JP6612419B1 - Vacuum 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 vacuum transfer film for electroless plating that can be used in vacuum transfer technology. A transfer film for electroless plating in which (A) at least (B) a catalyst layer and (C1) an adhesive layer or (C2) an adhesive layer are sequentially laminated on a substrate having releasability. The (B) catalyst layer comprises a catalyst composition containing (1) a composite of metal particles and a dispersant, (2) a solvent, and (3) a binder, and the metal particles are palladium particles. A transfer film for electroless plating, which is gold particles, silver particles or platinum particles, and the transfer is vacuum transfer. [Selection figure] None

Description

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

  The present applicants are a transfer film for electroless plating in which at least a catalyst layer and an adhesive layer or an adhesive layer are sequentially laminated on a substrate having releasability, wherein the catalyst layer is (1) a metal A composite of particles and a dispersant, (2) a catalyst composition comprising a solvent and (3) a binder, wherein the metal particles are palladium particles, gold particles, silver particles or platinum particles, and the transfer is in-mold. A transfer film for electroless plating, which is transfer, hot roll transfer, or adhesive transfer, is provided (Patent Document 1).

  In this technology, electroless plating is applied to non-conductive substrates such as plastics that have no catalytic activity, and various transfer technologies can be used to adhere catalyst materials such as metallic palladium to the non-conductive substrate. Then, electroless plating can be performed to satisfactorily form an electroless plating film. With this technology, the catalyst layer of the electroless plating film can be satisfactorily formed from the flat surface of plastic or the like to the surface of the third-order curved surface such as a cylindrical object, or for electroless plating on the substrate at the same time as molding in the mold A film can be formed satisfactorily.

  The applicants of the present application are a hydraulic transfer film for electroless plating in which at least a catalyst layer is laminated on a substrate for a 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 ( Patent Document 2).

  With this technology, using a hydraulic transfer film having a specific catalyst layer on a non-conductive substrate having no catalytic activity such as plastic, the catalyst layer can be transferred well, and then electroless plating is performed. An electroless plating film can be formed on the non-conductive substrate.

  The present applicants are a transfer base film for transferring a design to the surface of a molded body by a vacuum pressure thermal transfer method, and a base material layer made of a thermoplastic urethane resin, and an elongation rate at 10 kgf / m. And a support layer having a thickness of 0.3% or less, is peelably laminated via a support release layer, and the peel strength between the base material layer and the support release layer is 3 to 25 gf / 25 mm A substrate film for transfer with a support layer is provided (Patent Document 3).

  With this technology, the transfer base film has rigidity by laminating the support layer, and when printing a pattern on the surface, it can be accurately printed with accurate alignment. . In addition, by peeling the support layer from the printed transfer base film with a support layer, when transferring to the surface of the molded body, it has the flexibility to follow the details of the complicated molded body, A high-quality design expression can be achieved by decorating a molded body having a three-dimensional shape.

Patent No. 5843992 Patent No. 6072343 Japanese Patent No.5912501

  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 vacuum transfer film for electroless plating that can be used in vacuum transfer technology.

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

  As a technology for applying a metal plating gloss to the final part (housing), the present applicant has applied a transfer film for electroless plating (Patent Document 1) used for in-mold transfer, heat roll transfer or adhesive transfer, and water pressure transfer. Providing a hydraulic transfer film for electroless plating (Patent Document 2) to be used, and providing a transfer substrate film (Patent Document 3) for transferring a pattern to the surface of a molded body by a vacuum pressure thermal transfer method Yes.

  When these transfer films are used, the catalyst layer can be satisfactorily transferred to the non-conductive substrate, and in addition to the planar material, transfer to a three-dimensional housing and electroless plating are also possible. 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. For example, it is a substrate (transfer substrate) having a deep-drawn shape. 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 vacuum transfer film. The present inventor uses a vacuum transfer technique and a vacuum transfer film having the catalyst layer (catalyst composition) to form a catalyst layer (catalyst composition) against a non-conductive substrate (substrate, transfer substrate). Has been found to be well transferred.

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

Item 1.
(A) A transfer film for electroless plating in which at least (B) a catalyst layer and (C1) an adhesive layer or (C2) an adhesive layer are sequentially laminated on a substrate having releasability,
The (B) catalyst layer is composed of a catalyst composition containing (1) a composite of metal particles and a dispersant, (2) a solvent, and (3) a binder, and the metal particles include palladium particles and gold particles. , Silver particles or platinum particles,
A transfer film for electroless plating, wherein the transfer is vacuum transfer.

Item 2.
(1) The composite dispersant of the catalyst composition is 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 electroless plating transfer film according to Item 1, which is at least one dispersant selected from the group consisting of:

Item 3.
(2) solvent of the catalyst composition is water; aprotic polar solvent selected from the group consisting of water; N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide; dimethyl sulfoxide and γ-butyrolactone; Alcohol 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 monomethyl ether and ethylene Glycol ethers selected from the group consisting of glycol monobutyl ether; aromatic carboxylic acid esters selected from the group consisting of methyl benzoate, ethyl benzoate and methyl salicylate; toluene and Aromatic hydrocarbons selected from the group consisting of xylene; aliphatic hydrocarbons selected from the group consisting of n-hexane, n-heptane and mineral spirits; methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, methylcarb A glycol ether ester selected from the group consisting of tall acetate and butyl carbitol acetate; an alkanol ester selected from the group consisting of ethyl acetate and butyl acetate; and at least one solvent selected from the group consisting of 2-phenoxyethanol. The transfer film for electroless plating according to item 1 or 2.

Item 4.
(3) The binder of the catalyst composition 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 and olefin resin. The transfer film for electroless plating according to any one of Items 1 to 3, which is at least one binder selected.

Item 5.
Item 5. The transfer film for electroless plating according to any one of Items 1 to 4, wherein the (A) substrate having releasability is a substrate made of a stretchable film.

Item 6.
Item 6. The electroless plating according to Item 5, wherein the resin constituting the stretchable film is at least one resin selected from the group consisting of polyurethane, polyester, nylon, polypropylene, polyethylene, polyvinyl chloride, and rubber. Vacuum transfer film.

Item 7.
(A) The substrate having releasability is a melamine resin release agent, silicone release agent, fluororesin release agent, cellulose resin release agent, urea resin release agent, polyolefin resin release agent, paraffin type The transfer film for electroless plating according to any one of Items 1 to 6, which is a base material including a release layer made of at least one release agent selected from the group consisting of a release agent and an acrylic resin-based release agent.

Item 8.
The adhesive layer (C1) is an acrylic adhesive, polystyrene adhesive, polyamide adhesive, urea adhesive, melamine adhesive, phenol adhesive, vinyl acetate adhesive, rubber adhesive, epoxy An adhesive layer made of at least one adhesive selected from the group consisting of an adhesive, a polyurethane adhesive, a vinyl acetate resin emulsion, an EVA resin emulsion, and an acrylic resin emulsion, or the (C2) adhesive layer Is an adhesive layer composed of at least one adhesive selected from the group consisting of acrylic adhesives, polystyrene adhesives, polyamide adhesives, silicone adhesives, urethane adhesives and rubber adhesives, The transfer film for electroless plating according to any one of Items 1 to 7.

Item 9.
The transfer film for electroless plating according to any one of Items 1 to 8, wherein a support layer is further laminated on the side of the substrate having releasability (A) of the transfer film for electroless plating.

Item 10.
The transfer film for electroless plating according to any one of Items 1 to 9, wherein the transfer is a vacuum transfer to a substrate having a deep-drawn shape.

Item 11.
A method for producing a transfer film for electroless plating according to any one of Items 1 to 10,
(1) forming a layer having releasability on a substrate, and (A) producing a substrate having releasability,
(2) applying a catalyst composition to the layer side having releasability of the substrate, and (B) providing a catalyst layer; and
(3) A method for producing a transfer film for electroless plating, comprising the step of providing (C1) an adhesive layer or (C2) an adhesive layer on the (B) catalyst layer.

Item 12.
A method for producing an electroless plated product using the transfer film for electroless plating according to any one of Items 1 to 10,
(1) A process of attaching the (C1) adhesive layer or (C2) adhesive layer of the transfer film to a substrate,
(2) For the pasted material obtained in the above step, leave the (B) catalyst layer and (C1) adhesive layer or (C2) adhesive layer of the transfer film on the substrate, and (A) separate from the substrate. A step of peeling the base material having moldability, and (3) a step of performing electroless plating on the catalyst layer exposed by the step (B),
The step (1) is performed by vacuum transfer.
Method for producing electroless plating.

Item 13.
Item 13. The method for producing an electroless plated article according to Item 12, wherein the substrate is a substrate having a deep-drawn shape.

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

  The present invention provides a vacuum transfer film (electroless) having a specific catalyst layer (catalyst composition) on a non-conductive substrate (substrate, transfer substrate) having no catalytic activity, such as plastic, by a vacuum transfer technique. The catalyst layer can be transferred (attached) satisfactorily using a vacuum transfer film for plating. In the present invention, electroless plating can then be performed to form an electroless plating film on the nonconductive substrate (substrate, transfer substrate).

  By using the vacuum transfer film for electroless plating according to the present invention, the transferred catalyst layer (catalyst composition) allows a larger (complex) cubic curved surface or a deeper cubic curved surface. An electroless plating film having a smooth surface can be formed even on a three-dimensional housing having a surface.

  For example, it is a substrate (transfer substrate) having a deep-drawn shape.

  By using the vacuum transfer film for electroless plating according to the present invention, metal plating gloss can be applied to 3D housings with larger (complex) cubic curved surfaces and deep cubic curved surfaces. These technologies will lead to excellent three-dimensional decorative electroless plating technology.

It is a figure explaining the usage aspect of the vacuum transfer film for electroless plating of this invention. It is a figure explaining the usage aspect of the vacuum transfer film for electroless plating of this invention. It is the photograph of the embodiment which carried out the vacuum transfer to the resin molded product using the vacuum transfer film for electroless plating of this invention. It is the photograph of the embodiment which carried out the vacuum transfer to the resin molded product using the vacuum transfer film for electroless plating of this invention. It is the photograph of the embodiment which carried out the vacuum transfer to the resin molded product using the vacuum transfer film for electroless plating of this invention. It is explanatory drawing which shows the vacuum transfer film of this invention. It is the schematic which shows the film forming method which forms the vacuum transfer film of this invention. It is explanatory drawing which shows the method to transcribe | transfer to the surface of a molded object using the vacuum transfer film of this invention. It is a schematic sectional drawing of the transfer apparatus which performs a vacuum pressurization thermal transfer.

  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.

(I) Description of the Invention The present invention is a vacuum transfer film for electroless plating that can be used in vacuum transfer technology.

Hereinafter, the present invention is also referred to as a “vacuum transfer film of the present invention”. The present invention is a vacuum transfer having a specific catalyst layer (catalyst composition) on a non-conductive substrate having no catalytic activity, such as plastic, by a vacuum transfer technique. Using the film, the catalyst layer can be transferred (attached) satisfactorily, and then electroless plating can be performed to form an electroless plating film on the non-conductive substrate.

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 vacuum transfer film of the present invention is used, a three-dimensional housing having a larger (complex) cubic curved surface or a deeper cubic curved surface in addition to a planar material by vacuum transfer technology ( An electroless plating film having a smooth surface can be formed even on a deep-drawn substrate. According to the present invention, metal plating gloss can be applied to a three-dimensional housing having a more complicated cubic curved surface.

  When the vacuum transfer film of the present invention is used, transfer (decoration) with excellent adhesion can be performed on some engineer plastics and the like without being limited by the shape. The vacuum transfer technology using the vacuum transfer film of the present invention includes general-purpose resins such as acrylonitrile-butadiene-styrene copolymer synthetic resin (ABS resin), polypropylene (PP), acrylic resin, polycarbonate (PC), and combinations of these resins ( It can be applied to plastic products such as PC / ABS.

  When the vacuum transfer film of the present invention is used, it is possible to transfer (decorate) adhesiveness to substrates such as ceramics and earthenware by securing adhesiveness to those substrates. It is.

  When the vacuum transfer film of the present invention is used, pattern plating or partial plating is performed from the flat surface of a base material such as plastic (non-conductive substrate) to the surface of a tertiary curved surface base material such as a cylindrical object by a vacuum transfer technology. The plated film thus formed 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. .

  Using the vacuum transfer film of the present invention, the vacuum transfer technology provides high plating reactivity such as pattern plating, and excellent adhesion to chrome plating and excellent smoothness of decorative plating to the substrate. can do. In the plating, it is possible to suppress the spread of the pattern and to perform partial plating satisfactorily. When the vacuum transfer film of the present invention is used, a plating film having excellent thickness uniformity can be formed on the article substrate (base) by the vacuum transfer technique.

  When the vacuum 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 vacuum transfer technique. When the vacuum transfer film of the present invention is used, the layer serving as the base of the electroless plating film contains a catalyst in advance, so that a catalyst adsorption step is not necessary, and the steps included in the transfer and electroless plating technology are simplified. Can be

  When the vacuum transfer film of the present invention is used, accurate alignment can be performed and printing can be accurately performed by a vacuum transfer technique, and the details of a complicated molded body can be followed.

Formation of Metal Wiring Circuit Using the vacuum transfer film of the present invention, a catalyst layer (catalyst composition), that is, a film for applying 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, housings with larger (complex) cubic curved surfaces or deeper cubic curved surfaces (bases with deep-drawn shapes) Electroless plating can be performed using the “transfer film” of the present invention for forming a metal wiring circuit.

  By using the vacuum transfer film of the present invention, transfer to a housing having a tertiary curved surface as well as a flat plate or the like is possible by a vacuum transfer technique. Transfer processing can be performed without wrinkles on the substrate of the cubic surface (transfer base material). 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.

  By using the vacuum transfer film of the present invention, a larger or more complicated third-order curved surface or a deeper third-order curved surface can be formed on a printed wiring board or three-dimensional housing of an electronic device by a vacuum transfer technique. It is also possible to perform electroless plating to form a metal wiring circuit on a casing having a surface of (a base material having a deep-drawn shape). Using the vacuum transfer film of the present invention, the wiring layer (non-conductive substrate) is patterned (exposed) with a catalyst layer (catalyst composition), that is, a film for applying electroless plating. 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.

(II) Vacuum transfer film The transfer film for electroless plating of the present invention comprises (A) at least (B) a catalyst layer and (C1) an adhesive layer or (C2) an adhesive layer on a substrate having releasability. And (B) the catalyst layer is composed of a catalyst composition containing (1) a composite of metal particles and a dispersant, (2) a solvent, and (3) a binder. Are palladium particles, gold particles, silver particles, or platinum particles, and the transfer is a vacuum transfer.

  By using the vacuum transfer film of the present invention, a printed wiring board or a three-dimensional casing of an electronic device has a larger or complicated cubic curved surface or a deep cubic curved surface. When a circuit is manufactured on a base material having a deep-drawn shape, a metal wiring circuit can be formed satisfactorily.

(A) A substrate of a substrate vacuum transfer film having releasability .

It is preferable that the base material which has a base material (A) mold release property is a base material which consists of a film which has a stretching property. The resin constituting the stretchable film is preferably at least one resin selected from the group consisting of polyurethane, polyester, nylon, polypropylene, polyethylene, polyvinyl chloride, and rubber.

  As the polyester, it is preferable to use polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), or the like.

  PET is a crystalline resin that changes from amorphous to crystalline by external heating. Non-crystallized PET is called A-PET (Amorphous PET). G-PET is a glycol-modified polyester in which a certain content of ethylene glycol in PET is replaced by cyclohexane dimethanol (CHDM), and is a non-crystallized PET in which crystallization is prevented. As PET, A-PET and G-PET can be used.

  It is preferable to use a base material using a resin film such as polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), and nylon (PA, polyamide).

  In the vacuum (pressurized heat) transfer method, it is preferable to use a thermoplastic polyurethane resin having a large stretchability in that it can follow the complicated shape of the molded body as the material of the base material. In the vacuum transfer film of the present invention, since the base material is a thermoplastic polyurethane resin as a main material, the transfer film has high stretchability, and a molded article having a complicated three-dimensional shape by a vacuum (pressurized heat) transfer method. The design can be transferred to the surface. That is, it has flexibility to follow the details of a complicated molded body, and has excellent transfer performance.

  These can be used singly or can be arbitrarily combined.

  The thickness of the substrate is 10 to 60 μm because the strength of the vacuum transfer film can be maintained, the shape following property to the substrate (non-conductive substrate) is good and the catalyst layer can be transferred well. About 15 to 50 μm is more preferable, and about 20 to 40 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.

Release layer (release layer)
The substrate having releasability can impart releasability to the substrate by including a layer having releasability. A layer having releasability is referred to as a “release layer”.

  In the method for producing an electroless plated product using the vacuum transfer film of the present invention, the release layer is obtained by attaching the adhesive layer or the adhesive layer of the transfer film to a substrate by a vacuum transfer technique, and then obtaining the attached product. On the other hand, it is a boundary layer when the base material (base material and release layer) having releasability is peeled from the substrate, leaving the catalyst layer and the adhesive layer or the adhesive layer of the vacuum transfer film on the substrate. . The release layer is a layer for easily peeling the base material (base material sheet) from the catalyst layer in a state where the adhesive layer or the pressure-sensitive adhesive layer and the catalyst layer are attached to the substrate. The release layer remains on the substrate side when the substrate is peeled off.

  By providing the release layer, the catalyst layer can be reliably and easily transferred from the vacuum transfer film of the present invention to the substrate (non-conductive substrate), and the substrate and the release layer are provided from the substrate to which the catalyst layer is attached. The base material portion can be reliably peeled off.

  As release agents used in the release layer, melamine resin release agents, silicone release agents, fluororesin release agents, cellulose resin release agents, urea resin release agents, polyolefin resin release agents, paraffin release agents, acrylics It is preferable to use a resin-based release agent or the like. These can be used singly or can be combined release agents arbitrarily combined. Among these, it is more preferable to use a melamine resin release agent, a silicone release agent, or the like.

  In order to form a release layer on a substrate, it is preferable to use a release composition prepared by dissolving or dispersing an additive necessary for the release agent in an appropriate solvent. The release layer can further contain a resin, an additive, and the like. The resin used for forming the release layer is preferably formed using a thermoplastic resin. For example, it is preferable to use an acrylic resin, a polyester resin, a cellulose derivative resin, a polyvinyl acetal resin, a polyvinyl butyral resin, a vinyl chloride-vinyl acetate copolymer, a chlorinated polyolefin resin, or the like.

  A layer having a releasability (peeling layer) can be formed on the substrate by an extrusion method to be described later.

  In addition, this peeling composition may be applied and dried on a substrate by known means such as a gravure coating method, a roll coating method, a comma coating method, a gravure printing method, a screen printing method, a gravure reverse roll coating method, etc. It is also possible to form a release layer.

  The thickness of the release layer is preferably about 0.1 to 5 μm, more preferably about 0.2 to 3 μm.

(B) Catalyst layer In the vacuum transfer film of the present invention, (B) a catalyst layer is laminated on the (A) base material having releasability, and (B) the catalyst layer comprises (1) metal particles. And (2) a solvent, and (3) a catalyst composition containing a binder, wherein the metal particles are palladium particles, gold particles, silver particles or platinum particles.

Composition of catalyst composition
(1) A composite catalyst layer of metal particles and a dispersant is composed of a catalyst composition, and the catalyst composition contains 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.

As the dispersant 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 in the reduction. 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 complex 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.

(2) The solvent catalyst layer is composed of a catalyst composition, and this catalyst composition contains 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.

(3) The binder catalyst layer is composed of a catalyst composition, and the catalyst composition contains 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 Corp. XNR-3053, XNR3505, XN1244, XN1278; Arakawa Chemical Industries Arachid 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, 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.

  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 the method for producing an electroless plated product by the vacuum transfer technique using the vacuum transfer film of the present invention.

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 this.

  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 vacuum transfer technique can be manufactured.

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

  The catalyst composition has high reactivity of plating (electroless plating or electrolytic plating), has good adhesion to the plating, and can form a plating film that can exhibit good smoothness.

  With the vacuum transfer film, it is possible to form 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.

(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 process for producing a complex of a dispersant (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 composite of metal particles (Pd particles) and a dispersant is prepared.

  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, by reacting a metal ion (Pd ion or the like) with a reducing agent, the metal ion (Pd ion or the like) is reduced by the 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 dispersant, 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 a dispersing agent It is possible to make a mixture of

(Ii) (2) Step of preparing a mixture by mixing (3) a binder in a solvent (2) (3) Mixing a binder in a solvent to prepare a mixture.

  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 to consider the viscosity of the catalyst composition when using the binder. In addition, it is preferable to consider the adhesiveness between the catalyst composition and the nonconductive 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.

(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. Step of mixing a mixture of a solvent and (3) a binder (2) obtained in the step (i) (1) A mixture of a composite of a solvent and (1) metal particles (such as Pd particles) and a dispersant is added to the step ( Mix the mixture of (2) solvent and (3) binder obtained in ii).

Structure of catalyst layer The catalyst layer of the vacuum transfer film of the present invention is formed from the catalyst composition.

  In the method for producing an electroless plated product using the vacuum transfer film of the present invention, the adhesive layer of the vacuum transfer film is attached to a substrate (non-conductive substrate) by a vacuum transfer technique, and then the obtained attachment This is a layer provided on the substrate (non-conductive substrate) after leaving the catalyst layer and adhesive layer of the transfer film on the substrate and peeling the substrate and the release layer from the substrate. The catalyst layer is an exposed layer for performing electroless plating provided on the substrate via an adhesive layer. The catalyst layer remains on the substrate side when the substrate is peeled off.

  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, grain, stone, cloth, sand, geometric pattern, characters, stripes, gradation pattern, etc. can be given to the substrate.

  This catalyst composition is applied and dried on the substrate-peeling layer 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, a gravure reverse roll coating method, etc. Thus, a catalyst layer can be formed.

  The thickness of the catalyst layer is preferably about 20 μm or less, preferably about 0.01 to 10 μm, more preferably about 0.02 to 8 μm, and more preferably about 0.03 to 8 μm, because electroless plating can be satisfactorily performed and a plating film can be satisfactorily formed on the substrate. About 5 μm is more preferable, and about 0.05 μm (50 nm) to 2 μm is particularly preferable. The desired design can be expressed on the substrate by electroless plating. Even if the film thickness is less than 0.01 μm, the electroless plating reactivity can be obtained. When the film thickness exceeds 10 μm, the reaction rate of electroless plating tends to be inferior.

(C) Adhesive layer and adhesive layer In the vacuum transfer film of the present invention, (B) a catalyst layer is laminated on the substrate (A) having releasability, and (C) on this (B) catalyst layer. The adhesive layer or (C2) adhesive layer is laminated in order.

(C1) Adhesive layer The adhesive layer is a method of producing an electroless plated product using the transfer film of the present invention, and the vacuum transfer film is applied to the substrate (non-conductive substrate) by vacuum transfer technology. When attaching, it is a layer which adheres a substrate and a catalyst layer. The adhesive layer exists between the substrate and the catalyst layer. The adhesive layer remains on the substrate side when the substrate is peeled off. Due to the adhesive layer, the catalyst layer can be satisfactorily formed on the substrate, and thereafter electroless plating can be satisfactorily performed.

  Adhesive layer is acrylic adhesive, polystyrene adhesive, polyamide adhesive, urea adhesive, melamine adhesive, phenol adhesive, vinyl acetate adhesive, rubber adhesive, epoxy adhesive, It is preferably formed using an adhesive composition containing an adhesive (resin) such as polyurethane adhesive, vinyl acetate resin emulsion, EVA resin emulsion, and acrylic resin emulsion. These can be used alone or can be arbitrarily combined into a resin composition.

  The adhesive layer is preferably selected in consideration of the compatibility with the binder contained in the catalyst composition (catalyst composition) of the vacuum transfer film of the present invention and the adhesion to the substrate. For example, it is more preferable to use an acrylic resin or the like.

  This adhesive composition is applied onto the substrate-release layer-catalyst layer by a known means such as gravure coating method, roll coating method, comma coating method, gravure printing method, screen printing method, gravure reverse roll coating method, etc. -It can be dried to form an adhesive layer.

  The thickness of the adhesive layer is preferably about 0.1 to 5 μm, and more preferably about 1 to 5 μm because the catalyst layer can be satisfactorily formed (adhered) on the substrate.

  The adhesive is generally cured after solvent drying at room temperature (has thermosetting properties) (room temperature adhesive). When designing with a room temperature adhesive, the reaction proceeds at room temperature, so it is possible to limit the time and temperature until the vacuum transfer film is vacuum transferred. Moreover, since it hardens | cures at normal temperature, it is possible to suppress stickiness (it does not generate | occur | produce) when transferring a transfer film.

  Store the epoxy adhesive at low temperature (refrigerator etc.) (half-life state) and heat press it during processing. Epoxy resin can be used as an insulating material for circuit laminates.

  Epoxy adhesives are thermosetting adhesives that are generally cured by a thermal process. For production of an electronic circuit board, it is preferable to use an epoxy-based adhesive bonded with a hot roll, a hot press or the like. A thermoplastic resin such as an acrylic adhesive (having a high glass transition point (Tg)) functions as an adhesive because its viscosity is lowered by heating.

(C2) Adhesive layer The adhesive layer is a method for producing an electroless plated product using the vacuum transfer film of the present invention, and the adhesive layer of the vacuum transfer film is ground (non-conductive substrate) by vacuum transfer technology. This is a layer for bonding the substrate and the catalyst layer when pasting. The adhesive layer exists between the substrate and the catalyst layer. The adhesive layer remains on the substrate side when the substrate is peeled off. Due to the adhesive layer, the catalyst layer can be satisfactorily formed on the substrate, and thereafter electroless plating can be satisfactorily performed.

  The adhesive layer is formed using an adhesive composition containing an adhesive (resin) such as an acrylic adhesive, a polystyrene adhesive, a polyamide adhesive, a silicone adhesive, a urethane adhesive, or a rubber adhesive. It is preferable. These can be used alone or can be arbitrarily combined into a resin composition.

  The adhesive layer is preferably selected in consideration of the compatibility with the binder contained in the catalyst composition (catalyst composition) of the vacuum transfer film of the present invention and the adhesion to the substrate (non-conductive substrate). For example, it is more preferable to use an acrylic resin or the like.

  This adhesive composition is applied onto the substrate-release layer-catalyst layer 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. -It can be dried to form an adhesive layer.

  The thickness of the adhesive layer is preferably about 1 to 50 μm and more preferably about 10 to 30 μm because the catalyst layer can be satisfactorily formed (adhered) to the substrate (non-conductive substrate).

  The pressure-sensitive adhesive generally has a viscosity at room temperature even after solvent drying, and imparts fluidity to the adherend by applying pressure, and the cohesiveness against peeling becomes a holding force instead of curing. The pressure-sensitive adhesive is generally thermoplastic and is used in a room temperature process, and has a low glass transition point (Tg).

  It is preferable to use an adhesive (adhesive layer) for producing the electronic circuit.

(D) Support layer It is preferable that the support layer is further laminated | stacked on the (A) base material side which has mold release property of the vacuum transfer film of this invention.

  As the support layer, a plastic film, paper, or metal sheet can be used. As the plastic, it is preferable to use polyethylene terephthalate resin (PET), polybutylene terephthalate resin (PBT), polypropylene (PP) or the like having a high tensile elastic modulus.

(E) Substrate having a deep-drawn shape In the vacuum transfer film of the present invention, the transfer is preferably a vacuum transfer to a substrate having a deep-drawn shape.

(III) Vacuum transfer film production method The vacuum transfer film of the present invention comprises:
(1) forming a layer having releasability on a substrate, and (A) producing a substrate having releasability,
(2) applying a catalyst composition to the layer side having releasability of the substrate, and (B) providing a catalyst layer; and
(3) It can be produced by a production method including a step of providing (C1) an adhesive layer or (C2) an adhesive layer on the (B) catalyst layer.

  A catalyst layer can be formed on the vacuum transfer film by this production method. This vacuum transfer film is applied to the substrate (non-conductive substrate, molded product or molded product) by vacuum transfer technology, then the catalyst layer is exposed to the substrate by peeling, and then the molded product or molded product is electrolessly plated. An electroless plating film can be formed on the product. Thereby, an electroless plated product can be manufactured.

(1) Step of forming a layer having releasability on a substrate, and (A) Step of producing a substrate having releasability A layer having a releasability (release layer) on a substrate by an extrusion method described later ) Can be formed.

  In addition, it has release properties by applying and drying on a substrate by known means such as gravure coating method, roll coating method, comma coating method, gravure printing method, screen printing method, gravure reverse roll coating method, etc. It is also possible to form a layer (release layer).

(2) A step of applying a catalyst composition to the layer side of the substrate having releasability and (B) providing a catalyst layer
The method of apply | coating a catalyst composition to the peeling layer side of the base material which has a coating process mold release property is not limited.

  Examples of the coating method include a coating method using 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, and the like. 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 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 applying the catalyst composition to the curing treatment substrate, 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 a base material, 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 thickness of the catalyst composition after drying and curing (the thickness of the catalyst layer) depends on the solid content concentration of the catalyst composition. The film thickness is usually about 20 μm or less, 0.01 to 10 μm from the point that electroless plating can be efficiently performed, a plating film can be formed satisfactorily on the substrate, and sufficient plating adhesion is exhibited. The degree is preferably about 0.02 to 8 μm, more preferably about 0.03 to 5 μm, and particularly preferably about 0.05 μm (50 nm) to 2 μm. Even if the film thickness is less than 0.01 μm, the electroless plating reactivity can be obtained, but the plating adhesion tends not to be sufficiently exhibited. When the film thickness exceeds 10 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 substrate by performing a series of these treatments using this catalyst composition. 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.

(3) Step of providing (C1) adhesive layer or (C2) adhesive layer on the catalyst layer (B) The gravure coating method, roll coating method, comma coating method, gravure printing The adhesive layer or the pressure-sensitive adhesive layer is coated and dried on a substrate having a releasability (base material-peeling layer) -catalyst layer by known means such as a method, screen printing method, gravure reverse roll coating method, etc. Can be formed.

(4) Specific Example of Manufacturing Method of Vacuum Transfer Film FIG. 6 is an explanatory view showing the vacuum transfer film of the present invention.

  An example of the vacuum transfer film of the present invention will be described with reference to FIG.

In the transfer base film 11 with a support layer shown in FIG. 6 (1) , a base layer 21 made of a thermoplastic polyurethane resin and a support layer 31 having rigidity are laminated so as to be peelable.

  When using the substrate film for transfer 11 with a support layer to form a pattern on a molded body, the support layer 31 is peeled off and removed after printing to form the pattern on the surface of the substrate layer 21. The base material layer 21 (transfer base material film) on which a pattern is formed is used. Using the transfer substrate film on which this design is formed, after transferring the design to the surface of the molded product by vacuum pressure thermal transfer method, the design is transferred by peeling the transfer substrate film from the molded product The body is obtained.

  As the support layer 31, a sheet of plastic film, paper, metal or the like can also be used. As the plastic, polyethylene terephthalate resin, polybutylene terephthalate resin, polypropylene or the like having a large tensile elastic modulus can be used.

  The support layer preferably has an elongation percentage of 10% or less at 10 kgf / m. This value is the elongation when a sheet with a width of 1 m is pulled with a force of 10 kgf, and is determined by the tensile modulus of the material and the thickness of the sheet.

  When the elongation rate at 10 kgf / m exceeds 0.3%, the sheet cannot be printed at a predetermined position due to the large elongation of the sheet, and color misregistration occurs in the case of multiple colors. The elongation at 10kgf / m is preferably 0.3% or less in order to print a precise design and express an advanced design, and 0.2% or less in order to obtain a more precise design. preferable.

  Since the support layer 31 is peeled off after printing to form a pattern on the surface of the base material layer 21, the base material layer 21 and the support layer 31 must be detachably laminated. Therefore, the support layer 31 is preferably bonded to the base material layer 21 after being subjected to a surface treatment by a conventionally known method. For example, it can be made peelable by applying a silicone resin or a wax resin.

  The peel strength between the base material layer 21 and the support layer 31 is preferably about 2 to 30 gf / 25 mm width, and more preferably 3 to 25 gf / 25 mm width. When a force exceeding 30 gf / 25 mm width is required, there is a possibility that the pattern formed by the base material layer 21 being stretched excessively during the peeling. Further, when peeling with a force of less than 2 gf / 25 mm width, there is a possibility of peeling when not necessary in handling the transfer substrate film 11.

  After transferring the design to the surface of the molded body, the base material layer 21 is peeled off from the molded body. Therefore, before printing the design on the surface of the base material layer 21, a surface treatment is performed to facilitate peeling. Also good. In this case, it can be made peelable by applying a silicone resin or a wax resin to the surface of the base material layer 21.

  The peel strength between the molded body and the base material layer 21 is preferably about 5 to 100 gf / 50 mm width, and more preferably 8 to 50 gf / 50 mm width. When a force exceeding 100 gf / 50 mm width is required, there is a possibility that the base layer 21 is stretched too much at the time of peeling and the pattern formed is broken. In the case of peeling with a force of less than 5 gf / 50 mm width, there is a possibility that the pattern layer peels when it is unnecessary in handling the transfer base film 11.

  The substrate film for transfer 11 with a support layer on which the substrate layer 21 has been surface-treated can have a pattern printed thereon. When the design is printed, since the support layer 31 is provided with rigidity, the positioning can be easily performed and a precise design can be formed. Then, by removing the support layer 31 from the printed transfer base film 11 with a support layer, the transfer base film having a pattern can be obtained.

  The base film for transfer, which is mainly composed of the base material layer 21 made of thermoplastic polyurethane resin, has high stretchability, so the design is transferred to the surface of a molded product having a complicated three-dimensional shape by vacuum pressure thermal transfer. be able to. That is, it has flexibility to follow the details of a complicated molded body, and has excellent transfer performance. The molded body to which the design has been transferred becomes a decorated molded body by removing the base material layer 21.

The substrate film for transfer 12 with a support layer shown in FIG. 6 (2) has a substrate layer 21 made of a thermoplastic polyurethane resin and a support layer 31 having rigidity separated by a support release layer 32. They are stacked as possible. Here, the base material layer 21 and the support layer 31 are the same as the base material film for transfer 11 with a support layer, and thus description thereof is omitted.

  In the transfer base film 11 with the support layer, the surface of the support layer 31 is treated to give the release layer. However, the transfer base film 12 with the support layer has the support release layer 32 formed thereon. By providing, peeling performance can be imparted.

  As a general material for the support release layer 32, a polyolefin-based resin can be used, and appropriate release properties can be obtained by using polyethylene or polypropylene. As described above, the peel strength when peeling the support layer 31 from the base material layer 21 is preferably about 2 to 30 gf / 25 mm width, and more preferably 3 to 25 gf / 25 mm width.

  The substrate film for transfer 12 with a support layer can be printed with a pattern by subjecting the substrate layer 21 to surface treatment, like the substrate film for transfer with a support layer 11. When the design is printed, the support layer 31 provides rigidity, so that the positioning can be easily performed to form a precise design. Then, by removing the support layer 31 and the support release layer 32 from the printed transfer base film 12 with a support layer, the transfer base film having a pattern can be obtained.

  The base film for transfer, which is mainly composed of the base material layer 21 made of thermoplastic polyurethane resin, has high stretchability, so the design is transferred to the surface of a molded product having a complicated three-dimensional shape by vacuum pressure thermal transfer. be able to. That is, it has flexibility to follow the details of a complicated molded body, and has excellent transfer performance. The molded body to which the design has been transferred becomes a decorated molded body by removing the base material layer 21.

In the transfer base film 13 with a support layer shown in FIG. 6 (3) , the base layer 21 made of thermoplastic polyurethane resin and the support layer 31 having rigidity are peeled through the support release layer 32. The base material layer 21 is characterized in that the base material layer 21 is provided with a base material peeling layer 22 on the surface on which the design is printed. Since the support layer 31 and the support release layer 32 are the same as those of the transfer base film 12 with the support layer, description thereof is omitted.

  The base material peeling layer 22 is formed in order from the base material layer 21 side by a first layer 22a having adhesiveness with a thermoplastic polyurethane resin and a second layer 22b having peelability from the design layer. Is preferred. As the material for the first layer 22a, a polyethylene-vinyl acetate copolymer or a polyolefin-based elastomer can be considered, and as the material for the second layer 22b, a mixture of a polyolefin-based resin and a polyolefin-based elastomer can be considered.

  The first layer 22a is preferably a polypropylene elastomer, and the second layer 22b is preferably a mixture of polypropylene and a polypropylene elastomer. In the second layer 22b, the polypropylene used for mixing with the polypropylene elastomer is preferably a homopolymer rather than a copolymer. Furthermore, the mixing ratio of the polypropylene homopolymer and the polypropylene-based elastomer is preferably 80:20 to 0: 100 by weight. Each layer thickness of the first layer 22a and the second layer 22b is preferably 50 μm or less, and preferably 5 to 40 μm.

  With the configuration as described above, it is possible to form the substrate release layer 22 having excellent peelability, heat resistance, and storage stability. In addition, since the base material layer 21 includes the base material release layer 22, it is not necessary to apply the release layer at the time of use, and the work process is reduced when decorating the molded body by the vacuum pressure heat transfer method. can do. By making the surface of the substrate peeling layer 22 into a satin finish having fine irregularities, transferability can be improved.

  Since the substrate film 13 for transfer with a support layer has rigidity by having the support layer 31, it can be easily aligned to form a precise pattern when the pattern is printed. Then, by removing the support layer 31 and the support release layer 32 from the printed transfer base film 13 with a support layer, the transfer base film having a pattern can be obtained.

  The base film for transfer, which is mainly composed of the base material layer 21 made of thermoplastic polyurethane resin, has high stretchability, so the design is transferred to the surface of a molded product having a complicated three-dimensional shape by vacuum pressure thermal transfer. be able to. That is, it has flexibility to follow the details of a complicated molded body, and has excellent transfer performance. The molded body to which the design has been transferred becomes a decorated molded body by removing the base material layer 21 and the base material peeling layer 22.

A transfer base film 14 with a support layer shown in FIG. 6 (4) is a support having a rigidity with a base layer 21 made of a thermoplastic polyurethane resin, like the transfer base film 13 with a support layer. The layer 31 is laminated so as to be peelable through the support peeling layer 32, and the base material layer 21 includes the base material peeling layer 22 on the surface on which the design is printed. Further, the support layer 31 includes a blocking prevention layer 33 on the surface opposite to the support release layer 32. Since the support layer 31, the support release layer 32, and the substrate release layer 22 are the same as the transfer base film 13 with the support layer, description thereof is omitted.

  As a material for the anti-blocking layer 33, a polyolefin-based resin can be used, and polyethylene or polypropylene can be used. Thereby, when the substrate film for transfer 14 with a support layer is formed into a roll, the design layer 40 and the anti-blocking layer 33 do not cause blocking, and handling properties can be improved. In addition, by using the same material as the support peeling layer 32, it is possible to prevent warpage. The surface of the anti-blocking layer 33 is preferably a satin-like shape having fine irregularities.

  Since the substrate film for transfer 14 with the support layer includes the substrate release layer 22, printing can be performed directly on the surface of the substrate release layer 22. In addition, since the support layer 31 is provided with rigidity, when the design is printed, the positioning can be easily performed to form a precise design. Furthermore, by providing the anti-blocking layer 33, the substrate film for transfer 14 with a support layer provided with a pattern can be stored as it is for a long period of time in the state of a roll.

  By removing the antiblocking layer 33, the support layer 31, and the support release layer 32 from the transfer base film 14 with the support layer on which the design is printed, the transfer base film having the design is obtained. be able to. The base film for transfer, which is mainly composed of the base material layer 21 made of thermoplastic polyurethane resin, has high stretchability, so the design is transferred to the surface of a molded product having a complicated three-dimensional shape by vacuum pressure thermal transfer. be able to. That is, it has flexibility to follow the details of a complicated molded body, and has excellent transfer performance. The molded body to which the design has been transferred becomes a decorated molded body by removing the base material layer 21 and the base material peeling layer 22.

  The film forming method for producing the transfer film with a support layer of the present invention will be described.

  In the film forming method of the present invention, a base material layer 21 made of a thermoplastic polyurethane resin and a support layer 31 are laminated so that they can be peeled, and a base film for transfer with a support layer 11, 12, 13, 14 The support film 30 including at least the support layer 31 is prepared in advance in a roll shape, and the transfer base film 20 including at least the base layer 21 is extruded using a T die. In this case, a means is used in which the transfer base film 20 and the support film 30 immediately after being extruded are bonded together.

  FIG. 7 is a schematic view showing a film forming method for forming the vacuum transfer film of the present invention.

A method for forming the transfer base film 14 with the support layer will be specifically described with reference to FIG.

  The support film 30 including the support layer 31, the support release layer 32, and the anti-blocking layer 33 is previously formed into a roll shape and attached to the delivery roll 71. Polyethylene terephthalate resin can be used for the support layer 31. Polypropylene can be used for the support release layer 32 and the anti-blocking layer 33. These films can be formed by dry lamination to form the support film 30.

  The transfer base film 20 composed of the base layer 21 and the base release layer 22 (first layer 22a, second layer 22b) is formed by coextrusion using a T die 72. For the base material layer 21, thermoplastic polyurethane is used. A polypropylene elastomer can be used for the first layer 22a. For the second layer 22b, a mixture of homopolypropylene and polypropylene-based elastomer can be used. Then, the respective materials are supplied to the T die 72 with the temperature and pressure adjusted, and the respective layers are coextruded, whereby the transfer base film 20 in which these layers are laminated can be obtained.

  The molten transfer substrate film 20 immediately after extrusion is sent to the nip roll 73 together with the prepared support film 30 and bonded to the take-up roll 74 as the transfer substrate film 14 with the support layer. It is wound up into a roll product.

  The substrate film for transfer with support layer 11, 12, 13 can also be formed by the same method. For example, the support film 30 may be formed by extruding and laminating the support layer 31 with paper and the support release layer 32 with polyethylene. A transfer base film 20 with a support layer can be formed by laminating a transfer base film 20 composed of a single layer of a thermoplastic urethane base layer 21 extruded from a T die.

  The decoration method which transfers a design to the surface of a molded object using the base material film for transfer with a support body layer of this invention is demonstrated. In the decorating method of the present invention, a transfer base film 20 including at least a base layer 21 made of a thermoplastic polyurethane resin and a support film 30 including at least a support layer 31 are detachably laminated. A decoration method for transferring a pattern onto the surface of a molded body 80 using a transfer base film 11, 12, 13, 14 with a support layer, which is a printing process, a support layer peeling process, a vacuum pressure thermal transfer process The step and the base material layer peeling step are sequentially performed.

  FIG. 8 is an explanatory view showing a decoration method for transferring a design onto the surface of a molded body using the vacuum transfer film of the present invention.

  A decorating method for transferring a design to the surface of the molded body 80 using the transfer base film 14 with a support layer will be described in detail with reference to FIG.

FIG. 8 (1) shows a transfer base film 14 with a support layer obtained by the film forming method of the present invention. The substrate film for transfer 14 with a support layer is composed of a substrate film 20 for transfer consisting of a substrate layer 21 and a substrate release layer 22, and a support consisting of a support layer 31, a support release layer 32 and an antiblocking layer 33. It is composed of body film 30. Since the substrate film for transfer 14 with a support layer includes the substrate release layer 22, the design layer 40 can be formed by immediately printing a design on the surface of the substrate release layer 22.

FIG. 8 (2) shows the transfer base film 14 with the support layer on which the design layer 40 is formed, that is, the design. The pattern layer 40 to be formed can be formed by a method such as gravure printing or silk screen printing. As the ink for forming the design, a colorant composed of a pigment or a dye is mixed with a binder or the like. The pattern layer 40 needs to have adhesiveness with the molded body 80. However, the pattern layer 40 having adhesiveness can be obtained by mixing a hot-melt adhesive into the ink or printing. It can also be a pattern layer 40 composed of a layer and an adhesive layer.

  Since the substrate film for transfer 14 with a support layer is provided with the support layer 31, it is easy to align when printing the design, and a precise design can be formed. The substrate film for transfer 14 with a support layer on which the design layer 40 has been formed is peeled off from the support film 30 in the next support layer peeling step. If necessary, the transfer base film 14 with the support layer on which the design layer 40 is formed can be temporarily stored in a roll shape.

As shown in FIG. 8 (3) , the support film 30 is peeled off to become a transfer base film 20 on which a design layer 40 is formed, and this is used to decorate the surface of the molded body 80. Can do. The transfer base film 20 including the design layer 40 can decorate the surface of the molded body 80 by a vacuum pressure heat transfer method.

FIG. 8 (4) shows a state in which the transfer base film 20 provided with the pattern layer 40 is in close contact with the surface of the molded body 80 in the vacuum pressure thermal transfer step. The substrate film 20 for transfer, which has a base material layer 21 made of thermoplastic polyurethane resin as its main material, is highly stretchable, so the design can be transferred to the surface of a molded product with a complex three-dimensional shape by vacuum pressure thermal transfer. can do. That is, it has the flexibility to follow the details of a complex molded body, and has excellent transfer performance.

FIG. 8 (5) shows a state in which the transfer base film 20 is peeled from the surface of the molded body 80 in the base material layer peeling step. Only the design layer 40 is left on the surface of the molded body 80, and the molded body 80 is decorated with the design layer 40.

  In addition, when performing decoration using the substrate film for transfer 11 with a support layer, a step of performing a surface treatment for facilitating peeling is added before the above printing step. All other steps are performed in the same manner. This surface treatment can be performed by coating a surface of the base material layer 21 with a silicone resin or a wax resin.

(IV) Method for producing electroless plated product Using the vacuum transfer film of the present invention,
(1) A process of attaching the (C1) adhesive layer or (C2) adhesive layer of the transfer film to a substrate,
(2) For the pasted material obtained in the above step, leave the (B) catalyst layer and (C1) adhesive layer or (C2) adhesive layer of the transfer film on the substrate, and (A) separate from the substrate. A step of peeling the base material having moldability, and (3) a step of performing electroless plating on the catalyst layer exposed by the step (B),
An electroless plated product can be manufactured by a manufacturing method in which the step (1) is performed by vacuum transfer.

  The substrate is preferably a substrate having a deep-drawn shape.

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

  The electroless plating can be formed on the substrate by attaching the transfer film of the present invention to the substrate and then performing an electroless plating treatment.

  An electroless plated product can be produced by performing electroless plating on the catalyst layer exposed to the 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, grain, stone, cloth, sand, geometric pattern, characters, stripes, gradation pattern, etc. can be given to the substrate.

(1) The process of attaching the (C1) adhesive layer or (C2) adhesive layer of the transfer film to the substrate The vacuum transfer technology is used to apply the adhesive layer or adhesive layer of the vacuum transfer film to the substrate.

Base (non-conductive substrate)
An object to be subjected to electroless plating. The substrate used in the present invention is not particularly limited.

  As the substrate, it is preferable to use plastic (resin), glass, ceramics or the like.

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

  As the plastic, it is preferable to use an acrylonitrile-butadiene-styrene copolymer resin (ABS resin) or the like.

  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.

  Use of a thermoplastic resin or thermosetting resin (including a two-component curable resin) that can be molded (molded) as an injection resin used in manufacturing by injection molding (molding) such as in-mold molding (molding). Is preferred.

  When thermoplastic resin is used as injection resin, polystyrene (PS), polyolefin, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), acrylonitrile-styrene copolymer (copolymerization compound) (AS resin), polyphenylene oxide, polycarbonate It is preferable to use a resin such as (PC), polyacetal (POM), acrylic resin, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polysulfone, or polyphenylene sulfide.

  When a thermosetting resin is used as the injection resin, it is preferable to use a two-component curable urethane resin, an epoxy resin, or the like.

  As the injection resin, the resin may be used alone, or two or more kinds may be mixed and used.

  The shape of the 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 substrate (non-conductive substrate), a solvent, a binder and the like contained in the catalyst composition (catalyst layer of the transfer film) can be appropriately selected.

Vacuum Transfer Technology The vacuum transfer technology of the present invention will be described. Using a vacuum transfer technology, the catalyst layer of the vacuum transfer film can be attached to a non-conductive substrate (molded product). Next, using the electroless plating technique, the exposed catalyst layer can be subjected to electroless plating to decorate the non-conductive substrate (molded product). In the production of a printed wiring board for an electronic device, a metal wiring circuit can be formed by performing electroless plating using the vacuum transfer film of the present invention.

  Using the vacuum transfer film of the present invention, the wiring layer (non-conductive substrate) is patterned (exposed) with a catalyst layer (catalyst composition), that is, a film for applying electroless plating. 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.

  In the vacuum transfer technique, an electroless plating film (catalyst layer) can be formed from the plane of a non-conductive base material (molded product) such as plastic to the surface of a cubic surface such as a cylindrical object. And design, such as a pattern, a metallic tone, a pearl, and a matte tone can be provided (decorated) with an electroless-plating technique with respect to the nonelectroconductive board | substrate with which the film for electroless plating was formed.

  The vacuum transfer technology is a decorative method with little environmental impact caused by organic solvents. Thanks to the vacuum transfer technology, it is easy to paint multi-color and photo-separated patterns that are difficult to print directly on molded products. Since no solvent or the like is used during transfer processing, the working environment can be improved. Equipment can be simplified and productivity can be improved. Flexible response to various materials is possible.

  The vacuum transfer technology can be applied to household goods, stationery, cosmetics, home appliances, metal wiring circuits, and the like.

  In the vacuum transfer technology of the present invention, the step of adhering the catalyst layer side of the vacuum transfer film to a transfer substrate (substrate, non-conductive substrate, molded article, etc.), and fixing the catalyst layer to the transfer substrate; and The catalyst layer is provided on the substrate (non-conductive substrate) by a vacuum transfer technique (extending transfer technique) by washing the transfer substrate to which the catalyst layer is fixed and exposing the catalyst layer.

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

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

  Using the vacuum transfer film of the present invention, a smooth electroless plating film can be formed on a non-conductive substrate by a vacuum transfer technique.

  When a support layer (polyethylene terephthalate resin (PET), etc.) is laminated on the vacuum transfer film of the present invention, the base material (thermoplastic polyurethane resin (TPU), etc.) and the rigid support layer are detachably laminated. Has been.

  When using the vacuum transfer film of the present invention to form a pattern or circuit on a molded body, first, a printing that forms a layer (this is a catalyst layer) on which the pattern or circuit is based on the surface of the substrate. Then, the support layer is peeled off and removed from the vacuum transfer film, and then a vacuum transfer film on which a pattern or circuit is formed is prepared. Using the vacuum transfer film on which the design or circuit is formed, the design or circuit is transferred to the surface of the molded body by a vacuum pressure thermal transfer method. Next, the vacuum transfer film is peeled off from the molded body, and a molded body on which a pattern or circuit that is the basis of electroless plating is transferred can be obtained.

  After printing to form a pattern or circuit (catalyst layer) on the surface of the base material of the vacuum transfer film of the present invention, the support layer (PET layer, etc.) is peeled off, so the base material and the support layer are peelable Is done. The support layer is preferably bonded to the base material after surface treatment by a conventionally known method. By applying a silicone resin or a wax resin to the support layer, the support layer can be peeled off.

  After transferring the base layer (catalyst layer) of the design or circuit to the surface of the molded body, the base material (TPU layer, etc.) is peeled off from the molded body, so it becomes the base of the design or circuit on the surface of the base material. Before printing the layer (catalyst layer), a surface treatment for facilitating peeling may be performed. For example, by applying a silicone resin or a wax resin to the surface of the substrate, the substrate can be made peelable.

  In the vacuum transfer film of the present invention, a layer (catalyst layer) serving as a base of a pattern or circuit is printed on a base material (TPU or the like). When printing a layer (catalyst layer) that is the basis of a pattern or circuit on a vacuum transfer film, the film has rigidity by having a support layer (PET layer), so it is easy to align and precision A simple design can be formed. And a vacuum transfer film provided with the layer (catalyst layer) used as the base of a design or a circuit can be prepared by peeling and removing a support layer from the printed vacuum transfer film.

  In the vacuum transfer film of the present invention, the base material is a thermoplastic polyurethane resin (TPU) as a main material, and TPU is highly stretchable. Therefore, the molded body has a complicated three-dimensional shape by the vacuum pressure thermal transfer method. The design can be transferred to the surface of That is, it has flexibility to follow the details of a complicated molded body, and has excellent transfer performance.

  The vacuum transfer technique of the present invention is a method of transferring a layer (catalyst layer) serving as a base of a pattern or a circuit to the surface of a molded body, and includes a vacuum pressure thermal transfer step. By using the vacuum transfer film of the present invention, a layer (catalyst layer) serving as a base of a design or a circuit can be transferred to the surface of the molded body by a vacuum pressure thermal transfer method.

  In the vacuum pressure heat transfer step, the vacuum transfer film of the present invention is in close contact with the surface of the molded body. The vacuum transfer film of the present invention has a complicated three-dimensional shape by the vacuum pressure thermal transfer method because the base material is mainly a thermoplastic polyurethane resin (TPU), and TPU is highly stretchable. A layer (catalyst layer) serving as a base of a pattern or a circuit can be transferred to the surface of the molded body. That is, it has the flexibility to follow the details of a complex molded body and has excellent transfer performance.

  The vacuum-pressurized thermal transfer method uses a negative pressure and has a high degree of transfer accuracy for a molded body having a complicated three-dimensional shape.

  The vacuum-pressurized thermal transfer method is a method in which a film is brought into close contact with the surface of a molded body by applying a negative pressure on one side of the film in a treatment tank, and thermal transfer is performed in this state. As a transfer film material used in the vacuum pressure thermal transfer method, it is preferable to use a thermoplastic polyurethane resin (TPU) having a large elasticity so that it can follow the complex shape of the molded body. .

  The vacuum transfer process is performed in a box-shaped processing tank. The inside of the treatment tank can be hermetically sealed by bringing the tank lid into close contact with the upper part of the tank body. The tank body is provided with a set base for placing a molded body (transfer object).

  The inside of the tank body can be brought into a negative pressure state by a vacuum pump. By setting the negative pressure, the transfer film can be brought into close contact with the surface of the substrate (molded body). An infrared heater that heats the transfer film is provided inside the tank lid, and the pattern formed on the transfer film can be transferred to the surface of the molded body by heating.

  FIG. 9 is a schematic cross-sectional view of a transfer device that performs vacuum-pressure thermal transfer.

An apparatus for performing a transfer process will be described with reference to FIG. The transfer process is performed in a box-shaped processing tank 50. The processing tank 50 can seal the inside by bringing the tank lid 52 into close contact with the upper part of the tank body 51. The tank lid body 52 is moved up and down by the driving device 62 to open and close the processing tank 50. The tank body 51 is provided with a set base 55 on which a molded body (transfer object) 80 is placed. The set base 55 can be moved up and down by a driving device 61.

  The inside of the tank body 51 can be brought into a negative pressure state by the vacuum pump 63. By setting the negative pressure, the transfer film 90 can be pressed against the surface of the molded body 80 to be in close contact therewith. An infrared heater 64 for heating the transfer film 90 is provided inside the tank lid body 52, and the pattern formed on the transfer film 90 can be transferred to the surface of the molded body 80 by heating. .

  A base material using a thermoplastic polyurethane resin (TPU) is suitable for a vacuum pressure thermal transfer method because of its large stretchability. After the processing tank is hermetically sealed and the tank main body side and the tank lid body side are brought into a negative pressure state by a vacuum pump, the tank lid side is again returned to atmospheric pressure or is in a pressurized state, whereby the transfer film is ground ( It can be adhered to the surface of the molded body).

  The base material using thermoplastic polyurethane resin (TPU) is very stretchable, so the transfer film is wrapped from the upper side to the lower side of the substrate (molded body) to completely cover the surface. It is possible to cover up. When forming a layer (catalyst layer) that is the basis of a pattern or circuit on the surface of a substrate (molded body) having such a complicated three-dimensional shape, a vacuum transfer film equipped with a TPU substrate is an excellent transfer Can demonstrate its sexuality.

  By the vacuum transfer technique, an electroless plating film (catalyst layer) can be formed on the surface of a molded product (non-conductive substrate such as plastic) having a cubic surface. And, by applying electroless plating technology, various highly designable designs are applied to the non-conductive substrate (molded product) on which the electroless plating film is formed with high positional accuracy. (Decorate). The vacuum transfer technology is excellent in the positional accuracy of the pattern with respect to the molded product.

  The vacuum transfer technology can be applied to, for example, communication equipment, light electrical equipment, automobile parts, household goods, leisure goods, metal wiring circuits, and the like.

(2) For the pasted material obtained in step (1), leave (B) the catalyst layer and (C1) adhesive layer or (C2) adhesive layer of the transfer film on the substrate. Step of peeling the substrate having releasability By peeling the substrate (base material sheet, peeled portion) having the releasability of the transfer film, a molded product with the exposed catalyst layer can be obtained.

(3) Step of performing electroless plating on (B) catalyst layer exposed in step (2)
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. A transfer film may be used for the entire surface plating.

  For decoration purposes, use general processes such as electrolytic copper (Cu) plating, semi-bright nickel (Ni) plating, bright nickel (Ni) plating, 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.

(V) Electroless plating film and molded product on which the film is mounted. When the transfer film of the present invention is used, it is possible to perform good plating particularly on a substrate having a large curved surface, and both surfaces of the substrate having a large curved surface. It is also possible to perform good plating for the above.

  The catalyst layer of the transfer film of the present invention is applied to a substrate (non-conductive substrate, plastic (resin) or the like) to form a catalyst layer (catalyst film), and 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 is excellent in adhesion of the plating film. A smooth plating film (electroless plating film or electrolytic plating film) can be formed on the non-conductive substrate. The molded product can be used for, for example, a housing of an electric appliance such as a mobile phone, a personal computer, and a refrigerator; an automobile part such as an emblem, a switch base, a radiator grill, a door handle, and a wheel cover.

  Using the transfer film of the present invention, in electroless plating that performs pattern plating on the substrate, the electroless plating has high reactivity, and exhibits 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.

Electroless plating reactivity and adhesion improvement mechanism Metal particles (Pd particles) with electrocatalytic catalytic action of the catalyst composition (catalyst layer) formed on the base (non-conductive substrate) and electroless Contact with 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 has high electroless plating reactivity, especially when it is used for substrates such as ABS (non-conductive substrates, plastics, etc.), and can achieve good adhesion that can withstand multilayer plating up to plating. . 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, and 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 vacuum transfer technology (elongation transfer technology) of the present invention enables plating (decoration) on non-conductive substrates on three-dimensional curved surfaces, perforated molded products, and gentle uneven surfaces that were previously impossible. It is. Combining with a functional material such as a hard coat can increase the added value of the product.

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

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

  When the vacuum transfer film (extending transfer film) of the present invention is used, there is no need to increase the concentration of the reducing agent in the electroless plating for the purpose of improving the electroless plating reactivity, and the reaction temperature of the electroless plating is increased. There is no need. 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. Using the vacuum transfer film of the present invention, the wiring layer (non-conductive substrate) is patterned (exposed) with a catalyst layer (catalyst composition), that is, a film for applying electroless plating. 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)
Pd complex-containing liquid (Pd content 12.75 wt%, manufactured by Iox Corporation): 1.96 g,
PVC-vinyl acetate resin (solid content 10wt%, manufactured by DIC Graphics): 9.0g, and
NMP / terpineol / cyclohexanone mixed solvent (solvent)
The mixture was mixed so that the Pd concentration was 4,500 ppm (0.45 wt%) to prepare a catalyst composition for a metal plating transfer film for inkjet.

(2) Formation of stretchable transfer film for electroless plating A vacuum transfer film with a support layer was produced.

Vacuum transfer film production substrate: Thermoplastic polyurethane (TPU), thickness 50μm
Support layer: Polyethylene terephthalate (PET), thickness 38μm
A release layer (release layer) was formed on the substrate by an extrusion method.

  A film for vacuum transfer (PET / PU bonding) was prepared.

Using a printing inkjet printer (Aminto Co., Ltd.), pattern-printing the catalyst composition for metal plating transfer film obtained in (1) above on the TPU of an extended transfer film (thermoplastic polyurethane resin) for vacuum transfer did.

  Next, an adhesive was applied using a bar coater according to the transfer substrate.

  Next, the film on which the pattern was printed and the adhesive was applied was dried in a drying oven at 70 ° C. for 5 minutes.

  Next, the PET film of the support layer was peeled off from the vacuum transfer film.

(3) Vacuum transfer (extending transfer)
The vacuum transfer film was vacuum transferred to the substrate using a vacuum pressure transfer machine.

  Using the vacuum transfer device, the back side of the vacuum transfer film was decompressed to vacuum. The vacuum transfer film in which the pressure on the back side decreased was pressed by the pressure on the surface side, which is atmospheric pressure, and was brought into close contact with the surface of the substrate (transfer object).

  Next, the PU film on the surface was peeled off from the vacuum transfer film after the vacuum transfer.

Pattern Transfer (Example 1) The transfer film obtained in (2) (elongated for metal plating printed with a pattern by an ink jet method) was transferred to a molded product (ABS resin molded product).

  (Example 2) In the same manner as in Example 1, it was transferred to PC (polycarbonate).

Circuit formation (Example 3) The circuit was transferred to the inner surface of the PC (polycarbonate) of the back transfer substrate.

(4) Electroless plating Electroless plating was performed on the exposed catalyst layer on the substrate after vacuum transfer processing.

Electroless Cu plating bath and electroless Ni plating bath conditions The electroless copper (Cu) plating bath used was HFS manufactured by Okuno Kogyo Co., Ltd. The initial Cu concentration was 2.5 g / L, the bath volume was 1,000 mL, and the bath temperature was 40 ° C.

  BEL-18 manufactured by Uemura Kogyo Co., Ltd. was used as the electroless nickel (Ni) plating bath. The initial Ni concentration was 6 g / L, the bath volume was 1,000 mL, and the bath temperature was 60 ° C.

  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 In Example 3 above, the circuit was transferred to the PC inner surface of the back transfer substrate. Using an MS8233D tester manufactured by Crenova, the surface resistance of the electroless plating transfer circuit obtained by stretching transfer was measured as the electric resistance between the electrodes of the plating pattern or the plating film surface 10 mm.

  In either case, the electrical resistance value was 0.0Ω. Moreover, the phase (large ratio of the surface) that was transferred to the inside of the PC substrate phase and plated was 0Ω.

11, 12, 13, 14 Transfer base film with support layer
20 Transfer base film (21 + 22 (22a + 22b))
21 Base material layer
22a 1st layer (base material release layer)
22b 2nd layer (base material release layer)
22 Base material release layer
30 Support film (31 + 32 + 33)
31 Support layer
32 Support release layer
33 Anti-blocking layer

Claims (9)

(A) A transfer film for electroless plating in which at least (B) a catalyst layer and (C1) an adhesive layer or (C2) an adhesive layer are sequentially laminated on a substrate having releasability,
The (B) catalyst layer is composed of a catalyst composition containing (1) a composite of metal particles and a dispersant, (2) a solvent, and (3) a binder, and the metal particles include palladium particles and gold particles. , Silver particles or platinum particles,
(A) The substrate having releasability is a substrate made of a film composed of polyurethane,
A transfer film for electroless plating, wherein the transfer is a vacuum transfer to a substrate having a deep-drawn shape and is used for forming a metal wiring circuit.   (1) The composite dispersant of the catalyst composition is 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 transfer film for electroless plating according to claim 1, wherein the transfer film is at least one dispersant selected from the group consisting of:   (2) solvent of the catalyst composition is water; aprotic polar solvent selected from the group consisting of water; N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide; dimethyl sulfoxide and γ-butyrolactone; Alcohol 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 monomethyl ether and ethylene Glycol ethers selected from the group consisting of glycol monobutyl ether; aromatic carboxylic acid esters selected from the group consisting of methyl benzoate, ethyl benzoate and methyl salicylate; toluene and Aromatic hydrocarbons selected from the group consisting of xylene; aliphatic hydrocarbons selected from the group consisting of n-hexane, n-heptane and mineral spirits; methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, methylcarb A glycol ether ester selected from the group consisting of tall acetate and butyl carbitol acetate; an alkanol ester selected from the group consisting of ethyl acetate and butyl acetate; and at least one solvent selected from the group consisting of 2-phenoxyethanol. The transfer film for electroless plating according to claim 1 or 2.   (3) Binder of the catalyst composition is acetal resin, epoxy resin, ester resin, acrylic resin, urethane resin, amide resin, imide resin, amideimide resin, shellac resin, melamine resin, urea resin, polyvinyl chloride-vinyl acetate copolymer The transfer film for electroless plating according to any one of claims 1 to 3, which is at least one binder selected from the group consisting of a coalescence and an olefin resin.   (A) The substrate having releasability is a melamine resin release agent, silicone release agent, fluororesin release agent, cellulose resin release agent, urea resin release agent, polyolefin resin release agent, paraffin type The transfer film for electroless plating according to any one of claims 1 to 4, which is a base material comprising a release layer comprising at least one release agent selected from the group consisting of a release agent and an acrylic resin-based release agent. The adhesive layer (C1) is an acrylic adhesive, polystyrene adhesive, polyamide adhesive, urea adhesive, melamine adhesive, phenol adhesive, vinyl acetate adhesive, rubber adhesive, epoxy An adhesive layer made of at least one adhesive selected from the group consisting of an adhesive, a polyurethane adhesive, a vinyl acetate resin emulsion, an EVA resin emulsion, and an acrylic resin emulsion, or the (C2) adhesive layer Is an adhesive layer composed of at least one adhesive selected from the group consisting of acrylic adhesives, polystyrene adhesives, polyamide adhesives, silicone adhesives, urethane adhesives and rubber adhesives, The transfer film for electroless plating according to claim 1.   The transfer for electroless plating according to any one of claims 1 to 6, wherein (D) a support layer is further laminated on the side of the substrate having releasability (A) of the transfer film for electroless plating. the film. A method of producing a transfer film for electroless plating according to any one of claims 1 to 7
(1) forming a layer having releasability on a substrate, and (A) producing a substrate having releasability,
(2) applying a catalyst composition to the layer side having releasability of the substrate, and (B) providing a catalyst layer; and
(3) including a step of providing (C1) an adhesive layer or (C2) an adhesive layer on the (B) catalyst layer,
(A) The substrate having releasability is a substrate made of a film composed of polyurethane,
The said film is a film used for the vacuum transfer with respect to the base material of the shape drawn deeply , The manufacturing method of the transfer film for electroless plating which is a film used for formation of a metal wiring circuit. A method for producing an electroless plating material using a transfer film for electroless plating according to any one of claims 1 to 7
(1) A process of attaching the (C1) adhesive layer or (C2) adhesive layer of the transfer film to a substrate,
(2) For the pasted material obtained in the above step, leave the (B) catalyst layer and (C1) adhesive layer or (C2) adhesive layer of the transfer film on the substrate, and (A) separate from the substrate. A step of peeling the base material having moldability, and (3) a step of performing electroless plating on the catalyst layer exposed by the step (B),
(A) The substrate having releasability is a substrate made of a film composed of polyurethane,
The step (1) is performed by vacuum transfer on a deep-drawn shaped substrate ,
A method for producing an electroless plated product, wherein a metal wiring circuit is formed on the substrate by performing electroless plating in the step (3).