JPWO2019013040A1 - Laminated body, printed wiring board, flexible printed wiring board and molded product using the same - Google Patents

Abstract

The present invention is a laminate in which a primer layer (B), a metal nanoparticle layer (C), and a metal plating layer (D) are sequentially laminated on a support (A), the primer layer (B) Is a cured product of a resin (b1) having an epoxy group and a hydroxyl group and a crosslinking agent (b2) containing a polyvalent carboxylic acid, a printed wiring board using the laminate, and a flexible printed wiring Providing plates and molded products. The said laminated body can be manufactured by a simple method, without roughening the support body surface, and is excellent in the adhesiveness between a support body and a metal layer (metal plating layer).

Description

  The present invention relates to a laminate that can be used for a printed wiring board, a flexible printed wiring board, a molded product, and the like.

  Due to the downsizing and speeding up of electronic devices, higher density and higher performance of printed wiring boards are required. To meet this demand, printed wiring boards with a smooth and sufficiently thin conductive layer (metal layer) are required. Is required. A flexible copper-clad laminate (hereinafter abbreviated as “FCCL”) is known as a component of this printed wiring board. FCCL is mainly manufactured by a method in which a heat-resistant polymer film and a copper foil are bonded together using an epoxy resin adhesive.

  However, in the FCCL using this copper foil, the copper foil wound in a roll shape is stuck together while being drawn out, so that the copper foil cannot be made sufficiently thin for handling. Furthermore, the copper foil surface needs to be roughened in order to improve the adhesion with the polymer film, so the high frequency (GHz band) and high frequency required to increase the density and performance of the printed wiring board. There has been a problem of causing transmission loss in the transmission speed (several tens of Gbps) region.

  Here, as a method of thinning the FCCL copper layer, a metal thin film was formed on the surface of the polyimide film by vapor deposition or sputtering, and then electroplating, electroless plating, or a combination of both was formed on the metal thin film. A method of forming copper by a method has been proposed (see, for example, Patent Document 1). However, in this method, since a vapor deposition method or a sputtering method is used to form a metal thin film, a large-scale vacuum facility is required, and there is a problem that the substrate size is limited due to the facility.

  Therefore, without roughening the surface of a metal layer such as copper foil, it has sufficient adhesion to a support such as a polymer film, and without the need for extensive vacuum equipment when thinning the metal layer Therefore, there has been a demand for a laminate that can be produced by a simple method.

  Conventionally, decorative plating on plastic molded products has been used for mobile phones, personal computers, mirrors, containers, various switches, showerheads, and the like. Supports for these uses are only acrylonitrile-butadiene-styrene copolymers (hereinafter abbreviated as “ABS”) and polymer alloys of ABS and polycarbonate (hereinafter abbreviated as “ABS-PC”). Limited. For this reason, it is necessary to roughen the surface of the substrate in order to ensure adhesion between the substrate and the plating film. For example, in the case of ABS, the polybutadiene component is strongly oxidized such as hexavalent chromic acid and permanganate. Surface roughening is possible by etching and removing with an agent. However, since hexavalent chromic acid and the like are environmentally hazardous substances, it is preferable not to use them, and alternative methods have been developed (for example, see Patent Document 2).

  Thus, in plating for the purpose of decoration on plastic molded products, the base material is not limited to ABS or ABS-PC, and a metal plating film excellent in adhesion can be obtained even with other types of plastics, In addition, it has been required to reduce the amount of environmentally hazardous substances used.

JP 2015-118044 Japanese Patent No. 5830807

  The problem to be solved by the present invention is a laminate that can be produced by a simple method without roughening the surface of the support and has excellent adhesion between the support and the metal layer (metal plating layer), It is providing the printed wiring board, flexible printed wiring board, and molded article using this.

  As a result of diligent research to solve the above-mentioned problems, the inventors of the present invention provided a layer of a cured product of a crosslinking agent containing a resin having an epoxy group and a hydroxyl group and a carboxylic acid as a primer layer on the support. The present invention has been completed by finding that a laminate comprising a metal layer formed thereon and a metal layer formed of metal nanoparticles and a metal plating layer in order can solve the above problems.

  That is, the present invention is a laminate in which a primer layer (B), a metal nanoparticle layer (C), and a metal plating layer (D) are sequentially laminated on a support (A), the primer layer ( B) is a cured product of a resin (b1) having an epoxy group and a hydroxyl group and a cross-linking agent (b2) containing a polyvalent carboxylic acid, a printed wiring board using the laminate, and a flexible A printed wiring board and a laminate are provided.

  The laminate of the present invention has excellent adhesion between the support and the metal layer (metal plating layer) without roughening the support surface. Further, when the metal layer is thinned, the laminate has a sufficiently thin metal layer with a smooth surface without using a large-scale vacuum facility.

  In addition, the laminate of the present invention is obtained by patterning a metal layer, for example, a printed wiring board, a flexible printed wiring board, a conductive film for a touch panel, a metal mesh for a touch panel, an organic solar cell, an organic EL element, an organic transistor, It can be suitably used as an electronic member such as an RFID such as a non-contact IC card, an electromagnetic wave shield, an LED illumination base, or a digital signage. In particular, it is optimal for flexible printed wiring board applications such as FCCL. In addition, by applying to molded products, connectors for connecting wiring for optical communication, electrical components, electric motor peripheral members, electronic members such as battery members; automotive decorative parts, lamp reflectors, mobile phones, personal computers, mirrors, It can be suitably used for decoration of containers, home appliances, various switches, faucet parts, shower heads and the like.

  The laminate of the present invention is a laminate in which a primer layer (B), a metal nanoparticle layer (C), and a metal plating layer (D) are sequentially laminated on a support (A), the primer layer (B) is a cured product of a resin (b1) having an epoxy group and a hydroxyl group and a crosslinking agent (b2) containing a polyvalent carboxylic acid.

  The laminate of the present invention may be a laminate in which a primer layer (B) or the like is sequentially laminated on one side of the support (A), and a primer layer (B) or the like on both sides of the support (A). A laminated body in which the layers are sequentially laminated may be used.

  Examples of the support (A) include polyimide, polyamideimide, polyamide, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, acrylonitrile-butadiene-styrene (hereinafter abbreviated as “ABS”) resin, and ABS and polycarbonate. Polymer alloys, acrylic resins such as poly (meth) acrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polycarbonate, polyethylene, polypropylene, polyurethane, liquid crystal polymer (LCP), poly Ether ether ketone (PEEK), polyphenylene sulfide (PPS), polyphenylene sulfone (PPSU), epoxy resin, cellulose nanofiber, silicon Support made of ceramic, glass, etc., porous support made of them, steel plate, support made of metal such as copper, etc., the surface of which is silicon carbide, diamond-like carbon, aluminum, copper, titanium, stainless steel, etc. Examples include a support subjected to vapor deposition.

  Moreover, when using the laminated body of this invention for a printed wiring board etc., as said support body (A), a polyimide, a polyethylene terephthalate, a polyethylene naphthalate, a liquid crystal polymer (LCP), polyetheretherketone (PEEK), an epoxy resin It is preferable to use a support made of glass, cellulose nanofiber or the like.

  Furthermore, when using the laminated body of this invention for a flexible printed wiring board etc., the film-form or sheet-like support body which has the softness | flexibility which can be bend | folded as said support body (A) is preferable.

  When the shape of the support (A) is a film or a sheet, the thickness is usually preferably 1 μm or more and 5,000 μm or less, more preferably 1 μm or more and 300 μm or less, and further preferably 1 μm or more and 200 μm or less.

  Moreover, since the adhesiveness of the said support body (A) and the primer layer (B) mentioned later can be improved more, as needed, the surface of the said support body (A) is fine enough not to lose smoothness. Concavities and convexities may be formed, dirt adhering to the surface may be washed, or surface treatment may be performed to introduce functional groups such as hydroxyl groups, carbonyl groups, and carboxyl groups. Specific examples include plasma discharge treatment such as corona discharge treatment, dry treatment such as ultraviolet treatment, and wet treatment using water, an aqueous solution such as acid / alkali, or an organic solvent.

  The primer layer (B) is a cured product of a resin (b1) having an epoxy group and a hydroxyl group and a crosslinking agent (b2) containing a polyvalent carboxylic acid.

  The resin (b1) is a resin having an epoxy group and a hydroxyl group in the molecule, and examples of the resin species include an epoxy resin and an acrylic resin. The hydroxyl group possessed by the resin (b1) may be an alcoholic hydroxyl group or a phenolic hydroxyl group. Moreover, the said resin (b1) can be used by 1 type, and can use the thing of several resin types together 2 or more types.

  Examples of the epoxy resin used as the resin (b1) include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a phenol novolac type epoxy resin. The bisphenol A type epoxy resin and the bisphenol F type epoxy resin are obtained by reacting bisphenol A or the like with epichlorohydrin, and have an epoxy group and a hydroxyl group in the same molecule, so that the resin (b1) is used as it is. Since it can be used, it is preferable. In addition, the phenol novolac type epoxy resin can be used as the resin (b1) by reacting the phenol novolac resin and epichlorohydrin so that the phenolic hydroxyl group remains. These epoxy resins can be used alone or in combination of two or more.

  Examples of the acrylic resin used as the resin (b1) include those obtained by copolymerizing an (meth) acrylic monomer having an epoxy group and a (meth) acrylic monomer having a hydroxyl group as essential raw materials. . In addition, a (meth) acryl monomer means either one or both of an acrylic monomer and a methacryl monomer. (Meth) acrylic acid refers to one or both of acrylic acid and methacrylic acid, and (meth) acrylate refers to one or both of acrylate and methacrylate.

  Examples of the (meth) acrylic monomer having an epoxy group include glycidyl (meth) acrylate, 4-hydroxybutyl acrylate glycidyl ether, and allyl glycidyl ether. Among these (meth) acrylic monomers having an epoxy group, glycidyl methacrylate is preferable because adhesion can be further improved. These (meth) acrylic monomers having an epoxy group can be used alone or in combination of two or more.

  Examples of the (meth) acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth). Acrylate, 6-hydroxyhexyl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, glycerol (meth) acrylate, polyethylene glycol (meth) acrylate, N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (Meth) acrylamide, N-hydroxybutylacrylamide, etc. are mentioned. Among these (meth) acrylic monomers having a hydroxyl group, 2-hydroxyethyl (meth) acrylate is preferable because adhesion can be further improved. These (meth) acrylic monomers having a hydroxyl group can be used alone or in combination of two or more.

  Further, as the raw material of the acrylic resin, other polymerizable monomers copolymerizable with these other than the (meth) acrylic monomer having an epoxy group and the (meth) acrylic monomer having a hydroxyl group may be used. Good. Examples of such other polymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl. (Meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (Meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, adamantyl (meth) a Relate, dicyclopentanyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-pentafluoropropyl (meth) ) Acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, β- (perfluorohexyl) ethyl (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, neopentyl (Meth) acrylate compounds such as glycol di (meth) acrylate, polyneopentyl glycol di (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate; N, N′-methylenebis (meth) acrylamide, N, Examples thereof include acrylamide compounds such as N′-ethylenebis (meth) acrylamide; styrene such as styrene and α-methylstyrene, and derivatives thereof. Among these other polymerizable monomers, styrene is preferable because adhesion can be further improved. These other polymerizable monomers can be used alone or in combination of two or more.

  The acrylic resin can be produced by polymerizing a mixture of the (meth) acrylic monomer and the like by a known method. Examples of this polymerization method include a solution polymerization method in which polymerization is performed in an organic solvent, an emulsion polymerization method in which polymerization is performed in an aqueous medium, a suspension polymerization method, a precipitation polymerization method, and a bulk polymerization method in which polymerization is performed in the absence of a solvent. Can be mentioned.

  Examples of the polymerization initiator used in the production of the acrylic resin include azo initiators such as azonitrile, azoester, azoamide, azoamidine, azoimidazoline; peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, Organic peroxides such as peroxydicarbonate and peroxyester; inorganic peroxides such as ammonium persulfate, potassium persulfate, and hydrogen peroxide.

  In addition, even when radical polymerization is performed using only the peroxide, the peroxide and ascorbic acid, erythorbic acid, sodium erythorbate, metal salt of formaldehyde sulfoxylate, sodium thiosulfate, sodium bisulfite, chloride chloride You may superpose | polymerize by the redox polymerization initiator system used together with reducing agents, such as diiron.

  The epoxy group concentration in the resin (b1) is preferably 0.05 mmol / g or more and 8 mmol / g or less, more preferably 0.5 mmol / g or more and 3 mmol / g or less, because adhesion can be further improved. More preferably, it is 2 mmol / g or less.

  Further, the hydroxyl group concentration in the resin (b1) is preferably 0.05 mmol / g or more and 3 mmol / g or less, more preferably 0.1 mmol / g or more and 2 mmol / g or less, because adhesion can be further improved. 5 mmol / g or more and 1.5 mmol / g or less are more preferable.

  Among the resins that can be used as the resin (b1), an acrylic resin is preferable because adhesion can be further improved.

  The crosslinking agent (b2) contains a polyvalent carboxylic acid. The polyvalent carboxylic acid may be an anhydride. Specific examples of the polyvalent carboxylic acid include aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, mellitic acid, biphenyldicarboxylic acid, biphenyltetracarboxylic acid, and naphthalenedicarboxylic acid. Acids and their anhydrides; oxalic acid, malonic acid, succinic acid, methyl succinic anhydride, ethyl succinic anhydride, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, maleic acid , Fumaric acid, 2,3-butanedicarboxylic acid, 2,4-pentanedicarboxylic acid, 3,5-heptanedicarboxylic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, norbornane-2,3-dicarboxylic acid Acid, methylnorbornane-2,3-dicarboxylic acid, 1,2,4 Cyclohexane tricarboxylic acid, dodecyl succinic acid, nadic acid, methylnadic acid, bicyclo [2.2.2] octane-2,3-aliphatic, such as dicarboxylic acid with a polyvalent carboxylic acid and anhydrides thereof. Among these polyvalent carboxylic acids, trimellitic anhydride is preferable because adhesion can be further improved. These polyvalent carboxylic acids can be used alone or in combination of two or more.

  The molar ratio [carboxyl group / epoxy group] of the number of moles of the carboxyl group in the crosslinking agent (b2) and the number of moles of the epoxy group in the resin (b1) can be improved by 0.3 or more. The amount is preferably 3 or less, more preferably 0.5 or more and 2.5 or less.

  Further, a curing catalyst may be used to promote the reaction between the epoxy and the polyvalent carboxylic acid. Examples of the curing catalyst include tertiary amines, imidazoles, organic phosphines, and Lewis acid catalysts.

  Specific examples of the tertiary amine include trimethylamine, triethylamine, tripropylamine, tributylamine, triamylamine, trihexylamine, trioctylamine, trilaurylamine, dimethylethylamine, dimethylpropylamine, and dimethyl. Butylamine, dimethylamylamine, dimethylhexylamine, dimethylcyclohexylamine, dimethyloctylamine, dimethyllaurylamine, triallylamine, tetramethylethylenediamine, triethylenediamine (triethylenetetramine: TETA), N-methylmorpholine, 4,4'- (Oxydi-2,1-ethanediyl) bis-morpholine, N, N-dimethylbenzylamine, pyridine, picoline, dimethylaminomethylphenol Trisdimethylaminomethylphenol, triethanolamine, N, N′-dimethylpiperazine, tetramethylbutanediamine, bis (2,2-morpholinoethyl) ether, bis (dimethylaminoethyl) ether, N, N ′, N ′ '-Tris (dimethylaminopropyl) hexahydro-s-triazine, N, N', N ″ -tris (dimethylaminoethyl) hexahydro-s-triazine, N, N ′, N ″ -tris (2-hydroxyethyl ) Hexahydro-s-triazine, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 1,8-diazabicyclo [5.4.0] undecene-1, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] undec Such as 7-ene (DBU) and the like.

  Specific examples of the imidazole compound include 1-benzyl-2-imidazole (1B2MZ), 2-ethyl-4-imidazole, 2-underimidazole, 1,2-dimethylimidazole, and 1-benzyl-2. -Phenylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole (2P4MHZ) and the like.

  Specific examples of the organic phosphine include triphenylphosphine (TPP), triphenylphosphine-triphenylborate, tris (p-methoxyphenyl) phosphine, tetraphenylphosphonium / tetraphenylborate, and the like.

  Specific examples of the Lewis acid catalyst include Lewis acid catalysts such as a boron trifluoride amine complex, a boron trichloride amine complex, and a boron trifluoride ethylamine complex.

  Among these curing catalysts, tertiary amines and imidazole compounds are preferably used because adhesion can be further improved. These curing catalysts can be used alone or in combination of two or more.

  In order to form the primer layer (B) on the support (A), a primer composition (b) containing the resin (b1) and the crosslinking agent (b2) is prepared, and the primer composition ( It is preferable to apply b) on the support (A). You may mix | blend other resin other than the said resin (b1) and the said crosslinking agent (b2) with the said primer composition (b) as needed. Examples of other resins include urethane resins, acrylic resins, block isocyanate resins, melamine resins, and phenol resins. These other resins can be used alone or in combination of two or more.

  Moreover, it is preferable to mix | blend the organic solvent with the said primer composition (b) in order to make it the viscosity which is easy to apply when apply | coating to the said support body (A). Examples of the organic solvent include toluene, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone.

  The amount of the organic solvent used is preferably adjusted as appropriate depending on the coating method used when coating the support (A) and the desired film thickness of the primer layer (B).

  The primer composition (b) is appropriately added with known additives such as a film forming aid, a leveling agent, a thickener, a water repellent, an antifoaming agent, and an antioxidant, as necessary. May be used.

  For example, the primer layer (B) may be formed by coating the primer composition (b) on a part or all of the surface of the support (A), and removing an organic solvent contained in the primer composition (b). It can be formed by removing.

  Examples of a method for coating the primer composition (b) on the surface of the support (A) include a gravure method, a coating method, a screen method, a roller method, a rotary method, a spray method, and a capillary method. Can be mentioned.

  As a method for removing the organic solvent contained in the coating layer after coating the primer composition (b) on the surface of the support (A), for example, the organic solvent is dried using a dryer. The method of volatilizing is generally used. What is necessary is just to set as drying temperature as the temperature of the range which can volatilize the used organic solvent and does not give bad influences, such as a heat deformation, to the said support body (A).

  Although the film thickness of the primer layer (B) formed using the primer composition (b) varies depending on the use of the laminate of the present invention, the support (A) and the metal nanoparticle layer (C) described later are used. The thickness of the primer layer is preferably 10 nm to 30 μm, more preferably 10 nm to 1 μm, and still more preferably 10 nm to 500 nm.

  Since the surface of the primer layer (B) can further improve the adhesion with the metal nanoparticle layer (C), a dry method such as a plasma discharge treatment method such as a corona discharge treatment method, an ultraviolet treatment method or the like is required. Surface treatment may be performed by a treatment method, a wet treatment method using water, an acidic or alkaline chemical solution, an organic solvent, or the like.

  The metal nanoparticle layer (C) is formed on the primer layer (B), and the metal constituting the metal nanoparticle layer (C) includes a transition metal or a compound thereof. Ionic transition metals are preferred. Examples of the ionic transition metal include copper, silver, gold, nickel, palladium, platinum, and cobalt. Among these, silver is preferable because the metal plating layer (D) is easily formed.

  Moreover, copper, nickel, chromium, cobalt, tin etc. are mentioned as a metal which comprises the said metal plating layer (D). Among these, copper is preferable because a laminate that can be used for a printed wiring board that has low electrical resistance and is resistant to corrosion can be obtained.

  As a method for producing a laminate of the present invention, first, a primer layer (B) is formed on a support (A), and then a fluid containing nano-sized metal nanoparticles (c) is applied. Then, after the organic solvent contained in the fluid is removed by drying, the metal nanoparticle layer (C) is formed, and then the metal plating layer (D) is formed by electrolytic plating or electroless plating, or both. The method of forming is mentioned.

  The shape of the metal nanoparticles (c) used for forming the metal nanoparticle layer (C) is preferably in the form of particles or fibers. In addition, the size of the metal nanoparticles (c) is nano-sized. Specifically, when the shape of the metal nanoparticles (c) is particulate, a fine conductive pattern can be formed. The average particle size is preferably 1 nm or more and 100 nm or less, more preferably 1 nm or more and 50 nm or less because the resistance value can be further reduced. The “average particle size” is a volume average value measured by a dynamic light scattering method after diluting the conductive substance with a good dispersion solvent. For this measurement, “Nanotrack UPA-150” manufactured by Microtrack Co. can be used.

  On the other hand, when the shape of the metal nanoparticles (c) is fibrous, a fine conductive pattern can be formed and the resistance value can be further reduced. Therefore, the fiber diameter is preferably in the range of 5 nm to 100 nm, preferably 5 nm or more. The range of 50 nm or less is more preferable. Further, the length of the fiber is preferably 0.1 μm or more and 100 μm or less, and more preferably 0.1 μm or more and 30 μm or less.

  1 mass% or more and 90 mass% or less are preferable, as for the content rate of the said metal nanoparticle (c) in the said fluid, 1 mass% or more and 60 mass% or less are more preferable, and 1 mass% or more and 10 mass% or less are further. preferable.

  As a component to be blended in the fluid, a dispersant or solvent for dispersing the metal nanoparticles (c) in a solvent, and, if necessary, a surfactant, a leveling agent, a viscosity modifier, which will be described later, Examples include film forming aids, antifoaming agents, and preservatives.

  In order to disperse the metal nanoparticles (c) in a solvent, it is preferable to use a low molecular weight or high molecular weight dispersant. Examples of the dispersant include dodecanethiol, 1-octanethiol, triphenylphosphine, dodecylamine, polyethylene glycol, polyvinylpyrrolidone, polyethyleneimine, polyvinylpyrrolidone; fatty acids such as myristic acid, octanoic acid, stearic acid; cholic acid, Examples thereof include polycyclic hydrocarbon compounds having a carboxyl group such as glycyrrhizic acid and avintinic acid. Among these, a polymer dispersant is preferable because adhesion between the metal nanoparticle layer (C) and the metal plating layer (D) can be improved. Examples of the polymer dispersant include polyethyleneimine and polypropyleneimine. Polyalkyleneimine, a compound obtained by adding polyoxyalkylene to the polyalkyleneimine, a urethane resin, an acrylic resin, a compound containing a phosphate group in the urethane resin or the acrylic resin, and the like.

  The amount of the dispersant used for dispersing the metal nanoparticles (c) is preferably 0.01 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the metal nanoparticles (c). The amount is more preferably 01 parts by mass or more and 10 parts by mass or less.

  As the solvent used for the fluid, an aqueous medium or an organic solvent can be used. Examples of the aqueous medium include distilled water, ion exchange water, pure water, and ultrapure water. Examples of the organic solvent include alcohol compounds, ether compounds, ester compounds, and ketone compounds.

  Examples of the alcohol compound include methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, sec-butanol, tert-butanol, heptanol, hexanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, Tetradecanol, pentadecanol, stearyl alcohol, allyl alcohol, cyclohexanol, terpineol, terpineol, dihydroterpineol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono Chill ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tri And propylene glycol monobutyl ether.

  In addition to the metal nanoparticles (c) and the solvent, ethylene glycol, diethylene glycol, 1,3-butanediol, isoprene glycol, or the like can be used for the fluid as necessary.

  As the surfactant, a general surfactant can be used. For example, di-2-ethylhexylsulfosuccinate, dodecylbenzenesulfonate, alkyldiphenyletherdisulfonate, alkylnaphthalenesulfonate, hexametaphosphate Examples include salts.

  As the leveling agent, a general leveling agent can be used, and examples thereof include silicone compounds, acetylenic diol compounds, fluorine compounds, and the like.

  As the viscosity adjusting agent, a general thickening agent can be used, for example, an acrylic polymer or synthetic rubber latex that can be thickened by adjusting to alkalinity, or a urethane that can be thickened by association of molecules. Resins, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, polyvinyl alcohol, water-added castor oil, amide wax, oxidized polyethylene, metal soap, dibenzylidene sorbitol and the like can be mentioned.

  As the film forming aid, a general film forming aid can be used. For example, an anionic surfactant (dioctyl sulfosuccinate soda salt, etc.), a hydrophobic nonionic surfactant (sorbitan monooleate). Etc.), polyether-modified siloxane, silicone oil and the like.

  As the antifoaming agent, a general antifoaming agent can be used, and examples thereof include silicone antifoaming agents, nonionic surfactants, polyethers, higher alcohols, and polymer surfactants.

  As the preservative, general preservatives can be used, for example, isothiazoline preservatives, triazine preservatives, imidazole preservatives, pyridine preservatives, azole preservatives, iodo preservatives, pyrithione. And system preservatives.

  The viscosity of the fluid (measured using a B-type viscometer at 25 ° C.) is preferably 0.1 mPa · s to 500,000 mPa · s, and preferably 0.2 mPa · s to 10,000 mPa · s. More preferred. Moreover, when the fluid is coated (printed) by a method such as an ink jet printing method or letterpress reverse printing described later, the viscosity is preferably 5 mPa · s or more and 20 mPa · s or less.

  Examples of a method for coating or printing the fluid on the primer layer (B) include, for example, an ink jet printing method, a reverse printing method, a screen printing method, an offset printing method, a spin coating method, a spray coating method, and a bar coating. Method, die coating method, slit coating method, roll coating method, dip coating method, pad printing, flexographic printing method and the like.

  Among these coating methods, for example, in the case of forming the metal nanoparticle layer (C) patterned in a thin line shape of 0.01 μm or more and 100 μm or less, which is required when realizing high density of an electronic circuit or the like For this, it is preferable to use an inkjet printing method or a reverse printing method.

  As the inkjet printing method, what is generally called an inkjet printer can be used. Specific examples include Konica Minolta EB100, XY100 (manufactured by Konica Minolta IJ Co., Ltd.), Dimatics Material Printer DMP-3000, Dimatics Material Printer DMP-2831 (manufactured by Fuji Film Co., Ltd.), and the like.

  Further, as the reversal printing method, a letterpress reversal printing method and an intaglio reversal printing method are known, for example, the fluid is applied to the surface of various blankets and brought into contact with the plate from which the non-image portion protrudes, By selectively transferring a fluid corresponding to the non-image area to the surface of the plate, the pattern is formed on the surface of the blanket or the like, and then the pattern is formed on the support (A). The method of transferring to (surface) is mentioned.

  A pad printing method is known for printing a pattern on a three-dimensional molded product. This is done by placing the ink on the intaglio plate and writing it with a squeegee to uniformly fill the recess with the ink. Press the pad made of silicon rubber or urethane rubber on the plate on which the ink is placed, and place the pattern on the pad. This is a method of transferring and transferring to a three-dimensional molded product.

Mass per unit area of the metal nanoparticle layer (C) is preferably from 1 mg / ^{m 2} or more 30,000 / ^{m 2} or less, 1 mg / ^{m 2} or more 5,000 mg / ^{m 2} or less. The thickness of the metal nanoparticle layer (C) is adjusted by controlling the processing time, the current density, the usage amount of the plating additive, and the like in the plating process when forming the metal plating layer (D). be able to.

  The metal plating layer (D) constituting the laminate of the present invention is reliable, for example, when the laminate is used for a printed wiring board or the like, without causing disconnection or the like over a long period of time. This layer is provided for the purpose of forming a highly reliable wiring pattern.

  Although the said metal plating layer (D) is a layer formed on the said metal nanoparticle layer (C), the method of forming by a plating process is preferable as the formation method. Examples of the plating treatment include wet plating methods such as an electrolytic plating method and an electroless plating method that can easily form the metal plating layer (D). Two or more of these plating methods may be combined. For example, after the electroless plating is performed, the metal plating layer (D) may be formed by performing electrolytic plating.

  In the electroless plating method, for example, a metal such as copper contained in the electroless plating solution is deposited by bringing the electroless plating solution into contact with the metal constituting the metal nanoparticle layer (C). This is a method of forming an electroless plating layer (film) comprising a film.

  As said electroless-plating liquid, what contains metals, such as copper, nickel, chromium, cobalt, tin, gold | metal | money, silver, a reducing agent, and solvents, such as an aqueous medium and an organic solvent, is mentioned, for example.

  Examples of the reducing agent include dimethylaminoborane, hypophosphorous acid, sodium hypophosphite, dimethylamine borane, hydrazine, formaldehyde, sodium borohydride, phenol and the like.

  In addition, as the electroless plating solution, monocarboxylic acids such as formic acid and acetic acid; dicarboxylic acid compounds such as malonic acid, succinic acid, adipic acid, maleic acid, and fumaric acid; malic acid, lactic acid, glycol, as necessary Hydroxycarboxylic acid compounds such as acid, gluconic acid and citric acid; amino acid compounds such as glycine, alanine, iminodiacetic acid, arginine, aspartic acid and glutamic acid; iminodiacetic acid, nitrilotriacetic acid, ethylenediaminediacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, etc. Containing a complexing agent such as an organic compound such as an aminopolycarboxylic acid compound or a soluble salt (sodium salt, potassium salt, ammonium salt, etc.) of these organic acids, or an amine compound such as ethylenediamine, diethylenetriamine, or triethylenetetramine. thing It can be used.

  The electroless plating solution is preferably used at 20 ° C. or higher and 98 ° C. or lower.

  In the electrolytic plating method, for example, in a state in which an electrolytic plating solution is in contact with the surface of the metal constituting the metal nanoparticle layer (C) or the electroless plating layer (coating) formed by the electroless treatment. By applying electricity, a metal such as copper contained in the electrolytic plating solution is converted into a conductive substance constituting the metal nanoparticle layer (C) placed on the cathode or the electroless plating layer formed by the electroless treatment. This is a method of forming an electrolytic plating layer (metal film) by depositing on the surface of the film.

  Examples of the electrolytic plating solution include those containing metal sulfides such as copper, nickel, chromium, cobalt, and tin, sulfuric acid, and an aqueous medium. Specifically, what contains copper sulfate, sulfuric acid, and an aqueous medium is mentioned.

  The electrolytic plating solution is preferably used in the range of 20 ° C. or higher and 98 ° C. or lower.

  As a method for forming the metal plating layer (D), since the film thickness of the metal plating layer (D) can be easily controlled to a desired film thickness from a thin film to a thick film, A method of performing electrolytic plating is preferred.

  The thickness of the metal plating layer (D) is preferably in the range of 1 μm to 50 μm. The film thickness of the metal plating layer (D) is adjusted by controlling the processing time, current density, the amount of plating additive used, etc. in the plating process when forming the metal plating layer (D). Can do.

  Hereinafter, the present invention will be described in detail by way of examples.

(Production Example 1: Production of acrylic resin for primer (1))
Into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, a dropping funnel for dropping the monomer mixture and a dropping funnel for dropping the polymerization catalyst, 180 parts by mass of ethyl acetate is added, and the temperature is increased to 90 ° C. while blowing nitrogen. The temperature rose. In a reaction vessel heated to 90 ° C., a monomer mixture containing 25 parts by mass of glycidyl methacrylate, 12 parts by mass of 2-hydroxyethyl methacrylate, 55 parts by mass of styrene, and 8 parts by mass of methyl methacrylate with stirring, A polymerization initiator solution containing 1 part by mass of butyronitrile and 20 parts by mass of ethyl acetate was dropped from each separate funnel over 240 minutes while maintaining the temperature in the reaction vessel at 90 ± 1 ° C., and polymerized. After completion of dropping, the mixture was stirred at the same temperature for 120 minutes, and then the temperature in the reaction vessel was cooled to 30 ° C. Subsequently, it diluted with ethyl acetate and obtained the 2 mass% solution of the acrylic resin (1) for primers.

(Production Example 2: Production of acrylic resin for primer (2))
Into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, a dropping funnel for dropping the monomer mixture and a dropping funnel for dropping the polymerization catalyst, 180 parts by mass of ethyl acetate is added, and the temperature is increased to 90 ° C. while blowing nitrogen. The temperature rose. In a reaction vessel heated to 90 ° C., a monomer mixture containing 10 parts by mass of glycidyl methacrylate, 20 parts by mass of 2-hydroxyethyl methacrylate, 30 parts by mass of styrene, and 40 parts by mass of methyl methacrylate with stirring, A polymerization initiator solution containing 1 part by mass of butyronitrile and 20 parts by mass of ethyl acetate was dropped from each separate funnel over 240 minutes while maintaining the temperature in the reaction vessel at 90 ± 1 ° C., and polymerized. After completion of dropping, the mixture was stirred at the same temperature for 120 minutes, and then the temperature in the reaction vessel was cooled to 30 ° C. Subsequently, it diluted with ethyl acetate and obtained the 2 mass% solution of the acrylic resin (2) for primers.

(Production Example 3: Production of acrylic resin for primer (3))
Into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, a dropping funnel for dropping the monomer mixture and a dropping funnel for dropping the polymerization catalyst, 180 parts by mass of ethyl acetate is added, and the temperature is increased to 90 ° C. while blowing nitrogen. The temperature rose. In a reaction vessel heated to 90 ° C., a monomer mixture containing 40 parts by mass of glycidyl methacrylate, 5 parts by mass of 2-hydroxyethyl methacrylate, 20 parts by mass of styrene, and 35 parts by mass of methyl methacrylate with stirring, A polymerization initiator solution containing 1 part by mass of butyronitrile and 20 parts by mass of ethyl acetate was added dropwise from another dropping funnel over 240 minutes while maintaining the temperature in the reaction vessel at 90 ± 1 ° C., and polymerized. After completion of dropping, the mixture was stirred at the same temperature for 120 minutes, and then the temperature in the reaction vessel was cooled to 30 ° C. Subsequently, it diluted with ethyl acetate and obtained the 2 mass% solution of the acrylic resin (3) for primers.

(Production Example 4: Production of acrylic resin for primer (4))
Into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, a dropping funnel for dropping the monomer mixture and a dropping funnel for dropping the polymerization catalyst, 180 parts by mass of ethyl acetate is added, and the temperature is increased to 90 ° C. while blowing nitrogen. The temperature rose. A monomer mixture containing 20 parts by mass of glycidyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, 30 parts by mass of n-butyl acrylate, and 35 parts by mass of methyl methacrylate with stirring in a reaction vessel heated to 90 ° C. A polymerization initiator solution containing 1 part by weight of azoisobutyronitrile and 20 parts by weight of ethyl acetate was dropped from each separate funnel over 240 minutes while maintaining the temperature in the reaction vessel at 90 ± 1 ° C. for polymerization. . After completion of dropping, the mixture was stirred at the same temperature for 120 minutes, and then the temperature in the reaction vessel was cooled to 30 ° C. Subsequently, it diluted with ethyl acetate and obtained the 2 mass% solution of the acrylic resin (4) for primers.

(Production Example 5: Production of acrylic resin for primer (5))
Into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, a dropping funnel for dropping the monomer mixture and a dropping funnel for dropping the polymerization catalyst, 180 parts by mass of ethyl acetate is added, and the temperature is increased to 90 ° C. while blowing nitrogen. The temperature rose. In a reaction vessel heated to 90 ° C., 1 part by mass of glycidyl methacrylate, 1 part by mass of 2-hydroxyethyl methacrylate, 40 parts by mass of styrene, 39 parts by mass of methyl methacrylate and 19 parts by mass of n-butyl acrylate are contained with stirring. A monomer mixture and a polymerization initiator solution containing 1 part by mass of azoisobutyronitrile and 20 parts by mass of ethyl acetate were applied for 240 minutes while maintaining the temperature in the reaction vessel at 90 ± 1 ° C. from a separate dropping funnel. The solution was dropped and polymerized. After completion of dropping, the mixture was stirred at the same temperature for 120 minutes, and then the temperature in the reaction vessel was cooled to 30 ° C. Subsequently, it diluted with ethyl acetate and obtained the 2 mass% solution of the acrylic resin (5) for primers.

(Production Example 6: Production of acrylic resin for primer (6))
Into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, a dropping funnel for dropping the monomer mixture and a dropping funnel for dropping the polymerization catalyst, 200 parts by mass of ethyl acetate was added, and the temperature was increased to 90 ° C. while blowing nitrogen. The temperature rose. In a reaction vessel heated to 90 ° C., a monomer mixture containing 15 parts by mass of 2-hydroxyethyl methacrylate, 38 parts by mass of styrene, 30 parts by mass of n-butyl acrylate, and 17 parts by mass of methyl methacrylate with stirring; A polymerization initiator solution containing 1 part by mass of azoisobutyronitrile and 20 parts by mass of ethyl acetate was added dropwise from another dropping funnel over 240 minutes while maintaining the temperature in the reaction vessel at 90 ± 1 ° C., and polymerized. After completion of dropping, the mixture was stirred at the same temperature for 120 minutes, and then the temperature in the reaction vessel was cooled to 30 ° C. Subsequently, it diluted with ethyl acetate and obtained the 2 mass% solution of the acrylic resin (6) for primers.

(Production Example 7: Production of acrylic resin for primer (7))
Into a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, a dropping funnel for dropping the monomer mixture and a dropping funnel for dropping the polymerization catalyst, 180 parts by mass of ethyl acetate is added, and the temperature is increased to 90 ° C. while blowing nitrogen. The temperature rose. A monomer mixture containing 30 parts by mass of glycidyl methacrylate, 55 parts by mass of styrene, and 15 parts by mass of methyl methacrylate, 1 part by mass of azoisobutyronitrile, and ethyl acetate are stirred in a reaction vessel heated to 90 ° C. A polymerization initiator solution containing 20 parts by mass was dropped and polymerized from another dropping funnel over 240 minutes while maintaining the temperature in the reaction vessel at 90 ± 1 ° C. After completion of dropping, the mixture was stirred at the same temperature for 120 minutes, and then the temperature in the reaction vessel was cooled to 30 ° C. Subsequently, it diluted with ethyl acetate and obtained the 2 mass% solution of the acrylic resin (7) for primers.

(Preparation Example 1: Preparation of primer composition (1))
Epoxy resin (“EPICLON 1050” manufactured by DIC Corporation; bisphenol A type epoxy resin, epoxy equivalent 475 g / equivalent) was diluted with methyl ethyl ketone to a solid content of 2% by mass, and 100% by mass of anhydrous pyromerit as a curing agent A primer composition (1) was obtained by uniformly mixing 11.5 parts by weight of a 2% by weight methyl ethyl ketone solution of acid.

(Preparation Example 2: Preparation of primer composition (2))
Epoxy resin (“EPICLON 830S” manufactured by DIC Corporation; bisphenol F-type epoxy resin, epoxy equivalent 170 g / equivalent) diluted with methyl ethyl ketone to a solid content of 2% by mass, 100 parts by mass of anhydrous trimellit as a curing agent A primer composition (2) was obtained by uniformly mixing 38.9 parts by weight of a 2% by weight methyl ethyl ketone solution of acid.

(Preparation Example 3: Preparation of primer composition (3))
Primer 1100 parts by weight of acrylic resin for primer (1) obtained in Production Example 1 was uniformly mixed with 11.6 parts by weight of 2% by weight solution of trimellitic anhydride diluted with methyl ethyl ketone. A composition (3) was obtained.

(Preparation Example 4: Preparation of primer composition (4))
17.4 parts by weight of a 2% by weight solution obtained by diluting trimellitic anhydride with methyl ethyl ketone was uniformly mixed with 100 parts by weight of the 2% by weight solution of the acrylic resin for primer (1) obtained in Production Example 1. A composition (4) was obtained.

(Preparation Example 5: Preparation of primer composition (5))
To 2 parts by mass of the acrylic resin for primer (1) obtained in Production Example 1 100 parts by mass, 23.2 parts by mass of a 2% by mass solid solution obtained by diluting trimellitic anhydride with methyl ethyl ketone was uniformly mixed. Thus, a primer composition (5) was obtained.

(Preparation Example 6: Preparation of primer composition (6))
100 parts by mass of a 2% by mass solution of the acrylic resin for primer (1) obtained in Production Example 1 and 20.3 parts by mass of a 2% by mass solid solution obtained by diluting dodecanedioic acid with isopropyl alcohol were uniformly mixed. Thus, a primer composition (6) was obtained.

(Preparation Example 7: Preparation of primer composition (7))
To 100 parts by mass of a 2% by mass solution of the acrylic resin for primer (2) obtained in Production Example 2, 4.6 parts by mass of a 2% by mass solid solution obtained by diluting trimellitic anhydride with methyl ethyl ketone was uniformly mixed. Thus, a primer composition (7) was obtained.

(Preparation Example 8: Preparation of primer composition (8))
Primer primer was prepared by uniformly mixing 15.4 parts by weight of a 2% by weight solution obtained by diluting pyromellitic anhydride with methyl ethyl ketone into 100 parts by weight of a 2% by weight acrylic resin for primer (3) obtained in Production Example 3. A composition (8) was obtained.

(Preparation Example 9: Preparation of primer composition (9))
Primer composition was prepared by uniformly mixing 9.3 parts by weight of a 2% by weight solution of trimellitic anhydride diluted with methyl ethyl ketone into 2% by weight 100% by weight of the acrylic resin for primer (4) obtained in Production Example 4. A product (9) was obtained.

(Preparation Example 10: Preparation of primer composition (10))
Primer composition was prepared by uniformly mixing 0.46 parts by mass of a 2% by mass solution of trimellitic anhydride diluted with methyl ethyl ketone with 2% by mass of 100% by mass of the acrylic resin for primer (5) obtained in Production Example 5. A product (10) was obtained.

(Preparation Example 11: Preparation of primer composition (R1))
A primer was prepared by uniformly mixing 11.6 parts by weight of a 2% by weight solution of trimellitic anhydride diluted with methyl ethyl ketone with 100 parts by weight of a 2% by weight solution of the acrylic resin for primer (6) obtained in Production Example 6. A composition (R1) was obtained.

(Preparation Example 12: Preparation of primer composition (R2))
Primer primer was prepared by uniformly mixing 13.9 parts by weight of a 2% by weight solution of trimellitic anhydride diluted with methyl ethyl ketone with 100 parts by weight of a 2% by weight acrylic resin for primer (7) obtained in Production Example 7. A composition (R2) was obtained.

(Preparation Example 13: Preparation of primer composition (R3))
100 parts by mass of a 2% by mass solution of the acrylic resin for primer (1) obtained in Production Example 1 was used as it was as the primer composition (R3).

[Preparation of fluid (1)]
According to Example 1 described in Japanese Patent No. 4573138, a cationic silver nanoparticle comprising a grey-green metallic luster flake-like lump, which is a composite of silver nanoparticles and an organic compound having a cationic group (amino group) Particles were obtained. Thereafter, the powder of silver nanoparticles was dispersed in a mixed solvent of 45 parts by mass of ethylene glycol and 55 parts by mass of ion-exchanged water to prepare a fluid (1) having 5% by mass of cationic silver nanoparticles. .

Example 1
On the surface of a polyimide film (“Kapton 100H” manufactured by Toray DuPont Co., Ltd .; thickness 25 μm), the primer composition (1) obtained in Preparation Example 1 was placed on a tabletop small coater (manufactured by RK Print Coat Instrument “ Using a “K printing profiler”), coating was performed so that the thickness after drying was 100 nm. Next, a primer layer was formed on the surface of the polyimide film by drying at 150 ° C. for 5 minutes using a hot air dryer.

  The fluid (1) obtained above was applied to the surface of the primer layer formed above using a bar coater. Subsequently, the silver layer (film thickness of 20 nm) corresponding to the said metal nanoparticle layer (C) was formed by drying at 150 degreeC for 5 minute (s).

  The silver layer formed above is immersed in an electroless copper plating solution ("OIC Copper" manufactured by Okuno Pharmaceutical Co., Ltd., pH 12.5) at 45 ° C for 12 minutes, electroless copper plated, and copper obtained by electroless plating. A plating layer (film thickness 0.2 μm) was formed.

The copper plating layer obtained by electroless copper plating obtained above is set on the cathode side, phosphorous copper is set on the anode side, and the current density is 2.5 A / dm ² using an electrolytic plating solution containing copper sulfate. By performing electrolytic plating for 30 minutes, a copper plating layer (film thickness: 15 μm) by electrolytic copper plating was formed on the surface of the copper plating layer by electroless copper plating. As the electrolytic plating solution, 70 g / L of copper sulfate, 200 g / L of sulfuric acid, 50 mg / L of chloride ions, and 5 ml / L of additives (“Top Lucina SF-M” manufactured by Okuno Pharmaceutical Co., Ltd.) were used. In addition, what combined the copper plating layer by electroless copper plating and the copper plating layer by electrolytic copper plating formed on it corresponds to the said metal plating layer (D).

  By the above method, a laminate (1) in which the support (A), the primer layer (B), the metal nanoparticle layer (C), and the metal plating layer (D) were sequentially laminated was obtained.

(Examples 2 to 10 and Comparative Examples 1 to 3)
The same procedure as in Example 1 was conducted except that the primer compositions (2) to (10) and (R1) to (R3) were used instead of the primer composition (1) used in Example 1, and a laminate. (2) to (10) and (R1) to (R3) were obtained.

  The laminates (1) to (10) and (R1) to (R3) obtained in Examples 1 to 10 and Comparative Examples 1 to 3 were subjected to the following measurements and evaluations.

[Measurement of peel strength before heating]
About each laminated body obtained above, peeling strength was measured using "Autograph AGS-X 500N" by Shimadzu Corporation. The lead width used for measurement was 5 mm, and the peel angle was 90 °. Further, the peel strength tends to show a higher value as the thickness of the metal plating layer becomes thicker, but the measurement of the peel strength in the present invention was carried out based on the measurement value at a thickness of 15 μm of the metal plating layer.

[Evaluation of adhesion]
From the value of the peel strength before heating measured above, the adhesion was evaluated according to the following criteria.
A: The peel strength value is 650 N / m or more.
B: The peel strength value is 450 N / m or more and less than 650 N / m.
C: The peel strength value is 250 N / m or more and less than 450 N / m.
D: The peel strength value is less than 250 N / m.

[Measurement of peel strength after heating]
Each of the laminates obtained above was stored in a dryer set at 150 ° C. for 168 hours and heated. After heating, the peel strength was measured by the same method as described above.

[Evaluation of heat resistance]
Using the peel strength values measured before and after heating, the retention before and after heating was calculated, and the heat resistance was evaluated according to the following criteria.
A: Retention rate is 85% or more.
B: Retention rate is 70% or more and less than 85%.
C: Retention rate is 55% or more and less than 70%.
D: Retention rate is less than 55%.

  Tables 1 to 3 show the types of primer compositions used in Examples 1 to 10 and Comparative Examples 1 to 3, measurement results of peel strength before and after heating, and evaluation results of adhesion and heat resistance.

  The laminates (1) to (10) obtained in Examples 1 to 10, which are laminates of the present invention, have sufficiently high initial (before heating) adhesion, and a decrease in peel strength after heating. It was confirmed that the heat resistance was slightly superior.

  On the other hand, the laminate (R1) of Comparative Example 1 is an example in which an acrylic resin having no epoxy group is used for the primer resin used in the primer layer, but the initial (before heating) adhesion is extremely low, The subsequent peel strength was 0 kN / m, confirming that there was a problem with adhesion.

  The laminate (R2) of Comparative Example 2 is an example in which an acrylic resin having no hydroxyl group is used for the primer resin used in the primer layer, but the initial (before heating) adhesion is extremely low, and peeling after heating is performed. The strength was 0 kN / m, and it was confirmed that there was a problem in adhesion.

  The laminate (R3) of Comparative Example 3 is an example in which a crosslinking agent was not used, but although the initial (before heating) adhesion was relatively high, the peel strength retention after heating was 53%, and the heat resistance It was confirmed that there was a problem with sex.

That is, the present invention is a laminate in which a primer layer (B), a metal nanoparticle layer (C), and a metal plating layer (D) are sequentially laminated on a support (A), the primer layer ( B) is cured der resin having an epoxy group and a hydroxyl (b1) and a crosslinking agent comprising a polyvalent carboxylic acid (b2) is, the resin (b1) is Ru acrylic resin der having an aromatic ring It is an object of the present invention to provide a laminate, a printed wiring board using the laminate, a flexible printed wiring board, and a laminate.

Claims (9)

  A laminate in which a primer layer (B), a metal nanoparticle layer (C), and a metal plating layer (D) are sequentially laminated on a support (A), wherein the primer layer (B) is an epoxy group And a cured product of a crosslinking agent (b2) containing a polyvalent carboxylic acid (b1) and a resin having a hydroxyl group.   The laminate according to claim 1, wherein the polyvalent carboxylic acid is an aromatic compound.   The laminate according to claim 1 or 2, wherein the polyvalent carboxylic acid is an anhydride.   The laminate according to any one of claims 1 to 3, wherein the resin (b1) is a resin having an aromatic ring.   The laminate according to any one of claims 1 to 4, wherein the resin (b1) is an acrylic resin.   The molar ratio [carboxyl group / epoxy group] of the number of moles of carboxyl groups in the crosslinking agent (b2) and the number of moles of epoxy groups in the resin (b1) is 0.3 or more and 3 or less. The laminate according to any one of 5.   A printed wiring board comprising the laminate according to any one of claims 1 to 6.   It is a laminated body of any one of Claims 1-6, The flexible printed wiring board using the laminated body whose said support body (A) is a film.   A molded article using the laminate according to any one of claims 1 to 6.