JP2019116672A - Method for manufacturing electroless plating article - Google Patents

Abstract

To provide a method for manufacturing an electroless plating article.SOLUTION: A coating composition layer having mixed nanoparticles and an anchor layer formed between the coating layer and a plating film are physically stuck without spoiling the original characteristics of a base material. A coating material composition part does not include Pd, and Pd is unevenly distributed only in the surface layer of the coating layer contacting a plating solution and the anchor layer formed by alkali treatment.EFFECT: An electroless plating film can be excellently formed on a poor plating resin without using a medical having a high environmental load.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a method of forming an electroless plating film on a poorly plating resin which does not use a chemical with high environmental load, a film and a molded article.

  As a method of forming a partial decorative plating on a resin molded product such as polypropylene (PP) or acrylonitrile-butadiene-styrene copolymer synthetic resin (ABS resin), the currently generally used method is as follows: It is.

  There is a method of expressing partial plating by selectively plating only ABS with a two-color molded article of ABS and polycarbonate (PC). This process is approximately twice as expensive as the method using a single color mold as the mold. In addition, if there is contamination by forming gas at the parting off of ABS and PC, a defect such as a burr will occur at the parting after plating. As a result, the maintenance cycle of the molding die tends to be short.

  In addition, the ABS and PC may melt at the time of molding, so that the interface between the ABS and PC may not be clear, and the plating interface may not be clearly cut off.

  In addition, the entire surface is plated, then the coated portion is masked, the non-plated portion is coated and the like, and then the masking is peeled off to partially plate the plated portion and the coated portion (non-plated portion) in combination. There is a way to express it. This process requires a process such as masking, and the number of steps is increased, resulting in higher manufacturing costs. Moreover, the coating on the plating is required, and there is a problem in the adhesion between the plating and the coating.

  In addition, there is a method of expressing partial plating by performing masking on a non-plated portion after molding by a method such as coating, and then plating on the unmasked portion and then peeling off the masking. This process also requires a process such as masking, and the number of man-hours increases, resulting in higher manufacturing costs. Moreover, the coating on the plating is required, and there is a problem in the adhesion between the plating and the coating.

  Further, in the masking plating method, there is also a problem that moisture easily penetrates from the interface between the plating surface and the surface to be plated, and it is in a state in which liquid agent peeling such as solvent, artificial sweat, perfume and oil is likely to occur.

  In the plating of a resin molded product, excellent adhesion is required between the resin molded product and the plating. Therefore, by performing (roughening) etching for forming fine unevenness on the surface of the resin molded product, it is possible to impart an anchor effect (an anchor effect). However, this etching is complicated in the process, and it is necessary to use a chemical with high environmental load such as chromic acid.

  In the prior art, since physical adhesion is achieved by etching, there are disadvantages such as limitation of the base material that can be etched, frequent use of chromic acid in the etching process, and long process (FIG. 1) .

  Therefore, there is a need for a partial plating method to a three-dimensional shape having high adhesion and durability without using a chromic acid etching and having a clear parting off.

  The prior art is as follows.

  Patent Document 1 (FIG. 1) proposes a method of electroless plating using polyimide-silica composite fine particles. An alkoxy group-containing silane-modified polyamic acid composition is used for the composite fine particles. However, in patent document 1, since a silica particle is contained in the polyimide film used as a base material, the original characteristic of a base material is impaired. Moreover, a base material is limited to a polyimide resin.

  In patent document 2 (FIG. 1), the method of forming a plating film by a chemical bond is proposed by forming the coating film layer containing polypyrrole on a base material. However, in patent document 2, since it is only the adhesiveness by a chemical bond, there is no anchor effect and it does not adhere physically. Also, the process is long.

  Patent Document 3 is a method of electrically forming a plating film by forming an anionic adsorption layer on a substrate.

  Patent Document 4 proposes a method of applying a coating composition comprising a complex of palladium particles and a dispersant, a solvent, a binder, and nanoparticles to a substrate to form a strong plating film.

JP 2005-325147 A JP, 2010-95776, A Patent No. 5819020 Patent No. 6072330

  An object of the present invention is to provide a technique for forming an electroless plating film favorably for a difficult-plating resin without using a chemical with a high environmental load.

  The present invention is a technology for favorably forming an electroless plating film on a hard-to-plate resin without using a chemical with high environmental load.

Claim 1:
A method of producing an electroless plated article,
(1) The substrate contains (A) a solvent, (A) a binder, and (C) surface-treated nanoparticles, and the amount of the (B) surface-treated nanoparticles is the (B) binder. Applying the electroless plating pretreatment ink composition in the range of 0.01 to 100 parts by weight with respect to 1 part by weight;
(2) (a) volatilizing and / or drying a solvent contained in the ink composition applied in step (1), and (b) curing the binder,
(3) a step of alkali-treating the substrate obtained by curing the ink composition in the step (2) and degreasing the substrate;
(4) applying palladium (Pd) ions to the substrate degreased in step (3);
(5) a step of reducing the Pd ion applied to the substrate in the step (4),
(6) optionally washing the substrate to which Pd is added in step (5) with an acid,
(7) A method including the step of performing electroless plating on the base material reduced in step (5) or the base material washed in step (6).

Claim 2:
A method for producing an electrolessly plated material using a film for electroless plating used in insert molding,
The film includes (A) an insert layer, and the (A) insert layer contains (A) a solvent, (A) a binder, and (C) surface-treated nanoparticles, and the (C) surface. An electroless plating pretreatment ink composition is applied in which the additive amount of the treated nanoparticles is in the range of 0.01 to 100 parts by weight with respect to 1 part by weight of the (i) binder.
(1) a step of attaching the (A) insert layer of the film to a substrate and insert molding the attached material, and (2) a layer of the ink composition exposed by the insert molding of the step (1) Treatment with alkali and degreasing
(3) applying palladium (Pd) ions to the substrate degreased in step (2);
(4) a step of reducing the Pd ion applied to the substrate in the step (3),
(5) optionally washing the substrate to which Pd is added in step (4) with an acid,
(6) A method including the step of performing electroless plating on the base material reduced in step (4) or the base material washed in step (5).

Claim 3:
A method for producing an electrolessly plated material using a film for electroless plating used in insert molding,
The film includes (A) an insert layer,
(1) The (A) insert layer contains (A) a solvent, (B) a binder, and (C) surface-treated nanoparticles, and the amount of the (C) surface-treated nanoparticles is the above B) applying the electroless plating pretreatment ink composition in the range of 0.01 to 100 parts by weight with respect to 1 part by weight of the binder,
(2) (a) volatilizing and / or drying a solvent contained in the ink composition applied in step (1), and (b) curing the binder,
(3) A step of attaching the (A) insert layer of the film obtained by curing the ink composition in the step (2) to a substrate, and insert molding the attached material, and (4) insert molding of the step (3) Alkaline treatment and degreasing of the layer of the ink composition exposed by (B);
(5) applying palladium (Pd) ions to the substrate degreased in step (4);
(6) a step of reducing the Pd ion applied to the substrate in the step (5),
(7) optionally washing the substrate to which Pd is added in step (6) with an acid,
(8) A method including the step of performing electroless plating on the base material reduced in step (6) or the base material washed in step (7).

Claim 4:
The method according to claim 2 or 3, wherein the (B) insert layer comprises a sheet consisting of acrylonitrile-butadiene-styrene copolymer synthetic resin (ABS resin).

Claim 5:
The method according to any one of claims 1 to 4, wherein the electroless plating is a pattern plating.

Claim 6:
Electroless plating manufactured by the method in any one of Claims 1-5.

Claim 7:
An electroless plated article manufactured by the method according to any one of claims 1 to 5,
Pd reduced from the Pd ion is localized near the surface of the electroless plating film,
Electroless plating.

Claim 8:
A plated product in which a plating film is formed on a substrate,
(1) In the base material
(2) Coating film in which surface-treated nanoparticles are uniformly dispersed,
(3) A boundary layer in which Pd is unevenly distributed, and (4) a plated material in which a plating film is formed in order.

Claim 9:
A coating film in which surface-treated nanoparticles are uniformly dispersed and a plating film are formed in order on a substrate, and Pd is unevenly distributed at the boundary between the coating film and the plating film. Plating layer having a layer.

Claim 10:
The plated article according to claim 8, wherein the plated article is a pattern plated article.

Description of "Step of washing the substrate to which Pd is optionally applied with acid" In the method of producing the electroless plated article of the present invention, in the case of applying "partial plating", "acid to the substrate to which Pd is applied""Washingwith".

  In the method of producing the electroless plated product of the present invention, the "step of washing the substrate to which Pd is applied with an acid" is not required when "overall plating" is applied.

  Since the method of producing the electroless plated product of the present invention includes the case of applying "partial plating" and the case of applying "full surface plating", the process of "cleaning the substrate to which Pd is optionally applied with acid" Including. In the method of producing the electroless plated article of the present invention, the scope of the invention is clear because in this optional additional matter, it is clearly understood that the additional matter is optional as described above. .

  Unlike the patent document 1, this invention forms the coating composition layer which mix | blended the nanoparticle. The present invention does not impair the inherent properties of the substrate. The present invention can also be applied to various substrates as well as polyimides, depending on the choice of binder component.

  The present invention, unlike Patent Document 2, forms an anchor layer between a coating and a plating film. The present invention can be physically attached.

  In Patent Document 3 (FIG. 2), the amount of Pd used is small because Pd is not blended in the paint. However, Patent Document 3 has an effect on the base material (PP, easy-adhesion PET) that can be anionized, and there is room for examination that it is only chemical adhesion.

  The present invention (FIG. 2) forms an anchor layer between the coating and the plating film. The present invention is a technology different from Patent Document 3.

  According to Patent Document 4 (FIG. 2), since alkaline degreasing is performed on a paint containing silica, asperities can be formed on the surface of the coating film. However, since patent document 4 mix | blends Pd in a coating material, there exists room for examination about the amount of Pd usage.

  In the present invention (FIG. 2), the paint composition portion does not contain Pd, and Pd is unevenly distributed only in the surface layer of the coating film in contact with the plating solution and the anchor layer formed by the alkali treatment. The present invention is a technology different from Patent Document 4.

  The present invention provides a technique for favorably forming an electroless plating film on a difficult-to-plate resin without using a chemical with high environmental load.

It is a figure explaining the process of the conventional electroless plating. It is a figure explaining the process of the electroless plating of this invention. It is STEM observation explaining conventional electroless plating. It is STEM observation explaining the electroless plating of this invention.

  The present invention will be described in detail below.

Advantages of the Present Invention (1) In the past, in order to form an anchor in a resin material by etching, it has been necessary to use a chemical with high environmental load such as hexavalent chromium.

  Compared to the prior art, the present invention can form an anchor layer by alkali treatment.

  (2) Conventionally, since the anchor formed by etching has an unevenness of several μm, the appearance after electroless plating did not have a gloss.

  Compared to the prior art, the present invention can adjust the size of the asperities by the size of the nanoparticles, so that high appearance gloss can be obtained.

  (3) Conventionally, in the metalloid technology etc., since Pd is contained in the paint composition, there is Pd not in contact with the plating solution, and there is room for improvement in terms of efficiency (FIG. 3).

  Compared to the prior art, the present invention allows Pd to be deposited on the coating surface more efficiently because Pd is attached after anchor formation (FIG. 4).

  (4) In the present invention, the insert sheet is thermoplastic, has strong adhesion to various materials, and is welded and firmly adhered to a poorly plating resin such as polycarbonate (PC). In the present invention, the resin such as PP which is difficult to weld can be firmly adhered by forming the adhesive layer on the back surface of the insert sheet.

  (5) In the present invention, the insert sheet can be stretched upon heating because of its thermoplasticity. Further, the coating composition layer formed in a sheet shape can also maintain the function as the electroless plating pretreatment layer following the stretching. In the present invention, during insert molding, the sheet and the paint composition layer can follow and allow plating in a three-dimensional shape.

  (6) Conventionally, when thick plating is formed by masking plating, current concentrates on the plated end, and there is a problem that the end becomes plating failure.

  In the present invention, the sheet sinks to the base material side during insert molding compared to the prior art, and there is no difference in level between the coated area and the non-painted area. Even then, the end of the parting becomes clear. In the present invention, even if the film is thickened by electroplating, the plating does not spread in the lateral direction, so that the pattern shape can be suppressed from being broken.

  (7) Conventionally, when the end portion spreads laterally, the end surface is formed so that adhesion with the base material is not sufficiently obtained, so that water etc. easily penetrates from the end surface, leading to a decrease in water resistance. The

  Compared to the prior art, the present invention suppresses the spread of the end face, and high water resistance is obtained.

  (8) Conventionally, in the case of a substrate having a large difference between a plated film and a thermal expansion coefficient, peeling is likely to occur due to a stress difference when a thermal load is applied.

  Compared with the prior art, the present invention allows the insertion of the insert sheet to create a buffer action and to reduce the stress difference between the plating film and the substrate.

  (9) Conventionally, in metalloid technology and the like, a thermosetting resin is used to obtain a plated film having high adhesion and weatherability. When using a base material such as ABS or PC, which has a high curing temperature and low heat resistance, a long heat treatment is required.

  In the present invention, it is possible to expose to a high temperature of 200 to 300 ° C. during insert molding to shorten the heat curing time.

  In the present invention, since Pd is not blended in the paint, the amount of Pd used is small.

  In the present invention, irregularities can be formed on the coating film surface by alkaline degreasing the paint containing silica.

  In the present invention, since the commercially available materials and lines can be used other than the paint, the introduction barrier is small.

[1] Method of Producing Electroless Plated Material In the method of producing electroless plated material of the present invention,
(1) The substrate contains (A) a solvent, (A) a binder, and (C) surface-treated nanoparticles, and the amount of the (B) surface-treated nanoparticles is the (B) binder. Applying the electroless plating pretreatment ink composition in the range of 0.01 to 100 parts by weight with respect to 1 part by weight;
(2) (a) volatilizing and / or drying a solvent contained in the ink composition applied in step (1), and (b) curing the binder,
(3) a step of alkali-treating the substrate obtained by curing the ink composition in the step (2) and degreasing the substrate;
(4) applying palladium (Pd) ions to the substrate degreased in step (3);
(5) a step of reducing the Pd ion applied to the substrate in the step (4),
(6) optionally washing the substrate to which Pd is added in step (5) with an acid,
(7) An electroless plated product can be produced by a method including the step of performing electroless plating on the base material reduced in the step (5) or the base material washed in the step (6) .

Process (1)
The base material contains (A) a solvent, (B) a binder, and (C) surface-treated nanoparticles, and the amount of the (B) surface-treated nanoparticles is 1 part by weight of the (B) binder. The step of applying the electroless plating pretreatment ink composition is in the range of 0.01 to 100 parts by weight.

Substrate The substrate used in the present invention is not particularly limited.

  It is preferable to use plastics (resin), glass, metal, ceramics etc. as a base material.

  As plastic (resin), use polyolefin such as polyethylene (PE), polypropylene (PP), polystyrene (PS), polybutadiene, polybutene, polyisoprene, polychloroprene, polyisobutylene, polyisoprene, polymethylpentene (TPX), etc. Is preferred.

  As the plastic (resin), it is preferable to use ABS resin (copolymer synthesized resin of acrylonitrile, butadiene and styrene), AES resin (copolymer synthesized resin of acrylonitrile, ethylene and styrene), and the like.

  Furthermore, as the plastic (resin), polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polylactic acid ester, etc .; acrylic resins such as polymethyl methacrylate (PMMA); polycarbonate (PC) It is preferable to use PC / ABS; polyvinyl chloride or the like.

  Polyamide; Polyimide; Polyamide imide; Polyether imide; Polyacetal; Polyether ether ketone; Cyclic polyolefin having norbornene skeleton; Polyphenylene sulfide (PPS); Liquid crystal polymer (LCP); Modified polyphenyl ether; Polysulfone; Polysulfone; Phenol; polyphthalamide (PPA); polyarylate etc. are preferably used.

  It is preferable to use bio PC (biopolycarbonate resin), TSOP (Toyota super olefene polymer) or the like.

  The bio PC is a polycarbonate whose main raw material is a plant-derived isosorbide having an oxygen-containing cyclic skeleton, and examples thereof include Durabio (R) manufactured by Mitsubishi Chemical Corporation.

  TSOP is a high-performance PP-based resin material developed based on Toyota's unique molecular design theory, in which an elastomer is used as a continuous phase and polypropylene (PP) resin is used as finely dispersed crystals.

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

  The shape of the substrate is not particularly limited. For example, any of plate-like (or film-like), non-woven-like (or woven-like), thread-like, various shapes formed with a mold, etc. may be used.

  A solvent, a binder and the like contained in the ink composition can be appropriately selected depending on the substrate.

Electroless plating pretreatment ink composition Electroless plating pretreatment ink composition contains (A) solvent, (I) binder, and (U) surface-treated nanoparticles, and the above (U) surface-treated. The addition amount of the nanoparticles is in the range of 0.01 to 100 parts by weight with respect to 1 part by weight of the (i) binder.

(A) The solvent ink composition contains a solvent.

  The solvent (dispersion medium) can disperse (c) surface-treated nanoparticles. In addition, the solvent is excellent in affinity with the binder. It is selected from the group consisting of water and an aprotic polar solvent such as N-methylpyrrolidone (NMP) from the viewpoint of being able to impart the dispersibility of the surface-treated nanoparticles in the electroless plating pretreatment ink composition. At least one of the above is preferred.

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

  The solvent can, for example, be converted from water to NMP.

  The solvent further includes the viscosity of the ink composition, the evaporation rate, and the ink composition, taking into consideration (i) the solubility of the binder contained in the ink composition, and (ii) the dispersibility of the surface-treated nanoparticles. It is preferable to select from the viewpoint of the adhesion between the object and the base material (ABS resin, glass plate, etc.). In order to satisfy these points, another solvent can be additionally used.

  Specifically, alcohols such as methanol, ethanol, isopropyl alcohol (IPA), 1-butyl alcohol, isobutyl alcohol, etc .; acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, diacetone alcohol (4-hydroxy-4-methyl- It is preferable to additionally use ketones such as 2-pentanone) and cyclohexanone.

  It is preferable to additionally use glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monobutyl ether; and aromatic carboxylic acid esters such as methyl benzoate, ethyl benzoate and methyl salicylate.

  It is preferable to additionally use aromatic hydrocarbons such as toluene and xylene; and aliphatic hydrocarbons such as n-hexane, n-heptane and mineral spirits.

  It is preferable to additionally use glycol ether esters such as methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol acetate, butyl carbitol acetate and the like.

  Preferably, alkanol esters such as ethyl acetate and butyl acetate; 2-phenoxyethanol (ethylene glycol phenyl ether) and the like are additionally used.

  In particular, in consideration of printability and paintability, and a leveling process after printing and painting, the use of a solvent having a slow evaporation rate is preferred.

  Examples of solvents having a slow 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 can be used as dilution solvents.

  The solvents can be used alone or in combination of two or more.

(A) Binder ink composition contains a binder.

  As the binder, from the viewpoints of the viscosity of the ink composition, the adhesion between the ink composition and the substrate (ABS resin, glass plate, etc.), the curing conditions, etc., those which can obtain good reactivity for electroless plating are selected. Is preferred. The binder is one that is dispersed or dissolved in the solvent.

  Specifically, epoxy resin, polyester resin, acrylic resin, polyurethane resin, polyamide resin, polyimide resin, polyamide imide resin (PAI), shellac resin, melamine resin, urea resin, polyolefin resin, vinyl acetate / vinyl chloride copolymer resin, It is preferable to use butyral resin or the like.

  The acrylic resin is a polymer of acrylic acid ester, a polymer of methacrylic acid ester, or a copolymer comprising these as a comonomer, and examples thereof include polymethyl methacrylate resin, polymethyl acrylate resin, ethylene-methyl acrylate copolymer It is preferable to use a combination, an ethylene-methyl methacrylate copolymer and the like.

  The polyamide imide 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 the reaction of trimellitic anhydride and diisocyanate, the reaction of trimellitic anhydride chloride and diamine, and the like.

  The binder is preferably at least one selected from the group consisting of an epoxy resin, a polyester resin, a polyamide resin and a polyimide resin, and a polyolefin resin, and more preferably at least one selected from the group consisting of an epoxy resin and a polyolefin resin.

  The binders can be used alone or in combination of two or more.

(C) The nanoparticle ink composition contains nanoparticles.

  The nanoparticles are not particularly limited as long as they do not interfere with the electroless plating reaction.

  It is preferable to use an inorganic oxide as the nanoparticles.

  As the inorganic oxide, for example, silicon dioxide, aluminum oxide, titanium oxide, zirconium oxide or the like is preferably used.

Among the inorganic oxides, it is preferable to use nanoparticles mainly composed of silicon dioxide. Silica is a nanoparticle whose main component is silicon dioxide (SiO ₂ ). Silica is called, in addition to silicon dioxide, silicic acid, silicic acid and silicon oxide. The nanoparticles having silicon dioxide as a main component dissolve in the alkali treatment themselves, and therefore the reactivity and adhesion of electroless plating are high.

  Even if the nanoparticles do not dissolve in alkaline treatment, the binder resin swells and dissolves in alkaline treatment by using the binder resin, and as a result, a gap is generated between the nanoparticles and the binder, and the nanoparticles As a result, it is possible to obtain the same effect as nanoparticles dissolved by alkali treatment.

  When metal particles are used as the nanoparticles, the added metal may act as a catalyst for oxidative decomposition of the organic component as the binder. Therefore, in the present invention, it is not preferable to use metal particles as nanoparticles.

  The shape of the nanoparticles is not particularly limited. The shape of the nanoparticles is preferably spherical, polygonal or the like.

  The addition amount of the surface-treated nanoparticles is in the range of 0.01 to 100 parts by weight with respect to 1 part by weight of the (i) binder.

  The amount of nanoparticles added is preferably about 0.05 to 20 parts by weight, more preferably about 0.1 to 3 parts by weight, per part by weight of the binder. The viscosity of an ink composition is favorably maintained by the addition amount of a nanoparticle being the said range, and it becomes an ink composition which is easy to apply | coat.

  Further, the adhesion between the ink composition and the substrate is good, and the electroless plating film is not easily peeled off. In other words, when the addition amount of the nanoparticles is too large, the viscosity increase tends to be too large, making it difficult to apply. In addition, the adhesion between the ink composition and the base material tends to be low, which tends to cause a phenomenon in which the electroless plating film easily peels off with a tape. If the amount is small, the effect of addition can not be obtained sufficiently.

  The average particle diameter of the nanoparticles is preferably in the range of about 10 to 1,000 nm, more preferably about 10 to 500 nm, and still more preferably about 10 to 250 nm.

  Even if it contains particles which do not satisfy the range of the average particle diameter specified in the nanoparticles, it is not particularly limited as long as the effects of the present invention are not impaired.

  In the present invention, the average particle size of nanoparticles means the particle size of primary particles of nanoparticles.

  The particle size of the nanoparticles can be determined by dynamic light scattering or electron microscopy if it is about 0.1 μm or less depending on the particle size range. In addition, the particle diameter of the nanoparticles can be determined by the laser diffraction / scattering method if it is approximately 0.1 μm or more.

  The average particle size of the nanoparticles, as measured by the dynamic light scattering method, is the harmonic average particle size (diameter) according to the scattered light intensity standard. The average particle diameter of the nanoparticles is the volume-based median diameter measured by the laser diffraction / scattering method.

  When the average particle diameter of the nanoparticles is in the range of about 10 to 1,000 nm, the particles are not easily aggregated, the dispersibility is good, and the handleability of the ink composition is good. In addition, when using an ink composition containing nanoparticles, the appearance after plating is good.

  In other words, particles having an average particle diameter of less than 10 nm tend to have strong cohesiveness, are difficult to disperse, and can not obtain good handleability of the ink composition. In addition, when nanoparticles having an average particle size of more than 1,000 nm are used for the ink composition, the appearance tends to be inferior when plating using the ink composition.

Surface treatment of nanoparticles The nanoparticles are preferably surface treated. That is, the ink composition comprises nanoparticles, which are preferably surface-treated nanoparticles (surface-treated nanoparticles).

  By the surface treatment of the nanoparticles, the nanoparticles are well dispersed, reaggregation does not occur, and uniform plating can be obtained using the ink composition. In other words, without the surface treatment, dispersion failure and reaggregation of particles are likely to occur, and uniform plating tends not to be achieved.

  Both hydrophilic treatment and hydrophobic treatment can be used as surface treatment of nanoparticles. The surface treatment of the nanoparticles can be appropriately selected according to the type of the solvent and the binder contained in the ink composition.

  The surface treatment of the nanoparticles is preferably hydrophobic treatment because many of the binder and the solvent have hydrophobicity. As the hydrophobic treatment, surface treatment using a silane coupling agent is preferred.

  As a silane coupling agent used for surface treatment, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glyl Cidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane It is preferable to use N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane or the like.

  From the viewpoint of dispersion stability as surface treatment, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3- Acryloxypropyltrimethoxysilane is particularly preferred.

  The surface treatment of the nanoparticles (inorganic oxide) may be carried out, for example, by adding and spraying the silane coupling agent while stirring and dispersing an untreated inorganic filler with a mixer at normal temperature and stirring for 5 to 15 minutes. It can be done by As a mixer, a known mixer can be used. For example, a blender such as a blender, a ribbon blender, a bubble cone blender, a Henschel mixer, a mixer such as a concrete mixer, a ball mill or the like is preferably used. More preferable.

For example, when phenyltrimethoxysilane ((CH ₃ O) ₃ SiC ₆ H ₅ ), phenyltriethoxysilane ((C ₂ H ₅ O) ₃ SiC ₆ H ₅ ) or the like is used as a silane coupling agent, nanoparticles can be obtained. It is possible to phenylsilane-treat the surface of. The ink composition preferably comprises nanoparticles having a surface treated with phenylsilane, in other words, nanoparticles having a surface modified with a phenylsilane group and nanoparticles having a surface treated with phenylsilane.

  The processing amount of the silane coupling agent is preferably about 0.5 to 2 parts by weight per 100 parts by weight of the nanoparticles.

  The nanoparticles are preferably spherical silica having an average particle size of about 10 to 1,000 nm, and the silica is preferably surface-treated (hydrophobically treated) with a silane coupling agent.

  The ink composition comprises nanoparticles (such as silicon dioxide) and surface-treated nanoparticles (such as phenylsilane-treated silica). By performing coating treatment, curing treatment, alkali treatment, and then electroless plating treatment by a predetermined method using this, the reactivity of electroless plating is high, and excellent adhesion that can withstand chromium plating, It is possible to form a film that can exhibit excellent smoothness that can withstand decorative plating. When the ink composition is used, it is possible to form partial plating while suppressing the spread of the pattern on the substrate.

  Since the ink composition contains nanoparticles and surface-treated nanoparticles, a film formed using the same is excellent in the effect of alleviating the stress generated between the substrate and the plating film due to the temperature difference. The presence of the film between the substrate and the plating film makes it possible to relieve the stress and prevent the decrease in adhesion.

  The plated film formed using the ink composition can maintain high adhesion even when exposed to an environment having a large temperature difference for a long time.

(D) Method of Producing Electroless Plating Pretreatment Ink Composition In order to perform pattern plating or partial plating treatment, the ink composition is used in pretreatment of electroless plating.

  When the ink composition is used, it is possible to form a film which has high reactivity of electroless plating and can exhibit excellent adhesion that can withstand chromium plating and excellent smoothness that can withstand decorative plating. When the ink composition is used, it is possible to form partial plating while suppressing the spread of the pattern on the substrate. When the ink composition is used, no treatment such as increasing the reducing agent concentration of electroless plating or raising the reaction temperature is necessary for the purpose of improving the reactivity of the electroless plating. When the ink composition is used, an etching process by a harmful substance, a complicated catalyst application process and the like are not required.

  (A) The surface-treated nanoparticles are dispersed in a solvent, and then a binder is mixed to prepare a mixture.

  The nanoparticles are dispersed in a solvent (dispersion medium). As nanoparticles, the nanoparticles can be used, and it is preferable to use surface-treated nanoparticles. The nanoparticles are preferably spherical silica having an average particle size of about 10 to 1,000 nm, and the silica is preferably surface-treated (hydrophobically treated) with a silane coupling agent.

  As the solvent, (a) solvents such as 2-phenoxyethanol, diacetone alcohol and cyclohexanone can be used. The amount of the solvent used is not particularly limited as long as the nanoparticles can be uniformly present, and preferably about 100 to 10,000 parts by weight, and more preferably about 200 to 5,000 parts by weight with respect to 100 parts by weight of the nanoparticles.

  As the binder, the aforementioned (i) binder can be used. The amount of the binder used is 1 to 10,000 with respect to 100 parts by weight of nanoparticles from the viewpoint of the viscosity of the ink composition, the adhesion between the ink composition and the substrate (ABS resin, glass plate, etc.), curing conditions, etc. It is preferable that the amount is about parts by weight, more preferably about 5 to 2,000 parts by weight, and still more preferably about 33 to 1000 parts by weight.

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

  A mixture of (a) solvent, (c) surface-treated nanoparticles and (i) binder is mixed.

The method of applying the ink composition to the coated substrate is not limited.

  As a coating method, a bar coater, gravure printing machine (gravure offset), direct gravure, microgravure, die coater, flexo printing machine, inkjet printing machine, dispenser, dipping, spray, spin coater, roll coater, reverse coater, screen printing There is a coating method using a machine or the like.

  From the viewpoint of maskinglessness and production efficiency, gravure offset printing, pad printing and a dispenser are preferable. Depending on the pattern, spray coating is preferred.

  It is preferable to adjust the viscosity of the ink composition according to the application method.

  In the case of coating by gravure offset printing or pad printing, the viscosity of the ink composition is preferably about 50 to 1,000 mPa · s.

  In the case of coating with a dispenser or in the case of spray coating after masking, the viscosity of the ink composition is preferably about 100 mPa · s or less.

  The film thickness of the ink composition before drying and curing can be appropriately selected depending on the use application, and depends on the viscosity of the ink composition. The film thickness is preferably about 1 to 120 μm, and more preferably about 10 to 100 μm from the viewpoint of being able to apply the ink composition well. When the film thickness exceeds 120 μm, the ink composition tends to cause dripping.

Process (2)
In the step (1), the solvent contained in the ink composition applied in the step (1) is volatilized and / or dried, and the binder is cured.

After the ink composition is applied to the cured substrate, the solvent (solvent) contained in the ink composition is volatilized and / or dried, and then curing treatment is performed. By the curing treatment, (a) the binder is cured.

  After the ink composition is applied to the substrate, 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 and the substrate and the surface strength of the coating.

  About 60-400 degreeC is preferable, and, as for the temperature of a drying process, about 80-150 degreeC is more preferable. About 6 seconds-60 minutes are preferable according to drying temperature, and, as for the time of a drying process, about 10 minutes-30 minutes 1 minute-30 minutes are more preferable.

  The temperature of the curing treatment can be adjusted according to the type of the binder (i) contained in the ink composition. The temperature of the curing treatment is preferably about 40 to 400 ° C. Moreover, when using a plastics 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 plastics raw material.

  The film thickness of the ink composition after drying and curing depends on the solid content concentration of the ink composition. The film thickness is preferably about 0.05 to 20 μm, and more preferably 1 to 5 μm from the viewpoint that electroless plating can be efficiently performed and sufficient plating adhesion is exhibited. Even if the film thickness is less than 0.05 μm, although the reactivity of electroless plating can be obtained, there is a tendency that the plating adhesion is not sufficiently exhibited. If the film thickness exceeds 20 μm, the reaction rate of electroless plating tends to be poor.

Process (3)
In the step (2), the substrate on which the ink composition has been cured is alkali-treated and degreased.

After the solvent (a) contained in the alkali-treated ink composition is volatilized and / or dried, and the binder (b) contained in the ink composition is cured, the substrate coated with the ink composition is alkali-treated.

  By the alkali treatment, (i) the outermost layer nanoparticles not coated with the binder component can be dissolved and / or detached. As a result, the nanoparticle layer coated with the binder component of the thin film of the surface layer (the lower layer of the outermost layer) next to the outermost layer can be exposed.

  This alkali treatment is a very important step.

  An ink film can be formed on a base material by performing a series of these processes using an ink composition.

Process (4)
Pd ion is provided to the base material degreased in the step (3).

  The Pd ion supplied from the Pd compound can be obtained by reduction using a reducing agent.

  As a Pd compound for supplying the Pd ion, a catalyst comprising Sn-Pd colloid is preferable. As a catalyst, for example, Catalyst C, C-7, C-10 (manufactured by Okuno Seiyaku Kogyo Co., Ltd.), ENILEX CT-304, 580 (manufactured by JCU Corporation) or the like can be used.

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

Process (5)
This is a step of reducing the Pd ion applied to the substrate in the step (4).

  As a reducing agent for reducing Pd ion, for example, OPC 505 accelerator, OPC 555 accelerator M, OPC 500 accelerator MX, accelerator X (manufactured by Okuno Pharmaceutical Co., Ltd.), ES-400, JPB-400 (manufactured by JCU), etc. are used be able to.

Process (6)
Optionally, it is a step of washing the substrate to which Pd is added in the step (5) with an acid.

  This step is a step of selectively removing Pd attached to the outside of the pattern, whereby partial plating with excellent clearness of parting can be applied.

  As the acid, an aqueous solution containing a strong acid is preferable. For example, an aqueous solution containing sulfuric acid, hydrochloric acid, nitric acid, etc., or a mixture thereof can be used.

  The concentration of the acid in the aqueous solution is preferably 0.1 to 20%, and more preferably 1 to 10%.

  The immersion time in the acid is preferably 10 seconds to 30 minutes, and more preferably 30 seconds to 10 minutes.

  The bath temperature of the acid is not particularly limited, but is preferably 40 ° C. or less in terms of use environment.

  In the method of producing the electroless plated product of the present invention, when “partial plating” is applied, “the step of washing the substrate to which Pd is applied with an acid” is included.

  In the method of producing the electroless plated product of the present invention, the "step of washing the substrate to which Pd is applied with an acid" is not required when "overall plating" is applied.

  Since the method of producing the electroless plated product of the present invention includes the case of applying "partial plating" and the case of applying "full surface plating", the process of "cleaning the substrate to which Pd is optionally applied with acid" Including. In the method of producing the electroless plated article of the present invention, the scope of the invention is clear because in this optional additional matter, it is clearly understood that the additional matter is optional as described above. .

Process (7)
It is a step of performing electroless plating on the base material reduced in the step (5) or the base material washed in the step (6).

After the ink (composition) film after the electroless plating treatment alkali treatment is washed with water, pattern plating can be formed on the substrate by performing electroless plating.

  The substrate on which the ink film is formed is in contact with a plating solution for depositing a metal, whereby an electroless plating film is formed. The ink film formed of the ink composition has good reactivity with electroless plating, and the obtained electroless plating film has no unevenness and is excellent in adhesion and appearance.

  The plating solution is not particularly limited as long as it is a plating solution generally used for electroless plating. As a plating solution, for example, copper, gold, silver, nickel, chromium or the like is preferably used. As the plating solution, it is preferable to use a plating solution containing copper or nickel in view of the ink film formed of the ink composition.

  Plating conditions can follow a conventional method. Since the ink film has very good reactivity with electroless plating, it is not necessary to increase the concentration of the reducing agent or the concentration of the alkali component in the plating solution. Therefore, not only the life of the plating solution is extended but also plating is selectively deposited according to the pattern of the ink. That is, the ink film formed from the ink composition is excellent in pattern forming ability.

  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 process, a deposited film thickness of about 0.3 to 1.0 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 using an electroless nickel phosphorus bath in electroless plating treatment, 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.

  It is preferable that the technique which forms plating on a base material using an ink composition is directed to pattern plating. However, in the present invention, the ink composition may be used for overall plating.

  For the purpose of decoration, it is preferable to use a general process such as electrolytic copper plating, semi-bright nickel, bright nickel, chromium plating and the like after electroless plating.

When an electrolytic copper plating bath is used in the decoration 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 preferably about 10 to 60 minutes. By this decoration process, it is possible to form a deposited film thickness of about 5 to 40 μm.

When a semi-bright nickel plating bath is used in the decoration 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 preferably about 10 to 60 minutes. By this decoration process, it becomes a deposition film thickness of about 5-20 micrometers.

When a bright nickel plating bath is used in the decoration treatment, the treatment temperature is preferably about 45 to 55 ° C., the current density is preferably about 1 to 10 A / dm ² , and the treatment time is preferably about 10 to 60 minutes. By this decoration process, it becomes a deposition film thickness of about 5-20 micrometers.

When a chromium plating bath is used in the decoration treatment, the treatment temperature is preferably about 40 to 60 ° C., the current density is preferably about 10 to 60 A / m ² , and the treatment time is preferably about 1 to 5 minutes. By this decoration process, it becomes a deposited film thickness of about 0.1 to 0.3 μm.

[2] Method of producing electroless plated article using film for electroless plating used in insert molding
Manufacturing method (a)
(A) An electroless plated material can be manufactured using a film for electroless plating used in insert molding,
The film includes (A) an insert layer, and the (A) insert layer contains (A) a solvent, (A) a binder, and (C) surface-treated nanoparticles, and the (C) surface. An electroless plating pretreatment ink composition is applied in which the additive amount of the treated nanoparticles is in the range of 0.01 to 100 parts by weight with respect to 1 part by weight of the (i) binder.
(1) a step of attaching the (A) insert layer of the film to a substrate and insert molding the attached material, and (2) a layer of the ink composition exposed by the insert molding of the step (1) Treatment with alkali and degreasing
(3) applying palladium (Pd) ions to the substrate degreased in step (2);
(4) a step of reducing the Pd ion applied to the substrate in the step (3),
(5) optionally washing the substrate to which Pd is added in step (4) with an acid,
(6) An electroless plated product can be manufactured by a method including the step of performing electroless plating on the base material reduced in the step (4) or the base material washed in the step (5) .

  The (B) insert layer preferably includes a sheet made of acrylonitrile-butadiene-styrene copolymer synthetic resin (ABS resin).

Manufacturing method (b)
(B) An electroless plated product can be manufactured using a film for electroless plating used in insert molding,
The film includes (A) an insert layer,
(1) The (A) insert layer contains (A) a solvent, (B) a binder, and (C) surface-treated nanoparticles, and the amount of the (C) surface-treated nanoparticles is the above B) applying the electroless plating pretreatment ink composition in the range of 0.01 to 100 parts by weight with respect to 1 part by weight of the binder,
(2) (a) volatilizing and / or drying a solvent contained in the ink composition applied in step (1), and (b) curing the binder,
(3) A step of attaching the (A) insert layer of the film obtained by curing the ink composition in the step (2) to a substrate, and insert molding the attached material, and (4) insert molding of the step (3) Alkaline treatment and degreasing of the layer of the ink composition exposed by (B);
(5) applying palladium (Pd) ions to the substrate degreased in step (4);
(6) a step of reducing the Pd ion applied to the substrate in the step (5),
(7) optionally washing the substrate to which Pd is added in step (6) with an acid,
(8) An electroless plated product can be manufactured by a method including the step of performing electroless plating on the base material reduced in the step (6) or the base material washed in the step (7) .

  The (B) insert layer preferably includes a sheet made of acrylonitrile-butadiene-styrene copolymer synthetic resin (ABS resin).

[3] Electroless Plating Material The method of producing an electroless plating material of the present invention and the method of producing an electroless plating material using a film for electroless plating used in insert molding can produce an electroless plating material.

  In the electroless plated product, Pd in which the Pd ion is reduced is preferably localized near the surface of the coated film of the electroless plated product.

  "Pd is unevenly distributed near the coating film surface of the electroless plating product" means that Pd is unevenly distributed only at the surface of the coating film and at a location along the porous formed in the coating film. This can efficiently place Pd for the reduction reaction.

The electroless plating is a plating in which a plating film is formed on a substrate, and
(1) In the base material
(2) Coating film in which surface-treated nanoparticles are uniformly dispersed,
(3) It is preferable that a boundary layer in which Pd is unevenly distributed, and (4) a plating film be formed in order.

  “(2) Coating film in which surface-treated nanoparticles are dispersed uniformly” is formed between “(1) substrate” and “(3) Boundary layer in which Pd is unevenly distributed” The coating layer is a coating in which more surface-treated nanoparticles are uniformly dispersed as compared to the layers on both sides.

  “(3) Boundary layer in which Pd is localized” means “(2) coating film in which surface-treated nanoparticles are uniformly dispersed” and “(4) plating film” (boundary) It is a layer to be formed, and a layer containing Pd in a larger amount (a layer having uneven distribution) than the layers on both sides. Since the boundary layer in which Pd is unevenly distributed is formed, Pd is unevenly distributed in the vicinity of the coating film surface in the electroless plated material.

  "(4) Plating film" is a film formed by electroless plating.

  In the electroless plating, a coating film in which surface-treated nanoparticles are uniformly dispersed and a plating film are sequentially formed on a substrate, and Pd is unevenly distributed at the boundary between the coating film and the plating film. It is preferable to have a layer that

  The electroless plating can be a pattern plating.

  The ink composition is applied to a substrate, an ink film is formed, and electroless plating is performed. Thereby, in order to perform pattern plating or partial plating treatment, an electroless plating film used in pretreatment of electroless plating can be formed. The molded article (plated object) carrying the electroless plating film is excellent in the adhesion of the plating film.

  Molded articles on which electroless plating film is mounted are used, for example, in housings of electric appliances such as mobile phones, personal computers, refrigerators, etc .; automotive parts such as emblems, switch bases, radiator grills, door handles, wheel covers etc. Can.

  Electroless plating pretreatment ink composition for pattern plating is used, in electroless plating in which pattern plating is performed on a substrate (plastic (resin) etc.), the reactivity of electroless plating is high, and multilayers up to chromium plating It is possible to develop excellent adhesion that can withstand plating and excellent smoothness that can withstand decorative plating. In the electroless plating, it is possible to suppress the spread of a pattern and to perform partial plating well.

  When the ink composition is used, it is not necessary to increase the concentration of the reducing agent in the electroless plating for the purpose of improving the reactivity of the electroless plating, and it is not necessary to increase the reaction temperature of the electroless plating. Furthermore, it does not require an etching process with harmful substances, a complicated catalyst application process and the like.

  The reason why the ink composition has high reactivity for electroless plating and can achieve good adhesion that can withstand multilayer plating up to chromium plating is considered to be based on the following principle.

  First, the adhesion mechanism between the substrate (plastic etc.) and the ink composition is as follows. The solvent (solvent) component contained in the ink composition corrodes the substrate surface, and the binder component of the ink composition penetrates into the substrate to be compatible with the substrate to form a composite layer. For example, in the case of an ABS resin, the butadiene rubber contained in the ABS resin dissolves and swells, so the binder component of the ink composition penetrates into the substrate.

  The mechanism for improving the reactivity and adhesion of electroless plating is as follows. By alkali treatment of the substrate coated with the ink composition, the outermost layer nanoparticles not coated with the binder component dissolve and / or drop off. Thereby, the nanoparticle layer thinly coated with the binder component of the next surface layer (the lower layer of the outermost layer) of the outermost layer is exposed. As a result, the frequency of contact between the electroless plating solution and the Pd particles, which have a catalytic action for electroless plating, contained in the thin binder film covering the nanoparticle layer is increased.

  In addition, due to the alkali treatment, a gap is generated between the nanoparticles and the binder component, a capillary phenomenon occurs in the gap, and the permeability of the plating solution to the inside of the ink film is improved, and Pd particles and an electroless plating solution are formed. Contact frequency increases. By this phenomenon, the metal ions in the electroless plating solution are reduced by the Pd particles present at a deep position from the surface of the ink film to the inside of the film, and the reduced metal precipitates from the inside of the film so as to form a root. High adhesion between the ink film and the plating film can be obtained.

  Hereinafter, the present invention will be specifically described by showing Examples and Comparative Examples.

(1) Preparation of electroless plating pretreatment ink composition
Example 1-1
To 14 parts by weight of diacetone alcohol, 1.9 parts by weight of silica treated with phenylsilane and having an average particle diameter of 100 nm (Adma Nano YA100C-SP3 manufactured by Admatex Co., Ltd.) was added as nanoparticles, and was dispersed by stirring with a small spoonful (small). 5 parts by weight of an epoxy resin solution (solid content: 22% by weight) as a binder component was added to the nanoparticle dispersion solution, and the mixture was shaken and agitated to prepare an electroless plating pretreatment ink composition 1.

Example 1-2
To 14 parts by weight of diacetone alcohol, 1.9 parts by weight of silica treated with vinylsilane and having an average particle diameter of 100 nm (Adma Nano YA100C-SV2 manufactured by Admatex) was added as nanoparticles, and was dispersed by stirring with a small spoonful (small). 5 parts by weight of an epoxy resin solution (solid content: 22% by weight) as a binder component was added to the nanoparticle dispersion solution, and the mixture was shaken and stirred to prepare an electroless plating pretreatment ink composition 2.

Example 1-3
To 14 parts by weight of diacetone alcohol, 1.9 parts by weight of silica treated with phenylsilane and having an average particle diameter of 100 nm (Adma Nano YA100C-SP3 manufactured by Admatex Co., Ltd.) was added as nanoparticles, and was dispersed by stirring with a small spoonful (small). 10 parts by weight of a polyamide resin solution (solid content: 10% by weight) as a binder component was added to the nanoparticle dispersion solution, and the mixture was shaken and stirred to prepare an electroless plating pretreatment ink composition 3.

Example 1-4
To 14 parts by weight of diacetone alcohol, 1.9 parts by weight of silica treated with phenylsilane and having an average particle diameter of 10 nm (Adma Nano YA010C-SP3 manufactured by Admatex) was added as nanoparticles, and the mixture was steered with a medical spoon (small) and dispersed. 5 parts by weight of an epoxy resin solution (solid content: 22% by weight) as a binder component was added to the nanoparticle dispersion solution, and the mixture was shaken and stirred to prepare an electroless plating pretreatment ink composition 4.

Example 1-5
To 14 parts by weight of toluene, 1.9 parts by weight of silica (admanano YA010C-SP3 manufactured by Admatex Co., Ltd.) having a particle diameter of 10 nm treated with phenylsilane as nanoparticles was added, and the mixture was steered with a spoonful (small) and dispersed. 5 parts by weight of a polyolefin resin solution (solid content: 20% by weight) as a binder component was added to the nanoparticle dispersion solution, and the mixture was shaken and stirred to prepare an electroless plating pretreatment ink composition 5.

Example 1-6
To 14 parts by weight of cyclohexanone, 1.9 parts by weight of silica treated with phenylsilane and having an average particle diameter of 100 nm (Adma Nano YA100C-SP3 manufactured by Admatechs Co., Ltd.) as nanoparticles was added, and was steered and dispersed with a medicine spoon (small). 4 parts by weight of a polyester resin solution (solid content: 30% by weight) as a binder component was added to the nanoparticle dispersion solution, and the mixture was shaken and stirred to prepare an electroless plating pretreatment ink composition 6.

Comparative Example 1-1
To 14 parts by weight of diacetone alcohol, 5 parts by weight of an epoxy resin solution (solid content: 22% by weight) as a binder component was added, and the mixture was shaken and stirred to prepare an electroless plating pretreatment ink composition 7.

(2) Coating of the electroless plating pretreatment ink composition
Example 2-1
After coating the pretreatment ink composition 1 for electroless plating with an application film thickness of 47 μm on the ABS with a bar coater at a coating thickness of 47 μm, it is dried in a warm air drying oven at 80 ° C. for 45 minutes. I got

Example 2-2
After coating the pretreatment ink composition 2 for electroless plating with a coating film thickness of 47 μm on the ABS with a bar coater at a coating thickness of 47 μm, it is dried in a warm air drying oven at 80 ° C. for 45 minutes. I got

Example 2-3
After coating the pretreatment ink composition 3 for electroless plating with a coating film thickness of 47 μm on the ABS with a bar coater at a coating thickness of 47 μm, it is dried in a warm air drying oven at 80 ° C. for 45 minutes. I got

Example 2-4
After coating the pretreatment ink composition 4 for electroless plating with a coating thickness of 47 μm on the ABS by a bar coater with an applied film thickness of 47 μm, it is dried in a warm air drying furnace at 80 ° C. for 45 minutes. I got

Example 2-5
After applying the pretreatment ink composition 1 for electroless plating to a coating thickness of 47 μm on a PC / ABS resin by a bar coater, the ink is dried for 45 minutes in a warm air drying oven at 80 ° C. An application sample 5 was obtained.

Example 2-6
After coating the pretreatment ink composition 1 for electroless plating with a coating film thickness of 47 μm on polyamide (PA, nylon) resin by a bar coater, it is dried in a warm air drying oven at 80 ° C. for 45 minutes, and electroless plating A pretreated ink coated sample 6 was obtained.

Example 2-7
After applying the pretreatment ink composition 1 for electroless plating to a polyphenylene sulfide (PPS) resin by dip coating so as to give a coating film thickness of 24 μm, it is dried in a warm air drying oven at 80 ° C. for 45 minutes, An electroless plating pretreatment ink application sample 7 was obtained.

Example 2-8
After applying the pretreatment ink composition 1 for electroless plating on the polyetherimide (PEI) resin by spray coating so as to give a coating film thickness of 24 μm, it is dried in a warm air drying oven at 80 ° C. for 45 minutes The electroless plating pretreatment ink application sample 8 was obtained.

Example 2-9
After applying the pretreatment ink composition 5 for electroless plating with a coating film thickness of 24 μm on a TSOP resin (made by Nippon Polypropylene Corp.) by a bar coater, it is dried in a warm air drying oven at 80 ° C. for 45 minutes. A pre-plating treatment ink applied sample 9 was obtained.

Example 2-10
After applying the pretreatment ink composition 6 for electroless plating to a biopolycarbonate (Durabio D5380AR manufactured by Mitsubishi Chemical Corporation) with a coating film thickness of 47 μm by a bar coater, it was dried for 45 minutes in an 80 ° C. hot-air drying oven An electroless plating pretreatment ink application sample 10 was obtained.

Example 2-11
After applying a pre-treatment ink composition 1 for electroless plating with a coating thickness of 12 μm on a sheet for insert molding made of ABS (CA-502-M280 manufactured by CARD Co., Ltd.) by a bar coater, a hot air of 80 ° C. It was dried in a drying oven for 3 minutes to obtain a pre-electrolytic plating pretreated ink coated sample 11.

Comparative Example 2-1
After coating the pretreatment ink composition 7 for electroless plating with an application film thickness of 47 μm on the ABS with a bar coater at a coating thickness of 47 μm, it is dried in a warm air drying oven at 80 ° C. for 45 minutes. I got

Comparative Example 2-2
After applying a pre-treatment ink composition 7 for electroless plating with a coating thickness of 12 μm on a sheet for insert molding made of ABS (CA-502-M280 manufactured by CARD Co., Ltd.) by a bar coater, a hot air of 80 ° C. It was dried in a drying oven for 3 minutes to obtain a pre-electrolytic plating pretreated ink coated sample 13.

Reference Example 2-3
After applying the pretreatment ink composition 1 for electroless plating with a coating film thickness of 12 μm on a sheet of acrylic insert molding by a bar coater, it is dried for 45 minutes in a warm air drying oven at 80 ° C., before electroless plating A treated ink coated sample 14 was obtained.

(3) Insert molding
Example 3-1
The ink-coated sample 11 prepared in (2) was set in a plate-like mold, and the melted ABS resin was poured. The temperature of the mold at this time was 250.degree. After cooling, the sheet and resin integrated by insert molding were taken out, and a resin molded product 1 was obtained. At this time, the stretch ratio of the molded ABS sheet was 25%.

Example 3-2
The ink-coated sample 11 prepared in (2) was set in a plate-like mold, and the molten polycarbonate resin was poured. The temperature of the mold at this time was 260.degree. After cooling, the sheet and resin integrated by insert molding were taken out, and a resin molded product 2 was obtained. At this time, the stretch ratio of the molded ABS sheet was 25%.

Example 3-3
The ink-coated sample 11 prepared in (2) was set in a plate-like mold, and the melted biopolycarbonate resin was poured. The temperature of the mold at this time was 230.degree. After cooling, the sheet and resin integrated by insert molding were taken out, and a resin molded product 3 was obtained. At this time, the stretch ratio of the molded ABS sheet was 25%.

Example 3-4
The ink-coated sample 11 prepared in (2) was set in a plate-like mold, and the melted biopolycarbonate resin was poured. The temperature of the mold at this time was 230.degree. After cooling, the sheet and resin integrated by insert molding were taken out, and a resin molded product 4 was obtained. At this time, the stretch ratio of the molded ABS sheet was 80%.

Example 3-5
A polyolefin resin (Super Clon 930) manufactured by Nippon Paper Industries Co., Ltd. was coated to a back surface of the ink coated sample 11 prepared in (2) with a coating thickness of 2 μm, and dried at 80 ° C. for 10 minutes. The obtained sheet was set in a plate-like mold, and melted TSOP resin (manufactured by Japan Polypropylene Corp.) was poured. The temperature of the mold at this time was 250.degree. After cooling, the sheet and resin integrated by insert molding were taken out, and a resin molded product 5 was obtained. At this time, the stretch ratio of the molded TSOP sheet was 25%.

Comparative example 3-1
The ink-coated sample 13 prepared in (2) was set in a plate-like mold, and the melted ABS resin was poured. The temperature of the mold at this time was 250.degree. After cooling, the sheet and resin integrated by insert molding were taken out, and a resin molded product 6 was obtained. At this time, the stretch ratio of the molded ABS sheet was 25%.

Reference Example 3-2
The ink-coated sample 14 prepared in (2) was set in a plate-like mold, and the melted ABS resin was poured. The temperature of the mold at this time was 250.degree. After cooling, the sheet and resin integrated by insert molding were taken out, and a resin molded product 7 was obtained. At this time, the stretch ratio of the molded ABS sheet was 25%.

(4) Evaluation Item 1: Electroless Plating Reactive Electroless Plating Pretreatment The coated ink sample was plated in the following procedure.

Plating process (i) It was adjusted to pH 11 to 14 and immersed in an alkali-treated solution adjusted to 60 ° C. for 3 minutes. Thereafter, it was washed with municipal water and replaced with ion-exchanged water.

  (Ii) Catalyst C-7 (manufactured by Okuno Seiyaku Co., Ltd.) was heated to 32 ° C. and immersed for 3 minutes. Thereafter, it was washed with municipal water and replaced with ion-exchanged water. Catalyst C-7 contains Pd ions, and this operation imparts Pd ions to the degreased substrate.

  (Iii) Accelerator X (manufactured by Okuno Seiyaku Co., Ltd.) was heated to 35 ° C. and immersed for 3 minutes. Thereafter, it was washed with municipal water and replaced with ion-exchanged water.

  (Iv) The 10% aqueous hydrochloric acid solution was heated to 40 ° C. and immersed for 10 minutes. Thereafter, it was washed with municipal water and replaced with ion-exchanged water.

Precipitation of Plating Film By immersing in an electroless copper (Cu) plating bath, it was evaluated whether or not the plating film was deposited. It was evaluated by immersing in an electroless nickel (Ni) plating bath whether or not a plating film was deposited.

Examples 4-1 to 4-15, Comparative Examples 4-1 and 4-2, Reference Example 4-3
The obtained ink-coated samples 1 to 10, 12 and the resin molded products 1 to 7 are treated by the above procedures (i), (ii), (iii) and (iv) , and then electroless Ni By immersing in a plating bath, it was evaluated whether or not a plating film was deposited. As the electroless Ni plating bath, Chemical Nickel EXC (initial Ni concentration 5.0 g / L, bath volume 500 mL, 40 ° C., 5 minutes) manufactured by Okuno Pharmaceutical Industries, Ltd. was used.

Examples 4-16 and 4-17
A plated film is deposited by treating the resin molded product 1 obtained above according to the above procedures (i), (ii), (iii) and (iv) and then immersing in an electroless Cu plating bath. It was evaluated whether or not to As the electroless Cu plating bath, OPC kappa HFS (initial Cu concentration: 2.5 g / L, bath volume: 500 mL, 40 ° C., 20 minutes) manufactured by Okuno Pharmaceutical Industries, Ltd. was used.

Comparative Examples 4-4 and 4-5
The obtained resin molded product 1 was treated according to the procedures of (ii), (iii) and (iv) above , and was immersed in an electroless Ni plating bath to evaluate whether or not a plating film was deposited. As the electroless Ni plating bath, Chemical Nickel EXC (initial Ni concentration 5.0 g / L, bath volume 500 mL, 40 ° C., 5 minutes) manufactured by Okuno Pharmaceutical Industries, Ltd. was used.

Comparative Examples 4-6 and 4-7
The obtained resin molded product 1 was treated according to the procedures of (i), (iii) and (iv) above, and immersed in an electroless Ni plating bath to evaluate whether or not a plating film was deposited. As the electroless Ni plating bath, Chemical Nickel EXC (initial Ni concentration 5.0 g / L, bath volume 500 mL, 40 ° C., 5 minutes) manufactured by Okuno Pharmaceutical Industries, Ltd. was used.

Comparative Examples 4-8 and 4-9
The obtained resin molded product 1 was treated according to the procedures of (i), (ii) and (iv) above, and immersed in an electroless Ni plating bath to evaluate whether or not a plating film was deposited. As the electroless Ni plating bath, Chemical Nickel EXC (initial Ni concentration 5.0 g / L, bath volume 500 mL, 40 ° C., 5 minutes) manufactured by Okuno Pharmaceutical Industries, Ltd. was used.

Reference Examples 4-10 and 4-11
The obtained resin molded product 1 was treated according to the procedures of the above (i), (ii) and (iii) and immersed in an electroless Ni plating bath to evaluate whether or not a plating film was deposited. As the electroless Ni plating bath, Chemical Nickel EXC (initial Ni concentration 5.0 g / L, bath volume 500 mL, 40 ° C., 5 minutes) manufactured by Okuno Pharmaceutical Industries, Ltd. was used.

Evaluation criteria for electroless plating reactivity ○: plating was deposited on the entire application pattern within 3 minutes after immersion.
:: plating was partially deposited on the coating pattern.
×: not reacted at all, or stopped at plating deposition of 1/10 or less of the applied pattern area.

(5) Evaluation item 2: Achievement or not to Cr plating After electroless plating, in the case of electroless copper (Cu) plating, electrolytic Cu plating, semi-bright nickel (Ni), bright nickel (Ni), chromium ( Cr) Plating was sequentially performed to evaluate at which process the plating was peeled.

  In the case of electroless nickel (Ni) plating, after strike copper (Cu) plating, chromium (Cr) plating was sequentially performed in the same process as electroless Cu plating, and it was evaluated in which process the plating was exfoliated.

Criterion for evaluation of achievement to Cr plating ○: Cr plating was reached.
X: Peeled off by electrolytic Cu or electrolytic Ni on the way.

The strike Cu plating bath used a bath temperature of 45 ° C. and a current density of 1.5 A / dm ² .

The electrolytic Cu plating bath used a bath temperature of 30 ° C. and a current density of 1.5 A / dm ² .

The semi-bright Ni bath used a bath temperature of 50 ° C. and a current density of 1.5 A / dm ² .

For the bright Ni bath, a bath temperature of 50 ° C. and a current density of 1.5 A / dm ² were used.

The Cr plating bath used a bath temperature of 45 ° C. and 12 A / dm ² .

(6) Evaluation item 3: Evaluation of pattern formation ability (in the case of insert sheet)
The lateral spread of the plating was measured by 30 μm thickening by electroplating.

Evaluation criteria for pattern formation ability ○: Within the longitudinal direction, the lateral direction is within 10%.
Δ: 10% to 100% in the lateral direction with respect to the longitudinal direction.
X: The spread in the lateral direction is 100% or more with respect to the spread in the longitudinal direction.

(7) Evaluation Item 4: Peel Strength of Multilayer Plating Film up to Cr Plating The samples which reached Cr plating in the above evaluation item 3 were evaluated for peel strength by a 90 ° peeling test method.

  The pattern-plated multi-layered plating film of 10 mm in width was peeled off, and one end thereof was held by a tensile jig of a tensile tester (digital force gauge ZTS-50N manufactured by IMADA).

  The non-peeled side of the pattern-plated multilayer plating film was held on another tensile jig, and a tensile test was conducted at a test speed of 25 mm / min. The maximum load was taken as peel strength.

  In addition, as for the sample which reached to Cr plating, the glossiness similar to the pre-processing method which performed the conventional chromic acid etching was obtained, and cloudy etc. were not seen.

(8) Evaluation item 5: Peel strength before and after heat treatment of electroplated Cu film The samples which reached the electroplated Cu in the evaluation item 2 were evaluated for peel strength by a 90 ° peeling test method.

  Further, the sample after measurement was left at 80 ° C. for 24 hours, and the peel strength was evaluated again.

Evaluation criteria for adhesion before and after heat treatment ○: No decrease in adhesion after heat treatment.
X: A decrease in adhesion is observed after heat treatment, or peeling occurs.

(9) Evaluation item 6: Corrosivity of cut-off part by salt spray test The sample which reached to Cr plating by the above-mentioned evaluation item 3 was evaluated for corrosion resistance by CAS test.

Claims (10)

A method of producing an electroless plated article,
(1) The substrate contains (A) a solvent, (A) a binder, and (C) surface-treated nanoparticles, and the amount of the (B) surface-treated nanoparticles is the (B) binder. Applying the electroless plating pretreatment ink composition in the range of 0.01 to 100 parts by weight with respect to 1 part by weight;
(2) (a) volatilizing and / or drying a solvent contained in the ink composition applied in step (1), and (b) curing the binder,
(3) a step of alkali-treating the substrate obtained by curing the ink composition in the step (2) and degreasing the substrate;
(4) applying palladium (Pd) ions to the substrate degreased in step (3);
(5) a step of reducing the Pd ion applied to the substrate in the step (4),
(6) optionally washing the substrate to which Pd is added in step (5) with an acid,
(7) A method including the step of performing electroless plating on the base material reduced in step (5) or the base material washed in step (6). A method for producing an electrolessly plated material using a film for electroless plating used in insert molding,
The film includes (A) an insert layer, and the (A) insert layer contains (A) a solvent, (A) a binder, and (C) surface-treated nanoparticles, and the (C) surface. An electroless plating pretreatment ink composition is applied in which the additive amount of the treated nanoparticles is in the range of 0.01 to 100 parts by weight with respect to 1 part by weight of the (i) binder.
(1) a step of attaching the (A) insert layer of the film to a substrate and insert molding the attached material, and (2) a layer of the ink composition exposed by the insert molding of the step (1) Treatment with alkali and degreasing
(3) applying palladium (Pd) ions to the substrate degreased in step (2);
(4) a step of reducing the Pd ion applied to the substrate in the step (3),
(5) optionally washing the substrate to which Pd is added in step (4) with an acid,
(6) A method including the step of performing electroless plating on the base material reduced in step (4) or the base material washed in step (5). A method for producing an electrolessly plated material using a film for electroless plating used in insert molding,
The film includes (A) an insert layer,
(1) The (A) insert layer contains (A) a solvent, (B) a binder, and (C) surface-treated nanoparticles, and the amount of the (C) surface-treated nanoparticles is the above B) applying the electroless plating pretreatment ink composition in the range of 0.01 to 100 parts by weight with respect to 1 part by weight of the binder,
(2) (a) volatilizing and / or drying a solvent contained in the ink composition applied in step (1), and (b) curing the binder,
(3) A step of attaching the (A) insert layer of the film obtained by curing the ink composition in the step (2) to a substrate and subjecting the attached material to insert molding, and (4) insert molding of the step (3) Alkaline treatment and degreasing of the layer of the ink composition exposed by (B);
(5) applying palladium (Pd) ions to the substrate degreased in step (4);
(6) a step of reducing the Pd ion applied to the substrate in the step (5),
(7) optionally washing the substrate to which Pd is added in step (6) with an acid,
(8) A method including the step of performing electroless plating on the base material reduced in step (6) or the base material washed in step (7).   The method according to claim 2 or 3, wherein the (B) insert layer comprises a sheet consisting of acrylonitrile-butadiene-styrene copolymer synthetic resin (ABS resin).   The method according to any one of claims 1 to 4, wherein the electroless plating is a pattern plating.   Electroless plating manufactured by the method in any one of Claims 1-5. An electroless plated article manufactured by the method according to any one of claims 1 to 5,
Pd reduced from the Pd ion is localized near the surface of the electroless plating film,
Electroless plating. A plated product in which a plating film is formed on a substrate,
(1) In the base material
(2) Coating film in which surface-treated nanoparticles are uniformly dispersed,
(3) A boundary layer in which Pd is unevenly distributed, and (4) a plated material in which a plating film is formed in order.   A coating film in which surface-treated nanoparticles are uniformly dispersed and a plating film are formed in order on a substrate, and Pd is unevenly distributed at the boundary between the coating film and the plating film. Plating layer having a layer.   The plated article according to claim 8, wherein the plated article is a pattern plated article.