TW201629132A - Primer composition for plating, base to be plated, composite body of insulating base and metal layer, method for producing base to be plated, and method for producing composite body of insulating base and metal layer - Google Patents

Abstract

The present invention provides a primer composition for plating, which is characterized by containing (A) metal nanoparticles of at least one kind selected from the group consisting of silver nanoparticles, copper nanoparticles, silver core-copper shell nanoparticles and silver-copper anisotropic composite particles, (B) a blocked isocyanate and (C) a solvent. By using this primer composition for plating, a metal layer which exhibits high adhesion is able to be formed on an insulating base at low cost by a simple plating process without performing surface roughening.

Description

Primer composition for plating, substrate to be plated, composite of insulating substrate and metal layer, and manufacturing method therefor

The present invention relates to a plating primer composition for forming a metal layer on an insulating substrate by a plating treatment, a substrate to be plated having a plating primer layer, and a substrate to be plated. A composite of an insulating substrate and a metal layer obtained by plating as a material, and a method for producing the same.

The technique of forming a metal layer on an insulating substrate such as plastic, glass, or ceramics has been widely applied to decorative plating for imparting a metallic texture, circuit formation for electronic device packaging, and electromagnetic wave shield formation. On the other hand, it is generally difficult for such an insulating substrate and a metal layer to form a strong bond, and in order to obtain good adhesion, an insulating substrate is known for the purpose of utilizing an anchor effect. A method in which the surface is roughened by a chemical etching treatment. However, the method of roughening the surface is a troublesome step of using a strong oxidizing agent such as chromic acid or permanganic acid, and there is a concern that the etching agent has an environmental load.

On the other hand, in the method of not requiring the roughening step of the surface of the substrate, a method of applying a primer for electroless plating to an insulating substrate has been proposed. For example, Patent Document 1 has proposed a primer solution group for imparting a strong alkaline aqueous solution treatment, which is formed by hydrolysis of an ester bond of a polymer having a (meth) acrylate structure, and which can be imparted to a catalyst. Adult. However, in this method, it is necessary to carry out a complicated step of further activating the catalyst by providing a primer layer on the insulating substrate and then performing pretreatment for the catalyst.

Patent Document 2 proposes a coating composition for electroless plating comprising a composite of a palladium particle and a dispersant, a solvent, and a binder resin. In this method, it has been revealed that the catalyst activating step can be omitted by directly dispersing the palladium particles which become the catalyst for electroless plating; and in the drying step of the coating composition, on the surface of the uneven structure formed on the surface of the coating film. The palladium particles are unevenly distributed, and a registration effect occurs by the uneven structure, thereby improving the adhesion of the plating film. However, in this method, since the catalyst is segregated on the surface of the uneven structure generated during the drying process of the coating film, it is difficult to make the density of the catalyst on the surface uniform, and uneven deposition of the plating occurs. The possibility of a barrier in the uniform metal layer. In addition, in recent years, the price of palladium catalysts has risen, and the development of catalyst technology that is being replaced is being sought.

Patent Document 3 proposes a primer composition for electroless plating, which is characterized by containing a metal colloidal particle, a hardenable composition which is hardenable at 120 ° C or lower, and a solvent; a metal colloid used as a catalyst, except for a palladium colloid In addition, cheaper colloidal particles of silver colloidal particles and silver/palladium are also disclosed. In the proposed technique, it has been described that the hardening composition is hardened, and the metal colloid is fixed on the non-conductive substrate, and the adhered metal colloid becomes an electroless plating core, so that the plating film can also be used. Close to the substrate. Accordingly, in this method, the adhesion to the plating film on the non-conductive substrate depends on the adhesion between the metal colloid particles of the plating core and the plating film, and in order to improve the adhesion strength, it is necessary to improve the non-contact. Adhesion between the cured curable composition formed on the conductive substrate and the plating film.

Prior technical literature Patent literature

Patent Document 1 JP-A-10-317153

Patent Document 2, JP-A-2014-65909

Patent Document 3, JP-A-2008-07849

In view of the above-described circumstances, the problem to be solved by the present invention is to provide a technique for forming a metal layer having high adhesion on an insulating substrate at a low cost by a simple plating process without surface roughening. .

In order to solve the above problems, the inventors of the present invention have intensively studied and found a composition for use in a primer layer for forming a metal layer having high adhesion on an insulating substrate by a simple plating treatment. The present invention is completed in an effective manner; the composition contains nano particles and a block isocyanate, wherein the nano particles are inexpensive metal silver, copper nanoparticles, or silver compared to palladium. Composite nanoparticle of core-copper shell.

That is, the present invention provides a plating primer composition, a substrate to be plated having the plating primer layer, and an insulating substrate and metal obtained by plating the substrate to be plated. Layer complex and these In the manufacturing method, the plating primer composition is characterized by comprising metal nanoparticle (A), a blocked isocyanate (B), and a solvent (C), wherein the metal nanoparticle (A) is selected from the group consisting of silver At least one metal nanoparticle of the group of nanoparticle, copper nanoparticle, silver core-copper shell nanoparticle, and silver-copper anisotropic composite particle.

According to the present invention, it is possible to exhibit a so-called particularly remarkable effect by forming a metal layer which exhibits high adhesion and excellent in heat-resistant stability on an insulating base material by a simple plating treatment without requiring surface roughening. According to the present invention, it is possible to easily produce a composite system having a metal layer on an insulating substrate, and it is possible to use a decorative material such as a resin, a glass, or a ceramic to impart a metallic texture, a circuit for packaging an electronic device, or an electromagnetic wave shield. Manufacturing.

1‧‧‧Metal Nanoparticles

2‧‧‧Plastic coating layer

3‧‧‧ resin layer

4‧‧‧Insulating substrate

5‧‧‧ crack

Fig. 1 is a view showing a cross-sectional form of a plating primer layer obtained by using the plating primer composition of the present invention.

Fig. 2 is a view showing a cross-sectional view of a plating primer layer obtained by using the plating primer composition of the present invention.

Fig. 3 is a view showing a cross-sectional view of a plating primer layer obtained by using the plating primer composition of the present invention.

Fig. 4 is a view showing a cross-sectional view of a plating primer layer obtained by using the plating primer composition of the present invention.

Fig. 5 is a view showing a cross-sectional view of a plating primer layer obtained by using the plating primer composition of the present invention.

Fig. 6 is a view showing a cross-sectional view of a plating primer layer obtained by using the plating primer composition of the present invention.

Fig. 7 is a scanning electron microscope observation image (scale bar: 100 nm) on the surface of the plating primer layer prepared in Example 1 .

Fig. 8 is an enlarged view of a scanning electron microscope observation image on the surface of the plating primer layer produced in Example 1 (scale bar: 100 nm).

Fig. 9 is a scanning electron microscope observation image (scale bar: 100 nm) of the surface of the plating primer layer produced in Example 3.

Fig. 10 is a scanning electron microscope observation image (scale bar: 100 nm) of the surface of the plating primer layer produced in Example 3.

[Formation for implementing the invention]

The contents of the present invention are specifically described below.

<Insulating substrate>

In the present invention, for an insulating substrate on which a metal layer is formed on the surface, for example, a polyimide resin; a polyamide-imine resin; a polyamide resin; polyterephthalic acid can be suitably used. Polyester resin of ethylene glycol ester, polyethylene naphthalate, liquid crystal polymer, etc.; acrylic resin; polycarbonate; cycloolefin polymer; paper phenol; paper epoxy; Glass epoxy resin; ABS resin; glass; ceramics, etc. Further, any of the flexible material, the rigid material, and the rigid flexible material may be used as the insulating base material. Such a thin insulating substrate can be used as a film, and a thick one can be a molded article having a complicated shape in addition to a sheet or a plate.

Further, as the insulating base material used in the present invention, for example, a commercially available material formed into a film, a sheet, or a plate may be used, or a solution, a melt, or a dispersion of the above material may be used. Shaped material.

As the insulating substrate for flexible use, the above polyimine, polyamine-imine, polyester resin, polyamide, polyphenylene sulfide (PPS), polyether ether ketone (PEEK), etc. can be used. For the film of the commercially available polyimine resin, for example, Kapton (Toray‧Du Pont, registered trademark), UPILEX (Ube Industries, registered trademark), APICAL (KANEKA, registered trademark), POMIRAN can be suitably used. (Arakawa Chemical, registered trademark), Neoprim (Mitsubishi Gas Chemical, registered trademark) and other commercially available films. Further, as the commercially available polyester resin, a polyethylene terephthalate film such as Lumirror (Toray, registered trademark) or Mylar (DuPont) may be suitably used, and polyethylene naphthalate ( Teonex; Teijin Du Pont), liquid crystal polymer Vexter series (Kuraray, Vecstar is a registered trademark) and so on. Further, these films can be used in a state of being cut into a certain size, or can be used in a continuous film state.

The insulating base material used in the present invention is used for coating a plating primer composition for the purpose of improving the adhesion between the insulating base material and the primer layer formed using the plating primer composition of the present invention. Previously, surface treatment was possible. In the surface treatment method of the insulating base material, a conventionally known method may be appropriately selected. For example, a physical method such as UV treatment, ozone treatment, corona treatment, or plasma treatment may be suitably used. These treatment methods can be carried out by one type of method alone or in combination of a plurality of types. Further, in the case where the insulating base material is a polyimide resin, A chemical method in which the surface of the substrate of the polyimide resin is treated with an aqueous alkali solution can be used. In the case where the insulating substrate is a polyester resin, it is preferred that the surface of the polyester resin is subjected to UV treatment, corona treatment, or plasma treatment. These surface treatment methods can be carried out separately or in combination with a plurality of methods. These surface treatment methods are not roughening the number of sub-μm to μm steps formed by the usual roughening step, but merely changing the functional groups present on the surface of the insulating substrate or forming the surface at a nanometer level. Bump.

<Metal Nanoparticles (A)>

The metal nanoparticles (A) used in the present invention are in a state of being aggregated in a plating primer layer to be described later, and have electroconductivity which can be plated, and a metal which is relatively inexpensive as an electroless plating medium. Preferably, silver or copper nanoparticles or composite nanoparticles of silver and copper, that is, silver-copper core shell particles or silver-copper anisotropic composite particles, or the like can be suitably used. Among them, silver nanoparticles are preferred. In the present invention, the metal nanoparticle (A) may be used singly or in combination of plural kinds. Moreover, even if an oxide film or a vulcanization film exists on the surface of a metal nanoparticle, it is good if it exists as an electroless plating catalyst.

The shape of the metal nanoparticle (A) is not particularly limited as long as it is stably dispersed in the plating primer composition of the present invention, and may be appropriately selected depending on the purpose. A metal granule of various shapes such as a lenticular shape, a polyhedral shape, a flat plate shape, a rod shape, or a metal wire shape, or a mixture of a plurality of types.

The size of the metal nanoparticle (A) is observed by the particle shape of the electron microscope. When the shape is circular or polyhedral, the diameter is preferably 1 to 200 nm, and the plating of the present invention is preferred. From the viewpoint of dispersibility and stability of the metal nanoparticle in the primer composition, it is more preferable to use 2 to 100 nm. In addition, from the viewpoint of the activity of the catalyst for electroless plating contained in the conductive primer layer for plating, metal fine particles of 5 to 50 nm are particularly preferable.

The observation image in the electron microscope of the metal nanoparticle (A) has a symmetrical shape with respect to the short axis and the long axis, such as a lens shape, a rod shape, or a metal line shape, and has a short diameter of 1 to 200 nm, more preferably 2~100nm, further preferably 5~50nm. The particle size distribution of the metal nanoparticles (A) may be neatly monodispersed, and may be a mixture of particles having a particle diameter of the above preferred particle size range.

The method for producing the metal nanoparticles (A) used in the present invention is not particularly limited, and it can be produced by various methods. For example, it can be produced by a vapor phase method such as a vaporization method in a low vacuum gas. The metal compound can also be directly reduced in the liquid phase to directly prepare a dispersion of the metal fine particles. In the gas phase or liquid phase method, the stability in the composition for plating or the simplicity of the production steps can be particularly suitably used in the liquid phase method.

The metal nanoparticle (A) used in the present invention maintains dispersion stability without agglomeration, fusion, and precipitation in the primer composition for plating of the present invention, and is formed by the primer composition. The plating primer layer exhibits a function of being firmly fixed, and the surface of the metal nanoparticle (A) is protected by an organic compound protecting agent (also referred to as an organic protective agent (P) in the present specification). The composite is preferred. Chain end seal When a blocking agent is dissociated, a protective agent having a hydroxyl group or an amine group reactive with an isocyanate group is preferably used as a protective agent for such an organic compound, and polyvinyl alcohol, polyallylamine, and poly are preferably used. A compound having a block such as an imine or a polypropylenimine. In addition to such a structure, when the polyethylene glycol moiety is introduced, it is preferable because the dispersion stability of the metal nanoparticle (A) can be improved, and particularly, it is particularly suitable to use a polyethyleneimine block and a polyethylene glycol. Alcohol block compound (P1).

The above compound (P1) having a polyethyleneimine block and a polyethylene glycol block is particularly suitably used, for example, by introducing a functional group at the terminal of a commercially available polyethylene glycol to make it commercially available. A compound in which an imine is chemically bonded, and an amine group in a polyethyleneimine (x1) having a number average molecular weight of 500 to 50,000 is bonded to a polyethylene glycol (x2) having a number average molecular weight of 500 to 5,000. The compound (P1) having a polyethyleneimine block and a polyethylene glycol block which can be used in the present invention may have a specific structure of a polyethyleneimine block and a polyethylene glycol block, and may further Import other structures.

The method for producing a dispersion of the metal nanoparticles (A) by the liquid phase method described above can be suitably used in a liquid phase or a method of reducing a metal compound in the presence of the organic protective agent (P). It is produced by the method described in the Unexamined-Japanese-Patent No. 2008-007124, the Unexamined- For example, the compound (P1) having the polyethyleneimine block and the polyethylene glycol block described above is dissolved or dispersed in an aqueous medium, that is, water or a mixed solvent of water and a water-soluble organic solvent, which will be described later, in which Adding a metal compound and making a uniform score by using a wronging agent as necessary After the dispersion, or by mixing the reducing agent with the dismuting agent, the reduced metal becomes a nanoparticle (microparticle having a size of a nano metal grade), whereby the metal nanoparticle (A) can be obtained. In this method, while forming the metal nanoparticle (A), the surface of the metal nanoparticle (A) is protected by the organic protective agent (P1) to form the metal nanoparticle (A) and the organic protective agent ( Complex of P1).

In the production of the metal nanoparticle (A) of the present invention, the metal nanoparticle (A) is preferably dispersed in a solvent in the production of the primer composition for plating of the present invention. In the solvent (C-1) in which the metal nanoparticles (A) are dispersed, the block isocyanate (B) may be directly dissolved or dispersed, or may be dispersed as long as the metal nanoparticles (A) are stably dispersed. The solution or the dispersion of the blocked isocyanate (B) is not particularly limited, and various solvents can be used, and it can be a mixed solvent of water, a water-soluble organic solvent, or an organic solvent containing no water. One. In this case, the surface of the metal nanoparticle (A) is protected by the organic protective agent (P), and the composite system of the metal nanoparticle (A) and the organic protective agent (P) is used to improve the effect of the present invention. Preferably. The organic protective agent (P) used in the present invention may be added at the time of production of the metal nanoparticles (A), or may be added after the production of the metal nanoparticles (A).

The organic protective agent (P) used in the present invention is preferably 20% by mass or less based on the metal nanoparticles (A) from the viewpoint of dispersion stability, and is used as a seed for electrical plating. The viewpoint of the catalyst for electroless plating is preferably 10% by mass or less.

The aqueous dispersion of the metal nanoparticle (A) of the present invention or the mixed solvent dispersion of water and a water-soluble organic solvent can be obtained by the foregoing In the liquid phase synthesis method, if necessary, the dispersion liquid at the time of production and the dispersion of the nano metal (A) for producing a plating primer composition are changed by solvent exchange or solvent addition. The composition of the solvent is possible.

In the above-mentioned water-soluble solvent which can be mixed with water, for example, an alcohol such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol or tertiary butanol may be mentioned. Ketones such as acetone and 2-butanone, polyols or other esters such as ethylene glycol and glycerin, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol monobutyl ether, and diethylene glycol a glycol ether such as glyceryl ether, propylene glycol methyl ether acetate or butyl diethylene glycol acetate, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, A solvent such as a guanamine-based solvent such as N,N-dimethylformamide or the like can be used alone or in combination with water.

Further, the organic solvent may be used alone or in combination with water, by using a water-soluble solvent which can be mixed with water as described above or a mixture of plural kinds. In this case, there is a case where a certain amount of water is contained due to moisture absorption or the like, but since it is not intended to be mixed with water, in the present invention, it is treated as an organic solvent which does not contain water.

<Block isocyanate compound (B)>

The blocked isocyanate (B) used in the present invention has a functional group [b] in which an isocyanate group is blocked by a chain terminal blocking agent, and a commercially available blocked isocyanate can be used, and it can be produced as necessary. use.

The blocked isocyanate (B) can be produced by reacting a part or all of an isocyanate group of the isocyanate compound (b-1) with a chain terminal blocking agent.

For the isocyanate compound (b-1) used for the production of the aforementioned blocked isocyanate (B), those having an isocyanate group can be used, for example, 4,4'-diphenylmethane diisocyanate, 2,4' can be used. - an aromatic structure of diphenylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenyl diisocyanate, tolyl diisocyanate, naphthalene diisocyanate, etc. Polyisocyanate compound; hexamethylene diisocyanate, diazonium diisocyanate, cyclohexane diisocyanate, isophorone 'diisocyanate, dicyclohexylmethane diisocyanate, xylene diisocyanate, tetramethyl xylene diisocyanate An aliphatic polyisocyanate compound, a polyisocyanate compound having an aliphatic cyclic structure, a biuret, a trimer isocyanate, an adduct or the like.

Further, the isocyanate compound (b-1) can be obtained by reacting the above polyisocyanate compound with a compound having a hydroxyl group or an amine group.

In the case of the compound having a hydroxyl group, a compound having a hydrophilic group and a hydroxyl group is preferably used from the viewpoint of adhesion between the plating primer composition of the present invention and an insulating substrate. Further, when the blocked isocyanate (B) is used in combination with an aqueous medium, by using a compound having a hydrophilic group and a hydroxyl group, it is possible to impart good water dispersion stability to the blocked isocyanate (B). good.

As the compound having a hydrophilic group and a hydroxyl group, for example, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dihydroxymethylpentanoic acid, or the like can be used. a polyol having a carboxyl group; a polybasic group having a sulfonic acid group such as 5-sulfoisodecanoic acid, sulfoisophthalic acid, 4-sulfodecanoic acid or 5-(4-sulfophenoxy)isodecanoic acid Alcohol, etc.

Further, as the compound having a nonionic hydrophilic group and a hydroxyl group, for example, polyethylene glycol, polyethylene-polypropylene copolymer, polyethylene glycol monomethyl ether, polyethylene glycol single ethyl group can be used. Ethyl ether, polyethylene glycol monopropyl ether, polyethylene glycol monobutyl ether, and the like.

Further, as the compound having an amine group, a compound having a hydrophilic group and an amine group can be used, and for example, 2-aminopropionic acid, 2-aminoethylsulfonic acid, 4-aminobenzenesulfonate can be used. Acid, 2,6-diaminohexanoic acid, 2,5-diaminopentanoic acid, and the like.

From the viewpoint of improving the adhesion between the plating primer layer and the insulating base material obtained by using the plating primer composition of the present invention, the isocyanate compound (b-1) is used for the blocked isocyanate. It is preferred to introduce an aromatic structure into (B), and it is preferred to use a polyisocyanate compound having an aromatic structure. Among them, 4,4'-diphenylmethane diisocyanate, tolyl diisocyanate, 4,4'-diphenylmethane diisocyanate trimeric isocyanate, tolyl diisocyanate trimeric isocyanate are used. Better.

For the chain end sealant used for the production of the above-mentioned blocked isocyanate (B), for example, a phenol compound such as phenol, cresol or the like; ε-caprolactam, δ-valerolactone, γ- can be used. Indoleamine such as butyralamine; methotrexate, acetaldoxime, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, etc., 2-hydroxypyridine , butyl cyproterone, propylene glycol monomethyl ether, benzyl alcohol, methanol, ethanol, n-butanol, isobutanol, dimethyl malonate, diethyl malonate, methyl acetate, Acetylacetate, ethyl acetonylacetone, butyl mercaptan, dodecyl mercaptan, acetophenone, acetamide, amber imine, maleimide, imidazole, 2- Methylimidazole, urea, sulfur urea, ethyl ethyl urea, diphenylaniline, aniline, carbazole, ethylimine, polyethyleneimine, 1H-pyrazole, 3-methylpyrazole, 3,5-di Methylpyrazole and the like. In particular, it is preferred to use a chain end-blocking agent which is capable of dissolving an isocyanate group by heating to preferably 70 to 200 ° C, more preferably 110 to 180 ° C. Amine or bismuth is better.

The blocked isocyanate (B) can be produced by reacting the previously produced isocyanate compound (b-1) with the chain terminal blocking agent, and can be produced by the isocyanate compound (b-1). The raw materials used for production are produced by mixing and reacting with the above-mentioned chain terminal blocking agent.

More specifically, the blocked isocyanate (B) used in the present invention is produced by reacting the above-mentioned polyisocyanate compound (b-1-1) with a compound having a hydroxyl group or an amine group to have an isocyanate group at the terminal. The isocyanate compound (b-1) can be produced by reacting the above-mentioned isocyanate compound (b-1) with the above-mentioned chain terminal blocking agent.

For the purpose of imparting water dispersion stability or storage stability to the above-mentioned blocked isocyanate (B), a method of using a blocked isocyanate having a hydrophilic group as the above-mentioned blocked isocyanate (B), a method of using a surfactant, and the like are exemplified. .

As the hydrophilic group, for example, an anionic group, a cationic group, or a nonionic group can be used, and an anionic group is more preferably used.

As the aforementioned anionic group, for example, a carboxyl group, a carboxylate group, a sulfonic acid group, a sulfonate group or the like can be used, and among them, a part or all of a carboxyl group or a sulfonic acid group is neutralized with a basic compound. The carboxylate group or the sulfonate group can impart excellent water dispersion stability and is preferred.

The basic compound which can be used for the neutralization of the above anionic group may, for example, be ammonia, triethylamine or pyridine. An organic amine such as a phenyl group or an alkanolamine such as monoethanolamine; or a metal base compound containing sodium, potassium, lithium or calcium. The purpose of producing a conductive material by a plating treatment is that the metal alkali compound may hinder the conductivity or the like, and it is preferred to use the organic amine or the alkanolamine.

Further, as the cationic group, for example, a tertiary amine group can be used. For the acid which can be used for partially or completely neutralizing one of the above-mentioned tertiary amine groups, for example, an organic acid such as acetic acid, propionic acid, lactic acid or maleic acid, sulfonic acid, methanesulfonic acid or the like can be used. The inorganic acids such as organic sulfonic acid, hydrochloric acid, sulfuric acid, orthophosphoric acid, or orthophosphorous acid are used singly or in combination of two or more. For the purpose of producing a conductive material by a plating treatment, since chlorine or sulfur may hinder electrification, acetic acid, propionic acid, lactic acid, maleic acid or the like is preferably used.

Further, as the nonionic group, for example, a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, a poly(oxyethylene-oxypropylene) group, a polyoxyethylene-polyoxypropylene group, or the like can be used. Polyoxyalkylene group. Among them, the use of a polyoxyalkylene group having an oxyethylene unit particularly improves hydrophilicity.

The hydrophilic group is a compound having a hydrophilic group having a hydroxyl group such as 2,2-dimethylolpropionic acid and a hydroxyl group, and the isocyanate compound (b1-1) when the block isocyanate (A) is produced. The reaction is carried out to introduce a blocked isocyanate (B).

In addition, examples of the surfactant which can be used for the purpose of imparting water dispersion stability to the blocked isocyanate (B) include an anionic surfactant, a nonionic surfactant, and a cationic surfactant. , zwitterionic surfactants, and the like.

The above anionic surfactant may, for example, be a sulfate of a higher alcohol and a salt thereof, an alkylbenzenesulfonate, a polyoxyethylene alkylphenylsulfonate or a polyoxyethylene alkyl diphenyl ether. Sulfonic acid salt, sulfuric acid half ester of polyoxyethylene alkyl ether, alkyl diphenyl ether disulfonate, dialkyl sulfonate sulfonate, etc., for nonionic surfactants, can be used For example, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene diphenyl ether, polyoxyethylene-polyoxypropylene block copolymer, acetylene glycol surfactant, and the like.

Further, as the cationic surfactant, for example, an alkylammonium salt or the like can be used.

Further, as the zwitterionic surfactant, for example, an alkyl (decylamine) betaine, an alkyldimethylamine oxide or the like can be used.

As the surfactant, a fluorine-based surfactant, an anthrone-based surfactant, or the like can be used in addition to the above.

The blocked isocyanate (B) used in the present invention is a mixture of the metal nanoparticle (A) in a state of a solution or a dispersion when the primer composition for plating of the present invention is produced. Preferably.

The solvent (C-2) which dissolves or disperses the blocked isocyanate (B) used in the present invention may be water, a mixture of water and a water-soluble organic solvent, or an organic solvent which does not contain water, and the metal naphthalene may be used as described above. The solvent group exemplified as the solvent in which the rice particles (A) are dispersed is selected and used. on The solvent to be selected may be selected from the same solvent as the solvent in which the metal nanoparticles (A) are dispersed, or a different solvent may be selected.

<Solvent (C)>

The solvent (C) constituting the primer composition for plating of the present invention may form a stable dispersion in a state in which the metal nanoparticle (A) and the blocked isocyanate (B) are contained. There is no particular limitation, and it may be any one of a mixed solvent of water, water and a water-soluble organic solvent, and an organic solvent which does not contain water.

The water-soluble solvent which can be mixed with water, for example, an alcohol such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol or tertiary butanol; acetone a ketone such as 2-butanone; a polyhydric alcohol or other ester of ethylene glycol or glycerin; ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol monobutyl ether, Glycol ethers such as diethylene glycol dimethyl ether, propylene glycol methyl ether acetate, butyl diethylene glycol acetate; N-methyl-2-pyrrolidone, N, N-dimethyl A guanamine-based solvent such as acetalamine or N,N-dimethylformamide can be used alone or in combination with water and mixed with water.

Further, in the above organic solvent, the water-soluble solvent which can be mixed with water described above may be used alone or in combination with water without being mixed with water. In this case, there is a case where a certain amount of water is contained due to moisture absorption or the like, but since it is not attempted to be mixed with water, the present invention is treated as an organic solvent which does not contain water.

With respect to the aforementioned solvent (C) constituting the plating primer composition of the present invention, the primer composition for plating of the present invention is produced by dispersing a metal nanoparticle (A) with a blocked isocyanate. (B) solution or fraction When the dispersion liquid is mixed and mixed, it is a mixed solvent of a solvent (C-1) for dispersing metal nanoparticles and a solvent (C-2) for dissolving or dispersing the blocked isocyanate, and the mixed solvent can be further mixed. One or more kinds of solvents from the aforementioned solvent group.

<Compound (D) which is reactive toward isocyanate>

The primer composition for plating of the present invention can contain metal nanoparticles (A) and blocked isocyanate (B) and solvent (C) from the viewpoint of improving the strength of the formed plating primer layer. The plating primer composition further contains a compound (D) reactive with an isocyanate group. In the above solvent (C), the above-mentioned compound (D) can be used to dissolve or disperse stably with the metal nanoparticle (A) and the blocked isocyanate (B), and can be blocked with the chain end. A compound that dissociates the resulting isocyanate-reactive functional group.

The functional group capable of reacting with the isocyanate group formed by dissociation of the chain-side blocking agent may, for example, be a carboxyl group, a hydroxyl group or an amine group, and may be suitably used in one or more kinds of two or more such functional groups in the structure. compound of. In the case of the primer composition for plating of the present invention, the surface of the aforementioned metal nanoparticle (A) is protected by a compound having a block such as polyallylamine, polyethyleneimine or polyallyimide, and the primer is used. From the viewpoint of compatibility in the composition, a compound having an amine group is more preferable.

For such compounds, for example, an acrylic polyol, a polyester polyol, a polyether polyol, or a polycarbonate polyol may be used, and ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, or 1, may be used. Comparative low molecular weights such as 3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, sucrose, methylethylene glycol, glycerin, sorbitol Amount of polyol; 2,2-dimethylol acetic acid, 2,2-dimethylol lactic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2 - dimethylol butyric acid, 2,2-dimethylol valeric acid, lysine, arginine, hydrazine, ethylenediamine, propylenediamine, hexamethylenediamine, 1,2-diamino Alkane, 1,2-diaminopropane, 1,3-diaminopentane, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 4,4'-methylenediphenylamine In addition, one or a plurality of selected ones selected from the group consisting of polyalkylenimines, polyallylamines, and the like may be used. In the primer composition for plating of the present invention, the surface of the metal nanoparticle (A) is protected by a compound having a block such as polyethyleneimine or polyacryl, and is composed of a primer composition. From the standpoint of compatibility, it is more preferred to polyalkyleneimine.

<Plasing Primer Composition>

A suitable aspect of the plating primer composition of the present invention comprises the metal nanoparticle (A), the blocked isocyanate (B), and the solvent (C). Further, a suitable form of the plating primer composition of the present invention contains the metal nanoparticle (A), the blocked isocyanate (B), and the solvent (C), and further contains reactivity with an isocyanate group. Compound (D).

In the plating primer composition of the present invention, a primer-forming component (that is, the aforementioned metal nanoparticle (A) and the above-mentioned blocked isocyanate (B) are further added with a compound (D) reactive with an isocyanate group. The concentration of the entire amount of the primer composition may be appropriately adjusted as long as it is suitable for various printing, coating methods, and surface conditions and shapes of the insulating base material to be described later, and is used in an amount of 1% by mass to 70% by mass. Preferably, from the viewpoint of coatability on an insulating substrate, 1% by mass to 50% by mass is Better. In the case of forming a primer layer for thin plating of 500 nm or less in accordance with various printing and coating methods described later, it is more suitable to use 1% by mass to 20% by mass.

The primer composition for plating of the present invention, the mass of the metal nanoparticle (A) in the composition, the organic protective agent (P) of the metal nanoparticle (A), and the blocked isocyanate (B) And the ratio of the mass of the compound (D) reactive with isocyanate groups, that is, (the organic nanoparticle (A) of the metal nanoparticle (A) + the blocked isocyanate (B) + is reactive toward the isocyanate group) The compound (D))/metal nanoparticle (A) is preferably 0.01 to 0.5, more preferably 0.05 to 0.4. When the ratio is too low, the strength of the plating primer layer itself is lowered, and the peeling of the formed plating film changes, and the film collapses and the sufficient adhesion strength cannot be maintained. On the other hand, when the ratio becomes too high, the metal nanoparticles (A) in the plating primer layer are completely buried in the primer layer, and the conductivity required for the electroplating treatment cannot be expressed or cannot be performed. It is expressed as a catalyst for electroless plating.

In the plating primer composition of the present invention, the block isocyanate (B) is adjusted in the amount of the compound (D) reactive with respect to the isocyanate group, and the chain end sealant is detached. The reactive functional group equivalent of isocyanate in compound (D) which is reactive with isocyanate relative to the isocyanate functional equivalent, ie, adjusted (reactive functional group equivalent of (D)) / (N) equivalent of (B) It is preferable to become 10/1 to 1/5. Regarding the functional group equivalents and the NCO equivalents, commercially available materials may be measured by using a value described in a catalogue or a data sheet, and may be measured by a known method. For the sake of convenience, the molecular weight of the compound to be used may be divided by convenience. Use in functional groups.

The primer composition for plating of the present invention is mainly used for the improvement of coating film forming property, and various surface tension adjusting agents and leveling agents may be added as needed. The amount of the surface tension adjusting agent and the leveling agent to be added is preferably 1.0% by mass or less based on the active ingredient, and particularly preferably 0.5% by mass or less based on the active ingredient.

<Formation of a primer layer for plating using the primer composition for plating of the present invention>

In the present invention, a plating primer layer can be formed by the following steps: (1) on an insulating substrate, the coating contains a material selected from the group consisting of silver nanoparticles, copper nanoparticles, and silver core-copper shells. At least one metal nanoparticle (A), a blocked isocyanate (B), and a solvent (C) plating primer composition of a group of nano particles and silver-copper anisotropic composite particles Step; (2) a step of heating the insulating substrate coated with the plating primer composition.

In the step (1), the method for applying the plating primer composition of the present invention to an insulating substrate is not particularly limited as long as it depends on the shape and size of the insulating substrate. The various printing and coating methods known and used may be appropriately selected for the flexibility, and the like, and specific examples thereof include a gravure printing method, an offset printing method, a relief printing method, a letterpress inversion method, and a screen printing method. , micro contact method, inversion method, air doctor coater method, knife coating method, air knife coating method, extrusion coating method, impregnation coating method, transfer roll coating method, kiss coater Method, casting coating method, spray coating method, inkjet method, die coating method, spin coating method, bar coating method, dip coating method, and the like.

In the step (1) above, the primer composition for plating of the present invention may be entirely coated on the insulating substrate, or may be partially coated, printed, and only partially coated. In the case of pattern coating and printing, a metal plating film can be formed in accordance with a plating process to be described later in accordance with a coating pattern.

In the heating step described in the above step (2), various known heating methods can be used, and an electric furnace, a simmering furnace, a vacuum furnace, a gas furnace, a light irradiation heating device, an infrared heating device, a far infrared ray heating device, and a microwave can be used. One of a heating device, an electron beam heating device, or the like, or a plurality of heating devices are used in combination. Further, if necessary, the heat treatment may be carried out in the atmosphere, in a vacuum, in a nitrogen atmosphere, in an argon atmosphere, or in a hydrogen atmosphere having a concentration lower than the lower explosion limit. Further, in the case where the substrate on which the primer composition for plating is applied is a sheet-like film, sheet or plate, it can be carried out in the apparatus of the heat treatment apparatus, and in the case of a roll sheet, the sheet can be made by The object is continuously moved in a space heated by electric heating, light heating, (far) infrared heating, or microwave heating.

Further, in the present invention, the heat treatment described in the above step (2) may be carried out simultaneously with drying after applying the plating primer composition (B) to the insulating base material (A), or may be dried separately. And heat treatment.

In the present invention, the heat treatment in the above step (2) may be carried out at a temperature higher than the temperature at which the chain terminal blocking agent of the blocked isocyanate (B) contained in the plating primer composition is dissociated, and the insulating layer is used. The heat resistance temperature of the base material and the blocked isocyanate (B) contained in the composition may be appropriately set. For example, when the insulating base material (A) is a polyimide resin, it is 400 ° C or lower, preferably 300 ° C or lower, and if it is polyparaphenylene Ethylene glycol diester is 150 ° C or less, 200 ° C or less for polyethylene naphthalate, 380 ° C or lower for liquid crystal polymer, 130 for paper phenolic resin or paper epoxy resin Below °C, it is preferably 150 ° C or lower for the glass epoxy resin, and preferably 100 ° C or lower for the ABS resin. In the plating primer composition of the present invention, the dissociation temperature of the chain end sealant is preferably in the range of 70 ° C to 200 ° C, and the heat treatment temperature is higher than the dissociation temperature. Preferably, it can be selected at a temperature of from 70 ° C to 400 ° C depending on the type of blocked isocyanate. The heat treatment can be carried out under a constant temperature state, or the temperature can be changed over time. When it changes over time, it can change from the vicinity of the dissociation temperature of the chain-stopping agent further to high temperature, and can change from the dissociation temperature to the low temperature side. The heat treatment time can be appropriately selected depending on the type of the heating device or the insulating substrate to be used, but it is preferable to carry out the treatment time within one hour from the viewpoint of productivity.

The primer composition for plating of the present invention can be formed into a plating primer layer by heating in the above step (2), but is dissociated from the blocked isocyanate (B) and the chain end blocking agent by the aforementioned heat treatment. , and isocyanate-based regeneration, self-crosslinking. Further, the regenerated isocyanate group may react with the organic protective agent (P) of the metal nanoparticles (A), and further, the plating primer composition further contains a compound reactive with the aforementioned isocyanate group (D). In the case of the reaction of the compound (D) reactive with the isocyanate group, a crosslinked structure is formed in the primer layer. Thus, the strength of the primer layer is enhanced by the formation of the crosslinked structure in the primer layer for plating, and the aforementioned metal nanoparticles (A) in the primer layer are strongly fixed.

In the plating primer layer-based resin layer of the present invention, the metal nanoparticles (A) are immobilized in a resin, and the self-crosslinking resin of the blocked isocyanate (B) or the chain end sealer A resin formed by reacting an isocyanate formed by detachment with a compound (D) reactive with an isocyanate group, and a metal nanoparticle (A) is immobilized. In one embodiment, a part of the surface of the outermost layer of the metal nanoparticle (A) is in a form exposed on the surface of the resin layer (Figs. 1 to 3), and the other form is the most prime layer. The surface-based resin layer and the metal nanoparticle (A) are present in the resin layer (Figs. 4 to 6).

The plating primer composition of the present invention can form a plating primer layer by the heating of the above step (2), but by the above heat treatment, the chain end blocking agent is self-blocking isocyanate (B) Reducing the volume of detachment, self-crosslinking due to regenerated isocyanate groups or reaction of isocyanate groups with organic protective agents of metal nanoparticles (A), further by reacting with compounds having reactivity with isocyanate groups (D The reaction is formed in the crosslinked structure in the primer layer, and the resin portion constituting the primer layer is shrunk, whereby the metal nanoparticles (A) are densely filled in the primer layer, resulting in a primer The conductivity of the layer is improved and an effective primer layer can be formed by electrical plating in the subsequent step. Since the crosslinked structure contains the metal nanoparticle (A), the interface between the plating primer layer and the insulating substrate, or the primer layer itself does not collapse, the layer structure can be maintained, but the resin layer on the free surface On the outermost surface, a large number of micro-cracks are formed, and the heat treatment is performed at the volatilization temperature of the detached chain end sealant or the case where the thermal decomposition temperature is high, thereby further promoting the evapotranspiration of the detached chain end sealant or due to thermal decomposition. The evapotranspiration of the material promotes the formation of tiny cracks on the outermost surface of the primer layer (Figs. 1-6).

With regard to the plating primer layer of the present invention, in the plating treatment in the subsequent step, since the plating solution is impregnated by the micro crack generated by the heat treatment, good plating can be formed by contact with the metal nanoparticle (A). Apply film. In this case, the plating treatment is an electric plating treatment, the metal nanoparticle (A) functions as a conductive path, and the plating treatment is an electroless plating treatment, and the metal nanoparticle (A) is used as the metal nanoparticle (A). Electroless plating catalysts function. Therefore, both the electroplating treatment and the electroless plating treatment are small cracks generated on the surface of the primer layer, and the metal nanoparticles (A) that are in contact with the plating solution become the starting point of growth of the plated metal film. In the plating primer layer of the present invention, in addition to the metal nanoparticle (A), the primer layer is strongly fixed, and the micro crack generated on the surface of the primer layer serves as a anchor for the plated metal film ( The anchoring point functions to provide high adhesion to the plated metal film.

When the primer layer for plating of the present invention is used as a primer layer for electrical plating, the layer containing the metal nanoparticles (A) in the cross-sectional direction of the primer layer must be at least one layer or more, and two layers are used. It is preferable that the 10 layers are present from the viewpoint of imparting necessary conductivity to electrical plating. From the viewpoint of conductivity, the number of layers is preferably a large number, but since the cost is high, it is more preferably about 2 to 6 layers, and it is preferable to select conductivity or give priority to cost. In this case, the layer containing the metal nanoparticles (A) is not required to be the most densely packed in the planar direction, and as long as the contact points of the metal nanoparticles (A) are present, the conductivity in the entire surface can be confirmed.

When the primer layer for plating of the present invention is used as a primer layer for electroless plating, the primer layer for electrical plating may be suitably used. It is used as a primer layer for electroless plating. In the primer layer for electroless plating, the layer containing the metal nanoparticles (A) in the cross-sectional direction does not need to have one or more layers, and the discrete individual metal nanoparticles may be fixed to the resin layer. However, from the viewpoint of ensuring the stability of the plating property and ensuring the adhesion of the plated metal film, it is preferable that the layer containing the metal nanoparticles (A) is present in a layer of the layer in the cross-sectional direction of the layer. In the case of use as a primer layer for electroless plating, the layer containing the metal nanoparticles (A) does not have to have contact points with the entire metal nanoparticles (A) in the plane, and the layers are layered to about 6 layers. The layer containing the metal nanoparticle (A) may have a form which is separately present in the primer layer (Figs. 5 and 6).

The thickness of the plating primer layer of the present invention may be appropriately adjusted depending on the particle diameter of the metal nanoparticles (A) contained in the plating primer composition. As described above, in the primer layer for plating, the metal nanoparticles (A) are expected to exist in two to ten layers, and the plating primer composition to be used in terms of the thickness of the primer layer. The particle diameter of the metal nanoparticle (A) to be contained may be set by multiplying the number of layers by the film thickness. Actually, since the particles are not simply stacked and filled, the film thickness of about ±20% of the calculated film thickness is appropriate. For example, when a metal nanoparticle (A) having an average particle diameter of 20 nm is used to form a layer containing ten layers of the metal nanoparticles (A), a primer layer having a film thickness of about 160 to 240 nm is preferably used. When considering the cost and the like, it is more preferable to use about 6 layers, and a primer layer having a film thickness of about 100 nm to 150 nm can be used.

The thickness of the primer layer may be adjusted by adjusting the concentration of the primer layer forming component contained in the plating primer composition.

<plating treatment>

In the plating treatment for forming a metal layer on an insulating substrate using the primer composition for plating treatment of the present invention, any of electroless plating treatment and electrical plating treatment may be used. Electroplating can be performed after electroless plating. The electroless plating treatment is advantageous in the case where the shape to be applied or the pattern to be plated is complicated and difficult to supply power, but the formation speed of the metal layer is slow, and it is possible to form a thick metal layer when power is supplied. The electric plating processor is advantageous.

<electroless plating treatment>

The electroless plating treatment method of the plated substrate (the insulating substrate forming the primer layer for plating of the present invention) of the present invention may be a conventionally known method, and is not particularly limited. However, since the metal nanoparticles (A) functioning as a catalyst for electroless plating in the plating primer layer of the present invention are present in the primer layer, they have not undergone the touch in the conventional plating process. It is possible to perform electroless plating by the medium application and the activation step, and there is an advantage that the step is shortened. The substrate to be plated of the present invention may be subjected to an electroless plating solution after the degreasing step, but may be subjected to an acid or alkali cleaning operation after degreasing.

In the present invention, the type of the plated metal is not particularly limited, but the conductivity of the metal layer is necessary, and electroless copper plating is preferred from the viewpoint of electrical conductivity and industrial applicability. In this electroless copper plating, it can be used for plating preparation by the composition of the electroless copper plating solution described in the literature, and a commercially available electroless plating reagent can also be used. Commercially available electroless plating reagents are sold in various applications such as thick plating, thin plating, and selective precipitation. Therefore, it is suitable for the purpose, for example, special It is suitable for use with OPC COPPER SERIES and OIC COPPER manufactured by Okuno Pharmaceutical Co., Ltd.

<Electroplating treatment>

The case where the plated substrate of the present invention is subjected to electrolytic plating treatment is not particularly limited, and can be easily carried out by a conventionally known method. The plating solution can be used by preparing a liquid having various compositions as described in the literature, and can be used by purchasing a commercially available electrical plating solution.

[Examples]

Hereinafter, the present invention will be described in further detail by way of examples, but the invention is not limited thereto. Also, "%" means "% by mass" unless otherwise specified.

<Description of Machines Used in the Present Invention>

The machine type used in the present invention is as follows.

The analysis of the synthesized organic protective agent was carried out using AL300, 300 Hz ¹ H-NMR manufactured by JEOL Ltd., and the estimation of the organic protective dose of the metal nanoparticles and the composite was carried out using the TG/DTA6300 manufactured by SII Nanotechnology Co., Ltd. , calculated from the results of thermogravimetric analysis. The plasmonic absorption spectrum of the metal nanoparticles was a UV-3500 ultraviolet-visible spectrophotometer manufactured by Hitachi.

The morphological observation and particle diameter measurement of the metal nanoparticles were carried out using a transmission electron microscope JEM-2200FS manufactured by JEOL Ltd.

The SEM observation of the surface and the cross section of the primer layer for plating was performed by a Schottky field emission type scanning electron microscope manufactured by JEOL Ltd., JSM-7800F.

The surface resistivity of the primer layer and the metal plating layer was measured using a low resistivity meter Loresta EP (4-terminal method) manufactured by Mitsubishi Chemical Corporation.

The peeling strength of the plating film was measured by a special accessory attached to the Bond Tester SS-30WD manufactured by Sejin Corporation, and the plating film was peeled from the substrate into a rectangular shape of 1 cm, and the tensile strength in the direction of 90 ° C was measured.

Synthesis Example 1 Synthesis of Compound (P1) (Polyethyleneimine (PEI) Block and Polyethylene Glycol (PEG) Block) 1-1 [Synthesis of toluenesulfonated polyethylene glycol]

Each was prepared by mixing 150 ml of a mixed single-terminal methoxylated polyethylene glycol (hereinafter, PEGM) (number average molecular weight (Mn) 5000) (manufactured by Aldrich Co., Ltd.) 150 g [30 mmol] and pyridine 24 g (300 mmol) in chloroform, and A solution of 29 g (150 mmol) of toluenesulfonyl chloride and 30 ml of chloroform was uniformly mixed.

A mixed solution of PEGM and pyridine was added dropwise toluene solution of toluenesulfonyl chloride while stirring at 20 °C. After the completion of the dropwise addition, the reaction was allowed to proceed at 40 ° C for 2 hours. After completion of the reaction, the mixture was diluted with 150 ml of chloroform, washed with 250 ml of 5% aqueous HCl solution (340 mmol), and washed with saturated brine and water. After the obtained chloroform solution was dried over sodium sulfate, the solvent was distilled off with an evaporator and dried. The yield was 100%. The assignment of each peak by ¹ H-NMR spectroscopy (2.4 ppm: methyl group in toluenesulfonyl group; 3.3 ppm: methyl group at the end of PEMM; 3.6 ppm: EG chain of PEG; 7.3 to 7.8 ppm: toluenesulfonate) The benzene ring in the base was confirmed to be toluenesulfonated polyethylene glycol.

1-2 [Synthesis of Compound (P1) having (polyethylenimine (PEI) block and polyethylene glycol (PEG) block]

23.2 g (4.5 mmol) of toluenesulfonated polyethylene glycol obtained in the above 1-1, and 15.0 g (1.5 mmol) of polyethylenimine (hereinafter, PEI, manufactured by Nippon Shokubai Co., Ltd., EPOMIN SP200). After dissolving in 180 ml of dimethylacetamide (hereinafter, DMA), 0.12 g of potassium carbonate was added, and the mixture was reacted at 100 ° C for 6 hours under a nitrogen atmosphere. After completion of the reaction, the solid residue was removed, and a mixed solvent of 150 ml of ethyl acetate and 450 ml of hexane was added to obtain a precipitate. The precipitate was dissolved in 100 ml of chloroform, and a mixed solvent of 150 ml of ethyl acetate and 450 ml of hexane was added again to reprecipitate. It was filtered and dried under reduced pressure. The assignment of each peak by ¹ H-NMR spectroscopy (2.3 to 2.7 ppm: Ethylamine of PEI; 3.3 ppm: methyl group at the end of PEG; 3.6 ppm: EG chain of PEG); confirmed compound having PEI-PEG structure (P1). The yield was 99%.

<Manufacture of Metal Nanoparticles (A)> Synthesis Example 2

13.8 g of silver oxide was added to 138.8 g of an aqueous solution containing 0.592 g of the compound (P1) obtained in the above Synthesis Example 1, and the mixture was stirred at 25 ° C for 30 minutes. Next, 46.0 g of dimethylethanolamine was gradually added thereto while stirring, and the reaction solution became black-red. Although there was some heat generation, it was directly placed and stirred at 25 ° C for 30 minutes. Thereafter, 15.2 g of a 10% aqueous ascorbic acid solution was gradually added while stirring. A black-red dispersion was obtained while maintaining its temperature and stirring was continued for 20 hours.

After adding the mixed solvent of 200 ml of isopropyl alcohol and 200 ml of hexane to the dispersion liquid after completion of the reaction obtained above, the mixture was stirred for 2 minutes. The mixture was concentrated by centrifugation at 3000 rpm for 5 minutes. After removing the supernatant, a mixed solvent of 50 ml of isopropyl alcohol and 50 ml of hexane was added to the precipitate, and the mixture was stirred for 2 minutes, and then concentrated by centrifugation at 3000 rpm for 5 minutes. After removing the supernatant, 20 g of water was further added to the precipitate and stirred for 2 minutes, and the organic solvent was removed under reduced pressure to obtain an aqueous dispersion of silver nanoparticles.

The obtained dispersion was sampled, and the peak of the plasmonic absorption spectrum was observed at 400 nm by the visible absorption spectrum of a 10-fold dilution, and the formation of silver nanoparticles was confirmed. Further, spherical silver nanoparticles (average particle diameter: 17.5 nm) were confirmed by TEM observation. The silver content in the solid was measured using TG-DTA, and the result was 97.2%. It can be seen that the content of the organic protective agent (P1) containing PEI-PEG in the composite can be estimated by the composite of the silver nanoparticle obtained by the present synthesis method and the organic protective agent (P1) containing PEI-PEG. It is 2.8%.

<Manufacture of Block Isocyanate (B)> Synthesis Example 3

In a nitrogen-substituted reaction vessel equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 6.3 parts by mass of 2,2-dimethylolpropionic acid and a urea ester of 4,4'-diphenylmethane diisocyanate ( 71.1 parts by mass of the nurate) was reacted in 2-butanone to prepare an isocyanate compound, and 17.8 parts by mass of a phenol as a chain end-blocking agent was supplied to the reaction vessel to react it to prepare a block polyisocyanate (B- 1) Solvent solution. Thereafter, the solid content was adjusted by supplying 2-butanone to obtain a methyl ethyl ketone solution (solid content: 10%) of the blocked polyisocyanate (B-1).

Example 1 (Production of primer composition for plating)

The aqueous dispersion of the silver nanoparticles obtained in Synthesis Example 2 was placed in a freezer at -40 ° C for 1 day and night, and frozen, and treated with a freeze dryer (FDU-2200, manufactured by Tokyo Physicochemical Co., Ltd.). At 24 hours, a composite powder comprising silver nanoparticle having a flaky block having a gray-green metallic luster and an organic protective agent containing PEI-PEG was obtained. Ethanol was added to the powder and stirred to obtain a 70% ethanol dispersion of a composite of silver nanoparticles and an organic protective agent containing PEI-PEG.

To 0.093 g of BURNOCK D-500 (an aromatic block isocyanate manufactured by DIC Corporation), 0.852 g of a 1% ethanol solution of polyethyleneimine (hereinafter referred to as PEI, manufactured by Nippon Shokubai Co., Ltd.) was added and stirred, and it was confirmed. After sufficiently dissolving, 0.304 g of an ethanol dispersion of a composite of the silver nanoparticle obtained by the above step and an organic protective agent containing PEI-PEG was added and stirred. Further, 3.4 g of ethanol was added, and 0.4 g of a 1% ethanol solution of KF-351A (manufactured by Shin-Etsu Silicone Co., Ltd.) was added to prepare an active ingredient concentration of 5.29% (composite of silver nanoparticle and an organic protective agent containing PEI-PEG 4.14). %) Plating primer composition.

In the primer composition for plating (the metal nanoparticle (A) organic protective agent (P) + blocked isocyanate (B) + isocyanate group-reactive compound (D)) / metal nanoparticle ( A) is 0.20 and the amine/NCO ratio is 2.

(Production of a primer layer for plating on an insulating substrate)

The primer composition for plating thus obtained was coated with a K101 rod (wet film thickness: 4 μm) of No. 0, and a K-control coater (K101, RK Print Coat Instruments Ltd.) speed scale 10 was applied thereto. (bar coating) on a polyimide film (UPILEX) that is an insulating substrate SGA, 50μm thick, Ube Hiroshi production system). After the film was dried at room temperature, it was calcined at 210 ° C for 5 minutes to form a plating primer layer on the polyimide film. As a result of measuring the electric resistance of the plating primer layer, it was impossible to measure because it exceeded the range, and it was confirmed that the primer layer was a non-conductive film. As a result of observation by a scanning electron microscope, the surface of the produced primer layer was immobilized, and it was confirmed that a part of the surface of the silver nanoparticles was exposed on the surface of the resin (Fig. 7). Further, when observed in a magnified manner, a large number of pores were observed around the silver nanoparticles of the resin layer to which the silver nanoparticles were fixed (Fig. 8).

(electroless copper plating step)

Electroless copper plating is performed as described above using a polyimide film having a primer layer for plating on the surface. The electroless copper plating step is carried out by a step of degreasing, water washing, pickling, water washing, electroless plating, and water washing. Washing was carried out for 2 minutes in running water.

1. Degreasing: Using a degreasing agent (ICP Cleaner SC, manufactured by Okuno Pharmaceutical Co., Ltd.), it was immersed in a treatment liquid at 40 ° C for 5 minutes.

2. Pickling: immersed in an aqueous solution of sulfuric acid (6%) at 25 ° C for 2 minutes.

3. Electroless plating: immersed in an electroless copper plating solution (OPC Copper ARG, manufactured by Okuno Pharmaceutical Co., Ltd.) at 45 ° C for 30 minutes.

The entire surface of the coated side of the test piece silver particles extracted from the electroless copper plating solution was pale red, and it was confirmed that the electroless plating of copper was favorably performed. The test piece was washed with water and air-dried, and then baked at 100 ° C for 60 minutes. The surface resistivity of the copper film formed by electroless plating was 0.04 Ω/□, and a conductive material having a conductive layer of copper on a 38 μm-thick polyimide film which is an insulating substrate can be produced. So shaped As a result of the tape peeling test of the cellophane tape (Nichiban), no peeling was observed and the adhesiveness was favorable.

(Electrical plating step)

As described above, electrical (copper sulfate) plating is performed using a film-form material in which a copper layer is formed on a polyimide film by electroless copper plating. The copper sulfate plating is carried out by a conventional method, by pickling, copper sulfate plating, water washing, rustproofing, and water washing.

1. Pickling: immersed in an aqueous solution of sulfuric acid (9%) at 25 ° C for 1 minute.

2. Copper sulfate plating: The copper sulfate plating solution containing Top Lucina SF-M (manufactured by Okuno Pharmaceutical Co., Ltd.) was immersed for 43 minutes at 23 ° C under conditions of 1.66 A/dm ² .

3. Anti-rust treatment: rust inhibitor (Top Rinse CU-5, manufactured by Okuno Pharmaceutical Co., Ltd.), immersed at 25 ° C for 1 minute.

The sample subjected to electrical plating was washed with water, wiped off water, dried by hot air, and dried at 120 ° C for 60 minutes. The average thickness of the copper layer formed on the polyimide film after electrical plating is 16 μm, and the insulating layer having a copper layer of 16 μm thick can be formed on the 50 μm-thick polyimide film which is an insulating substrate. Substrate-metal composite. The peel strength of copper formed on the polyimide film showed good adhesion of more than 0.5 kgf/cm, and maintained excellent heat resistance stability of 0.75 kgf/cm after being kept at 150 ° C for 50 hours.

Example 2

In addition to BURNOCK D-500, polyethylenimine 1% ethanol solution, silver nanoparticles, and organic compounds containing polyethylenimine (PEI) blocks and polyethylene glycol (PEG) blocks (P1) Protective agent complex The compounding amount of the dispersion, the ethanol, and the 1% ethanol solution of KF-351A) was changed to 0.092 g, 1.996 g, 0.356 g, 2.984 g, and 0.5 g, respectively, and the concentration of the active ingredient was 6.18% as in Example 1. A primer composition for plating of a composite of silver nanoparticles and an organic protective agent containing PEI-PEG (4.09%).

In the primer composition for plating (the metal nanoparticle (A) organic protective agent (P) + blocked isocyanate (B) + isocyanate group-reactive compound (D)) / metal nanoparticle ( A) is 0.33 and the amine/NCO ratio is 2.

A plating primer layer was formed in the same manner as in Example 1, and electroless copper plating and electrical copper plating treatment were performed to form a copper layer having a thickness of 16 μm on a 50 μm-thick polyimide film which is an insulating substrate. Insulating substrate - metal composite. As a result of the peeling strength test of the copper layer on the insulating base material, the initial peel strength was 0.5 kgf/cm, and after maintaining at 150 ° C for 144 hours, the peeling strength was excellent in heat stability of 0.6 kgf/cm.

Example 3

The aqueous dispersion of the silver nanoparticles obtained in Synthesis Example 2 was placed in a freezer at -40 ° C for 1 day and night, and frozen, and treated by a freeze dryer (FDU-2200, manufactured by Tokyo Physicochemical Co., Ltd.) 24 In an hour, a silver nanoparticle comprising a flaky block having a metallic tone of grayish green, and an organic compound comprising a compound (P1) having a polyethyleneimine (PEI) block and a polyethylene glycol (PEG) block are obtained. A composite powder of a protective agent. Ethanol was added to the powder and stirred to obtain a 64.5% ethanol dispersion of a composite of silver nanoparticles and an organic protective agent containing PEI-PEG.

To 0.26 g of a 10% 2-butanone solution of the blocked isocyanate obtained in Synthesis Example 3, 3.05 g of a 1% dimethylacetamide solution of PEI was added and stirred, and it was confirmed that the solution was sufficiently dissolved, and then added to the above-mentioned steps. The mixture was stirred with 0.59 g of an ethanol dispersion of a composite of silver nanoparticles and an organic protective agent containing PEI-PEG. Further, 0.3 g of ethanol was added, and 0.8 g of an ethanol solution of KF-351A (manufactured by Shin-Etsu Silicone Co., Ltd.) was added to prepare an active ingredient concentration of 8.9% (a composite of silver nanoparticle and an organic protective agent containing PEI-PEG was 7.4%). A primer composition for plating.

In the primer composition for plating (the metal nanoparticle (A) organic protective agent (P) + blocked isocyanate (B) + isocyanate group-reactive compound (D)) / metal nanoparticle ( A) is 0.15 and the amine/NCO ratio is 1.

A plating primer layer was formed on a 50 μm-thick polyimide film in the same manner as in Example 1 except that the calcination conditions were changed from 210 ° C for 5 minutes to 30 minutes. The average thickness of the primer layer estimated by the SEM observation image of the film profile is about 100 nm (Fig. 9), and the surface of the primer layer is silver nanoparticle which is immobilized in the resin and a part of the surface of the silver nanoparticle is exposed. In the state of the surface of the resin, a large number of pores were observed in the resin portion around the silver nanoparticles (Fig. 10).

On the substrate to be plated with the primer layer for plating thus obtained, electroless copper plating and electric copper plating treatment were carried out in the same manner as in Example 1, and the thickness of the insulating substrate was 50 μm. An insulating substrate-metal composite having a copper layer of 16 μm thick was formed on the polyimide film. As a result of the peeling strength test of the copper layer on the insulating base material, the initial peel strength was 0.55 kgf/cm and the temperature was maintained at 150 ° C for 144 hours, and the heat resistance stability of 0.7 kgf/cm was also excellent.

Example 4

The primer composition for plating obtained in Example 3 was applied to a 38 μm-thick polyimine film (Kapton 150EN-C, manufactured by Toray‧Du Pont Co., Ltd.) in the same manner as in Example 1 to prepare a polyfluorene. A plated substrate on which a primer composition for plating is formed on the imide film. The surface resistance of the plating primer layer was measured and found to be a resistance value of 10 ³ Ω/□.

In the same manner as in Example 1, an electroplating treatment was carried out to form an insulating substrate-metal composite having a copper layer having a thickness of 16 μm on a 38 μm-thick polyimide film having an insulating base material. As a result of performing the peel strength test of the copper layer on the insulating base material, a good peel strength of 0.55 kgf/cm was exhibited even after being kept at 150 ° C for 24 hours.

Comparative example 1

In addition to the use of a 5% ethanol dispersion of a composite of silver nanoparticles and an organic protective agent comprising PEI-PEG (based on Example 1, adjusted concentration) instead of using Example 1, the use of silver nanoparticles, including polyethylene The same procedure as in Example 1 except that the composite of the amine (PEI) block and the organic protective agent of the polyethylene glycol (PEG) block compound (P1), and the primer composition for plating of BURNOCK D-500 and PEI A composite of a silver nanoparticle and a PEI-PEG-containing organic protective agent was coated on a 50 μm thick polyimine film (UPILEX SGA) to prepare a substrate to be plated.

The plated substrate was subjected to a plating treatment in the same manner as in Example 1, and as a result of the peel strength test, the peeling strength of the plated film was about 0.2 to 0.3 kgf/cm, and a plating primer layer was provided. In contrast, the adhesion is low.

Claims (15)

A primer composition for plating, characterized by comprising metal nanoparticle (A), a blocked isocyanate (B) and a solvent (C), wherein the metal nanoparticle (A) is selected from the group consisting of silver nanoparticles, At least one of a group of copper nanoparticles, silver core-copper shell nanoparticles, and silver-copper anisotropic composite particles. The primer composition for plating according to claim 1, wherein the blocked isocyanate (B) is a functional group [b] having an isocyanate group blocked by a chain end-blocking agent, and the functional group [b] is derived from 70 The range of °C to 200 °C is heated and the chain end blocking agent dissociates to form an isocyanate group. The plating primer composition of claim 1 or 2, which further contains a compound (D) reactive with an isocyanate group. The primer composition for plating according to claim 3, wherein the compound (D) is a compound having two or more functional groups in the structure, the functional group being at least selected from the group consisting of a carboxyl group, a hydroxyl group, and an amine group. 1 species. The plating primer composition of claim 4, wherein the functional group in the structure of the compound (D) is an amine group. The plating primer composition of claim 5, wherein the functional group in the configuration of the compound (D) is a polyalkyleneimine. The primer composition for plating according to any one of claims 1 to 6, wherein the metal nanoparticle (A) is a complex with an organic protective agent (P). The primer composition for plating according to claim 7, wherein the organic protective agent (P) is one or more of a polyethyleneimine block, a polypropylenimine block, and a polyallylamine block in the molecule. Composition of the compound. The primer composition for plating according to claim 7, wherein the organic protective agent (P) is composed of a compound having a polyethyleneimine block and a polyethylene glycol block. A plated substrate characterized by having a plating primer layer formed of the plating primer composition according to any one of claims 1 to 9 on an insulating substrate. A composite of an insulating substrate and a metal layer, characterized in that the plating primer layer of the substrate to be plated according to claim 10 has a plating layer. A method for producing a substrate to be plated, characterized by the following steps: (1) a step of applying a primer composition for plating on an insulating substrate, the primer composition for coating plating Containing metal nanoparticle (A), blocked isocyanate (B) and solvent (C), wherein the metal nanoparticle (A) is selected from the group consisting of silver nanoparticles, copper nanoparticles, silver core-copper shell nano At least one of a group of particles and silver-copper anisotropic composite particles; (2) a step of heating an insulating substrate coated with a plating primer composition at a temperature of from 70 ° C to 400 ° C. A method of producing a substrate to be plated having a plating primer layer according to claim 12, wherein the plating primer composition further contains a compound (D) reactive with an isocyanate group. A method for producing a composite of an insulating substrate and a metal layer, comprising the steps of: (1) applying a plating primer composition to an insulating substrate, the coating plating Primer composition contains metal nanoparticles (A), a blocked isocyanate (B) and a solvent (C), wherein the metal nanoparticles (A) are selected from the group consisting of silver nanoparticles, copper nanoparticles, silver core-copper nano particles, and silver-copper At least one of the group of anisotropic composite particles; (2) an insulating substrate coated with a primer composition for plating is heated at a temperature of 70 ° C to 400 ° C, and plating is formed on the insulating substrate a step of applying a primer layer; (3) a step of applying a plating treatment to the substrate to be plated including the insulating substrate on which the plating primer layer is formed. The method for producing a composite of an insulating substrate and a metal layer according to claim 14, wherein the plating primer composition further contains a compound (D) reactive with an isocyanate group.