JP2008248001A - Curable resin composition - Google Patents

Abstract

The present invention relates to a curable resin composition comprising a soluble polyfunctional vinyl aromatic polymer having a phenolic hydroxyl group at a terminal having excellent heat resistance and adhesiveness and excellent curability and molding processability, and a thermoplastic resin. And the film obtained from this, metal foil with resin, and a resin substrate are provided.
The component (A) is a copolymer obtained by copolymerizing a divinyl aromatic compound and a monovinyl aromatic compound, and has a phenolic hydroxyl group derived from a polymerization additive at a part of its terminal. And a soluble polyfunctional vinyl aromatic copolymer in which the content of structural units containing unreacted vinyl groups derived from divinyl aromatic compounds is 10 to 90 mol%, and component (B): thermoplastic resin , Wherein the blending amount of the component (A) is 2 to 98 wt% and the blending amount of the component (B) is 98 to 2 wt% with respect to the total of the components (A) and (B). Resin composition.
[Selection figure] None

Description

  The present invention relates to a curable resin composition comprising a soluble polyfunctional vinyl aromatic polymer having a phenolic hydroxyl group at a terminal and a thermoplastic resin, a film obtained from the curable resin composition, a metal foil with a resin, and a resin substrate. .

  Many of the monomers having a reactive active unsaturated bond can generate a multimer by selecting an appropriate reaction condition and a catalyst that causes a chain reaction by cleavage of the unsaturated bond. As a general-purpose monomer representing such a monomer having an unsaturated bond, vinyl aromatic compounds such as styrene, alkylstyrene and alkoxystyrene can be exemplified. A wide variety of resins have been synthesized by using such vinyl aromatic compounds alone or by copolymerizing them.

  However, the applications of polymers obtained from such vinyl aromatic compounds are mainly limited to the field of relatively inexpensive consumer equipment, and are highly functional and advanced like printed wiring boards in the electrical and electronic fields. There is almost no application to advanced technology that requires thermal and mechanical properties. The reason is that thermal characteristics such as heat resistance or heat decomposability and workability such as solvent solubility or film formability cannot be satisfied at the same time.

  As a method for solving such drawbacks of the conventional vinyl aromatic polymer, Japanese Patent Application Laid-Open No. 2004-123873 (Patent Document 1) discloses divinyl aromatic compounds (a) and monovinyl aromatic compounds (b) as organic. A soluble polyfunctional vinyl aromatic copolymer obtained by polymerizing at a temperature of 20 to 100 ° C. in a solvent in the presence of a Lewis acid catalyst and an initiator having a specific structure is disclosed. JP-A-2005-213443 (Patent Document 2) contains 20 to 100 mol% of a divinyl aromatic compound (a) in the presence of a quaternary ammonium salt with a Lewis acid catalyst and an initiator having a specific structure. A method for producing a soluble polyfunctional vinyl aromatic copolymer having a controlled molecular weight distribution by cationic polymerization of the monomer component at a temperature of 20 to 120 ° C. is disclosed. The soluble polyfunctional vinyl aromatic copolymer obtained by the techniques disclosed in these documents is excellent in solvent solubility and processability, and by using this, a cured product having a high glass transition temperature and excellent heat resistance is obtained. be able to.

  And although the curable resin composition using the soluble polyfunctional vinyl aromatic copolymer obtained by these techniques is disclosed by Unexamined-Japanese-Patent No. 2004-131638, the hardened | cured material with a high glass transition temperature is given. Although it can be said that it is a curable resin composition excellent in heat resistance, from the viewpoint of adhesion and compatibility with polar polymers, its characteristics are not sufficient and high-temperature thermal history In some cases, poor adhesion occurs. Furthermore, since the curable resin composition obtained by this technique does not have a polar group that provides adhesion to metal, it has a problem that adhesion to metal wiring is not sufficient.

JP 2004-123873 A Japanese Patent Laid-Open No. 2005-213443 JP 2004-131638 A

  Therefore, the object of the present invention is to solve the various problems of the prior art described above, to have excellent heat resistance and adhesiveness against heat history at high temperatures, excellent curability, and molding processing. It is providing the curable resin composition excellent in property. In addition, the present invention provides a soluble polyfunctional vinyl having a phenolic hydroxyl group at the terminal, which has excellent heat resistance and adhesiveness against high-temperature heat history, excellent curability, and excellent moldability. It aims at providing the curable resin composition which consists of an aromatic polymer and a thermoplastic resin, the film obtained from this, metal foil with resin, and a resin substrate.

（式中、Ｒ¹は炭素数６〜３０の芳香族炭化水素基を示す。）で表される未反応のビニル基を含有する構造単位の含有量が１０〜９０モル％である末端にフェノール性水酸基を有する可溶性多官能ビニル芳香族共重合体と、
（Ｂ）成分：熱可塑性樹脂
からなる樹脂組成物であって、（Ａ）成分及び（Ｂ）成分の合計に対する（Ａ）成分の配合量が２〜９８ｗｔ％、（Ｂ）成分の配合量が９８〜２ｗｔ％であることを特徴とする硬化性樹脂組成物である。 The present invention is a copolymer obtained by copolymerizing (A) component: divinyl aromatic compound (a) 20 to 99 mol% and monovinyl aromatic compound (b) 80 to 1 mol%, Having a phenolic hydroxyl group derived from the polymerization additive (c) in a part thereof and the following formula (a1) derived from the divinyl aromatic compound (a)

(Wherein R ¹ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms.) The content of the structural unit containing an unreacted vinyl group represented by A soluble polyfunctional vinyl aromatic copolymer having a functional hydroxyl group;
(B) component: It is a resin composition consisting of a thermoplastic resin, and the blending amount of the (A) component with respect to the sum of the (A) component and the (B) component is 2 to 98 wt%, and the blending amount of the (B) component is It is 98-2 wt%, It is a curable resin composition characterized by the above-mentioned.

  Here, the number average molecular weight Mn of the soluble polyfunctional vinyl aromatic copolymer having a phenolic hydroxyl group at the terminal is 500 to 100,000, and the molecular weight distribution (Mw) represented by the ratio of the weight average molecular weight Mw and the number average molecular weight Mn. Satisfying that / Mn) is 50.0 or less, or that the amount of phenolic hydroxyl group introduced to the terminal is 2.2 / molecule or more, gives an excellent curable resin composition.

  Examples of thermoplastic resins include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyesters such as polyethylene terephthalate / polyethylene glycol block copolymers and derivatives thereof, polyphenylene ether, modified polyphenylene ether, polycarbonate, polysulfone, and polymethyl methacrylate. , Polystyrenes such as acrylic acid (or methacrylic acid) ester copolymers, polystyrenes, acrylonitrile styrene copolymers, acrylonitrile styrene butadiene copolymers and their copolymers, polyvinyl acetates, ethylene acrylic acid Rubbers such as ester copolymers, styrene conjugated diene block copolymers, rubbers such as hydrogenated styrene conjugated diene block copolymers, polybutadiene , Rubbers such as polyisoprene, polyvinyl ethers such as polymethoxyethylene and polyethoxyethylene, polyacrylamides, polyphosphazenes, polyethersulfone, polyetherketone, polyetherimide, polyphenylene sulfide, polyamideimide and heat One or more thermoplastic resins selected from the group consisting of plastic polyimides are preferred.

  In addition to the components (A) and (B), the present invention includes a thermosetting resin as the component (C), a flame retardant as the component (D), or an inorganic filler as the component (E). The curable resin composition. Here, the blending amount of the (C) component with respect to the sum of the (A) component, the (B) component, and the (C) component is 2 to 40 wt%, the (A) component, the (B) component, and the (C) component. And the blending amount of the component (D) with respect to the sum of the components (D) is 2 to 40 wt%, or the components (A), (B), (C), (D) and (E) It is preferable to satisfy one of the blending amounts of the component (E) with respect to the total being 2 to 60 wt%.

  Furthermore, the present invention provides a curable resin film comprising the above curable resin composition, a metal foil with a resin having a film of the curable resin composition, or a cured product of the curable resin composition, and a resin substrate comprising the cured product. It is.

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

  The curable resin composition of the present invention comprises a soluble polyfunctional vinyl aromatic copolymer having a phenolic hydroxyl group at the terminal as the component (A) (hereinafter also referred to as copolymer) and a thermoplastic resin as the component (B). The blending amount of the component (A) with respect to the total of the components (A) and (B) is 2 to 98 wt%, and the blending amount of the component (B) is 98 to 2 wt%.

  The copolymer of component (A) is a copolymer obtained by copolymerizing divinyl aromatic compound (a) 20 to 99 mol% and monovinyl aromatic compound (b) 80 to 1 mol%, It has a phenolic hydroxyl group derived from the polymerization additive (c) at a part of the terminal and an unreacted vinyl group represented by the above formula (a1) derived from the divinyl aromatic compound (a). The soluble polyfunctional vinyl aromatic copolymer having a structural unit (hereinafter referred to as structural unit (a1)) content of 10 to 90 mol% and having a phenolic hydroxyl group at the terminal. Here, soluble means that it is soluble in toluene, xylene, tetrahydrofuran, dichloroethane or chloroform. The number average molecular weight Mn of this copolymer is 500 to 100,000, the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight Mw and the number average molecular weight Mn is 50.0 or less, The amount introduced at the end is preferably 2.2 / molecule or more.

  Since the copolymer is obtained by copolymerizing a monomer containing a divinyl aromatic compound, it has several structural units derived from the divinyl aromatic compound. And it is the polyfunctional vinyl aromatic copolymer which has a fixed quantity of structural units (a1) represented by the said Formula (a1). The unreacted vinyl group in the structural unit (a1) is also referred to as a pendant vinyl group, which exhibits polymerizability and can be polymerized by further polymerization treatment to give a solvent-insoluble thermosetting resin. In addition, although it has a branched structure for imparting polyfunctionality and a structural unit for imparting a vinyl group in the main chain, the crosslinked structural unit is limited to such a degree that it is soluble. Furthermore, the copolymer of the present invention has a phenolic hydroxyl group derived from the polymerization additive at the terminal.

  The copolymer has a phenolic hydroxyl group at a part of the terminal, and the terminal phenolic hydroxyl group is preferably introduced in an amount of 2.2 (number / molecule) or more. By introducing a phenolic hydroxyl group at the terminal, a resin composition with improved adhesion can be obtained.

  The copolymer is obtained by copolymerizing 20 to 99 mol% of the divinyl aromatic compound (a) and 1 to 80 mol% of the monovinyl aromatic compound (b). It has a structural unit derived from the divinyl aromatic compound (a) and a structural unit derived from the monovinyl aromatic compound (b) in a composition ratio. This copolymer preferably contains 25 to 95 mol% of structural units derived from the divinyl aromatic compound (a) based on structural units derived from all monomers.

  The divinyl aromatic compound (a) branches the copolymer of the present invention and generates a structural unit (a1) having a pendant vinyl group. The cured product obtained by thermosetting the copolymer has heat resistance. It plays an important role as a cross-linking component for the expression of.

  Examples of the divinyl aromatic compound (a) include divinylbenzene (both isomers of m- and p-), divinylnaphthalene (including each isomer), divinylbiphenyl (including each isomer), and the like. However, it is not limited to these. Moreover, these can be used individually or in combination of 2 or more types. In particular, from the viewpoint of cost and availability, divinylbenzene (both isomers of m- and p-), and when higher heat resistance is required, divinylnaphthalene (including each isomer), divinylbiphenyl ( Each isomer is preferred).

Since the structural unit (a1) is derived from the divinyl aromatic compound (a), R ¹ in the formula (a1) can be understood from the divinyl aromatic compound (a). That is, when divinylbenzene is used as the divinyl aromatic compound, it is an R ¹ phenylene group, and other divinyl aromatic compounds such as divinylbiphenyl are also understood to be residues generated by removing two vinyl groups therefrom.

  Monovinyl aromatic compound (b) is used with divinyl aromatic compound (a) to improve the solvent solubility and processability of the copolymer.

  Examples of monovinyl aromatic compounds (b) include, but are not limited to, styrene, nuclear alkyl substituted monovinyl aromatic compounds, α-alkyl substituted monovinyl aromatic compounds, β-alkyl substituted styrenes, alkoxy substituted styrenes, and the like. It is not a thing.

  In addition to the monovinyl aromatic compound (b) and the divinyl aromatic compound (a), a small amount of the other monomer component (d) can be used. Specific examples of the other monomer component (d) include 1,3,5-trivinylbenzene, 1,3,5-trivinylnaphthalene, 1,2,4-trivinylcyclohexane, ethylene glycol diene. Examples thereof include, but are not limited to, acrylate and butadiene. These can be used alone or in combination of two or more. The structural unit derived from the other monomer component (d) is within a range of less than 30 mol% with respect to the total amount of the structural unit derived from the monomer component (a) and the structural unit derived from the monomer component (b). Used in.

  The number average molecular weight Mn of the copolymer (where Mn is the number average molecular weight in terms of standard polystyrene measured using gel permeation chromatography) is preferably 500 to 100,000, more preferably 700 to 50,000, More preferably, it is 1000-20000. If the Mn is less than 500, the viscosity of the soluble polyfunctional vinyl aromatic polymer is too low, so that it becomes difficult to form a thick film, and the workability is lowered. Since it becomes easy to generate | occur | produce and a viscosity becomes high, when it shape | molds to a film etc., since the fall of an external appearance is caused, it is unpreferable. The molecular weight distribution (Mw / Mn) obtained from Mn and the weight average molecular weight Mw is 50.0 or less, preferably 30.0 or less. Particularly preferred is 2 to 20.0. When Mw / Mn exceeds 50.0, problems such as deterioration of the processing characteristics of the copolymer and generation of gel occur.

  The copolymer used as component (A) is the presence of one or more polymerization additives (c) selected from a Lewis acid catalyst, one or more co-catalysts selected from ester compounds and phenolic compounds. It can obtain by carrying out cationic copolymerization under.

  In order to produce the copolymer, the divinyl aromatic compound (a) is 20 to 99 mol%, preferably 25 to 95 mol%, more preferably 30 to 90 mol%, and the monovinyl aromatic compound is 80 to 1 mol. A monomer component containing mol%, preferably 75 to 5 mol%, more preferably 70 to 10 mol% is copolymerized. At this time, as described above, the other monomer component (d) can be used in an amount of less than 30 mol%.

  The Lewis acid catalyst used in the production of this copolymer can be used without particular limitation as long as it is a compound comprising a metal ion (acid) and a ligand (base) and can accept an electron pair. .

  Examples of the cocatalyst include one or more selected from ester compounds. Among them, ester compounds having 4 to 30 carbon atoms are preferably used from the viewpoint of polymerization rate and control of molecular weight distribution of the polymer. From the viewpoint of availability, ethyl acetate, propyl acetate and butyl acetate are preferably used.

  The polymerization additive (c) causes a chain transfer reaction with the polymerization active species during the polymerization reaction, and introduces a phenolic hydroxyl group that enables functionalization such as adhesiveness to the terminal of the copolymer of the present invention. It is a compound that fulfills

  The polymerization additive (c) is not particularly limited as long as it is a phenol compound, but a phenolic hydroxyl group having 6 to 30 carbon atoms such as phenol, alkylphenol, dialkylphenol, phenylphenol, alkylphenylphenol, naphthol, alkylnaphthol and the like. One or more polymerization additives selected from the group consisting of aromatic hydrocarbon compounds having Of these phenol compounds, phenol and 2,6-xylenol are preferably used from the viewpoint of reactivity and availability.

  The Lewis acid catalyst is used in the range of 0.001 to 10 mol, more preferably 0.001 to 0.01 mol, per 1 mol of the polymerization additive (c).

  The cocatalyst is used in the range of 0.001 to 10 mol, more preferably 0.01 to 1 mol, relative to 1 mol of the polymerization additive (c).

  Moreover, it is preferable to use a polymerization additive (c) in the range of 0.005-50 mol with respect to a total of 1 mol of all the monomers, More preferably, it is 0.01-10 mol. In this case, the polymerization additive (c) is not calculated as a monomer.

  The polymerization temperature is in the range of 20 to 120 ° C, preferably 40 to 100 ° C. When the polymerization temperature exceeds 120 ° C., the selectivity of the reaction decreases, causing problems such as an increase in the molecular weight distribution and the generation of gel, and when the polymerization is carried out at a temperature below 20 ° C., the molecular weight of the resulting copolymer increases. However, it is not preferable because it causes a decrease in molding processability.

  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.

  In the curable resin composition of the present invention, the thermoplastic resin used as the component (B) includes a soluble polyfunctional vinyl aromatic copolymer having a phenolic hydroxyl group at the terminal as the component (A). What was excellent in compatibility can be used conveniently. Examples of such thermoplastic resins include polyamides such as nylon 4, nylon 6, nylon 6,6, nylon 6,10, nylon 12, and derivatives thereof, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate, Polyesters such as polyethylene glycol block copolymers and derivatives thereof, polyphenylene ether, modified polyphenylene ether, polycarbonate, polyacetal, polysulfone, polymethyl methacrylates, acrylic acid (or methacrylic acid) ester copolymers, polystyrenes, acrylonitrile Polystyrenes such as styrene copolymers, acrylonitrile styrene butadiene copolymers and copolymers thereof, polyvinyl acetates, ethylene Rubbers such as lauric acid ester copolymer and styrene conjugated diene block copolymer, rubbers such as hydrogenated styrene conjugated diene block copolymer, rubbers such as polybutadiene and polyisoprene, polymethoxyethylene, polyethoxyethylene, etc. Polyvinyl ethers, polyacrylamides, polyphosphazenes, polyether sulfones, polyether ketones, polyether imides, polyphenylene sulfides, polyamide imides, thermoplastic polyimides, aromatic polyesters, etc., liquid crystal components in the side chain Or a thermoplastic block copolymer into which at least one functional group selected from an epoxy group, a hydroxyl group, and a maleic anhydride group is introduced.

  Among the above thermoplastic resins, the glass transition temperature is 20 ° C. or less from the viewpoints of excellent compatibility with the copolymer of the component (A), great synergistic effect on improving adhesiveness, and excellent effect of improving toughness. Preferably, rubbers having a polymer segment of 0 ° C. or lower are used. It is advantageous to use a thermoplastic resin other than rubbers and rubbers in combination. Here, rubbers having a polymer segment having a glass transition temperature of 20 ° C. or lower are rubbers such as a styrene conjugated diene block copolymer, an ethylene acrylate copolymer, or a hydrogenated styrene conjugated diene block copolymer. It is preferable to use rubbers such as From the viewpoint of heat-resistant oxidative degradation and compatibility of the curable resin composition of the present invention, hydrogenated rubbers such as ethylene acrylate copolymer or hydrogenated styrene conjugated diene block copolymer are most preferred.

  Moreover, in the curable resin composition of this invention, the compounding quantity of (A) component with respect to the sum total of (A) component and (B) component is 2-98 wt%, and the compounding quantity of (B) component is 98-2 wt%. Yes, preferably the blending amount of component (A) is 5 to 95 wt%, the blending amount of component (B) is 95 to 5 wt%, more preferably the blending amount of component (A) is 10 to 90 wt%, (B ) Component content is 90 to 10 wt%. When the blending amount of the component (A) is less than 2 wt%, the heat resistance of the curable resin composition is lowered, and if it exceeds 98 wt%, the toughness is significantly lowered, which is not preferable.

  In addition to the components (A) and (B), the curable resin composition of the present invention includes a thermosetting resin as the component (C), a flame retardant as the component (D), an inorganic filler as the component (E) or ( A silane coupling agent can be mix | blended as a component F).

  Component (C) includes thermosetting polyphenylene ether, polyfunctional epoxy compound, diallyl phthalate, polyfunctional acryloyl compound, polyfunctional methacryloyl compound, polyfunctional maleimide, polyfunctional cyanate ester, polyfunctional isocyanate. And compounds composed of unsaturated polyesters and their prepolymers. These are used alone or in combination of two or more.

  Examples of the component (D) include one or more flame retardants selected from the group consisting of halogen flame retardants, phosphorus-nitrogen flame retardants, phosphate ester flame retardants, nitrogen flame retardants, and inorganic flame retardants.

  Here, as the halogen flame retardant, decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, ethane-1,2-bis (pentabromophenyl), bis (2,4,6-tribromophenoxy) Ethane, ethylenebistetrabromophthalimide, polydibromophenylene oxide, tris (2,3-dibromopropyl-1) isocyanurate, tris (tribromophenyl) cyanurate, brominated polystyrene, brominated styrene-methyl methacrylate copolymer, Tetrabromobisphenol-A, tetrabromobisphenol-A-epoxy oligomer, brominated epoxy compounds (for example, diepoxy compounds and odors produced by the reaction of brominated bisphenol A and epichlorohydrin) Phenols and epoxy compounds obtained by the reaction of epichlorohydrin), poly (pentabromobenzyl acrylate), a halogen-based flame retardants such as octabromodiphenyl trimethylphenyl indane.

  Further, the phosphorus-nitrogen compound needs to be a compound having both a nitrogen atom and a phosphorus atom in one molecule. Examples of such phosphorus-nitrogen compounds include phosphazene compounds such as phenoxyphosphazene, methylphenoxyphosphazene, and aminophosphazene; nitrogen-containing heterocyclic compounds such as aliphatic amine compounds, triazine, melamine, and cyanuric acid. And phosphoric acid amides such as N, N-diethylphosphamide; polyphosphoric acid amides such as poly (N, N-diethylphosphamide), etc. it can.

  Examples of the phosphate ester flame retardant include triphenyl phosphate, tricresyl phosphate, resorcinol bis (diphenyl) phosphate, and the like.

  As the nitrogen-based flame retardant, known ones can be used without limitation, but aliphatic amine compounds, aromatic amine compounds, triazine, melamine, benzoguanamine, methylguanamine, nitrogen-containing heterocyclic compounds such as cyanuric acid, cyanide compounds, fats Examples thereof include aromatic amides, aromatic amides, urea, thiourea and the like.

Furthermore, examples of the inorganic flame retardant 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-x M _x (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 inorganic filler used as the component (E) is not particularly limited. Specifically, for example, wollastonite, sericite, kaolin, mica, clay, talc, bentonite, alumina silicate, pyrophyllite, montmorillonite, Silicates such as calcium silicate, molybdenum disulfide, alumina, silicon chloride, magnesium oxide, zirconium oxide, iron oxide, titanium oxide and other metal compounds, calcium carbonate, magnesium carbonate, dolomite and other carbonates, calcium sulfate, barium sulfate, etc. Sulfates, phosphates such as calcium polyphosphate, calcium pyrophosphate, glass beads, glass microballoons, glass flakes, boron nitride, silicon carbide and silica powders, plate-like or granular fillers, etc. These are hollow There. Among these, carbonates, phosphates, silicates, or fused silica of Group 2 (Group 2A) metals (for example, magnesium, calcium, etc.) of the periodic table are preferable from the viewpoint of strength and adhesion. From the viewpoint that the anisotropy of the properties of the cured product is small and the appearance is excellent, fused silica is a preferred example.

  As the silane coupling agent of component (F), vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropyl Dimethylmethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyldimethylethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, hexyltrimethoxysilane, hexyltriethoxy Silane, N-β- (aminoethyl) γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) γ-aminopropyltriethoxysilane, N-β- (aminoethyl) γ-aminopropyl Pyrmethyldimethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxy Silane etc. are mentioned.

The blending amount (wt%) of the above (C) component, (D) component, (E) component, and (F) component should satisfy the following formula.
(C) Component blending amount = 2 to 40 (wt%) with respect to the total of component (A), component (B), and component (C). Preferably it is 5-35 (wt%). When the blending amount of the component (C) is less than 2 wt%, the degree of improvement in adhesion and heat resistance due to the addition of the thermosetting resin is insufficient, and when it exceeds 40 wt%, the mechanical properties of the composition It is not preferable because the physical properties are remarkably lowered.
(D) Component blending amount = 2 to 40 wt% with respect to the sum of component (A), component (B), component (C) and component (D). Preferably, (D) component compounding quantity is 5-30 (wt%). When the blending amount of component (D) is less than 2 wt%, the degree of improvement in flame retardancy due to the addition of the flame retardant is insufficient, and when it exceeds 40 wt%, the mechanical properties of the composition are significantly reduced. This is not preferable.

(E) Component blending amount = 2 to 60 wt% with respect to the total of (A) component, (B) component, (C) component, (D) component and (E) component. Preferably, (E) component compounding quantity is 10-50 (wt%). If the blending amount of the component (E) is less than 2 wt%, the degree of improvement in mechanical properties and dimensional stability due to the addition of the inorganic filler is insufficient, and if it exceeds 60 wt%, the mechanical properties of the composition It is not preferable because the physical properties are remarkably lowered.
(F) Component blending amount = 0.01 to 10 wt% with respect to the total of (A) component, (B) component, (C) component, (D) component, (E) component and (F) component. Preferably, it is 0.1-5 (wt%).

  If necessary, the curable resin composition of the present invention may contain other various additives such as a colorant and a stabilizer within a range not impairing the effects of the present invention.

  Next, the manufacturing method of the curable resin film of this invention is demonstrated. The curable resin film of the present invention is obtained by dissolving a curable resin composition containing the components (A) and (B) in a solvent such as an aromatic hydrocarbon such as toluene and xylene to form a varnish, which is then converted into polyethylene terephthalate. It is obtained by coating a base film such as a film, a polyimide film or an aramid film to form a two-layer film and then peeling the base film.

  As a method for curing the curable resin composition or the curable resin film of the present invention, curing can be performed by heating, irradiation with actinic light, or the like. Curing by heating varies depending on the presence or absence of the curing agent and the type thereof, but is 70 to 300 ° C., more preferably at a heating temperature in the range of 100 to 250 ° C., and the heating time is 30 seconds to 5 hours, preferably 1 Min to 2 hours.

  As will be described later, the curable resin composition of the present invention is cured by causing a crosslinking reaction by means of heating or the like, but it is a radical for the purpose of lowering the reaction temperature or promoting the crosslinking reaction of unsaturated groups. An initiator may be contained and used. The amount of the radical initiator used for this purpose is 0.1 to 10% by weight, preferably 0.1 to 8% by weight, based on the sum of the components (A) and (B).

  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-bis (t-butylperoxy) octane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, di (tri Although there are peroxides such as methylsilyl) peroxide and trimethylsilyltriphenylsilyl peroxide, they are not limited thereto. Although not a peroxide, 2,3-dimethyl-2,3-diphenylbutane can also be used as a radical initiator. However, the initiator used for curing the resin composition is not limited to these examples.

  The metal foil with resin having the film of the curable resin composition of the present invention is composed of the curable resin composition of the present invention and the 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.

  A cured product can be obtained by heat-curing the curable resin composition of the present invention. Further, the curable resin composition of the present invention can be used as a prepreg by impregnating a glass substrate in an appropriate solvent, and further, after drying using this prepreg, heating By curing, it can be used as a resin substrate such as a laminate or a printed wiring board.

  And resin substrates, such as a laminated board and a printed wiring board using the curable resin composition of the present invention, complete curing at a low temperature in a short time while maintaining the physical properties of the glass transition temperature and the linear expansion coefficient. As a result, production efficiency can be improved.

  The curable resin composition of the present invention can be processed into a molding material, a sheet or a film, and can be processed into a molded material, a sheet or a film, and can satisfy the properties such as low dielectric constant, low water absorption, high heat resistance, and good adhesiveness, It can be applied to semiconductor-related materials or transparent materials for optical devices, as well as paints / inks, photosensitive materials, and adhesives.

  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. Moreover, the measurement of the softening temperature etc. in an Example performed sample preparation and a measurement with the method shown below.

1) Molecular weight and molecular weight distribution of polymer GPC (Tosoh, HLC-8120GPC) was used for measuring the molecular weight and molecular weight distribution of the soluble polyfunctional aromatic copolymer, tetrahydrofuran as the solvent, flow rate of 1.0 ml / min, column temperature of 38. The measurement was carried out using a calibration curve of monodisperse polystyrene at ° C.

2) Polymer structure Determined by ¹³ C-NMR and ¹ H-NMR analysis using a JNM-LA600 nuclear magnetic resonance spectrometer manufactured by JEOL. Using chloroform -d ₁ as a solvent, was used resonance line of tetramethylsilane as an internal standard.

3) Terminal phenolic hydroxyl group The terminal phenolic hydroxyl group was calculated from the number average molecular weight obtained from the GPC measurement, the ¹ H-NMR measurement, and the terminal phenolic hydroxyl group obtained from the results of elemental analysis.

4) Sample preparation and measurement of glass transition temperature (Tg) and softening temperature (Sp) measurement A soluble polyfunctional vinyl aromatic copolymer solution was uniformly applied to a glass substrate so that the thickness after drying was 20 μm. The sample was heated for 30 minutes at 90 minutes using a hot plate and dried. The resin film obtained together with the glass substrate is set in TMA (thermomechanical analyzer), heated to 220 ° C. at a temperature rising rate of 10 ° C./min under a nitrogen stream, and further heat-treated at 220 ° C. for 20 minutes. The remaining solvent was removed. After allowing the glass substrate to cool to room temperature, an analytical probe is brought into contact with the sample in the TMA measuring apparatus, and scan measurement is performed from 30 ° C. to 360 ° C. at a temperature rising rate of 10 ° C./min under a nitrogen stream. Tg and Sp values were determined.

5) Evaluation of heat resistance and measurement of heat discoloration The copolymer is set in a TGA (thermal balance) measuring device, and measurement is performed by scanning from 30 ° C. to 320 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen stream. By determining the weight loss at 300 ° C. as heat resistance and visually confirming the amount of discoloration of the sample after measurement, and classifying it as A: no thermal discoloration, B: light yellow, C: brown, D: black The heat discoloration was evaluated.

Synthesis example 1
4230 g (32.4 mol) of divinylbenzene, 169 g (1.35 mol) of ethyl vinylbenzene, 1170 g (11.3 mol) of styrene, 158 g (1.8 mol) of ethyl acetate, 1649 g (13.5 g) of 2,6-xylenol Mol) and 12745 g of toluene were charged into a 30 L reactor, and 18 g (120 mmol) of diethyl ether complex of boron trifluoride was added at 70 ° C. and reacted for 2 hours. After stopping the polymerization solution with 53.3 g of 1-butanol, the reaction mixture was poured into a large amount of n-hexane at room temperature to precipitate a copolymer. The obtained copolymer was washed with n-hexane, filtered, dried and weighed to obtain 3948 g of copolymer A (yield: 70.9 wt%).

Mn of the obtained copolymer A was 2820, Mw was 10800, and Mw / Mn was 3.84. By performing ¹³ C-NMR and ¹ H-NMR analyses, resonance lines derived from the 2,6-xylenol end of copolymer A were observed. As a result of conducting an elemental analysis result of the copolymer A, it was C: 88.2 wt%, H: 7.9 wt%, and O: 3.3 wt%. The amount of phenolic hydroxyl groups introduced into the soluble polyfunctional vinyl aromatic polymer calculated from the elemental analysis results and the number average molecular weight in terms of standard polystyrene was 5.8 (pieces / molecule). Further, it contained 79.2 mol% of structural units derived from divinylbenzene and 20.7 mol% in total of structural units derived from styrene and ethylbenzene. The content of the structural unit (a1) contained in the copolymer A was 32 mol%.
As a result of the TMA measurement, Tg was 275 ° C., and the softening temperature was 300 ° C. or higher. As a result of TGA measurement, the weight loss at 300 ° C. was 1.5 wt%, and the heat discoloration was A. Copolymer A was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was formed.

Synthesis example 2
4230 g (32.4 mol) of divinylbenzene, 169 g (1.35 mol) of ethyl vinylbenzene, 1170 g (11.3 mol) of styrene, 209 g (1.8 mol) of butyl acetate, 2771 g (16.5 mol) of phenol, toluene 11956 g was put into a 30 L reactor, 8 g of diethyl ether complex of boron trifluoride was added at 70 ° C., and reacted for 2.5 hours. After the polymerization solution was stopped with 26.7 g of 1-butanol, the reaction mixture was poured into a large amount of n-hexane at room temperature to precipitate a polymer. The obtained polymer was washed with n-hexane, filtered, dried and weighed to obtain 2606 g of copolymer B (yield: 46.8 wt%).

Mn of the obtained copolymer B was 1940, Mw was 5640, and Mw / Mn was 2.91. By performing ¹³ C-NMR and ¹ H-NMR analysis, the copolymer B was observed to have a resonance line derived from the phenol end. As a result of conducting an elemental analysis result of the copolymer B, it was C: 85.8 wt%, H: 7.2 wt%, and O: 4.7 wt%. The introduction amount (a) of phenolic hydroxyl groups in the soluble polyfunctional vinyl aromatic polymer calculated from the elemental analysis results and the number average molecular weight in terms of standard polystyrene was 4.0 (pieces / molecule). Further, 71.8 mol% of the structural units derived from divinylbenzene and 28.2 mol% of the structural units derived from styrene and ethylbenzene were contained. Content of the structural unit (a1) contained in the copolymer B was 36 mol%.
As a result of the TMA measurement, Tg was 282 ° C., and the softening temperature was 300 ° C. or higher. As a result of TGA measurement, the weight loss at 300 ° C. was 1.5 wt%, and the heat discoloration was A. The result of measuring the total light transmittance with a turbidimeter was 88%. Copolymer B was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was formed.

Synthesis example 3
Dichlorobenzene solution (0.634 mmol) of 28.2 g (0.216 mol) of divinylbenzene, 1.1 g (9 mmol) of ethylvinylbenzene, 7.8 g (0.075 mol) of styrene and 1-chloroethylbenzene (12.0 mmol). / ML) 23.8 g, 4.2 g of a dichloroethane solution (0.135 mmol / mL) of n-tetrabutylammonium bromide (0.45 mmol) and 189 g of dichloroethane (dielectric constant: 10.3) were put into a 300 mL flask. Then, 8.3 g of a dichloroethane solution (0.068 mmol / mL) of 0.45 mmol of SnCl ₄ was added at 70 ° C. 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 7.07 g of copolymer C (yield: 27.1 wt%).

Mn of the obtained copolymer C was 2010, Mw was 2780, and Mw / Mn was 1.6. By performing ¹³ C-NMR and ¹ H-NMR analyses, Copolymer C has a structural unit derived from divinylbenzene of 76.6 mol%, a structural unit derived from ethylbenzene of 2.3 mol%, and a structural unit derived from styrene. The resonance line derived from the phenol end was not observed. As a result of conducting the elemental analysis result of the copolymer C, it was C: 86.8 wt%, H: 7.4 wt%, O: 0.3 wt%, Cl: 5.06 wt%. The amount of chlorine introduced into the terminal of the soluble polyfunctional vinyl aromatic polymer calculated from the elemental analysis results and the number average molecular weight in terms of standard polystyrene was 3.8 (pieces / molecule). As a result of the TMA measurement, Tg was 290 ° C., and the softening temperature was 300 ° C. or higher. As a result of TGA measurement, the weight loss at 300 ° C. was 12.1 wt%, and the heat discoloration resistance was D. The result of measuring the total light transmittance with a turbidimeter was 52%. Copolymer C was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was formed.

Example 1
Copolymer A obtained in Synthesis Example 1: 4.5 parts by weight, polyphenylene ether containing vinyl groups at both ends (MGC OPE-2ST): 18 parts by weight, rubber component 1 (KRATON GRP6935): 11.5 Parts by weight, rubber component 2 (Tuftec M1913): 4.5 parts by weight, rubber component 3 (Tuftec H1041): 4.5 parts by weight, rubber component 4 (Tuftec H1053): 4.5 parts by weight, phosphorus-nitrogen-based difficulty Flame retardant (SPB-100): 2.5 parts by weight, and spherical silica (SO-C2) having an average particle diameter of 0.5 μm: 25.0 parts by weight, thermosetting resin (EOCN-1020-65): 2.5 Parts by weight, silane coupling agent (A-1289): 0.5 part by weight and xylene: 132 parts by weight as a solvent, and after stirring, reaction initiator (perbutyl P): 0.5 part by weight and curing Accelerator Curazole (2E4MZ): 0.05 parts by weight was added to prepare a curable resin composition solution.

A curable 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 was dried at 80 ° C. for 10 minutes in an inert oven in which nitrogen gas was passed. The obtained film had a thickness of about 50 μm, had no stickiness, and was excellent in film formability. This film was sandwiched between a polyimide film (Kapton EN25 μm manufactured by DuPont) and an FR-4 substrate etched out of copper foil, and thermally cured at 180 ° C. for 1 hour in a vacuum press molding machine to obtain a laminate.
As a result of testing the peel strength of the polyimide film of this laminate, the peel strength of the polyimide film was 1.02 (kN / m). Moreover, Tg was 203 degreeC as a result of the TMA measurement.

Example 2
Copolymer B obtained in Synthesis Example 2: 8.0 parts by weight, GMA-modified E-MA copolymer (glycidyl methacrylate-modified ethylene methyl methacrylate random copolymer: LOTADAR AX8900): 2.0 parts by weight and solvent Toluene: 150 parts by weight as a mixture, and after stirring, a reaction initiator perbutyl P: 1.0 part by weight and triphenylphosphine (TPP): 0.1 part by weight are added, and a curable resin composition solution Was prepared.
Thereafter, a laminate was produced in the same manner as in Example 1 and tested for the peel strength of the polyimide film of the laminate. As a result, the peel strength of the polyimide film was 0.92 (kN / m). Further, as a result of the TMA measurement, no inflection point was observed, and the Tg was not observed.

Comparative Example 1
Copolymer C obtained in Synthesis Example 3: 8.0 parts by weight, GMA modified E-MA copolymer (LOTADER AX8900): 2.0 parts by weight and toluene: 150 parts by weight as a solvent, After stirring, reaction initiators perbutyl P: 1.0 part by weight and triphenylphosphine (TPP): 0.1 part by weight were added to prepare a curable resin composition solution.
Thereafter, a laminate was produced in the same manner as in Example 1 and tested for the peel strength of the polyimide film of the laminate. As a result, the peel strength of the polyimide film was 0.23 (kN / m). Moreover, Tg was 200 degreeC as a result of the TMA measurement.

Synthesis example 4
Divinylbenzene 32.4 mol (4618 mL), ethyl vinylbenzene 1.35 mol (192 mL), styrene 11.3 mol (1291 mL), butyl acetate 1.8 mol (175.5 mL), 2,6-xylenol 37.5 Mole (4581 g) and 14.8 L of toluene were charged into a 30 L reactor, and 90 mmol of boron trifluoride diethyl ether complex was added at 80 ° C. and reacted for 4 hours. After the polymerization solution was stopped with 49.4 mL of 1-butanol, the reaction mixture was poured into a large amount of n-hexane at room temperature to precipitate a polymer. The obtained polymer was washed with n-hexane, filtered, dried and weighed to obtain 4979 g of copolymer D (yield: 89.4 wt%).

Mn of the obtained copolymer D was 1100, Mw was 2300, and Mw / Mn was 2.10. By performing ¹³ C-NMR and ¹ H-NMR analysis, a resonance line derived from the 2,6-xylenol end of the copolymer D was observed. As a result of conducting the elemental analysis result of the copolymer D, they were C: 85.0 wt%, H: 7.9 wt%, and O: 5.3 wt%. The introduction amount (a) of hydroxy groups in the soluble polyfunctional vinyl aromatic polymer calculated from the elemental analysis results and the number average molecular weight in terms of standard polystyrene was 3.6 (pieces / molecule). Moreover, 78.1 mol% of structural units derived from divinylbenzene and 21.9 mol% in total of structural units derived from styrene and ethylbenzene were contained. Content of the structural unit (a1) contained in the copolymer D was 26 mol%. 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 weight loss at 300 ° C. was 1.9 wt%, and the heat discoloration resistance was A.
Copolymer D was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was observed.

Example 3
Except that the copolymer D obtained in Synthesis Example 4 was used, the peel strength of the polyimide film of the laminate was tested in the same manner as in Example 1. As a result, the peel strength of the polyimide film was 0.73 (kN / m). Moreover, Tg was 204 degreeC as a result of the TMA measurement.

Synthesis example 5
Divinylbenzene 32.4 mol (4618 mL), ethyl vinylbenzene 1.35 mol (192 mL), styrene 11.3 mol (1291 mL), butyl acetate 1.8 mol (175.5 mL), 2,6-xylenol 37.5 Mole (4581 g) and 14.8 L of toluene were charged into a 30 L reactor, and 90 mmol of boron trifluoride methyl ether complex was added at 80 ° C. and reacted for 4 hours. After the polymerization solution was stopped with 49.4 mL of 1-butanol, the reaction mixture was poured into a large amount of n-hexane at room temperature to precipitate a polymer. The obtained polymer was washed with n-hexane, filtered, dried, and weighed to obtain 3569 g of a copolymer E (yield: 64.08 wt%).

Mn of the obtained copolymer E was 1270, Mw was 2570, and Mw / Mn was 2.30. By performing ¹³ C-NMR and ¹ H-NMR analyses, a resonance line derived from the end of 2,6-xylenol was observed in copolymer E. As a result of conducting the elemental analysis result of the copolymer E, it was C: 85.3 wt%, H: 8.1 wt%, and O: 5.3 wt%. The introduction amount (a) of hydroxy groups in the soluble polyfunctional vinyl aromatic polymer calculated from the elemental analysis results and the number average molecular weight in terms of standard polystyrene was 3.5 (pieces / molecule). Moreover, the structural unit derived from divinylbenzene was 77.8 mol%, and the total structural unit derived from styrene and ethylbenzene was 22.0 mol%. Content of the structural unit (a1) contained in the copolymer E was 25 mol%. 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 weight loss at 300 ° C. was 1.9 wt%, and the heat discoloration resistance was A.
Copolymer E was soluble in toluene, xylene, THF, dichloroethane, dichloromethane, and chloroform, and no gel was observed.

Example 4
Except that the copolymer E obtained in Synthesis Example 4 was used, the peel strength of the polyimide film of the laminate was tested in the same manner as in Example 2. As a result, the peeling strength of the polyimide film was 0.72 (kN / m). Further, as a result of the TMA measurement, no inflection point was observed, and the Tg was not observed.

Example 5
Copolymer B obtained in Synthesis Example 2: 3.0 parts by weight, polycarbonate resin (Iupilon S-3000R): 7.0 parts by weight and toluene: 150 parts by weight as a solvent, and after stirring, reaction Initiator (perbutyl P): 1.0 part by weight was added to prepare a curable resin composition solution.
Thereafter, a laminate was produced in the same manner as in Example 1 and tested for the peel strength of the polyimide film of the laminate. As a result, the peel strength of the polyimide film was 0.65 (kN / m). Moreover, Tg was 167 degreeC as a result of the TMA measurement.

Comparative Example 2
Copolymer C obtained in Synthesis Example 3: 3.0 parts by weight, polycarbonate resin (Iupilon S-3000R): 7.0 parts by weight and toluene: 150 parts by weight as a solvent were mixed, and the reaction was conducted after stirring. Initiator perbutyl P: 1.0 part by weight was added to prepare a curable resin composition solution.
Thereafter, a laminate was produced in the same manner as in Example 1 and tested for the peel strength of the polyimide film of the laminate. As a result, the peel strength of the polyimide film was 0.05 (kN / m). Moreover, Tg was 149 degreeC as a result of the TMA measurement.

Claims (11)

Component (A): a copolymer obtained by copolymerizing divinyl aromatic compound (a) 20 to 99 mol% and monovinyl aromatic compound (b) 80 to 1 mol%, with a part of its ends The following formula (a1) having a phenolic hydroxyl group derived from the polymerization additive (c) and derived from the divinyl aromatic compound (a)

(Wherein R ¹ represents an aromatic hydrocarbon group having 6 to 30 carbon atoms.) The content of the structural unit containing an unreacted vinyl group represented by A soluble polyfunctional vinyl aromatic copolymer having a functional hydroxyl group;
(B) component: It is a resin composition consisting of a thermoplastic resin, and the blending amount of the (A) component with respect to the sum of the (A) component and the (B) component is 2 to 98 wt%, and the blending amount of the (B) component is It is 98-2 wt%, The curable resin composition characterized by the above-mentioned.   A soluble polyfunctional vinyl aromatic copolymer having a phenolic hydroxyl group at the end has a number average molecular weight Mn of 500 to 100,000, and a molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight Mw to the number average molecular weight Mn. ) Is 50.0 or less, The curable resin composition of Claim 1 characterized by the above-mentioned.   The soluble polyfunctional vinyl aromatic copolymer having a phenolic hydroxyl group at the end has an introduction amount of phenolic hydroxyl group at the end of 2.2 / molecule or more, according to claim 1 or 2. Curable resin composition.   The thermoplastic resin is polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyesters such as polyethylene terephthalate / polyethylene glycol block copolymer and derivatives thereof, polyphenylene ether, modified polyphenylene ether, polycarbonate, polysulfone, polymethyl methacrylate, Acrylic acid (or methacrylic acid) ester copolymers, polystyrenes, acrylonitrile styrene copolymers, polystyrenes such as acrylonitrile styrene butadiene copolymers and their copolymers, polyvinyl acetates, ethylene acrylates Rubbers such as copolymers, styrene conjugated diene block copolymers, rubbers such as hydrogenated styrene conjugated diene block copolymers, polybutadiene, Rubbers such as isoprene, polyvinyl ethers such as polymethoxyethylene and polyethoxyethylene, polyacrylamides, polyphosphazenes, polyethersulfone, polyetherketone, polyetherimide, polyphenylene sulfide, polyamideimide, and thermoplastic polyimide The curable resin composition according to claim 1, wherein the curable resin composition is one or more thermoplastic resins selected from the group consisting of:   Furthermore, it is a curable resin composition containing a thermosetting resin as the component (C), and the blending amount of the component (C) with respect to the sum of the components (A), (B) and (C) is 2 to 40 wt. % Curable resin composition according to claim 1.   Furthermore, it is a curable resin composition containing a flame retardant as the component (D), and the blending amount of the component (D) with respect to the sum of the components (A), (B), (C) and (D) is It is 2-40 wt%, The curable resin composition in any one of Claims 1-5.   Furthermore, it is a curable resin composition containing an inorganic filler as the component (E), and (E) with respect to the sum of the components (A), (B), (C), (D) and (E) The compounding quantity of a component is 2-60 wt%, The curable resin composition in any one of Claims 1-6.   A curable resin film formed from the curable resin composition according to claim 1.   A metal foil with a resin, comprising the film of the curable resin composition according to claim 1 on one side of the metal foil.   A cured resin product obtained by curing the curable resin composition according to claim 1.   A resin substrate comprising the cured resin according to claim 10.