CN110753617A

CN110753617A - Laminate, printed wiring board using same, flexible printed wiring board, and molded article

Info

Publication number: CN110753617A
Application number: CN201880040445.9A
Authority: CN
Inventors: 平林宪一; 富士川亘; 白发润; 深泽宪正
Original assignee: Dainippon Ink and Chemicals Co Ltd
Current assignee: DIC Corp
Priority date: 2017-07-10
Filing date: 2018-07-03
Publication date: 2020-02-04
Also published as: WO2019013038A1; KR102372638B1; JP6579295B2; KR20200015695A; TW201908427A; JPWO2019013038A1; TWI707928B

Abstract

The present invention provides a laminate, a printed wiring board using the same, a flexible printed wiring board and a molded article, wherein the laminate is characterized in that a primer layer (B), a metal nanoparticle layer (C) and a metal plating layer (D) are sequentially laminated on a support (A), and the primer layer (B) is a layer containing a compound (B1) having an aminotriazine ring. The laminate can be produced by a simple method without roughening the surface of the support, and has excellent adhesion between the support and the metal layer (metal plating layer).

Description

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

Technical Field

The present invention relates to a laminate useful for a printed wiring board, a flexible printed wiring board, a molded article, and the like.

Background

With the miniaturization and high speed of electronic devices, printed wiring boards are required to have higher density and higher performance, and in order to meet these requirements, printed wiring boards having a smooth surface and a sufficiently thin conductive layer (metal layer) are required. As a material constituting this printed wiring board, a flexible copper clad laminate (hereinafter, abbreviated as "FCCL") is known. FCCL is mainly produced by a method of bonding a heat-resistant polymer film and a copper foil using an epoxy resin adhesive.

However, in the FCCL using the copper foil, since the copper foil wound in a roll shape is pulled out and bonded, the copper foil cannot be sufficiently thinned in operation. Further, in order to improve the adhesion to the polymer film, the surface of the copper foil must be roughened, and therefore, there is a problem that transmission loss occurs in a field of high frequency (GHz band) and high transmission speed (several tens of Gbps) required for high density and high performance of the printed wiring board.

Here, as a method for making the copper layer of FCCL thin, there has been proposed a method in which a metal thin film is formed on the surface of a polyimide film by a vapor deposition method or a sputtering method, and then copper is formed on the metal thin film by an electroplating method, an electroless plating method, or a method combining both (for example, see patent document 1). However, in this method, since a vapor deposition method or a sputtering method is used to form a metal thin film, a large-scale vacuum apparatus is required, and there is a problem that the size of the substrate is limited in the apparatus.

Therefore, there is a need for a laminate which has sufficient adhesion to a support such as a polymer film without roughening the surface of a metal layer such as a copper foil, and which can be produced by a simple method without requiring a large-scale vacuum equipment when forming the metal layer.

In addition, conventionally, the metal plating is used as a decorative plating on a plastic molded product, for example, in a mobile phone, a personal computer, a mirror, a container, various switches, and a shower head. The supports for these applications are limited to acrylonitrile-butadiene-styrene copolymers (hereinafter, abbreviated as "ABS") or polymer alloys of ABS and polycarbonate (hereinafter, abbreviated as "ABS-PC"). The reason for this is that the surface of the substrate must be roughened in order to ensure adhesion between the substrate and the plating film, and in the case of ABS, for example, the surface can be roughened by etching and removing the polybutadiene component with a strong oxidizing agent such as hexavalent chromic acid or permanganate. However, hexavalent chromic acid and the like are environmentally-friendly substances and are preferably not used, and alternative methods have been developed (for example, see patent document 2).

Therefore, in plating for the purpose of decoration or the like on plastic molded articles, a method is required in which a plating film having excellent adhesion is obtained even with other types of plastics without limiting the substrate to ABS or ABS-PC, and the amount of environmental load substances to be used is reduced.

Documents of the prior art

Patent document 1: japanese laid-open patent publication No. 2015-118044

Patent document 2: japanese patent application laid-open No. 5830807

Disclosure of Invention

Technical problem to be solved

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

Means for solving the problems

The present inventors have intensively studied to solve the above problems, and as a result, have found that: the present inventors have found that the above problems can be solved by providing a layer containing a compound having an aminotriazine ring as a primer layer on a support and sequentially laminating a metal layer comprising metal nanoparticles and a metal plating layer thereon, and have completed the present invention.

That is, the present invention provides a laminate comprising a base coat layer (B), a metal nanoparticle layer (C), and a metal plating layer (D) laminated in this order on a support (a), wherein the base coat layer (B) is a layer containing a compound (B1) having an aminotriazine ring, and a printed wiring board, a flexible printed wiring board, and a molded article using the same.

Effects of the invention

The laminate of the present invention has excellent adhesion between the support and the metal layer (metal plating layer) without roughening the surface of the support. In addition, when the metal layer is made thin, a laminate having a smooth surface and a sufficiently thin metal layer is obtained without using a large-scale vacuum apparatus.

The laminate of the present invention can be suitably used as electronic components such as printed wiring boards, flexible printed wiring boards, conductive films for touch panels, metal meshes for touch panels, organic solar cells, organic EL elements, organic transistors, RFIDs such as non-contact IC cards, electromagnetic wave barriers, LED lighting substrates, and digital signage by patterning the metal layer. In particular, it is most suitable for flexible printed wiring board applications such as FCCL.

Further, the use of the resin composition in molded articles can be suitably applied to electronic components such as connectors, electric components, electric motor peripheral components, and battery components for connecting wires for optical communication and the like; automotive trim parts, lamp reflectors, mobile phones, personal computers, mirrors, containers, home appliances, various switches, faucet parts, sprinklers, and the like.

Detailed Description

The laminate of the present invention is a laminate in which a primer layer (B), a metal nanoparticle layer (C), and a metal plating layer (D) are laminated in this order on a support (a), wherein the primer layer (B) is a layer containing a compound (B1) having an aminotriazine ring.

The laminate of the present invention may be a laminate in which a primer layer (B) or the like is sequentially laminated on one surface of the support (a), or may be a laminate in which a primer layer (B) or the like is sequentially laminated on both surfaces of the support (a).

Examples of the support (a) include supports comprising polyimide, polyamideimide, polyamide, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, acrylonitrile-butadiene-styrene (ABS) resin, a polymer alloy of ABS and polycarbonate, an acrylic resin such as poly (methyl) acrylate, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polycarbonate, polyethylene, polypropylene, polyurethane, Liquid Crystal Polymer (LCP), polyether ether ketone (PEEK), polyphenylene sulfide (PPS), polyphenylene sulfone (PPSU), epoxy resin, cellulose nanofiber, silicon, ceramics, glass, and the like, porous supports comprising these materials, steel plates, supports comprising metal such as copper, and supports having silicon carbide, silicon nitride, silicon oxide, silicon nitride, silicon oxide, And a support made of diamond-like carbon, aluminum, copper, titanium, or the like.

When the laminate of the present invention is used for a printed wiring board or the like, a support containing polyimide, polyethylene terephthalate, polyethylene naphthalate, Liquid Crystal Polymer (LCP), polyether ether ketone (PEEK), glass, cellulose nanofibers, or the like is preferably used as the support (a).

When the laminate of the present invention is used for a flexible printed wiring board or the like, the support (a) is preferably a film-like or sheet-like support having flexibility capable of being bent.

When the support (A) is in the form of a film or a sheet, the thickness thereof is preferably 1 μm or more and 5000 μm or less, more preferably 1 μm or more and 300 μm or less, and particularly preferably 1 μm or more and 200 μm or less.

In addition, from the viewpoint of further improving the adhesion between the support (a) and the primer layer (B) described later, if necessary, fine irregularities may be formed on the surface of the support (a) to such an extent that smoothness is not lost, dirt may be washed off from the surface of the support (a), or a surface treatment may be performed for introducing a functional group such as a hydroxyl group, a carbonyl group, or a carboxyl group. Specifically, there may be mentioned a method of ion discharge treatment such as corona discharge treatment, dry treatment such as ultraviolet treatment, or wet treatment using an aqueous solution such as water or an acid-base or an organic solvent.

The primer layer (B) is a layer containing a compound (B1) having an aminotriazine ring. The compound (b1) having an aminotriazine ring may be a low-molecular-weight compound or a resin having a higher molecular weight.

As the low molecular weight compound having an aminotriazine ring described above, various additives having an aminotriazine ring can be used. Examples of commercially available products include 2, 4-diamino-6-vinyl-s-triazine ("VT" manufactured by Shikoku Kogyo Co., Ltd), "VD-3" and "VD-4" (a compound having an aminotriazine ring and a hydroxyl group) manufactured by Shikoku Kogyo Co., Ltd, "VD-5" (a compound having an aminotriazine ring and an ethoxysilyl group) manufactured by Shikoku Kogyo Co., Ltd. These additives may be used in an amount of 1 kind, or 2 or more kinds may be used in combination.

When the above-mentioned low molecular weight compound having an aminotriazine ring is used, a resin is preferably used for forming the primer layer (B). Examples of the resin used at this time include urethane resin, acrylic resin, urethane-vinyl composite resin, epoxy resin, imide resin, amide resin, melamine resin, phenol resin, urea-formaldehyde resin, blocked polyisocyanate using phenol as a blocking agent, polyvinyl alcohol, and polyvinyl pyrrolidone. These resins may be used in 1 kind, or 2 or more kinds may be used in combination. Among these, from the viewpoint of further improving the adhesion, an epoxy resin is preferable, and a novolac resin and an epoxy resin are more preferably used in combination.

The amount of the low-molecular weight compound having an aminotriazine ring used is preferably 0.1 part by mass or more and 50 parts by mass or less, and more preferably 0.5 part by mass or more and 10 parts by mass or less, with respect to 100 parts by mass of the resin.

Examples of the resin having an aminotriazine ring include a resin in which an aminotriazine ring is covalently introduced into a polymer chain of the resin. Specifically, an aminotriazine-modified novolak resin (b1-1) can be mentioned.

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) can be obtained, for example, by co-condensing an aminotriazine compound such as melamine, benzoguanamine, or acetoguanamine with a phenol compound such as phenol, cresol, butylphenol, bisphenol a, phenylphenol, naphthol, or resorcinol with formaldehyde in the vicinity of neutrality in the presence or absence of a weakly basic catalyst such as an alkylamine, or by reacting an alkyl ether compound of an aminotriazine compound such as methyl etherified melamine with the phenol compound.

The aminotriazine-modified novolak resin (b1-1) preferably has substantially no methylol group. In addition, the aminotriazine-modified novolak resin (b1-1) may contain a molecule in which only an aminotriazine structure is bonded to a methylene group, a molecule in which only a phenol structure is bonded to a methylene group, and the like, which are generated as by-products during the production thereof. Further, some amount of unreacted raw materials may be contained.

Examples of the phenol structure include a phenol residue, a cresol residue, a butyl phenol residue, a bisphenol a residue, a phenylphenol residue, a naphthol residue, and a resorcinol residue. The term "residue" as used herein means a structure obtained by removing at least 1 hydrogen atom bonded to a carbon of an aromatic ring. For example, when phenol, it refers to hydroxyphenyl.

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

The phenol structure and the three triazine structure can be used in 1, also can be combined with more than 2. In addition, from the viewpoint of further improving the adhesion, the phenol structure is preferably a phenol residue, and the triazine structure is preferably a structure derived from melamine.

The hydroxyl value of the aminotriazine-modified novolak resin (b1-1) is preferably 50mgKOH/g or more and 200mgKOH/g or less, more preferably 80mgKOH/g or more and 180mgKOH/g or less, and particularly preferably 100mgKOH/g or more and 150mgKOH/g or less, from the viewpoint of further improving the adhesion.

The aminotriazine-modified novolak resin (b1-1) may be used in 1 kind, or 2 or more kinds may be used in combination.

In addition, as the compound having an aminotriazine ring (b1), when an aminotriazine-modified novolak resin (b1-1) is used, it is preferable to use an epoxy resin (b2) in combination.

Examples of the epoxy resin (b2) include bisphenol a type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, cresol novolac type epoxy resins, phenol novolac type epoxy resins, bisphenol a novolac type epoxy resins, alcohol ether type epoxy resins, tetrabromobisphenol a type epoxy resins, naphthalene type epoxy resins, phosphorus-containing epoxy compounds having a structure derived from 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives, epoxy resins having a structure derived from dicyclopentadiene derivatives, and epoxides of fats and oils such as epoxidized soybean oil. These epoxy resins may be used in 1 kind, or 2 or more kinds may be used in combination.

Among the above epoxy resins (b2), bisphenol a type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, cresol novolac type epoxy resins, phenol novolac type epoxy resins, bisphenol a novolac type epoxy resins are preferable from the viewpoint of further improving the adhesion, and bisphenol a type epoxy resins are particularly preferable.

The epoxy equivalent of the epoxy resin (b2) is preferably 100 g/equivalent or more and 300 g/equivalent or less, more preferably 120 g/equivalent or more and 250 g/equivalent or less, and still more preferably 150 g/equivalent or more and 200 g/equivalent or less, from the viewpoint of further improving the adhesion.

When the primer layer (B) is a layer containing the aminotriazine-modified novolak resin (B1-1) and the epoxy resin (B2), the molar ratio [ (y)/(x) ] of the phenolic hydroxyl group (x) in the aminotriazine-modified novolak 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, from the viewpoint of further improving the adhesion.

The primer composition (B) is used for forming the primer layer (B). The primer composition (b) contains the compound having an aminotriazine ring (b1) and the epoxy resin (b2), and may further contain a crosslinking agent (b3) if 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 in 1 kind, or 2 or more kinds may be used in combination. Among these crosslinking agents, trimellitic anhydride is preferable from the viewpoint of further improving adhesion.

Further, in the primer composition (B) for forming the primer layer (B), another resin (B4) may be blended as necessary as components other than the above components (B1) to (B3). Examples of the other resin (b4) include urethane resin, acrylic resin, blocked isocyanate resin, melamine resin, and phenol resin. These other resins may be used in 1 kind, or 2 or more kinds may be used in combination.

In the primer composition (b), an organic solvent is preferably blended in order to obtain a viscosity that facilitates application when the primer composition is applied to the support (a). Examples of the organic solvent include toluene, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and isopropyl alcohol.

The amount of the organic solvent used is preferably adjusted as appropriate in accordance with the coating method used when coating the support (a) described later and the desired film thickness of the primer layer (B).

In addition, 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 may be added to the primer composition (b) and used as appropriate.

The primer layer (B) may be formed by applying the primer composition (B) to a part or the whole of the surface of the support (a) and removing the organic solvent contained in the primer composition (B).

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

After the primer composition (b) is applied to the surface of the support (a), the organic solvent contained in the coating layer is removed, for example, by drying with a dryer to evaporate the organic solvent. The drying temperature may be set within a range in which the organic solvent used is volatilized and the support (a) is not adversely affected by thermal deformation or the like.

The thickness of the primer layer (B) formed using the primer composition (B) varies depending on the application in which the laminate of the present invention is used, but is preferably within a range in which the adhesion between the support (a) and the metal nanoparticle layer (C) described later is further improved, and the thickness of the primer layer (B) is preferably 10nm or more and 30 μm or less, more preferably 10nm or more and 1 μm or less, and particularly preferably 10nm or more and 500nm or less.

From the viewpoint of further improving the adhesion to the metal nanoparticle layer (C), the surface of the primer layer (B) may be surface-treated by an ion discharge treatment method such as a corona discharge treatment method, a dry treatment method such as an ultraviolet treatment method, or a wet treatment method using water, an acidic or basic chemical solution, an organic solvent, or the like, as necessary.

The metal nanoparticle layer (C) is formed on the primer layer (B), and examples of the metal constituting the metal nanoparticle layer (C) include transition metals and compounds thereof, and among them, ionic transition metals are preferable. Examples of the ionic transition metal include copper, silver, gold, nickel, palladium, platinum, and cobalt. Among these, silver is preferable from the viewpoint of ease of formation of the metal plating layer (D).

Examples of the metal constituting the metal plating layer (D) include copper, gold, silver, nickel, chromium, cobalt, and tin. Among these, copper is preferable from the viewpoint of low electrical resistance and obtaining a laminate usable for a corrosion-resistant printed wiring board.

Examples of the method for producing the laminate of the present invention include: a method in which a primer layer (B) is formed on a support (a), a fluid containing nano-sized metal nanoparticles (C) is applied, an organic solvent or the like contained in the fluid is dried and removed to form a metal nanoparticle layer (C), and then the metal plating layer (D) is formed by electrolytic plating or electroless plating, or both.

The shape of the metal nanoparticles (C) for forming the metal nanoparticle layer (C) is preferably a particle shape or a fiber shape. The size of the metal nanoparticles (c) is a nanosize, and specifically, when the metal nanoparticles (c) are in a particle form, the average particle diameter is preferably 1nm or more and 100nm or less, more preferably 1nm or more and 50nm or less, from the viewpoint of forming a fine conductive pattern and further reducing the resistance value. The "average particle diameter" is a volume average value measured by a dynamic light scattering method using a well-dispersed solvent to dilute the conductive material. For this measurement, "NanotracUPA-150" manufactured by Microtrac corporation can be used.

On the other hand, when the metal nanoparticles (c) are in the form of fibers, the diameter of the fibers is also preferably 5nm or more and 100nm or less, more preferably 5nm or more and 50nm or less, from the viewpoint of forming a fine conductive pattern and further reducing the resistance value. The length of the fiber is preferably 0.1 to 100 μm, more preferably 0.1 to 30 μm.

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

Examples of the component to be added to the fluid include a dispersant or a solvent for dispersing the metal nanoparticles (c) in a solvent, and if necessary, a surfactant, a leveling agent, a viscosity adjuster, a film-forming aid, an antifoaming agent, and an antiseptic agent, which will be described later.

In order to disperse the metal nanoparticles (c) in the solvent, it is preferable to use a low-molecular-weight or high-molecular-weight dispersant. Examples of the dispersant include dodecyl mercaptan, 1-octyl mercaptan, triphenylphosphine, dodecylamine, polyethylene glycol, polyvinylpyrrolidone, polyethyleneimine, and polyvinylpyrrolidone; fatty acids such as myristic acid, caprylic acid, and stearic acid; and 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 preferable, and examples of the polymer dispersant include polyethyleneimine such as polyethyleneimine or polypropyleneimine, a compound obtained by adding a polyoxyalkylene to the polyalkyleneimine, a urethane resin, an acrylic resin, and a compound containing a phosphoric group in the urethane resin or the acrylic resin.

The amount of the dispersant to be used for dispersing the metal nanoparticles (c) is preferably 0.01 to 50 parts by mass, more preferably 0.01 to 10 parts by mass, per 100 parts by mass of the metal nanoparticles (c).

As the solvent used in 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, 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, i-butanol, sec-butanol, t-butanol, heptanol, hexanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, stearyl alcohol, allyl alcohol, cyclohexanol, terpineol, 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 monobutyl ether, tripropylene glycol monobutyl ether, and the like.

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

As the surfactant, a common surfactant can be used, and examples thereof include di-2-ethylhexyl sulfosuccinate, dodecylbenzene sulfonate, alkyldiphenyl ether disulfonate, alkylnaphthalene sulfonate, hexametaphosphate, and the like.

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

As the viscosity modifier, a general thickener can be used, and examples thereof include an acrylic polymer or a synthetic rubber latex which can be thickened by being adjusted to be alkaline, a urethane resin which can be thickened by molecular association, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, polyvinyl alcohol, hydrogenated castor oil, amide wax, oxidized polyethylene, a metal soap, dibenzylidene sorbitol, and the like.

As the above-mentioned film-forming assistant, a usual film-forming assistant can be used, and examples thereof include an anionic surfactant (e.g., dioctyl sodium sulfosuccinate), a hydrophobic nonionic surfactant (e.g., sorbitan monooleate), a polyether-modified silicone, and a silicone oil.

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

As the preservative, a common preservative can be used, and examples thereof include an isothiazoline-based preservative, a triazine-based preservative, an imidazole-based preservative, a pyridine-based preservative, an azole-based preservative, an iodine-based preservative, and a pyrithione-based preservative.

The viscosity of the above-mentioned fluid (measured at 25 ℃ using a B-type viscometer) is preferably 0.1 to 500000 mPas, more preferably 0.2 to 10000 mPas. When the fluid is applied (printed) by an ink jet printing method, a relief reverse printing method, or the like, which will be described later, the viscosity is preferably 5mPa · s or more and 20mPa · s or less.

Examples of the 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 printing method, a spin coating method, a spray coating method, a bar coating method, a die coating method, a slit coating method, a roll coating method, a dip coating method, a pad printing method, and a flexographic printing method.

Among these coating methods, the inkjet printing method and the reverse printing method are preferably used for forming the metal nanoparticle layer (C) patterned in a fine line shape of about 0.01 to 100 μm required for realizing high density of electronic circuits and the like.

As the above ink jet printing method, an apparatus generally called an ink jet printer can be used. Specific examples thereof include Konica-Minolta EB100, XY100(Konica-Minolta IJ Co., Ltd.), Dimatix-Material Printer DMP-3000, and Dimatix-Material Printer DMP-2831 (Fuji film Co., Ltd.).

As the reverse printing method, a relief reverse printing method and a gravure reverse printing method are known, and examples thereof include a method in which the fluid is applied to the surface of various blankets and brought into contact with a plate having a non-image area protruding therefrom, and the fluid corresponding to the non-image area is selectively transferred to the surface of the plate, thereby forming the pattern on the surface of the blanket or the like, and then the pattern is transferred to (on) the support (a).

Further, a pad printing method is known as pattern printing on a three-dimensional molded product. This is a method in which a printing ink is placed on a gravure plate, the printing ink is scraped by a doctor blade to uniformly fill the concave portion, a silicone rubber or urethane rubber gasket is pressed against the plate on which the printing ink is placed, and a pattern is transferred to the gasket, thereby transferring the pattern to a three-dimensional molded product.

The mass per unit area of the metal nanoparticle layer (C) is preferably 1mg/m²Above 30000mg/m²Hereinafter, more preferably 1mg/m²Above 5000mg/m²The following. The thickness of the metal nanoparticle layer (C) can be adjusted by controlling the treatment time, current density, and the amount of the additive for plating used in the plating step in forming the metal plating layer (D).

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

The metal plating layer (D) is a layer formed on the metal nanoparticle layer (C), and is preferably formed by plating. Examples of the plating treatment include a wet plating method such as an electrolytic plating method and an electroless plating method, which can easily form the metal plating layer (D). In addition, 2 or more of these plating methods may be combined. For example, the metal plating layer (D) may be formed by performing electroless plating and then electrolytic plating.

The electroless plating method is a method of forming an electroless plating layer (coating) of a metal coating by bringing an electroless plating solution into contact with a metal constituting the metal nanoparticle layer (C) to deposit a metal such as copper contained in the electroless plating solution.

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

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

Further, as the electroless plating solution, those containing 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; hydroxycarboxylic acid compounds such as malic acid, lactic acid, glycolic acid, gluconic acid, and citric acid; amino acid compounds such as glycine, alanine, iminodiacetic acid, arginine, aspartic acid, and glutamic acid; and organic acids such as aminopolycarboxylic acid compounds such as iminodiacetic acid, nitrilotriacetic acid, ethylenediamine diacetic acid, ethylenediamine tetraacetic acid, and diethylenetriamine pentaacetic acid, and soluble salts (sodium salts, potassium salts, ammonium salts, etc.) of these organic acids, and amine compounds such as ethylenediamine, diethylenetriamine, and triethylenetetramine.

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

The electrolytic plating method is, for example, a method of forming an electrolytic plating layer (metal film) by depositing a metal such as copper contained in an electrolytic plating solution on a conductive material constituting the metal nanoparticle layer (C) provided on a cathode or on the surface of an electroless plating layer (film) formed by the electroless plating treatment by applying an electric current in a state where the electrolytic plating solution is brought into contact with the metal constituting the metal nanoparticle layer (C) or the surface of the electroless plating layer (film) formed by the electroless plating treatment.

Examples of the electrolytic plating solution include a plating solution containing a sulfide of a metal such as copper, nickel, chromium, cobalt, or tin, sulfuric acid, and an aqueous medium. Specifically, a plating solution containing copper sulfate, sulfuric acid and an aqueous medium is exemplified.

The electrolytic plating solution is preferably used at 20 ℃ or higher and 98 ℃ or lower.

As a method for forming the metal plating layer (D), a method of performing electroless plating and then electrolytic plating is preferable from the viewpoint of easily controlling the film thickness of the metal plating layer (D) to a desired film thickness from a thin film to a thick film.

The 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) can be adjusted by controlling the processing time, current density, and amount of plating additive used in the plating process when forming the metal plating layer (D).

Examples

The present invention will be described in detail below with reference to examples.

Production example 1 production of aminotriazine-modified novolak resin

In a flask equipped with a thermometer, a cooling tube, a fractionating tube, and a stirrer, 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 were added, and the temperature was raised to 100 ℃ while paying attention to heat generation. After reacting at 100 ℃ for 2 hours under reflux, the temperature was raised to 180 ℃ for 2 hours while removing water under normal pressure. Next, unreacted phenol was removed under reduced pressure to obtain an aminotriazine-modified novolak resin. The hydroxyl equivalent weight was 120 g/equivalent.

Preparation example 1 preparation of primer composition (1)

A primer composition (1) was obtained by mixing 35 parts by mass of a novolak resin ("PHONOLITE TD-2131" manufactured by DIC K.K., hydroxyl equivalent 104 g/equivalent), 64 parts by mass of an epoxy resin ("EPICLON 850-S" manufactured by DIC K.K., bisphenol A type epoxy resin, epoxy equivalent 188 g/equivalent), and 1 part by mass of 2, 4-diamino-6-vinyl-S-triazine ("VT" manufactured by Sikko chemical Co., Ltd.), diluting the mixture with methyl ethyl ketone until the nonvolatile content became 2 mass%.

Preparation example 2 preparation of primer composition (2)

A primer composition (2) was obtained by mixing 35 parts by mass of a novolak resin ("PHONOLITE TD-2131" manufactured by DIC K.K., hydroxyl equivalent 104 g/equivalent), 64 parts by mass of an epoxy resin ("EPICLON 850-S" manufactured by DIC K.K., bisphenol A epoxy resin, epoxy equivalent 188 g/equivalent), and 1 part by mass of a silane coupling agent having a triazine ring ("VD-5" manufactured by Sikko Kagaku K.K.), diluting the mixture with methyl ethyl ketone until the nonvolatile content became 2% by mass, and uniformly mixing the mixture.

Preparation example 3 preparation of primer composition (3)

A primer composition (3) was obtained by mixing 65 parts by mass of the aminotriazine novolak resin obtained in production example 1 and 35 parts by mass of an epoxy resin ("EPICLON 850-S" manufactured by DIC corporation: bisphenol A epoxy resin, epoxy equivalent 188 g/eq), and then diluting the mixture with methyl ethyl ketone until the nonvolatile fraction became 2% by mass.

Preparation example 4 preparation of primer composition (4)

A primer composition (4) was obtained by mixing 48 parts by mass of the aminotriazine novolak resin obtained in production example 1 and 52 parts by mass of an epoxy resin ("EPICLON 850-S" available from DIC corporation: bisphenol A epoxy resin, epoxy equivalent 188 g/eq), and then diluting the mixture with methyl ethyl ketone until the nonvolatile fraction became 2% by mass.

Preparation example 5 preparation of primer composition (5)

39 parts by mass of the aminotriazine novolak resin obtained in production example 1 and 61 parts by mass of an epoxy resin ("EPICLON 850-S" available from DIC corporation: bisphenol A epoxy resin, epoxy equivalent 188 g/eq) were mixed, and then diluted with methyl ethyl ketone until the nonvolatile fraction 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 aminotriazine novolak resin obtained in production example 1 and 69 parts by mass of an epoxy resin ("EPICLON 850-S" available from DIC corporation: bisphenol A epoxy resin, epoxy equivalent 188 g/eq) were mixed, and then diluted with methyl ethyl ketone until the nonvolatile fraction became 2% by mass, and uniformly mixed to obtain a primer composition (6).

Preparation example 7 preparation of primer composition (7)

47 parts by mass of the aminotriazine novolak resin obtained in production example 1, 52 parts by mass of an epoxy resin ("EPICLON 850-S" available from DIC corporation: bisphenol A type epoxy resin, epoxy equivalent 188 g/eq) and 1 part by mass of trimellitic anhydride were mixed, and then diluted with methyl ethyl ketone so that the nonvolatile matter becomes 2% by mass, and uniformly mixed to obtain a primer composition (7).

Preparation example 8 preparation of primer composition (R1)

The blocked isocyanate resin (25 mass% aqueous solution of the resin component) was diluted with methyl ethyl ketone so that the nonvolatile content became 2 mass%, to obtain a primer composition (R1).

Preparation example 9 preparation of primer composition (R2)

100 parts by mass of an epoxy resin ("EPICLON 850-S", manufactured by DIC corporation; bisphenol A epoxy resin) was diluted with methyl ethyl ketone so that the nonvolatile content became 2% by mass, and the mixture was uniformly mixed to obtain a primer composition (R2).

[ preparation of fluid (1) ]

According to example 1 described in japanese patent No. 4573138, a composite of silver nanoparticles and an organic compound having a cationic group (amino group) is obtained, which is cationic silver nanoparticles including a flaky block having a grayish green metallic luster. Then, this silver nanoparticle powder 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)

The primer composition (1) obtained in production example 1 was applied to the surface of a polyimide film (Kapton 150EN-C, manufactured by Toho-DuPont corporation; thickness: 38 μm) using a desktop mini-coater ("KPring applicator", manufactured by RKprint-Coat Instrument Co.) so that the thickness after drying became 100 nm. Next, by using a hot air dryer, drying was performed at 150 ℃ for 5 minutes, thereby forming a primer layer on the surface of the polyimide film.

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

The silver layer thus formed was immersed in an electroless Copper plating solution ("OIC Copper", manufactured by Oneye pharmaceutical industries, Ltd., pH12.5) at 45 ℃ for 12 minutes to perform electroless Copper plating, thereby forming a Copper plated layer (film thickness: 0.2 μm) by electroless Copper plating.

The copper plating layer obtained by electroless copper plating was set to the cathode side and the phosphorus-containing copper was set to the anode side, and an electrolytic plating solution containing copper sulfate was used to obtain a copper plating film having a current density of 2.5A/dm²Electrolytic plating was performed for 30 minutes to form a copper plated layer (film thickness: 15 μm) by electrolytic copper plating on the surface of the copper plated layer by electroless copper plating. As the electrolytic plating solution, 70g/L copper sulfate, 200g/L sulfuric acid, 50mg/L chloride ion, and 5ml/L additive ("Top Lucina SF-M", manufactured by Orye pharmaceutical industries, Ltd.) were used. The layer including the electroless copper plating copper-plated layer and the electrolytic copper plating copper-plated layer formed thereon corresponds to the metal plating layer (D).

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

(examples 2 to 7 and comparative examples 1 to 2)

Laminates (2) to (7), (R-1) and (R-2) were obtained in the same manner as in example 1, except that the primer compositions (2) to (7), (R-1) and (R-2) were used in place of the primer composition (1) used in example 1.

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 to 2.

[ measurement of peeling Strength before heating ]

The obtained laminates were measured for peel strength using "Autograph AGS-X500N" manufactured by Shimadzu corporation. The lead used for the measurement had a width of 5mm and a peel angle of 90 °. Further, the peel strength tends to show a higher value as the thickness of the metal plating layer becomes thicker, but the peel strength in the present invention is measured based on a measurement value of 15 μm in thickness of the metal plating layer.

[ evaluation of adhesion ]

From the measured value of the peel strength before heating, the adhesion was evaluated according to the following criteria.

A: the peel strength is 650N/m or more.

B: the peel strength is 450N/m or more and less than 650N/m.

C: the peel strength is 250N/m or more and less than 450N/m.

D: the value of the peel strength is less than 250N/m.

[ measurement of peeling Strength after heating ]

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

[ evaluation of Heat resistance ]

The peel strength values before and after heating measured as described above were used to calculate the retention before and after heating, 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 was less than 55%.

Table 1 shows the compositions of the primer compositions used in examples 1 to 4 and comparative examples 1 and 2, the results of measurement of peel strength before and after heating, and the results of evaluation of adhesion and heat resistance. The composition of the primer composition is only shown as non-volatile.

[ Table 1]

It was confirmed that the laminates (1) to (7) obtained in examples 1 to 7 of the laminate of the present invention had sufficiently high adhesion in the initial stage (before heating), had slight decrease in peel strength after heating, and had excellent heat resistance.

On the other hand, it was confirmed that the laminates (R1) and (R2) obtained in comparative examples 1 and 2 had a problem in heat resistance because the peel strength after heating was greatly reduced although the initial (before heating) adhesion was sufficient.

Claims

1. A laminate comprising a base coat layer (B), a metal nanoparticle layer (C), and a metal plating layer (D) laminated in this order on a support (A), wherein the base coat layer (B) is a layer containing a compound (B1) having an aminotriazine ring.

2. The laminate according to claim 1, wherein the compound having an aminotriazine ring (b1) is an aminotriazine-modified novolak resin (b 1-1).

3. The laminate according to claim 1 or 2, wherein the primer layer (B) is a layer further containing an epoxy resin (B2).

4. The laminate according to claim 1, wherein the primer layer (B) is a layer containing an aminotriazine-modified novolak resin (B1-1) and an epoxy resin (B2), and the molar ratio of phenolic hydroxyl groups x in the aminotriazine-modified novolak resin (B1-1) to epoxy groups y in the epoxy resin (B2) is in the range of 0.1 to 5 in terms of (y/x).

5. The laminate according to claim 2 or 4, wherein the hydroxyl value of the aminotriazine-modified novolak resin (b1-1) is in the range of 50 to 200 mgKOH/g.

6. The laminate according to any one of claims 3 to 5, wherein the epoxy resin (b2) is a bisphenol A type epoxy resin.

7. The laminate according to any one of claims 1 to 6, wherein the primer layer (B) is a layer further containing a crosslinking agent of a polycarboxylic acid.

8. A printed wiring board using the laminate according to any one of claims 1 to 7.

9. A flexible printed wiring board, characterized by using a laminate according to any one of claims 1 to 7, wherein the support (A) is a film.

10. A molded article comprising the laminate according to any one of claims 1 to 7.