TW201908427A - Laminated body, printed wiring board using the same, flexible printed wiring board, and molded article - Google Patents

Abstract

The present invention provides: a laminated body which has a primer layer (B), a metallic nanoparticle layer (C), and a metal plating layer (D) layered in order on a support body (A), and which is characterized in that the primer layer (B) contains a compound (b1) having an aminotriazine ring; a printed wiring board using the laminated body; a flexible printed wiring board; and a molded article. The laminated body can be produced by a simple method without involving roughening of a surface of the support body, and provides excellent adhesion between the support body and the metal layer (metal plated layer).

Description

   Laminated body, printed wiring board using it, flexible printed wiring board, and molded article   

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

With the miniaturization and high speed of electronic devices, high density and high performance of printed wiring boards are required. To meet this demand, printed wiring boards with smooth surfaces and sufficiently thin conductive layers (metal layers) are required. Further, as a constituent of this printed wiring board, a flexible copper-clad laminated board (hereinafter, referred to as "FCCL") is known. FCCL is mainly manufactured by a method of bonding a heat-resistant polymer film and a copper foil using an epoxy-based adhesive.

However, in the FCCL using this copper foil, the copper foil cannot be sufficiently thin in operation because it is attached while pulling out the rolled copper foil. In addition, in order to improve the adhesion with the polymer film, the surface of the copper foil must be roughened. Therefore, there are high frequency (GHz band), high frequency required for high density and high performance of printed wiring boards. A problem of transmission loss occurs in a transmission speed (tens of Gbps) range.

Here, as a method for thinning the copper layer of FCCL, there is a proposal to form a metal thin film on the surface of a polyimide film by a vapor deposition method or a sputtering method, and then use the plating method on the metal thin film, A method for forming copper by an electroless plating method or a combination of both methods (for example, refer to Patent Document 1). However, in this method, in order to form a metal thin film, a vapor deposition method or a sputtering method is used. Therefore, large-scale vacuum equipment is required, and there is a problem that the size of the substrate is limited on the equipment.

Therefore, it is required to have sufficient adhesion with a support such as a polymer film under the surface of a metal layer such as a copper foil that is not roughened, and large-scale vacuum equipment is not required when the metal layer is formed. A laminated body that can be manufactured by a simple method.

In addition, conventionally, it is used for decorative plating of plastic molded articles in mobile phones, personal computers, mirrors, containers, various switches, shower heads, and the like. Support systems for these applications are limited to acrylonitrile-butadiene-styrene copolymers (hereinafter, referred to as "ABS") or polymer blends of ABS and polycarbonate (hereinafter, referred to as "ABS-PC") . The reason is that in order to ensure the adhesion between the substrate and the plating film, the surface of the substrate must be roughened. For example, if it is ABS, it can be etched with a strong oxidant such as hexavalent chromic acid and permanganate. 3. Remove the polybutadiene component and roughen the surface. However, since hexavalent chromic acid and the like are environmentally hazardous substances, they are preferably not used, and alternative methods have been developed so far (for example, refer to Patent Document 2).

In this way, in the plating for the purpose of decoration of plastic molded products, the base material is not limited to ABS or ABS-PC, and even if it is other types of plastic, a plating film with excellent adhesion is obtained. It also reduces the amount of environmentally hazardous substances used.

Prior art literature Patent literature

Patent Document 1 Japanese Patent Application Publication No. 2015-118044

Patent Document 2 Japanese Patent Publication No. 5830807

The problem to be solved by the present invention is to provide a laminated body which can be manufactured by a simple method without roughening the surface of the support body, and which has excellent adhesion between the support body and a metal layer (metal plating layer), and use the same. Printed wiring boards, flexible printed wiring boards, and molded products.

The present inventors have intensively studied in order to solve the above-mentioned problems, and as a result, have found that the support layer, as a primer layer, The layer of the cyclic compound has a laminated body formed of a metal layer and a metal plating layer formed of metal nano particles in this order, which solves the above-mentioned problems and completes the present invention.

That is, the present invention provides a laminated body, a printed wiring board using the same, a flexible printed wiring board, and a molded article. The laminated system is sequentially laminated on the support (A) with a primer layer (B) and a metal nano. The laminated body of the particle layer (C) and the metal plating layer (D) is characterized in that the primer layer (B) contains A layer of the cyclic compound (b1).

Even if the laminated system of the present invention does not roughen the surface of the support, the adhesion between the support and the metal layer (metal plating layer) is excellent. In addition, when the metal layer is formed into a thin film, it is a laminated body having a smooth surface and a sufficiently thin metal layer without using a large-scale vacuum equipment.

The multilayer system of the present invention is suitable for use as a printed wiring board, a flexible printed wiring board, a conductive film for a touch panel, a metal grid for a touch panel, or an organic solar cell by patterning a metal layer. Electronic components such as RFID for batteries, organic EL elements, organic transistors, non-contact IC cards, electromagnetic wave barriers, LED lighting substrates, and digital signage. In particular, it is most suitable for flexible printed wiring boards such as FCCL.

In addition, by applying it to molded products, it can be suitably used for electronic components such as connectors, electrical components, electric motor peripheral components, battery components, etc. for connecting optical communication wiring; automotive decorative parts, lamp reflectors, mobile phones, Decoration for personal computers, mirrors, containers, home appliances, various switches, faucet parts, shower heads, etc.

A form for implementing the invention

The laminated system of the present invention is a laminated body having a primer layer (B), a metal nanoparticle layer (C), and a metal plating layer (D) laminated on the support (A) in this order, wherein the aforementioned primer layer ( B) contains three amino groups A layer of the cyclic compound (b1).

The laminated system of the present invention may be a laminated body having a primer layer (B) and the like laminated in order on one side of the aforementioned support (A), or may be laminated on both sides of the aforementioned support (A) in order. Laminated body of lacquer layer (B).

Examples of the support (A) include polyimide, polyimide, imine, polyimide, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, and the like. Acrylonitrile-butadiene-styrene (ABS) resin, polymer blend of ABS and polycarbonate, acrylic resin such as poly (meth) acrylate, polytetrafluoroethylene, polyvinylidene fluoride, Polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polycarbonate, polyethylene, polypropylene, polyurethane, liquid crystal polymer (LCP), polyetheretherketone (PEEK), polyphenylene sulfide (PPS), polyphenylene terephthalate (PPSU), epoxy resin, cellulose nanofiber, silicon, ceramic, glass, etc. support, porous support made of them, steel plate, Supports made of metals such as copper, and supports having silicon carbide, diamond-like carbon, aluminum, copper, titanium, and the like are vapor-deposited on their surfaces.

Moreover, when using the laminated body of this invention for a printed wiring board etc., as said support body (A), it is preferable to use polyimide, polyethylene terephthalate, and polyethylene naphthalate. , Liquid crystal polymer (LCP), polyether ether ketone (PEEK), glass, cellulose nanofiber, etc.

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

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

In addition, in order to further improve the adhesion between the support (A) and a primer layer (B) described later, if necessary, the surface of the support (A) can be formed to a degree without loss of smoothness. Fine unevenness, or cleaning the dirt attached to the surface, or surface treatment for the introduction of functional groups such as hydroxyl, carbonyl, and carboxyl groups. Specifically, methods such as plasma discharge treatment such as corona discharge treatment, dry treatment such as ultraviolet light treatment, and wet treatment using an aqueous solution such as water, acid, alkali or the like, or an organic solvent, can be mentioned.

The primer layer (B) contains A layer of the cyclic compound (b1). Amino Tris The cyclic compound (b1) may be a low molecular weight compound or a higher molecular weight resin.

Amine tris Low molecular weight cyclic compounds. Various additives for the ring. Examples of commercially available products include 2,4-diamino-6-vinyl-s-tri ("VT" by Shikoku Chemical Co., Ltd.), "VD-3" or "VD-4" by Shikoku Chemical Co., Ltd. Ring and hydroxy compound), Shikoku Chemical Co., Ltd. "VD-5" (with amine tris Ring and ethoxysilyl compounds) and the like. These additives may be used singly or in combination of two or more kinds.

Use the aforementioned In the case of a cyclic low-molecular-weight compound, it is preferable to use a resin for forming the primer layer (B). Examples of the resin used at this time include a urethane resin, an acrylic resin, a urethane-vinyl composite resin, an epoxy resin, a fluorene imine resin, a fluorene resin, a melamine resin, and a phenol resin. , Urea formaldehyde resin, blocked polyisocyanate using phenol as a blocking agent, polyvinyl alcohol, polyvinylpyrrolidone and the like. These resins may be used singly or in combination of two or more kinds. Among these, from the viewpoint of further improving the adhesion, an epoxy resin is preferable, and a novolak resin and an epoxy resin are more preferably used in combination.

The above-mentioned amine-based tris The use amount of the cyclic low-molecular-weight compound is preferably from 0.1 to 50 parts by mass, more preferably from 0.5 to 10 parts by mass.

Amine tris Examples of cyclic resins include the introduction of amine groups into the polymer chain of the resin by covalent bonds. Ringer. Specifically, aminotris Modified novolac resin (b1-1).

Amino Tris Modified novolac resin (b1-1) based amino Novolak resin in which a ring structure and a phenol structure are bonded via a methylene group. Amino Tris The modified novolac resin (b1-1) can be obtained by, for example, melamine, benzoguanamine, and ethylguanidine. Amine tris Compounds, phenol compounds with phenol, cresol, butylphenol, bisphenol A, phenylphenol, naphthol, resorcinol, etc., and formaldehyde, in the presence of weakly basic catalysts such as alkylamines, or No catalyst, co-condensation reaction near neutrality, or methyl etherification of amine groups such as melamine The alkyl etherate of the compound is obtained by reacting the aforementioned phenol compound.

Amino Tris The modified novolac resin (b1-1) is preferably one having substantially no methylol group. Moreover, in the aforementioned amine group The modified novolac resin (b1-1) may contain only the amine group three produced as a by-product during its production. A molecule having a methylene structure and a molecule having only a phenol structure having a methylene bond. Furthermore, a certain amount of unreacted raw materials may be included.

Examples of the phenol structure include a phenol residue, a cresol residue, a butylphenol residue, a bisphenol A residue, a phenylphenol residue, a naphthol residue, and a resorcinol residue. The term "residue" herein refers to a structure in which at least one hydrogen atom of a carbon bonded to an aromatic ring has been removed. For example, when it is phenol, it means hydroxyphenyl.

As the aforementioned three Examples of the structure include melamine, benzoguanamine, and ethylguanidine Amine tris Structure of the compound.

The aforementioned phenol structure and the aforementioned three Each of the structural systems may be used alone, or two or more of them may be used in combination. From the viewpoint of further improving the adhesion, the phenol structure is preferably a phenol residue. The structure is preferably a structure derived from melamine.

Moreover, the aforementioned amino group tri The hydroxyl value of the modified novolac resin (b1-1) is more preferably from 50 mgKOH / g to 200 mgKOH / g, and more preferably from 80 mgKOH / g to 180 mgKOH / g, and more preferably It is 100 mgKOH / g or more and 150 mgKOH / g or less.

Amino Tris The modified novolac resin (b1-1) may be used alone or in combination of two or more.

In addition, as the aforementioned Cyclic compound (b1) when using aminotris When the novolak resin (b1-1) is modified, it is preferred to use an epoxy resin (b2) in combination.

Examples of the epoxy resin (b2) include bisphenol A epoxy resin, bisphenol F epoxy resin, biphenyl epoxy resin, cresol novolac epoxy resin, and phenol novolac epoxy resin. Resin, bisphenol A novolac type epoxy resin, alcohol ether type epoxy resin, tetrabromobisphenol A type epoxy resin, naphthalene type epoxy resin, has a source from 9,10-dihydro-9-oxa-10 -Phosphaphenanthrene-10-oxide derivatives containing phosphorus-containing epoxy compounds, epoxy resins having a structure derived from dicyclopentadiene derivatives, epoxides such as epoxidized soybean oil and the like. These epoxy resins may be used singly or in combination of two or more kinds.

Among the aforementioned epoxy resins (b2), bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, biphenyl-type epoxy resin, and cresol novolac are preferred from the viewpoint of further improving adhesion. Lacquer-type epoxy resin, phenol novolac-type epoxy resin, bisphenol A novolac-type epoxy resin, particularly preferably bisphenol A-type epoxy resin.

The epoxy equivalent of the epoxy resin (b2) is more preferably from 100 g / equivalent to 300 g / equivalent, and more preferably from 120 g / equivalent to 250 g / equivalent, and more preferably It is 150 g / equivalent or more and 200 g / equivalent or less.

When the aforementioned primer layer (B) contains amine group When the layer of the novolac resin (b1-1) and the epoxy resin (b2) is modified, from the viewpoint of improving the adhesion more, The molar ratio [(y) / (x)] of the phenolic hydroxyl group (x) in the modified novolac resin (b1-1) to the epoxy group (y) in the epoxy resin (b2) is preferably 0.1 or more and 5 or less, more preferably 0.2 or more and 3 or less, and particularly preferably 0.3 or more and 2 or less.

In the formation of the primer layer (B), a primer composition (b) is used. The said primer composition (b) contains the said amine group The cyclic compound (b1) or the epoxy resin (b2) may further contain a crosslinking agent (b3) as necessary. As the crosslinking agent (b3), a polycarboxylic acid is preferably used. Examples of the polycarboxylic acid include trimellitic anhydride, pyromellitic anhydride, maleic anhydride, and succinic acid. These crosslinking agents may be used singly or in combination of two or more kinds. Among these crosslinking agents, trimellitic anhydride is preferred from the viewpoint of further improving the adhesion.

Furthermore, in the primer composition (b) for forming the primer layer (B), if necessary, other resins (b4) may be blended as components other than the above-mentioned components (b1) to (b3). . Examples of the other resin (b4) include a urethane resin, an acrylic resin, a blocked isocyanate resin, a melamine resin, and a phenol resin. These other resin systems may be used alone or in combination of two or more.

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

The usage-amount of the said organic solvent is suitably adjusted according to the coating method used when apply | coating to the said support body (A) mentioned later, and the desired film thickness of the said primer layer (B).

In addition, in the primer composition (b), well-known additives such as a film-forming aid, a leveling agent, a thickener, a water-repellent agent, an antifoaming agent, and an antioxidant may be appropriately added and used as necessary.

The primer layer (B) can be applied to part or all of the surface of the support (A) to coat the primer composition (b) to remove the organic solvent contained in the primer composition (b). And formed.

Examples of the method for applying the primer composition (b) to the surface of the support (A) include a gravure method, a coating method, a screen method, a roll method, a rotation method, a spray method, and a capillary method. method.

After the primer composition (b) is coated on the surface of the support (A), as a method for removing the organic solvent contained in the coating layer, for example, a method of drying with a dryer to volatilize the organic solvent is generally used. . The drying temperature may be set to a temperature within a range that allows the organic solvent used to volatilize and does not cause adverse effects such as thermal deformation to the support (A).

Although the film thickness of the primer layer (B) formed by using the primer composition (b) is different depending on the use of the laminated body of the present invention, it is preferable to further increase the support (A) and to be described later. The thickness of the metal nanoparticle layer (C) ranges from 10 nm to 30 μm, more preferably 10 nm to 1 μm, and even more preferably 10 nm to 500 nm.

In order to further improve the adhesion with the metal nanoparticle layer (C), the surface of the primer layer (B) may be treated by a plasma discharge treatment method such as a corona discharge treatment method or ultraviolet rays as needed. Surface treatment is performed by a dry treatment method such as a treatment method, or 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). As a metal constituting the metal nanoparticle layer (C), a transition metal or a compound thereof is mentioned, and among them, an ion is preferred. Sexual transition metal. Examples of the ionic transition metal include copper, silver, gold, nickel, palladium, platinum, and cobalt. Among these, silver is preferable because the metal plating layer (D) can be easily formed.

Examples of the metal constituting the metal plating layer (D) include copper, gold, silver, nickel, chromium, cobalt, and tin. Among these, from the viewpoint of obtaining a multilayer body usable in a printed wiring board having low resistance and corrosion resistance, copper is preferred.

As a method for manufacturing the laminated body of the present invention, first, a primer layer (B) is formed on the support (A), and then a fluid body containing nano-sized metal nano particles (c) is applied, The metal nanoparticle layer (C) is formed by drying and removing the organic solvent and the like contained in the fluid, and then the metal plating layer (D) is formed by electrolytic plating, electroless plating, or both. ).

The shape of the metal nanoparticle (c) used in the formation of the metal nanoparticle layer (C) is preferably particulate or fibrous. In addition, the size of the metal nano particles (c) is a nano size. Specifically, when the shape of the metal nano particles (c) is particulate, a fine conductive pattern can be formed, and the size can be further improved. From the viewpoint of reducing the resistance value, the average particle diameter is preferably 1 nm to 100 nm, and more preferably 1 nm to 50 nm. The "average particle diameter" refers to a volume average value obtained by diluting the conductive material with a good dispersing solvent and measuring it by a dynamic light scattering method. For this measurement, "Nanotrac UPA-150" manufactured by Microtrac can be used.

On the other hand, it is the same when the shape of the metal nanoparticle (c) is fibrous. From the viewpoint of forming a fine conductive pattern and further reducing the resistance value, the diameter of the fiber is preferably 5 nm to 100 nm. More preferably, it is 5 nm or more and 50 nm or less. The length of the fiber is preferably from 0.1 μm to 100 μm, and more preferably from 0.1 μm to 30 μm.

The content of the metal nanoparticle (c) in the fluid is preferably 1% by mass or more and 90% by mass or less, more preferably 1% by mass or more and 60% by mass or less, and even more preferably 1% by mass or more and 10% by mass. %the following.

Examples of the component to be blended in the fluid include a dispersant or a solvent for dispersing the metal nanoparticle (c) in a solvent, and a surfactant, a leveling agent, and the like described later if necessary. Viscosity adjuster, film-forming aid, defoamer, preservative, etc.

In order to disperse the metal nanoparticle (c) in a solvent, it is preferable to use a low molecular weight or high molecular weight dispersant. Examples of the dispersant include dodecanethiol, 1-octanethiol, triphenylphosphine, dodecylamine, polyethylene glycol, polyvinylpyrrolidone, polyethyleneimine, and polyvinylpyrrole. Pyridone; fatty acids such as myristic acid, caprylic acid, stearic acid; polycyclic hydrocarbon compounds having a carboxyl group, such as cholic acid, glycyrrhizic acid, and abietic acid. Among these, from the viewpoint of improving the adhesion between the metal nanoparticle layer (C) and the metal plating layer (D), a polymer dispersant is preferred. As the polymer dispersant, Examples include polyethylenimines such as polyethyleneimine and polypropyleneimine, compounds obtained by adding polyoxyalkylenes to the polyeneimines, urethane resins, acrylic resins, and the aforementioned urethanes. The resin or the acrylic resin contains a phosphate group-containing compound and the like.

The amount of the dispersant required to disperse the metal nano particles (c) is preferably 0.01 to 50 parts by mass, and more preferably 100 parts by mass of the metal nano particles (c). 0.01 to 10 parts by mass.

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

Examples of the alcohol compound include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutyl alcohol, second butanol, third butanol, heptanol, hexanol, octanol, Nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, stearyl alcohol, allyl alcohol, cyclohexanol, terpineol, terpineol, dihydropine oil Alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether 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, tripropylene glycol monobutyl ether, and the like.

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

As the surfactant, a general surfactant can be used, and examples thereof include di-2-ethylhexylsulfosuccinate, dodecylbenzenesulfonate, alkyldiphenyl ether disulfonate, Alkyl naphthalene sulfonate, hexametaphosphate, etc.

As said leveling agent, a general leveling agent can be used, For example, a polysiloxane type compound, an acetylene glycol type compound, a fluorine type compound, etc. are mentioned.

As the viscosity modifier, a general thickener can be used, and examples thereof include an acrylic polymer or a synthetic rubber latex that can be thickened by adjusting to alkalinity, and an amino methyl ester that can be thickened by molecular association. Ester resin, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, polyvinyl alcohol, hydrogenated castor oil, ammonium wax, oxidized polyethylene, metal soap, dibenzylidene sorbitol, and the like.

As the film-forming aid, a general film-forming aid can be used, and examples thereof include an anionic surfactant (such as sodium dioctyl sulfosuccinate), and a hydrophobic nonionic surfactant (sorbitol). Anhydride monooleate, etc.), polyether modified siloxane, polysiloxane, etc.

As the antifoaming agent, a general antifoaming agent can be used, and examples thereof include a polysiloxane-based antifoaming agent, a nonionic surfactant, a polyether, a higher alcohol, and a polymer-based surfactant.

As the preservative, a general preservative can be used, and examples thereof include an isothiazoline preservative, Preservatives, imidazole preservatives, pyridine preservatives, azole preservatives, iodine preservatives, pyrithione preservatives, etc.

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

Examples of a method for applying or printing the fluid on the primer layer (B) include an inkjet printing method, a reverse printing method, a screen printing method, a lithographic method, a spin coating method, and a spray coating method. , Bar coating method, die coating method, slit coating method, roll coating method, dip coating method, pad printing, flexographic printing method, etc.

Among these coating methods, when forming the aforementioned metal nanoparticle layer (C), which is patterned in a thin line of about 0.01 to 100 μm required to achieve high density of electronic circuits and the like, it is preferably used Inkjet printing method, reverse printing method.

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

In addition, as a reverse printing method, a letterpress reverse printing method and a gravure reverse printing method are known. For example, the surface of various blankets may be coated with the above-mentioned fluid and brought into contact with a plate protruding from a non-printed portion. By selectively transferring the fluid corresponding to the non-printed portion on the surface of the plate, the pattern is formed on the surface of the blanket or the like, and then the pattern is transferred onto the support (A). (Surface) method.

In addition, a pad printing method is known for pattern printing on a three-dimensional molded product. In this system, the ink is placed on the intaglio plate, and the ink is evenly filled in the concave portion by scraping with a scraper. On the plate on which the ink is placed, a pad made of silicone rubber or urethane rubber is pressed. , A method of transferring a pattern to a gasket and transferring it to a three-dimensional molded product.

Mass per unit area of the metal nanoparticle layer (C) is preferably of 1mg / m ² or more 30,000mg / m ² or less, more preferably 1mg / m ² or more 5,000mg / m ² or less. The thickness of the metal nanoparticle layer (C) can be adjusted by controlling the processing time, current density, and the amount of plating additives used in the plating processing step when the metal plating layer (D) is formed. .

The metal plating layer (D) constituting the laminated body of the present invention, for example, when the aforementioned laminated body is used in a printed wiring board or the like, does not cause disconnection or the like for a long period of time, and forms a reliability capable of maintaining good electrical conductivity. A layer provided with a highly efficient wiring pattern.

The metal plating layer (D) is a layer formed on the metal nanoparticle layer (C). As a method for forming the metal plating layer (D), a method of forming the metal plating layer by a plating treatment is preferred. Examples of the plating treatment include a wet plating method such as an electrolytic plating method and an electroless plating method that can easily form the metal plating layer (D). Furthermore, two or more of these plating methods may be combined. For example, after electroless plating is applied, electrolytic plating may be applied to form the aforementioned metal plating layer (D).

The above-mentioned electroless plating method is formed, for example, by contacting an electroless plating solution with the metal constituting the metal nanoparticle layer (C), and depositing metals such as copper contained in the electroless plating solution. A method of an electroless plating layer (film) composed of a metal film.

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

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

In addition, as the electroless plating solution, a monocarboxylic acid containing acetic acid, formic acid, or the like; a dicarboxylic acid compound such as malonic acid, succinic acid, adipic acid, maleic acid, or fumaric acid can be used as needed; apple Acid, lactic acid, glycolic acid, gluconic acid, citric acid and other hydroxycarboxylic acid compounds; glycine, alanine, imino diacetic acid, arginine, aspartic acid, glutamic acid and other amino acid compounds ; Organic acids such as amine polycarboxylic acid compounds such as iminodiacetic acid, nitrotriacetic acid, ethylenediaminediacetic acid, ethylenediaminetetraacetic acid, diethylene glycol triaminepentaacetic acid, or the like Soluble salts (sodium salt, potassium salt, ammonium salt, etc.), amine compounds such as ethylenediamine, ethylenediamine, triethylenetetraamine, etc.

The electroless plating solution is preferably used at 20 ° C to 98 ° C.

The electrolytic plating method is to contact the surface of the electrolytic plating solution by contacting the surface of the electroless plating layer (film) formed on the metal constituting the metallic nanoparticle layer (C) or the electroless treatment. It is energized in a state to cause metals such as copper contained in the electrolytic plating solution to be deposited on a conductive material constituting the metallic nanoparticle layer (C) provided on a cathode, or electroless formed by the electroless treatment. A method for forming an electrolytic plating layer (metal film) on the surface of a plating layer (film).

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

The electrolytic plating solution is preferably used at 20 ° C to 98 ° C.

As the method for forming the metal plating layer (D), it is easy to control the film thickness of the metal plating layer (D) from a thin film to a thick film to a desired film thickness. After electrolytic plating, a method of electrolytic plating is applied.

The film thickness of the metal plating layer (D) is preferably 1 μm to 50 μm. The film thickness of the metal plating layer (D) can be adjusted by controlling the processing time, current density, and the amount of plating additives used in the plating treatment step when the metal plating layer (D) is formed. .

    [Example]    

Hereinafter, the present invention will be described in detail through examples.

(Production Example 1: Amine Tri Manufacture of modified novolac 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, cooling tube, fractionation tube, and stirrer. While exothermic, the temperature was raised to 100 ° C. After reacting at 100 ° C for 2 hours under reflux, the temperature was raised to 180 ° C over 2 hours while removing water under normal pressure. Next, unreacted phenol was removed under reduced pressure to obtain amine tris Modified novolac resin. The hydroxyl equivalent was 120 g / equivalent.

    (Preparation Example 1: Preparation of Primer Composition (1))    

35 parts by mass of a novolac resin ("PHENOLITE TD-2131" manufactured by DIC Corporation, hydroxyl equivalent 104 g / equivalent) and 64 parts by mass of an epoxy resin ("EPICLON 850-S" manufactured by DIC Corporation; bisphenol A-type epoxy resin, epoxy equivalent 188g / equivalent) and 1 part by mass of 2,4-diamino-6-vinyl-s-tri ("Shikoku Chemical Co., Ltd.""VT"), diluted with methyl ethyl ketone until the non-volatile content became 2% by mass, and uniformly mixed to obtain a primer composition (1).

    (Preparation Example 2: Preparation of Primer Composition (2))    

35 parts by mass of a novolac resin ("PHENOLITE TD-2131" manufactured by DIC Corporation, hydroxyl equivalent 104 g / equivalent) and 64 parts by mass of an epoxy resin ("EPICLON 850-S" manufactured by DIC Corporation; bisphenol A type epoxy resin, epoxy equivalent 188g / equivalent) and 1 part by mass with three After the cyclosilane coupling agent ("VD-5" manufactured by Shikoku Chemical Co., Ltd.), it was diluted with methyl ethyl ketone to a non-volatile content of 2% by mass, and uniformly mixed to obtain a primer composition (2 ).

    (Preparation Example 3: Preparation of Primer Composition (3))    

65 parts by mass of the amine group three obtained in Production Example 1 Novolac resin and 35 parts by mass of epoxy resin ("EPICLON 850-S" manufactured by DIC Corporation; bisphenol A type epoxy resin, epoxy equivalent 188 g / equivalent), diluted with methyl ethyl ketone until The volatile matter became 2% by mass, and uniformly mixed to obtain a primer composition (3).

    (Preparation example 4: Preparation of primer composition (4))    

48 parts by mass of the amine tri group obtained in Production Example 1 Novolac resin and 52 parts by mass of epoxy resin ("EPICLON 850-S" manufactured by DIC Corporation; bisphenol A epoxy resin, epoxy equivalent 188 g / equivalent), diluted with methyl ethyl ketone The volatile matter became 2% by mass and was uniformly mixed to obtain a primer composition (4).

    (Preparation example 5: Preparation of primer composition (5))    

39 parts by mass of the amine group three obtained in Production Example 1 Novolac resin and 61 parts by mass of epoxy resin ("EPICLON 850-S" manufactured by DIC Corporation; bisphenol A type epoxy resin, epoxy equivalent 188 g / equivalent), diluted with methyl ethyl ketone until The volatile matter became 2% by mass, and uniformly mixed to obtain a primer composition (5).

    (Preparation example 6: Preparation of primer composition (6))    

31 parts by mass of the amine tri group obtained in Production Example 1 Novolac resin and 69 parts by mass of epoxy resin ("EPICLON 850-S" manufactured by DIC Corporation; bisphenol A type epoxy resin, epoxy equivalent 188 g / equivalent), diluted with methyl ethyl ketone until The volatile matter became 2% by mass and was uniformly mixed to obtain a primer composition (6).

    (Preparation example 7: Preparation of primer composition (7))    

47 parts by mass of the amine tri group obtained in Production Example 1 After novolac resin and 52 parts by mass of epoxy resin ("EPICLON 850-S" manufactured by DIC Corporation; bisphenol A type epoxy resin, epoxy equivalent 188 g / equivalent), and 1 part by mass of trimellitic anhydride, It was diluted with methyl ethyl ketone until the nonvolatile matter became 2% by mass, and uniformly mixed to obtain a primer composition (7).

    (Preparation example 8: Preparation of primer composition (R1))    

The blocked isocyanate resin (resin component 25% by mass aqueous solution) was diluted with methyl ethyl ketone until the nonvolatile matter became 2% by mass to obtain a primer composition (R1).

    (Preparation example 9: Preparation of primer composition (R2))    

100 parts by mass of epoxy resin ("EPICLON 850-S" manufactured by DIC Corporation; bisphenol A type epoxy resin) was diluted with methyl ethyl ketone to a non-volatile content of 2% by mass, and uniformly mixed. This gave a primer composition (R2).

    [Modulation of Flowing Body (1)]    

According to Example 1 described in Japanese Invention Patent No. 4573138, cationic silver nano particles composed of scaly blocks having a gray-green metallic luster were obtained, which are silver nano particles and have a cationic group (amine group). Complex of organic compounds. Then, the powder of this silver nanoparticle 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 cationic silver nanoparticle as a fluid (5) by mass (1).

    (Example 1)    

On the surface of the polyimide film ("Kapton 150EN-C" manufactured by Toray-DuPont Co., Ltd .; thickness: 38 µm), a desktop compact coater ("K Printing Proofer" manufactured by RK Print-Coat Instrument) was used. The primer composition (1) obtained in Preparation Example 1 was applied so that the thickness after drying became 100 nm. Then, a primer layer was formed on the surface of the polyimide film by using a hot-air dryer and drying at 150 ° C. for 5 minutes.

On the surface of the primer layer formed above, a bar coater was used to apply the fluid body (1) obtained above. Then, it dried at 150 degreeC for 5 minutes, and the silver layer (film thickness 20nm) corresponding to the said metal nanoparticle layer (C) was formed.

The silver layer formed above was immersed in an electroless copper plating solution ("OIC Copper", manufactured by Okano Pharmaceutical Industry Co., Ltd., pH 12.5) at 45 ° C for 12 minutes, and electroless copper plating was performed. The copper plating layer (film thickness 0.2 μm) caused by the application.

The copper plating layer formed by the electroless copper plating obtained above was set on the cathode side, and phosphorus-containing copper was set on the anode side. The electrolytic plating solution containing copper sulfate was used at a current density of 2.5 A / dm ² . For 30 minutes electrolytic plating, a copper plating layer (film thickness 15 μm) caused by electrolytic copper plating was formed on the surface of the copper plating layer caused by electroless copper plating. As the aforementioned electrolytic plating solution, 70 g / L of copper sulfate, 200 g / L of sulfuric acid, 50 mg / L of chloride ion, and 5 ml / L of additives ("Top Lucina SF-M" manufactured by Okano Pharmaceutical Industry Co., Ltd.) were used. . A copper plating layer formed by electroless copper plating and a copper plating layer formed by electrolytic copper plating formed thereon are equivalent to the aforementioned metal plating layer (D).

By the above method, a laminated body (1) having a support (A), a primer layer (B), a metal nanoparticle layer (C), and a metal plating layer (D) laminated in this order is obtained.

    (Examples 2 to 7 and Comparative Examples 1 to 2)    

Except that the primer composition (1) used in Example 1 was used instead of the primer composition (2) to (7), (R-1), or (R-2), the same method as in Example 1 was used. To obtain a multilayer body (2) to (7), (R-1), or (R-2).

The laminated bodies (1) to (7), (R1), and (R2) obtained in the above-mentioned Examples 1 to 7 and Comparative Examples 1 to 2 were subjected to the following measurements and evaluations.

    [Measurement of peel strength before heating]    

About each laminated body obtained above, the peeling strength was measured using "Autograph AGS-X 500N" made by Shimadzu Corporation. The lead width used in the measurement was 5 mm, and the peeling angle was 90 °. In addition, the peeling strength tends to show a higher value as the thickness of the metal plating layer becomes thicker. However, the measurement of the peeling strength in the present invention is performed based on a measurement value of the thickness of the metal plating layer of 15 μm.

    [Evaluation of adhesion]    

From the value of the peel strength before heating measured as described above, adhesion was evaluated in accordance with the following criteria.

A: The value of the peeling 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 peeling strength after heating]    

The laminates obtained as described above were each stored in a dryer set at 150 ° C. for 168 hours and heated. After heating, the peel strength was measured in the same manner as described above.

    [Evaluation of heat resistance]    

Using the measured peel strength values before and after heating, 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 4 and Comparative Examples 1 and 2, measurement results of the peel strength before and after heating, and evaluation results of adhesion and heat resistance. The composition of the primer composition only indicates non-volatile content.

It can be confirmed that the laminated bodies (1) to (7) obtained in Examples 1 to 7 of the laminated body of the present invention are sufficiently high in initial stage (before heating), and the decrease in peel strength after heating is also slight. It is also excellent in heat resistance.

On the other hand, it was confirmed that the laminates (R1) and (R2) obtained in Comparative Examples 1 and 2 had sufficient adhesion at the initial stage (before heating), but had a large decrease in peel strength after heating and had problems with heat resistance .

Claims (10)

A laminated body is a laminated body having a primer layer (B), a metal nanoparticle layer (C), and a metal plating layer (D) laminated in this order on a support (A), which is characterized in that: The primer layer (B) contains A layer of the cyclic compound (b1). The laminated body as claimed in claim 1, wherein the The cyclic compound (b1) is amine tri Modified novolac resin (b1-1).     The laminate according to claim 1 or 2, wherein the primer layer (B) is a layer further containing an epoxy resin (b2).     The laminate according to claim 1, wherein the primer layer (B) contains amine group Modified layer of novolac resin (b1-1) and epoxy resin (b2). The molar ratio [(y) / (x)] of the phenolic hydroxyl group (x) in the modified novolac resin (b1-1) to the epoxy group (y) in the epoxy resin (b2) is 0.1 ~ 5 range. The laminated body of claim 2 or 4, wherein the amine group The hydroxyl value of the modified novolac resin (b1-1) is in the range of 50 to 200 mgKOH / g.     The laminated body according to any one of claims 3 to 5, wherein the epoxy resin (b2) is a bisphenol A type epoxy resin.         The laminated body according to any one of claims 1 to 6, wherein the primer layer (B) is a layer further containing a cross-linking agent of a polycarboxylic acid.         A printed wiring board characterized by using a laminated body according to any one of claims 1 to 7.         A flexible printed wiring board, which is a laminated body according to any one of claims 1 to 7, characterized in that the support (A) is a laminated body of a thin film.         A molded article characterized by using a laminated body according to any one of claims 1 to 7.