JP5494098B2 - Resin composition, resin varnish, composite material and method for producing the same, prepreg and resin film - Google Patents

Description

  The present invention relates to a resin composition suitably used for electronic uses such as a printed wiring board and an electronic device mounting package; decoration uses such as automobile exterior parts; a resin varnish using the same; a composite material; and a method for producing the same , Prepreg and resin film.

  In recent years, there has been an increasing demand for downsizing, weight reduction, and speeding up of electronic devices, and the density of printed wiring boards has been increasing. Therefore, it is required to further reduce the wiring width and the wiring interval. In order to keep the wiring width small, it is necessary that the metal layer (metal film) serving as the wiring and the resin base material have sufficient adhesion. In conventional printed wiring boards, the adhesion between the metal layer and the resin is mainly obtained by roughening the roughened metal foil, or by roughening the resin surface by physical roughening such as plasma treatment or chemical roughening such as permanganate etching. Most of them depend on the anchor effect due to the surface irregularities (the arithmetic average roughness Ra of the surface is about 0.2 μm or more). In addition, even in resin parts having a metallized surface used for automobile exterior parts, the resin surface is chemically roughened by chromic acid solution etching or the like to obtain an anchor effect due to unevenness.

  For example, when a smooth copper foil that is not roughened is used, or when the wiring is formed without roughening the resin surface, the adhesion between the metal layer and the resin base material cannot be secured. Pattern peeling becomes a problem.

  On the other hand, as a method for producing a printed wiring board that can improve the adhesion between the metal layer and the resin without relying on the anchor effect as described above, for example, in order to ensure the adhesion, infiltration and sublimation using a sublimable metal complex A method for modifying the surface layer by adhesion is disclosed (for example, see Patent Document 1).

JP 2000-281821 A

However, when the anchor effect is obtained by unevenness, the uneven recesses formed to ensure adhesiveness cause etching delay when the metal layer is removed by etching to form wirings and patterns on the metal layer, and the wiring In addition, there is a risk that a short circuit failure may occur due to an increase in electrical resistance due to side etching of the pattern, or a plating runout between wirings.
In addition, the surface layer modification method using permeation / adhesion using a sublimable metal complex requires equipment, labor, and time, for example, it is necessary to sublimate the organic compound that penetrates the resin material in advance. .

  On the other hand, in recent years, signal attenuation (transmission loss) due to handling high-frequency signals has become a problem in high-frequency printed circuit board applications such as large servers and antennas. In order to reduce the transmission loss, the necessity for reducing the conductor loss as well as the loss of the dielectric (resin layer) cannot be ignored. As a method for reducing the conductor loss, it is effective to apply a conductor layer with small surface irregularities.

  Therefore, the present invention has been made in view of such a situation, and a resin that is excellent in adhesiveness between a metal layer (metal film) and a resin base material and has a smooth surface without depending on the anchor effect. An object is to provide a composition. Moreover, an object of this invention is to provide the resin varnish using the said resin composition, a composite material, its manufacturing method, a prepreg, and a resin film.

  As a result of intensive research to solve the above problems, the present inventors have mixed a sublimable metal compound and an organic compound to form a resin composition, so that a metal layer (metal film) can be used without depending on the anchor effect. It was found that a composite material having excellent adhesion between the resin layer and the resin layer (organic layer) and the like and having a smooth surface can be easily obtained, and the present invention has been completed.

That is, the present invention is as follows.
[1] A resin composition for a molded body that is used in a molded body for metallizing at least a part of the surface and is molded through a thermoforming process, wherein (A) a sublimable metal compound and (B) an organic The resin composition which contains a compound and (B) an organic compound is at least 1 sort (s) chosen from a thermosetting resin and a thermoplastic resin.
[2] A resin composition for a molded body, which is used for a molded body selected from a metal-clad film or a metal-clad laminate, and is molded through a heat molding process, comprising (A) a sublimable metal compound, ( A resin composition comprising B) an organic compound, wherein (B) the organic compound is at least one selected from a thermosetting resin and a thermoplastic resin.

[3] The resin composition according to [1] or [2], wherein (B) the sublimable metal compound in the organic compound (B) diffuses and moves in the thermoforming step.
[4] The resin composition according to [3], wherein all or part of (A) the sublimable metal compound moves to the surface of a molded product obtained by molding in the thermoforming step.
[5] In at least a part of the thermoforming step, the entire system is in a reduced pressure state, and (A) the sublimable metal compound moves under conditions of a temperature of 100 to 400 ° C. and a degree of vacuum of 1 to 10,000 Pa [3] or [ 4].
[6] The metal according to any one of [1] to [5], wherein the metal in the sublimable metal compound is at least one selected from the group consisting of ruthenium, cobalt, copper, platinum, iron, nickel, chromium, and palladium. Resin composition.

[7] The organic compound is epoxy resin, cyanate ester resin, phenol resin, urethane resin, melamine resin, maleimide resin, benzoxazine resin, benzocyclobutene resin, dicyclopentadiene resin, acrylate compound, triallyl isocyanurate, and polybutadiene. The resin composition according to any one of [1] to [6], which is at least one thermosetting resin selected from the group consisting of resins.
[8] The organic compound is the thermoplastic resin, and the thermoplastic resin is a fluororesin, polyolefins and derivatives thereof, polyesters and derivatives thereof, polycarbonate, polyacetal, polysulfone, (meth) acrylic acid ester copolymer Polymers, polystyrene, acrylonitrile styrene copolymers, acrylonitrile styrene butadiene copolymers, polyvinyl acetals, polyvinyl butyrals, polyvinyl alcohols, polyphenylene ether, styrene-butadiene copolymer complete or partial hydrogenated products, polybutadiene Fully or partially hydrogenated, polyethersulfone, polyetherketone, polyetherimide, polyphenylene sulfite, polyamideimide, polyamide, thermoplastic polyimide and aromatic The resin composition according to any one of [1] to [6], which is at least one thermoplastic resin selected from the group consisting of reesters.
[9] The blending ratio of (A) the sublimable metal compound is 0.1 to 20% by mass in the entire resin composition containing (A) the sublimable metal compound and (B) the organic compound. [8] The resin composition according to any one of [8].

[10] A resin varnish obtained by dissolving or dispersing the resin composition according to any one of [1] to [9] in a solvent.
[11] A sheet molding step in which the resin composition according to any one of [1] to [9] is molded into a sheet shape to obtain a sheet molded body, and the sheet molded body is sandwiched between a pair of metal plates. And a heating and pressurizing step of heating the sheet molded body after or simultaneously with pressurizing the sheet molded body.
[12] The method for producing a composite material according to [11], wherein the entire system is in a reduced pressure state in at least a part of the heating and pressurizing step.
[13] The method for producing a composite material according to [11] or [12], wherein the heating temperature in the heating and pressing step is 100 ° C. or more and 400 ° C. or less and the pressure is 0.1 MPa or more and 50 MPa or less.
[14] The method for producing a composite material according to [12] or [13], wherein the degree of vacuum in the reduced pressure state is 10 Pa or more and 1000 Pa or less.
[15] The method for producing a composite material according to any one of [11] to [14], further including a reduction step of reducing the sublimable metal compound diffused on the surface of the sheet compact after the heating and pressing step.
[16] After the heating and pressing step, further increasing the thickness of the metal film portion composed of the metal or the sublimable metal compound with the sublimable metal compound diffused on the surface of the sheet compact as a nucleus. The manufacturing method of the composite material in any one of [11]-[15] including a process.
[17] The method for producing a composite material according to any one of [11] to [16], wherein the sublimable metal compound contains copper.

[18] A composite material produced by the production method according to any one of [11] to [17].
[19] A composite material obtained by thermoforming the resin composition according to any one of [1] to [9], wherein a sublimable metal compound is localized on the surface.
[20] The storage elastic modulus of the cured product of the resin composition constituting the composite material is 3 × 10 ⁶ Pa or more and 3 × 10 ⁷ Pa or less at the sublimation temperature of the sublimable metal compound. 19. The composite material according to 19.
[21] The composite material according to [20], wherein the organic compound includes a phenol aralkyl resin having a phenyl skeleton or a biphenyl skeleton.
[22] A prepreg obtained by impregnating the substrate with the resin varnish described in [10] above, followed by drying or semi-curing at 60 to 200 ° C.
[23] A resin film obtained by drying or semi-curing the resin varnish according to [10] at 60 to 200 ° C.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition which is excellent in the adhesiveness of a metal layer (metal film), a resin base material, etc., and can obtain the composite material with a smooth surface without relying on an anchor effect can be provided. . Moreover, the resin varnish using the said resin composition, a composite material, its manufacturing method, a prepreg, and a resin film can be provided.

<Resin composition and resin varnish>
Hereinafter, each component of the resin composition of this invention, its suitable manufacturing method, and the resin varnish of this invention are demonstrated.

The resin composition of the present invention is a resin composition for a molded body that is molded through a heat molding step. As the molded body, a molded body that metalizes at least a part of its surface (for example, an automobile exterior part to which metal plating is applied), a molded body selected from a metal-clad film or a metal-clad laminate. It is.
The resin composition of the present invention comprises (A) a sublimable metal compound (hereinafter sometimes referred to as “(A) component”) and (B) an organic compound (hereinafter sometimes referred to as “(B) component”). Containing. In the resin composition, the component (B) is at least one selected from a thermosetting resin and a thermoplastic resin, and the component (A) inside the component (B) diffuses and moves in the thermoforming step. be able to. Hereafter, each said component is demonstrated.

As described above, the component (A) is a sublimable metal compound in which the component (A) can move by diffusion from the inside of the component (B) in the thermoforming step of the resin composition. Although it does not specifically limit as a sublimable metal compound, What contains ruthenium, cobalt, copper, platinum, iron, nickel, chromium, palladium etc. is preferable, and what contains copper is more preferable.
When the resin composition is molded in the heat molding step, the component (A) is molded entirely or partially (preferably 50% by mass or more, more preferably 80% by mass or more of the component (A)). It can move to the surface of the molded product obtained. As a result, a sublimable metal compound high concentration region in which the component (A) is present in a high concentration is formed on the surface of the molded product.

  Here, “sublimation” means that an element or compound has a property of phase transition from a solid to a gas or from a gas to a solid without passing through a liquid, but the sublimable metal used in the present embodiment. As the compound, those that sublime at a heating temperature of about 100 ° C. or more and about 400 ° C. or less (preferably about 150 ° C. or more and about 300 ° C. or less) under reduced pressure (1 Pa or more and about 10,000 Pa or less (preferably about 10 Pa or more and 1000 Pa or less)) are preferable. . Furthermore, in the present embodiment, those that are stable in the air and that do not undergo the decomposition reaction at the sublimation temperature are preferred.

As the sublimable metal compound, those having a metal complex structure in which an organic ligand is coordinated around a metal atom are preferable. Although it does not specifically limit about the kind of ligand, As a specific sublimable metal compound, (beta) -diketone complexes, such as an acetylacetonato complex, are mentioned, for example, More specifically, Fe (acac) ₃ , Ru Complexes such as (acac) ₃ , Co (acac) ₃ , Cr (acac) ₃ , Pd (acac) ₂ , Ni (acac) ₂ , Pt (acac) ₂ , Cu (acac) ₂ are suitable for sublimation. Therefore, it is preferably used. In the above, acac represents an acetylacetonato ligand.

In these acetylacetonato complexes, a trifluoropropyl group may be introduced instead of the terminal methyl group. Among the complexes described above, Cu (acac) ₂ is more preferable because it has excellent sublimation properties and high adaptability to wiring etching.

  As the organic compound of the component (B) preferably used in the resin composition of the present invention, a synthetic polymer compound of a thermoplastic resin and a thermosetting resin and a natural polymer compound are usually used, and a glass transition temperature is 200. Synthetic thermoplastic resins having a temperature of ≦ ° C. or thermosetting resins having a curing temperature of 200 ° C. or less are preferable, such as polyamides such as nylon 6 and nylon 66, polyamideimide, polyimide, polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate. Acrylic resin such as polyester, polystyrene, polymethylmethacrylate, unsaturated hydrocarbon polymer such as polypropylene, polyvinyl alcohol, polycarbonate, epoxy resin, cyanate ester resin, phenol resin, urethane resin, melamine tree Synthetic polymer compounds such as maleimide resin, bismaleimide triazine (BT) resin, benzoxazine resin, benzocyclobutene resin, dicyclopentadiene resin, polybutadiene resin, or low dielectric constant resin such as polyphenylene oxide resin and fluorine resin. Can be mentioned. Those derived from natural polymer compounds such as cellulose acetate can also be used. Among these, acrylic resins such as polymethyl methacrylate and epoxy resins are preferred from the viewpoint of moldability, but heat resistance, moisture resistance, mechanical strength, metal layer (metal) (metal) It is more preferable to use an epoxy resin from the viewpoint of properties such as adhesion between the film) and the resin (organic layer) and the balance between these and cost.

Preferable specific examples of the thermoplastic resin include fluororesins such as polytetrafluoroethylene, polyolefins such as polyethylene, polypropylene, polybutene, ethylene / propylene copolymer, poly (4-methyl-pentene) and derivatives thereof, and polyester. And derivatives thereof, polycarbonate, polyacetal, polysulfone, (meth) acrylic acid ester copolymers, polystyrene, acrylonitrile styrene copolymers, acrylonitrile styrene butadiene copolymers, polyvinyl acetals, polyvinyl butyrals, polyvinyl alcohols , Polyphenylene ether, complete or partial hydrogenation of styrene-butadiene copolymer, complete or partial hydrogenation of polybutadiene, polyethersulfone, polyetherketone, polyether Ruimido, polyphenylene sulfide, polyamideimide, polyamide, thermoplastic polyimide, an aromatic polyester or the like.
Moreover, the said thermosetting resin or thermoplastic resin may be used individually or in combination of 2 or more types.

Here, when an epoxy resin is used, any resin may be used as long as it has two or more epoxy groups in one molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy Resin, naphthalene skeleton type epoxy resin, bifunctional biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, dihydroanthracene type epoxy resin, diphenol of diglycidyl ether of biphenol, diglycidyl ether of phenol Of diglycidyl ethers, and alkyl-substituted products, halides and the like thereof, and these may be used in combination.
In order to improve Tg and heat resistance of the cured resin composition, it is preferable to use an epoxy resin having three or more epoxy groups in the molecule. Examples of such resins include phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, bisphenol F novolac type epoxy resins, naphthalene skeleton type epoxy resins, biphenylaralkyl type epoxy resins, dicyclopentadiene. Type epoxy resin.

  Furthermore, the organic compound according to the present invention preferably includes a phenol aralkyl resin having a phenyl skeleton or a biphenyl skeleton, from the viewpoint of flame retardancy and dielectric properties after forming a laminate.

  The resin composition in the present embodiment may include a resin curing agent. When the resin is an epoxy resin, for example, there are polyfunctional phenols, amines, imidazole compounds, acid anhydrides, organic phosphorus compounds, and halides thereof, but the curing reaction is caused by the added component (A). Those that are not inhibited are preferred.

Examples of polyfunctional phenols include hydroquinone, resorcinol, catechol, which are monocyclic bifunctional phenols, bisphenol A, bisphenol F, bisphenol S, naphthalenediols, biphenols, and halides thereof, which are polycyclic bifunctional phenols. And alkyl group-substituted products.
Moreover, phenol resins such as phenol novolac resins, resol resins, bisphenol A novolak resins and cresol novolac resins which are polycondensates of these phenols and aldehydes.

  Phenol resins as curing agents for preferred epoxy resins that are commercially available include, for example, Phenolite LF2882, Phenolite LF2822, Phenolite TD-2090, Phenolite TD-2149, Phenolite VH4150, Phenolite VH4170 (above, DIC University) Nippon Ink Chemical Co., Ltd., trade name) and the like.

Examples of amines include aliphatic or aromatic primary amines, secondary amines, tertiary amines, quaternary ammonium salts and aliphatic cyclic amines, guanidines, urea derivatives, and the like.
Examples of these compounds include N, N-benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, tetramethylguanidine, triethanolamine, N, N '-Dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.4.0] -5 -Nonene, hexamethylenetetramine, pyridine, picoline, piperidine, pyrrolidine, dimethylcyclohexylamine, dimethylhexylamine, cyclohexylamine, diisobutylamine, di-n-butylamine, diphenylamine, N-methylaniline, tri-n-propylamine, tri -N-octylamine, tri-n -Butylamine, triphenylamine, tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, triethylenetetramine, diaminodiphenylmethane, diaminodiphenyl ether, dicyandiamide, tolylbiguanide, guanylurea, dimethylurea and the like.

  Examples of imidazole compounds include imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2- Heptadecylimidazole, 4,5-diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4 -Methylimidazole, 2-ethylimidazoline, 2-phenyl-4-methylimidazoline, benzimidazole, 1-cyanoethylimidazole and the like.

  Examples of the acid anhydride include phthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, and the like.

  As the organic phosphorus compound, any phosphorus compound having an organic group can be used without particular limitation. For example, hexamethylphosphoric triamide, tri (dichloropropyl) phosphate, tri (chloropropyl) phosphate, phosphorous acid Examples include triphenyl, trimethyl phosphate, phenylphosphonic acid, triphenylphosphine, tri-n-butylphosphine, diphenylphosphine and the like. These curing agents can be used alone or in combination.

  You may mix | blend a hardening accelerator with the resin composition in this embodiment as needed. Typical curing accelerators include tertiary amines, imidazoles, organophosphorus compounds, quaternary ammonium salts and the like, but are not limited thereto.

  Examples of imidazoles include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecyl. Imidazole, 4,5-diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4-methyl Examples include imidazole, 2-ethylimidazoline, 2-isopropylimidazoline, 2,4-dimethylimidazoline, 2-phenyl-4-methylimidazoline.

  These imidazole compounds may be masked with a masking agent. Examples of the masking agent include acrylonitrile, phenylene diisocyanate, toluidine isocyanate, naphthalene diisocyanate, methylene bisphenyl isocyanate, and melamine acrylate.

  Examples of organophosphorus compounds include ethylphosphine, propylphosphine, butylphosphine, phenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, trioctylphosphine, triphenylphosphine, tricyclohexylphosphine, triphenylphosphine / triphenylborane complex, tetra Examples include phenylphosphonium tetraphenylborate.

  Tertiary amines include benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (diaminomethyl) phenol, and the like.

  In the resin composition of the present invention, various acrylate compounds, polymerizable compounds such as triallyl isocyanurate, and various thermal polymerization initiators such as peroxides and azo compounds can be used in combination.

  The blending ratio of the (A) component and the (B) component used in the resin composition of the present invention is not particularly limited, but the blending ratio of the (A) component is sufficient in the heating and pressurizing step described later. In order to diffuse to the surface and not lower the insulating properties of the composite material, a range of 0.1 to 20% by mass in the entire resin composition containing the component (A) and the component (B) is preferable, and 0.5 to 10 mass% is more preferable, and 1-5 mass% is further more preferable.

  Moreover, in the resin composition of this invention, a flame retardant, an inorganic filler, and various additives can be used together as needed.

  Although it does not specifically limit as said flame retardant, Flame retardants, such as a bromine type, a phosphorus type, and a metal hydroxide, are used suitably. More specifically, brominated flame retardants include brominated epoxy resins such as brominated bisphenol A type epoxy resin and brominated phenol novolac type epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl). , Ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated Brominated flame retardants such as polystyrene and 2,4,6-tris (tribromophenoxy) -1,3,5-triazine, tribromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromide Bisphenol A dimethacrylate, brominated reactive flame retardant unsaturated double bond-containing, such as pentabromobenzyl acrylate and brominated styrene.

Phosphorus flame retardants include aromatic phosphoric acids such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl di-2,6-xylenyl phosphate and resorcinol bis (diphenyl phosphate) Esters, phosphonic esters such as divinyl phenylphosphonate, diallyl phenylphosphonate and bis (1-butenyl) phenylphosphonate, phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phos Phosphinic acid esters such as faphenanthrene-10-oxide derivatives, phosphazene compounds such as bis (2-allylphenoxy) phosphazene, dicresyl phosphazene, melamine phosphate, melamine pyrophosphate, Li Lin melamine, melam polyphosphate, ammonium polyphosphate, phosphorus-containing vinylbenzyl compounds and phosphorus-based flame retardant of red phosphorus and the like.
Examples of the metal hydroxide flame retardant include magnesium hydroxide and aluminum hydroxide.
Moreover, the above-mentioned flame retardant may be used individually by 1 type, and may be used in combination of 2 or more types.

  The blending ratio of the flame retardant is not particularly limited, but is preferably in the range of 1 to 50% by mass, more preferably 5 to 40% by mass in the entire resin composition containing the component (A) and the component (B). 30 mass% is more preferable.

The inorganic filler is not particularly limited, and specifically, alumina, titanium oxide, mica, silica, beryllia, barium titanate, potassium titanate, strontium titanate, calcium titanate, aluminum carbonate, magnesium hydroxide Aluminum hydroxide, aluminum silicate, calcium carbonate, calcium silicate, magnesium silicate, silicon nitride, boron nitride, clay such as calcined clay, talc, aluminum borate, aluminum borate, silicon carbide, etc. are used.
These inorganic fillers may be used alone or in combination of two or more. Moreover, there is no restriction | limiting in particular also about the shape and particle size of an inorganic filler, Usually, the particle size of 0.01-50 micrometers, Preferably 0.1-15 micrometers is used suitably.

  The blending ratio of the inorganic filler is not particularly limited, but is preferably in the range of 1 to 70% by mass, more preferably 5 to 60% by mass in the entire resin composition containing the component (A) and the component (B). -50 mass% is more preferable.

Various additives are not particularly limited, but specific examples include silane coupling agents, titanate coupling agents, antioxidants, heat stabilizers, antistatic agents, ultraviolet absorbers, pigments, colorants, lubricants, and the like. Can be mentioned.
These various thermosetting resins, various thermoplastic resins and various additives may be used alone or in combination of two or more. Moreover, the compounding quantity of the said various additives will not be specifically limited if it is a range which does not exert a bad influence on each characteristic when it is set as the composite material shown above.

  In the present invention, the method for mixing the component (A), the component (B) and the flame retardant, inorganic filler, and various additives used in combination as required is not particularly limited, but the component (A) is added to the component (B). Is added and stirred. In this case, in order to improve the dispersibility of the component (A) in the resin composition, an organic solvent excellent in solubility of the organic compound is added and stirred, dissolved, and dispersed (hereinafter referred to as the resin composition and the organic solvent). The mixture may be referred to as varnish).

  The organic solvent is not particularly limited, but specific examples include alcohols such as methanol, ethanol, butanol, isopropanol, tetrahydrofuran, ethyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, carbitol, Ethers such as butyl carbitol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Aromatic hydrocarbons such as toluene, xylene and mesitylene; Methoxyethyl acetate, ethoxyethyl acetate, butoxyethyl acetate, ethyl acetate, etc. Esters of: N, N-dimethylformamide, N, N-dimethylacetamide, N, N′-diethylacetamide, N-methyl-2-pyro Nitrogens such as Don; aromatic hydrocarbon solvents such as benzene, toluene, xylene and trimethylbenzene; ester solvents such as ethyl acetate, methyl cellosolve acetate and propylene glycol monomethyl ether acetate; nitrile solvents such as butyronitrile; dimethyl And a solvent such as a sulfur compound solvent such as sulfoxide. Moreover, these may be used individually by 1 type and may be used in combination of 2 or more types.

In addition, when the resin varnish is formed, the solid content (nonvolatile content) concentration in the varnish is not particularly limited and can be appropriately changed depending on the composition of the resin composition, but is 5 to 80% by mass (preferably 10 to 60% by mass). %)), It is preferable to adjust the amount of the solvent used, but when manufacturing the prepreg, the resin film, etc. using the resin varnish of the present invention, the amount of the solvent is adjusted to be optimal for the coating work. It can be adjusted to a solid content (non-volatile content) concentration and varnish viscosity (for example, so as to have excellent film formability, a good appearance, and an appropriate resin adhesion amount).
When the solid content concentration is in the above range, the film-forming property when cast into a film is excellent, and when the prepreg is obtained, the resin content and the appearance can be prevented from being lowered.

<Composite material and its manufacturing method>
In the method for producing a composite material of the present invention, a sheet molding step in which the resin composition of the present invention is formed into a sheet shape to form a sheet molded body, the sheet molded body is sandwiched between a pair of metal plates, and the sheet is formed. A heating and pressing step of heating the molded body after pressing or simultaneously with pressing. Hereinafter, these steps will be described.

(Sheet forming process)
In this step, the resin composition of the present invention is used as a sheet-like sheet molded body. By using a sheet molded body, the finally obtained composite material can be suitably used for applications such as a printed wiring board.

Although it does not restrict | limit especially as a shaping | molding method, When setting it as a sheet-like molded object like a film, for example, when obtaining the resin composition in the state (varnish) melt | dissolved in the organic solvent as mentioned above, this solution Is preferably cast on a base such as a PET film and dried to remove the organic solvent and then peel from the base.
When the resin composition is obtained in the form of powder or lump, these may be sandwiched between a pair of base films and heated and pressed to form a sheet molded body. In this case, the sheet forming step may also serve as a heating and pressing step described later.

  Further, when forming a sheet molded body such as a prepreg, for example, it is preferable to mold a solution-like resin composition by impregnating a substrate such as a fibrous substance or cloth with the resin composition as the varnish. After impregnation, it is preferably dried at 80 ° C. or higher and 200 ° C. or lower.

  The substrate is not particularly limited as long as it is used when producing a metal foil-clad laminate or a multilayer printed wiring board, but a fiber substrate such as a woven fabric or a nonwoven fabric is preferably used. Examples of the fiber substrate include inorganic fibers such as glass, alumina, boron, silica alumina glass, silica glass, tyrano, silicon carbide, silicon nitride, zirconia, aramid, polyether ether ketone, polyether imide, polyether sulfone. Further, there are organic fibers such as carbon and cellulose, and mixed papers thereof, and glass fiber woven fabrics are particularly preferably used. The type of the glass woven fabric is not particularly specified, and those having a thickness of 20 μm to 200 μm can be used according to the thickness of the target prepreg or laminate.

The method for impregnating the base material with the varnish is not particularly limited. Examples thereof include a method of impregnating a base material into a varnish by a wet method or a dry method, a method of applying a varnish to a base material, and the like.
Further, the thickness of the sheet molded body formed as described above is preferably 0.01 mm or more and 1 mm or less, and more preferably 0.05 mm or more and 0.5 mm or less.

(Heat-pressing process (also called heating molding process))
In this step, the sublimable metal compound in the prepreg or the resin film is diffused on the surface by sandwiching the prepreg or resin film of the present invention described above between the metal plates and pressurizing and heating. The step of diffusing the sublimable metal compound to the surface is preferably performed during the present step (heating and pressing step), which is indispensable for the composite material forming step of the present embodiment, from the viewpoint of simplification of the step. That is, a step of curing a prepreg or a resin film to form a molded body and a step of diffusing a sublimable metal compound on the surface of the molded body are performed simultaneously.

  The diffusion of the sublimable metal compound to the surface of the molded body in this step is preferably by diffusion in a gas state, that is, sublimation, from the viewpoint of uniform diffusibility and diffusion rate. For this reason, in this embodiment, a sublimable metal compound is disperse | distributed inside a prepreg and a resin film in the above-mentioned process.

  That is, in this step, by heating and pressurizing the prepreg or resin film containing the sublimable metal compound therein, the sublimable metal compound moves to the front and back sides so as to escape to the outside of the molded body, and as a result, the surface of the film Will be diffused. At this time, in the present embodiment, since the molded body is sandwiched between a pair of metal plates, the sublimation metal compound is prevented from being dispersed (blocked) from the prepreg or the resin film surface accompanying sublimation, and the molded body after curing. It is considered that the sublimable metal compound efficiently remains on the surface side of the film.

Pressurization of the sheet molded body can be easily performed by a pressure press machine or the like. The pressurizing pressure at this time is preferably 0.1 MPa or more and 50 MPa or less, and more preferably 0.2 MPa or more and 40 MPa or less.
When the pressure is in the above range, the sublimable metal compound is efficiently diffused on the surface of the sheet molded body such as a film, and breakage of the sheet molded body can be prevented.

The sheet compact can be easily heated by a heating / pressing press or the like in which a heating function is added to the pressing press. The heating temperature at this time is preferably not less than the glass transition temperature of the resin composition in order to promote diffusion due to sublimation of the sublimable metal compound, and specifically preferably not less than 100 ° C. and not more than 400 ° C. More preferably, the temperature is 150 ° C. or higher and 300 ° C. or lower.
When the heating temperature is in the above range, the sublimable metal compound is efficiently diffused on the surface of the sheet molded body such as a film, and the deterioration of the resin composition and the decomposition of the sublimable metal compound can be prevented. Moreover, 400 degrees C or less is preferable also from economical aspects, such as a required apparatus and energy. In addition, the said heating can also be performed simultaneously with the said pressurization.

  Furthermore, in the present embodiment, in order to more efficiently diffuse the sublimable metal compound to the surface of the sheet molded body, it is preferable that the entire system is in a reduced pressure state in at least a part of the heating and pressing step. The reduced pressure state may be performed, for example, by installing the high-temperature vacuum press device or the heating and pressing press machine inside a reduced-pressure dryer or the like, and heating and pressurizing the sheet compact in a state where the inside is decompressed. it can.

The degree of vacuum in the reduced pressure state is not particularly limited as long as it is lower than atmospheric pressure, but is preferably 10 Pa or more and 1000 Pa or less, and more preferably 50 Pa or more and 800 Pa or less.
When the degree of vacuum is in the above range, the sublimable metal compound is efficiently diffused on the surface of the sheet molded body such as a film, and the generation of bubbles in the film or the like and the release of the sublimable metal compound from the film surface are prevented. Can do.
In addition, although the said pressure reduction state should just be achieved in at least one part of a heating-pressing process, it is desirable to make it a pressure reduction state from the pressurization start to the end time.

In the present embodiment, the time for the heating and pressing step is preferably 10 minutes or more and 5 hours or less, and more preferably 30 minutes or more and 3 hours or less in order to sufficiently advance the diffusion.
More specifically, for example, after the pressurization and depressurization, the heating is performed at a temperature rising rate of 5 ° C./min, the temperature is reached at 230 ° C., held for 2 hours, and then cooled at the temperature decreasing rate of 5 ° C./min. It is preferable to carry out the cycle.

  In the present embodiment, it is desirable to use a metal plate such as a SUS plate or a galvanized steel plate as the metal plate. In addition, when sandwiching the sheet molded body between a pair of metal plates, a release film such as a Teflon (registered trademark) film, an aluminum foil, a copper foil is used between the two to prevent the metal plate and the sheet molded body from sticking to each other. Etc. are preferably interposed.

(Reduction process)
In the present embodiment, it is necessary to make the sublimable metal compound diffused on the surface of the molded body after the heating and pressurizing step into a conductor. The method of making the conductor is not particularly limited, and a special process is not necessary if the conductor is already made after diffusion. On the other hand, when the sublimable metal compound diffused on the surface is oxidized and becomes a non-conductor, it is preferably made into a conductor by a reduction process.

  The reduction process can be performed by heating in a hydrogen stream or by immersing in a reducing agent solution such as sodium borohydride or dimethylamine borane. From the viewpoint of simplicity of the processing apparatus, the reducing agent solution It is more preferable to perform the reduction by dipping in. Moreover, as this reducing agent solution, a commercially available reducing agent solution for electroless plating can also be used suitably.

(Thickening process)
In the present embodiment, the molded body (composite material) having the metal film portions on the front and back surfaces manufactured through the respective steps is subjected to, for example, electroplating, for example, so that the thickness as the metal film is increased. It can be increased as appropriate.
Specifically, for example, the metal film portion can be thickened by performing electroless plating using a sublimable metal compound (or metal) made conductive by a reduction process as a nucleus. The thickness of the metal film after thickening is preferably 1 to 40 μm or less. In addition, in the metal film portion in the present embodiment, not only the metal is densely arranged to form a metal film, but also the (A) component before the film is present in a high concentration as described above. Also included is a high concentration region of a sublimable metal compound. Here, the “sublimation metal compound high concentration region” refers to a region where the component (A) is present in an amount of 80% by mass or more in a region that becomes a metal film by the reduction process.

  As described above, in the molded body (composite material) having the metal film portions on the front and back surfaces manufactured by the manufacturing method of the present embodiment, the interface between the metal film portion and the resin substrate is caused by diffusion of the sublimable metal compound. It has a mixed state of molecular level formed. Therefore, the adhesion between the metal film portion and the resin layer can be ensured without forming irregularities on the surface by physical roughening or chemical roughening.

  As described above, the metal film portion includes the sublimable metal compound high concentration region before the film is formed. In this sublimable metal compound high concentration region, the sublimable metal compound is localized on the surface. This sublimable metal compound in a localized state plays an effective role in improving the adhesion between the metal film and the resin layer, particularly when the film thickness is increased. That is, the mixed state at the molecular level formed by the diffusion of the sublimable metal compound present at the interface between the metal film part and the resin layer improves the adhesion with the metal film formed on the surface side. it is conceivable that.

In the composite material of the present embodiment, sufficient adhesion between the metal film and the resin layer can be ensured without forming irregularities on the surface as described above. For this reason, especially when forming a circuit pattern using a printed wiring board or the like, the accuracy of pattern formation in the depth direction is improved, and a wiring board having fine wiring can be manufactured.
In order to enable the fine wiring effectively, it is preferable that the arithmetic average roughness Ra of the front and back surfaces of the composite material formed on the laminated board or the cured film including the base material is 0.005 to 0.15 μm. More preferably, the thickness is 0.01 to 0.1 μm. A method for measuring the arithmetic average roughness Ra will be described later.

Furthermore, in the composite material of the present embodiment, it is preferable that the insulation resistance value in the thickness direction (direction between the front and back surfaces) after application of a constant voltage is a certain level or more (insulation resistance characteristics) in use for a wiring board or the like.
Specifically, the insulation resistance measured in accordance with JIS-C-6481: 1996 in the thickness direction after applying a DC voltage of 500 V between the front and back surfaces of the sheet-like composite material for 1 minute. The value is preferably 1 × 10 ⁹ Ω or more, and more preferably 1 × 10 ¹¹ Ω or more.

The storage elastic modulus of the cured product of the resin composition constituting the composite material is preferably 3 × 10 ⁶ Pa or more and 3 × 10 ⁷ Pa or less at the sublimation temperature of the sublimable metal compound. It is preferably 10 ⁶ Pa or more and 2.8 × 10 ⁷ Pa or less. When the storage elastic modulus is in the above range, sufficient copper peeling strength can be satisfied.

<Prepreg and resin film>
The prepreg of the present invention and the resin film of the present invention can be produced by a known method using the above-described resin composition and resin varnish of the present invention. Hereinafter, these will be described.

(Prepreg)
After impregnating the reinforcing fiber substrate with the resin composition or resin varnish of the present invention, in a drying furnace or the like, the temperature is 60 to 200 ° C., preferably 80 to 170 ° C., 2 to 30 minutes, preferably 3 to The prepreg of the present invention is obtained by drying for 15 minutes. As the reinforcing fiber base, it is preferable to use a fiber base such as a woven fabric or a non-woven fabric.

  Examples of the fiber substrate include inorganic fibers such as glass, alumina, boron, silica alumina glass, silica glass, tyrano, silicon carbide, silicon nitride, zirconia, aramid, polyether ether ketone, polyether imide, polyether sulfone. Further, there are organic fibers such as carbon and cellulose, and mixed papers of these, and glass fiber woven fabrics are particularly preferably used. The type of the glass woven fabric is not particularly specified, and those having a thickness of 10 μm to 200 μm can be used according to the thickness of the target prepreg or laminate.

(Resin film)
The resin composition or resin varnish of the present invention is cast on a base substrate such as a PET film, and is heated in a drying furnace or the like at a temperature of 60 to 200 ° C., preferably 80 to 170 ° C. for 2 to 30 minutes, preferably 3 to The resin film of the present invention can be obtained by drying for 15 minutes to be semi-cured in a B-stage shape or by removing the organic solvent.
In addition, as a base substrate, what is used for the composite material of this invention can be used.

  Using the prepreg or resin film obtained as described above, a conductor-clad laminate for a printed wiring board and a cured conductor-clad resin sheet can be produced by the method according to each step of the composite material described above.

  In addition, using the prepreg, resin film, and composite material (laminated plate, cured film) manufactured as described above, hole forming, metal plating, and circuit formation by etching metal foil, etc., by known methods In addition, a single-sided, double-sided, or multi-layer printed wiring board can be obtained by performing a multi-layer bonding process.

  As mentioned above, although this invention was demonstrated by embodiment, this invention is not limited to said form, In the range which does not deviate from the objective of the invention, arbitrary change and a change can be performed.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. In the following, “part” means part by mass and “%” means mass% unless otherwise specified.

<Examples 1-4, Comparative Examples 1-3>
Example 1
A resin composition prepared by dissolving 100 parts of polymethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) and 3 parts of bis (acetylacetonato) copper (II) (manufactured by Wako Pure Chemical Industries, Ltd.) in 500 parts of acetone. It was. This was applied onto a PET film, dried at 120 ° C. and then peeled off from the PET film to obtain a resin composition film (sheet molded body). This was put in a spacer having a flat recess of 0.5 mm depth made of Teflon (registered trademark), and then the upper and lower sides were sandwiched with a metal plate made of SUS, and the temperature was 230 ° C., the pressure was 1 MPa, The film was heated and pressed for 1.5 hours under a pressing condition of 500 Pa in vacuum to obtain a film having a thickness of 0.5 mm and a metallic luster on the front and back surfaces. As described above, since the surface state is changed before and after the heat and pressure molding, the copper in the film diffuses and moves to the surface, and as a result, the metal is localized on the surface. I understood it.
The heating and cooling were performed at a temperature increase / decrease rate of 5 ° C./min, respectively, and the reduced pressure state with a vacuum degree of 500 Pa was in the entire process from the start to the end of the press. The same applies to the following examples and comparative examples.

  Next, this film was immersed in a 5% aqueous solution of sodium borohydride for 10 minutes to reduce the metal on the surface, and then electroless copper plating solution CUST-2000 (manufactured by Hitachi Chemical Co., Ltd.) at 40 ° C. for 30 minutes. A film having a metal copper film with a film thickness of 2 μm on the front and back surfaces was obtained by dipping for a minute. The film having the double-sided metal copper film was further subjected to electrolytic copper plating to obtain a film 1 (composite material) having a metal copper film having a thickness of 20 μm on the front and back surfaces.

(Example 2)
100 parts of polymethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) and 1 part of bis (acetylacetonato) palladium (II) (manufactured by Mitsuwa Chemicals Co., Ltd.) were dissolved in 500 parts of acetone. This was applied onto a PET film, dried at 120 ° C. and then peeled off from the PET film to obtain a resin composition film (sheet molded body). This was put into a spacer having a planar recess of 0.3 mm depth made of Teflon (registered trademark), and then the upper and lower sides were sandwiched with a metal plate made of SUS, and the temperature was 170 ° C., the pressure was 1 MPa, The film was heat-pressed for 1 hour under a press condition of a vacuum degree of 50 Pa to obtain a film having a metal luster on the front and back surfaces with a thickness of 0.3 mm. As described above, since the state of the surface is changed before and after the heat and pressure molding, palladium inside the film diffuses and moves to the surface, and as a result, the metal is localized on the surface. I understood it.

  Next, this film was immersed in 5% dimethylamine borane aqueous solution for 5 minutes to reduce the metal on the surface, and then immersed in electroless copper plating solution CUST-2000 (manufactured by Hitachi Chemical Co., Ltd.) at 40 ° C. for 30 minutes. And the film which has a metal copper film | membrane with a film thickness of 2 micrometers on the front and back was obtained. The film having the double-sided metal copper film was further subjected to electrolytic copper plating to obtain a film 2 (composite material) having a metal copper film having a thickness of 20 μm on the front and back surfaces.

(Example 3)
556 parts of dicyclopentadiene type epoxy resin (HP-7200H made by DIC, epoxy equivalent: 278), 210 parts novolac type phenol resin (TD-2090 made by DIC, OH equivalent: 105), 2-ethyl-4-methylimidazole 2.8 parts and 23 g of bis (acetylacetonato) copper (II) were dissolved in 1850 parts of methyl ethyl ketone to obtain a varnish of the resin composition. This was impregnated into a 0.2 mm thick glass cloth and dried by heating at 140 ° C. for 10 minutes to obtain a prepreg (sheet molded body) having a resin content of 40%. Four prepregs are stacked, aluminum foil is stacked on the uppermost and lowermost surfaces, the upper and lower sides are sandwiched between metal plates, and heated for 2 hours under high-temperature vacuum press equipment at a temperature of 230 ° C, a pressure of 4 MPa, and a vacuum of 500 Pa. After pressure forming, the aluminum foil on both sides was peeled off to obtain a black-brown laminate with a metallic luster. As described above, since the surface state is changed before and after the heat and pressure molding, the copper in the film diffuses and moves to the surface, and as a result, the metal is localized on the surface. I understood it.

  Next, this laminate was immersed in a 5% dimethylamine borane aqueous solution for 5 minutes to reduce the metal on the surface, then immersed in an electroless copper plating solution CUST-2000 at 40 ° C. for 30 minutes, and a film thickness of 2 μm on the front and back surfaces. A laminate having a metallic copper film was obtained. The laminated plate having the metal copper film was further subjected to electrolytic copper plating to obtain a laminated plate 1 (composite material) having a metal copper film having a thickness of 20 μm on the front and back surfaces.

(Example 4)
100 parts of polymethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) and 1 part of bis (acetylacetonato) palladium (II) (manufactured by Mitsuwa Chemicals Co., Ltd.) were dissolved in 500 parts of acetone. This was applied onto a PET film, dried at 120 ° C. and then peeled off from the PET film to obtain a resin composition film (sheet molded body). This is put in a Teflon (registered trademark) made flat spacer with a depth of 0.3 mm, and then aluminum foil is stacked on each of the upper and lower surfaces, and the upper and lower surfaces are sandwiched between metal plates, and a heating and pressing machine Was heated and pressed for 30 minutes under press conditions of a temperature of 350 ° C. and a pressure of 1 MPa to obtain a film having a metal luster on the front and back surfaces with a thickness of 0.3 mm. As described above, since the state of the surface is changed before and after the heat and pressure molding, palladium inside the film diffuses and moves to the surface, and as a result, the metal is localized on the surface. I understood it.
Next, this film was immersed in a 5% aqueous solution of sodium borohydride for 10 minutes to reduce the metal on the surface, and then electroless copper plating solution CUST-2000 (manufactured by Hitachi Chemical Co., Ltd.) at 40 ° C. for 30 minutes. A film having a metal copper film with a film thickness of 2 μm on the front and back surfaces was obtained by dipping for a minute. The film having the double-sided metal copper film was further subjected to electrolytic copper plating to obtain a film 3 (composite material) having a metal copper film having a thickness of 20 μm on the front and back surfaces.

(Comparative Example 1)
100 parts of polymethyl methacrylate was dissolved in 500 parts of acetone. This was applied onto a PET film, dried at 120 ° C. and then peeled off from the PET film to obtain a resin composition film. This was put into a spacer having a flat recess of 0.1 mm depth made of Teflon (registered trademark), and then the upper and lower sides were sandwiched with a metal plate made of SUS, and the temperature was 230 ° C., the pressure was 1 MPa, Heat-press molding was performed for 2 hours under press conditions with a vacuum degree of 500 Pa to obtain a transparent film having a thickness of 0.1 mm.

  This film was immersed in a 5% aqueous solution of sodium borohydride for 10 minutes, and then immersed in an electroless copper plating solution CUST-2000 at 40 ° C. for 30 minutes. It was not possible to obtain a film having

(Comparative Example 2)
556 parts of dicyclopentadiene type epoxy resin (HP-7200H made by DIC, epoxy equivalent: 278), 210 parts novolac type phenol resin (TD-2090 made by DIC, OH equivalent: 105), 2-ethyl-4-methylimidazole 2.8 parts was melt | dissolved in 1850 parts of methyl ethyl ketone, and the varnish of the resin composition was obtained. This was impregnated into a 0.2 mm thick glass cloth and dried by heating at 140 ° C. for 10 minutes to obtain a prepreg (sheet molded body) having a resin content of 40%. Four prepregs are stacked, aluminum foil is stacked on the uppermost and lowermost surfaces, the upper and lower sides are sandwiched between metal plates, and heated for 2 hours under high-temperature vacuum press equipment at a temperature of 230 ° C, a pressure of 4 MPa, and a vacuum of 500 Pa. After pressure forming, the aluminum foil on both sides was peeled off to obtain a black-brown laminate.

  Next, this laminate was immersed in a 5% dimethylamine borane aqueous solution for 5 minutes and then immersed in an electroless copper plating solution CUST-2000 at 40 ° C. for 30 minutes, but a laminate having metal copper films on the front and back surfaces was obtained. There wasn't.

(Comparative Example 3)
556 parts of dicyclopentadiene type epoxy resin (HP-7200H made by DIC, epoxy equivalent: 278), 210 parts novolac type phenol resin (TD-2090 made by DIC, OH equivalent: 105), 2-ethyl-4-methylimidazole 2.8 parts and 23 parts of copper oxide (CuO) were dissolved in 1850 parts of methyl ethyl ketone to obtain a varnish of the resin composition. This was impregnated into a 0.2 mm thick glass cloth and dried by heating at 140 ° C. for 10 minutes to obtain a prepreg (sheet molded body) having a resin content of 40%. Four prepregs are stacked, aluminum foil is stacked on the uppermost and lowermost surfaces, the upper and lower sides are sandwiched between metal plates, and heated for 2 hours under high-temperature vacuum press equipment at a temperature of 230 ° C, a pressure of 4 MPa, and a vacuum of 500 Pa. After pressure forming, the aluminum foil on both sides was peeled off to obtain a black-brown laminate.

  On this laminate, a palladium plating catalyst is applied by a known catalyzer / accelerator method, immersed in an electroless copper plating solution CUST-2000 at 40 ° C. for 30 minutes, and a metal copper film having a thickness of 2 μm is formed on the front and back surfaces. A laminate was obtained. The laminated plate having the double-sided metal copper film was further subjected to electrolytic copper plating to obtain a laminated plate 2 having a metal copper film having a thickness of 20 μm on the front and back surfaces.

(Characteristic evaluation)
About the films 1-3 obtained by the above-mentioned Example and comparative example, and the laminated plates 1-2, copper foil peeling strength, solder heat resistance, and insulation resistance characteristics were evaluated. The results are shown in Table 1.
In addition, about the comparative examples 1 and 2, since the film and laminated board which can be evaluated were not obtained, evaluation is not performed. Moreover, about the films 1-3 (Examples 1, 2, 4), solder heat resistance is not evaluated from the heat resistant surface of resin (polymethylmethacrylate) itself.

The evaluation method of each characteristic is as follows.
-Strength of copper foil peeling-
The copper foil peeling strength in the obtained film or laminate was measured according to the copper-clad laminate test standard JIS-C-6481: 1996.

-Solder heat resistance-
Each laminated board was cut | disconnected so that it might become a 50 mm x 50 mm surface, and the copper foil of the single side | surface of each sample was etched. This was immersed in molten solder at 288 ° C. for 20 seconds, and the appearance of the obtained sample was visually examined. In addition, OK in the table means that there is no occurrence of blistering or measling between the copper foil and the laminate or film substrate after the solder immersion. On the other hand, NG means that there is at least one of the bulges in the observation range.

−Insulation resistance characteristics−
The insulation resistance characteristic of the obtained laminated board or film was measured based on copper-clad laminated board test specification JIS-C-6481: 1996.

-Surface roughness-
The metal copper film in the obtained laminate or film was removed by etching with an aqueous solution of ammonium persulfate, and the arithmetic average roughness Ra of the laminate or film surface was determined as an optical interference type non-contact surface roughness meter (manufactured by Ryoka System Co., Ltd.). Measured by.

  As is clear from the results shown in Table 1, the films of Examples 1, 2, and 4 and the laminated board of Example 3 were all made of copper foil peel strength and solder heat resistance, although the surface roughness was small. The properties (only Example 3) were good, and the insulation resistance characteristics were at a level with no problem. On the other hand, in the laminated board of Comparative Example 3, there was a problem in copper foil peeling strength and solder heat resistance because the adhesion between the metal film and the resin base material was low.

<Examples 5-7, Comparative Examples 4-7>
(Preparation of resin varnish (resin composition))
-Preparation Example 1
In a 1 liter separable flask equipped with a thermometer, a reflux condenser, a vacuum concentrator, and a stirrer, 200 parts of toluene and 50 parts of polyphenylene ether (S202A, manufactured by Asahi Kasei Chemicals Corporation, Mn: 16000, hereinafter referred to as PPE) The temperature in the flask was set at 90 ° C. and dissolved by stirring. After confirming the dissolution of PPE, 30 parts of phenol novolac type epoxy resin (N770, manufactured by DIC) and 20 parts of cresol novolac resin (KA1165, manufactured by DIC) were respectively added and stirred and dissolved. Next, after cooling the solution to room temperature, 3 parts of bis (acetylacetonato) copper (II) (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.5 part of 2-ethyl-4-methylimidazole were added. Then, methyl ethyl ketone (MEK) was blended to prepare the resin varnish of Preparation Example 1 (solid content concentration of about 30% by mass).

-Preparation Example 2-
In a 1 liter separable flask equipped with a thermometer, reflux condenser, vacuum concentrator, and stirrer, 200 parts of methyl ethyl ketone (hereinafter referred to as MEK) and dicyclopentadiene type epoxy resin (HP-7200H, manufactured by DIC) 200 parts, 120 parts of cresol novolac resin (KA1165, manufactured by DIC), 10 parts of bis (acetylacetonato) copper (II), and 1 part of 2-ethyl-4-methylimidazole are added, and then MEK is blended to prepare. The resin varnish of Example 2 (solid content concentration of about 60% by mass) was prepared.

-Preparation Example 3-
In a 1 liter separable flask equipped with a thermometer, reflux condenser, reduced pressure concentrator and stirrer, 200 parts of methyl ethyl ketone (hereinafter referred to as MEK) and biphenyl aralkyl type epoxy resin (NC-3000H, manufactured by Nippon Kayaku Co., Ltd.) ) After adding 300 parts, 120 parts of cresol novolac resin (KA1165, manufactured by DIC), 10 parts of bis (acetylacetonato) copper (II), and 2 parts of 2-ethyl-4-methylimidazole, MEK was added, The resin varnish of Preparation Example 3 (solid content concentration: about 65% by mass) was prepared.

-Comparative Preparation Example 1
A resin varnish (solid content concentration of about 30% by mass) of Comparative Preparation Example 1 was prepared in the same manner as in Preparation Example 1 except that bis (acetylacetonato) copper (II) was not blended in Preparation Example 1.

-Comparative Preparation Example 2-
A resin varnish (solid content concentration of about 60% by mass) of Comparative Preparation Example 2 was prepared in the same manner as Preparation Example 2 except that bis (acetylacetonato) copper (II) was not blended in Preparation Example 2.

-Comparative Preparation Example 3-
Resin varnish (solid content) of Comparative Preparation Example 3 was prepared in the same manner as Preparation Example 2 except that 10 parts of copper oxide (CuO) was blended in place of bis (acetylacetonato) copper (II). A concentration of about 60% by mass) was prepared.

(Production of resin film and prepreg)
The resin varnish obtained in Preparation Example 1 and Comparative Preparation Example 1 was applied onto a PET film, dried at 120 ° C. for 10 minutes, and then peeled off from the PET film to obtain a B-stage resin film having a thickness of 50 μm.
Moreover, after impregnating the resin varnish obtained in Preparation Examples 2 and 3 and Comparative Preparation Examples 2 and 3 into a glass woven cloth (E glass, manufactured by Nittobo Co., Ltd.) having a thickness of 0.1 mm, The prepregs each having a resin content of 42% by mass (thickness: 0.1 mm) were prepared by heating and drying for minutes.

(Molded body (production of metal-clad film and metal-clad laminate)
Aluminum foil is stacked on the uppermost surface and lowermost surface of each of the resin film (1 sheet) and prepreg (4 sheets stacked) obtained above, and the upper and lower surfaces are sandwiched between metal plates, and the temperature is 230 ° C. by a high-temperature vacuum press. Heat pressing was performed for 2 hours under pressing conditions of a pressure of 4 MPa and a degree of vacuum of 500 Pa. Thereafter, the aluminum foil on both sides was peeled off to obtain a cured film and a laminate. At this time, the surfaces of the cured film made of the resin varnish of Preparation Example 1 and the laminates made of the resin varnishes of Preparation Examples 2 and 3 were blackish-brown with metallic luster (that is, before and after the heat and pressure molding as described above. Since the state of the surface has changed, it was found that the copper inside the film diffused and moved to the surface, and as a result, the metal was localized on the surface). The surface of the cured film or laminate made of the resin varnish of 2 was transparent, and the laminate made of the resin varnish of Comparative Preparation Example 3 was blackish brown.

  In addition, using the four prepregs obtained using Comparative Preparation Example 2 above, using a low-profile copper foil (F3-WS-18, manufactured by Furukawa Electric) having a thickness of 18 μm instead of the aluminum foil, the above and A double-sided copper-clad laminate was produced under the same pressing conditions.

  The cured film and laminate obtained using the resin varnishes of Preparation Examples 1 to 3 obtained above were immersed in a 5% dimethylamine borane aqueous solution for 5 minutes to reduce the surface metal, and then electroless copper It was immersed in a plating solution CUST-2000 at 60 ° C. for 30 minutes to obtain a metal-clad film and a metal-clad laminate having a metal copper film with a film thickness of 2 μm on the front and back surfaces. On the other hand, the cured films or laminates made of the resin varnishes of Comparative Preparation Examples 1 to 3 tried the same electroless copper plating process, but the films or laminates of Comparative Preparation Examples 1 and 2 still remained transparent, Films and laminates having metal copper films on the front and back surfaces could not be obtained, and the laminate of Comparative Preparation Example 3 was almost entirely blackish brown (metal spots were very slightly scattered), and the metal copper A film could not be formed.

  Various composites having a metal copper film having a thickness of 20 μm on the front and back surfaces of the metal-clad film and metal-clad laminate having the metal copper film produced using the resin varnishes of each of the above preparation examples. Materials (double-sided metal-clad film, double-sided metal-clad laminate) were prepared.

In addition, the case where the resin varnish of the preparation examples 1-3 is used corresponds to Examples 5-7, respectively. Moreover, let the film and laminated board which do not have the metal copper film | membrane using the resin varnish of the comparative preparation examples 1-3 be the comparative examples 4-6, respectively.
Moreover, the copper foil of the double-sided copper clad laminate produced using the copper foil is removed by whole surface etching, and after the plating catalyst application treatment step, the electroless copper plating and the electroplating step are performed under the same conditions as described above. A metal-clad laminate was produced. This is referred to as Comparative Example 7.

(Characteristic evaluation)
About the cured film and laminated board obtained above, the peeling strength of the copper metal film, solder heat resistance, insulation resistance, and surface roughness were evaluated. The evaluation results are shown in Table 1. The characteristic evaluation method is as follows. In addition, the characteristic evaluation of the laminated board of Comparative Example 6 is only solder heat resistance, insulation resistance, and surface roughness, and the characteristic evaluation of the cured film of Comparative Example 4 and the laminated board of Comparative Example 5 in which the metal copper film could not be formed is Only insulation resistance and surface roughness.

-Stripping strength of copper metal film-
The peel strength of the metallic copper film was measured in the same manner as in Example 1 in accordance with the copper-clad laminate test standard JIS-C-6481.

-Evaluation of solder heat resistance-
The above-described cured film cut to a 50 mm square, and the metal layer on one side of the laminated plate removed by etching using a 20% aqueous solution of ammonium persulfate were immersed in molten solder at 288 ° C. for 20 seconds, and the appearance of the sample after the test Was examined visually. “No abnormality” in the table means that there is no occurrence of blistering or measling between the resin layer and the metal layer of the laminated plate or film after immersion in molten solder. On the other hand, “NG” means that there is at least one swelling or the like in the observation range.

−Insulation resistance characteristics−
The insulation resistance characteristics were measured in the same manner as in Example 1 in accordance with the copper clad laminate test standard JIS-C-6481.

-Surface roughness-
In the same manner as in Example 1, the arithmetic average roughness Ra of the laminated plate or film surface from which the metal copper film was removed by etching was measured with an optical interference type non-contact surface roughness meter (manufactured by Ryoka System Co., Ltd.).

  As is clear from the results shown in Table 2, the cured films and laminates of Examples 5 to 7 are both excellent in metal film peeling strength and solder heat resistance, although the surface roughness is small. In addition, the insulation resistance characteristics were at a satisfactory level. In contrast, the cured films and laminates of Comparative Examples 4 and 5 attempted the electroless copper plating process, but the laminates remained transparent and had a metal copper film on the front and back surfaces, laminates Could not get. In addition, the laminated plate of Comparative Example 6 in which the metal spots were slightly scattered and a uniform metal film could not be formed had a problem in heat resistance due to peeling of the scattered metal during immersion in the solder. It was. The laminate of Comparative Example 7 had high adhesion between the metal film and the resin substrate, and had no problem with the copper foil peel strength and solder heat resistance, but the surface roughness was large.

<Example 8>
56 parts of a dicyclopentadiene type epoxy resin (DIC-7HP, epoxy equivalent: 278), 43 parts of phenol aralkyl resin (MEH-7851M, OH equivalent: 214, Meiwa Kasei), 2-ethyl-4-methylimidazole 1.1 parts and 3 parts of bis (acetylacetonato) copper (II) were dissolved in 53 parts of methyl ethyl ketone to obtain a varnish of the resin composition. This was impregnated into a 0.2 mm thick glass cloth and dried by heating at 140 ° C. for 10 minutes to obtain a prepreg (sheet molded body) having a resin content of 40%. Four prepregs are stacked, and aluminum foil is stacked on the top and bottom surfaces of the prepreg. The top and bottom of the prepreg are sandwiched between metal plates, and heated for 1 hour under high-temperature vacuum press equipment at a temperature of 180 ° C., a pressure of 4 MPa, and a vacuum degree of 500 Pa. Then, it was pressure-molded and then heat-molded for 10 minutes under the press conditions of a temperature of 230 ° C., a pressure of 4 MPa, and a vacuum of 500 Pa, and then the aluminum foil on both sides was peeled off to obtain a black-brown laminate with a metallic luster.
The heating and cooling were performed at a temperature increase / decrease rate of 5 ° C./min, respectively, and the reduced pressure state with a vacuum degree of 500 Pa was in the entire process from the start to the end of the press. The same applies to the following examples and comparative examples.

  Moreover, the varnish of the resin composition was applied on a PET film, dried at 120 ° C., and then peeled off from the PET film to obtain a semi-cured product of the resin composition. This is put into a Teflon (registered trademark) made flat spacer having a depth of 0.3 mm, and then the upper and lower sides are sandwiched with a metal plate made of SUS, and a temperature of 180 ° C., a pressure of 1 MPa, Heat-press molding was performed for 1 hour under press conditions with a vacuum degree of 500 Pa to obtain a cured product 1 of a resin composition having a thickness of 0.3 mm.

  Next, this laminate was immersed in a 5% dimethylamine borane aqueous solution for 5 minutes to reduce the metal on the surface, and then immersed in an electroless copper plating solution CUST-2000 at 60 ° C. for 15 minutes. A laminate having a metal copper film of 5 μm was obtained. The laminated plate having the metallic copper film was further subjected to electrolytic copper plating to obtain a laminated plate A (composite material) having a metallic copper film having a thickness of 20 μm on the front and back surfaces.

<Example 9>
56 parts phenyl aralkyl type epoxy resin (Nippon Kayaku NC-3000H, epoxy equivalent: 288), 41 parts phenol aralkyl resin (Maywa Kasei MEH-7851M, OH equivalent: 214), 2-ethyl-4-methyl 1.1 parts of imidazole and 3 parts of bis (acetylacetonato) copper (II) were dissolved in 53 parts of methyl ethyl ketone to obtain a varnish of a resin composition. This was impregnated into a 0.2 mm thick glass cloth and dried by heating at 140 ° C. for 10 minutes to obtain a prepreg (sheet molded body) having a resin content of 40%. Four prepregs are stacked, and aluminum foil is stacked on the top and bottom surfaces of the prepreg. The top and bottom of the prepreg are sandwiched between metal plates, and heated for 1 hour under high-temperature vacuum press equipment at a temperature of 180 ° C., a pressure of 4 MPa, and a vacuum degree of 500 Pa. Then, it was press-molded and then heat-molded for 5 minutes under the press conditions of a temperature of 230 ° C., a pressure of 4 MPa, and a vacuum of 500 Pa, and then the aluminum foil on both sides was peeled off to obtain a black-brown laminate with a metallic luster.

  Moreover, the varnish of the resin composition was applied on a PET film, dried at 120 ° C., and then peeled off from the PET film to obtain a semi-cured product of the resin composition. This is put into a Teflon (registered trademark) made flat spacer having a depth of 0.3 mm, and then the upper and lower sides are sandwiched with a metal plate made of SUS, and a temperature of 180 ° C., a pressure of 1 MPa, Heat-press molding was performed for 1 hour under press conditions with a vacuum degree of 500 Pa to obtain a cured product 2 of a resin composition having a thickness of 0.3 mm.

  Next, this laminate was immersed in a 5% aqueous sodium borohydride solution for 5 minutes to reduce the metal on the surface, and then immersed in an electroless copper plating solution CUST-2000 at 60 ° C. for 15 minutes. A laminated plate having a metal copper film of 0.5 μm was obtained. The laminated plate having the metallic copper film was further subjected to electrolytic copper plating to obtain a laminated plate B (composite material) having a metallic copper film having a thickness of 20 μm on the front and back surfaces.

<Example 10>
56 parts of dicyclopentadiene type epoxy resin (DIC-7HP, epoxy equivalent: 278), 21 parts of novolak type phenolic resin (TD-2090, OH equivalent: 105), 2-ethyl-4-methylimidazole 0.3 part and 3 parts of bis (acetylacetonato) copper (II) were dissolved in 185 parts of methyl ethyl ketone to obtain a varnish of the resin composition. This was impregnated into a 0.2 mm thick glass cloth and dried by heating at 140 ° C. for 10 minutes to obtain a prepreg (sheet molded body) having a resin content of 40%. Four prepregs are stacked, aluminum foil is stacked on the uppermost and lowermost surfaces, the upper and lower sides are sandwiched between metal plates, and heated for 2 hours under high-temperature vacuum press equipment at a temperature of 230 ° C, a pressure of 4 MPa, and a vacuum of 500 Pa. After pressure forming, the aluminum foil on both sides was peeled off to obtain a black-brown laminate with a metallic luster.

  Moreover, the varnish of the resin composition was applied on a PET film, dried at 120 ° C., and then peeled off from the PET film to obtain a semi-cured product of the resin composition. This is put into a Teflon (registered trademark) made flat spacer having a depth of 0.3 mm, and then the upper and lower sides are sandwiched with a metal plate made of SUS, and a temperature of 180 ° C., a pressure of 1 MPa, Heat-press molding was performed for 1 hour under press conditions with a vacuum degree of 500 Pa to obtain a cured product 3 of a resin composition having a thickness of 0.3 mm.

  Next, this laminate was immersed in a 5% dimethylamine borane aqueous solution for 5 minutes to reduce the metal on the surface, and then immersed in an electroless copper plating solution CUST-2000 at 60 ° C. for 15 minutes. A laminate having a metal copper film of 5 μm was obtained. The laminated plate having the metallic copper film was further subjected to electrolytic copper plating to obtain a laminated plate C (composite material) having a metallic copper film having a thickness of 20 μm on the front and back surfaces.

<Comparative Example 8>
56 parts of a dicyclopentadiene type epoxy resin (DIC-7HP, epoxy equivalent: 278), 43 parts of phenol aralkyl resin (MEH-7851M, OH equivalent: 214, Meiwa Kasei), 2-ethyl-4-methylimidazole 1.1 parts was dissolved in 53 parts of methyl ethyl ketone to obtain a varnish of the resin composition. This was impregnated into a 0.2 mm thick glass cloth and dried by heating at 140 ° C. for 10 minutes to obtain a prepreg (sheet molded body) having a resin content of 40%. Four prepregs are stacked, and aluminum foil is stacked on the top and bottom surfaces of the prepreg. The top and bottom of the prepreg are sandwiched between metal plates, and heated for 1 hour under high-temperature vacuum press equipment at a temperature of 180 ° C., a pressure of 4 MPa, and a vacuum degree of 500 Pa. Then, the aluminum foil on both sides was peeled off to obtain a black-brown laminate 4 having a metallic luster.

  Moreover, the varnish of the resin composition was applied on a PET film, dried at 120 ° C., and then peeled off from the PET film to obtain a semi-cured product of the resin composition. This is put into a Teflon (registered trademark) made flat spacer having a depth of 0.3 mm, and then the upper and lower sides are sandwiched with a metal plate made of SUS, and a temperature of 180 ° C., a pressure of 1 MPa, Heat-press molding was performed for 1 hour under a press condition with a vacuum degree of 500 Pa to obtain a cured product 4 of a resin composition having a thickness of 0.3 mm.

  Next, the laminate 4 was immersed in a 5% dimethylamine borane aqueous solution for 5 minutes and then immersed in an electroless copper plating solution CUST-2000 at 60 ° C. for 30 minutes, but a laminate having metal copper films on the front and back surfaces was obtained. I couldn't.

<Comparative Example 9>
A palladium plating catalyst is applied to both surfaces of the laminate 4 obtained in Comparative Example 1 by a known catalyzer / accelerator method, and immersed in an electroless copper plating solution CUST-2000 at 60 ° C. for 15 minutes. A laminate having a metal copper film with a thickness of 0.5 μm was obtained. The laminated plate having the double-sided metal copper film was further subjected to electrolytic copper plating to obtain a laminated plate D having a metal copper film having a thickness of 20 μm on the front and back surfaces.

  About the obtained laminated body, it evaluated similarly to the above-mentioned Example. Moreover, the storage elastic modulus was also performed as follows. These results are shown in the table below.

−Storage modulus−
The obtained cured product having a thickness of 0.3 mm was cut into a 5 mm × 30 mm rod shape, and using a longitudinal vibration type dynamic viscoelasticity measuring apparatus (Rheogel-E4000 manufactured by UBM Co., Ltd.), the tensile mode and the strain amplitude (sinusoidal). Wave) Measured from 40 ° C. to 300 ° C. under the conditions of 0.5% and a heating rate of 5 ° C./min, and the storage elastic modulus E ′ at 230 ° C. was determined.

  In Examples 8 to 10, a sufficient copper foil peel strength could be obtained, but a comparative example prepared by applying a palladium plating catalyst by a known catalyzer / accelerator method and dipping in an electroless copper plating solution In No. 9, the copper foil peeling strength was not sufficient.

  According to the present invention, a resin composition for obtaining a composite material in which adhesion between a metal layer and a resin base material is ensured without forming irregularities due to physical roughening or chemical roughening on the surface of the resin layer. And resin varnishes can be provided. Therefore, the metal-clad film and laminated board obtained using these can be used suitably for manufacture of the printed wiring board used in the high frequency field. Therefore, it is useful as a member / part of an electronic device mounting package that requires a narrow pitch / fine pattern or a printed wiring board for a high-frequency circuit that requires high-speed signal processing.

Claims (20)

A resin composition for a molded body that is used in a molded body that metalizes at least a part of the surface and is molded through a thermoforming process,
(A) a sublimable metal compound and (B) an organic compound,
(B) The organic compound is an epoxy resin, cyanate ester resin, phenol resin, urethane resin, melamine resin, benzoxazine resin, benzocyclobutene resin, dicyclopentadiene resin, acrylate compound, triallyl isocyanurate and polybutadiene resin, fluorine resin , Polyolefins and derivatives thereof, polyesters and derivatives thereof, polycarbonate, polyacetal, polysulfone, (meth) acrylic acid ester copolymers, polystyrene, acrylonitrile styrene copolymers, acrylonitrile styrene butadiene copolymers, polyvinyl acetal , Polyvinyl butyrals, polyvinyl alcohols, polyphenylene ether, fully or partially hydrogenated styrene-butadiene copolymers, polybutadiene Completely or partially hydrogenated product, polyether sulfone, polyether ketone, polyphenylene sulfide, at least one selected from polyamides, and aromatic polyesters, the metallization, the resin composition is molded in a heat molding process (A) all or part of the sublimable metal compound moves to the surface of the molded product, and the metal in the (A) sublimable metal compound is ruthenium, copper, platinum, A resin composition which is at least one selected from the group consisting of iron, nickel, chromium and palladium . A resin composition for a molded body that is used in a molded body selected from a metal-clad film or a metal-clad laminate, and is molded through a thermoforming process, comprising (A) a sublimable metal compound and (B) an organic Containing a compound,
(B) The organic compound is an epoxy resin, cyanate ester resin, phenol resin, urethane resin, melamine resin, benzoxazine resin, benzocyclobutene resin, dicyclopentadiene resin, acrylate compound, triallyl isocyanurate and polybutadiene resin, fluorine resin , Polyolefins and derivatives thereof, polyesters and derivatives thereof, polycarbonate, polyacetal, polysulfone, (meth) acrylic acid ester copolymers, polystyrene, acrylonitrile styrene copolymers, acrylonitrile styrene butadiene copolymers, polyvinyl acetal , Polyvinyl butyrals, polyvinyl alcohols, polyphenylene ether, fully or partially hydrogenated styrene-butadiene copolymers, polybutadiene Completely or partially hydrogenated product, polyether sulfone, polyether ketone, polyphenylene sulfide, polyamide, and at least one selected from aromatic polyester, metals in the (A) sublimable metal compound, ruthenium, copper , A resin composition that is at least one selected from the group consisting of platinum, iron, nickel, chromium and palladium .   The resin composition according to claim 1 or 2, wherein (B) the sublimable metal compound (B) in the organic compound diffuses and moves in the thermoforming step.   The resin composition according to claim 3, wherein all or part of the sublimable metal compound (A) moves to the surface of a molded product obtained by molding in the thermoforming step.   5. The sublimable metal compound moves according to claim 3, wherein (A) the sublimable metal compound moves under conditions of a reduced pressure of the entire system and a temperature of 100 to 400 ° C. and a degree of vacuum of 1 to 10,000 Pa in at least part of the thermoforming step. Resin composition. The mixing ratio of the (A) sublimable metal compound, any of claim 1 to 5 from 0.1 to 20 mass% in the entire resin composition comprising (A) a sublimable metal compound (B) an organic compound 2. The resin composition according to item 1. A resin varnish obtained by dissolving or dispersing the resin composition according to any one of claims 1 to 6 in a solvent. A sheet molding step of molding the resin composition according to any one of claims 1 to 6 into a sheet shape,
A heating and pressing step of sandwiching the sheet molded body between a pair of metal plates and heating the sheet molded body after or simultaneously with pressurization of the sheet molded body;
The manufacturing method of the composite material containing this. The method for producing a composite material according to claim 8 , wherein the entire system is brought into a reduced pressure state in at least a part of the heating and pressing step. The heating temperature in the hot pressing step is 100 ° C. or higher 400 ° C. A method for fabricating a composite material according to claim 8 or 9, the pressure is 0.1MPa or more 50MPa or less. The method for producing a composite material according to claim 9 or 10 , wherein the degree of vacuum in the reduced pressure state is 10 Pa or more and 1000 Pa or less. The method for producing a composite material according to any one of claims 8 to 11 , further comprising a reduction step of reducing the sublimable metal compound diffused on the surface of the sheet compact after the heating and pressing step. After the heating and pressing step, the method further includes a thickening step of thickening a metal film portion composed of a metal or a sublimable metal compound with a sublimable metal compound diffused on the surface of the sheet compact as a nucleus. the method of producing a composite material according to any one of claims 8-12. The method for producing a composite material according to any one of claims 8 to 13 , wherein the sublimable metal compound contains copper. Composite material produced by the production method according to any one of claims 8-14. A composite material obtained by thermoforming the resin composition according to any one of claims 1 to 6 , wherein the sublimable metal compound is localized on the surface. The storage modulus of the cured product of the resin composition constituting the composite material, the sublimation temperature of the sublimable metal compound, according to claim 15 or 16 or less 3 × 10 ⁶ Pa or more 3 × 10 ⁷ Pa Composite material. The composite material according to claim 17 , wherein the organic compound includes a phenol aralkyl resin having a phenyl skeleton or a biphenyl skeleton. A prepreg obtained by impregnating a base material with the resin varnish according to claim 7 and then drying or semi-curing at 60 to 200 ° C. A resin film obtained by drying or semi-curing the resin varnish according to claim 7 at 60 to 200 ° C.