JPWO2021131565A1 - Laminates, printed wiring boards, flexible printed wiring boards, electromagnetic wave shields and molded products - Google Patents

Abstract

A laminate that can be manufactured 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) even after a long-term heat resistance test, and a laminate thereof. Provided are a printed wiring board, a flexible printed wiring board, and a molded product using the above. A laminate in which a primer layer (B) and a metal particle layer (C) are sequentially laminated on a support (A), and the primer layer (B) is a primer resin (b1) and a silane coupling agent. A laminate characterized by being a layer containing the treated silica particles (b2) is used.

Description

The present invention relates to a laminate, a printed wiring board, a flexible printed wiring board, an electromagnetic wave shield, and a molded product.

Due to the miniaturization and speeding up of electronic devices, high density and high performance of printed wiring boards are required. To meet these demands, printed wiring boards having a smooth surface and a sufficiently thin conductive layer (metal layer). Is required. Further, a flexible copper-clad laminate (hereinafter, abbreviated as "FCCL") is known as constituting this printed wiring board. FCCL is mainly manufactured by a method of laminating a heat-resistant polymer film and a copper foil.

However, in FCCL using this copper foil, the copper foil wound in a roll shape is pulled out and bonded to the insulating polymer film, or a solution of the insulating polymer is applied, so that the copper foil is easy to handle. Cannot be thin enough. Furthermore, since it is necessary to roughen the surface of the copper foil in order to improve the adhesion with the polymer film, the high frequency (GHz band) and high required for high density and high performance of the printed wiring board. There is a problem of causing a transmission loss in the transmission speed (several tens of GHz) region.

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 electrolytic plating method, an electrolytic plating method, or a combination thereof is combined on the metal thin film. A method for forming copper by a method has been proposed (see, for example, Patent Document 1). However, in this method, since a thin film 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 size of the base material is limited in terms of the facility.

Therefore, it does not roughen the surface of the metal layer such as copper foil, has sufficient adhesion to the support such as a polymer film, and does not require a large-scale vacuum equipment to form the metal layer. There has been a demand for a laminate that can be manufactured by a simple method.

Further, conventionally, as decorative plating for plastic molded products, it has been used for mobile phones, personal computers, mirrors, containers, various switches, shower heads and the like. Supports for these applications are limited to acrylonitrile-butadiene-styrene copolymers (hereinafter abbreviated as "ABS") and ABS-polycarbonate polymer alloys (hereinafter abbreviated as "ABS-PC"). Has been limited. The reason for this is that it is necessary to roughen the surface of the base material in order to ensure the adhesion between the base material and the plating film. For example, in the case of ABS, the polybutadiene component is strongly oxidized with hexavalent chromic acid, permanganate, etc. The surface can be roughened by etching with an agent and removing it. 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).

As described above, in plating for the purpose of decorating plastic molded products, the base material is not limited to ABS or ABS-PC, and a plating film having excellent adhesion can be obtained even with other types of plastics. It was required to reduce the amount of environmentally hazardous substances used.

Japanese Unexamined Patent Publication No. 2015-118044 Japanese Patent No. 5830807

The problem to be solved by the present invention is that it can be manufactured by a simple method without roughening the surface of the support, and further, even after a long-term heat resistance test, between the support and the metal layer (metal plating layer). It is an object of the present invention to provide a laminated body having excellent adhesion, and a printed wiring board, a flexible printed wiring board and a molded product using the same.

As a result of diligent research to solve the above problems, the present inventors provided a layer containing a primer resin and silica particles as a primer layer on the support, and formed a metal layer on the support with metal particles. The present invention has been completed by finding that a laminated body in which metal-plated layers are sequentially laminated can solve the above-mentioned problems.

That is, the present invention is a laminated body in which a primer layer (B) and a metal particle layer (C) are sequentially laminated on a support (A), and the primer layer (B) is a primer resin (b1). The present invention provides a laminate characterized by being a layer containing silica particles (b2), a printed wiring board using the same, a flexible printed wiring board, and a molded product.

The laminated body of the present invention has excellent adhesion between the support and the metal layer (metal plating layer) without roughening the surface of the support. Further, when the metal layer is thinned, it is a laminate having a metal layer having a smooth surface and a sufficiently thin surface without using a large-scale vacuum facility. Further, it is a laminated body having excellent adhesion even after the heat resistance test.

Further, the laminate of the present invention has, 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 non-contact IC card, an electromagnetic wave shield, an LED lighting substrate, and an electronic member such as digital signage. In particular, it is most suitable for flexible printed wiring board applications such as FCCL.

In addition, by applying it to molded products, electronic parts such as connectors for connecting wiring such as optical communication, electrical parts, electric motor peripheral parts, battery parts; decorative parts for automobiles, lamp reflectors, mobile phones, personal computers, mirrors, etc. 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 particle layer (C), and a metal plating layer (D) are sequentially laminated on a support (A), and the primer layer ( B) is a layer containing a primer resin (b1) and silica particles (b2).

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

Examples of the support (A) include polyimide, transparent polyimide, polyamideimide, polyamide, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, acrylonitrile-butadiene-styrene (ABS) resin, polymer alloy of ABS and polycarbonate, and poly (A). Meta) Acrylic resin such as methyl acrylate, polytetrafluoroethylene, ethylene tetrafluoroalkyl vinyl ether copolymer, ethylene tetrafluoride-propylene hexafluoride propylene copolymer, ethylene tetrafluoride-ethylene copolymer, foot Vinylene sulfide resin, ethylene trifluoride resin, ethylene trifluoride-ethylene copolymer, ethylene tetrafluoride / perfluorodioxysole copolymer, vinyl fluoride resin, vinylidene fluoride, polyvinyl chloride, poly Vinylidene chloride, polyvinyl alcohol, polycarbonate, polyethylene, polypropylene, polyurethane, liquid crystal polymer (LCP), polyether ether ketone (PEEK), polyphenylene sulfide (PPS), polyphenylene sulfide (PPSU), epoxy resin, cellulose nanofibers, silicon, ceramics , A support made of glass, etc., a porous support made of them, a steel plate, a support made of a metal such as copper, and a support whose surface is vapor-deposited with silicon carbide, diamond-like carbon, aluminum, copper, titanium, etc. The body etc. can be mentioned.

When the laminate of the present invention is used for a printed wiring board or the like, the support (A) may be polyimide, transparent polyimide, polytetrafluoroethylene, tetrafluoroethylene-ethylene copolymer, polyethylene terephthalate, or polyethylenener. It is preferable to use a support made of phthalate, liquid crystal polymer (LCP), polyetheretherketone (PEEK), glass, cellulose nanofibers and the like.

Further, when the laminated body of the present invention is used for a flexible printed wiring board or the like, a film-shaped or sheet-shaped support having foldable flexibility is preferable as the support (A).

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

Further, since the adhesion between the support (A) and the primer layer (B) described later can be further improved, if necessary, the surface of the support (A) is fine enough not to lose its smoothness. Concavities and convexities may be formed, stains adhering to the surface thereof may be cleaned, and surface treatment may be performed for the introduction of functional groups such as hydroxyl groups, carbonyl groups, and carboxyl groups. Specific examples thereof include plasma discharge treatment such as corona discharge treatment, dry treatment such as ultraviolet treatment, and wet treatment using water, an aqueous solution of acid / alkali or the like, or an organic solvent.

The primer layer (B) is a layer containing a primer resin (b1) and silica particles (b2).

Examples of the primer resin (b1) include a urethane resin, an acrylic resin, a core-shell type composite resin having a urethane resin as a shell and an acrylic resin as a core, an epoxy resin, an imide resin, an amide resin, a melamine resin, and a phenol resin. Examples thereof include blocked isocyanate polyvinyl alcohol, polyvinylpyrrolidone and the like obtained by reacting a urea formaldehyde resin and polyisocyanate with a blocking agent such as phenol. The core-shell type composite resin having a urethane resin as a shell and an acrylic resin as a core can be obtained, for example, by polymerizing an acrylic monomer in the presence of a urethane resin. Further, these resins can be used alone or in combination of two or more.

Among the resins forming the primer layer (B), it is preferable to use a resin containing an aminotriazine-modified novolak resin (b1-1).

The aminotriazine-modified novolak resin (b1-1) is a novolak resin in which an aminotriazine ring structure and a phenol structure are bonded via a methylene group. The aminotriazine-modified novolak resin (b1-1) includes, for example, an aminotriazine compound such as melamine, benzoguanamine and acetguanamine, a phenol compound such as phenol, cresol, butylphenol, bisphenol A, phenylphenol, naphthol and resorcin, and formaldehyde. In the presence or absence of a weak alkaline catalyst such as an alkylamine or in the absence of a catalyst, a cocondensation reaction is carried out in the vicinity of neutrality, or an alkyl etherified product of an aminotriazine compound such as methyl etherified melamine is reacted with the phenol compound. Obtained by

The aminotriazine-modified novolak resin (b1-1) preferably has substantially no methylol group. Further, the aminotriazine-modified novolak resin (b1-1) may contain a molecule in which only the aminotriazine structure generated as a by-product during its production is methylene-bonded, a molecule in which only the phenol structure is methylene-bonded, and the like. No. Further, a small amount of unreacted raw material may be contained.

Examples of the phenol structure include phenol residues, cresol residues, butylphenol residues, bisphenol A residues, phenylphenol residues, naphthol residues, resorcin residues and the like. Further, the residue here means a structure in which at least one hydrogen atom bonded to the carbon of the aromatic ring is removed. For example, in the case of phenol, it means a hydroxyphenyl group.

Examples of the triazine structure include structures derived from aminotriazine compounds such as melamine, benzoguanamine, and acetoguanamine.

The phenol structure and the triazine structure can be used alone or in combination of two or more. Further, since the adhesion can be further improved, a phenol residue is preferable as the phenol structure, and a melamine-derived structure is preferable as the triazine structure.

The hydroxyl value of the aminotriazine-modified novolak resin (b1-1) is preferably in the range of 50 to 200 mgKOH / g, more preferably in the range of 80 to 180 mgKOH / g, and more preferably in the range of 100 to 150 mgKOH, because the adhesion can be further improved. The / g range is even more preferred.

The aminotriazine-modified novolak resin (b1-1) can be used alone or in combination of two or more.

When an aminotriazine-modified novolak resin (b1-1) is used as the compound (b1) having an aminotriazine ring, it is preferable to use an epoxy resin (b1-2) in combination.

Examples of the epoxy resin (b1-2) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A novolak type epoxy resin, and alcohol ether type. Epoxy resin, tetrabrombisphenol A type epoxy resin, naphthalene type epoxy resin, phosphorus-containing epoxy compound having a structure derived from 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, dicyclopentadiene derivative Examples thereof include an epoxy resin having a derived structure and an epoxidized product of fats and oils such as epoxidized soybean oil. These epoxy resins can be used alone or in combination of two or more.

Among the epoxy resins (b1-2), bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A can be further improved. Novolak type epoxy resin is preferable, and bisphenol A type epoxy resin is particularly preferable.

Further, the epoxy equivalent of the epoxy resin (b1-2) is preferably in the range of 100 to 300 g / equivalent, more preferably in the range of 120 to 250 g / equivalent, and more preferably 150 to 200 g / equivalent, because the adhesiveness can be further improved. The range is even more preferred.

When the primer layer (B) is a layer containing an aminotriazine-modified novolak resin (b1-1) and an epoxy resin (b1-2), the adhesion can be further improved. Therefore, the aminotriazine-modified novolak resin (b1) can be further improved. The molar ratio [(x) / (y)] of the phenolic hydroxyl group (x) in -1) and the epoxy group (y) in the epoxy resin (b1-2) is in the range of 0.1 to 5 or less. Is preferable, the range of 0.2 to 3 or less is more preferable, and the range of 0.3 to 2 is further preferable.

In order to accelerate the reaction between the aminotriazine-modified novolak resin (b1-1) and the epoxy resin (b1-2), a curing accelerator may be used in combination. Examples of the curing accelerator include amine compounds having a primary, secondary or tertiary amino group. Further, as the amine compound, any of an aliphatic, alicyclic, and aromatic compound can be used. Further, as the curing accelerator, mercaptan, acid anhydride, boron acid fluoride, boric acid ester, organic acid hydrazite, Lewis acid, organic metal compound, onium salt, cationic compound and the like can also be used.

As the silica particles (b2), either natural silica particles produced from natural raw materials or synthetic silica particles produced by chemical synthesis can be used. Further, the silica particles (b2) may be dispersed in water or an organic solvent, or may be used as a slurry or colloidal solution in which silica particles are dispersed in advance.

When the silica particles (b2) are used in electronics applications, it is preferable to use those having few impurities. For example, examples of the impurities include sodium ion, potassium ion, iron ion, aluminum ion, chloride ion and the like.

The silica particles (b2) are not particularly limited, but examples of commercially available products that can be used include the SFP series and the UFP series (UFP-30, UFP) manufactured by the synthetic method manufactured by Denka Co., Ltd. -40, SFP-20M, SFP-30M, SFP-130MC, SFP-120MC, SFP-120MC, SFP-30MHE, UFP-30HH), FB series manufactured by natural method (FB-5D, FB-8S, FB- 15D, FB-20D, FB-40R); Snowtex series (ST-XS, ST-OXS, ST-NXS, ST-CXS, ST-S), which is a colloidal solution made by Nissan Chemical Co., Ltd. using water as a dispersion medium. , ST-OS, ST-NS, ST-30, ST-O, ST-N, ST-C, ST-AK, ST-50-T, ST-O-40, ST-CM, ST-30L, ST -OL, ST-AK-L, ST-YL, ST-OYL, ST-AK-YL, ST-ZL, MP-1040, MP-2040, MP-4540M, ST-UP, ST-OUP, ST-PS -S, ST-PS-SO, ST-PS-M, ST-PS-MO), organo silica sol series (methanol silica sol, MA-ST-M, MA-ST-), which is a colloidal solution using an organic solvent as a dispersion medium. L, IPA-ST, IPA-ST-L, IPAST-ZL, IPA-ST-UP, EG-ST, NPC-ST-30, PGM-ST, DMAC-ST, MEK-ST-40, MEK-ST- L, MEK-ST-ZL, MEK-ST-UP, MIBK-ST-L, CHO-ST-M, EAC-ST, PMA-ST, TOR-ST, MEK-AC-2140Z, MEK-AC-4130Y, MEK-AC5140Z, PMG-AC2140Y, PGM-AC-4130Y, MIBK-AC-2140Z, MIBK-SD-L, MEK-EC-2130Y, EP-M2130Y; SO-C type (SO-) manufactured by Admatex Co., Ltd. C1, SO-C2, SO-C4, SO-C5, SO-C6), SO-E types (SO-E1, SO-E2, SO-E3, SO-E4, SO-E5, SO-E6), etc. Can be mentioned.

Further, in the present invention, the silica particles (b2) are imparted with dispersibility and affinity with the solvent and the primer resin (b1), and high adhesion with the support and the metal particle layer (C). The surface of the silica particles (b2) is treated with a silane coupling agent for the purpose of treating the silica particles (b2). The silane coupling agent is not particularly limited, and examples thereof include epoxysilane, aminosilane, vinylsilane, and mercaptosilane. Further, after the surface of the silica particles (b2) is treated with a silane coupling agent, the silica treated with a silane coupling agent for the purpose of further improving dispersibility and affinity with the primer resin (b1). A resin may be attached to the surface of the particles (b2). Examples of the resin to be adhered include acrylic resin, epoxy resin, urethane resin, polyester resin and the like, and it is preferable to use the same type of resin as the primer resin (b1).

Examples of the epoxy silane include 2- (3,4-epoxide cyclohexyl) ethyltrialkoxymethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxy. Propyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 8-glycidoxyoctyltrimethoxysilane, a polyfunctional group-type silane coupling agent having an organic main chain and a plurality of alkoxysilyl groups and epoxy groups (for example). , "X-12-981S", "X-12-984S", etc. manufactured by Shin-Etsu Chemical Industry Co., Ltd.) "KR-516", "KR-517", etc. manufactured by Co., Ltd.) and the like can be mentioned. Among these silane coupling agents, those having an alicyclic structure are preferable, and specifically, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane is preferable.

Examples of the aminosilane include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, and 3 -Aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl -3-Aminopropyltrimethoxysilane hydrochloride, N-2- (aminoethyl) -8-aminooctyltrimethoxysilane, amino group-protected silane coupling agent (for example, "KBE-9103P" manufactured by Shin-Etsu Chemical Industry Co., Ltd. (Ketimine type), "X-12-1172ES" (Aldimine type), etc.), a polyfunctional silane coupling agent having an organic chain as the main chain and having a plurality of alkoxysilyl groups and amino groups (for example, Shin-Etsu Chemical Industry Co., Ltd.) Company-made "X-12-972F" etc.) and the like can be mentioned.

The vinylsilane refers to a silane compound having a double bond in the present invention. For example, as a silane coupling agent having a vinyl group, vinyltrimethoxysilane, vinyltriethoxysilane, 7-octenyltrimethoxysilane, and a polyfunctional group type silane coupling having a siloxane chain as the main chain and a plurality of vinyl groups and phenyl groups. Agents (for example, "KR-511" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) and the like can be mentioned. Further, examples of the silane compound having a double bond include acrylic silane, methacrylic silane, and styryl silane.

The acrylic silane is 3-acryloxypropyltrimethoxysilane, a polyfunctional group-type silane coupling agent having an organic main chain and a plurality of alkoxysilyl groups and acrylic groups (for example, "X-" manufactured by Shin-Etsu Chemical Industry Co., Ltd. 12-1048 "," X-12-1050 ", etc.), a polyfunctional group-type silane coupling agent having a siloxane chain as the main chain and having a plurality of acrylic groups and methyl groups (for example," KR-513 "manufactured by Shin-Etsu Chemical Industry Co., Ltd." "Etc.) and so on.

Examples of the methacrylsilane include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and 8-methacryloxyoctylrimethoxy. Examples thereof include silane and a polyfunctional group-type run-coupling agent having a siloxane chain as the main chain and having a plurality of methacryl groups and methyl groups (for example, "KR-503" manufactured by Shin-Etsu Chemical Industry Co., Ltd.).

Examples of the styrylsilane include P-styryltrimethoxysilane and the like.

Examples of the mercaptosilane include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and a polyfunctional group-type silane coupling agent having an organic main chain and a plurality of alkoxysilyl groups and mercaptoki groups (for example,). "X-12-1154", "X-12-1156", etc. manufactured by Shin-Etsu Chemical Industry Co., Ltd.), a polyfunctional group-type silane coupling agent having a siloxane chain as the main chain and a plurality of mercapto groups (for example, Shin-Etsu Chemical Industry Co., Ltd.) Examples thereof include "KR-518", "KR-519", etc. manufactured by the company), a mercapto group-protected silane coupling agent ("X-12-1056ES" manufactured by Shin-Etsu Chemical Co., Ltd., etc.) and the like.

Other silane coupling agents include, for example, 3-ureidopropyltrialkoxysilane, tris- (trimethoxysilylpropyl) isocyanurate, tris- (triethoxysilylpropyl) isocyanurate, 3-isocyanatepropyltriethoxysilane, 3-. Trimethoxysilylpropyl succinic acid anhydride, a polyfunctional group-type silane coupling agent having an organic chain as the main chain and having a plurality of alkoxysilyl groups and isocyanate groups (for example, "X-12-1159L" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) And so on.

Among the silane coupling agents, epoxysilane, aminosilane, and methacrylicsilane are preferable, and epoxysilane is more preferable.

The content of the silica particles (b2) in the primer layer (B) is preferably in the range of 1 to 400 parts by mass with respect to 100 parts by mass of the primer resin (b1) because the adhesion can be further improved. Further, since the heat resistance adhesion after the heat resistance test can be further improved, the content of the silica particles (b2) in the primer layer (B) is 5 to 200 with respect to 100 parts by mass of the primer resin (b1). The range of parts by mass is preferable, the range of 8 to 100 parts by mass is more preferable, and the range of 10 to 80 parts by mass is further preferable.

Further, the average particle diameter of the silica particles (b2) is preferably in the range of 0.001 to 0.5 μm, more preferably in the range of 0.01 to 0.1 μm, and 0. The range of 01 to 0.05 μm is more preferable. The average particle size in the present invention is a volume average value measured by a dynamic light scattering method obtained by diluting the silica particles (b2) with a good dispersion solvent.

The primer composition (b) is used for forming the primer layer (B). The primer composition (b) contains the primer resin (b1) and silica particles (b2), but may further contain a cross-linking agent (b3), if necessary. As the cross-linking agent (b3), a polyvalent carboxylic acid is preferable. Examples of the polyvalent carboxylic acid include trimellitic anhydride, pyromellitic anhydride, maleic anhydride, succinic acid and the like. These cross-linking agents (b3) can be used alone or in combination of two or more. Further, among these cross-linking agents (b3), trimellitic anhydride is preferable because the adhesion can be further improved.

Further, in the primer composition (b) used for forming the primer layer (B), another resin (b4) is blended as a component other than the above components (b1) to (b3), if necessary. May be. Examples of the other resin (b4) include urethane resin, acrylic resin, blocked isocyanate resin, melamine resin, phenol resin and the like. These other resins (b4) can be used alone or in combination of two or more.

Further, it is preferable to add an organic solvent to the primer composition (b) in order to have a viscosity that makes it easy to apply the support (A). Examples of the organic solvent include toluene, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isopropyl alcohol, diacetone alcohol, ethylene glycol, toluene and the like. These solvents may be used alone or in combination of two or more.

The amount of the organic solvent used is preferably adjusted as appropriate according to the coating method used when coating the support (A), which will be described later, and the desired film thickness of the primer layer (B).

Further, if necessary, known additives such as a film forming aid, a leveling agent, a thickener, a water repellent agent, an antifoaming agent, and an antioxidant are appropriately added to the primer composition (b). May be.

The primer layer (B) is coated with the primer composition (b) on a part or all of the surface of the support (A) to remove the organic solvent contained in the primer composition (b). Can be formed by

As a method of applying the primer composition (b) to the surface of the support (A), for example, a gravure method, a coating method, a screen method, a roller method, a rotary method, a spray method, a capillary method and the like can be used. Can be mentioned.

As a method of applying the primer composition (b) to the surface of the support (A) and then removing the organic solvent contained in the coating layer, for example, the primer composition (b) is dried using a dryer and the organic solvent is removed. The method of volatilizing is common. The drying temperature may be set to a temperature within a range in which the organic solvent used can be volatilized and the support (A) is not adversely affected by thermal deformation or the like.

The film thickness of the primer layer (B) formed by using the primer composition (b) varies depending on the application for which the laminate of the present invention is used, but the support (A) and the metal particle layer (C) described later are used. The range for further improving the adhesion of the primer layer is preferable, and the film thickness of the primer layer is preferably in the range of 10 nm to 30 μm, more preferably in the range of 10 nm to 1 μm, and further preferably in the range of 10 nm to 500 nm.

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

The metal particle layer (C) is formed on the primer layer (B), and examples of the metal constituting the metal particle layer (C) include transition metals or compounds thereof, and among them, ionicity. Transition metals are preferred. Examples of this ionic transition metal include copper, silver, gold, nickel, palladium, platinum, cobalt and the like. Among these, silver is preferable because the metal plating layer (D) is easily formed.

Examples of the metal constituting the metal plating layer (D) include copper, gold, silver, nickel, chromium, cobalt, tin and the like. Among these, copper is preferable because a laminate that has low electrical resistance and can be used for a printed wiring board that is resistant to corrosion can be obtained.

As a method for producing a laminated body of the present invention, first, a primer layer (B) is formed on a support (A), and then a fluid containing metal particles (c) is coated to form the fluid. Examples thereof include a method of forming a metal particle layer (C) by removing an organic solvent and the like contained therein by drying, and then forming the metal plating layer (D) by electrolytic plating, electroless plating, or both. Be done.

The shape of the metal particles (c) used for forming the metal particle layer (C) is preferably particulate or fibrous. Further, the size of the metal particles (c) is preferably nano-sized. Specifically, when the metal particles (c) are in the form of particles, a fine conductive pattern can be formed and the resistance value can be further reduced, so that the average particle diameter is preferably in the range of 1 to 100 nm. The range of ~ 50 nm is more preferable. This average particle diameter means the same as that described in the silica particles (b2), but "Nanotrack UPA-150" manufactured by Microtrac Co., Ltd. can be used for the measurement.

On the other hand, even when the shape of the metal particles (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 in the range of 5 to 100 nm or less, preferably 5 to 50 nm. It is more preferable that the range is less than or equal to the range of. The length of the fiber is preferably in the range of 0.1 to 100 μm or less, more preferably in the range of 0.1 to 30 μm.

The content of the metal particles (c) in the fluid is preferably in the range of 1 to 90% by mass, more preferably in the range of 1 to 60% by mass, still more preferably in the range of 1 to 10% by mass.

The components that may be blended in the fluid include a dispersant and a solvent for dispersing the metal particles (c) in a solvent, and if necessary, a surfactant, a leveling agent, and a viscosity modifier described later. , Film forming aids, antifoaming agents, preservatives and the like.

In order to disperse the metal particles (c) in a solvent, it is preferable to use a dispersant. Examples of the dispersant include dodecanethiol, 1-octanethiol, triphenylphosphine, dodecylamine, polyethylene glycol, polyvinylpyrrolidone, polyethyleneimine, polyvinylpyrrolidone; fatty acids such as myristic acid, octanoic acid and stearic acid; Examples thereof include polycyclic hydrocarbon compounds having a carboxyl group such as glycyrrhizic acid and avietic acid. Among these, the polymer dispersant is preferable because the adhesion between the metal particle layer (C) and the metal plating layer (D) described later can be improved by making the metal particle layer (C) porous. As the polymer dispersant, polyalkyleneimine such as polyethyleneimine and polypropyleneimine, a compound in which polyoxyalkylene is added to the polyalkyleneimine, a urethane resin, an acrylic resin, a urethane resin and a phosphoric acid group in the acrylic resin. Examples thereof include compounds containing.

As described above, by using the polymer dispersant as the dispersant, the dispersant in the metal particle layer (C) is removed to make it porous as compared with the low molecular weight dispersant, and the void size thereof is obtained. Can be increased, and voids having a size of nano-order to sub-micron order can be formed. The voids are easily filled with the metal constituting the metal plating layer (D) described later, and the filled metal serves as an anchor to improve the adhesion between the metal particle layer (C) and the metal plating layer (D) described later. It can be greatly improved.

The amount of the dispersant used for dispersing the metal particles (c) is preferably in the range of 0.01 to 50 parts by mass, preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the metal particles (c). The range of parts is more preferable.

Further, for the purpose of further improving the adhesion between the metal particle layer (C) and the metal plating layer (D) described later, the dispersant is removed by firing to form the porous metal layer (C). In this case, the range of 0.1 to 10 parts by mass is preferable, and the range of 0.1 to 5 parts by mass is more preferable with respect to the range of 100 parts by mass of the metal particles (c).

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-exchanged water, pure water, ultrapure water and the like. Examples of the organic solvent include alcohol compounds, ether compounds, ester compounds, ketone compounds and the like.

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, and tridecanol. Tetradecanol, pentadecanol, stearyl alcohol, allyl alcohol, cyclohexanol, terpineol, turpineol, dihydroterpineol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol Monobutyl 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, Examples thereof include tripropylene glycol monobutyl ether.

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

As the surfactant, a general surfactant can be used, for example, di-2-ethylhexyl sulfosuccinate, dodecylbenzene sulfonate, alkyldiphenyl ether disulfonate, alkylnaphthalene sulfonate, hexamethaphosphate. Examples include salt.

As the leveling agent, a general leveling agent can be used, and examples thereof include silicone-based compounds, acetylenediol-based compounds, and fluorine-based 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 alkaline, or a urethane that can be thickened by associating molecules. Examples thereof include resins, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, polyvinyl alcohol, water-added castor oil, amido wax, polyethylene oxide, metal soap, dibenzylidene sorbitol and the like.

As the film-forming auxiliary, a general film-forming auxiliary can be used, for example, an anionic surfactant (dioctylsulfosuccinate sodium salt, etc.), a hydrophobic nonionic surfactant (sorbitan monooleate, etc.). Etc.), polyether-modified siloxane, silicone oil, etc.

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

As the preservative, a general preservative can be used, and examples thereof include isothiazoline-based preservatives, triazine-based preservatives, imidazole-based preservatives, pyridine-based preservatives, azole-based preservatives, and pyrithione-based preservatives. Can be mentioned.

The viscosity of the fluid (value measured using a B-type viscometer at 25 ° C.) is preferably in the range of 0.1 to 500,000 mPa · s, more preferably in the range of 0.2 to 10,000 mPa · s. .. Further, when the fluid is coated (printed) by a method such as an inkjet printing method or letterpress reverse printing described later, its viscosity is preferably in the range of 5 to 20 mPa · s.

Examples of the method of coating or printing the fluid on the primer layer (B) include an inkjet printing method, a reverse printing method, a screen printing method, an offset printing method, a gravure printing method, a flexo printing method, and pad printing. Examples thereof include a method, a spin coat method, a spray coat method, a bar coat method, a die coat method, a slit coat method, a roll coat method, a dip coat method, a rotary coat method, and a capillary coat method.

Mass per unit area of the metal particle layer (C) is preferably in the range of 1~30,000mg / ^{m 2,} the range of 1~5,000mg / ^{m 2} is preferred. The thickness of the metal particle layer (C) can be adjusted by controlling the treatment time, the current density, the amount of the plating additive used, and the like in the plating treatment step when the metal plating layer (D) is formed.

The metal-plated 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, it is possible to maintain good electrical conductivity without causing disconnection or the like for a long period of time. It is a layer provided for the purpose of forming a highly high-quality wiring pattern.

The metal plating layer (D) is a layer formed on the metal particle layer (C), and a method of forming the metal plating layer (D) by a plating treatment is preferable. Examples of this 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). Moreover, you may combine two or more of these plating methods. For example, the metal plating layer (D) may be formed by electroless plating and then electroplating.

In the above electroless plating method, for example, the metal constituting the metal particle layer (C) is brought into contact with the electroless plating solution to precipitate a metal such as copper contained in the electroless plating solution and form a metal film. It is a method of forming an electroless plating layer (film) composed of.

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

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

Further, as the electroless plating solution, if necessary, monocarboxylic acids such as acetic acid and formic 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 acid, gluconic acid and citric acid; amino acid compounds such as glycine, alanine, iminodiacetic acid, arginine, aspartic acid and glutamate; Contains an organic acid such as an aminopolycarboxylic acid compound, or a complexing agent such as a soluble salt of these organic acids (sodium salt, potassium salt, ammonium salt, etc.), an amine compound such as ethylenediamine, diethylenetriamine, triethylenetetramine, etc. Things can be used.

In the electroless plating method, for example, the metal constituting the metal particle layer (C) or the surface of the electroless plating layer (film) formed by the electroless treatment is energized in a state where the electroless plating solution is in contact with the surface. By doing so, the metal such as copper contained in the electroless plating solution is placed on the cathode, and the metal particles (c) constituting the metal particle layer (C) or the electroless plating layer formed by the electroless treatment. This is a method of forming an electrolytic plating layer (metal film) by precipitating it on the surface of the (film).

Examples of the electrolytic plating solution include those containing a sulfide of a metal such as copper, nickel, chromium, cobalt, and tin, sulfuric acid, and an aqueous medium. Specific examples thereof include those containing copper sulfate, sulfuric acid, and an aqueous medium.

The electroless plating solution and the electrolytic plating solution are preferably used in the range of 20 to 98 ° C.

As a method for forming the metal plating layer (D), since it is easy to control the film thickness of the metal plating layer (D) to a desired film thickness from a thin film to a thick film, electroless plating is performed after the metal plating layer (D) is formed. The method of applying electrolytic plating is preferable.

The film thickness of the metal plating layer (D) is preferably 1 μm or more and 50 μm or less. The film thickness of the metal plating layer (D) is adjusted by controlling the processing time, current density, amount of plating additive used, etc. in the plating processing step when the metal plating layer (D) is formed. Can be done.

Examples of the patterning method of the metal plating layer (D) include a photolitho-etching method such as a subtractive method and a semi-additive method, and a method of plating on a printing pattern of the metal particle layer (C).

In the subtractive method, an etching resist layer having a shape corresponding to a desired pattern shape is formed on the metal plating layer (D) constituting the laminated body of the present invention manufactured in advance, and the subsequent development treatment is performed. This is a method of forming a desired pattern by dissolving and removing the metal plating layer (D) and the metal particle layer (C) of the removed portion of the resist with a chemical solution. As the chemical solution, a chemical solution containing copper chloride, iron chloride or the like can be used.

In the semi-additive method, the primer layer (B) and the metal particle layer (C) are formed on the support (A), surface treatment is performed as necessary, and then the surface thereof is desired. The metal plating layer (D) was formed by an electroless plating method, an electrolytic plating method, or a combination thereof, and then contacted with the plating resist layer. This is a method of forming a desired pattern by dissolving and removing the metal particle layer (C) in a chemical solution or the like.

Further, as a method of plating on the printing pattern of the metal particle layer (C), the metal is formed on the primer layer (B) formed on the support (A) by an inkjet method, an inversion printing method or the like. After printing the pattern of the particle layer (C) and performing surface treatment by plasma discharge treatment or the like as necessary, the surface of the formed metal particle layer (C) is subjected to an electroless plating method, an electrolytic plating method, or an electrolytic plating method. It is a method of forming a desired pattern by forming the metal plating layer (D) by a combination thereof.

The laminate of the present invention obtained as described above 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, and an organic EL. It can be suitably used as an element, an organic transistor, an RFID such as a non-contact IC card, an electromagnetic wave shield, an LED lighting substrate, and an electronic member such as digital signage. In particular, it is most suitable for flexible printed wiring board applications such as FCCL.

Hereinafter, the present invention will be described in detail with reference to Examples. The present invention is not limited to the following examples.

(Manufacturing Example 1: Production of Primer Resin (1) / Melamine Resin)
In a reaction flask equipped with a reflux cooler, a thermometer and a stirrer, 600 parts by mass of formalin containing 37% by mass of formaldehyde and 7% by mass of methanol (formalin content: 222 parts by mass (7.4 mol), methanol content:: To 42 parts by mass (1.31 mol)), 200 parts by mass of water and 350 parts by mass (10.92 mol) of methanol were added to prepare a uniform solution. Next, a 25% by mass sodium hydroxide aqueous solution was added to adjust the pH to 10, then 310 parts by mass (2.46 mol) of melamine was added, the liquid temperature was raised to 85 ° C., and a methylolation reaction was carried out (reaction time: 1 hour). ).

Then, formic acid was added to adjust the pH to 7, and then the mixture was cooled to 60 ° C. and subjected to an etherification reaction. A 25% by mass sodium hydroxide aqueous solution was added at a cloudiness temperature of 40 ° C. to adjust the pH to 9, and the etherification reaction was stopped (reaction time: 1 hour). Residual methanol was removed under reduced pressure at a temperature of 50 ° C. (methanol removal time: 4 hours). Then, methyl ethyl ketone was added to obtain a melamine resin solution having a non-volatile content of 2% by mass.

(Manufacturing Example 2: Production of Primer Resin (2) / Urethane-Acrylic Composite Resin)
A polyester polyol (a polyester polyol obtained by reacting 1,4-cyclohexanedimethanol, neopentyl glycol, and adipic acid) in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer. 100 parts by mass, 17.6 parts by mass of 2,2-dimethylolpropionic acid, 21.7 parts by mass of 1,4-cyclohexanedimethanol, and 106.2 parts by mass of dicyclohexylmethanediisocyanate are reacted in 178 parts by mass of methyl ethyl ketone. As a result, an organic solvent solution of a urethane prepolymer having an isocyanate group at the terminal was obtained.

Next, 13.3 parts by mass of triethylamine is added to the organic solvent solution of the urethane resin to neutralize a part or all of the carboxyl groups of the urethane resin, and 380 parts by mass of water is further added and sufficiently stirred. To obtain an aqueous dispersion of urethane resin.

Next, 8.8 parts by mass of a 25% by mass ethylenediamine aqueous solution was added to the aqueous dispersion, and the mixture was stirred to extend the chain of the particulate polyurethane resin, and then the aging / solvent removal was performed to obtain a non-volatile content of 30% by mass. An aqueous dispersion of% urethane resin was obtained. The weight average molecular weight of the urethane resin was 53,000.

Next, 140 parts by mass of deionized water was placed in a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, a thermometer, a dropping funnel for dropping a monomer mixture, and a dropping funnel for dropping a polymerization catalyst. 100 parts by mass of the aqueous dispersion of the above was added, and the temperature was raised to 80 ° C. while blowing nitrogen.

In a reaction vessel heated to 80 ° C., a monomer mixture consisting of 60 parts by mass of methyl methacrylate, 30 parts by mass of n-butyl acrylate and 10 parts by mass of Nn-butoxymethylacrylamide and ammonium persulfate under stirring 20 parts by mass of an aqueous solution (concentration: 0.5% by mass) was added dropwise from a separate dropping funnel over 120 minutes while maintaining the temperature inside the reaction vessel at 80 ± 2 ° C. for polymerization.

After the completion of the dropping, the mixture was stirred at the same temperature for 60 minutes to obtain a urethane-acrylic composite resin composed of the shell layer of the urethane resin and the core layer of the acrylic resin.

Next, after cooling the temperature inside the reaction vessel to 40 ° C., deionized water was added so that the non-volatile content was 2% by mass, and the mixture was filtered through a 200-mesh filter cloth to disperse the urethane-acrylic composite resin in water. Obtained liquid.

(Production Example 3: Production of Primer Resin (3) / Mixed Resin of Aminotriazine-Modified Novolac Resin and Epoxy Resin)
Add 750 parts by mass of phenol, 75 parts by mass of melamine, 346 parts by mass of 41.5% by mass of formalin, and 1.5 parts by mass of triethylamine to a flask equipped with a thermometer, a cooling tube, a fractionation tube, and a stirrer to generate heat. The temperature was raised to 100 ° C. with caution. After reacting at 100 ° C. under reflux for 2 hours, the temperature was raised to 180 ° C. over 2 hours while removing water under normal pressure. Then, unreacted phenol was removed under reduced pressure to obtain an aminotriazine-modified novolak resin. The hydroxyl group equivalent was 120 g / equivalent.

Next, 65 parts by mass of aminotriazine-modified novolak resin and 35 parts by mass of epoxy resin (“EPICLON 850-S” manufactured by DIC Co., Ltd .; bisphenol A type epoxy resin, epoxy group equivalent 188 g / equivalent) are mixed, and then non-volatile with methyl ethyl ketone. A mixed resin solution of an aminotriazine-modified novolak resin and an epoxy resin was obtained by diluting the mixture to a content of 2% by mass and mixing uniformly.

(Production Example 4: Production of Primer Resin (4) / Blocked Polyisocyanate)
In a nitrogen-substituted reaction vessel equipped with a thermometer, a nitrogen gas introduction tube and a stirrer, 6.3 parts by mass of 2,2-dimethylolpropionic acid and a nurate compound of 4,4'-diphenylmethane diisocyanate 71.1. An isocyanate compound was prepared by reacting with parts by mass in methyl ethyl ketone, and then a solvent solution of blocked polyisocyanate was prepared by supplying 17.8 parts by mass of phenol as a blocking agent to the reaction vessel and reacting.

Next, 4.8 parts by mass of triethylamine was added to the solvent solution of the blocked polyisocyanate to neutralize the carboxyl group of the blocked polyisocyanate. Then, methyl ethyl ketone was added to obtain a blocked polyisocyanate solution having a non-volatile content of 2% by mass.

(Production Example 5: Production of silica particles (1) treated with a silane coupling agent)
A flask equipped with a thermometer, a cooling tube, and a stirrer is charged with 500 parts by mass of a silica particle dispersion (“Snowtex-OL” manufactured by Nissan Chemical Industries, Ltd .; average particle diameter 45 nm, non-volatile content 20% by mass) at 50 ° C. The temperature was raised to. Then, 20 parts by mass of a silane coupling agent containing an epoxy group (“KBM-402” manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropylmethyldimethoxysilane, non-volatile content 100% by mass) was added. After confirming the heat generation, the mixture was stirred at 50 ° C. for 24 hours. Then, the mixture was cooled to 30 ° C., diluted with isopropyl alcohol so that the non-volatile content was 2% by mass, and mixed uniformly to obtain a dispersion liquid of silica particles (1).

(Production Example 6: Production of silica particles (2) treated with a silane coupling agent)
The silane coupling agent used in Production Example 5 is a silane coupling agent containing an epoxy group (“KBM-303” manufactured by Shin-Etsu Chemical Co., Ltd., 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, non-volatile. A dispersion of silica particles (2) having a non-volatile content of 2% by mass was obtained by the same method except that the content was changed to 100% by mass.

(Production Example 7: Production of silica particles (3) treated with a silane coupling agent)
The silane coupling agent used in Production Example 5 is a silane coupling agent containing an amino group (“KBM-573” manufactured by Shin-Etsu Chemical Co., Ltd., N-phenyl-3-aminopropyltrimethoxysilane, non-volatile content 100 mass). %) Was used in the same manner to obtain a dispersion of silica particles (3) having a non-volatile content of 2% by mass.

(Production Example 8: Production of silica particles (4) treated with a silane coupling agent)
The silane coupling agent used in Production Example 5 is a silane coupling agent containing a methacryl group (“KBE-502” manufactured by Shin-Etsu Chemical Co., Ltd., 3-methacryloxypropylmethyldiethoxysilane, non-volatile content 100% by mass). A dispersion liquid of silica particles (4) having a non-volatile content of 2% by mass was obtained by the same method except that it was changed to.

(Preparation Example 1: Preparation of Primer Composition (1))
To 100 parts by mass of the melamine resin solution having a non-volatile content of 2% by mass obtained in Production Example 1, 1 part by mass of the dispersion liquid of the silica particles (1) obtained in Production Example 5 was added and mixed for 30 minutes to form a primer composition. I got the thing (1).

(Preparation Example 2: Preparation of Primer Composition (2))
To 100 parts by mass of the aqueous dispersion of the urethane-acrylic composite resin having a non-volatile content of 2% by mass obtained in Production Example 2, 5 parts by mass of the dispersion of the silica particles (1) obtained in Production Example 5 was added to 30 parts. Mixing for minutes gave the primer composition (2).

(Preparation Example 3: Preparation of Primer Composition (3))
To 100 parts by mass of the mixture solution of aminotriazine-modified novolak and epoxy resin having a non-volatile content of 2% by mass obtained in Production Example 3, 10 parts by mass of the dispersion liquid of the silica particles (1) obtained in Production Example 5 was added. Mixing for 30 minutes gave the primer composition (3).

(Preparation Example 4: Preparation of Primer Composition (4))
To 100 parts by mass of the mixed resin solution of the aminotriazine-modified novolak resin and the epoxy resin having a non-volatile content of 2% by mass obtained in Production Example 3, 25 parts by mass of the dispersion liquid of the silica particles (2) obtained in Production Example 6 was added. Then, it was mixed for 30 minutes to obtain a primer composition (4).

(Preparation Example 5: Preparation of Primer Composition (5))
To 100 parts by mass of the mixed resin solution of the aminotriazine-modified novolak resin and the epoxy resin having a non-volatile content of 2% by mass obtained in Production Example 3, 75 parts by mass of the dispersion liquid of the silica particles (2) obtained in Production Example 6 was added. Then, it was mixed for 30 minutes to obtain a primer composition (5).

(Preparation Example 6: Preparation of Primer Composition (6))
To 100 parts by mass of the blocked polyisocyanate solution having a non-volatile content of 2% by mass obtained in Production Example 4, 150 parts by mass of the dispersion liquid of the silica particles (3) obtained in Production Example 7 was added, mixed for 30 minutes, and mixed with a primer. The composition (6) was obtained.

(Preparation Example 7: Preparation of Primer Composition (7))
To 100 parts by mass of the melamine resin solution having a non-volatile content of 2% by mass obtained in Production Example 1, 400 parts by mass of the dispersion liquid of the silica particles (4) obtained in Production Example 8 was added and mixed for 30 minutes to form a primer composition. I got the thing (7).

(Preparation Example 8: Preparation of Primer Composition (R1))
The mixed resin solution of the aminotriazine-modified novolak resin and the epoxy resin obtained in Production Example 3 having a non-volatile content of 2% by mass was used as the primer composition (R1) without adding the silica particle dispersion.

(Preparation Example 9: Preparation of Primer Composition (R2))
Silica particle dispersion (“Snowtex-OL” manufactured by Nissan Chemical Industries, Ltd .; average particle diameter 45 nm, non-volatile content 20% by mass) is diluted with isopropyl alcohol so as to have a non-volatile content of 2% by mass, and treated with a silane coupling agent. 75 parts by mass of untreated silica particles were prepared. These silica particles are added to 100 parts by mass of a mixed resin solution of an aminotriazine-modified novolak resin and an epoxy resin having a non-volatile content of 2% by mass obtained in Production Example 3, and mixed for 30 minutes for use as a primer composition (R2). board.

(Preparation Example 10: Preparation of fluid (1))
According to Example 1 described in Japanese Patent No. 4573138, a cationic silver nano composed of a grayish green metallic glossy flake-like mass which is a composite of silver nanoparticles and an organic compound having a cationic group (amino group). Obtained particles. Then, the powder of the 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) containing 5% by mass of cationic silver nanoparticles. ..

(Example 1)
On the surface of a polyimide film (“Kapton 50EN-C” manufactured by Toray DuPont Co., Ltd .; thickness 12.5 μm), the primer composition (1) obtained in Preparation Example 1 was applied to a desktop compact coater (RK print coat instrument). Using a "K printing loafer" manufactured by the same company, the coating was applied so that the thickness after drying was 100 nm. 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 dryer.

The fluid (1) obtained above was coated on the surface of the primer layer formed above using a bar coater. Then, by drying at 200 ° C. for 5 minutes, a silver layer (thickness 100 nm) corresponding to the metal particle layer (C) was formed.

The silver layer obtained above is set on the cathode side, phosphorus-containing copper is set on the anode side, and electrolytic plating is performed for 30 minutes at ^{a current density of 2.5 A / dm 2 using an electrolytic plating solution containing copper sulfate.} As a result, a copper plating layer (thickness 15 μm) by electrolytic copper plating was formed on the surface of the copper plating layer by electrolytic 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 Lucina SF-M” manufactured by Okuno Pharmaceutical Co., Ltd.) were used. The combination of the copper plating layer by electrolytic copper plating and the copper plating layer by electrolytic copper plating formed on the copper plating layer corresponds to the metal plating layer (D).

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

(Examples 2 to 7, Comparative Examples 1 and 2)
The laminated body (1) was subjected to the same method as in Example 1 except that the primer composition (1) used in Example 1 was changed to the primer compositions (2) to (7), (R1) or (R2). 2) to (7), (R1) and (R2) were obtained.

The following measurements and evaluations were performed on the laminates (1) to (7), (R1) and (R2) obtained in Examples 1 to 7 and Comparative Examples 1 and 2 above.

[Measurement of peel strength before heating]
The peel strength of each of the above-mentioned laminates was measured using "Autograph AGS-X 500N" manufactured by Shimadzu Corporation. The lead width used for the 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 measured value at the thickness of the metal plating layer of 15 μm.

[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 value of peel strength is 650 N / m or more.
B: The value of the peel strength is 450 N / m or more and less than 650 N / m.
C: The value of the peel strength is 250 N / m or more and less than 450 N / m.
D: The value of the peel strength is less than 250 N / m.

[Measurement of peel strength after heating]
Each of the above-mentioned laminates was stored in a dryer set at 150 ° C. for 300 hours and heated. After heating, the peel strength was measured by the same method as above.

[Evaluation of heat resistance]
Using the peel strength values before and after heating measured above, the retention rate before and after heating was calculated, and the 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%.

Table 1 shows the composition of the primer compositions used in Examples 1 to 7, the measurement results of the peel strength before and after heating, and the evaluation results of adhesion and heat resistance. The composition of the primer composition shows only the non-volatile content.

It was confirmed that the laminates (1) to (7) obtained in Examples 1 to 7, which are the laminates of the present invention, had high initial peel strength (before heating) and excellent adhesion. In addition, it was confirmed that the peel strength was slightly reduced after the heat resistance test at 150 ° C. for 300 hours, and the heat resistance and adhesion were excellent.

On the other hand, the laminate (R1) obtained in Comparative Example 1 is an example using a primer layer containing no silica particles, and although the initial peel strength (before heating) is relatively high, it is at 150 ° C. for 300 hours. It was confirmed that the peel strength after the heat resistance test was significantly reduced and the heat resistance and adhesion were inferior.

Further, the laminate (R2) obtained in Comparative Example 2 is an example using a primer layer containing silica particles not treated with a silane coupling agent, but the initial peel strength (before heating) is low. As a result, the retention rate of the peel strength after the heat resistance test at 150 ° C. for 300 hours was high.

Claims (9)

A laminate in which a primer layer (B) and a metal particle layer (C) are sequentially laminated on a support (A), and the primer layer (B) is a primer resin (b1) and a silane coupling agent. A laminate characterized by being a layer containing the treated silica particles (b2). The laminate according to claim 1, wherein the content of the silica particles (b2) in the primer layer (B) is in the range of 1 to 400 parts by mass with respect to 100 parts by mass of the primer resin (b1). The laminate according to claim 1 or 2, wherein the silica particles (b2) have an average particle diameter of 0.001 to 0.5 μm. The laminate according to any one of claims 1 to 3, wherein the metal plating layer (D) is further laminated on the metal particle layer (C). The laminate according to any one of claims 1 to 4, wherein the primer resin (b1) contains an aminotriazine-modified novolak resin. A printed wiring board having the laminate according to any one of claims 1 to 5. The flexible printed wiring board according to any one of claims 1 to 5, wherein the support (A) is a film. An electromagnetic wave shield comprising the laminate according to any one of claims 1 to 5. A molded product having the laminate according to any one of claims 1 to 5.