JP6072343B1 - Hydraulic transfer film for electroless plating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a technique for performing electroless plating on a non-conductive substrate having no catalytic activity such as plastic. The present invention provides a hydraulic transfer film for electroless plating that can be used in hydraulic transfer technology. SOLUTION: A hydraulic transfer film for electroless plating in which at least a catalyst layer is laminated on a substrate for hydraulic transfer film, wherein the catalyst layer is (1) a composite of metal particles and a dispersant, 2) A hydraulic transfer film for electroless plating comprising a catalyst composition containing a solvent and (3) a binder, wherein the metal particles are palladium particles, gold particles, silver particles or platinum particles. [Selection figure] None

Description

  The present invention relates to a hydraulic transfer film for electroless plating.

Hydraulic transfer technology is generally
(A) Create a hydraulic transfer film by printing a decorative layer (pattern) on a thin film.
(I) Float this thin film on the liquid surface (water surface, etc.) with the decorative layer for transfer up.
(C) A solvent (an activator composition such as an organic solvent) is applied to the thin film to swell and stick (activate) the decorative layer,
(D) While pressing the object (article to be transferred) with the decoration layer on top, all or part of it is submerged in the liquid,
(E) The decorative layer is transferred to the object surface by the pressure of the liquid (water pressure),
(F) After that, the technique removes the thin film from the object surface and transfers the decoration layer.

  In general, a water-soluble thin film is used as the thin film of the hydraulic transfer film.

  The hydraulic transfer film is suitable for makeup of an object surface having a complicated outer shape such as a curved surface or an uneven surface. In a hydraulic transfer film containing a water-soluble thin film (film), the water-soluble thin film dissolves and disappears in water during transfer, and the decorative layer covers the surface of the transferred material and exhibits a decorative effect.

  Patent Document 1 discloses a hydraulic transfer sheet having a colored printing layer, a metal vapor deposition layer and the like on the surface. The metal vapor deposition layer is formed, for example, by vacuum vapor deposition of a metal such as Al, tin, silver, or copper. However, in Patent Document 1, no consideration is given to cracks such as a colored printing layer and a metal vapor deposition layer in the hydraulic transfer technique.

  Patent Document 2 discloses a hydraulic transfer sheet in which a vapor-deposited metal layer is formed on a transparent resin layer on a water-soluble film, and the transparent resin layer is embossed between the vapor-deposited metal layer and the transparent resin layer. ing. Patent Document 3 discloses a hydraulic transfer method for decorating a metal thin film layer or the like with a curved surface. Since the decorative layer containing a flaky pigment such as a metal pigment is used for the hydraulic transfer film of Patent Document 4, the metallic gloss is different from the plating quality.

  The present applicant has so far provided a coating composition for electroless plating containing palladium colloid or the like (Patent Documents 5 to 7). When this electroless plating coating composition is used, an electroless plating film excellent in adhesion and appearance film can be formed on an object to be plated (non-conductive substrate).

  The present applicant further provides a transfer film for electroless plating in which a catalyst layer containing metal particles such as palladium particles is laminated on a substrate, and used for in-mold transfer, hot roll transfer, or adhesive transfer. (Patent Document 8). Using this electroless plating transfer film, the catalyst layer can be transferred to a non-conductive substrate, and in addition to planar materials, transfer to a three-dimensional housing and electroless plating are also possible. It becomes. An electroless plating film having a smooth surface can be formed by the catalyst layer transferred to the non-conductive substrate.

JP-A-1-22378 Patent No. 4382964 JP 2013-893 JP 2006-51672 A Patent No.5674561 Patent No. 5428812 Patent No. 5458366 Patent No. 5843992

  The present invention provides a technique for performing electroless plating on a non-conductive substrate having no catalytic activity such as plastic.

  The present invention provides a hydraulic transfer film for electroless plating that can be used in hydraulic transfer technology.

  In the present invention, by using a hydraulic transfer film for electroless plating, a catalytic substance (catalyst composition) is attached to the non-conductive substrate, followed by electroless plating, and the non-conductive A technique for forming an electroless plating film on a substrate is provided.

  In the conventional technique, in the transfer technique using a transfer film, the catalyst surface exposed after transfer is not a material capable of electroless plating. In the prior art, a catalyst adsorption process is required after transfer. In the prior art, only transfer and plating to a flat material (such as an electromagnetic wave shielding material for plasma display) were possible using a transparent roll substrate.

  As described above, conventionally, the hydraulic transfer technology for imparting a metallic luster to a substrate is mainly a technology for producing a hologram effect by combining a vapor-deposited metal layer and embossing (Patent Document 2), or a bright pigment. This is a technique (Patent Document 4) for producing glitter using flake-like (scale-like) metal particles. These conventional water pressure transfer techniques are not techniques for applying a metal plating gloss to the final part (housing) even if a water pressure transfer method (water pressure transfer sheet) is adopted.

  The present applicant provides a transfer film for electroless plating in which a catalyst layer containing metal particles such as palladium particles is laminated as a technique for applying a metal plating gloss to the final part (housing) (Patent Document). 8). The transfer technique is in-mold transfer, hot roll transfer, or adhesive transfer.

  Using this electroless plating transfer film, the catalyst layer can be transferred to a non-conductive substrate, and in addition to planar materials, transfer to a three-dimensional housing and electroless plating are also possible. It becomes. An electroless plating film having a smooth surface can be formed by the catalyst layer transferred to the non-conductive substrate.

  At this time, the three-dimensional housing to which transfer or electroless plating is applied may have a larger (complex) cubic curved surface or a deeper cubic curved surface. In this case, further innovation is required for the technique of transferring or electroless plating to the three-dimensional housing.

  As a result of intensive studies, the present inventors have found that a specific catalyst composition is applied to a hydraulic transfer film. The present inventors have found that a catalyst layer (catalyst composition) can be satisfactorily transferred to a non-conductive substrate using a hydraulic transfer film having the catalyst layer (catalyst composition) by hydraulic transfer technology. It was.

  By the transferred catalyst layer (catalyst composition), the present inventors also have a larger (complex) cubic curved surface and a three-dimensional housing having a deeper cubic curved surface. It has been found that an electroless plating film having a smooth surface can be formed. The present inventors can apply a metallic plating gloss to a larger (complex) cubic curved surface or a three-dimensional housing having a deeper cubic curved surface. It has been found that this technology leads to excellent electroless plating technology with three-dimensional decoration.

  That is, the present invention is the following hydraulic transfer film for electroless plating.

Item 1.
A hydraulic transfer film for electroless plating in which at least a catalyst layer is laminated on a hydraulic transfer film substrate,
The catalyst layer comprises (1) a composite of metal particles and a dispersant, (2) a solvent and (3) a catalyst composition containing a binder, and the metal particles are palladium particles, gold particles, silver particles or platinum particles. Is,
Hydraulic transfer film for electroless plating.

Item 2.
The dispersant of the catalyst composition is at least selected from the group consisting of a polycarboxylic acid polymer dispersant, a block copolymer type polymer dispersant having a hydroxyl group, and a block copolymer type polymer dispersant having a carboxyl group. Item 2. The hydraulic transfer film for electroless plating according to Item 1, which is one type of dispersant.

Item 3.
The catalyst composition solvent is water; an aprotic polar solvent selected from the group consisting of N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide; dimethyl sulfoxide and γ-butyrolactone Polar solvents; alcohols selected from the group consisting of methanol, ethanol, isopropyl alcohol, 1-butyl alcohol and isobutyl alcohol; ketones selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol and cyclohexanone; ethylene glycol Glycol ethers selected from the group consisting of monomethyl ether and ethylene glycol monobutyl ether; aromatic carboxylic acids selected from the group consisting of methyl benzoate, ethyl benzoate and methyl salicylate Sterols; aromatic hydrocarbons selected from the group consisting of toluene and xylene; aliphatic hydrocarbons selected from the group consisting of n-hexane, n-heptane and mineral spirits; methyl cellosolve acetate, ethyl cellosolve acetate, At least one selected from the group consisting of glycol ether esters selected from the group consisting of butyl cellosolve acetate, methyl carbitol acetate and butyl carbitol acetate; alkanol esters selected from the group consisting of ethyl acetate and butyl acetate; 2-phenoxyethanol Item 3. The hydraulic transfer film for electroless plating according to Item 1 or 2, which is a seed solvent.

Item 4.
The catalyst composition binder is acetal resin, epoxy resin, ester resin, acrylic resin, urethane resin, amide resin, imide resin, amidoimide resin, shellac resin, melamine resin, urea resin, nitrified cotton, alkyd resin, petroleum resin, Any one of Items 1 to 3, which is at least one binder selected from the group consisting of a rosin resin, a styrene / maleic resin, a silicon resin, a vinyl chloride-vinyl acetate copolymer, an acrylic monomer / oligomer, and an olefin resin. The hydraulic transfer film for electroless plating as described in 1.

Item 5.
Item 5. The transfer film for electroless plating according to any one of Items 1 to 4, wherein the hydraulic transfer film substrate is a substrate made of a water-soluble film.

Item 6.
The resin constituting the water-soluble film is polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, acetyl cellulose, polyacrylamide, polyacrylamide, sodium polyacrylate, acetylbutylcellulose, gelatin, glue, sodium alginate, methylcellulose, hydroxy Selected from the group consisting of ethyl cellulose, carboxymethyl cellulose, dextrin, casein, shellac, gum arabic, starch, protein, copolymer of methyl vinyl ether and maleic anhydride, polyethylene oxide and copolymer of vinyl acetate and itaconic acid Item 6. The hydraulic transfer film for electroless plating according to Item 5, which is at least one resin.

Item 7.
A method for producing a hydraulic transfer film for electroless plating according to any one of Items 1 to 6,
(1) A step of applying a catalyst composition on a hydraulic transfer film substrate and providing a catalyst layer;
including,
A method for producing a hydraulic transfer film for electroless plating.

Item 8.
A method for producing an electroless plated product using the hydraulic transfer film for electroless plating according to any one of Items 1 to 6,
(1) A step of floating the hydraulic transfer film substrate side of the electroless plating hydraulic transfer film on the water surface, and dissolving the hydraulic transfer film substrate;
(2) A step of spraying a solvent onto the catalyst layer side of the hydraulic transfer film for electroless plating,
(3) Adhering the catalyst layer side of the hydraulic transfer film for electroless plating to the transfer substrate, and fixing the catalyst layer to the transfer substrate;
(4) A method for producing an electroless plated product, comprising: a step of washing the transfer substrate on which the catalyst layer is fixed to expose the catalyst layer; and (5) a step of performing electroless plating on the exposed catalyst layer.

  The present invention is a hydraulic transfer film for electroless plating that can be used in hydraulic transfer technology.

  The present invention uses a hydraulic transfer film (hydraulic transfer film for electroless plating) having a specific catalyst layer (catalyst composition) with respect to a non-conductive substrate having no catalytic activity, such as plastic, by hydraulic transfer technology. Thus, the catalyst layer can be transferred (attached) satisfactorily. The present invention can then perform electroless plating to form an electroless plating film on the non-conductive substrate.

It is the schematic explaining the usage aspect of the hydraulic transfer film for electroless plating of this invention. It is a photograph of the hydraulic transfer film (Example) for electroless plating of the present invention. It is the photograph after transcribe | transferring the hydraulic transfer film (Example) for electroless plating of this invention to an ABS resin molded product.

  The present invention is described in detail below. However, this embodiment is specifically described for better understanding of the gist of the invention, and does not limit the content of the invention unless otherwise specified.

(1) Description of the Invention The present invention is a hydraulic transfer film for electroless plating (hereinafter also referred to as "transfer film of the present invention") that can be used in the hydraulic transfer technique.

  The present invention uses a hydraulic transfer film (hydraulic transfer film for electroless plating) having a specific catalyst layer (catalyst composition) with respect to a non-conductive substrate having no catalytic activity, such as plastic, by hydraulic transfer technology. Thus, the catalyst layer can be transferred (attached) satisfactorily. The present invention can then perform electroless plating to form an electroless plating film on the non-conductive substrate.

(I) Excellent plating technology for large molded products In transfer by in-mold, the size of the transfer area may be limited. In transfer by a roll, the size may be limited in width and length.

  When the transfer film of the present invention is used, the catalyst layer can be transferred (attached) satisfactorily to a large (large area) molded product (non-conductive substrate) by hydraulic transfer technology, and then electroless plating is performed. It is possible to form an electroless plating film on the molded product.

(Ii) Excellent plating technology for molded products with complex shapes
Specific examples of the three-dimensional housing include a spherical molded product, a molded product having fine irregularities, a molded product having a hole periphery, and a thin molded product. When transferring to a spherical molded product, a molded product having fine irregularities, etc., it may be difficult to ensure the drawing depth and adhesion of the plated film after drawing around the hole. In addition, when transferring a thin molded product or the like, if the thin molded product is heated, deformation (warping) occurs, so that plating (decoration) may be difficult.

  When the transfer film of the present invention is used, a hydraulic transfer technique can be applied to a three-dimensional housing having a larger (complex) cubic curved surface or a deep cubic curved surface in addition to a planar material. However, an electroless plating film having a smooth surface can be formed. According to the present invention, metal plating gloss can be applied to a three-dimensional housing having a more complicated cubic curved surface.

(Iii) When transferring to a product having an excellent plating technology fit that does not require heating, if the product is heated, deformation may occur and the fit may not be met.

  When the transfer film of the present invention is used, there is no need to heat by the hydraulic transfer technique, and it is possible to transfer well to a product having a fit. Further, when the transfer film of the present invention is used, there is no need to heat a thin molded product, and deformation such as warpage does not occur. Metal plating luster (decoration) can be applied to the product.

  Since the material used for hydraulic transfer (transfer substrate) does not need to be heated during the transfer operation, the material (transfer substrate) has a wide selection range and is flexible without considering heat resistance. Selection is possible.

(Iv) Excellent plating technology for resin and materials of molded products Using the transfer film of the present invention, even for molded products using various resins and materials that cannot be adopted by in-mold transfer technology and injection molding technology. It is possible to transfer (decorate) satisfactorily by hydraulic transfer technology. For example, in terms of shape and adhesion, even for materials that are not suitable for injection molding technology, such as some engineer plastics, using the transfer film of the present invention provides excellent adhesion without being limited by shape. Transcription (decoration) is possible.

  When the transfer film of the present invention is used, it is possible to transfer (decorate) the adhesive to the base material such as ceramics or earthenware by securing the adhesiveness to the base material by dissolving the adhesive. is there.

(V) Excellent plating technology for molded product after transfer In the conventional in-mold transfer technology, after transferring (decorating) to the molded product from the specification of the manufacturing method, on the surface of the molded product after the transfer, It is difficult to newly provide a functional surface. If a functional surface is newly added to the surface of the molded product after the transfer, a new coating process is required.

  The hydraulic transfer technology includes a painting process in the manufacturing method. Using the transfer film of the present invention, by using the existing line of the manufacturing process by hydraulic transfer technology, it is possible to add new performance such as anti-fingerprint (AF) directly to the molded product after transfer (after decoration) Can be given. When the transfer film of the present invention is used, functionality can be imparted to the surface of a molded product at a lower cost by hydraulic transfer technology compared to conventional in-mold transfer technology and thermal transfer technology.

(Vi) Excellent plating technology that does not require special jigs and molds The hydraulic transfer technology using the transfer film of the present invention has an initial investment cost (initials) compared to the conventional in-mold transfer technology and thermal transfer technology. Cost) and operating costs (running costs) can be kept low, which is economical.

(Vii) Excellent plating technology that can handle various specifications Considering the above (i) to (vi), when the transfer film of the present invention is used, the amount required for one-time production is suppressed by the hydraulic transfer technology. It is possible to handle small lot production.

  The hydraulic transfer technology using the transfer film of the present invention includes acrylonitrile-butadiene-styrene copolymer synthetic resin (ABS resin), polypropylene (PP), acrylic resin, polycarbonate (PC) and other general-purpose resins, and combinations of these resins (PC / ABS etc.) It can be applied to plastic products.

  When the transfer film of the present invention is used, pattern plating or partial plating is performed from the surface of a substrate such as plastic (non-conductive substrate) to the surface of a third-order curved substrate such as a cylindrical object by hydraulic transfer technology. A plated film can be formed. A molded product (plating object) on which a plating film is placed has excellent adhesion of the plating film.

  The molded product on which the plating film is placed can be used, for example, for automobile parts such as a casing, an emblem, a switch base, a radiator grille, a door handle, and a wheel cover of an electric appliance such as a mobile phone, a personal computer, and a refrigerator. .

  When the transfer film of the present invention is used, the hydraulic transfer technology provides high plating reactivity such as pattern plating, and exhibits excellent adhesion to chrome plating and excellent smoothness of decorative plating to the substrate. be able to. In the plating, it is possible to suppress the spread of the pattern and to perform partial plating satisfactorily.

  When the plating transfer film of the present invention is used, it is not necessary to increase the concentration of the reducing agent in the plating and to increase the reaction temperature of the plating for the purpose of improving the reactivity of the plating. Furthermore, there is no need for an etching step with a harmful substance, a complicated catalyst application step, or the like.

  When the transfer film of the present invention is used, a plating film having excellent thickness uniformity can be formed on the article substrate (substrate) by the hydraulic transfer technique.

  When the transfer film of the present invention is used, an electroless plating film having a smooth surface can be formed by the transferred catalyst layer by a hydraulic transfer technique.

  When the transfer film of the present invention is used, the layer that becomes the base of the electroless plating film contains a catalyst in advance, and no catalyst adsorption process is required, and the processes included in the transfer and electroless plating technology are simplified. can do.

(2) Hydraulic transfer technology (Figure 3)
The hydraulic transfer film for electroless plating of the present invention is a hydraulic transfer film for electroless plating, wherein at least a catalyst layer is laminated on a substrate for hydraulic transfer film, the catalyst layer comprising (1) a metal It consists of a catalyst composition containing a composite of particles and a dispersant, (2) a solvent, and (3) a binder, wherein the metal particles are palladium particles, gold particles, silver particles, or platinum particles.

  Using the hydraulic transfer film for electroless plating of the present invention, a catalyst layer (catalyst composition), that is, a film for performing electroless plating can be formed (exposed) on a non-conductive substrate. By performing electroless plating on the nonconductive substrate on which the electroless plating film (catalyst layer) is formed, a smooth electroless plating film can be formed on the nonconductive substrate. .

  In the production of printed circuit boards and three-dimensional housings for electronic devices, the formation of metal wiring circuits on housings with larger (complex) cubic curved surfaces and deeper cubic curved surfaces, Electroless plating can be performed using the “transfer film” of the present invention.

  The hydraulic transfer technology of the present invention is a substrate (transfer layer) in which a hydraulic transfer film (catalyst layer) for electroless plating is floated on the water surface, and a catalyst layer for electroless plating (the layer on which a pattern is subsequently applied by electroless plating) is applied. This is a technique for transferring the catalyst layer for electroless plating by submerging the substrate or non-conductive substrate) from above, or by submerging it in water.

  When the hydraulic transfer technology of the present invention is used, a catalyst layer can be applied by utilizing the fact that the hydraulic pressure is applied even in a complicated shape. By performing electroless plating on the nonconductive substrate on which the electroless plating film (catalyst layer) is formed, a smooth electroless plating film can be formed on the nonconductive substrate. .

  The hydraulic transfer technique can transfer not only to a flat plate, but also to a housing having a cubic curved surface. Dissolving the hydraulic transfer film substrate for electroless plating makes a soft catalyst layer that is different from conventional seals and labels. Transferring in this soft state was impossible in the past. Transfer processing can also be applied to a substrate having a cubic surface (transfer substrate) without wrinkles. A film for electroless plating (catalyst layer) is formed on the surface of the tertiary curved substrate, and then a design such as a pattern, metal tone, pearl, matte tone is applied (decorated) by electroless plating technology )be able to.

  When the transfer film of the present invention is used, a larger (complex) cubic curved surface or a deeper cubic curved surface can be used for printed circuit boards and three-dimensional housings of electronic devices by hydraulic transfer technology. Electroless plating can also be performed to form a metal wiring circuit on a housing having a surface. The transfer film of the present invention is used to pattern-form (expose) a catalyst layer (catalyst composition), that is, a film for performing electroless plating on a wiring board (non-conductive substrate). An electroless plating film for forming an electronic circuit is formed on the wiring board by performing electroless plating on the wiring board on which the film (catalyst layer) for electroless plating is formed.

(3) Hydraulic transfer film for electroless plating The hydraulic transfer film for electroless plating of the present invention comprises at least a catalyst layer laminated on a substrate for hydraulic transfer film, and the catalyst layer comprises (1) metal particles and It comprises a catalyst composition containing a composite with a dispersant, (2) a solvent, and (3) a binder, wherein the metal particles are palladium particles, gold particles, silver particles, or platinum particles.

  The hydraulic transfer film for electroless plating of the present invention can be applied to a transfer technique for decorating a nonconductive substrate (molded product).

  The hydraulic transfer film for electroless plating of the present invention can be produced by a method comprising the steps of (1) applying a catalyst composition on a hydraulic transfer film substrate and providing a catalyst layer.

Using the hydraulic transfer film for electroless plating of the present invention,
(1) A step of floating the hydraulic transfer film substrate side of the electroless plating hydraulic transfer film on the water surface, and dissolving the hydraulic transfer film substrate;
(2) A step of spraying a solvent onto the catalyst layer side of the hydraulic transfer film for electroless plating,
(3) Adhering the catalyst layer side of the hydraulic transfer film for electroless plating to a transfer substrate (substrate, non-conductive substrate, molded article, etc.), and fixing the catalyst layer to the transfer substrate;
(4) a step of washing the transfer substrate on which the catalyst layer is fixed and exposing the catalyst layer; and (5) a method of performing electroless plating on the exposed catalyst layer, Can be manufactured.

  In the case of printed circuit boards and three-dimensional housings for electronic devices, the electroless process of the present invention is suitable for circuit manufacturing on housings with larger (complex) cubic curved surfaces or deeper cubic curved surfaces. A metal wiring circuit can be formed using a hydraulic transfer film for plating.

Substrate for hydraulic transfer film In the hydraulic transfer film for electroless plating of the present invention, at least a catalyst layer is laminated on a substrate for hydraulic transfer film.

  The hydraulic transfer film substrate is preferably a substrate made of a water-soluble film. The water-soluble film should just be water-soluble.

  The resin constituting the water-soluble film is polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, acetyl cellulose, polyacrylamide, polyacrylic acid amide, sodium polyacrylate, acetylbutyl cellulose, gelatin, glue, sodium alginate, methyl cellulose, hydroxy Selected from the group consisting of ethyl cellulose, carboxymethyl cellulose, dextrin, casein, shellac, gum arabic, starch, protein, copolymer of methyl vinyl ether and maleic anhydride, polyethylene oxide and copolymer of vinyl acetate and itaconic acid At least one resin is preferred.

  These resins may be used alone or in combination of two or more. In addition, rubber components such as mannan, xanthan gum and guar gum may be added to the water-soluble film.

  Among the water-soluble films, it is preferable to use a polyvinyl alcohol (PVA) resin film, particularly from the viewpoint of production stability, solubility in water and economy. The PVA resin film may contain additives such as starch and rubber in addition to PVA.

  A water-soluble film (PVA-based resin film) forms a transfer catalyst layer on a water-soluble film by changing the polymerization degree, saponification degree, and compounding amount of additives such as starch and rubber. Has the necessary mechanical strength.

  For water-soluble films, moisture resistance during handling, speed of softening due to water absorption after floating on the water surface, time required for spreading or spreading in water, ease of deformation in the transfer process, etc. can be adjusted as appropriate. it can.

  As the water-soluble film made of a PVA resin film, for example, a composition composed of a mixed composition of 80% by mass of PVA resin, 15% by mass of a polymer water-soluble resin and 5% by mass of starch and having an equilibrium water content of about 3% by mass is preferable. .

  Although the PVA-based resin film is water-soluble, it is preferable that the PVA-based resin film remain as a film while being swollen and softened in the water before being dissolved in water. This is because, by performing the hydraulic transfer while the film is still alive, it is possible to prevent an excessive flow and deformation of the printing layer for transfer during the hydraulic transfer.

  The thickness of the hydraulic transfer film substrate (water-soluble film) is preferably about 1 to 100 μm. When the thickness of the hydraulic transfer film substrate (water-soluble film) is 1 μm or more, the uniformity of the film is good and the production stability is high. Further, when the thickness of the hydraulic transfer film substrate (water-soluble film) is 100 μm or less, the solubility in water is appropriate and the printability is excellent. The thickness of the water-soluble film is more preferably in the range of about 2 to 50 μm, and further preferably in the range of about 3 to 20 μm.

  The substrate for the hydraulic transfer film is a water-soluble film such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyester such as polybutylene terephthalate (PBT); polypropylene (PP), polycarbonate (PC), polyethylene (PE ), Polystyrene (PS), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), polyamide (PA, nylon), polyimide (PI), polymethyl methacrylate (PMMA), urethane (PU), cellophane, cellulose acetate It can also be used by being laminated with a base material (mounting paper) using a resin film such as an ionomer.

  Among these, polyethylene terephthalate (PET), which is a versatile plastic that can be thinned and is inexpensive, is preferable.

  The thickness of a substrate (mounting paper) such as PET can be adjusted as appropriate. From the viewpoint of normal usability, about 10 to 60 μm is preferable, and about 15 to 50 μm is more preferable. For example, PET having a thickness of about 38 μm is generally preferable in terms of handling, cost, and the like.

  When a base material (mounting paper) such as PET is laminated on the water-soluble film, the base material (mounting paper) such as PET is preferably separated from the water-soluble film before the hydraulic transfer film base material is floated on the water surface. Alternatively, it is preferable that the substrate (mounting paper) such as PET is separated from the water-soluble film having water solubility by the action of water after the hydraulic transfer film substrate is floated on the water surface.

  The thickness of the hydraulic transfer film substrate can maintain the strength of the electroless plating hydraulic transfer film, has good shape followability to the substrate (non-conductive substrate), and can transfer the catalyst layer well. There are reasons such as. In addition, handling of the hydraulic transfer film for electroless plating, costs, and the like can be considered.

  Hydrostatic transfer film substrate (water-soluble film) is formed by known means such as gravure coating, roll coating, comma coating, gravure printing, screen printing, gravure reverse roll coating, etc. can do.

  It is also possible to laminate a water-soluble film on a base material (mounting paper) such as PET by applying and drying.

Catalyst layer In the hydraulic transfer film for electroless plating of the present invention, at least a catalyst layer is laminated on a substrate for a hydraulic transfer film.

  The catalyst layer comprises (1) a catalyst composition containing a composite of metal particles and a dispersant (metal composite), (2) a solvent, and (3) a binder, and the metal particles are palladium particles, gold particles, silver It is characterized by being particles or platinum particles.

Composition of catalyst composition
Composite of metal particles and dispersant (1)
The catalyst composition includes a composite of metal particles and a dispersant.

  As the complex, a palladium complex (Pd complex) containing palladium particles (Pd particles) is preferable. For example, Pd composites can be prepared from palladium ions (Pd ions) supplied from palladium compounds (Pd compounds) such as palladium chloride (Pd chloride) in the presence of dispersants such as polycarboxylic acid polymers, hydrazine hydrates, etc. Can be obtained by reduction with a secondary or tertiary amine.

Dispersant As the dispersant, it is preferable to use a polycarboxylic acid dispersant, a block copolymer type polymer dispersant having a hydroxyl group or a carboxyl group, and the like. A commercial item can also be used for a dispersing agent.

  As the polycarboxylic acid polymer dispersant, it is preferable to use polycarboxylic acid ammonium salt, polycarboxylic acid sodium salt, polycarboxylic acid triethylamine salt, polycarboxylic acid triethanolamine salt or the like. For example, Nopco Santo K, R, RFA, Nop Cospers 44-C, SN Dispersant 5020, 5027, 5029, 5034, 5045, 5468 manufactured by San Nopco Co., Ltd. 532A etc. can be used.

  As the block copolymer type polymer dispersant having a hydroxyl group, polyoxyethylene alkyl ether carboxylate, alkyl hydroxy ether carboxylate or the like is preferably used. For example, DISPERBYK190, 2010 manufactured by Big Chemie Japan Co., Ltd. can be used.

  As the block copolymer type polymer dispersant having a carboxyl group, an acrylic acid-maleic acid copolymer, a styrene-maleic acid copolymer, an acrylic acid-sulfonic acid copolymer, or the like is preferably used. For example, Big Chemie Japan Co., Ltd. DISPERBYK180, 187, 191, 194, Nippon Shokubai Co., Ltd. Aquaric TL, GL, LS can be used.

  A dispersing agent can be used 1 type or in combination of 2 or more types. Among the dispersants, a block copolymer type polymer dispersant having a carboxyl group is preferable.

Metal particles Metal particles function as an electroless plating catalyst. Ultra fine particles of noble metals such as palladium particles (Pd particles), gold particles (Au particles), silver particles (Ag particles), platinum particles (Pt particles), etc. It is. Pd particles are particularly preferable as the metal particles.

Pd particles
Pd particles can be obtained by reducing Pd ions supplied from a Pd compound using a reducing agent in the presence of a dispersant (liquid phase reduction method).

  As a Pd compound that supplies Pd ions, palladium chloride (Pd chloride), palladium sulfate, palladium nitrate, palladium acetate, palladium benzoate, palladium salicylate, palladium paratoluenesulfonate, palladium perchlorate, palladium benzenesulfonate, etc. are used. It is preferable.

  Pd compounds can be used alone or in combination of two or more.

  As a reducing agent, primary, secondary or tertiary amines such as hydrazine hydrate (hydrazine monohydrate), sodium borohydride, N, N dimethylethanolamine, diethanolamine, triethanolamine, ascorbic acid, 2, It is preferable to use enediols such as 3-dihydroxymaleic acid.

  Examples of the reducing agent include hydroxylamine compounds such as N, N-dialkylhydroxylamine; hydrazine compounds such as N, N-dialkylhydrazine; phenols such as hydroquinone and aminophenol; and phenylenediamines; 2-hydroxy Hydroxy ketones and hydroxycarboxylic acids such as acetone, 2-hydroxyhexane-1,3-dione, citric acid and malic acid; enediols such as ascorbic acid and 2,3-dihydroxymaleic acid; diethanolamine, triethanolamine, It is preferable to use amino alcohols such as N, N-dimethylethanolamine; various amines such as primary amines, secondary amines and tertiary amines;

  The following (2) solvent can be used for the solvent (solvent for making a dispersing agent and Pd ion exist) used when reducing. A solvent can be used 1 type or in combination of 2 or more types.

  Examples of the method for reducing Pd ions include a method in which a dispersing agent and Pd ions are present in a solvent and then the reducing agent is added to the solvent. Thereby, Pd ion and a reducing agent contact and it can reduce Pd ion.

  Most of the Pd particles are considered to be attached to the outside of the dispersant. For example, when the shape of the Pd composite (the shape of the entire dispersant) is a dense sphere, it is considered that most of the Pd particles are attached to the spherical surface side (outside).

  The weight ratio of the Pd particles to the dispersant in the Pd composite is preferably about Pd particles: dispersant = 50: 50 to 95: 5, more preferably about Pd particles: dispersant = 65: 35 to 85:15. .

  For example, Pd chloride (about 1 part by weight) is dissolved in purified water (about 89 parts by weight), and trisodium citrate (about 10 parts by weight) is further dissolved and stirred uniformly. Subsequently, sodium borohydride (about 0.01 part by weight) is added to reduce the salt Pd, whereby a palladium colloid (Pd colloid) that is stabilized with citric acid and is made into a protective colloid can be obtained. Thereafter, concentration desalting is performed by ultrafiltration to obtain a Pd colloid containing Pd (about 0.5 parts by weight).

  The average particle diameter of the Pd particles alone is not particularly limited, and is preferably about 2 to 10 nm. The particle diameter of the Pd particles can be measured using a transmission electron microscope. The average particle size of the Pd particles can be calculated by randomly selecting 10 Pd particles, measuring the particle size of the Pd particles with a transmission electron microscope, and averaging the number (number-based average diameter). ).

  The average particle size of the Pd composite is not particularly limited, and preferably has a spherical structure with an average particle size of about 20 to 300 nm as a whole. The average particle diameter of the Pd composite can be measured with a particle size analyzer (Otsuka Electronics Co., Ltd., FPAR-1000) (weight-based average diameter).

Other metal particles Other metal particles that function as an electroless plating catalyst are preferable. Metal particles produced by a plasma method in a microwave liquid, metal particles produced by an ultrasonic method, gas phase method (CVD laser) Etc.) and noble metal-supported fine particles are preferred. These metal particles are preferably noble metal ultrafine particles such as Pd particles, Au particles, Ag particles, and Pt particles.

  When the metal particles are Pt particles, platinum ions (Pt ions) supplied from platinum compounds (Pt compounds, noble metal compounds) such as platinum chloride (IV) in the presence of a dispersant are converted to secondary grades such as hydrazine hydrate. Alternatively, it can be obtained by reduction with a tertiary amine. The composite is preferably obtained by reducing Pt ions in the presence of a dispersant.

  As Pt compounds (noble metal compounds) that supply Pt ions, platinum chloride (II), platinum chloride (IV), hexachloride platinum (IV) acid, tetrachloride platinum (II) acid, potassium hexachloride platinum (IV) acid, Potassium tetrachloride platinum (II), ammonium hexachloride platinum (IV), platinum (IV) oxide, platinum (II) bromide, platinum (IV) bromide, platinum (II) hydroxide, platinum fluoride (VI Etc.) are preferred.

  Other conditions are the same as in the case of the Pd particles.

  Pd particles are particularly preferable as the metal particles.

Solvent (2)
The catalyst composition includes a solvent.

  The solvent (dispersion medium) can disperse the metal complex (Pd complex or the like). Moreover, the solvent is excellent in affinity with the binder.

  The solvent is determined by considering the (1) dispersibility of the composite of metal particles and dispersant (metal composite) contained in the catalyst composition, (3) the solubility of the binder, and the viscosity and evaporation of the catalyst composition. It is preferable to select from the viewpoint of speed or the like. Moreover, it is preferable to satisfy the point that the catalyst composition is in good contact with a non-conductive substrate (molded product, molded product (plastic material such as ABS resin, glass plate, etc.)) through the adhesive layer.

  Specifically, alcohols such as methanol, ethanol, isopropyl alcohol (IPA), 1-butyl alcohol, isobutyl alcohol; acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), diacetone alcohol (4-hydroxy-4 -Methyl-2-pentanone), ketones such as cyclohexanone; glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monobutyl ether; aromatic carboxylic acid esters such as methyl benzoate, ethyl benzoate and methyl salicylate; toluene, Aromatic hydrocarbons such as xylene; Aliphatic hydrocarbons such as n-hexane, n-heptane and mineral spirits; methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol acetate Over DOO, glycol ether esters such as butyl carbitol acetate; ethyl acetate, alkanol esters such as ethyl acetate and butyl acetate; 2-phenoxyethanol be used in addition (ethylene glycol phenyl ether) or the like.

  In particular, it is preferable to use a solvent having a low evaporation rate in consideration of printability and paintability, and a leveling process after printing and painting. Examples of the solvent having a low evaporation rate include diacetone alcohol, cyclohexanone, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol acetate, butyl carbitol acetate, and 2-phenoxyethanol. These solvents are preferably used.

  From the viewpoint that the metal complex (Pd complex etc.) in the catalyst composition can be dispersed well, at least one selected from the group consisting of water and an aprotic polar solvent such as N-methylpyrrolidone is preferable.

  As aprotic polar solvents, aprotic polar solvents such as N-methylpyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAc); dimethyl sulfoxide; γ-butyrolactone, etc. It is preferable to use it. Of the aprotic polar solvents, at least one selected from the group consisting of NMP, DMF and DMAc is more preferable.

  The solvent can be converted after the reduction reaction of metal ions (such as Pd ions). For example, the solvent can be converted from water to NMP.

  A solvent can be used 1 type or in combination of 2 or more types.

The content of the dispersion solvent in the catalyst composition (the total amount when two or more solvents are used) is not particularly limited, and is 1 × 10 4 with respect to 100 parts by weight of the metal composite (Pd composite etc.). ^{About 2} to 1 × 10 ⁶ parts by weight is preferable. The metal complex (Pd complex or the like) is preferably contained in about 1% by weight in the dispersion solvent. The dispersion solvent is more preferably about 5 × 10 ^{2 to} 3 × 10 ⁵ parts by weight, more preferably about 1 × 10 ³ to 2 × 10 ⁵ parts by weight with respect to 100 parts by weight of the metal composite (Pd composite etc.). More preferred is about 5 × 10 ³ to 2 × 10 ⁴ parts by weight.

Binder (3)
The catalyst composition includes a binder.

  Binder is good from the viewpoint of viscosity of catalyst composition, adhesion between catalyst composition and non-conductive substrate (molded product, molded product (plastic material such as ABS resin, glass plate, etc.)), curing conditions, etc. It is preferable to select a material that can obtain electroless plating reactivity. The binder is dispersed or dissolved in the solvent.

  Specifically, acetal resin (POM), epoxy resin, ester resin, acrylic resin, urethane resin, amide resin (PA, polyamide, nylon), imide resin (polyimide), amideimide resin (PAI, polyamideimide), shellac resin , Melamine resin, urea resin, nitrified cotton, alkyd resin, petroleum resin, rosin resin, styrene / maleic acid resin, silicone resin, PVC-vinyl acetate copolymer, acrylic monomer / oligomer, olefin resin (polyolefin), etc. It is preferable.

  The vinyl chloride-vinyl acetate copolymer (vinyl chloride / vinyl acetate modified resin) is a copolymer resin of vinyl chloride and vinyl acetate.

  As the acetal resin (POM), polyvinyl acetal or the like is preferably used. Polyvinyl acetal is a resin obtained by acetalizing polyvinyl alcohol with an aldehyde. Polyvinyl formal is acetalized using formalin (formaldehyde 37% aqueous solution) as an aldehyde. Acetalized with butanol (butyl alcohol) as an aldehyde is polyvinyl butyral (butyral resin, PVB).

  Amide resin is nylon 6 (ε-caprolactam), nylon 11 (undecane lactam), nylon 12 (lauryl lactam), nylon 66 (hexamethylenediamine + adipic acid), nylon 610 (hexamethylenediamine + sebacic acid), nylon 6T (Hexamethylenediamine + terephthalic acid), nylon 6I (hexamethylenediamine + isophthalic acid), nylon 9T (nonanediamine + terephthalic acid), nylon M5T (methylpentadiamine + terephthalic acid), nylon 612 (caprolactam and lauryl lactam ω It is preferable to use a co-condensation polymer of amino acids) or the like.

  The amidoimide resin is a resin in which an amide bond is introduced into the polyimide main chain, and it is preferable to use a resin obtained by a reaction between trimellitic anhydride and diisocyanate, a reaction between trimellitic anhydride chloride and diamine, or the like.

  It is preferable to use an epoxy resin. By using an epoxy resin, an electroless plating coating film can be more firmly adhered to an article containing an ABS resin or the like. The epoxy resin becomes a polymer base material (matrix resin) constituting the coating film for electroless plating.

  As the epoxy resin, either a one-component or two-component epoxy resin can be used. Epoxy resins include modified epoxy resins.

  As the one-component epoxy resin, it is preferable to use bisphenol A type, bisphenol F type, novolak type, phenol novolak type, cresol novolak type, glycidyl ester type, glycidyl ether type, biphenyl type and the like.

  Examples of the one-component epoxy resin include EPICLON830, 830-S, 835, 840, 840-S, 850, 850-S, N-730A, N-740A, N-770, and N-775 manufactured by DIC Corporation; Nagase ChemteX Co., Ltd. XNR-3053, XNR3505, XN1244, XN1278; Arakawa Chemical Industries Arakid 9201N, 9203N, 9205, 9208, Modix 301,302,401; Toagosei Co., Ltd. Aron Mighty AP-0786, AS- Commercially available products such as 60, BX-60, AS-315 can be used.

  As the two-component epoxy resin, a resin containing the above epoxy resin as a main agent can be used. As the curing agent used with this agent, it is preferable to use polyamide, polyamine, polyamidoamine, ketimine, imidazole, diamine, diaminediamide, tetrahydrophthalic anhydride and the like.

  The two-part epoxy resin is, for example, jER-806, 807, 825, 827, 828, 1256, 4250, 4275, W2821R70 manufactured by Mitsubishi Chemical Corporation; Adeka Resin EP-4100HF, EP- manufactured by ADEKA Corporation Commercially available products such as 4088S, EPR-4030; AV138-HV998, XNR3106-XNH3103 manufactured by Nagase ChemteX Corporation; Aronmite AP-400BD manufactured by Toagosei Co., Ltd. can be used.

  Examples of the curing agent for the two-component epoxy resin include lacamide 17-202, TD-961, TD-977, TD-992, WN-155, WN-170, WN-405, and WN-505 manufactured by DIC Corporation; Mitsubishi Chemical Corporation jER Cure-ST11, ST12, St13, ST14, LV11, DC11, RC11, FL11, QX11, H3, WD11M60; ADEKA Adeka Hardener EH-3636AS, EH-5010S, EH-5015S; Commercial products such as Hitachi Chemical Co., Ltd. HN-2200, HN-2000, HN-5500; T & K TOKA Co., Ltd. tomide 245, 275, 210, 241, Fuji Cure-5000, FXS-654, FXS-8077 Can be used.

  The epoxy resin is preferably a one-component epoxy resin from the viewpoints of workability, stability over time, and the like. Epoxy resins can be used alone or in combination of two or more.

  The curing temperature of the epoxy resin is preferably 60 to 200 ° C, more preferably 80 to 150 ° C.

  Amide resin is nylon 6 (ε-caprolactam), nylon 11 (undecane lactam), nylon 12 (lauryl lactam), nylon 66 (hexamethylenediamine + adipic acid), nylon 610 (hexamethylenediamine + sebacic acid), nylon 6T (Hexamethylenediamine + terephthalic acid), nylon 6I (hexamethylenediamine + isophthalic acid), nylon 9T (nonanediamine + terephthalic acid), nylon M5T (methylpentadiamine + terephthalic acid), nylon 612 (caprolactam and lauryl lactam ω It is preferable to use a co-condensation polymer of amino acids) or the like.

  The amidoimide resin is a resin in which an amide bond is introduced into the polyimide main chain, and it is preferable to use a resin obtained by a reaction between trimellitic anhydride and diisocyanate, a reaction between trimellitic anhydride chloride and diamine, or the like.

  The acrylic resin is a polymer of an acrylate ester or a polymer of a methacrylic ester or a copolymer using these as a comonomer, for example, a polymethyl methacrylate resin, a polymethyl acrylate resin, an ethylene-methyl acrylate copolymer. It is preferable to use ethylene-methyl methacrylate copolymer.

  The binder is selected from the group consisting of acetal resin, epoxy resin, ester resin, acrylic resin, urethane resin, amide resin, imide resin, amideimide resin, shellac resin, melamine resin, urea resin, PVC-vinyl acetate copolymer and olefin resin. At least one selected is preferred. Two or more binders can be used in combination.

The content of the binder is preferably about 1 to 1 × 10 ⁵ parts by weight and more preferably about 50 to 5 × 10 ⁴ parts by weight with respect to 100 parts by weight of the metal composite (Pd composite or the like).

  The binder preferably has a solid content ratio of about 1 to 50% by weight.

  The binder is suitable in a method for producing an electroless plating product by a hydraulic transfer technique using the hydraulic transfer film for electroless plating of the present invention.

Using the hydraulic transfer film for electroless plating of the present invention, a method for producing an electroless plated product is as follows:
(1) A step of floating the hydraulic transfer film substrate side of the electroless plating hydraulic transfer film on the water surface, and dissolving the hydraulic transfer film substrate;
(2) A step of spraying a solvent onto the catalyst layer side of the hydraulic transfer film for electroless plating,
(3) Adhering the catalyst layer side of the hydraulic transfer film for electroless plating to the transfer substrate, and fixing the catalyst layer to the transfer substrate;
(4) a step of washing the transfer substrate on which the catalyst layer is fixed and exposing the catalyst layer; and (5) a step of performing electroless plating on the exposed catalyst layer.

  In particular, when the solvent (organic solvent, activator) is sprayed on the catalyst layer side of the electroless plating hydraulic transfer film (step (2)), the binder is easily softened and dissolved by the solvent, and the state is as follows. It can be maintained for a relatively long time.

  In particular, the binder is bonded to the transfer substrate when the catalyst layer side of the electroless plating hydraulic transfer film is adhered, and the catalyst layer is fixed to the transfer substrate (step (3)). The catalyst layer side of the electroless plating hydraulic transfer film is easy to adhere to the transfer substrate, and the catalyst layer is easily fixed to the transfer substrate.

Production method of catalyst composition As described above, metal particles (Pd particles, etc.) are prepared by using, as a reducing agent, metal ions (Pd ions, etc.) supplied from metal compounds (Pd compounds, etc.) in the presence of a dispersant. It can be obtained by reduction.

The catalyst composition is
(I) (2) A metal ion (Pd ion, etc.) and a dispersant are present in a solvent, and the metal ion (Pd ion, etc.) is reduced using a reducing agent. (1) Metal particles (Pd particles) Etc.) and a composite of a dispersant,
(Ii) (2) in a solvent, (3) a step of mixing a binder to produce a mixture, and
(Iii) (2) obtained in the step (ii) to the mixture of the complex of (2) the solvent obtained in the step (i) and (1) metal particles (Pd particles, etc.) and the dispersant. Mixing a solvent and (3) a mixture of binders;
It is preferable to manufacture by the manufacturing method containing.

  Either step (i) or step (ii) may be the previous step.

  According to the said manufacturing method, the catalyst composition applicable to the plating transfer film utilized with a transfer technique can be manufactured.

  Using this plating transfer film, a catalyst layer (catalyst composition) and a plating film can be formed (exposed) on a non-conductive substrate.

  The catalyst composition of the present invention is highly reactive in plating (electroless plating or electrolytic plating), has good adhesion to plating, and can form a plating film that can exhibit good smoothness. .

  With the plating transfer film, it is possible to form a partial plating while suppressing the spread of the pattern on a non-conductive substrate (molded product, molded product (plastic material such as ABS resin, glass plate, etc.)). When a plating transfer film is used, an etching process using a harmful substance, a complicated catalyst application process, and the like are not required.

Process (i)
(2) A metal ion (Pd ion, etc.) and a dispersant are present in a solvent, and the Pd ion is reduced using a reducing agent. (1) A complex of metal particles (Pd particles) and a dispersant. Is made.

  First, a metal ion (Pd ion or the like) and a dispersant are present in a solvent (dispersion medium). As a metal ion (Pd ion or the like), a metal compound (Pd compound or the like) that supplies the metal ion (Pd ion) as a supply source can be used.

  Use amount (parts by weight) of each component is based on “metal compound (Pd compound, etc.)”.

  As the dispersant, the dispersant can be used. The use ratio (weight ratio) between the metal ions (Pd ions, etc.) and the dispersant is preferably about 10-200 parts by weight of the dispersant with respect to 100 parts by weight of the metal compound (Pd compound, etc.), 30 About 150 parts by weight is more preferable, and about 50-100 parts by weight is even more preferable.

As the solvent, the solvent (2) can be used. The amount of the solvent used is not particularly limited as long as the metal ions (Pd ions, etc.) and the dispersant can be uniformly present, and 1 × 10 ^{4 to} 3 × with respect to 100 parts by weight of the metal compound (Pd compound, etc.). About 10 ⁵ parts by weight is preferable, and about 1 × 10 ⁴ to 1 × 10 ⁵ parts by weight is more preferable.

  Next, a metal ion (Pd ion or the like) is reduced by the reducing agent by reacting the metal ion (Pd ion or the like) with a reducing agent. That is, a reduction reaction of metal ions (Pd ions, etc.) occurs, and as a result, a complex (metal complex (Pd complex, etc.)) of the above-mentioned (1) metal particles (Pd particles, etc.) and a dispersant can be obtained. it can. As the reducing agent, a reducing agent used for producing the metal complex (Pd complex or the like) can be used. The amount of the reducing agent to be used is not particularly limited, and is preferably about 100 to 800 parts by weight, more preferably about 200 to 600 parts by weight with respect to 100 parts by weight of the metal compound (Pd compound or the like).

  The reaction using the reducing agent is preferably carried out at a temperature of about 35 to 45 ° C, and preferably raised to about 50 to 60 ° C. The reaction time is not particularly limited, and is preferably about 1 to 5 hours.

  The pressure and atmosphere during the reaction are not particularly limited, and the reaction is preferably performed under atmospheric pressure or air (air) atmosphere. The reaction can be carried out in an open system such as a beaker. As a reaction method, it is preferable to stir a solution containing a metal ion (Pd ion or the like) (metal compound (Pd compound or the like)), a dispersant and a reducing agent with a bladed stirring rod.

  A mixture containing a complex of a solvent and metal particles (Pd particles, etc.) and a dispersant (metal complex-containing liquid (Pd complex-containing liquid, etc.)) is ultrafiltered to obtain metal particles (Pd particles, etc.) and a dispersant. It is preferable to separate the complex. By this operation, it is possible to remove inorganic salts, excess dispersants, and the like contained in the metal complex-containing liquid (Pd complex-containing liquid and the like). For example, the Pd complex-containing liquid can be filtered to make up for the dispersion solvent. This process can be repeated.

  It is possible to convert the solvent after the reduction reaction of metal ions (Pd ions, etc.). For example, by using water as the solvent and then converting the water to NMP or the like (solvent, dispersion medium), NMP ((2) solvent) and (1) metal particles (Pd particles etc.) and dispersant It is possible to make a mixture of

Step (ii)
(2) A mixture is prepared by mixing (3) a binder in a solvent.

  As the solvent, (2) solvent such as 2-phenoxyethanol, diacetone alcohol, methyl isobutyl ketone, cyclohexanone and the like can be used. The amount of solvent used is not particularly limited.

  As the binder, the above (3) binder can be used. It is preferable that the amount of the binder used considers the viscosity of the catalyst composition. Moreover, it is preferable to consider the adhesiveness between the catalyst composition and the non-conductive substrate (ABS resin, glass plate, etc.), curing conditions, and the like via the adhesive layer.

  The mixing is not particularly limited, and it is preferable to perform the mixing under atmospheric pressure or air (air) atmosphere. Mixing can be performed in an open system such as a beaker. As a mixing method, it is preferable to stir the mixture containing the solvent and the binder with a bladed stirring rod.

Step (iii)
(2) The solvent obtained in the step (ii) and the mixture of the complex of (2) the solvent obtained in the step (i) and (1) the metal particles (Pd particles etc.) and the dispersant 3) Mix the binder mixture.

(4) Method for producing hydraulic transfer film for electroless plating The hydraulic transfer film for electroless plating of the present invention is:
(1) A step of applying a catalyst composition on a hydraulic transfer film substrate and providing a catalyst layer;
It can manufacture by going through.

As described above, the hydraulic transfer film substrate is preferably a substrate made of a water-soluble film. The water-soluble film should just be water-soluble or water-swellable.

  As described above, the resin constituting the water-soluble film is polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, acetyl cellulose, polyacrylamide, polyacrylic acid amide, sodium polyacrylate, acetylbutyl cellulose, gelatin, glue, sodium alginate. , Methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, dextrin, casein, shellac, gum arabic, starch, protein, copolymer of methyl vinyl ether and maleic anhydride, polyethylene oxide and copolymer of vinyl acetate and itaconic acid It is preferably at least one resin selected from the group.

  In addition, about the base material for hydraulic transfer films, it is as above-mentioned.

Formation of Catalyst Layer The hydraulic transfer film for electroless plating of the present invention can be produced by applying a catalyst composition on a hydraulic transfer film substrate and providing a catalyst layer.

  This transfer film is applied to the substrate (non-conductive substrate, molded product or molded product) by hydraulic transfer technology, the catalyst layer is exposed on the substrate, and then electroless plating is applied to the molded product or molded product. A film can be formed.

  The catalyst composition for forming the catalyst layer is applied onto the substrate for a hydraulic transfer film by a known means such as a gravure coating method, a roll coating method, a comma coating method, a gravure printing method, a screen printing method, or a gravure reverse roll coating method. The catalyst layer can be formed by coating and drying.

  For coating, a bar coater, a gravure printing machine (gravure offset), a flexographic printing machine, an ink jet printing machine, dipping, spraying, a spin coater, a roll coater, a reverse coater, a screen printing machine or the like can be used.

  Gravure offset printing and pad printing are preferable from the viewpoint of masking-less and production efficiency.

  Depending on the pattern, spray coating is preferred.

  It is preferable to adjust the viscosity of the catalyst composition in accordance with the coating method.

  When applied by gravure offset printing or pad printing, the viscosity of the catalyst composition is preferably about 50 to 1,000 mPa · s. When spray coating is performed after masking, the viscosity of the catalyst composition is preferably about 100 mPa · s or less.

  The thickness of the catalyst layer is preferably about 0.01 to 10 μm, more preferably about 0.02 to 8 μm, and more preferably about 0.03 to 5 μm because electroless plating can be satisfactorily performed and a plating film can be satisfactorily formed on the substrate. A thickness of about 0.05 μm (50 nm) to 2 μm is particularly preferable.

  By applying electroless plating to the catalyst layer, the target design can be expressed on the substrate.

  The film thickness of the catalyst composition before drying and curing can be appropriately selected depending on the intended use, and depends on the viscosity of the catalyst composition. The film thickness is preferably about 1 to 120 μm from the viewpoint of satisfactorily applying the catalyst composition. When the film thickness exceeds 120 μm, the catalyst composition tends to cause dripping.

After the catalyst composition is applied to the substrate for the curing treatment hydraulic transfer film, the solvent (solvent) contained in the catalyst composition is volatilized and / or dried, and then the curing treatment is performed.

  The binder is cured by the curing process.

  After apply | coating a catalyst composition to the base material for hydraulic transfer films, a drying process can be performed. The drying treatment can efficiently remove an unnecessary solvent when performing electroless plating, and can improve the adhesion between the coating film and the substrate and the surface strength of the coating film. The temperature for the drying treatment is preferably about 60 to 400 ° C, more preferably about 80 to 150 ° C. The time for the drying treatment is preferably about 6 seconds to 60 minutes, more preferably about 10 minutes to 30 minutes, in accordance with the drying temperature.

  The temperature of the curing treatment can be adjusted according to the type of the (3) binder contained in the catalyst composition. The temperature of the curing treatment is preferably about 40 to 400 ° C. Moreover, when using a plastic as a base material, it is preferable to set the temperature of a hardening process to about 40-200 degreeC in consideration of the softening temperature of a plastic raw material.

  The film thickness of the catalyst composition after drying and curing depends on the solid content concentration of the catalyst composition. The film thickness is preferably about 0.05 to 20 μm from the viewpoint that electroless plating can be efficiently performed and sufficient plating adhesion is exhibited. Even if the film thickness is less than 0.05 μm, the electroless plating reactivity can be obtained, but the plating adhesion tends not to be sufficiently exhibited. When the film thickness exceeds 20 μm, the reaction rate of electroless plating tends to be inferior.

  The solvent contained in the catalyst composition is volatilized and / or dried, and the binder contained in the catalyst composition is cured.

  A catalyst layer (catalyst film) can be formed on the hydraulic transfer film substrate. The catalyst layer includes a metal complex (Pd complex or the like). A metal complex (Pd complex etc.) exists in the state uniformly disperse | distributed with respect to the coating film. Therefore, electroless plating can be performed more efficiently on the catalyst film.

  An electroless plated product can be produced by performing electroless plating on the catalyst layer exposed on the substrate (non-conductive substrate). By the electroless plating, design properties can be imparted to the substrate (molded product or molded product). It is a layer for expressing patterns, characters, pattern-like patterns, etc. on the substrate. For example, wood, stone, cloth, sand, geometric patterns, characters, stripes, gradation patterns and the like can be given to the substrate.

(5) Method of forming plating (hydraulic transfer technology, Fig. 3)
Using the hydraulic transfer film for electroless plating of the present invention,
(1) A step of floating the hydraulic transfer film substrate side of the electroless plating hydraulic transfer film on the water surface, and dissolving the hydraulic transfer film substrate;
(2) A step of spraying a solvent onto the catalyst layer side of the hydraulic transfer film for electroless plating,
(3) Adhering the catalyst layer side of a hydraulic transfer film for electroless plating to a transfer substrate (substrate, non-conductive substrate, molded product, etc.), and fixing the catalyst layer to the transfer substrate; 4) A step of washing the transfer substrate on which the catalyst layer is fixed to expose the catalyst layer,
Through this, the catalyst layer is provided on the substrate (non-conductive substrate) by the hydraulic transfer technique.

  The catalyst layer is a layer for performing electroless plating provided on the substrate.

Next, (5) an electroless plated product can be manufactured by performing a process of performing electroless plating on the exposed catalyst layer.

  By using the hydraulic transfer film for electroless plating of the present invention, a smooth electroless plating film can be formed on a non-conductive substrate by hydraulic transfer technology.

(1) The process of floating the hydraulic transfer film substrate side of the electroless plating hydraulic transfer film on the surface of the water and dissolving the hydraulic transfer film substrate with the catalyst layer facing upward, the hydraulic pressure Float in water with the transfer film substrate side down, activate the catalyst layer with an organic solvent (activation may be performed before floating in water), transfer the catalyst layer to the transfer target, Remove.

  Specifically, the hydraulic transfer film for electroless plating is floated on the water in the water tank with the hydraulic transfer film substrate side down, and the hydraulic transfer film substrate is dissolved or swollen with water.

(2) Process of spraying the solvent on the catalyst layer side of the electroless plating hydraulic transfer film Activate the catalyst layer by spraying the solvent (organic solvent, activator) on the catalyst layer side of the electroless plating hydraulic transfer film Let An organic solvent serving as an activator is applied or sprayed on the catalyst layer. The activation of the catalyst layer with the solvent (organic solvent) may be performed before or after the film is floated on water.

  The step of spraying (coating) the solvent (activator) is to apply the solvent to the catalyst layer side of the electroless plating hydraulic transfer film before or after the hydraulic transfer film is floated on the water surface, so that the surface of the catalyst layer is Roughness, the catalyst layer and the transfer substrate (transfer object, substrate, non-conductive substrate, molded product, etc.) are likely to be in close contact.

Solvent (organic solvent, activator)
The solvent is preferably a component that can roughen the surface of the transfer catalyst layer of the electroless plating hydraulic transfer film. The solvent is preferably an organic solvent that solubilizes the catalyst layer.

  The solvent is preferably a component having a function of dissolving the surface of a transfer substrate (transfer body, substrate, non-conductive substrate, molded article, etc.).

  The solvent preferably has such a property that it does not evaporate until the catalyst layer is transferred to the transfer surface of the transfer substrate.

  As the solvent, the same activator as used in general hydraulic transfer can be used. As the solvent, it is preferable to use a composition containing, for example, esters, acetylene glycols, ethers, resins and the like.

  As esters, use of ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, dibutyl oxalate, dibutyl phthalate, dimethyl phthalate, dioctyl phthalate, diisooctyl phthalate, etc. preferable.

  As acetylene glycols, it is preferable to use methoxybutyl acetate, ethoxybutyl acetate, ethyl carbitol acetate, propyl carbitol acetate, butyl carbitol acetate, or the like.

  As ethers, it is preferable to use methyl cellosolve, butyl cellosolve, isoamyl cellosolve and the like.

  Solvents include toluene, xylene, ethyl cellosolve, butyl cellosolve, methoxypropanol, butyl carbitol acetate, carbitol, carbitol acetate, cellosolve acetate, diisobutyl ketone, methyl isobutyl ketone (MIBK), amyl acetate, isoamyl acetate, isobutyl alcohol, isopropyl It is preferable to use solvents such as alcohol, n-butanol, methoxybutyl acetate, sol-fit acetate, diacetone alcohol, and mixtures thereof.

  As the resin, it is preferable to use a thermoplastic resin such as an acrylate monomer alone or a copolymer. By including the resin component in the solvent, the adhesion between the printing ink or paint and the molded product can be enhanced.

  As the resin, it is preferable to use a thermosetting resin such as polyamide, polyester, phenol resin, melamine resin, urea resin, epoxy resin, phthalic acid alkyd resin, diallyl phthalate resin, alkyd resin, or polyurethane.

  It is preferable to use a thermosetting resin as the resin.

  The preferred composition (content ratio) of the solvent includes about 5 to 40% by mass of esters, about 40 to 80% by mass of acetylene glycols, about 5 to 30% by mass of ethers, and 1 to 20% by mass of resin. It is preferable to include a degree.

  The solvent can be applied by a spray coating method or the like.

The application amount of the solvent is usually about 1 to 50 g / m ² , preferably about 3 to 30 g / m ² , and more preferably about 10 to ²⁰ g / m ² .

  The binder contained in the catalyst composition is softened and dissolved by the solvent when spraying a solvent (organic solvent, activator) on the catalyst layer side of the hydraulic transfer film for electroless plating (step (2)). It is easy to maintain this state for a relatively long time.

(3) The process of adhering the catalyst layer side of the hydraulic transfer film for electroless plating to the transfer substrate and fixing the catalyst layer to the transfer substrate While pressing the transfer substrate against the catalyst layer, A water pressure transfer film for electroless plating is submerged in water, and the catalyst layer is brought into close contact with the transfer substrate by water pressure and transferred.

Transfer substrate (transfer body, substrate, non-conductive substrate, molded product, etc.)
The transfer substrate is an object to be subjected to electroless plating.

  The transfer substrate used in the present invention is not particularly limited. As the transfer substrate, it is preferable to use a non-conductive substrate such as plastic (resin), glass, or ceramic.

  As the plastic, it is preferable to use a polyolefin such as polyethylene (PE), polypropylene (PP), polystyrene (PS), polybutadiene, polybutene, polyisoprene, polychloroprene, polyisobutylene, and polyisoprene.

  It is preferable to use an acrylonitrile-butadiene-styrene copolymer resin (ABS resin) or the like as the plastic.

  Polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polylactic acid ester; acrylic resins such as polymethyl methacrylate (PMMA); polycarbonate (PC); polyvinyl chloride; polyamide; polyimide; It is preferable to use ether imide, polyacetal, polyether ether ketone, cyclic polyolefin having norbornene skeleton, polyphenylene sulfide, liquid crystal polymer, modified polyphenyl ether, polysulfone, phenol, polyphthalamide (PPA), polyarylate and the like.

  Examples of ceramics include glass and alumina. Moreover, when using a nonwoven fabric as a base material, nonwoven fabrics, such as a wood fiber, glass fiber, asbestos, polyester fiber, vinylon fiber, rayon fiber, polyolefin fiber, are mentioned.

  The shape of the transfer substrate is not particularly limited. For example, it may be any of a plate shape (or film shape), a nonwoven fabric shape (or woven fabric shape), a thread shape, various shapes formed by a mold, and the like.

  Depending on the transfer substrate, a solvent, a binder, and the like contained in the catalyst composition (catalyst layer of the transfer film) can be appropriately selected.

  When the catalyst layer is transferred from the electroless plating hydraulic transfer film to the transfer substrate, the catalyst layer is softened, and is performed to such a degree that it can sufficiently follow the three-dimensional curved surface of the transfer substrate.

  By the hydraulic transfer technique, the catalyst layer of the transfer film can be attached to the transfer substrate (non-conductive substrate).

  The water in the water tank in the hydraulic transfer works as a hydraulic medium for bringing the catalyst layer of the hydraulic transfer film into close contact with the three-dimensional curved surface of the transfer substrate when transferring the catalyst layer.

  The substrate for a hydraulic transfer film is preferably made of a water-soluble film having water solubility or water swellability. The water in the water tank in the hydraulic transfer can swell or dissolve the hydraulic transfer film substrate. The transfer substrate is pressed onto the catalyst layer of the hydraulic transfer film for electroless plating, and the catalyst layer is brought into close contact with the transfer surface of the transfer substrate by water pressure.

  It is preferable to use water such as tap water, distilled water, or ion exchange water as water in the water tank in the hydraulic transfer. In consideration of the substrate for a hydraulic transfer film, inorganic salts such as boric acid or the like may be dissolved in water by about 10% by mass or less, or alcohols may be dissolved by about 50% by mass or less.

  The water for applying the floating water pressure to the electroless plating hydraulic transfer film is preferably adjusted to an appropriate water temperature according to the type of the hydraulic transfer film substrate of the electroless plating hydraulic transfer film. The water temperature is preferably about 25 to 50 ° C, more preferably about 25 to 35 ° C.

The transfer time between the electroless plating hydraulic transfer film and the transfer substrate is preferably about 20 to 120 seconds, more preferably about 30 to 60 seconds. The transfer time is the time from when the electroless plating hydraulic transfer film is suspended in water until the transfer to the transfer substrate is completed. To increase the crack width, it is necessary to increase the coating amount. Preferably, the water temperature is set higher, and the transfer time is preferably set longer.

  In particular, the binder contained in the catalyst composition adheres the catalyst layer side of the electroless plating hydraulic transfer film to the transfer substrate, and fixes the catalyst layer to the transfer substrate (step (3)). On the dissolved surface, the catalyst layer side of the electroless plating hydraulic transfer film is easy to adhere to the transfer substrate, and the catalyst layer is easily fixed to the transfer substrate.

(4) Step of washing the transfer substrate on which the catalyst layer is fixed and exposing the catalyst layer The transfer substrate on which the catalyst layer is fixed is washed to expose the catalyst layer.

  The hydraulic transfer film substrate is removed from the electroless plating hydraulic transfer film discharged from water to obtain a hydraulic transfer body (transfer substrate + catalyst layer) transferred to the transfer substrate.

  After the catalyst layer is hydraulically transferred to the transfer substrate, the hydraulic transfer film substrate is removed by dissolving or peeling with water and then dried. Removal of the hydraulic transfer film substrate from the transfer substrate is performed by dissolving or peeling the hydraulic transfer film substrate with a water flow in the same manner as in the conventional hydraulic transfer method.

  In the hydraulic transfer body, the catalyst layer is sufficiently adhered to the surface of the transfer substrate. When a resin component having high solvent absorbability such as ABS resin or SBS rubber is used as a transfer substrate, the adhesion of the catalyst layer is good.

  Thereafter, using the electroless plating technique, the exposed catalyst layer can be subjected to electroless plating to decorate the non-conductive substrate (molded product).

(5) A process of performing electroless plating on the exposed catalyst layer
By performing electroless plating on the substrate on which the electroless plating treatment catalyst layer (catalyst film) is formed, pattern plating can be formed on the substrate. The substrate on which the catalyst layer is formed comes into contact with a plating solution for depositing a metal, thereby forming an electroless plating film.

  The catalyst layer formed by the catalyst composition (transfer film) has good electroless plating reactivity, and the obtained electroless plating film has no unevenness and excellent adhesion and appearance.

  The plating solution is not particularly limited as long as it is a plating solution usually used for electroless plating. For example, copper, gold, silver, nickel or the like is preferably used as the plating solution. As the plating solution, it is preferable to use a plating solution containing copper or nickel in view of the relationship with the catalyst layer (catalyst film).

  The plating conditions can follow a conventional method. Since the catalyst layer (catalyst film) has very good electroless plating reactivity, it is not necessary to increase the reducing agent concentration or alkali component concentration of the plating solution. Therefore, not only the life of the plating solution is prolonged, but the plating is selectively deposited according to the pattern of the catalyst layer. That is, the catalyst (catalyst film) formed from the catalyst composition (transfer film) is excellent in pattern forming ability.

  The thickness of the plating film is preferably about 0.05 to 10 μm, more preferably about 0.1 to 6 μm, and still more preferably about 0.2 to 4 μm, because it can give a good design to the substrate in the case of decorative use. A thickness of about 0.3 to 2 μm is particularly preferable. The target design can be expressed on the substrate by plating.

  When an electroless copper plating bath is used in the electroless plating treatment, the treatment temperature is preferably about 25 to 65 ° C., and the treatment time is preferably about 10 to 20 minutes. By this electroless plating treatment, a deposited film thickness of about 0.3 to 1 μm can be formed.

  When an electroless nickel boron bath is used in the electroless plating treatment, the treatment temperature is preferably about 55 to 70 ° C., and the deposition rate is preferably about 5 μm / hr (60 ° C.).

  When an electroless nickel phosphorus bath is used for electroless plating, the treatment temperature is preferably about 30 to 95 ° C., and the deposition rate is about 3 μm / hr at a bath temperature of 30 ° C. and about 20 μm / hr at 90 ° C. Is preferred.

  The technique for forming plating on the substrate using the catalyst composition (transfer film) preferably targets pattern plating. However, in the present invention, the catalyst composition (transfer film) of the present invention may be used for the entire plating.

  For decoration purposes, use general processes such as electrolytic copper (Cu) plating, semi-bright nickel (Ni) plating, bright nickel (Ni) plating, and chromium (Cr) plating after electroless plating. Is preferred.

When using an electrolytic copper (Cu) plating bath in the decorating treatment, the treatment temperature is preferably about 20 to 60 ° C., the current density is preferably about 1 to 10 A / m ² , and the treatment time is about 10 to 60 minutes. preferable. By this decorating treatment, a deposited film thickness of about 5 to 40 μm can be formed.

When using a semi-bright nickel (Ni) plating bath in the decorating treatment, the treatment temperature is preferably about 45 to 55 ° C., the current density is preferably about 1 to 10 A / m ² , and the treatment time is about 10 to 60 minutes. Is preferred. By this decorating treatment, a deposited film thickness of about 5 to 20 μm is obtained.

When a bright nickel (Ni) plating bath is used in the decorating treatment, the treatment temperature is preferably about 45 to 55 ° C., the current density is preferably about 1 to 10 A / m ² , and the treatment time is about 10 to 60 minutes. preferable. By this decorating treatment, a deposited film thickness of about 5 to 20 μm is obtained.

When a chromium (Cr) plating bath is used in the decoration treatment, the treatment temperature is preferably about 40 to 60 ° C. Current density is preferably about 10~60A / m ^2. The treatment time is preferably about 1 to 5 minutes. By the decorating process using a Cr plating bath, a deposited film thickness of about 0.1 to 0.3 μm is obtained.

(6) Electroless plating film and molded product on which the film is mounted The catalyst layer of the transfer film of the present invention is applied to a substrate (non-conductive substrate, plastic (resin), etc.) to form a catalyst layer (catalyst film) Then, electroless plating is performed. Thereby, the electroless plating film by which pattern plating or partial plating was carried out can be formed. A molded product (to-be-plated object) on which an electroless plating film is placed has excellent adhesion of the plating film. A smooth plating film (electroless plating film or electrolytic plating film) can be formed on the non-conductive substrate.

  Molded products with an electroless plating film should be used for automobile parts such as emblems, switch bases, radiator grills, door handles, wheel covers, etc. Can do.

  When the catalyst composition is used, electroless plating with pattern plating on the substrate has high electroless plating reactivity, excellent adhesion to chrome plating and excellent smoothness of decorative plating. Can do. In the electroless plating, it is possible to suppress the spread of the pattern and to perform partial plating satisfactorily.

  When the catalyst composition (transfer film) is used, it is not necessary to increase the concentration of the reducing agent in electroless plating and to increase the reaction temperature of electroless plating for the purpose of improving the reactivity of electroless plating. Furthermore, there is no need for an etching step with a harmful substance, a complicated catalyst application step, or the like.

  The mechanism for improving the reactivity and adhesion of electroless plating will be described.

  Metal particles (Pd particles) having a catalytic action of electroless plating of the catalyst composition (catalyst layer) formed on the substrate (non-conductive substrate) are brought into contact with the electroless plating solution. Due to this phenomenon, metal ions (Pd particles, etc.) existing deep inside the membrane from the surface of the catalyst layer (catalyst membrane) reduce the metal ions in the electroless plating solution, and the reduced metal takes root. Thus, since it precipitates from the inside of a film | membrane, the high adhesiveness of a catalyst layer (catalyst film | membrane) and a plating film is acquired.

  The catalyst composition of the present invention has a high electroless plating reactivity, particularly when it is applied to a base such as ABS (non-conductive substrate, plastic, etc.), and has good adhesion that can withstand multilayer plating up to plating. Can be realized. The adhesion mechanism between the base material such as ABS and the catalyst composition will be explained. The substrate surface is eroded by the solvent (solvent) component contained in the catalyst composition of the present invention, the binder component of the catalyst composition enters the substrate, and is mixed with the substrate to form a hybrid layer. Since the butadiene rubber contained in the ABS resin dissolves and swells, the binder component of the catalyst composition enters the substrate.

  The hydraulic transfer technology of the present invention can plate (decorate) a non-conductive substrate on a three-dimensional curved surface, a perforated molded product, and a gentle uneven surface, which has been impossible in the past. Combining with a functional material such as a hard coat can increase the added value of the product.

  The hydraulic transfer technology can reduce the cost by simplifying the process. Energy saving and space saving can be achieved, which leads to improvement of working environment. The hydraulic transfer technology can perform (decorate) various highly designable designs (plating) on the surface of the cubic surface with high positional accuracy on a non-conductive substrate (molded product).

  When the plating transfer film of the present invention is used, in the plating for pattern plating on the substrate, the electroless plating has high reactivity and can exhibit excellent adhesion and excellent smoothness of decorative plating. In the plating, it is possible to suppress the spread of the pattern and to perform partial plating satisfactorily.

  When the hydraulic transfer film for electroless plating of the present invention is used, there is no need to increase the concentration of the reducing agent in electroless plating and the reaction temperature of electroless plating needs to be increased for the purpose of improving the electroless plating reactivity. Nor. Furthermore, there is no need for an etching step with a harmful substance, a complicated catalyst application step, or the like.

  The present invention is suitable for forming a metal wiring circuit on a case where a printed wiring board or a three-dimensional casing of an electronic device has a larger (complex) cubic curved surface or a deeper cubic curved surface. Electroless plating can be performed using the transfer film. The transfer film of the present invention is used to pattern-form (expose) a catalyst layer (catalyst composition), that is, a film for performing electroless plating on a wiring board (non-conductive substrate). An electroless plating film for forming an electronic circuit is formed on the wiring board by performing electroless plating on the wiring board on which the film (catalyst layer) for electroless plating is formed.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

(1) Ink (catalyst composition for transfer film)
1-1
Pd complex-containing liquid (Pd content 12.75 wt%, manufactured by Iox Corporation): 1.96 g,
Vinyl chloride-vinyl acetate resin (solid content 10 wt%, manufactured by DIC Graphics): 9.0 g, and cyclohexane / MIBK / MEK mixed solvent (solvent)
A catalyst composition for a metal plating transfer film was prepared by mixing so that the Pd concentration was 5,000 ppm (0.5 wt%).

1-2
Pd complex-containing liquid (Pd content 16.7 wt%, manufactured by Iox Corporation): 0.075 g,
Alkyd resin (6% solid content manufactured by DIC Graphics): 0.75 g, and cyclohexane / MIBK mixed solvent (solvent)
A catalyst composition for a metal plating transfer film was prepared by mixing so that the Pd concentration was 6,000 ppm (0.6 wt%).

1-3
ML-100 (Iox Co., Ltd.) Offset printing, circuit ink

(2) Formation of hydraulic transfer film for electroless plating
2-1
Using bar coater # 4 (coating thickness: 4μm), the resulting metal plating transfer film catalyst compositions 1-1 and 1-2 were transferred to a hydraulic transfer film (trade name: Solvron, PVA resin, manufactured by Aicero Chemical). It was applied on top (coating thickness: 4 μm).

  Subsequently, it was dried in a drying oven at 70 ° C. for 5 minutes.

2-2
Using the printing pattern plate (Fig. 1) on the hydraulic transfer film (trade name: Solvron, PVA resin, manufactured by Aicero Chemical) And printed.

  Next, it was dried at 80 ° C. for 15 minutes in a drying oven.

(3) Hydraulic transfer
Solid surface transfer: 3-1 and 3-2
The water pressure transfer film side of the resulting water pressure transfer film for metal plating 2-1 is floated on the water surface (25 ° C, tap water, volume 10 L), and the water pressure transfer film base material (PVA resin) is placed in water. Dissolved (1-2: about 100 sec, 1-1: about 40 sec).

  At that time, in order to adhere the transfer substrate to the catalyst composition application side, a spray (the spray, manufactured by Maruhachi Sangyo Co., Ltd.) is used and a solvent (toluene: MIBK: ethyl acetate = 3: 3: 3). ) Was sprayed once every 3 seconds.

  After a predetermined time, a molded product (ABS resin molded product, Komori Resin Co., Ltd.) was slowly submerged in the hydraulic transfer film at an angle of about 45 ° to 80 °. Subsequently, after fixing in water, it took out slowly and washed with running water.

Circuit formation: 3-3.
The water pressure transfer film side of the obtained water transfer film for metal plating 3-1 is floated on the water surface (25 ° C, tap water, volume 10 L), and the water pressure transfer film substrate (PVA resin) is used as water. Dissolved (about 40 sec).

  About 30 seconds after the film floats on the surface of the water, a solvent (toluene, MIBK, etc.) is used in order to adhere the transfer substrate to the catalyst composition application side using a spray (The Spray, Maruhachi Sangyo Co., Ltd.) Ethyl acetate = 3: 3: 3) was sprayed on the printed pattern portion once every 3 seconds.

  After a predetermined time, a molded product (ABS resin molded product, Komori Resin Co., Ltd.) was slowly submerged in the hydraulic transfer film at an angle of about 45 ° to 80 °. Next, after fixing in water, it was slowly taken out, fixed, and washed with running water.

  There was no problem with hydraulic transfer.

  Fig. 2 shows the image after transfer to an ABS resin molded product.

(4) Electroless plating
Solid surface transfer: 3-1 and 3-2
Electroless Cu Plating Bath and Electroless Ni Plating Bath Conditions As an electroless copper (Cu) plating bath, HFS (initial Cu concentration 2.5 g / L, bath volume 500 mL, 40 ° C.) manufactured by Okuno Kogyo Co., Ltd. was used.

  As the electroless nickel (Ni) plating bath, HX manufactured by Okuno Kogyo Co., Ltd. (initial Ni concentration 6 g / L, bath volume 500 mL, 60 ° C.) was used.

The evaluation of electroless plating property is as follows.
◯: When electroless plating is performed for 5 minutes and good metal deposition occurs immediately after immersion in the plating bath, and a copper (Cu) or nickel (Ni) plating film can be formed.
Δ: A metal deposition reaction occurs, but a uniform plating film cannot be formed on the entire surface.

(5) Conductivity measurement
Circuit formation: 3-3
Using a KM-320N tester manufactured by Custom Co., Ltd., the surface resistance of the electroless plating transfer circuit obtained by hydraulic transfer was measured and the electrical resistance between the electrodes of the plating pattern or plating film surface 10 mm.

  In either case, the electric resistance value was 0.0Ω.

Claims (8)

A hydraulic transfer film for electroless plating in which at least a catalyst layer is laminated on a hydraulic transfer film substrate,
The catalyst layer comprises (1) a composite of metal particles and a dispersant, (2) a solvent and (3) a catalyst composition containing a binder, and the metal particles are palladium particles, gold particles, silver particles or platinum particles. Is,
Hydraulic transfer film for electroless plating.   The dispersant of the catalyst composition is at least selected from the group consisting of a polycarboxylic acid polymer dispersant, a block copolymer type polymer dispersant having a hydroxyl group, and a block copolymer type polymer dispersant having a carboxyl group. The hydraulic transfer film for electroless plating according to claim 1, which is a kind of dispersant.   The catalyst composition solvent is water; an aprotic polar solvent selected from the group consisting of N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide; dimethyl sulfoxide and γ-butyrolactone Polar solvents; alcohols selected from the group consisting of methanol, ethanol, isopropyl alcohol, 1-butyl alcohol and isobutyl alcohol; ketones selected from the group consisting of acetone, methyl ethyl ketone, methyl isobutyl ketone, diacetone alcohol and cyclohexanone; ethylene glycol Glycol ethers selected from the group consisting of monomethyl ether and ethylene glycol monobutyl ether; aromatic carboxylic acids selected from the group consisting of methyl benzoate, ethyl benzoate and methyl salicylate Sterols; aromatic hydrocarbons selected from the group consisting of toluene and xylene; aliphatic hydrocarbons selected from the group consisting of n-hexane, n-heptane and mineral spirits; methyl cellosolve acetate, ethyl cellosolve acetate, At least one selected from the group consisting of glycol ether esters selected from the group consisting of butyl cellosolve acetate, methyl carbitol acetate and butyl carbitol acetate; alkanol esters selected from the group consisting of ethyl acetate and butyl acetate; 2-phenoxyethanol The hydraulic transfer film for electroless plating according to claim 1 or 2, which is a seed solvent.   The catalyst composition binder is acetal resin, epoxy resin, ester resin, acrylic resin, urethane resin, amide resin, imide resin, amidoimide resin, shellac resin, melamine resin, urea resin, nitrified cotton, alkyd resin, petroleum resin, The rosin resin, styrene / maleic acid resin, silicone resin, vinyl chloride-vinyl acetate copolymer, acrylic monomer / oligomer, and at least one binder selected from the group consisting of olefin resins. The hydraulic transfer film for electroless plating as described in 1.   The transfer film for electroless plating according to claim 1, wherein the hydraulic transfer film substrate is a substrate made of a water-soluble film.   The resin constituting the water-soluble film is polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl methyl ether, acetyl cellulose, polyacrylamide, polyacrylamide, sodium polyacrylate, acetylbutylcellulose, gelatin, glue, sodium alginate, methylcellulose, hydroxy Selected from the group consisting of ethyl cellulose, carboxymethyl cellulose, dextrin, casein, shellac, gum arabic, starch, protein, copolymer of methyl vinyl ether and maleic anhydride, polyethylene oxide and copolymer of vinyl acetate and itaconic acid The hydraulic transfer film for electroless plating according to claim 5, which is at least one resin. A method for producing a hydraulic transfer film for electroless plating according to any one of claims 1 to 6,
(1) A step of applying a catalyst composition on a hydraulic transfer film substrate and providing a catalyst layer;
including,
A method for producing a hydraulic transfer film for electroless plating. A method for producing an electroless plated product using the hydraulic transfer film for electroless plating according to any one of claims 1 to 6,
(1) A step of floating the hydraulic transfer film substrate side of the electroless plating hydraulic transfer film on the water surface, and dissolving the hydraulic transfer film substrate;
(2) A step of spraying a solvent onto the catalyst layer side of the hydraulic transfer film for electroless plating,
(3) Adhering the catalyst layer side of the hydraulic transfer film for electroless plating to the transfer substrate, and fixing the catalyst layer to the transfer substrate;
(4) A method for producing an electroless plated product, comprising: a step of washing the transfer substrate on which the catalyst layer is fixed to expose the catalyst layer; and (5) a step of performing electroless plating on the exposed catalyst layer.