WO2019013040A1

WO2019013040A1 - Laminate, printed wiring board in which same is used, flexible printed wiring board, and molded article

Info

Publication number: WO2019013040A1
Application number: PCT/JP2018/025167
Authority: WO
Inventors: 亘冨士川; 憲一平林; 深澤　憲正; 白髪　潤
Original assignee: Dic株式会社
Priority date: 2017-07-10
Filing date: 2018-07-03
Publication date: 2019-01-17
Also published as: CN110785282B; JPWO2019013040A1; CN110785282A; KR102364792B1; KR20200015697A; TW201908428A; TWI726222B; JP6579293B2

Abstract

The present invention provides: 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 body (A), the laminate being characterized in that 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 in which the laminate is used; a flexible printed wiring board; and a molded article. The laminate can be manufactured by a simple method and exhibits exceptional adhesion between the support body and the metal layer (metal plating layer) without the surface of the support body being roughened.

Description

Laminate, printed wiring board using it, flexible printed wiring board and molded article

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

With the miniaturization and speeding up of electronic devices, high density and high performance of printed wiring boards are required. In order to meet this demand, printed wiring boards having a conductive layer (metal layer) having a smooth surface and a sufficiently thin surface. 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 of bonding a heat resistant polymer film and a copper foil using an epoxy resin adhesive.

However, in the FCCL using this copper foil, the copper foil can not be made sufficiently thin for handling since it is pasted while pulling out the copper foil wound in a roll shape. Furthermore, it is necessary to roughen the surface of the copper foil in order to enhance the adhesion to the polymer film, so the high frequency (GHz band) and high frequency required to achieve high density and high performance of the printed wiring board There is a problem that transmission loss occurs in the transmission speed (tens of Gbps) area.

Here, as a method of thinning the copper layer of FCCL, a metal thin film is formed on the surface of a polyimide film by a vapor deposition method or a sputtering method, and then an electroplating method, an electroless plating method or both are combined 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, in order to use a vapor deposition method or a sputtering method in order to form a metal thin film, extensive vacuum equipment is required, and there is a problem that the substrate size is limited on equipment.

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 when thinning the metal layer, a large vacuum facility is not required. There has been a demand for a laminate that can be manufactured by a simple method.

In addition, conventionally, as decorative plating on a plastic molded product, it has been used for mobile phones, personal computers, mirrors, containers, various switches, shower heads, and the like. The support for these uses is limited to acrylonitrile-butadiene-styrene copolymer (hereinafter abbreviated as "ABS") or polymer alloy of ABS and polycarbonate (hereinafter abbreviated as "ABS-PC"). It has been limited. For this reason, it is necessary to roughen the substrate surface in order to secure the adhesion between the substrate and the plating film. For example, in the case of ABS, the polybutadiene component is a strong oxidation such as hexavalent chromic acid or permanganate. Surface roughening is possible by etching with an agent and removing. 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 (see, for example, Patent Document 2).

Thus, in plating for the purpose of decoration to a plastic molded product, a metal plating film having excellent adhesion can be obtained even with other types of plastic without being limited to ABS or ABS-PC as a substrate. In addition, it has been required to reduce the amount of environmentally harmful substances used.

JP, 2015-118044, A Patent No. 5830807 gazette

The problem to be solved by the present invention is a laminate which 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), Printed wiring board, a flexible printed wiring board, and a molded article using the same.

As a result of intensive studies to solve the above problems, the present inventors have found, as a primer layer, 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. It discovered that the laminated body which provided and was laminated | stacked sequentially and the metal layer formed with the metal nanoparticle, and the metal plating layer can solve the said subject, and completed this invention.

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), and the primer layer A laminate characterized in that 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 same, and a flexible Provided is a printed wiring board and a laminate.

The laminate of the present invention is excellent in the adhesion between the support and the metal layer (metal plating layer) without roughening the surface of the support. In addition, when thinning the metal layer, it is a laminate having a sufficiently thin metal layer with a smooth surface, without using extensive vacuum equipment.

In addition, the laminate of the present invention is, 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, by patterning a metal layer. It can be suitably used as an RFID such as a noncontact IC card, an electromagnetic wave shield, an LED illumination base, an electronic member such as a digital signage. In particular, it is most suitable for flexible printed wiring board applications such as FCCL. Also, by applying to molded articles, electronic components such as connectors for connecting wires for optical communication etc., electrical components, electric motor peripheral components, battery components, etc .; decorative components for automobiles, 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), and 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 the primer layer (B) and the like are sequentially laminated on one side of the support (A), and the primer layer (B) and the like may be formed on both sides of the support (A). The laminated body which laminated | stacked sequentially may be sufficient.

Examples of the support (A) include polyimide, polyamideimide, polyamide, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, acrylonitrile-butadiene-styrene (hereinafter abbreviated as "ABS") resin, ABS and polycarbonate. Polymer alloy, acrylic resin such as methyl 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, sili Supports made of iron, ceramics, glass, etc., porous supports made of them, steel plates, supports made of metal such as copper, their surfaces are silicon carbide, diamond like carbon, aluminum, copper, titanium, stainless steel etc. And the like.

When the laminate of the present invention is used for a printed wiring board etc., polyimide, polyethylene terephthalate, polyethylene naphthalate, liquid crystal polymer (LCP), polyetheretherketone (PEEK), epoxy resin as the support (A) It is preferable to use a support made of glass, cellulose nanofibers 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 which has the bendable softness | flexibility as said support body (A) is preferable.

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

In addition, since the adhesion between the support (A) and the primer layer (B) described later can be further improved, the surface of the support (A) may be as fine as possible without losing smoothness, as necessary. Irregularities may be formed, soil attached to the surface may be washed, or surface treatment may be performed to introduce functional groups such as hydroxyl group, carbonyl group, carboxyl group and the like. Specifically, methods such as plasma discharge treatment such as corona discharge treatment, dry treatment such as ultraviolet light treatment, wet treatment using an aqueous solution of water, acid or alkali, an organic solvent or the like may be mentioned.

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 said resin (b1) is a resin which has an epoxy group and a hydroxyl group in a molecule | numerator, and an epoxy resin, an acrylic resin, etc. are mentioned as a resin seed | species. The hydroxyl group contained in the resin (b1) may be either an alcoholic hydroxyl group or a phenolic hydroxyl group. The resin (b1) may be used alone or in combination of two or more of plural resin types.

Examples of the epoxy resin used as the resin (b1) include bisphenol A epoxy resin, bisphenol F epoxy resin, and phenol novolac 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 since they have an epoxy group and a hydroxyl group in the same molecule, they are used as the resin (b1) as they are. It is preferable because it can be used. Further, the phenol novolac epoxy resin can be used as the resin (b1) by reacting the phenol novolac resin and epichlorohydrin so as to leave a phenolic hydroxyl group. These epoxy resins can be used alone or in combination of two or more.

As an acrylic resin used as said resin (b1), what co-polymerized the (meth) acrylic monomer which has an epoxy group, and the (meth) acrylic monomer which has a hydroxyl group as an essential raw material is mentioned, for example . In addition, the (meth) acrylic monomer refers to any one or both of an acrylic monomer and a methacrylic monomer. Also, (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, allyl glycidyl ether and the like. Among these (meth) acrylic monomers having an epoxy group, glycidyl methacrylate is preferable because adhesion can be further improved. Moreover, these (meth) acrylic monomers having an epoxy group may be used alone or in combination of two or more.

Moreover, as the (meth) acrylic monomer having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 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 Examples include (meth) acrylamide, N-hydroxybutyl acrylamide and the like. Among these (meth) acrylic monomers having a hydroxyl group, 2-hydroxyethyl (meth) acrylate is preferable because adhesion can be further improved. Moreover, these (meth) acrylic monomers having a hydroxyl group may be used alone or in combination of two or more.

Moreover, even if it uses the (meth) acrylic monomer which has an epoxy group, and the other polymerizable monomer copolymerizable with these other than the (meth) acrylic monomer which has a hydroxyl group as a raw material of the said acrylic resin Good. As such other polymerizable monomers, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, 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 Lilate, 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) acrylic acid ester compounds such as glycol di (meth) acrylate, polyneopentyl glycol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate; N, N′-methylene bis (meth) acrylamide, N, 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. Moreover, 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. As the polymerization method, for example, solution polymerization method in which polymerization is performed in an organic solvent, emulsion polymerization method in which polymerization is performed in an aqueous medium, suspension polymerization method, precipitation polymerization method, bulk polymerization method in which polymerization is performed without solvent It can be mentioned.

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

Further, even if radical polymerization is carried out using only the peroxide, the peroxide, ascorbic acid, erythorbic acid, sodium erythorbate, metal salt of formaldehyde sulfoxylate, sodium thiosulfate, sodium bisulfite, chloride It may be polymerized by a redox polymerization initiator system in combination with a reducing agent such as diiron.

From the viewpoint that adhesion can be further improved, the epoxy group concentration in the resin (b1) is preferably 0.05 mmol / g or more and 8 mmol / g or less, and more preferably 0.5 mmol / g or more and 3 mmol / g or less, and 1 mmol / g More than 2 mmol / g is further preferable.

In addition, 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, since 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 also 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, methylsuccinic anhydride, ethylsuccinic 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, methyl norbornane-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 crosslinker (b2) and the number of moles of the epoxy group in the resin (b1) is more than 0.3 because adhesion can be further improved. An amount of 3 or less is preferable, and 0.5 or more and 2.5 or less is more preferable.

In addition, a curing catalyst may be used to accelerate the reaction of 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, trihexylamine, trioctylamine, trilaurylamine, dimethylethylamine, dimethylpropylamine and dimethylamine. 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-hydroxy) Ethyl) Hexahydro-s-triazine, 2,4-diamino-6- [2′-methylimidazolyl- (1 ′)]-ethyl-s-triazine, 1,8-diazabicyclo [5.4.0] undecen-1 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] unde And the like-7-ene (DBU).

Specifically, examples of the imidazole compound include 1-benzyl-2-imidazole (1B2MZ), 2-ethyl-4-imidazole, 2-unimidazole, 1,2-dimethylimidazole, 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 phosphines 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 boron trifluoride amine complex, boron trichloride amine complex and boron trifluoride ethylamine complex.

Among these curing catalysts, tertiary amines and imidazole compounds are preferably used because adhesion can be further improved. Moreover, 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 preferred to coat 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. As other resin, a urethane resin, an acrylic resin, block isocyanate resin, a melamine resin, a phenol resin etc. are mentioned, for example. These other resins may be used alone or in combination of two or more.

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

It is preferable that the amount of the organic solvent used be appropriately adjusted according to the coating method used when coating on the support (A) and the desired film thickness of the primer layer (B).

In addition, known additives such as a film forming auxiliary, a leveling agent, a thickener, a water repellent, an antifoamer, an antioxidant, etc. are appropriately added to the primer composition (b), as necessary. You may use it.

In the primer layer (B), for example, the primer composition (b) is applied to part or all of the surface of the support (A), and the organic solvent contained in the primer composition (b) is used. It can be formed by removing.

Examples of the method for applying the primer composition (b) to the surface of the support (A) include methods such as gravure method, coating method, screen method, roller method, rotary method, spray method and capillary method. It can be mentioned.

As a method of removing the organic solvent contained in the coating layer after applying the said primer composition (b) on the surface of the said support body (A), it is made to dry using a dryer, for example, and an organic solvent The method of volatilizing is generally used. The drying temperature may be set to a temperature in which the used organic solvent can be volatilized and the support (A) is not adversely affected by heat deformation and the like.

Although the film thickness of the primer layer (B) formed using the said primer composition (b) changes with uses which use the laminated body of this invention, the said metal support (A) and the metal nanoparticle layer (C) mentioned later The range in which the adhesion with it can be further improved is preferable, and the film 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.

The surface of the primer layer (B) can further improve the adhesion to the metal nanoparticle layer (C), and therefore, if necessary, it can be a dry process such as a plasma discharge treatment method such as corona discharge treatment method or an ultraviolet treatment method The 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 as the metal constituting the metal nanoparticle layer (C), a transition metal or a compound thereof can be mentioned, among which Ionizable transition metals are preferred. Examples of the ionic transition metal include copper, silver, gold, nickel, palladium, platinum, cobalt and the like. Among these, silver is preferable because it is easy to form the metal plating layer (D).

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 can be obtained which has a low electrical resistance and is resistant to corrosion.

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 coated. And forming the metal nanoparticle layer (C) by removing the organic solvent and the like contained in the fluid by drying, and then the metal plating layer (D) by electrolytic plating, electroless plating, or both. Methods to form

The shape of the metal nanoparticles (c) used to form the metal nanoparticle layer (C) is preferably particulate or fibrous. In addition, although the size of the metal nanoparticles (c) is nanosize, specifically, when the shape of the metal nanoparticles (c) is particulate, a fine conductive pattern can be formed. The average particle diameter is preferably 1 nm or more and 100 nm or less, and more preferably 1 nm or more and 50 nm or less because the resistance value can be further reduced. The “average particle diameter” is a volume average value measured by dynamic light scattering method after diluting the conductive substance with a dispersion good solvent. For this measurement, "Nanotrack UPA-150" manufactured by Microtrac, Inc. can be used.

On the other hand, even 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 diameter of the fiber is preferably 5 nm or more and 100 nm or less, and 5 nm or more The range of 50 nm or less is more preferable. The length of the fiber is preferably 0.1 μm to 100 μm, and more preferably 0.1 μm to 30 μm.

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 preferable.

As components 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 as described later, Film forming aids, antifoaming agents, preservatives and the like can be mentioned.

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, polyvinyl pyrrolidone, polyethylene imine, polyvinyl pyrrolidone; fatty acids such as myristic acid, octanoic acid and stearic acid; cholic acid, Examples thereof include polycyclic hydrocarbon compounds having a carboxyl group such as glycyrrhizic acid and aventic acid. Among these, a polymer dispersant is preferable because the adhesion between the metal nanoparticle layer (C) and the metal plating layer (D) can be improved, and as the polymer dispersant, polyethyleneimine, polypropyleneimine, etc. And a compound obtained by adding a polyoxyalkylene to the polyalkyleneimine, a urethane resin, an acrylic resin, the urethane resin, a compound having a phosphoric acid group in the acrylic resin, and the like.

The amount of the dispersing agent required to disperse 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), and 0. More than 01 mass parts and below 10 mass parts are more preferred.

As a solvent used for the said fluid, an aqueous medium and an organic solvent can be used. Examples of the aqueous medium include distilled water, ion exchanged water, pure water, ultrapure water and the like. Moreover, an alcohol compound, an ether compound, an ester compound, a ketone compound etc. are mentioned as said organic solvent.

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, and the like. 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 The Butyl 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 Propylene glycol monobutyl ether and the like can be mentioned.

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

A common surfactant can be used as the surfactant, and examples thereof include di-2-ethylhexyl sulfosuccinate, dodecylbenzene sulfonate, alkyl diphenyl ether disulfonate, alkyl naphthalene sulfonate, hexametaphosphoric acid Salt etc. are mentioned.

A general leveling agent can be used as the leveling agent, and examples thereof include silicone compounds, acetylene diol compounds, and fluorine compounds.

As the viscosity modifier, a general thickener 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 Resin, hydroxyethylcellulose, carboxymethylcellulose, methylcellulose, polyvinyl alcohol, castor oil with water, amide wax, polyethylene oxide, metal soap, dibenzylidene sorbitol and the like.

As the film forming aid, a general film forming aid can be used, and examples thereof include anionic surfactants (such as dioctyl sulfosuccinic acid ester soda salt) and hydrophobic nonionic surfactants (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, a general preservative can be used, for example, isothiazoline preservative, triazine preservative, imidazole preservative, pyridine preservative, azole preservative, iodine preservative, pyrithione Examples include antiseptics and the like.

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

Examples of methods for coating or printing the fluid on the primer layer (B) include inkjet printing, reverse printing, screen printing, offset printing, spin coating, spray coating, and bar coating. Methods, die coating methods, slit coating methods, roll coating methods, dip coating methods, pad printing, flexographic printing methods and the like.

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

As the inkjet printing method, one generally referred to as an inkjet printer can be used. Specifically, Konica Minolta EB 100, XY 100 (manufactured by Konica Minolta IJ Co., Ltd.), Dymatics Material Printer DMP-3000, Dimatics Material Printer DMP-2831 (manufactured by Fuji Film Co., Ltd.), etc. may be mentioned.

Further, as the reverse printing method, the letterpress reverse printing method and the intaglio reverse printing method are known, and for example, the fluid is coated on the surface of various blankets and brought into contact with a plate in which non-image areas are projected; The pattern is formed on the surface of the blanket or the like by selectively transferring the fluid corresponding to the non-image area onto the surface of the plate, and then the pattern is formed on the support (A). A method of transferring to (surface) may be mentioned.

Moreover, the pad printing method is known about printing of the pattern to a three-dimensional molded article. This is done by placing the ink on the intaglio plate, filling the ink uniformly into the recess by writing with the squeegee, pressing the pad made of silicone rubber or urethane rubber onto the plate loaded with the ink, the pattern on the pad It 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 amount of use of the additive for plating, etc. 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, for example, a reliable member capable of maintaining good conductivity without causing disconnection or the like over a long period of time when the laminate is used for a printed wiring board or the like. It is a layer provided for the purpose of forming a highly conductive 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 the plating process is preferable as the formation method. As this plating process, wet plating methods, such as an electrolytic plating method which can form the said metal plating layer (D) simply, and an electroless plating method, are mentioned. Also, two or more of these plating methods may be combined. For example, after the electroless plating is performed, electrolytic plating may be performed to form the metal plating layer (D).

In the above electroless plating method, for example, a metal such as copper contained in the electroless plating solution is precipitated by bringing the electroless plating solution into contact with the metal constituting the metal nanoparticle layer (C). It is a method of forming an electroless plating layer (coating) composed of a coating.

Examples of the electroless plating solution include those containing a metal such as copper, nickel, chromium, cobalt, tin, gold, silver and the like, a reducing agent, and a solvent such as an aqueous medium and an organic solvent.

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

Further, as the electroless plating solution, if necessary, 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 and glycol Hydroxycarboxylic acid compounds such as 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 acid such as aminopolycarboxylic acid compound of the above or a soluble salt of such an organic acid (sodium salt, potassium salt, ammonium salt etc.), an amine compound such as ethylenediamine, diethylenetriamine, triethylenetetramine etc. Also It can be used.

The electroless plating solution is preferably used at 20 ° C. or more and 98 ° C. or less.

The electrolytic plating method is performed, for example, in a state in which an electrolytic plating solution is in contact with the surface of the metal forming the metal nanoparticle layer (C) or the electroless plating layer (film) formed by the electroless processing. A conductive substance constituting the metal nanoparticle layer (C) in which a metal such as copper contained in the electrolytic plating solution is disposed at the cathode by energization, or an electroless plating layer formed by the electroless treatment It is a method of depositing on the surface of (coating) to form an electrolytic plating layer (metal coating).

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

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

As a method of forming the metal plating layer (D), after electroless plating is performed because the film thickness of the metal plating layer (D) can be easily controlled to a desired film thickness from thin film to thick film, The method of 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, the current density, the use amount of the additive for plating, etc. in the plating treatment step in forming the metal plating layer (D). Can.

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

(Production Example 1: Production of Acrylic Resin for Primer (1))
In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen introduction pipe, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for dropping a polymerization catalyst, 180 parts by mass of ethyl acetate is charged, and nitrogen is blown up to 90 ° C. The temperature rose. 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 under stirring in a reaction vessel heated to 90 ° C. A polymerization initiator solution containing 1 part by mass of butyronitrile and 20 parts by mass of ethyl acetate was dropped and polymerized from separate dropping funnels over 240 minutes while maintaining the temperature in the reaction vessel at 90 ± 1 ° C. After completion of the dropwise addition, after stirring for 120 minutes at the same temperature, the temperature in the reaction vessel was cooled to 30 ° C. Then, the reaction solution was diluted with ethyl acetate to obtain a 2% by mass solution of a primer acrylic resin (1).

(Production Example 2: Production of Acrylic Resin for Primer (2))
In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen introduction pipe, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for dropping a polymerization catalyst, 180 parts by mass of ethyl acetate is charged, and nitrogen is blown up to 90 ° C. The temperature rose. 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 under stirring in a reaction vessel heated to 90 ° C. A polymerization initiator solution containing 1 part by mass of butyronitrile and 20 parts by mass of ethyl acetate was dropped and polymerized from separate dropping funnels over 240 minutes while maintaining the temperature in the reaction vessel at 90 ± 1 ° C. After completion of the dropwise addition, after stirring for 120 minutes at the same temperature, the temperature in the reaction vessel was cooled to 30 ° C. Then, the reaction solution was diluted with ethyl acetate to obtain a 2% by mass solution of a primer acrylic resin (2).

Production Example 3 Production of Acrylic Resin for Primer (3)
In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen introduction pipe, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for dropping a polymerization catalyst, 180 parts by mass of ethyl acetate is charged, and nitrogen is blown up to 90 ° C. The temperature rose. 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 under stirring in a reaction vessel heated to 90 ° C. A polymerization initiator solution containing 1 part by mass of butyronitrile and 20 parts by mass of ethyl acetate was dropped and polymerized from separate dropping funnels over 240 minutes while maintaining the temperature in the reaction vessel at 90 ± 1 ° C. After completion of the dropwise addition, after stirring for 120 minutes at the same temperature, the temperature in the reaction vessel was cooled to 30 ° C. Then, the reaction solution was diluted with ethyl acetate to obtain a 2% by mass solution of a primer acrylic resin (3).

Production Example 4: Production of Acrylic Resin for Primer (4)
In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen introduction pipe, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for dropping a polymerization catalyst, 180 parts by mass of ethyl acetate is charged, and nitrogen is blown up to 90 ° C. 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 under stirring in a reaction vessel heated to 90 ° C. A polymerization initiator solution containing 1 part by mass of azoisobutyronitrile and 20 parts by mass of ethyl acetate was added dropwise over 240 minutes while maintaining the temperature in the reaction vessel at 90 ± 1 ° C. from separate dropping funnels. . After completion of the dropwise addition, after stirring for 120 minutes at the same temperature, the temperature in the reaction vessel was cooled to 30 ° C. Subsequently, it diluted with ethyl acetate and obtained 2 mass% solution of acrylic resin (4) for primers.

(Production Example 5: Production of Acrylic Resin for Primer (5))
In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen introduction pipe, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for dropping a polymerization catalyst, 180 parts by mass of ethyl acetate is charged, and nitrogen is blown up to 90 ° C. The temperature rose. 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 in a reaction vessel heated to 90 ° C. A monomer mixture, and a polymerization initiator solution containing 1 part by mass of azoisobutyronitrile and 20 parts by mass of ethyl acetate are added from separate dropping funnels for 240 minutes while maintaining the temperature in the reaction vessel at 90 ± 1 ° C. It dripped and polymerized. After completion of the dropwise addition, after stirring for 120 minutes at the same temperature, the temperature in the reaction vessel was cooled to 30 ° C. Then, the reaction solution was diluted with ethyl acetate to obtain a 2% by mass solution of a primer acrylic resin (5).

Production Example 6: Production of Acrylic Resin for Primer (6)
In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for dropping a polymerization catalyst, 200 parts by mass of ethyl acetate is added, and nitrogen is blown up to 90 ° C. The temperature rose. 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 under stirring in a reaction vessel heated to 90 ° C .; A polymerization initiator solution containing 1 part by mass of azoisobutyronitrile and 20 parts by mass of ethyl acetate was added dropwise over 240 minutes while maintaining the temperature in the reaction vessel at 90 ± 1 ° C. from separate dropping funnels. After completion of the dropwise addition, after stirring for 120 minutes at the same temperature, the temperature in the reaction vessel was cooled to 30 ° C. Subsequently, it diluted with ethyl acetate and obtained 2 mass% solution of acrylic resin (6) for primers.

(Production Example 7: Production of Acrylic Resin for Primer (7))
In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen introduction pipe, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for dropping a polymerization catalyst, 180 parts by mass of ethyl acetate is charged, and nitrogen is blown up to 90 ° C. 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 under stirring in a reaction vessel heated to 90 ° C., 1 part by mass of azoisobutyronitrile, and ethyl acetate A polymerization initiator solution containing 20 parts by mass was polymerized dropwise over 240 minutes while maintaining the temperature in the reaction vessel at 90 ± 1 ° C. from each separate dropping funnel. After completion of the dropwise addition, after stirring for 120 minutes at the same temperature, the temperature in the reaction vessel was cooled to 30 ° C. Then, the reaction solution was diluted with ethyl acetate to obtain a 2% by mass solution of a primer acrylic resin (7).

Preparation Example 1: Preparation of Primer Composition (1)
Anhydrous pyromellitic as a curing agent in 100 parts by mass of a solution in which an epoxy resin ("EPICLON 1050" manufactured by DIC Corporation; bisphenol A type epoxy resin, epoxy equivalent 475 g / equivalent) is diluted with methyl ethyl ketone to make the solid content 2 mass% A primer composition (1) was obtained by uniformly mixing 11.5 parts by mass of a 2% by mass methyl ethyl ketone solution of an 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 make the solid content 2 mass% 100 parts by weight of an aqueous dry trimet as a curing agent The primer composition (2) was obtained by uniformly mixing 38.9 parts by mass of a 2% by mass methyl ethyl ketone solution of an acid.

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

Preparation Example 4 Preparation of Primer Composition (4)
In 100 parts by mass of a 2% by mass solution of acrylic resin (1) for a primer obtained in Production Example 1, 17.4 parts by mass of a 2% by mass solution in which trimellitic anhydride is diluted with methyl ethyl ketone is uniformly mixed. A composition (4) was obtained.

Preparation Example 5 Preparation of Primer Composition (5)
In 100 parts by mass of a 2% by mass solution of acrylic resin (1) for a primer obtained in Production Example 1, 23.2 parts by mass of a solid 2% by mass solution of trimellitic anhydride diluted with methyl ethyl ketone is uniformly mixed. The primer composition (5) was obtained.

Preparation Example 6 Preparation of Primer Composition (6)
In 2 parts by mass of a 2% by mass solution of acrylic resin (1) for primers obtained in Production Example 1, 20.3 parts by mass of a solution of 2% by mass of solid content obtained by diluting dodecanedioic acid with isopropyl alcohol is uniformly mixed The primer composition (6) was obtained.

Preparation Example 7 Preparation of Primer Composition (7)
100 parts by mass of a 2% by mass solution of acrylic resin (2) for primers obtained in Production Example 2 was uniformly mixed with 4.6 parts by mass of a 2% by mass solid solution obtained by diluting trimellitic anhydride with methyl ethyl ketone The primer composition (7) was obtained.

Preparation Example 8 Preparation of Primer Composition (8)
In 100 parts by mass of a 2% by mass solution of acrylic resin (3) for a primer obtained in Production Example 3, 15.4 parts by mass of a 2% by mass solution in which pyromellitic anhydride is diluted with methyl ethyl ketone is uniformly mixed, A composition (8) was obtained.

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

Preparation Example 10 Preparation of Primer Composition (10)
The 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 parts by mass of 100% by mass of the acrylic resin (5) for primer obtained in Production Example 5 Obtained object (10).

Preparation Example 11 Preparation of Primer Composition (R1)
100 parts by mass of a 2% by mass solution of acrylic resin (6) for a primer obtained in Production Example 6 is uniformly mixed with 11.6 parts by mass of a 2% by mass solution of trimellitic anhydride diluted with methyl ethyl ketone A composition (R1) was obtained.

Preparation Example 12 Preparation of Primer Composition (R2)
100 parts by mass of a 2% by mass solution of acrylic resin (7) for a primer obtained in Production Example 7 is uniformly mixed with 13.9 parts by mass of a 2% by mass solution obtained by diluting trimellitic anhydride with methyl ethyl ketone 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 primers (1) obtained in Production Example 1 was used as it is as a primer composition (R3).

[Preparation of fluid (1)]
According to Example 1 described in Japanese Patent No. 4573138, a cationic silver nano consisting of a flake-like lump having an ash green color which is a complex of silver nanoparticles and an organic compound having a cationic group (amino group) I got the particles. 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 divided into a bench type small coater (manufactured by RK Print Coat Instrument Co., Ltd.) It applied so that the thickness after the drying might be set to 100 nm using K printing prober "). Then, a primer layer was formed on the surface of the polyimide film by drying at 150 ° C. for 5 minutes using a hot air drier.

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

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

The copper plating layer by electroless copper plating obtained above is set on the cathode side, phosphorus-containing copper is set on the anode side, and an electrolytic plating solution containing copper sulfate is used at a current density of 2.5 A / dm ² 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 chlorine ion, and 5 ml / L of an additive (“Top Rutina SF-M” manufactured by Okuno Pharmaceutical Co., Ltd.) were used. A combination of a copper plating layer by electroless copper plating and a copper plating layer by electrolytic copper plating formed thereon corresponds to the metal plating layer (D).

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

(Examples 2 to 10 and Comparative Examples 1 to 3)
Example 1 was repeated 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 was obtained. (2) to (10) and (R1) to (R3) were obtained.

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

[Measurement of peel strength before heating]
The peel strength of each of the laminates obtained above was measured using "Autograph AGS-X 500N" manufactured by Shimadzu Corporation. The lead width used for measurement was 5 mm, and the peel angle was 90 °. Although the peel strength tends to increase as the thickness of the metal plating layer increases, the measurement of the peel strength in the present invention was performed based on the measurement value at a thickness of 15 μm of the metal plating layer.

[Evaluation of adhesion]
The adhesion was evaluated according to the following criteria from the value of the peel strength before heating measured above.
A: The peel strength value is 650 N / m or more.
B: The value of peel strength 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 and heated in a dryer set at 150 ° C. for 168 hours. After heating, the peel strength was measured by the same method as described above.

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

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

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

On the other hand, the laminate (R1) of Comparative Example 1 is an example using an acrylic resin not having an epoxy group as a resin for a primer used in the primer layer, but the adhesion at the initial stage (before heating) is extremely low. The peel strength after that was 0 kN / m, and it could be confirmed 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 as a resin for a primer used in the primer layer, but the adhesion in the initial stage (before heating) is extremely low and peeling after heating The strength was 0 kN / m, confirming that there was a problem with adhesion.

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

Claims

It 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), and the primer layer (B) is an epoxy group A laminate characterized in that it is a cured product of a resin (b1) having at least one hydroxyl group and a crosslinking agent (b2) containing a polyvalent carboxylic acid.
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 polybasic 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 group in the crosslinker (b2) and the number of moles of epoxy group in the resin (b1) is 0.3 or more and 3 or less. 5. The laminate according to any one of 5.
A printed wiring board using the laminate according to any one of claims 1 to 6.
A flexible printed wiring board according to any one of claims 1 to 6, characterized in that the support (A) is a film.
A molded article comprising the laminate according to any one of claims 1 to 6.