KR20200015695A - Laminate, printed wiring board, flexible printed wiring board and molded article using the same - Google Patents

Abstract

The present invention is a laminate in which a primer layer (B), a metal nanoparticle layer (C), and a metal plating layer (D) are sequentially stacked on a support (A), wherein the primer layer (B) has an aminotriazine ring. It is a layer containing a compound (b1), The laminated body, the printed wiring board using this, a flexible printed wiring board, and the molded article are provided. The said laminated body can be manufactured by a simple method, without roughening the surface of a support body, and is excellent in the adhesiveness between a support body and a metal layer (metal plating layer).

Description

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

This invention relates to the laminated body which can be used for a printed wiring board, a flexible printed wiring board, a molded article, etc.

Due to the miniaturization and high speed of electronic devices, high-density and high-performance of printed wiring boards are required. In order to cope with this demand, printed wiring boards having smooth and sufficiently thin conductive layers (metal layers) are required. Moreover, the flexible copper clad laminated board (it abbreviates as "FCCL" hereafter) is known as what comprises this printed wiring board. FCCL is mainly manufactured by the method of bonding a heat resistant polymer film and copper foil together using an epoxy resin adhesive.

However, in FCCL using this copper foil, since it sticks together, taking out the copper foil wound by roll shape, copper foil cannot be made thin enough in handling. In addition, in order to improve the adhesion with the polymer film, it is necessary to harmonize the surface of the copper foil. Therefore, in the high frequency (GHz band) and high transmission speed (tens of tens of Gbps) areas necessary for high density and high performance of the printed wiring board. There was a problem that caused transmission loss.

Here, as a method for thinning the copper layer of FCCL, a metal thin film is formed on the surface of a polyimide film by vapor deposition or sputtering, and then copper is coated on the metal thin film by an electroplating method, an electroless plating method, or a combination thereof. A method of forming a metal is proposed (for example, refer patent document 1). However, in this method, in order to form a metal thin film, since a vapor deposition method or a sputtering method is used, a large-scale vacuum installation is needed, and there exists a problem that a base material size is limited on a facility.

Therefore, without laminating the surface of metal layers, such as copper foil, and having sufficient adhesiveness with support bodies, such as a polymer film, and the formation of this metal layer, lamination | stacking which can be manufactured by a simple method, without requiring a large-scale vacuum installation. Sieve was required.

Also, conventionally, decorative plating on plastic molded articles has been used for mobile phones, PCs, mirrors, containers, various switches, shower heads, and the like. Supports for these uses are limited to acrylonitrile-butadiene-styrene copolymers (hereinafter abbreviated as "ABS") and polymer alloys of ABS and polycarbonate (hereinafter abbreviated as "ABS-PC"). come. For this reason, it is necessary to roughen the surface of the base material in order to secure the adhesion between the base material and the plated film. For example, in the case of ABS, the polybutadiene component is etched with a strong oxidizing agent such as hexavalent chromic acid and permanganate, and then surface removed. Is possible. However, since hexavalent chromic acid etc. are environmentally loaded substances, it is preferable not to use them, and the alternative method has been developed (for example, refer patent document 2).

As described above, in plating for the purpose of decoration on a plastic molded article, the base material is not limited to ABS or ABS-PC, and even if other types of plastics, a plated film excellent in adhesion is obtained, and the amount of environmental load substance used is reduced. Was required.

Japanese Patent Application Laid-Open No. 2015-118044 Japanese Patent No. 5830807

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

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, the present inventors provided the layer which contains the compound which has an amino triazine ring as a primer layer on a support body, and the metal layer formed by the metal nanoparticle on it, The laminated body which laminated | stacked the metal plating layer one by one was able to solve the said subject, and completed this invention.

That is, this invention is a laminated body in which the primer layer (B), the metal nanoparticle layer (C), and the metal plating layer (D) were laminated | stacked sequentially on the support body (A), The said primer layer (B) is an amino triazine ring. It is a layer containing the compound (b1) which has a laminated body, The printed wiring board, the flexible printed wiring board, and the molded article using the same are provided.

The laminated body of this invention is excellent in adhesiveness between a support body and a metal layer (metal plating layer), even if it does not match a support surface. In addition, in the thinning of the metal layer, even if a large-scale vacuum equipment is not used, it is a laminate having a smooth and sufficiently thin metal layer.

In addition, the laminate of the present invention is, for example, by patterning a metal layer, for example, a printed wiring board, a flexible printed wiring board, a conductive film for a touch panel, a metal mesh for a touch panel, an organic solar cell, an organic EL element, an organic transistor, and a non-contact. It can be used suitably as electronic members, such as RFID, an electromagnetic shield, such as an IC card, an LED lighting base material, and a digital signage. In particular, it is suitable for the use of flexible printed wiring boards, such as FCCL.

Moreover, by applying to a molded article, Electronic members, such as a connector which connects wiring, such as optical communication, an electrical component, an electric motor peripheral member, a battery member; It can be favorably used for decoration of automobile decorative parts, lamp reflectors, mobile phones, PCs, mirrors, containers, home appliances, various switches, faucet parts, shower heads, and the like.

The laminate of the present invention is a laminate in which a primer layer (B), a metal nanoparticle layer (C), and a metal plating layer (D) are sequentially laminated on a support (A), wherein the primer layer (B) is an aminotria. It is a layer containing compound (b1) which has a ring substitution.

The laminate of the present invention may be a laminate obtained by sequentially laminating a primer layer (B) on one side of the support (A), or a laminate obtained by sequentially laminating a primer layer (B) on both surfaces of the support (A). You may lean.

As the support (A), for example, polyimide, polyamideimide, polyamide, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, acrylonitrile-butadiene-styrene (ABS) resin, ABS and polycarbonate Acrylic resins such as polymer alloy, poly (meth) 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, etc. Porous supports, steel plates, supports made of metals such as copper, and the surfaces thereof are silicon carbide, diamond la The greater the carbon, aluminum, copper, titanium, etc. may be mentioned the vapor deposition process, such as a support.

In addition, when using the laminated body of this invention for a printed wiring board etc., as said support body (A), a polyimide, a polyethylene terephthalate, a polyethylene naphthalate, a liquid crystal polymer (LCP), a polyether ether ketone (PEEK), glass, It is preferable to use a support made of cellulose nanofibers or the like.

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

When the shape of the said support body A is a film form or a sheet form, 1 micrometer or more and 5,000 micrometers or less are preferable, as for the thickness, 1 micrometer or more and 300 micrometers or less are more preferable, and 1 micrometer or more and 200 micrometers or less More preferred.

Moreover, since the adhesiveness of the said support body A and the primer layer B mentioned later can be improved more, fine unevenness | corrugation of the grade which does not lose smoothness is formed in the surface of the said support body A as needed, The contamination adhering to the surface may be washed or surface treated for introduction of functional groups such as hydroxy, carbonyl and carboxyl groups. Specifically, methods such as plasma discharge treatment such as corona discharge treatment, dry treatment such as ultraviolet ray treatment, wet treatment using water, aqueous solutions such as acid and alkali or organic solvents, and the like can be given.

The said primer layer (B) is a layer containing the compound (b1) which has an amino triazine ring. A low molecular weight compound may be sufficient as the compound (b1) which has the said amino triazine ring, and a higher molecular weight resin may be sufficient as it.

As the low molecular weight compound having the aminotriazine ring, various additives having an aminotriazine ring can be used. As a commercial item, 2, 4- diamino-6-vinyl-s-triazine ("VT" made by Shikoku Chemical Co., Ltd.), "VD-3" made by Shikoku Chemical Co., Ltd. and "VD-4" (The compound which has an amino triazine ring and a hydroxyl group), "VD-5" (compound which has an amino triazine ring and an ethoxysilyl group) by Shikoku Chemical Co., Ltd., etc. are mentioned. These additives may be used by 1 type and may be used together 2 or more types.

When using the low molecular weight compound which has the said amino triazine ring, it is preferable to use resin in order to form the said primer layer (B). As the resin used at this time, for example, a urethane resin, an acrylic resin, a urethane-vinyl composite resin, an epoxy resin, an imide resin, an amide resin, a melamine resin, a phenol resin, a urea formaldehyde resin, and a phenol are used as blocking agents. Block polyisocyanate, polyvinyl alcohol, polyvinylpyrrolidone, etc. are mentioned. These resin may be used by 1 type and may be used together 2 or more types. Among these, since adhesiveness can be improved more, an epoxy resin is preferable and it is more preferable to use a novolak resin and an epoxy resin together.

As a usage-amount of the low molecular weight compound which has the said amino triazine ring, 0.1 mass part or more and 50 mass parts or less are preferable with respect to 100 mass parts of resin, and 0.5 mass part or more and 10 mass parts or less are more preferable.

As resin which has the said amino triazine ring, the thing in which the amino triazine ring was introduce | transduced by a covalent bond in the polymer chain of resin is mentioned. Specifically, aminotriazine modified novolak resin (b1-1) is 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) is, for example, aminotriazine compounds such as melamine, benzoguanamine, acetoguanamine, phenol, cresol, butylphenol, bisphenol A, phenylphenol and naphthol. And alkyl ether compounds of phenol compounds such as resorcin and formaldehyde in the presence of a weakly alkaline catalyst such as alkylamine or non-catalytically, in the presence of a non-catalyzed cocondensation reaction, or of an aminotriazine compound such as methyl ether melamine It is obtained by reacting with the phenolic compound.

It is preferable that the said aminotriazine modified novolak resin (b1-1) does not have a methylol group substantially. In addition, the aminotriazine-modified novolak resin (b1-1) may include a molecule in which only the aminotriazine structure generated as a by-product in the production of methylene bond, a molecule in which the phenol structure is methylene bond, or the like may be contained. . In addition, some unreacted raw material may be included.

As said phenol structure, a phenol residue, a cresol residue, a butylphenol residue, a bisphenol A residue, a phenylphenol residue, a naphthol residue, a resorcin residue etc. are mentioned, for example. In addition, the residue here means the structure in which at least one hydrogen atom couple | bonded with the carbon of an aromatic ring was missing. For example, in the case of phenol, it means a hydroxyphenyl group.

As said triazine structure, the structure derived from aminotriazine compounds, such as melamine, benzoguanamine, and acetoguanamine, is mentioned, for example.

The said phenol structure and the said triazine structure may be used individually by 1 type, and may be used together 2 or more types. Moreover, since adhesiveness can be improved more, a phenol residue is preferable as said phenol structure, and a structure derived from melamine is preferable as said triazine structure.

Moreover, since the hydroxyl value of the said aminotriazine modified novolak resin (b1-1) can improve adhesiveness more, 50 mgKOH / g or more and 200 mgKOH / g or less are preferable, 80 mgKOH / g or more and 180 mgKOH / g or less Preferably, 100 mgKOH / g or more and 150 mgKOH / g or less are more preferable.

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

Moreover, when using an amino triazine modified novolak resin (b1-1) as a compound (b1) which has the said amino triazine ring, it is preferable to use an epoxy resin (b2) together.

As said epoxy resin (b2), a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a biphenyl type epoxy resin, a cresol novolak-type epoxy resin, a phenol novolak-type epoxy resin, a bisphenol A novolak-type epoxy resin, alcohol ether Epoxy compound having a structure derived from a type epoxy resin, a tetrabromobisphenol A type epoxy resin, a naphthalene type epoxy resin, a 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivative, a dish Epoxy resins of fats and oils, such as the epoxy resin which has a structure derived from a clopentadiene derivative, and epoxidized soybean oil, etc. are mentioned. These epoxy resins may be used by 1 type and may be used together 2 or more types.

Since the adhesiveness can be improved more among the said epoxy resin (b2), bisphenol-A epoxy resin, bisphenol F-type epoxy resin, biphenyl-type epoxy resin, cresol novolak-type epoxy resin, phenol novolak-type epoxy resin, bisphenol A A novolak-type epoxy resin is preferable and a bisphenol A type epoxy resin is especially preferable.

Moreover, since epoxy adhesive of the said epoxy resin (b2) can improve adhesiveness more, 100 g / equivalent or more and 300 g / equivalent or less are preferable, 120 g / equivalent or more and 250 g / equivalent or less are more preferable, 150 g / equivalent or more 200 g / equivalent or less is more preferable.

When the said primer layer (B) is made into the layer containing an aminotriazine modified novolak resin (b1-1) and an epoxy resin (b2), since adhesiveness can be improved more, the said aminotriazine modified novolak resin The molar ratio [(y) / (x)] between the phenolic hydroxyl group (x) in (b1-1) and the epoxy group (y) in the epoxy resin (b2) is preferably 0.1 or more and 5 or less, and 0.2 or more and 3 or less More preferably, 0.3 or more and 2 or less are more preferable.

The primer composition (b) is used for formation of the said primer layer (B). Although the said primer composition (b) contains the compound (b1) and epoxy resin (b2) which have the said amino triazine ring, you may further contain a crosslinking agent (b3) as needed. It is preferable to use polyhydric carboxylic acid as said crosslinking agent (b3). As said polyhydric carboxylic acid, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, succinic acid etc. are mentioned, for example. These crosslinking agents may be used by 1 type, and may be used together 2 or more types. Moreover, in these crosslinking agents, since adhesiveness can be improved more, trimellitic anhydride is preferable.

In addition, you may mix | blend other resin (b4) with the primer composition (b) used for formation of the said primer layer (B) as components other than said component (b1)-(b3) as needed. As said other resin (b4), a urethane resin, an acrylic resin, a block isocyanate resin, a melamine resin, a phenol resin etc. are mentioned, for example. These other resins may be used by 1 type, or may be used together 2 or more types.

In addition, it is preferable to mix | blend an organic solvent with the said primer composition (b) in order to make it the viscosity which is easy to coat, when coating to the said support body (A). As said organic solvent, toluene, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isopropyl alcohol, etc. are mentioned, for example.

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

Moreover, you may use the said primer composition (b) by adding appropriately well-known additives, such as a film formation aid, a leveling agent, a thickener, a water repellent, an antifoamer, antioxidant.

The said primer layer (B) can be formed by coating the said primer composition (b) on one part or all part of the surface of the said support body (A), and removing the organic solvent contained in the said primer composition (b).

As a method of coating the said primer composition (b) on the surface of the said support body (A), methods, such as a gravure system, a coating system, a screen system, a roller system, a rotary system, a spray system, a capillary system, are mentioned, for example. Can be mentioned.

After coating the said primer composition (b) on the surface of the said support body (A), as a method of removing the organic solvent contained in the coating layer, it is made to dry using a dryer, for example, and volatilizes an organic solvent. This is common. What is necessary is just to set it as temperature of the range which volatilizes the used organic solvent as a drying temperature, and does not adversely affect the said support body A, such as heat deformation.

Although the film thickness of the primer layer (B) formed using the said primer composition (b) differs according to the use using the laminated body of this invention, the said support body (A) and the metal nanoparticle layer (C) mentioned later, The range which improves the adhesiveness of this further is preferable, As for the film thickness of the said primer layer (B), 10 nm or more and 30 micrometers or less are preferable, 10 nm or more and 1 micrometer or less are more preferable, 10 nm or more and 500 nm or less More preferred.

Since the surface of the said primer layer (B) can improve adhesiveness with the said metal nanoparticle layer (C) further, if necessary, the plasma discharge treatment methods, such as a corona discharge treatment method, dry treatment methods, such as an ultraviolet-ray treatment method, water, and acidity Or you may surface-treat by the wet processing method using alkaline chemical liquid, an organic solvent, etc.

The said metal nanoparticle layer (C) is formed on the said primer layer (B), As a metal which comprises the said metal nanoparticle layer (C), a transition metal or its compound is mentioned, Especially, an ionic transition metal is desirable. Copper, silver, gold, nickel, palladium, platinum, cobalt etc. are mentioned as this ionic transition metal. Among these, silver is preferable because it is easy to form the metal plating layer (D).

Moreover, as metal which comprises the said metal plating layer (D), copper, gold, silver, nickel, chromium, cobalt, tin, etc. are mentioned. Among these, copper is preferable since the laminated body which is low in electrical resistance and can be used for a printed wiring board resisting corrosion is obtained.

As a manufacturing method of the laminated body of this invention, first, a primer layer (B) is formed on the support body (A), and after that, the fluid containing a nano size metal nanoparticle (c) is coated, and it is in a fluid. The method of forming the said metal plating layer (D) by electrolytic plating, electroless plating, or both after forming the metal nanoparticle layer (C) by removing the organic solvent contained etc. by drying is mentioned. .

It is preferable that the shape of the said metal nanoparticle (c) used for formation of the said metal nanoparticle layer (C) is particulate or fibrous. In addition, although the size of the said metal nanoparticle (c) uses the thing of a nano size, Specifically, when the shape of the said metal nanoparticle (c) is a particulate form, a fine electroconductive pattern can be formed and a resistance value is changed. Since it can reduce more, 1 nm or more and 100 nm or less of an average particle diameter are preferable, and 1 nm or more and 50 nm or less are more preferable. In addition, said "average particle diameter" is a volume average value which diluted the said electroconductive substance with a dispersion amount solvent and measured by the dynamic light scattering method. The nanotrack "nanotrack UPA-150" can be used for this measurement.

On the other hand, even when the shape of the said metal nanoparticle (c) is fibrous, since a fine electroconductive pattern can be formed and a resistance value can be reduced more, the diameter of a fiber is 5 nm or more and 100 nm or less, 5 More preferably, they are more than 50 nm. Moreover, 0.1 micrometer or more and 100 micrometers or less are preferable, and, as for the length of a fiber, 0.1 micrometer or more and 30 micrometers or less are more preferable.

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

As a component mix | blended with the said fluid, the dispersing agent and solvent for disperse | distributing the said metal nanoparticle (c) in a solvent, and also surfactant mentioned later, a leveling agent, a viscosity modifier, a film forming adjuvant, an antifoamer, an antiseptic etc. are mentioned as needed. Can be.

In order to disperse | distribute the said metal nanoparticle (c) in a solvent, it is preferable to use the dispersing agent of low molecular weight or high molecular weight. Examples of the dispersant include dodecanethiol, 1-octanethiol, triphenylphosphine, dodecylamine, polyethylene glycol, polyvinylpyrrolidone, polyethyleneimine and polyvinylpyrrolidone; Fatty acids such as myristic acid, octanoic acid and stearic acid; Polycyclic hydrocarbon compounds which have carboxyl groups, such as a cholic acid, glycyrrhizinic acid, and abiete acid, etc. are mentioned. Among these, since the adhesiveness of the said metal nanoparticle layer (C) and the said metal plating layer (D) can be improved, a polymer dispersing agent is preferable, As this polymer dispersing agent, Polyalkylene imines, such as polyethyleneimine and polypropylene imine, The compound which polyoxyalkylene added to the said polyalkylene imine, a urethane resin, an acrylic resin, the compound which contains a phosphoric acid group in the said urethane resin or the said acrylic resin, etc. are mentioned.

As for the usage-amount of the said dispersing agent required in order to disperse | distribute the said metal nanoparticle (c), 0.01 mass part or more and 50 mass parts or less are preferable with respect to 100 mass parts of said metal nanoparticles (c), 0.01 mass part or more and 10 mass parts The following is more preferable.

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

Examples of the alcohol compound include methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, sec-butanol, tert-butanol, heptanol, hexanol, octanol, nonanol and decane. Ol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, stearyl alcohol, allyl alcohol, cyclohexanol, terpineol, terpineol, dihydroterpineol, ethylene glycol monomethyl ether , Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol Monomethyl ether, tripropylene glycol monomethyl ether, propylene glycol monopropyl ether, dipropylene glycol monopropyl ether, propylene And the like can be recalled monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monobutyl ether.

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

As said surfactant, a general surfactant can be used, For example, di-2-ethylhexyl sulfosuccinate, dodecyl benzene sulfonate, alkyl diphenyl ether disulfonate, alkyl naphthalene sulfonate, hexamethaphosphate, etc. Can be mentioned.

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

As the viscosity modifier, a general thickener can be used, for example, an urethane resin, hydroxyethyl cellulose, carboxymethyl cellulose, methyl which can be thickened by association of an acrylic polymer, a synthetic rubber latex, and a molecule which can be thickened by adjusting to alkaline. Cellulose, polyvinyl alcohol, hydrogenated castor oil, amide wax, polyethylene oxide, metal soap, dibenzylidene sorbitol and the like.

As the film forming aid, a general film forming aid can be used. For example, anionic surfactants (dioctylsulfosuccinic acid ester soda salt, etc.), hydrophobic nonionic surfactants (sorbitan monooleate, etc.), polyether modifications Siloxane, silicone oil, and the like.

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

As the preservative, general preservatives can be used, and examples thereof include isothiazoline preservatives, triazine preservatives, imidazole preservatives, pyridine preservatives, azole preservatives, iodo based preservatives, and pyrithione preservatives. have.

0.1 mPa * s or more and 500,000 mPa * s or less are preferable, and, as for the viscosity (value measured using the Brookfield viscometer at 25 degreeC) of the said fluid, 0.2 mPa * s or more and 10,000 mPa * s or less are more preferable. Moreover, when apply | coating (printing) the said fluid by methods, such as the inkjet printing method and convex plate inversion printing mentioned later, the viscosity is 5 mPa * s or more and 20 mPa * s or less.

As a method of coating and printing the said fluid on the said primer layer (B), the inkjet printing method, the reverse printing method, the screen printing method, the offset printing method, the spin coating method, the spray coating method, the bar coat method, Die coating, slit coating, roll coating, dip coating, pad printing, flexographic printing, and the like.

Among these coating methods, when forming the said metal nanoparticle layer (C) patterned by the thin wire of about 0.01-100 micrometers required when realizing high density of an electronic circuit etc., the inkjet printing method and the reverse printing method are used. It is preferable.

As said inkjet printing method, what is generally called an inkjet printer can be used. Specifically, Konica Minolta EB100, XY100 (manufactured by Konica Minolta IJ), Dymatics Printer DMP-3000, Dymatics Printer DMP-2831 (manufactured by Fujifilm Co., Ltd.), and the like can be given. have.

Moreover, as the reverse printing method, the convex plate inversion printing method and the concave plate inversion printing method are known, For example, the said fluid is coated on the surface of various blankets, and it makes contact with the board which the non-fire line part protruded. By selectively transferring the fluid corresponding to the non-wire portion to the surface of the plate, the pattern is formed on the surface of the blanket or the like, and then the pattern is placed on the surface (surface) of the support A. And a method of transferring it.

Moreover, about the printing of the pattern to a three-dimensional molded article, the pad printing method is known. This puts the ink on the concave plate and scrapes it with a squeegee to fill the concave with the ink homogeneously, presses a pad made of silicone rubber or urethane rubber on the plate on which the ink is raised, transfers the pattern onto the pad, It is a method of transferring to a three-dimensional molded article.

The mass per unit area of the metal nanoparticle layer (C) is preferably 1 mg / m 2 or more and 30,000 mg / m 2 or less, and preferably 1 mg / m 2 or more and 5,000 mg / m 2 or less. The thickness of the said metal nanoparticle layer (C) can be adjusted by controlling the processing time, current density, the usage-amount of the additive for plating, etc. in the plating process at the time of forming the said metal plating layer (D).

The metal plating layer (D) constituting the laminate of the present invention is reliable, for example, when using the laminate in a printed wiring board or the like, without causing disconnection or the like over a long period of time, and maintaining good electrical conductivity. It is a layer provided for the purpose of forming this high wiring pattern.

Although the said metal plating layer (D) is a layer formed on the said metal nanoparticle layer (C), as a formation method, the method of forming by a plating process is preferable. As this plating process, wet plating methods, such as an electrolytic plating method and an electroless plating method which can easily form the said metal plating layer (D), are mentioned. Moreover, you may combine 2 or more of these plating methods. For example, after electroless plating is performed, electrolytic plating may be performed to form the metal plating layer (D).

In the electroless plating method described above, for example, an electroless plating solution is brought into contact with the metal constituting the metal nanoparticle layer (C), thereby depositing a metal such as copper contained in the electroless plating solution to form an electroless film formed of a metal film. It is a method of forming a plating layer (film).

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

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

Moreover, as said electroless plating liquid, Monocarboxylic acids, such as an acetic acid and formic acid, as needed; 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, citric acid; Amino acid compounds such as glycine, alanine, iminodiacetic acid, arginine, aspartic acid and glutamic acid; Organic acids such as aminopolycarboxylic acid compounds such as iminodiacetic acid, nitrilotriacetic acid, ethylenediaminediacetic acid, ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, or soluble salts of these organic acids (sodium salt, potassium salt, ammonium salt, etc.) And those containing complexing agents such as amine compounds such as ethylenediamine, diethylenetriamine and triethylenetetramine can be used.

It is preferable to use the said electroless plating liquid at 20 degreeC or more and 98 degrees C or less.

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

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

It is preferable to use the said electrolytic plating liquid at 20 degreeC or more and 98 degrees C or less.

As the formation method of the said metal plating layer (D), since the film thickness of the said metal plating layer (D) is easy to control to a desired film thickness from a thin film to a thick film, the method of electroplating after electroless plating is preferable. Do.

As for the film thickness of the said metal plating layer (D), 1 micrometer or more and 50 micrometers or less are preferable. The film thickness of the said metal plating layer (D) can be adjusted by controlling the processing time, the current density, the usage-amount of the additive for plating, etc. in the plating process at the time of forming the said metal plating layer (D).

(Example)

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

(Manufacture example 1: manufacture of aminotriazine modified novolak resin)

750 mass parts of phenols, 75 mass parts of melamine, 346 mass parts of 41.5 mass% formalin, and 1.5 mass parts of triethylamines were added to the flask with a thermometer, a cooling tube, a dividing tube, and a stirrer, and it heated up to 100 degreeC, paying attention to heat generation. did. After reacting at 100 degreeC under reflux for 2 hours, it heated up to 180 degreeC over 2 hours, removing water under normal pressure. Next, the unreacted phenol was removed under reduced pressure to obtain an aminotriazine-modified novolak resin. The hydroxyl equivalent was 120 g / equivalent.

Preparation Example 1: Preparation of Primer Composition (1)

35 mass parts of novolak resin ("PHENOLITE TD-2131" made by DIC Corporation, hydroxyl group equivalent 104 g / equivalent), epoxy resin ("EPICLON 850-S" made by DIC Corporation; bisphenol A type epoxy resin, epoxy group equivalent 188 g) / Equivalent) 64 mass parts and 1 mass part of 2, 4- diamino-6-vinyl-s-triazine ("VT" by the Shikoku Chemical Co., Ltd.) are mixed, and a non volatile matter is substituted with methyl ethyl ketone. The primer composition (1) was obtained by diluting so that it may become 2 mass% and mixing uniformly.

Preparation Example 2: Preparation of Primer Composition (2)

35 mass parts of novolak resin ("PHENOLITE TD-2131" made by DIC Corporation, hydroxyl group equivalent 104 g / equivalent), epoxy resin ("EPICLON 850-S" made by DIC Corporation; bisphenol A type epoxy resin, epoxy group equivalent 188 g) / Equivalent) 64 mass parts and 1 mass part of silane coupling agents ("VD-5" by Shikoku Chemical Co., Ltd.) which have a triazine ring are mixed, and it diluted by methyl ethyl ketone so that a non volatile matter may be 2 mass%. And the primer composition (2) was obtained by mixing uniformly.

Preparation Example 3: Preparation of Primer Composition (3)

Methyl ethyl after mixing 65 mass parts of amino triazine novolak resin obtained by the manufacture example 1, and 35 mass parts of epoxy resins ("EPICLON 850-S" by DIC Corporation; bisphenol-A epoxy resin, epoxy group equivalent 188 g / eq.) The primer composition (3) was obtained by diluting so that a non volatile matter might be 2 mass% with ketone, and mixing uniformly.

Preparation Example 4 Preparation of Primer Composition (4)

Methyl ethyl after mixing 48 mass parts of amino triazine novolak resin obtained by the manufacture example 1, and 52 mass parts of epoxy resins ("EPICLON 850-S" by DIC Corporation; bisphenol-A epoxy resin, epoxy group equivalent 188 g / equivalent) The primer composition (4) was obtained by diluting so that a non volatile matter might be 2 mass% with ketone, and mixing uniformly.

Preparation Example 5: Preparation of Primer Composition (5)

Methyl ethyl after mixing 39 mass parts of amino triazine novolak resin obtained by the manufacture example 1, and 61 mass parts of epoxy resins ("EPICLON 850-S" by DIC Corporation; bisphenol-A epoxy resin, epoxy group equivalent 188 g / equivalent) The primer composition (5) was obtained by diluting so that a non volatile matter might be 2 mass% with a ketone, and mixing uniformly.

Preparation Example 6 Preparation of Primer Composition (6)

31 mass parts of amino triazine novolak resin obtained by the manufacture example 1, and 69 mass parts of epoxy resins ("EPICLON 850-S" by DIC Corporation; bisphenol-A epoxy resin, epoxy group equivalent 188 g / equivalent), methyl ethyl, after mixing The primer composition (6) was obtained by diluting so that a non volatile matter might be 2 mass% with ketone, and mixing uniformly.

Preparation Example 7: Preparation of Primer Composition (7)

47 mass parts of amino triazine novolak resin obtained by the manufacture example 1, and 52 mass parts of epoxy resins ("EPICLON 850-S" by DIC Corporation; bisphenol-A epoxy resin, epoxy group equivalent 188 g / equivalent), trimellitic anhydride After mixing 1 part by mass, the mixture was diluted with methyl ethyl ketone so as to have a nonvolatile content of 2% by mass, and mixed uniformly to obtain a primer composition (7).

Preparation Example 8 Preparation of Primer Composition (R1)

The block isocyanate resin (resin 25 mass% aqueous solution) was diluted with methyl ethyl ketone so that a non volatile matter might be 2 mass%, and the primer composition (R1) was obtained.

Preparation Example 9 Preparation of Primer Composition (R2)

Primer composition (R2) by diluting 100 mass parts of epoxy resins ("EPICLON 850-S" made by DIC Corporation; bisphenol-A epoxy resin) so that non volatile matter may be 2 mass% with methyl ethyl ketone, and it mixes uniformly. Got.

[Preparation of Fluid 1]

According to Example 1 of Unexamined-Japanese-Patent No. 4573138, the cationic silver nanoparticle which consists of flake-like flakes of gray-green metal luster which is a composite of silver nanoparticles and the organic compound which has a cationic group (amino group) was obtained. Then, the powder of this silver nanoparticle was disperse | distributed in the mixed solvent of 45 mass parts of ethylene glycol and 55 mass parts of ion-exchange water, and the fluid 1 which has 5 mass% of cationic silver nanoparticles was prepared.

(Example 1)

On the surface of a polyimide film (" Kapton 150EN-C " manufactured by Doré DuPont Co., Ltd .; 38 μm in thickness), the primer composition 1 obtained in Preparation Example 1 is placed on a table-type small coater (RK Print Coat Instruments Co., Ltd.) K printing prop "), and it coated so that the thickness after drying might be set to 100 nm. Next, the primer layer was formed on the surface of the polyimide film by drying at 150 degreeC for 5 minutes using a hot air dryer.

The fluid 1 obtained above was coated on the surface of the primer layer formed above using the bar coater. Next, the silver layer (film thickness 20nm) corresponded to the said metal nanoparticle layer (C) was formed by drying at 150 degreeC for 5 minutes.

The silver layer formed above was immersed in an electroless copper plating solution ("OIC Kappa", pH 12.5, manufactured by Okuno Seiyaku Kogyo Co., Ltd.) at 45 ° C. for 12 minutes, electroless copper plating was performed, and copper by electroless plating. The plating layer (film thickness 0.2 micrometer) was formed.

The copper plating layer obtained by electroless copper plating obtained above was set on the cathode side, copper containing copper was set on the anode side, and electrolytic plating was carried out for 30 minutes at a current density of 2.5 A / dm 2 using an electrolytic plating solution containing copper sulfate. By this, the copper plating layer (film thickness 15 micrometers) by electrolytic copper plating was formed in the surface of the copper plating layer by electroless copper plating. As said electrolytic plating liquid, copper sulfate 70g / L, sulfuric acid 200g / L, chlorine ion 50mg / L, and 5 ml / L of additives ("Toprutina SF-M" by Okuno Seiyaku Kogyo Co., Ltd.) were used. Moreover, what combined the copper plating layer by electroless copper plating and the copper plating layer by electrolytic copper plating formed on it corresponds to the said metal plating layer (D).

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

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

Lamination | stacking by the method similar to Example 1 except having used primer composition (2)-(7), (R-1), or (R-2) instead of the primer composition (1) used in Example 1 Sieves (2) to (7), (R-1) or (R-2) were obtained.

The following measurement and evaluation were performed about the laminated bodies (1)-(7), (R1), and (R2) obtained in said Example 1-7 and Comparative Examples 1-2.

[Measurement of Peel Strength Before Heating]

About each laminated body obtained above, peeling strength was measured using "autograph AGS-X 500N" by the company. In addition, the lead width used for the measurement was 5 mm, and the angle of the peel was 90 degrees. In addition, although the peeling strength tends to show a high value, so that the thickness of a metal plating layer becomes thick, the peeling strength in this invention was measured based on the measured value in 15 micrometers in thickness of a metal plating layer.

[Evaluation of Adhesiveness]

From the value of the peeling strength before the heating measured above, adhesiveness was evaluated according to the following criteria.

A: The value of peeling strength is 650 N / m or more

B: Peel strength is 450 N / m or more but less than 650 N / m

C: value of peeling strength is 250N / m or more and less than 450N / m

D: value of peeling strength is less than 250N / m

[Measurement of Peel Strength After Heating]

About each laminated body obtained above, it stored in the dryer set to 150 degreeC for 168 hours, and heated. After heating, the peel strength was measured by the method similar to the above.

[Evaluation of Heat Resistance]

The retention rate before and after heating was computed using the peeling strength value before and behind the heating measured above, and heat resistance was evaluated according to the following reference | standard.

A: The retention rate is 85% or more

B: Retention rate is 70% or more but less than 85%

C: The retention rate is 55% or more but less than 70%

D: retention rate is less than 55%

Table 1 shows the results of measuring the composition of the primer compositions used in Examples 1 to 4, Comparative Examples 1 and 2, the peel strength before and after heating, and the results of evaluation of adhesion and heat resistance. In addition, the composition of a primer composition shows only a non volatile matter.

TABLE 1

The laminates (1) to (7) obtained in Examples 1 to 7, which are the laminates of the present invention, were found to have sufficiently high initial adhesiveness (before heating), and also less degradation of peeling strength after heating and excellent heat resistance. there was.

On the other hand, although the adhesiveness of initial stage (before heating) was sufficient for the laminated bodies R1 and R2 obtained by the comparative examples 1 and 2, the fall of the peeling strength after heating was large, and it was confirmed that there was a problem in heat resistance.

Claims (10)

A compound (b1) in which the primer layer (B) has an aminotriazine ring as a laminate in which a primer layer (B), a metal nanoparticle layer (C), and a metal plating layer (D) are sequentially stacked on the support (A). It is a layer containing the laminated body characterized by the above-mentioned. The method of claim 1,
The laminated body whose compound (b1) which has the said amino triazine ring is aminotriazine modified novolak resin (b1-1). The method according to claim 1 or 2,
The laminated body whose said primer layer (B) is a layer which further contains an epoxy resin (b2). The method of claim 1,
The said primer layer (B) is a layer containing an aminotriazine modified novolak resin (b1-1) and an epoxy resin (b2), The phenolic hydroxyl group in the said aminotriazine modified novolak resin (b1-1) ( The laminated body whose molar ratio [(y) / (x)] of x) and the epoxy group (y) in the said epoxy resin (b2) is the range of 0.1-5. The method according to claim 2 or 4,
The laminated body whose hydroxyl value of the said aminotriazine modified novolak resin (b1-1) is 50-200 mgKOH / g. The method according to any one of claims 3 to 5,
The laminated body whose said epoxy resin (b2) is a bisphenol-A epoxy resin. The method according to any one of claims 1 to 6,
Laminated body whose said primer layer (B) is a layer which further contains the crosslinking agent of polyhydric carboxylic acid. The laminated body of any one of Claims 1-7 was used, The printed wiring board characterized by the above-mentioned. The laminated body in any one of Claims 1-7, and the laminated body whose said support body (A) is a film was used, The flexible printed wiring board characterized by the above-mentioned. The laminated body of any one of Claims 1-7 was used. The molded article characterized by the above-mentioned.