JP2006089683A - Flame retardant resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame retardant resin composition which is free from antimony compounds and yet has high flame retardance, heat resistance, thermal shock resistance and reliability and a low dielectric property. <P>SOLUTION: The resin composition contains component (A): one or more thermoplastic resins selected from the group consisting of aromatic vinyl-based resins and polyphenylene ether-based resins as component (A-1) and/or a thermosetting resin having an aromatic structure as component (A-2), component (B): a halogenic flame retardant and component (C) at least one kind of layered silicate selected from the group consisting of montmorillonite, swelling mica and hectorite. The mixing ratios of component (A), (B) and (C) to the total of component (A), (B) and (C) are 4-99.8, 0.1-95.9 and 0.1-95.9 wt% respectively. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an aromatic vinyl resin, a polyphenylene ether resin, or a thermosetting resin having an aromatic structure that exhibits high flame retardancy and heat resistance without containing an antimony compound such as antimony trioxide. The present invention relates to a flame retardant resin composition obtained by blending a flame retardant and a layered silicate. From this flame retardant resin composition, a flame retardant resin cured product, a flame retardant film, a flame retardant composite material, a flame retardant cured composite material, a flame retardant laminate and a metal foil with a flame retardant resin are obtained. It is done.

  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. And one or more thermoplastic resins selected from the group consisting of aromatic vinyl resins, polyphenylene ether resins and polyphenylene ether resins with functional groups modified, and / or thermosetting resins having an aromatic structure, and When flame-retarding a resin composition comprising a precursor, a halogen-based flame retardant and antimony trioxide are generally blended in order to achieve V-0 of UL-94, which is a flame retardant standard. There are many cases. This combination of the halogen-based flame retardant and antimony trioxide has a large radical trap and air blocking effect in the gas phase, and as a result, a high flame retardant effect can be obtained.

However, since antimony trioxide is a toxic substance itself and has powder toxicity, it is preferable that antimony trioxide is not included in the resin composition in consideration of the influence on the human body and the environment. In response to such demands, as a substitute for flame retardant formulations using antimony trioxide, conventionally metal hydroxides such as Al (OH) ₃ and Mg (OH) ₂ , phosphorus such as red phosphorus and phosphate esters Studies on flame retardants have been made. However, when metal hydroxides such as Al (OH) ₃ and Mg (OH) ₂ are used, these metal hydroxides must be blended in large quantities due to low flame retardancy. In other words, it cannot be used as a material in a field where mechanical properties are remarkably deteriorated and high toughness is required. In addition, since the heat resistance is insufficient, there is a problem that defects such as poor appearance and blistering occur when the processing temperature is high. The method using red phosphorus has a problem in moisture resistance, and various surface coating methods for red phosphorus particles have been studied. However, the stability of the surface coating remains uneasy and satisfies the reliability as a substrate material. However, it is currently not in practical use. In addition, the incorporation of phosphate esters causes a significant decrease in heat resistance, and cannot be used as a material in fields requiring high heat resistance. Electronic devices such as portable terminal devices, computers and displays, etc. It was not satisfactory as a material used in advanced technology fields such as equipment.

  Further, in such advanced technology fields, the environmental characteristics required more than ever are becoming stricter. For example, in the field of electronic parts for automobiles, electronic control and system modularization are being studied, and improvement in high heat resistance and thermal shock resistance is required. In the communication field, in information communication technologies such as cellular phones, with the increase in the 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. .

  Thermosetting polyphenylene ether has attracted attention in recent years as a new material that solves the demand for low dielectric loss tangent to circuit boards, especially the insulating layers adjacent to the metal that forms the circuit, as the frequency of electronic devices increases. Copper-clad laminates, etc. Application to is being 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, in the conventional technology for thermosetting polyphenylene ethers that are used by introducing a crosslinkable functional group into the chain of the conventional polyphenylene ether and further curing it, the flame retardancy and mechanical properties and curing in thinning are achieved. So far, no satisfactory solution has been obtained in terms of both compatibility and / or moldability.

JP-A-7-166049 JP 2003-82185 A JP 2003-26915 A

  Specifically, Patent Document 1 discloses (a) a reaction product of polyphenylene ether and unsaturated carboxylic acid or acid anhydride, (b) triallyl cyanurate and / or triallyl isocyanurate, (c). A curable resin composition comprising a brominated aromatic compound containing at least one imide ring is disclosed. In the detailed description of Patent Document 1, it is described that an antimony oxide compound can be added as the component (d) in order to further improve the flame retardancy. Accordingly, since the curable resin composition disclosed in this example does not have sufficient flame retardancy, even in a molded product having a thickness of 1 mm, in addition to the halogen-based flame retardant, a flame retardant aid is obtained over a wide composition range. It was necessary to add antimony trioxide as an agent, which was a concern for safety. Further, the curable resin composition containing no antimony trioxide disclosed in this example further lacks the flame retardancy, so that a thick molded article of 1 mm exhibits V-0 flame retardancy. However, in a thin film of 25 to 75 μm, a large amount of a halogen-based flame retardant has to be added, resulting in a decrease in mechanical properties.

  Further, in Patent Document 1, the curable resin composition may be used by blending an amount of fillers and additives in a range that does not impair the original properties for the purpose of imparting desired performance depending on the application. It is described that the filler may be fibrous or powdery, and silica, alumina, talc, mica, glass beads, glass hollow spheres and the like can be blended. However, it has not been described that a specific layered silicate which is at least one selected from the group consisting of montmorillonite, swellable mica, and hectorite is used. Further, there is no description as to whether or not the filler described therein has an effect as a flame retardant aid, and a combination of a specific resin, a specific layered silicate and a specific halogenated flame retardant. However, there has been no description or suggestion of a specific high synergistic effect in flame retardancy, appearance and mechanical properties. Moreover, since the softening temperature of the reaction product of polyphenylene ether and unsaturated carboxylic acid or acid anhydride is higher than the normal 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.

  Patent Document 2 discloses a styrene-based polymer comprising (A) a styrene-based (co) polymer having a syndiotactic structure, (B) a layered compound, and (C) a polyphenylene ether-based polymer modified with at least one functional group. A polymer is disclosed. Patent Document 2 describes that a styrene monomer containing halogen can be used as a monomer component of a styrene (co) polymer having a syndiotactic structure. However, the purpose of adding the layered compound was to improve rigidity and heat resistance. There is no specific description about the effect of using a styrene monomer containing halogen as the monomer component of a styrene (co) polymer having a syndiotactic structure, and also in the examples There is no description regarding the use of a styrene (co) polymer having a syndiotactic structure using a halogen-containing styrene monomer. Since a styrenic (co) polymer having a syndiotactic structure is poorly soluble in a solvent and partially soluble, when a film is formed from a varnish, the swollen syndiotactic structure The styrenic (co) polymer having a significant reduction in the appearance of the film, or the solvent in the swollen styrenic (co) polymer having a syndiotactic structure significantly reduces the flame retardancy. . In addition, since the styrene-based (co) polymer having a syndiotactic structure has poor compatibility with other resins, there are problems such as a decrease in tensile breaking elongation and impact strength after blending even in the melting process. Had. Therefore, there is no description that the combination of a specific resin, a specific layered silicate and a specific halogenated flame retardant expresses a particularly high synergistic effect in flame retardancy, appearance and mechanical properties, There can be no suggestion.

  Patent Document 3 discloses a flame retardant thermoplastic comprising (a) a polyphenylene ether resin or a mixture of a polyphenylene ether resin and a polystyrene resin, (b) a layered silicate, and (c) a non-halogen flame retardant. A resin composition is disclosed. The flame retardant thermoplastic resin composition disclosed in Patent Document 3 is characterized by not using a halogen flame retardant and a phosphorus flame retardant. This is because the allowable content of halogen-containing compounds is, for example, the blue label of Germany, which is an eco label, or the eco label of Japan, a compound containing bromine or chlorine cannot be used in a molded product of 25 g or more. Only the fluororesin used as is defined as 0.5% by weight or less. In TCO'01, the halogen compound is defined as 0.05% or less. Therefore, since Patent Document 3 is characterized by the non-halogen flame retardant technology, even if it contains a compound or resin containing a halogen element, its content is generally considered as a range of non-halogen flame retardant materials. It is reasonable to consider that the value is within the standard value at the eco level. In the detailed description, it is described that the alicyclic hydrocarbon-based resin in the specific examples of the thermoplastic resin may contain a halogen atom as a substituent. However, such a small amount of halogen atom present as a substituent of the alicyclic alicyclic hydrocarbon resin has a low flame retardant effect, and there is a problem that a synergistic effect is not exhibited with a specific layered silicate. It was. Therefore, there is no description that the combination of a specific resin, a specific layered silicate and a specific halogenated flame retardant expresses a particularly high synergistic effect in flame retardancy, appearance and mechanical properties, There can be no suggestion.

  The present invention has been made in view of the above circumstances, and does not contain a substantial amount of antimony compound such as antimony trioxide, which is concerned about toxicity, and has flame retardancy, high heat resistance, thermal shock resistance, low dielectric property, reliability. Flame retardant resin composition having excellent properties, a cured product obtained by curing the composition, a film formed from the resin composition, and the present invention further comprises a curable composite material comprising the resin composition and a substrate. An object of the present invention is to provide a cured body, a laminate composed of a curable composite material and a metal foil, and a copper foil with a resin. In addition, the present invention combines a specific halogen-based flame retardant and a specific layered silicate with a specific aromatic resin, so that a high degree of flame retardancy and good appearance can be obtained even in a thin molded product or a cured product. Exhibits molding processability, curing properties, dielectric properties, heat resistance, and heat hydrolysis properties, and is used in advanced technology fields such as the electronics industry, space and aircraft industries, and dielectric materials, insulating materials, heat resistant materials, packaging materials for thin molded products, Flame retardant resin composition, flame retardant resin cured product, flame retardant film, flame retardant composite material, flame retardant cured composite material, flame retardant laminate, which can be used for adhesive materials, housing materials, etc. It aims at providing metal foil with a flame-retardant resin.

The present invention comprises (A) component: one or more thermoplastic resins selected from the group consisting of aromatic vinyl resins and polyphenylene ether resins as component (A-1), and / or component (A-2). A thermosetting resin having an aromatic structure,
(B) component: halogen flame retardant,
(C) Component: Layered silicate which is at least one selected from the group consisting of montmorillonite, swellable mica, and hectorite,
(B) component halogen flame retardant is decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, ethane-1,2-bis (pentabromophenyl), bis ( 2,4,6-tribromophenoxy) ethane, ethylenebistetrabromophthalimide, polydibromophenylene oxide, tetrabromobisphenol-S, 1,1-sulfonyl [3,5-dibromo-4- (2,3-dibromopropoxy) )] Benzene, tris (2,3-dibromopropyl-1) isocyanurate, tris (tribromophenyl) cyanurate, atactic brominated polystyrene, atactic brominated styrene-methyl methacrylate copolymer, atactic bromine Styrene-methyl methacrylate-glycidyl methacrylate copolymer, atactic brominated styrene-glycidyl methacrylate copolymer, atactic brominated styrene-polypropylene copolymer, brominated polyethylene, tetrabromobisphenol-A, tetra Bromobisphenol-A-epoxy oligomers, brominated epoxy compounds (for example, diepoxy compounds produced by the reaction of brominated bisphenol A and epichlorohydrin, and epoxy compounds obtained by the reaction of brominated phenols with epichlorohydrin), tetrabromobisphenol- A-carbonate oligomer, tetrabromobisphenol-A-bis (2-hydroxydiethyl ether), tetrabromobisphenol-A-bis (2 3-dibromopropyl ether), poly (pentabromobenzyl acrylate), and one or more halogen-based flame retardants selected from the group consisting of octabromotrimethylphenylindane, comprising (A) component, (B) component, and ( C) The amount of component (A) is 4-99.8 wt%, the amount of component (B) is 0.1-95.9 wt%, and the amount of component (C) is 0.1 It is a flame retardant resin composition characterized by being 95.9 wt%.

（式中、Ｒ¹は炭素数６〜３０の芳香族炭化水素基を示し、Ｒ²は炭素数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マトグラフィー（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、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芳香族エポキシ化合物からなる群から選ばれる１種以上の芳香族構造を含有する熱硬化性樹脂であること。
４） (A-2)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の主鎖骨格中に下記一般式（１）

（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多官能ビニル芳香族共重合体であること。 Here, the curable resin composition satisfying one or more of the following requirements 1) to 13) gives a better curable resin composition.
1) (A-1) component is a monomer homopolymer or copolymer containing 20 to 100 mol% of a monovinyl aromatic compound, and an aromatic structure-containing block copolymer having a polymer segment having a glass transition temperature of 20 ° C. or lower. And at least one thermoplastic resin selected from the group consisting of polyphenylene ether resins whose functional groups may be modified.
2) Thermosetting in which component (A-2) contains one or more functional groups selected from the group consisting of vinyl group, ethynyl group, epoxy group, oxetane group, cyanate group, isocyanate group and hydroxyl group and an aromatic structure Must be a functional resin.
3) A polyfunctional vinyl aromatic copolymer having a structural unit derived from a monomer in which the component (A-2) is composed of a divinyl aromatic compound (a) and an ethyl vinyl aromatic compound (b), It contains 20 mol% or more of repeating units derived from the compound (a) and has the following formulas (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 a polyfunctional vinyl aromatic copolymer in which the molar fraction of the structural unit containing a vinyl group derived from satisfies (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. One or more aromatic structures selected from the group consisting of a solvent-soluble polyfunctional vinyl aromatic copolymer, a thermosetting polyphenylene ether, a polyphenylene ether oligomer having functional groups at both ends, and a polyfunctional aromatic epoxy compound. Contains thermosetting It is fat.
4) In the main chain skeleton of the polyfunctional vinyl aromatic copolymer, the component (A-2) has a structural unit derived from a monomer comprising the divinyl aromatic compound (a) and the 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). It is a polyfunctional vinyl aromatic copolymer having an indane structure represented.

5) In the polyfunctional vinyl aromatic copolymer in which the component (A-2) 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 It is a polyfunctional vinyl aromatic copolymer containing a structural unit derived from the monovinyl aromatic compound (c) other than (b).
6) The halogen flame retardant of component (B) is decabromodiphenyl oxide, ethane-1,2-bis (pentabromophenyl), bis (2,4,6-tribromophenoxy) ethane, ethylene bistetrabromophthalimide, Polydibromophenylene oxide, tris (tribromophenyl) cyanurate, atactic brominated polystyrene, atactic brominated styrene-methyl methacrylate copolymer, atactic brominated styrene-methyl methacrylate-glycidyl methacrylate copolymer Abrominated styrene-glycidyl methacrylate copolymer with atactic structure, brominated styrene-polypropylene copolymer with atactic structure, tetrabromobisphenol-A-epoxy oligomer, brominated epoxy Compounds (for example, diepoxy compounds produced by the reaction of brominated bisphenol A with epichlorohydrin or epoxy compounds obtained by the reaction of brominated phenols with epichlorohydrin), tetrabromobisphenol-A-carbonate oligomers, tetrabromobisphenol-A- It is one or more halogen-based flame retardants selected from the group consisting of brominated flame retardants consisting of bis (2-hydroxydiethyl ether), poly (pentabromobenzyl acrylate), and octabromotrimethylphenylindane.
7) Furthermore, it is a resin composition containing a thermoplastic resin other than the component (A-1) as the component (D), the sum of the components (A), (B), (C) and (D) The blending amount of component (D) is 1 to 60 wt%.
8) One type of component (A-1) selected from the group consisting of a block copolymer having a polymer segment with a glass transition temperature of 20 ° C. or lower and containing an aromatic structure and a polyphenylene ether resin It must be a thermoplastic resin as described above.
9) The component (A-2) contains one or more aromatic structures selected from the group consisting of thermosetting polyphenylene ethers, polyphenylene ether oligomers having functional groups at both ends, and polyfunctional aromatic epoxy compounds. It must be a thermosetting resin.
10) The (C) component has an average interlayer distance of (001) plane measured by a wide angle X-ray diffraction measurement method of 3 nm or more, and part or all of them are dispersed in 5 layers or less.
11) Furthermore, as the component (E), a flame retardant resin composition containing a thermosetting resin not containing an aromatic structure, the component (A), the component (B), the component (C), (D) The blending amount of the component (E) with respect to the sum of the component and the component (E) is 1 to 60 wt%.
12) Furthermore, it is a flame retardant resin composition containing a filler as the component (F), the component (A), the component (B), the component (C), the component (D), the component (E) and ( The blending amount of the component (F) with respect to the sum of the components F) is 2 to 90 wt%.
13) The component (C) is a swellable layered silicate having an affinity for an organic solvent.

Moreover, this invention is a flame retardant resin hardened | cured material obtained by hardening | curing the flame retardant resin composition containing a thermosetting resin among the said flame retardant resin compositions.
Furthermore, the present invention is a flame retardant film obtained by forming the flame retardant resin composition into a film shape.
Moreover, this invention is a flame retardant composite material which is a composite material which consists of said flame retardant resin composition and a base material, Comprising: A base material is contained in the ratio of 5-90 wt%.
Furthermore, the present invention is a flame retardant curable composite material obtained by curing a composite material containing a thermosetting resin among the above composite materials.
Moreover, this invention is a flame-retardant laminated body characterized by having the said flame-retardant composite material layer and metal foil layer.
Furthermore, this invention is a metal foil with a flame retardant resin characterized by having the resin layer formed from the said flame retardant resin composition on the single side | surface of metal foil.

Hereinafter, the flame retardant resin composition of the present invention will be further described.
The flame retardant resin composition of the present invention contains (A) component, (B) component and (C) component as essential components. The flame retardant resin composition of the present invention preferably further contains any one or more optional components (D), (E), and (F) depending on the application.

  As the component (A), one or both of the components (A-1) and (A-2) are used. The component (A-1) is a thermoplastic resin, the component (A-2) is a thermosetting resin, and if the component (A-2) contains a certain amount or more, it is a thermosetting flame retardant resin. Give the composition.

  The aromatic vinyl resin that can be used as the component (A-1) is one or more aromatic vinyls selected from rubber-modified aromatic vinyl resins, rubber non-modified aromatic vinyl resins, and aromatic vinyl thermoplastic elastomers. System polymers.

  The rubber-modified aromatic vinyl resin comprises an aromatic vinyl resin matrix and rubber particles dispersed therein, and is copolymerized with an aromatic vinyl monomer in the presence of a rubber-like polymer and, if desired, the same. It can be obtained by adding a possible vinyl monomer and graft polymerization to a rubbery polymer by a known bulk polymerization method, bulk suspension polymerization method, solution polymerization method or emulsion polymerization method. Examples of such rubber-modified aromatic vinyl resins include impact-resistant polystyrene, ABS resin (acrylonitrile-butadiene-styrene copolymer), AAS resin (acrylonitrile-acrylic rubber-styrene copolymer), AES resin ( Acrylonitrile-ethylene propylene rubber-styrene copolymer) and the like.

  Here, the rubbery polymer preferably has a glass transition temperature (Tg) of −30 ° C. or lower, and if it exceeds −30 ° C., impact resistance is lowered. Examples of such rubbery polymers include diene rubbers such as polybutadiene, poly (styrene-butadiene), poly (acrylonitrile-butadiene), saturated rubbers obtained by hydrogenating the diene rubbers, isoprene rubbers, chloroprene rubbers, polyacrylics. An acrylic rubber such as butyl acid and an ethylene-propylene-diene monomer terpolymer (EPDM) can be exemplified, and a diene rubber is particularly preferable. The aromatic vinyl monomer as an essential component in the graft-polymerizable monomer mixture to be polymerized in the presence of the rubbery polymer is, for example, styrene, α-methylstyrene, paramethylstyrene, etc. Is most preferable, but the other aromatic vinyl monomer may be copolymerized mainly with styrene.

  In addition, one or more monomer components copolymerizable with the aromatic vinyl monomer can be introduced as necessary as a component of the rubber-modified aromatic vinyl resin in the component (A). When it is necessary to improve oil resistance, unsaturated nitrile monomers such as acrylonitrile and methacrylonitrile can be used.

  And when it is necessary to reduce the melt viscosity at the time of a blend or mixing, the acrylic ester which consists of a C1-C8 alkyl group can be used. Moreover, when it is necessary to further improve the heat resistance of the resin composition, monomers such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide may be copolymerized.

When a mixture of vinyl monomers copolymerizable with the vinyl aromatic monomer is used, the content of the copolymerizable vinyl monomer in the monomer mixture is 1 to 40% by weight. .
The amount of the rubber-like polymer constituting the rubber-modified aromatic vinyl resin is preferably 5 to 80% by weight, particularly preferably 10 to 50% by weight, and the amount of the monomer capable of graft polymerization is preferably 95 to It is in the range of 20% by weight, more preferably 90-50% by weight. Within this range, the balance between impact resistance and rigidity of the intended resin composition is improved. Furthermore, the rubber particle diameter of the rubber-modified aromatic vinyl resin is preferably 0.1 to 5.0 μm, particularly preferably 0.2 to 3.0 μm. Within the above range, impact resistance is particularly improved.

  Reduced viscosity ηsp / c (0.5 g / dl, 30 ° C. measured as a measure of molecular weight of rubber-modified aromatic vinyl resin: toluene solution when matrix resin is polystyrene, matrix resin is unsaturated nitrile-aromatic In the case of a group vinyl copolymer, methyl ethyl ketone) is preferably in the range of 0.30 to 0.80 dl / g, more preferably in the range of 0.40 to 0.60 dl / g. Examples of means for satisfying the above-described requirements regarding the reduced viscosity ηsp / c of the rubber-modified styrene resin include adjustment of the polymerization initiator amount, the polymerization temperature, and the chain transfer agent amount. The aromatic vinyl monomer remaining in the polymer composition and the dimer and trimer amount of the aromatic vinyl monomer can be controlled by changing the polymerization temperature and the amount of chain transfer agent or by vacuum distillation. Or by solvent extraction.

  As a method for producing a rubber-modified aromatic vinyl resin, in particular, a uniform polymerization stock solution composed of a rubber-like polymer, a monomer (or a monomer mixture) and a polymerization solvent is used as a continuous multistage block with a stirrer. A bulk polymerization method in which the polymerization reactor is continuously fed and continuously polymerized and devolatilized is preferable. When the rubber-modified styrene polymer is produced by the bulk polymerization method, the reduced viscosity ηsp / c can be controlled by the polymerization temperature, the initiator type and amount, the solvent, and the chain transfer agent amount. When a monomer mixture is used, the copolymer composition can be controlled by the charged monomer composition. And control of a rubber particle diameter can be performed with stirring rotation speed. That is, small particles can be achieved by increasing the rotational speed, and large particles can be achieved by decreasing the rotational speed.

  Another component (A-1) used in the present invention is an aromatic vinyl resin that is not rubber-modified. Examples of such aromatic non-rubber-modified vinyl resins include polystyrene, poly (styrene-acrylonitrile), poly (styrene-methyl methacrylate) and the like.

  Another component (A-1) used in the present invention is an aromatic vinyl-based thermoplastic elastomer. From the viewpoint of improving toughness, it is preferable to use an aromatic vinyl-based thermoplastic elastomer having a polymer segment having a glass transition temperature of 20 ° C. or lower. What has a polymer segment whose glass transition temperature is 0 degrees C or less is more preferable. Examples of such aromatic vinyl thermoplastic elastomers include aromatic vinyl thermoplastic elastomers such as styrene conjugated diene block copolymers (also referred to as diene block copolymers) or hydrogenated styrene conjugated diene block copolymers. It can be mentioned as a suitable example. The hydrogenated styrene conjugated diene block copolymer referred to here is a block copolymer in which a part or all of the conjugated diene polymer block in the block copolymer is hydrogenated (also referred to as a hydrogenated diene block copolymer). Say). From the viewpoint of heat-resistant oxidative degradation, an aromatic vinyl hydrogenated thermoplastic elastomer such as a hydrogenated styrene conjugated diene block copolymer is more preferable.

In the present invention, the hydrogenated diene block copolymer used as a preferred aromatic vinyl thermoplastic elastomer is a polymer mainly composed of at least one vinyl aromatic compound as shown in the following structural formula. This is obtained by hydrogenating a diene block copolymer comprising a block A and a polymer block B mainly composed of at least one conjugated diene compound. 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. When this is hydrogenated, B becomes B '. Here, B ′ means a hydride of a polymer block mainly composed of a conjugated diene compound unit.
A-B,
A-B-A,
B-A-B-A,
[A-B-] ₄ -Si,
[B-A-B-] ₄ -Si,
This hydrogenated diene 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%.

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

  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. Most preferred is butadiene from the viewpoint of compatibility with the components (A-1) and (A-2) of the present invention. On the other hand, isoprene is preferred for the purpose of increasing the chemical resistance and flexibility of the cured product of the flame-retardant resin composition of the present invention.

  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.

  The polyphenylene ether resin used as the component (A-1) of the present invention is a homopolymer or copolymer having a repeating unit represented by the general formula (2) and / or (3). Is preferred.

（ここで、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸は独立に炭素数１〜４のアルキル基、アリール基又は水素であるが、Ｒ⁷、Ｒ⁸は同時に水素ではない。）

(Wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ are each independently an alkyl group having 1 to 4 carbon atoms, an aryl group or hydrogen, but R ⁷ and R ⁸ are simultaneously hydrogen atoms. Absent.)

  Representative examples of polyphenylene ether-based homopolymers include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-14-phenylene) ether, poly (2, 6-diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether poly (2,6-di-n-propyl-1,4-phenylene) ether Poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-) And homopolymers such as 1,4-phenylene) ether.

  Of these, poly (2,6-dimethyl-1,4-phenylene) ether is preferable, and 2- (dialkylaminomethyl) -6-methylphenylene ether unit described in JP-A-63-301222 and the like. Polyphenylene ether containing 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit or the like as a partial structure is particularly preferable.

  The polyphenylene ether copolymer is a copolymer having a phenylene ether structure as a main monomer unit. Examples thereof include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of 2,6-dimethylphenol and o-cresol, or 2,6-dimethylphenol and 2 , 3,6-trimethylphenol and a copolymer of o-cresol, a copolymer of 2,6-dimethylphenol and bisphenol represented by the following general formula (4), and the like.

（ここで、Ｒ⁹、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²は独立に炭素数１〜４のアルキル基、アリール基又は水素を表す。また、式中Ｘは、―Ｃ（ＣＨ₃）₂−、−ＳＯ₂−、−Ｓ−又はＯ−を表し、ｙは０又は１を表す）

(Here, R ⁹ , R ¹⁰ , R ¹¹ , R ¹² independently represent an alkyl group having 1 to 4 carbon atoms, an aryl group, or hydrogen. In the formula, X represents —C (CH ₃ ) ₂ —, -SO ₂ -, - represents S- or O- a, y represents 0 or 1)

  In the present invention, the polyphenylene ether-based resin as the component (A-1) may be modified even if the functional group at the end is modified in order for some of the functional groups to improve characteristics such as heat resistance and adhesiveness. In addition, the main chain may have a functional group. For example, a part or all of the terminal OH group may be modified with a reactive functional group such as a carboxyl group, an epoxy group, an amino group, a hydroxyl group, or an anhydrous dicarboxyl group. In addition, a functional group other than an alkyl group or an aryl group may be introduced by some method such as graft reaction or copolymerization, or the functional group may be further modified. However, since it needs to be a thermoplastic resin, there are limitations on the type and number of functional groups.

  The molecular weight of the polyphenylene ether resin (used in the meaning including the modified polyphenylene ether resin) that can be used in the present invention is not limited as long as the effect of the present invention is not impaired. . Specifically, those having a number average molecular weight of 500 to 50,000 can be suitably used. When it is necessary to obtain a composition excellent in molding processability, a polyphenylene ether resin having a number average molecular weight of 500 or more and 3000 or less, preferably 1200 or more and 20000 or less can be suitably used. .

  One or more of the above aromatic vinyl resins and polyphenylene ether resins can be used as the component (A-1).

On the other hand, the thermosetting resin having an aromatic structure used as the component (A-2) in the present invention includes a vinyl group, an ethynyl group, an epoxy group, an oxetane group, a cyanate group, an isocyanate group, and a hydroxyl group. Mention may be made of thermosetting resins containing one or more functional groups selected and an aromatic structure. Specific examples of such thermosetting resins include solvent-soluble polyfunctional vinyl aromatic copolymers, thermosetting polyphenylene ethers, polyphenylene ether oligomers having functional groups at both ends, and polyfunctional aromatic epoxy compounds. , Polyfunctional aromatic oxetane compound, diallyl phthalate, polyfunctional aromatic acryloyl compound, polyfunctional aromatic methacryloyl compound, polyfunctional aromatic maleimide, polyfunctional aromatic cyanate compound, polyfunctional aromatic isocyanate compound, Examples include unsaturated aromatic polyester compounds and their prepolymers. These are used alone or in combination of two or more.
Hereinafter, the thermosetting resin of the component (A-2) that can be suitably used will be described.

  The solvent-soluble polyfunctional vinyl aromatic copolymer (hereinafter referred to as soluble polyfunctional vinyl aromatic copolymer) used as component (A-2) is the component (B) and component (C) used in the present invention. Due to the synergistic effect with the components, it not only exhibits a high degree of flame retardancy, but also has good dielectric properties due to its molecular structure. Furthermore, in the case of a thin film film, a problem related to moldability such as low reactivity of a general thermosetting vinyl resin is solved by a synergistic effect with the component (C) of the present invention. Effective as an effective ingredient.

  The soluble polyfunctional vinyl aromatic copolymer used as the component (A-2) has a structural unit derived from a monomer composed of a divinyl aromatic compound (a) and an ethyl vinyl aromatic compound (b). A soluble polyfunctional vinyl aromatic containing a structural unit derived from a monovinyl aromatic compound other than the ethylvinyl aromatic compound (b) (hereinafter referred to as monovinyl aromatic compound (c)) in the polyfunctional vinyl aromatic copolymer. A group copolymer is also preferable from the viewpoint of improving compatibility with other thermoplastic resins such as polyphenylene ether resins and thermosetting resins.

The copolymer may contain a structural unit represented by (1) in addition to the above formulas (a1) and (a-2) 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.

  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 compatible with the thermoplastic resin of the component (A-1) and the other thermosetting resin of the component (A-2). Provides structural units that improve conditioning, solvent solubility and processability. 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 the mechanical properties such as tensile elongation at break of the cured product of the flame retardant resin composition of the present invention 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, p-methylstyrene, pt-butylstyrene, pn-hexylstyrene, 3-vinyl-4′-propylbiphenyl, Nuclear alkyl-substituted aromatic vinyl compounds such as 2-vinyl-6-propylnaphthalene, alkoxy-substituted styrenes such as pt-butoxystyrene, mt-butoxystyrene, p-phenoxystyrene, α-methylstyrene, α-ethylstyrene, α- α-alkyl-substituted styrene such as n-hexylstyrene, α-alkyl-substituted aromatic vinyl compounds, aromatic vinyl compounds substituted with vinyl groups such as β-alkyl-substituted styrene, and indene, methylindene, ethylindene Alkyl-substituted indene, methoxyindene, ethoxyindene, t-butoxy Indene such as cyindene such as cyindene, acenaphthylene, alkylacenaphthylene such as 1-methylacenaphthylene and 3-methylacenaphthylene, 1-chloroacenaphthylene, 5-chloroacenaphthylene Halogenated acenaphthylenes such as 1-bromoacenaphthylene, 5-bromoacenaphthylene, 1-phenylacenaphthylene, 3-phenylacenaphthylene, 4-phenylacenaphthylene, 5-phenylacenaphthylene, etc. And cyclic olefins such as acenaphthylenes such as phenylacenaphthylenes.

  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-2) includes a monomer containing a divinyl aromatic compound (a) and an ethyl vinyl aromatic compound (b) and, if necessary, a monovinyl aromatic compound (c). Obtained by polymerization. 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, the monomer that forms the polyfunctional vinyl aromatic copolymer of component (A-2) includes divinyl aromatic compound (a), ethyl vinyl aromatic compound (b), and monovinyl aromatic compound (c). In addition, a small amount of other monomers (d) such as trivinyl aromatic compounds, 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)] preferably satisfies ≧ 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, the heat resistance and the solubility in a solvent are insufficient, and the compatibility with the component (B) and the component (C) Is unfavorable because it decreases.

  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 20,000, more preferably 700. -10,000. Most preferably, it is 800-5,000. 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. In addition, when Mn is 30,000 or more, gel is likely to be formed, and compatibility with other resin components is reduced, and when formed into a film or the like, appearance deterioration and physical property deterioration are caused. Absent.

  Moreover, the value of the molecular weight distribution (Mw / Mn) of the soluble polyfunctional vinyl aromatic copolymer is 20 or less, preferably 15 or less, more preferably 10 or less. Most preferably, it is 5 or less. The lower limit is not limited, but is preferably 1.5 or more from the viewpoint of polymerization efficiency. 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 500 ppm or less, more preferably 100 ppm or less for each metal ion. Most preferably, it is 20 ppm or less. When the metal ion content is 500 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-2) is a monomer component containing, for example, a divinyl aromatic compound (a), an ethyl vinyl aromatic compound (b), and a monovinyl aromatic compound (c). Is polymerized 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). be able to.

(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.

  Next, the thermosetting polyphenylene ether resin 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 alkenyl groups, alkynyl groups, epoxy groups, oxazoline groups, ester groups, hydroxyl groups, and the like.

  As a typical example of the structural unit into which the reactive functional group of the thermosetting polyphenylene ether resin having a reactive functional group is introduced, a structural unit represented by the following general formula (4) can be given.

（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, p55-57, 1993”, “Polymer Papers Vol.54, No.4, p171-182, 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.

Next, a polyphenylene ether oligomer having functional groups at both ends will be described. These polyphenylene ether oligomers having functional groups at both ends have reactive functional groups introduced at the ends of their molecular chains in order to improve properties such as moldability, heat resistance and adhesiveness. The polyphenylene ether oligomer having functional groups at both ends is a polyphenylene ether oligomer represented by the structural formula (7) obtained by oxidative copolymerization of divalent phenol and monovalent phenol (hereinafter referred to as bifunctional OPE). ) Is reacted with a thermosetting functional group-containing compound such as chloromethylstyrene, glycidyl methacrylate, glycidyl acrylate, epichlorohydrin 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 '-(1,4-phenylenebismethylene) bis (2,6-dimethylphenol), 4,4'-(9H-fluorene-9-ylidene) Examples thereof include, but are not limited to, bis (2,6-dimethylphenol).

  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.

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 polyphenylene ether oligomer having functional groups at both ends described above 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. T is a thermosetting functional group selected from a vinyl group, an epoxy group, a cyanate group, an oxazone phosphorus group, a carboxyl group, and a hydroxyl group. Of these thermosetting functional groups, vinyl groups are most preferably used from the viewpoint of compatibility with the A1 component and the polyfunctional vinyl aromatic copolymer.
There are two methods for adding functional groups at both ends to the bifunctional OPE: 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. It is not limited to these.

  Moreover, in order to produce a polyphenylene ether oligomer having functional groups at both ends, the bifunctional OPE represented by the above structural formula (7) is used, but the powder is separated from the reaction solution or dissolved in the reaction solution. Either can be used.

  An example of a method for producing a polyphenylene ether oligomer having functional groups at both ends will be described. Synthesis by reacting a compound having a phenolic hydroxyl group at both ends represented by the structural formula (7) with a thermosetting functional group-containing compound such as chloromethylstyrene, glycidyl methacrylate, glycidyl acrylate, or epichlorohydrin. it can. The reaction temperature is preferably between -10 ° C and 110 ° C.

  The number average molecular weight Mn of the polyphenylene ether oligomer having functional groups at both ends 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. Among the above polyphenylene ether oligomers having functional groups at both ends, the compatibility with the A1 component and the polyfunctional vinyl aromatic copolymer is excellent, the strength and heat resistance of the resin composition are good, and the cured product A polyphenylene ether oligomer (OPE-2Vn) having vinyl groups at both ends is most preferably used because of its superior strength during heating.

The thermosetting resin used as the other component (A-2) will be described.
The polyfunctional epoxy compound may be an aromatic 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. , Biphenyl type epoxy resins, epoxy resins obtained by halogenating these resins, triphenylmethane type epoxy resins, tetraphenyl glycidyl ether ethane (tetrafunctional epoxy resin), various novolak type epoxy resins, and the like. You may use the above together. In addition, within the range which does not impair the effect of this invention, the aromatic epoxy resin which has one epoxy group in a molecule | numerator can also be used together.

  When using a polyfunctional aromatic epoxy compound, the flame retardant resin composition of the present invention can contain a curing agent. The curing agent used for the curing reaction of the polyfunctional aromatic epoxy compound is not particularly limited, and conventionally known curing agents for epoxy resins can be used. For example, amine compounds, polyaminoamide compounds synthesized from amine compounds And the like, tertiary amine compounds, imidazole compounds, hydrazide compounds, melamine compounds, acid anhydrides, phenol compounds, thermal latent cationic polymerization catalysts, photolatent cationic polymerization initiators, dicyanamide and derivatives thereof. These hardening | curing agents may be used independently and 2 or more types may be used together.

  The polyfunctional aromatic oxetane compound may be an oxetane resin having two or more oxetane groups in the molecule, such as 1,4-bis [{(3-ethyl-3-oxetanyl) methoxy} methyl] benzene. (XDO), 9,9-bis [2-methyl-4- {2- (3-oxetanyl)} butoxyphenyl] fluorene, 9,9-bis [4- [2- {2- (3-oxetanyl)} Bifunctional oxetane compounds such as butoxy] ethoxyphenyl] fluorene, and polyfunctional aromatic oxetane compounds such as oxetaneated novolak resins. These compounds are readily available on the market. Moreover, these may use together 2 or more types. In addition, the aromatic 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 aromatic 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.

（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 aromatic 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 aromatic 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.

(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 (A-2), any of ortho, meta, and para isomers can be used as the component (A-2).

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

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

In the above formula, as the residue R ²⁵ of the aromatic polyvalent hydroxy compound, xylene glycol, an aromatic polyol in which a plurality of benzene rings represented by bisphenol A are connected via a bridge portion, and these aromatics An aromatic polyol residue exemplified by an alkylene oxide adduct of an aromatic polyol; a residue of a benzene polynuclear product obtained by reacting phenol with formaldehyde (usually those having a 10-nuclear compound or less are preferably used); There is a residue derived from an aromatic epoxy resin having two or more epoxy groups; a residue derived from an aromatic polyester resin having two or more hydroxyl groups at the terminal.

（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価の芳香族有機基を示す） As the polyfunctional aromatic 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 organic group)

This polyfunctional aromatic maleimide is produced by reacting maleic anhydride with an aromatic 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, 4,4-diaminobiphenyl, bis (4-aminophenyl) methane, bis (4-aminophenyl) ether, bis Examples include polyamines obtained by reacting (4-aminophenyl) sulfone and the like with formaldehyde (usually those having a benzene 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、シアネート基は有機基Ｒ³⁰の芳香環に直接結合している） As polyfunctional aromatic cyanate, there is one represented by the following formula.

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

  Examples of such polyfunctional aromatic cyanates include 1,3-dicyanate benzene, 1,4-dicyanate benzene, 1,3,5-tricyanate benzene, 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, tris (4-cyanate) Phenyl) phosphate, benzene polynuclear aromatic polycyanate compound obtained by reaction of phenol resin with cyanogen halide, and the like.

（式中、ｑは２〜１０の整数であり、Ｒ³¹は２〜１０価の芳香族有機基を示す） Examples of the polyfunctional aromatic isocyanate include those represented by the following formula.

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

  Examples of such polyfunctional aromatic isocyanates include 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, metaphenylene diisocyanate, paraphenylene diisocyanate, metaxylylene diisocyanate, 1,5-naphthalene diisocyanate, 4,4- And diphenylmethane diisocyanate.

  These polyfunctional aromatic isocyanates can be converted into polyfunctional aromatic 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.

Unsaturated aromatic polyesters include those obtained by reacting glycols with aromatic unsaturated polybasic acids and aromatic saturated polybasic acids, or anhydrides, esters, and acid chlorides thereof. Is used.
For details of the unsaturated polyester, reference is made, for example, to Teiyama Shinichiro, “Polyester Resin Handbook” (Nikkan Kogyo Shimbun, 1988).

  When the component (A-2) is blended with the flame retardant resin composition of the present invention, the component (A-2) may be a single compound or a combination of two or more compounds as described above. Can be used. 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. described later is also a component (A-2) of the present invention. It can be used as one of

  Among the components (A-2) used in the flame retardant resin composition of the present invention, the viewpoint of the components (B) and (C) of the flame retardant resin composition of the present invention, and machine From the viewpoint of improvement of mechanical properties and moldability, polyfunctional vinyl aromatic copolymers and polyphenylene ether oligomers having functional groups at both ends at both ends are most preferably used. On the other hand, a polyfunctional vinyl aromatic copolymer is most preferably used from the viewpoint of curability in a thin film molded product. 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 flame-retardant resin composition of the present invention contains one or more resins selected from the above components (A-1) and (A-2) as essential components (A).

  The halogen-based flame retardant of the component (B) used in the present invention is decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, ethane-1,2-bis (pentabromophenyl), bis (2,4,6). -Tribromophenoxy) ethane, ethylenebistetrabromophthalimide, polydibromophenylene oxide, tetrabromobisphenol-S, 1,1-sulfonyl [3,5-dibromo-4- (2,3-dibromopropoxy)] benzene, tris (2,3-dibromopropyl-1) isocyanurate, tris (tribromophenyl) cyanurate, brominated polystyrene having an atactic structure, brominated styrene-methyl methacrylate copolymer having an atactic structure, brominated styrene-meth having an atactic structure Methacrylate-glycidyl methacrylate copolymer, atactic brominated styrene-glycidyl methacrylate copolymer, atactic brominated styrene-polypropylene copolymer, brominated polyethylene, tetrabromobisphenol-A, tetrabromobisphenol -A-epoxy oligomers, brominated epoxy compounds (for example, diepoxy compounds produced by the reaction of brominated bisphenol A and epichlorohydrin or epoxy compounds obtained by the reaction of brominated phenols with epichlorohydrin), tetrabromobisphenol-A- Carbonate oligomer, tetrabromobisphenol-A-bis (2-hydroxydiethyl ether), tetrabromobisphenol-A-bis (2,3-dibromo) Ropirueteru), poly (pentabromobenzyl acrylate), a halogen-based flame retardant one or more kinds selected from the group consisting of consisting of octa-bromo-trimethylphenyl indane. These halogen flame retardants may be used alone or in combination of two or more.

  From the viewpoint of the synergistic effect in the flame retardancy with the component (A) and the component (C) and the heat resistance, the halogen flame retardant of the component (B) is decabromodiphenyl oxide, ethane-1,2-bis (pentabromophenyl) ), Bis (2,4,6-tribromophenoxy) ethane, ethylenebistetrabromophthalimide, polydibromophenylene oxide, tris (tribromophenyl) cyanurate, brominated polystyrene with atactic structure, brominated styrene-methyl with atactic structure Methacrylate copolymer, atactic brominated styrene-methyl methacrylate-glycidyl methacrylate copolymer, atactic brominated styrene-glycidyl methacrylate copolymer, atactic brominated styrene-polypropylene copolymer , Tetrabromobisphenol-A-epoxy oligomers, brominated epoxy compounds (for example, diepoxy compounds produced by the reaction of brominated bisphenol A with epichlorohydrin or epoxy compounds obtained by the reaction of brominated phenols with epichlorohydrin), tetrabromo It is one or more halogen-based flame retardants selected from the group consisting of bisphenol-A-carbonate oligomers, tetrabromobisphenol-A-bis (2-hydroxydiethyl ether), poly (pentabromobenzyl acrylate), and octabromotrimethylphenylindane. It is more preferable.

Furthermore, the halogen-based flame retardant of component (B) is ethane-1,2-bis (pentabromophenyl), polydibromophenylene oxide, tris (tribromophenyl) cyanurate, brominated polystyrene having an atactic structure, tetrabromobisphenol-A One or more selected from the group consisting of epoxy oligomers, brominated epoxy compounds (for example, diepoxy compounds produced by the reaction of brominated bisphenol A and epichlorohydrin and epoxy compounds obtained by the reaction of brominated phenols and epichlorohydrin) Most preferably, it is a halogen flame retardant.
On the other hand, from the viewpoint of low dielectric properties of the flame retardant resin composition of the present invention, the halogen flame retardant of component (B) is ethane-1,2-bis (pentabromophenyl), polydibromophenylene oxide, atactic structure. One or more halogenated flame retardants selected from the group consisting of brominated polystyrene are preferred.

  The layered silicate of component (C) 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. As the layered silicate, at least one selected from the group consisting of montmorillonite, hectorite and swellable mica is 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 (20). By using a layered silicate having a large shape anisotropy effect (E), the flame-retardant curable resin obtained from the flame-retardant 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 (20)

  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. For example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-aminopropyltrimethoxysilane, methyltriethoxysilane, trimethylmethoxysilane, γ- Examples include glycidoxypropyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, octadecyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane. It is done. 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 component (A), the component (B) and the component (C) for making the flame retardant resin composition of the present invention can be varied over a wide range, but the component (A), (B The blending amount (wt%) of the component (A), the component (B) and the component (C) with respect to the sum of the component (C) and the component (C) needs to satisfy the following formula.
(A) Component blending amount = 4 to 99.8 (wt%)
(B) Component blending amount = 0.1-95.9 (wt%)
(C) Component blending amount = 0.1 to 95.9 (wt%)
Preferably, the amount of component (A) is 6 to 99 wt%, more preferably 30 to 96 wt%. Moreover, about the compounding quantity of (B) component, Preferably it is 0.5-90 wt%, More preferably, it is 2-70 (wt%). Furthermore, about (C) component compounding quantity, Preferably it is 0.5-80 wt%, More preferably, it is 1-50 (wt%).

If the amount of the specific halogen-based flame retardant as the component (B) is less than 0.1 wt%, the synergistic effect on the flame retardancy with the component (A) and the component (C) is lowered, which is not preferable. If it exceeds 9 wt%, the mechanical strength is lowered, which is not preferable.
When the blending amount of the component (C) is less than 0.1 wt%, the synergistic effect in flame retardancy, which is the effect of the layered silicate, and the curing accelerating action in molding are lowered, and when it exceeds 95.9 wt%, the mechanical properties are lowered. Further, in the component (A) used in the present invention: As the component (A-1), one kind selected from the group consisting of aromatic vinyl resins, polyphenylene ether resins, and polyphenylene ether resins modified with functional groups The above thermoplastic resins and / or (A-2) component (A-2) component polyfunctional vinyl aromatic copolymer, thermosetting polyphenylene ether, and polyphenylene ether oligomer having functional groups at both ends are Since the material has low dielectric properties, a cured product having a low dielectric constant can be formed. In addition, the polyfunctional vinyl aromatic copolymer of component (A-2) has excellent curing characteristics, and exhibits good curability in a thin film molding synergistically with component (C) of the present invention.

The component (A-1) and component (A-2) of the present invention can be mixed at an arbitrary ratio, but the blending ratio differs depending on the additional characteristics required for the resin composition of the present invention. . When the resin composition of the present invention requires moldability to a large-sized molded product or a molded product having a complicated shape, (A-1) component / (A-2) component = 1.0 to A blending ratio of 0.4 is preferable. More preferably, (A-1) component / (A-2) component = 1.0 to 0.6, and most preferably (A-1) component / (A-2) component = 1.0 to 0.8.
On the other hand, when it is required that the resin composition of the present invention has both high heat resistance and toughness, (A-1) component / (A-2) component = 0.9 to 0.1 A ratio is preferred. More preferably, (A-1) component / (A-2) component = 0.8 to 0.2, and most preferably (A-1) component / (A-2) component = 0.7 to 0.3. Furthermore, when it is required that the resin composition of the present invention has both high heat resistance and rigidity, (A-1) component / (A-2) component = 0.2 to 1.0 A ratio is preferred. More preferably, (A-1) component / (A-2) component = 0.3 to 1.0, and most preferably (A-1) component / (A-2) component = 0.4 to 0.3.

  The flame-retardant resin composition of the present invention can contain other components in addition to the component (A), the component (B), and the component (C). As other components, preferred are (D) component, (E) component and (F) component. These blending amounts are the total amount of the component to be blended among the total amount of the component (A), the component (B) and the component (C) and the optional component (D), component (E) and component (F). It is desirable to determine from the sum (hereinafter referred to as the reference amount).

  The component (D) is a thermoplastic resin other than the component (A-1), and one or more of them can be blended. The blending amount (weight ratio) of the component (D) with respect to the total amount of the component (D) component or the sum of the components (A), (B), (C) and (D) is 1 to 60 wt%. Preferably, it is 5-55 wt%. When the amount of component (C) is less than 1 wt%, the mechanical properties deteriorate, and when it exceeds 60 wt%, the synergistic effect of components (A), (B), and (C) in flame retardancy is decreased. Absent.

  (D) Component thermoplastic resins include ethylene / propylene copolymers, polyolefins such as poly (4-methyl-pentene) and derivatives thereof, polyamides such as nylon 6 and nylon 6/6, and derivatives thereof, polyethylene terephthalate Polyesters such as polybutylene terephthalate and polyethylene naphthalate and derivatives thereof, polycarbonate, polysulfone, polymethyl methacrylate, acrylic acid (or methacrylic acid) ester copolymers, rubbers such as polybutadiene and polyisoprene, polyphos Examples include phazenes, polyethersulfone, polyetherketone, polyetherimide, polyphenylene sulfide, polyamideimide, thermoplastic polyimide, and liquid crystal polymer such as aromatic polyester.

  The component (E) is a thermosetting resin other than the component (A-2). The blending amount of the component (E) relative to the total amount of the component (E) or the sum of the component (A), the component (B), the component (C), the component (D) and the component (E) is 1 to The amount is preferably 60 wt%, and preferably 5 to 55 wt%. (E) If the component blending amount is less than 1 wt%, the degree of improvement in curability, adhesion and chemical resistance due to the addition of a thermosetting resin not containing an aromatic structure is insufficient, and 60 wt% When exceeding, the mechanical physical property of a composition will fall remarkably.

  The component (E) is not particularly limited as a thermosetting resin not containing an aromatic structure. For example, epoxy resin, urea resin, silicon resin, benzoxazine resin, unsaturated polyester resin, alkyd resin, furan resin, Examples thereof include thermosetting resins that do not contain an aromatic structure such as melamine resins and polyurethane resins. Of these, epoxy resin, silicon resin, benzoxazine resin, and the like are preferable. These thermosetting resins that do not contain an aromatic structure may be used alone or in combination of two or more.

  Component (F) is a filler. (F) Reference amount in the case of mix | blending a component, or (A) component, (B) component, (C) component, (D) component, (E) component, and (F) component mix | blending with respect to the sum total of (F) component The amount may be 2 to 90 wt%, preferably 5 to 85 wt%. When the blending amount of the component (F) is less than 2 wt%, the degree of improvement in mechanical properties due to the addition of the filler is insufficient, and when it exceeds 90 wt%, the fluidity of the composition is significantly lowered.

  Examples of the filler of component (F) include carbon black, silica, alumina, talc, mica, glass beads, and glass hollow spheres. The shape of the filler is arbitrary and may be fibrous or powdery. The component (C) is not treated as the component (F).

  When using a polyfunctional vinyl aromatic copolymer that is a thermosetting resin having an aromatic structure as the component (A-2) in the flame retardant resin composition of the present invention, heating or the like as described later. A crosslinking reaction is caused by the means to cure, but a radical initiator may be contained for the purpose of lowering the reaction temperature or promoting the crosslinking reaction of unsaturated groups. The amount of the radical initiator used for this purpose is 0.01 to 15 wt%, preferably 0.05 to 10 wt%, based on the sum of the components (A-2) and (E) containing vinyl groups. Especially preferably, it is 0.1-8 wt%. If the amount of the radical initiator is less than 0.01 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 flame retardant resin composition of the present invention is not limited to these examples.

In addition, as a suitable curing agent for the polyfunctional aromatic maleimide used as the component (A-2) in the flame retardant resin composition of the present invention, polyamine is a suitable catalyst for the polyfunctional aromatic cyanate. Mineral acids, Lewis acids, salts such as sodium carbonate or lithium chloride, phosphate esters such as tributylphosphine, and the like, as catalysts and curing agents suitable for polyfunctional aromatic isocyanates, for example, edited by Keiji Iwata, “Polyurethane” Examples include amines, organic metals, polyhydric alcohols and the like as taught in “Resin Handbook” (Nikkan Kogyo Shimbun, 1987), pages 118-123.
The catalyst, initiator, curing agent and the like are appropriately selected and used according to the type of the crosslinking component.

  In addition, the flame-retardant resin composition of the present invention is a nitrogen-based flame retardant or phosphorus-based flame retardant in an amount that does not impair the effects of the present invention as the component (G) for the purpose of further improving the flame retardancy. One or more flame retardants selected from the group consisting of nitrogen / phosphorous flame retardants and inorganic flame retardants can be blended and used.

  As the nitrogen-based flame retardant used as the component (G), when the compounded resin is exposed to a high temperature, it absorbs heat from the resin by endothermic decomposition, and forms an inert atmosphere to exert a flame retardant effect. It is a flame retardant shown. Among them, those having an endotherm at the time of decomposition in differential thermal analysis of 50 mJ or more per mg, particularly 150 mJ or more are preferable. As such a nitrogen-based flame retardant, known ones can be used without limitation, but aliphatic amine compounds, aromatic amine compounds, triazine, melamine, benzoguanamine, methylguanamine, cyanuric acid and other nitrogen-containing heterocyclic compounds, cyanide Examples thereof include compounds, aliphatic amides, aromatic amides, urea, thiourea and the like.

(G) The salt of each compound mentioned above can also be used as a nitrogen-type flame retardant used as a component. Examples of the salt include sulfate, nitrate, borate and isocyanurate.
Among the nitrogen-based flame retardants described above, aliphatic amine compounds, triazine compounds, and salts thereof exhibit an excellent flame retarding effect, and therefore these compounds can be particularly preferably used in the present invention.

  The phosphorus-based flame retardant used as the component (G) forms a heat-resistant film by forming a polyphosphoric acid compound when the blended resin is exposed to a high temperature, and it is also flame retardant by a mechanism for promoting carbonization by a solid acid. It is thought to show an effect. As such phosphorus flame retardants, known ones can be used without limitation. Specific examples include phosphorus alone such as red phosphorus; phosphates such as calcium phosphate and titanium phosphate; tributyl phosphate and triphenyl phosphate. Polyphosphates such as calcium phosphate, polyphosphates such as poly (diphenylphosphate), phosphine oxides such as triphenylphosphine oxide, phosphoranes such as phenylphosphorane Phosphonic acid such as diphenylphosphonic acid; phosphine sulfide, and the like.

  Among these, phosphorus simple substance, phosphate, and polyphosphate can be suitably used because they have a large flame retarding effect. In addition, when one or more thermoplastic resins selected from the group consisting of aromatic vinyl resins, polyphenylene ether resins and polyphenylene ether resins having a modified functional group are used as the component (A-1), molding is performed. From the viewpoint of processability, phosphate esters are preferably used.

  In the present invention, a nitrogen / phosphorous flame retardant having both a nitrogen atom and a phosphorus atom in one molecule as a compound having the functions of the nitrogen flame retardant and the phosphorus flame retardant described above as the component (G). Can be used. By using such a flame retardant, a resin composition particularly excellent in flame retardancy can be obtained. Examples of such flame retardants include phosphates and polyphosphates of the respective compounds exemplified above as nitrogen-based flame retardants; phosphazene compounds such as phenoxyphosphazene and methylphenoxyphosphazene; N, N-diethylphosphami And phosphoric acid amides such as poly (N, N-diethylphosphamide). In particular, the phosphates and polyphosphates of the aliphatic amine compounds represented by the above formula, and the phosphates and polyphosphates of the triazine compounds represented by the above formula have a large flame retardant effect, and thus the present invention. Can be preferably used.

Specific examples of the nitrogen / phosphorous flame retardant that can be suitably used as the component (G) of the present invention include ammonium phosphate, ethylenediamine phosphate, melamine phosphate, ammonium polyphosphate, ethylenediamine polyphosphate, and the like. Can do.
Among these nitrogen / phosphorous flame retardants, melamine phosphate is preferably used from the viewpoint of heat resistance and appearance of the molded product.

The above nitrogen / phosphorous flame retardants can be used alone or in admixture of two or more.
Furthermore, examples of the inorganic flame retardant that can be suitably used as the component (G) include one or more inorganic flame retardants selected from the group consisting of metal hydroxides and metal oxides.
Examples of the metal hydroxide that can be suitably used as such an inorganic flame retardant include, for example, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, hydrotalcites, calcium aluminate hydrate, and a composite represented by the following formula: Examples thereof include magnesium hydroxide.

Mg ₁ -xMx (OH) ₂
(Here, M is at least one selected from Mn, Fe, Co, Ni, Cu, and Zn, and X is a value greater than 0 and less than or equal to 0.1)

  The metal hydroxide that can be suitably used as the component (G) is preferably surface-treated. The surface treatment is preferable because the heat resistance of the metal hydroxide is improved, and the appearance and flame retardancy of the molded product are improved.

  The surface treatment of the metal hydroxide means that a part or the whole of the surface of the metal hydroxide particles is covered with a substance or the like mentioned as an example of the surface treatment agent described later. The surface treatment has a function of controlling the interaction between the matrix resin / metal hydroxide interface, and as a result, greatly affects the flame retardancy of the composition, the appearance of the molded product, and the mechanical strength. Examples of the surface treatment agent include higher fatty acids (for example, stearic acid and oleic acid), and alkali metal salts thereof, anionic surfactants (for example, sulfate esters of higher alcohols), phosphate esters (for example, ortholine). Acid and higher alcohol esters), silane coupling agents (eg, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, etc.), titanate coupling agents (eg, isopropyltriisostearoyl titanate), Examples include aluminum coupling agents (acetoalkoxyaluminum diisopropylate, etc.), polyhydric alcohol and fatty acid esters (glycerin monostearate, etc.), and the like.

The metal hydroxide that can be suitably used as the inorganic flame retardant of component (G) is an average secondary particle measured by a laser diffraction scattering method from the viewpoint of the mechanical strength of the resin composition and the dispersibility of the metal hydroxide. A diameter of 0.2 to 6 μm is preferable.
On the other hand, examples of the metal oxide that can be suitably used as the inorganic flame retardant of the component (G) include copper oxide (I), copper oxide (II), magnesium oxide, tungsten oxide (IV), tungsten oxide (VI), and titanium oxide. (II), titanium oxide (III), titanium oxide (IV), zinc oxide, iron oxide (II), iron oxide (III), barium oxide, manganese oxide (II), manganese oxide (III), manganese oxide (IV ), Manganese oxide (VII), molybdenum oxide (IV), molybdenum oxide (VI), and other metal oxides. In addition, an antimony oxide compound is not used as a component (G) of the present invention from the viewpoint of harmfulness. However, it does not interfere with the presence of the amount of impurities.

  The amount of nitrogen flame retardant, phosphorus flame retardant, nitrogen / phosphorus flame retardant and inorganic flame retardant of component (G) above is the sum of component (A), component (B) and component (C). The reference is 0.1 to 25 wt%, preferably 0.1 to 20 wt%. Most preferably, it is 0.2-15 wt%. When the blending amount is less than 0.1 wt%, a sufficient flame retardant effect cannot be obtained, and when it exceeds 25 wt%, the moldability and mechanical properties are deteriorated, which is not preferable.

  In addition, it is preferable that the flame retardant resin composition of this invention contains a flame retardant adjuvant as (H) component. By blending the flame retardant aid, the oxygen index can be improved and the maximum heat generation rate can be greatly reduced. As the flame retardant aid, for example, at least one flame retardant aid selected from the group consisting of hindered amine compounds, fluororesins, silicone oils, and silicone-acrylic composite rubbers is preferably used. By using these flame retardant aids, decomposition of the resin as component (A) can be prevented and the maximum heat generation rate can be suppressed.

  The blending amount of the flame retardant aid as the component (H) is 0.1 to 25 wt%, preferably 0.1 based on the sum of the components (A), (B) and (C) of the present invention. ~ 20 wt%. Most preferably, it is 0.2-15 wt%. When the blending amount is less than 0.1 wt%, a sufficient flame retardant effect cannot be obtained, and when it exceeds 25 wt%, the moldability, the flexibility and the elongation at break decrease, which is not preferable.

  The flame-retardant 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 flame retardant resin composition of the present invention contains the components (A), (B), and (C) as essential components, and the components (D) to (F) or components (D) to (H) are optional components. However, if necessary, other components as described above can be blended. When it divides roughly, it contains the resin component which consists of (A), (D) and (E) component, and the non-resin component which consists of (B), (C), (F) and (H) component. The preferred blending ratio is as follows. The resin component is 2 to 99.9% by weight, preferably 30 to 97% by weight. (A) component in a resin component is 5-100 wt%, Preferably it is 30-100 wt%. The component (D) in the resin component is 0 to 70 wt%, preferably 10 to 40 wt%. (E) component in a resin component is 0 to 70 wt%, preferably 10 to 40 wt%.

The proportion of each component in the flame retardant resin composition of the present invention is preferably in the following range.
Component (A): 4 to 99.8 wt%, preferably 30 to 96 wt%
Component (B): 0.1 to 95.9 wt%, preferably 4 to 70 wt%
Component (C): 0.1 to 95.9 wt%, preferably 4 to 70 wt%
Component (D): 0 to 60 wt%, preferably 5 to 55 wt%
Component (E): 0 to 90 wt%, preferably 5 to 85 wt%
Component (F): 0 to 90 wt%, preferably 5 to 85 wt%
Component (G): 0 to 25 wt%, preferably 0.1 to 20 wt%
(H) component: 0 to 25 wt%, preferably 0.1 to 20 wt%

  The method for producing the flame retardant resin composition of the present invention is not particularly limited. For example, the resin having a specific aromatic structure as the component (A), the specific halogen flame retardant as the component (B), (C) The specific layered silicate of the component and, if desired, a method of directly blending and mixing other predetermined components, and a resin having a specific aromatic structure as the component (A) C) The specific layered silicate layered silicate of the component and the flame retardant aid are blended and mixed to prepare a masterbatch, and then the prepared masterbatch has a predetermined blending amount of the component (A). Examples thereof include a so-called master batch method in which a resin having a specific aromatic structure and a specific halogen-based flame retardant as the component (B) are added for dilution.

The mixing method for producing the flame retardant resin composition of the present invention is not particularly limited, and various methods can be used. For example, a solution mixing method in which each component is uniformly dissolved or dispersed in a solvent, a blending method in which stirring and mixing are performed with a Henschel mixer, a melt kneading method in an extruder, a two-roll, a Banbury mixer, and the like can be used. .
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 flame retardant resin composition is dissolved in the above-described solvent and molded into a predetermined shape, or a heat melting method in which the flame retardant resin composition is heated and melted to be molded into a predetermined shape is used.

When the flame retardant fat composition of the present invention is a curable resin composition, a cured product is obtained by curing the composition. 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, this curable resin composition can be used together with a metal foil (meaning including a metal plate, the same shall apply hereinafter) as in the case of the cured composite material described later.

  Next, a flame retardant film, a flame retardant composite material, a flame retardant cured composite material, a flame retardant resin cured product, a flame retardant laminate and a flame retardant resin obtained from the flame retardant resin composition of the present invention The attached metal foil will be described. The flame retardant resin cured product of the present invention can be obtained by, for example, heat curing the flame retardant resin composition of the present invention.

The flame retardant film of the present invention may be composed of a single layer or may be composed of a plurality of layers. As the flame retardant film composed of a plurality of layers, for example, a film having a multilayer structure composed of an intermediate layer and a surface layer sandwiching the intermediate layer is preferable.
When the flame retardant film has a multilayer structure composed of an intermediate layer and a surface layer sandwiching the intermediate layer, the layered silicate is preferably contained in the flame retardant resin composition constituting the surface layer. .

  The preferable lower limit of the thickness of the flame-retardant film of the present invention is 5 μm, and the preferable upper limit is 300 μm. If it is less than 5 μm, the strength tends to be insufficient, and if it exceeds 300 μm, the thermal conductivity during hot press molding may deteriorate. Moreover, the influence on the circuit pattern at the time of hot press molding is greatly influenced by the shrinkage force of the flame retardant film in addition to the dimensional change rate of the flame retardant film. Furthermore, since the shrinkage force has a large correlation with the cross-sectional area of the film, in order to reduce the shrinkage force and reduce the influence on the circuit pattern during hot press molding, the thickness of the flame retardant film should be 100 μm or less. More preferably. A more preferred lower limit is 10 μm and a still more preferred upper limit is 50 μm. When the flame retardant film has a multilayer structure composed of an intermediate layer and a surface layer sandwiching the intermediate layer, the ratio of the intermediate layer when the total thickness is 1 is 0.5 or less. Preferably there is.

  The surface of the flame-retardant film of the present invention preferably has smoothness, but may have been provided with slipping properties, anti-blocking properties, etc. necessary for handling, and is intended for air escape during hot press molding. As a matter of course, an appropriate embossed pattern may be provided on at least one side.

The method for producing the flame-retardant film of the present invention is not particularly limited, and examples thereof include a melt molding method and a solution casting method.
The melt molding method is not particularly limited, and examples thereof include conventionally known methods for forming a resin film such as air-cooled or water-cooled inflation extrusion method and T-die extrusion method.
In addition, as a solution casting method, a flame retardant resin composition and, if necessary, other components are uniformly dissolved or dispersed in an aromatic or ketone solvent or a mixed solvent thereof, and a resin such as a PET film. The method of drying after apply | coating to a film is 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 flame retardant film of the present invention may be heat-treated after molding in order to improve heat resistance and dimensional stability. The treatment temperature is more effective as the temperature is lower than the melting point of the flame retardant resin composition constituting the film, and is preferably 90 ° C. or higher, more preferably 100 ° C. or higher. Other methods for improving the heat resistance and dimensional stability include a method of stretching a flame retardant film in a uniaxial or biaxial direction, a method of rubbing the surface of the flame retardant film with buffalo or the like.

The laminate obtained by laminating the flame-retardant film of the present invention on at least one side has cushioning properties and strength for applying pressure uniformly during hot press molding, for example, to a circuit pattern on a flexible printed circuit board. Excellent uniform filling and adhesion.
On the other hand, a laminated flame retardant film comprising a laminate in which the flame retardant film of the present invention is laminated on at least one surface of the resin film is also one aspect of the present invention.

  The flame retardant composite material of the present invention is obtained by adding a base material to a flame retardant resin composition in order to increase mechanical strength and increase dimensional stability. Here, when aiming at a curable flame-retardant composite material (hereinafter also referred to as a curable composite material), a curable flame-retardant composite material is used. In addition, although a base material contains the thing which cannot be distinguished from (F) component, the fiber, paper, and cloth mainly aimed 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 Woven or non-woven fabrics obtained from liquid crystal fibers such as polyester fibers and polybenzoxal fibers, woven or non-woven fabrics obtained from synthetic fibers such as polyvinyl alcohol fibers, polyester fibers, and acrylic fibers, and natural fiber fabrics such as cotton cloth, linen, and felt. , Carbon fiber cloth, kraft paper, cotton paper, cloth such as natural cellulosic cloth such as paper-glass mixed paper, paper, etc. are used singly 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 flame retardant 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 flame-retardant 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.

  Examples of the method for producing the flame retardant composite material of the present invention include the above-mentioned flame retardant resin composition of the present invention and other components, if necessary, the above-mentioned aromatic or ketone solvents or mixed solvents thereof. A method of uniformly dissolving or dispersing in the substrate, impregnating the substrate, and drying the substrate may be mentioned. 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.

  When the flame retardant composite material of the present invention contains a thermosetting resin, the flame retardant composite material is obtained by curing by a method such as heating. The manufacturing method is not particularly limited. For example, a plurality of flame retardant composite materials are overlapped, and each layer is bonded under heat and pressure, and at the same time, thermosetting is performed, and a flame retardant cured composite material having a desired thickness is obtained. Can be obtained. It is also possible to obtain a flame retardant cured composite material having a new layer structure by combining the flame retardant cured composite material once bonded and cured with the flame retardant 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, an uncured or semi-cured flame retardant 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 flame-retardant laminate of the present invention comprises a layer of the flame-retardant 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 flame retardant laminate of the present invention, for example, a flame retardant composite material obtained from the flame retardant resin composition of the present invention described above and a base material, and a layer depending on the purpose of the metal foil A method of laminating with a structure and bonding each layer under heat and pressure and simultaneously thermosetting can be mentioned. In the laminate of the flame retardant resin composition of the present invention, the flame retardant 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 flame retardant cured composite material of the present invention.

  The metal foil with a flame retardant resin of the present invention is composed of the flame retardant 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 flame retardant resin composition of the present invention contains a high degree of flame retardancy, good appearance, molding processability, curing characteristics, even in a thin molded product or cured product without containing an antimony compound such as antimony trioxide. It exhibits dielectric properties, heat resistance, and heat hydrolysis resistance, and is used for dielectric materials, insulating materials, heat resistant materials, structural materials, packaging materials, adhesive materials, housing materials, barrier materials, etc. in fields such as the electrical industry, space and aircraft industries. Can be used. 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 tetrachloroethane-d ₂ which is an NMR measurement solvent was used as an internal standard.

3) Sample preparation and measurement of glass transition temperature (Tg) and softening temperature measurement Tg measurement of the cured film obtained by hot press molding is carried out by setting the sample film in a TMA (thermomechanical analyzer) measuring device and nitrogen. The measurement was performed by scanning from 30 ° C. to 360 ° C. at a heating rate of 10 ° C./min under an air flow, and Tg was determined from the inflection point where the linear expansion coefficient changed, and the softening temperature was obtained 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. .
8) Average interlayer distance of layered silicate 2θ of diffraction peak obtained from diffraction of layered surface of layered silicate in 2 mm thick plate using X-ray diffractometer (RINT1100, manufactured by Rigaku Corporation) The (001) plane spacing (d) of the layered silicate was calculated from the following black diffraction formula, and the obtained d was defined as the average interlayer distance (nm).
λ = 2 dsin θ (4)
In the formula, λ is 1.54, d represents the interplanar spacing of the layered silicate, and θ represents the diffraction angle.

9) Ratio of layered silicate dispersed in 5 layers or less The total number of layered silicate laminates that can be observed in a certain area by observation with a transmission electron microscope at 50,000 to 100,000 times The number (Y) of the layered silicate dispersed in 5 layers or less in (X) was measured, and the ratio P (%) of the layered silicate dispersed in 5 layers or less was calculated by the following formula. .
Ratio of layered silicate dispersed in 5 layers or less P (%) = (Y / X) × 100
10) Flammability Flammability was evaluated by performing a combustion test in accordance with the vertical combustion test method of US UL standard subject 94 (UL94) to evaluate flame retardancy.

12) Surface property The surface property of the molded product was observed using a stereomicroscope, and evaluated according to the following three steps according to the smoothness of the surface.
A: High smoothness and good surface properties.
Δ: Small irregularities exist, and the smoothness is slightly inferior.
X: Large unevenness exists, and the surface property has low smoothness.
13) DTUL
Measurements were performed according to ASTM D648. Load: 18.6 kg / cm ²

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%.
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. Moreover, it turned out that the indane structure exists in the copolymer B. 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%.
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 having an intrinsic viscosity of 0.45 (manufactured by Mitsubishi Gas Chemical Company)
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-2 St-2: Polyphenylene oligomer having vinyl groups at both ends (Mn = 2270, manufactured by Mitsubishi Gas Chemical Company, 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)
Curing catalyst C-1: 2-ethyl-4-methylimidazole (manufactured by Shikoku Kasei Co., Ltd., Curazole 2E4MZ)
Curing catalyst C-2: 1-cyanoethyl-2-methylimidazole (manufactured by Shikoku Kasei Co., Ltd., Curazole 2MZ-CN)
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, trade name: KRATON G1652)
Thermoplastic resin T-3: hydrogenated styrene butadiene block copolymer (manufactured by Kraton Polymer Japan, trade name: KRATON GRP6935)
Thermoplastic resin T-4: hydrogenated styrene butadiene block copolymer (manufactured by Kraton Polymer Japan, trade name: KRATON G1730)
Thermoplastic resin T-5: styrene butadiene block copolymer (manufactured by 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（東都化成社製、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（東都化成社製、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（東亜合成社製、商品名：アロニックスＭ−３１５） 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)

Halogen flame retardant F-1: ethane-1,2-bis (pentabromophenyl) (Cytex 8010 manufactured by Albemarle)
Halogen flame retardant F-2: Brominated polystyrene with atactic structure (Firemaster PBS-64HW manufactured by Great Lakes)
Halogen flame retardant F-3: Polydibromophenylene oxide (Daiichi F.R., Pyroguard SR-460B)
Halogen flame retardant F-4: Octabromotrimethylphenylindane (Cytex 8010 manufactured by Albemarle)
Halogen flame retardant F-5: Brominated epoxy compound (BROC manufactured by Nippon Kayaku Co., Ltd.)
Layered silicate H-1: synthetic hectorite treated with trioctylmethylammonium salt (Corp Chemical Co., Lucentite STN)
Spherical silica S-1: Average particle diameter: 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, PPE, OPE-2St-1, thermoplastic resin T-1, halogen flame retardant F-1, halogen flame retardant F-5, and layered silicate H-1 obtained by the above synthesis example The amount shown in Table 1 and toluene as a solvent were blended, and after stirring, a reaction initiator P-1 and a curing catalyst C-1 were added to prepare a flame retardant resin composition solution.
A flame retardant 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. The film was 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.
Tensile strength, elongation rate, dielectric constant, dielectric loss tangent, average interlayer distance of layered silicate, ratio P (%) of layered silicate dispersed as a laminate of 5 layers or less, flame retardancy, The surface properties and moldability were measured.

Copolymer A, PPE, OPE-2St-1, thermoplastic resin T-2, halogen flame retardant F-1, halogen flame retardant F-5, and layered silicate H- obtained by the above synthesis example 1 was used, and toluene was blended as an amount shown in Table 1 and a solvent. After stirring, a reaction initiator P-1 and a curing catalyst C-2 were added to prepare a flame retardant resin composition solution.
The obtained flame-retardant 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.
Tensile strength, elongation rate, dielectric constant, dielectric loss tangent, average interlayer distance of layered silicate, ratio P (%) of layered silicate dispersed as a laminate of 5 layers or less, flame retardancy, The surface properties and moldability were measured.

  The cured product film and evaluation result which consisted of a flame retardant resin composition were obtained by the method similar to Example 1 except having changed the flame retardant addition amount and having added thermosetting resin E-1.

Except having added thermosetting resin E-2, the cured | curing material film and evaluation result which consist of a flame-retardant resin composition were obtained by the method similar to Example 3. FIG.
The composition and the evaluation results are shown in Table 1.

Comparative Examples 1-4
Copolymer A, PPE, OPE-2St-1, thermoplastic resin T-1, halogen flame retardant F-1, halogen flame retardant F-5, and layered silicate H-1 obtained by the above synthesis example And the flame retardancy prepared by adding toluene as a solvent and the amount shown in Table 2 for calcium carbonate-1 having an average particle diameter of 50 μm and adding the initiator P-1 and the curing catalyst C-1 after stirring. The flame retardant resin composition was evaluated in the same manner as in Example 2 except that a film of about 15 μm was prepared by casting the resin composition solution on a PET sheet. The results are shown in Table 2.

Comparative Examples 5-8
Brominated polystyrene having a syndiotactic structure as copolymer A, PPE, OPE-2St-1, thermoplastic resin T-1 and halogen flame retardant F-6 obtained by the above synthesis example (bromine content: 51 %, Syndiotacticity: 95% or more, number average molecular weight: 670,000, Mw / Mn: 2.75), hexabromocyclododecane (fire master CD-75P manufactured by Great Lakes Co., Ltd.) as halogen flame retardant F-7 , And layered silicate H-1 and calcium carbonate-1 having an average particle size of 50 μm, the amount shown in Table 3 and toluene as a solvent were blended, and after stirring, reaction initiator P-1 and curing catalyst C-1 The flame retardant resin composition was evaluated in the same manner as in Example 2 except that a film having a thickness of about 15 μm was prepared by casting the flame retardant resin composition solution prepared by adding on the PET sheet. Was Tsu. The results are shown in Table 3.

  As layered silicate H-2, swelling fluorine mica-1 (manufactured by Co-op Chemical Co., somasif MAE-100) treated with distearyldimethyl quaternary ammonium salt, and layered silicate H-3 A natural montmorillonite-1 (New S-Ben D, manufactured by Toyoshun Yoko Co., Ltd.) treated with stearyldimethyl quaternary ammonium salt was used, and a thermosetting resin composition solution was applied to a polyethylene terephthalate resin (PET) sheet. The obtained film (about 50-60 μm thick) was 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. Except for this, the flame retardant resin composition was evaluated in the same manner as in Example 1. Table 4 shows the composition and evaluation results.

  In a small extruder TEX30 manufactured by Nippon Steel Works, PPE, HIPS-1 (H-625S manufactured by Nippon Steel Chemical Co., Ltd., rubber content: 9.6%), halogen flame retardant F-1, layered silicate H -1 and layered silicate H-3 were melted and kneaded at a set temperature of 280 ° C., and the extruded strand was pelletized with a pelletizer. A test piece and a flat plate were prepared by an injection molding machine in which the obtained pellets were temperature-controlled at 280 ° C. Using the obtained test piece and flat plate, the tensile test, DTUL, combustion test, and surface property of the molded product were evaluated. The results are shown in Table 5.

Comparative Examples 9-12
A flame retardant resin composition in the same manner as in Example 6 except that no layered silicate was added, calcium carbonate-1 was used, and the amounts shown in Table 6 were blended for other components. Was evaluated. The results are shown in Table 6.

  Copolymer B, thermoplastic resin T-3, thermoplastic resin T-4, thermoplastic resin T-5, thermosetting resin E-3, thermosetting resin E-4, heat obtained by the above synthesis example The flame retardant resin composition was evaluated in the same manner as in Example 1 except that the curable resin E-5, the halogen flame retardant F-3, and the halogen flame retardant F-4 were used. The results are shown in Table 7.

A glass cloth (E glass, weight per unit area: 71 g / m ² ) was immersed in the resin composition solution obtained in Example 2 for impregnation, and dried in an air oven at 60 ° C. for 30 minutes. The resin content (RC) of the obtained prepreg was 67%.
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 60 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 209 ° C. In the solder heat resistance test, no change was observed in the appearance of the laminate. The dielectric constant was 2.65, and the dielectric loss tangent was 0.0023.

  Melamine phosphate (manufactured by Sanwa Chemical Co., Ltd., trade name: P-7202, flame retardant G-1), melamine pyrophosphate (manufactured by Sanwa Chemical Co., Ltd., trade name: MPP-A, flame retardant G-2), melamine shear Example 1 except that nurate (Nissan Chemical Co., Ltd., MC-440, flame retardant G-3) and hexaphenoxycyclotriphosphazene (Otsuka Chemical Co., Ltd., SPB-100, flame retardant G-4) were used. The flame retardant resin composition was evaluated by this method. Table 8 shows the composition and evaluation results.

Claims (16)

Component (A): One or more thermoplastic resins selected from the group consisting of aromatic vinyl resins and polyphenylene ether resins as component (A-1), and / or aromatic structure as component (A-2) A thermosetting resin having,
(B) component: halogen flame retardant,
(C) component: at least one layered silicate selected from the group consisting of montmorillonite, swellable mica and hectorite,
(B) component halogen flame retardant is decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, ethane-1,2-bis (pentabromophenyl), bis ( 2,4,6-tribromophenoxy) ethane, ethylenebistetrabromophthalimide, polydibromophenylene oxide, tetrabromobisphenol-S, 1,1-sulfonyl [3,5-dibromo-4- (2,3-dibromopropoxy) )] Benzene, tris (2,3-dibromopropyl-1) isocyanurate, tris (tribromophenyl) cyanurate, atactic brominated polystyrene, atactic brominated styrene-methyl methacrylate copolymer, atactic bromine Styrene-methyl methacrylate-glycidyl methacrylate copolymer, atactic brominated styrene-glycidyl methacrylate copolymer, atactic brominated styrene-polypropylene copolymer, brominated polyethylene, tetrabromobisphenol-A, tetra Bromobisphenol-A-epoxy oligomer, brominated epoxy compound, tetrabromobisphenol-A-carbonate oligomer, tetrabromobisphenol-A-bis (2-hydroxydiethyl ether), tetrabromobisphenol-A-bis (2,3-dibromo) Propyl ether), poly (pentabromobenzyl acrylate) and one or more halogen-based flame retardants selected from the group consisting of octabromotrimethylphenylindane The blending amount of the component (A) is 4 to 99.8 wt%, the blending amount of the component (B) is 0.1 to 95.9 wt% with respect to the sum of the components (A), (B) and (C). The flame-retardant resin composition, wherein the amount of component C) is 0.1 to 95.9 wt%.   The polyphenylene ether resin is a polyphenylene ether resin having an unmodified terminal functional group, a polyphenylene ether resin having a modified terminal functional group, or a polyphenylene ether resin having a substituent other than an alkyl group on a main chain benzene ring. The flame-retardant resin composition as described.   The aromatic vinyl resin is a polymer of a monomer containing 20 to 100 mol% of a monovinyl aromatic compound or an aromatic structure-containing block copolymer having a polymer segment having a glass transition temperature of 20 ° C or lower. 2. The flame retardant resin composition according to 2.   (A-2) The thermosetting resin in which the component contains at least one functional group selected from the group consisting of vinyl group, ethynyl group, epoxy group, oxetane group, cyanate group, isocyanate group and hydroxyl group and an aromatic structure The flame retardant resin composition according to any one of claims 1 to 3. The component (A-2) is a polyfunctional vinyl aromatic copolymer having a structural unit derived from a monomer comprising the divinyl aromatic compound (a) and the ethyl vinyl aromatic compound (b), and the divinyl aromatic compound The repeating unit derived from (a) is contained in an amount of 20 mol% or more, and the following formulas (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 a polyfunctional vinyl aromatic copolymer in which the molar fraction of the structural unit containing a vinyl group derived from satisfies (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. One or more aromatic structures selected from the group consisting of a solvent-soluble polyfunctional vinyl aromatic copolymer, a thermosetting polyphenylene ether, a polyphenylene ether oligomer having functional groups at both ends, and a polyfunctional aromatic epoxy compound Thermosetting containing The flame retardant resin composition according to any one of claims 1 to 4 sex resin. In the main chain skeleton of the polyfunctional vinyl aromatic copolymer, the component (A-2) has a structural unit derived from a monomer comprising the divinyl aromatic compound (a) and the 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). The flame-retardant resin composition according to claim 1, which is a polyfunctional vinyl aromatic copolymer having an indane structure represented.   The layered silicic acid characterized in that the component (C) has an average interlaminar distance of (001) plane measured by wide-angle X-ray diffraction measurement method of 3 nm or more and part or all are dispersed in 5 layers or less It is a salt, The flame-retardant resin composition in any one of Claims 1-6.   Furthermore, it is a resin composition containing a thermoplastic resin other than the component (A-1) as the component (D), and is based on the sum of the components (A), (B), (C) and (D) ( The flame-retardant resin composition according to any one of claims 1 to 7, wherein the blending amount of component D) is 1 to 60 wt%.   Furthermore, as the component (E), a flame retardant resin composition containing a thermosetting resin not containing an aromatic structure, the component (A), the component (B), the component (C), the component (D) and The flame-retardant resin composition according to any one of claims 1 to 8, wherein the amount of the component (E) is 1 to 60 wt% with respect to the total of the components (E).   Furthermore, a flame retardant resin composition containing a filler as the component (F), the component (A), the component (B), the component (C), the component (D), the component (E), and the component (F) The flame-retardant resin composition according to any one of claims 1 to 9, wherein the blending amount of the component (F) is 2 to 90 wt% with respect to the total of the components.   A flame retardant resin curing obtained by curing a flame retardant resin composition containing a thermosetting resin among the flame retardant resin composition according to any one of claims 1 to 10. object.   A flame retardant film obtained by molding the flame retardant resin composition according to claim 1 into a film shape.   A flame retardant composite material comprising the flame retardant resin composition according to any one of claims 1 to 10 and a base material, wherein the base material is contained at a ratio of 5 to 90 wt%. .   A flame-retardant curable composite material obtained by curing a composite material containing a thermosetting resin among the flame-retardant composite materials according to claim 13.   A flame retardant laminate comprising a layer of the flame retardant composite material according to claim 13 and a metal foil layer.   A metal foil with a flame-retardant resin, comprising a resin layer formed from the flame-retardant resin composition according to claim 1 on one side of the metal foil.