unsaturated polyester include those obtained by reacting glycols with an unsaturated polybasic acid and a saturated polybasic acid, or anhydrides, esters, and acid chlorides thereof, and general ones are used.
Representative examples of glycols include ethylene glycol, propylene glycol, diethylene glycol, diflopyrene glycol, neopentyl glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, hydrogenated bisphenol. A, bisphenol A propylene oxide adduct, dibromoneopentol glycol and the like.

Representative examples of unsaturated polybasic acids include maleic anhydride, fumaric acid, itaconic acid and the like. Representative examples of saturated polybasic acids include phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, adipic acid, sebacic acid, tethic acid, tetrabromo And phthalic anhydride.
For details of the unsaturated polyester, reference is made, for example, to Teiyama Shinichiro, “Polyester Resin Handbook” (Nikkan Kogyo Shimbun, 1988).

When (D) component is mix | blended with the curable resin composition of this invention, as (D) component, only 1 type from the compound group described above can be used, or 2 or more types can be used in combination. In addition, a prepolymer obtained by prereacting these compounds with heat, light or the like in the presence or absence of a known catalyst, initiator, curing agent, etc., which will be described later, is also used as the component (D) of the present invention. Can do.
Among these components (D) used in the curable resin composition of the present invention, vinyl groups are present at both ends from the viewpoint of improving mechanical properties and molding processability of the curable resin composition of the present invention. Polyphenylene ether oligomers having the following are most preferably used. From the viewpoint of improving the adhesiveness between the curable resin composition of the present invention and different materials such as metals, a polyfunctional epoxy compound is most preferable.

  The curable resin composition of this invention can mix | blend a filler as (E) component. The blending amount of the component (E) with respect to the reference amount in the case of blending the component (E) or the sum of the component (A), the component (B), the component (C), the component (D) and the component (E) is 2 to 2. It is preferably 90 wt%, and preferably 5 to 85 wt%. If the amount of component (E) is less than 2 wt%, the degree of improvement in mechanical properties due to the addition of the filler is insufficient, and if it exceeds 90 wt%, the fluidity of the composition is significantly reduced.

  Examples of the filler of component (E) include carbon black, silica, alumina, glass beads, and glass hollow spheres. The shape of the filler is arbitrary and may be powder. The component (B) is not treated as the component (E).

  As described later, the resin composition of the present invention is cured by causing a crosslinking reaction by means of heating or the like, but contains a radical initiator for the purpose of lowering the reaction temperature or promoting the crosslinking reaction of unsaturated groups. You may use it. The amount of the radical initiator used for this purpose is 0.1 to 15 wt%, preferably 0.1 to 10 wt%, based on the sum of the components (A), (C) and (D). Most preferably, it is 0.2-8 wt%. If the amount of the radical initiator is less than 0.1 wt%, it takes a long time to cure and the glass transition temperature of the cured product is lowered, which is not preferable. If it exceeds 15 wt%, the mechanical properties of the cured product are not preferable. Is unfavorable because it decreases.

  Representative examples of radical initiators include benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di (t -Butylperoxy) hexyne-3, di-t-butyl peroxide, t-butylcumyl peroxide, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2 , 5-di (t-butylperoxy) hexane, dicumyl peroxide, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis (t-butylperoxy) butane, 2 , 2-bis (t-butylperoxy) octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di (tri Although there are peroxides such as methylsilyl) peroxide and trimethylsilyltriphenylsilyl peroxide, they are not limited thereto. Although not a peroxide, 2,3-dimethyl-2,3-diphenylbutane can also be used as a radical initiator. However, the initiator used for curing the resin composition is not limited to these examples.

  In addition, polyamine is a suitable curing agent for the polyfunctional maleimide used as the component (D) in the curable resin composition of the present invention, and a mineral acid or Lewis acid is a suitable catalyst for the multifunctional cyanate ester. Salts such as sodium carbonate or lithium chloride, phosphate esters such as tributylphosphine, and other suitable catalysts and curing agents for polyfunctional isocyanates include, for example, Keiji Iwata, “Polyurethane Resin Handbook” (Nikkan Kogyo Shimbun) 1987) 118-123, amines, organometallics, polyhydric alcohols and the like.

  The catalyst, initiator, curing agent and the like are appropriately selected and used according to the type of the crosslinking component. The resin composition of the present invention can be used by blending an amount of additives in a range that does not impair the original properties for the purpose of imparting desired performance depending on the application. Examples of the additive include an antioxidant, a heat stabilizer, an antistatic agent, a plasticizer, a pigment, a dye, and a colorant.

  The curable resin composition of the present invention contains the components (A) and (B) as essential components and the components (C), (D) and (E) as optional components. Such other components can be blended. When it divides roughly, it contains the resin component which consists of (A), (C) and (D) component, and the non-resin component which consists of (B) and (E) component. The preferred blending ratio is as follows. The resin component is 2 to 99.9% by weight, preferably 50 to 97% by weight. The component (A) in the resin component is 5 to 100 wt%, preferably 10 to 50 wt%. The component (C) in the resin component is 0 to 80 wt%, preferably 10 to 70 wt%. (D) component in a resin component is 0-80 wt%, Preferably it is 4-70 wt%. (B) component in a non-resin component is 10-100 wt%, Preferably it is 50-100 wt%.

  In producing the curable resin composition of the present invention, as a method of mixing each component, a solution mixing method in which each component is uniformly dissolved or dispersed in a solvent, or a blending method in which stirring and mixing are performed 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 molded into a desired shape in advance 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 predetermined shape, or a heat melting method in which the resin composition is heated and melted to be molded into a predetermined shape is used.

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

  Moreover, the curable resin composition of this invention can be used together with metal foil (it is the meaning containing a metal plate. The following is the same) similarly to the hardening composite material mentioned later.

  Next, a film obtained from the curable resin composition of the present invention, a curable composite material, a cured product thereof, and a laminate will be described.

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 other components as required may be uniformly mixed in an aromatic or ketone solvent or a mixed solvent thereof. The method of drying after melt | dissolving or disperse | distributing and apply | coating to resin films, such as PET film, etc. are mentioned. The application can be repeated multiple times as necessary. In this case, the application can be repeated using a plurality of solutions having different compositions and concentrations, and finally the desired resin composition and resin amount can be adjusted. It is.

  The curable composite material of the present invention can be obtained by adding a substrate to the curable resin composition in order to increase mechanical strength and increase dimensional stability. In addition, although a base material contains the thing indistinguishable from (E) component, the fiber, paper, and cloth which mainly aim at reinforcement are called a base material.

  Such base materials 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 cloth, wholly aromatic polyamide fiber, wholly aromatic Natural fibers such as woven or non-woven fabrics obtained from liquid crystal fibers such as polyester fibers and polybenzooxozar fibers, woven or non-woven fabrics obtained from synthetic fibers such as polyvinyl alcohol fibers, polyester fibers and acrylic fibers, cotton fabrics, linens and felts. Cloths such as cloth, carbon fiber cloth, kraft paper, cotton paper, natural cellulosic cloth such as paper-glass mixed paper, papers, and the like may be used alone or in combination of two or more.

The proportion of the base material is 5 to 90 wt%, preferably 10 to 80 wt%, more preferably 20 to 70 wt% in the curable composite material. If the base material is less than 5 wt%, the composite material is insufficient in dimensional stability and strength after curing, and if the base material is more than 90 wt%, the dielectric properties of the composite material are inferior.
In the curable composite material of the present invention, a coupling agent can be used for the purpose of improving the adhesiveness at the interface between the resin and the substrate, if necessary. As the coupling agent, general materials such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, 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 in the above-mentioned aromatic or ketone solvent or a mixed solvent thereof. A method of uniformly dissolving or dispersing, impregnating the base material, and then drying is exemplified. Impregnation is performed by dipping or coating. The impregnation can be repeated multiple times as necessary, and at this time, the impregnation can be repeated using a plurality of solutions having different compositions and concentrations, and finally adjusted to a desired resin composition and resin amount. Is possible.

  A cured composite material is obtained by curing the curable composite material of the present invention by a method such as heating. The manufacturing method is not particularly limited. For example, a plurality of curable composite materials are stacked, and each layer is bonded under heat and pressure, and at the same time, thermosetting is performed to obtain a cured composite material having a desired thickness. it can. It is also possible to obtain a cured composite material having a new layer structure by combining a cured composite material once cured with adhesive and a 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.

Molding and curing are performed at a temperature of 80 to 300 ° C., a pressure of 0.1 to 1000 kg / cm ² , a time of 1 minute to 10 hours, and more preferably a temperature of 150 to 250 ° C. and a pressure of 1 to 500 kg / cm. ² , Time: 1 minute to 5 hours.

  The laminate of the present invention comprises a layer of the cured composite material of the present invention and a metal foil layer. Examples of the metal foil used here include a copper foil and an aluminum foil. The thickness is not particularly limited, but is in the range of 3 to 200 μm, more preferably 3 to 105 μm.

  As a method for producing the laminate of the present invention, for example, the curable composite composition of the present invention described above and a curable composite material obtained from a substrate, and a metal foil are laminated in a layer configuration according to the purpose, An example is a method in which the respective layers are bonded under heat and pressure, and at the same time, thermally cured. In the laminate of the curable resin composition of the present invention, the cured composite material and the metal foil are laminated in an arbitrary layer configuration. The metal foil can be used as a surface layer or an intermediate layer. In addition to the above, it is possible to make a multilayer by repeating lamination and curing a plurality of times.

  An adhesive can also be used for adhesion to the metal foil. Examples of the adhesive include, but are not limited to, epoxy, acrylic, phenol, and cyanoacrylate. The above lamination molding and curing can be performed under the same conditions as in the production of the cured composite material of the present invention.

  The metal foil with resin of the present invention is composed 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 in the range of 3 to 200 μm, more preferably 5 to 105 μm.

  The method for producing the resin-coated metal foil of the present invention is not particularly limited. For example, the curable resin composition and other components as necessary in an aromatic or ketone solvent or a mixed solvent thereof. A method of uniformly dissolving or dispersing in, applying to a metal foil, and drying. The application can be repeated a plurality of times as necessary. At this time, the application can be repeated using a plurality of solutions having different compositions and concentrations, and finally adjusted to a desired resin composition and resin amount. Is possible.

  The curable resin composition of the present invention has molding processability derived from excellent curability, and exhibits excellent chemical resistance, dielectric properties, low water absorption, heat resistance, flame resistance, and mechanical properties after curing. Therefore, it can be used for dielectric materials, insulating materials, heat-resistant materials, structural materials, packaging materials, adhesive materials and the like in the fields of the electric industry, space / aircraft industry, 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.

  EXAMPLES Next, the present invention will be described with reference to examples, but the present invention is not limited thereto. In addition, all the parts in each example are parts by weight. In addition, the measurement results in the examples are those obtained by sample preparation and measurement by the following methods.

1) Molecular weight and molecular weight distribution of polymer GPC (manufactured by Tosoh Corporation, HLC-8120GPC) was used for measuring the molecular weight and molecular weight distribution of the soluble polyfunctional vinyl aromatic copolymer, solvent: tetrahydrofuran (THF), flow rate: 1.0 ml / min, column temperature: 40 ° C. The molecular weight of the copolymer was measured as a molecular weight in terms of polystyrene using a calibration curve with monodisperse polystyrene.
2) Polymer structure It was determined by ¹³ C-NMR and ¹ H-NMR analysis using a JNM-LA600 type nuclear magnetic resonance spectrometer manufactured by JEOL. Chloroform-d ₁ was used as a solvent. The resonance line of chloroform-d ₁ which is an NMR measurement solvent was used as an internal standard.

3) Measurement of glass transition temperature (Tg) and softening temperature Measurement of Tg and softening temperature of the cured film obtained by hot press molding is performed by setting the sample film in a TMA (thermomechanical analyzer) measuring device and using a nitrogen stream. The measurement was carried out by scanning from 30 ° C. to 360 ° C. at a rate of temperature increase of 10 ° C./min. The Tg was determined from the inflection point where the linear expansion coefficient changed, and the softening temperature was determined by the tangential method.
4) Tensile strength and elongation rate Tensile strength and elongation rate were measured using a tensile test apparatus. The elongation was measured from a tensile test chart.
5) Copper foil peel strength A test piece having a width of 20 mm and a length of 100 mm was cut out from the laminate, and a parallel cut having a width of 10 mm was made on the copper foil surface, and then 50 mm / min in a direction of 180 ° with respect to the surface. The copper foil was peeled off continuously at a speed of 5 mm, and the stress at that time was measured with a tensile tester to show the minimum value of the stress (according to JIS C 6481).
6) Dielectric constant and dielectric loss tangent As for the dielectric constant and dielectric loss tangent, a value of 2 GHz was observed by a cavity resonance method (manufactured by Agilent Technologies, 8722ES network analyzer, cavity resonator manufactured by Kanto Electronics Application Development).
7) Formability An uncured film of a curable resin composition is laminated on a blackened copper-clad laminate, and vacuum is applied at a temperature of 110 ° C. and a press pressure of 0.1 MPa using a vacuum laminator. Lamination was performed, and evaluation was performed based on the adhesion state between the blackened copper foil and the film. Evaluation was evaluated as “◯” when the adhesion state of the blackened copper foil and the film was good, and “x” when the blackened copper foil and the film could be easily peeled off. .

Synthesis example 1
0.481 mol (68.4 ml) of divinylbenzene, 0.0362 mol (5.16 ml) of ethylvinylbenzene, 63 ml of a dichloroethane solution (concentration: 0.634 mmol / ml) of 1-chloroethylbenzene (40 mmol), n-tetrabutyl 11 ml of dichloroethane solution (concentration: 0.135 mmol / ml) of ammonium bromide (1.5 mmol) and 500 ml of dichloroethane (dielectric constant: 10.3) were put into a 1000 ml flask, and 1.5 mmol of SnCl at 70 ° C. 1.5 ml of ₄ dichloroethane solution (concentration: 0.068 mmol / ml) was added and reacted for 1 hour. After the polymerization reaction was stopped with a small amount of methanol bubbled with nitrogen, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a polymer. The obtained polymer was washed with methanol, filtered, dried and weighed to obtain 54.6 g of copolymer A (yield: 49.8 wt%). The polymerization activity was 49.8 (g polymer / mmolSn · hr).

Mw of the obtained copolymer A was 4180, Mn was 2560, and Mw / Mn was 1.6. ^{According to 13} C-NMR and ¹ H-NMR analysis, the copolymer A contained 52 mol% of structural units derived from divinylbenzene and 48 mol% of structural units derived from ethylvinylbenzene. Further, it was found that the copolymer A has an indane structure. The indane structure was present at 7.5 mol% with respect to all monomer structural units. Furthermore, the molar fraction of the structural unit represented by the general formula (a1) in the total amount of the structural units represented by the general formulas (a1) and (a2) was 0.99. As a result of TMA measurement, Tg was 287 ° C. and softening temperature was 300 ° C. or higher. As a result of TGA measurement, the thermal decomposition temperature was 413 ° C. and the carbonization yield was 26%. Furthermore, ionic metal content was measured, sodium ion was 1 ppm or less, and chlorine ion was 3.2 ppm.
Copolymer A was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was formed. The cast film of copolymer A was a transparent film without fogging.

Synthesis example 2
Divinylbenzene 0.481 mol (68 ml), ethylvinylbenzene 0.362 mol (52 ml), 1-chloroethylbenzene (30 mmol) in dichloroethane (concentration: 0.634 mmol / ml) 47 ml, n-tetrabutylammonium chloride ( 2.25 mmol) dichloroethane solution (concentration: 0.035 mmol / ml) 65 ml and dichloroethane (dielectric constant: 10.3) 500 ml were put into a 1000 ml flask, and 1.5 mmol SnCl ₄ dichloroethane solution at 70 ° C. (Concentration: 0.068 mmol / ml) 22 ml was added and reacted for 1 hour. After the polymerization reaction was stopped with a small amount of methanol bubbled with nitrogen, the reaction mixture was poured into a large amount of methanol at room temperature to precipitate a polymer. The obtained polymer was washed with methanol, filtered, dried and weighed to obtain 67.4 g of copolymer B (yield: 61.4 wt%). The polymerization activity was 44.9 (g polymer / mmolSn · hr).

Mw of the obtained copolymer B was 7670, Mn was 3680, and Mw / Mn was 2.1. ^{According to 13} C-NMR and ¹ H-NMR analysis, the copolymer B contained 51 mol% of structural units derived from divinylbenzene and 49 mol% of structural units derived from ethylvinylbenzene. Further, it was found that the indane structure exists in the copolymer A. The indane structure was present at 7.5 mol% with respect to all monomer structural units. Furthermore, the molar fraction of the structural unit represented by the general formula (a1) in the total amount of the structural units represented by the general formulas (a1) and (a2) was 0.99. As a result of TMA measurement, Tg was 291 ° C. and softening temperature was 300 ° C. or higher. As a result of TGA measurement, the thermal decomposition temperature was 417 ° C. and the carbonization yield was 28%. Furthermore, ionic metal content was measured, sodium ion was 1 ppm or less, and chlorine ion was 4.8 ppm.
Copolymer B was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was formed. Further, the cast film of the copolymer B was a transparent film without fogging.

Abbreviations of components used in the following examples are shown below.
PPE: Polyphenylene ether with intrinsic viscosity of 0.45 (Mitsubishi Gas Chemical Co., Ltd.)
OPE-2St-1: Polyphenylene oligomer having vinyl groups at both ends (Mn = 1160, manufactured by Mitsubishi Gas Chemical Co., Inc., 2,2 ', 3,3', 5,5'-hexamethylbiphenyl-4,4 Reaction product of '-diol, 2,6-dimethylphenol polycondensate and chloromethylstyrene)
OPE-2St-2: Polyphenylene oligomer having vinyl groups at both ends (Mn = 2270, manufactured by Mitsubishi Gas Chemical Co., Inc., 2,2 ′, 3,3 ′, 5,5′-hexamethylbiphenyl-4,4 Reaction product of '-diol, 2,6-dimethylphenol polycondensate and chloromethylstyrene)
OPE-2St-3: Polyphenylene oligomer having vinyl groups at both ends (Mn = 3560, manufactured by Mitsubishi Gas Chemical Co., Inc., 2,2 ', 3,3', 5,5'-hexamethylbiphenyl-4,4 Reaction product of '-diol, 2,6-dimethylphenol polycondensate and chloromethylstyrene)
Reaction initiator P-1: 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (manufactured by NOF Corporation, trade name: Perhexa 25B)
Thermoplastic resin T-1: hydrogenated styrene butadiene block copolymer (Asahi Kasei Kogyo Co., Ltd., trade name: Tuftec H1041)
Thermoplastic resin T-2: hydrogenated styrene butadiene block copolymer (manufactured by Kraton Polymer Japan Co., Ltd., trade name: KRATON G1652)
Thermoplastic resin T-3: hydrogenated styrene butadiene block copolymer (manufactured by Kraton Polymer Japan Co., Ltd., trade name: KRATON G1726)
Thermoplastic resin T-4: Styrene butadiene block copolymer (Asahi Kasei Kogyo Co., Ltd., trade name: TUFPRENE 315P)

熱硬化性樹脂Ｅ−３：下記構造式で示されるエポキシ樹脂（東都化成（株）製、商品名：ＹＤ−８１７０）

熱硬化性樹脂Ｅ−４：下記構造式で示されるエポキシ樹脂（東都化成（株）製、商品名：ＺＸ−１６５８）

熱硬化性樹脂Ｅ−５：トリアリルイソシアヌレート（東亜合成（株）製、商品名：アロニックスＭ−３１５）
球状シリカＳ平均粒径：０．５μｍ（（株）アドマテックス製、商品名：アドマファインＳＯ−Ｃ２）
炭酸カルシウム−１：平均粒子径５０μｍの炭酸カルシウム Thermosetting resin E-1: Liquid bisphenol A type epoxy resin (Japan Epoxy Resin, Epicoat 828)
Thermosetting resin E-2: Epoxy resin represented by the following structural formula (manufactured by Nippon Kayaku Co., Ltd., trade name: EOCN-1020)

Thermosetting resin E-3: Epoxy resin represented by the following structural formula (manufactured by Toto Kasei Co., Ltd., trade name: YD-8170)

Thermosetting resin E-4: Epoxy resin represented by the following structural formula (manufactured by Toto Kasei Co., Ltd., trade name: ZX-1658)

Thermosetting resin E-5: triallyl isocyanurate (manufactured by Toa Gosei Co., Ltd., trade name: Aronix M-315)
Spherical silica S average particle size: 0.5 μm (manufactured by Admatechs, trade name: Admafine SO-C2)
Calcium carbonate-1: Calcium carbonate having an average particle size of 50 μm

Copolymer A obtained by the above synthesis example, and amounts shown in Table 1 for PPE, OPE-2St-1, reaction initiator P-1, thermoplastic resin T-1, and thermosetting resin E-1 And toluene as a solvent were mixed, and after stirring, a reaction initiator P-1 was added to prepare a thermosetting resin composition solution.
A thermosetting resin composition solution was cast on a table on which a polyethylene terephthalate resin (PET) sheet was attached to obtain a film. The obtained film had a thickness of about 50 to 60 μm, had no stickiness, and was excellent in film formability. This film was dried and dried in an air oven at 80 ° C. for 10 minutes and then thermally cured at 180 ° C. for 1 hour in a vacuum press molding machine to obtain a cured product film of about 50 μm.
The cured film was measured for tensile strength, elongation, dielectric constant, and dielectric loss tangent.

Copolymers A and B obtained by the above synthesis examples, synthetic hectorite-1 (manufactured by Co-op Chemical Co., Lucentite STN) treated with trioctylmethylammonium salt as a layered silicate, heat Plastic resin T-1, liquid bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin, Epicoat 828) E-1 as a thermosetting resin, and PPE as another thermoplastic resin, the amounts and solvents shown in Table 1 As a mixture, toluene was added, and after stirring, a reaction initiator P-1 was added to prepare a thermosetting resin composition solution.
The obtained thermosetting resin composition solution is cast on a PET sheet to form a film of about 15 μm, and the cast surface is laminated with a PET sheet and cured in an air oven at 180 ° C. A film was obtained.
The cured film was measured for tensile strength, elongation, dielectric constant, and dielectric loss tangent.

Here, using a layered silicate average interlayer distance X-ray diffractometer (RINT1100, manufactured by Rigaku Corporation), a diffraction peak obtained from diffraction of the layered surface of the layered silicate in a 2 mm-thick plate-shaped body is obtained. 2θ was measured, the (001) plane distance d of the layered silicate was calculated by the black diffraction formula of the following formula (16), and the obtained d was defined as the average interlayer distance (nm).
λ = 2 dsin θ (16)
In formula (16), λ is 1.54, and θ represents a diffraction angle.

Further, a layered silicate laminate in which a plate-like molded body having a thickness of 100 μm dispersed as a laminate of 5 layers or less is observed with a transmission electron microscope at a magnification of 100,000 times and observed in a fixed area. The total number of layers X and the number Y of layered silicates dispersed in 5 layers or less are measured, and the ratio P (% of the layered silicate dispersed as a laminate of 5 layers or less according to the following formula (17) ) Was calculated.
P (%) = (Y / X) × 100 (17)
The tensile strength, elongation, dielectric constant, and dielectric loss tangent of this cured film were also measured. The results are shown in Table 1.

Comparative Example Copolymer A, synthetic hectorite-1, and PPE, reaction initiator P-1, thermoplastic resin T-1, thermosetting resin E-1 and average particle diameter of 50 μm obtained by the above synthesis example Evaluation of the thermosetting resin composition in the same manner as in Example 1 except that a film of about 15 μm was prepared by casting a thermosetting resin composition solution using calcium carbonate-1 on a PET sheet. Went. The results are shown in Table 2.

  As a layered silicate, swellable fluorine mica-1 (Somacif MAE-100, manufactured by Corp Chemical Co., Ltd.) treated with distearyldimethyl quaternary ammonium salt and organically treated with distearyldimethyl quaternary ammonium salt. Using the applied natural montmorillonite-1 (manufactured by Toyoshiro Yoko Co., Ltd., New S-Ben D), a thermosetting resin composition solution was cast on a polyethylene terephthalate resin (PET) sheet, and the resulting film (about 50- 60 μm thickness) was dried and dried in an air oven at 80 ° C. for 10 minutes and then thermally cured at 180 ° C. for 1 hour in a vacuum press molding machine to obtain a cured product film of about 50 μm. The thermosetting resin composition was evaluated. The results are shown in Table 3.

The thermosetting resin composition solution obtained in Experiment No. 2 of Example 1 was impregnated by dipping glass cloth (E glass, basis weight 71 g / m ² ) and dried in an air oven at 50 ° C. for 30 minutes. It was. The resin content (RC) of the obtained prepreg was 69%.
Using this prepreg, when a core material having a thickness of 0.8 mm in which through holes having a diameter of 0.35 mm were arranged at a pitch of 5 mm was laminated, the number of through holes not filled with resin was 0 out of 4500 holes. .
A plurality of the above curable composite materials are stacked as necessary so that the thickness after molding is about 0.6 mm to 1.0 mm, and a copper foil having a thickness of 35 μm is placed on both sides thereof by a press molding machine. Molded and cured to obtain a laminate. The curing condition of each example was to raise the temperature at 3 ° C./min and hold at 180 ° C. for 90 minutes. The pressure was 30 kg / cm ^{2 in} all cases.

Various physical properties of the laminate thus obtained were measured by the following methods.
1) Trichlorethylene resistance: The laminate from which the copper foil had been removed was cut into 25 mm squares, boiled in trichlorethylene for 5 minutes, and the change in appearance was visually observed (based on JIS C6481).
2) Solder heat resistance: The laminate from which the copper foil had been removed was cut into 25 mm squares, floated in a 260 ° C. solder bath for 120 seconds, and the change in appearance was visually observed (conforms to JIS C6481).
In the trichlorethylene resistance test, no change was observed in the appearance of the laminate. The Tg of the laminate was 212 ° C. In the solder heat resistance test, no change was observed in the appearance of the laminate. The dielectric constant was 2.61, and the dielectric loss tangent was 0.0042.

  Heat was produced in the same manner as in Example 2 except that the copolymer B, the thermoplastic resins T-2 to T-3, and the thermosetting resins E-2 to E-3 obtained by the synthesis example were used. The curable resin composition was evaluated. The results are shown in Table 4.

  Thermosetting in the same manner as in Example 2 except that OPE-2St-2 to 3, obtained from the synthesis example, thermoplastic resin T-4, and thermosetting resins E-4 to E-5 were used. Of the functional resin composition. The results are shown in Table 5.

Claims (14)

(A) component: a polyfunctional vinyl aromatic copolymer having a structural unit derived from a monomer comprising a divinyl aromatic compound (a) and an ethyl vinyl aromatic compound (b), the divinyl aromatic compound (a) Containing 20 mol% or more of a repeating unit derived from the formula (a1) and (a2)

(Wherein R ¹ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms, and R ² represents an aromatic hydrocarbon group having 6 to 30 carbon atoms) (a) Gel Permeation Chromatography of Polyfunctional Vinyl Aromatic Copolymers with Molar Fraction of Structural Units Containing Vinyl Group Derived from (a1) / [(a1) + (a2)] ≧ 0.5 The number average molecular weight (Mn) in terms of polystyrene measured by (GPC) is 600 to 30,000, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 20.0 or less. A solvent-soluble polyfunctional vinyl aromatic copolymer,
(B) component: layered silicate,
The blending amount of the component (A) with respect to the sum of the components (A) and (B) is 2 to 99.9 wt%, and the blending amount of the component (B) is 0.1. A curable resin composition characterized by being -98 wt%. In the main chain skeleton of the polyfunctional vinyl aromatic copolymer in which the component (A) has a structural unit derived from a monomer composed of a divinyl aromatic compound (a) and an ethyl vinyl aromatic compound (b), the following general formula ( 1)

(Wherein Q represents a saturated or unsaturated aliphatic hydrocarbon group, an aromatic hydrocarbon group or an aromatic ring or a substituted aromatic ring condensed with a benzene ring, and n is an integer of 0 to 4). The curable resin composition according to claim 1, which is a polyfunctional vinyl aromatic copolymer having an indane structure represented.   (A) In the polyfunctional vinyl aromatic copolymer in which the component has a structural unit derived from a monomer comprising the divinyl aromatic compound (a) and the ethyl vinyl aromatic compound (b), other than the ethyl vinyl aromatic compound (b) The curable resin composition according to claim 1 or 2, which is a polyfunctional vinyl aromatic copolymer containing a structural unit derived from the monovinyl aromatic compound (c).   Furthermore, it is a curable resin composition containing a thermoplastic resin as the component (C), and the blending amount of the component (C) with respect to the sum of the components (A), (B) and (C) is 1 to 80 wt. The curable resin composition according to any one of claims 1 to 3.   The curable resin according to claim 4, wherein the component (C) is one or more thermoplastic resins selected from the group consisting of a block copolymer having a polymer segment with a glass transition temperature of 20 ° C or lower and a polyphenylene ether. Composition.   Furthermore, it is a curable resin composition containing a thermosetting resin as the component (D), the component (D) with respect to the sum of the components (A), (B), (C) and (D). The curable resin composition according to any one of claims 1 to 5, wherein the blending amount is 1 to 80 wt%.   The component (D) is at least one thermosetting resin selected from the group consisting of a thermosetting polyphenylene ether, a polyphenylene ether oligomer having functional groups at both ends, and a polyfunctional epoxy compound. Curable resin composition.   Furthermore, it is a curable resin composition containing a filler as the component (E), and is based on the sum of the components (A), (B), (C), (D) and (E) (E The curable resin composition according to claim 1, wherein the compounding amount of the component is 2 to 90 wt%.   The curable resin composition according to any one of claims 1 to 8, wherein the component (B) is a swellable layered silicate having an affinity for an organic solvent.   A film obtained by forming the curable resin composition according to claim 1 into a film shape.   A curable composite material comprising the curable resin composition according to any one of claims 1 to 9 and a base material, wherein the base material is contained at a ratio of 5 to 90 wt%. .   A cured composite material obtained by curing the curable composite material according to claim 11.   A laminate comprising a layer of the curable composite material according to claim 11 and a metal foil layer. A metal foil with resin, comprising a resin layer formed from the curable resin composition according to claim 1 on one side of the metal foil.