JP6072330B2 - Electroless plating pretreatment ink composition for pattern plating and formation method of electroless plating film - Google Patents

Description

  The present invention relates to an electroless plating pretreatment ink composition for pattern plating, a method for forming an electroless plating film, a film, and a molded article.

  As a method for forming a partial decorative plating on a resin molded product such as polypropylene (PP) or ABS resin (ABS), the following methods are generally used.

  There is a method of expressing partial plating by selectively plating only ABS in a two-color molded product of ABS and polycarbonate (PC). This process is approximately twice as expensive as using a single color mold as the mold. Also, if ABS and PC parting is contaminated with molding gas, defects such as burrs will occur in parting after plating. As a result, the maintenance cycle of the molding die tends to be shortened.

  In addition, by plating the entire surface, then masking the plating body, coating the non-plated part, etc., and then peeling off the masking, and then partially plating the combination of the plated part and the coated part (non-plated part) There is a way to express. This process requires steps such as masking and increases the number of man-hours, resulting in higher manufacturing costs. In addition, coating on the plating is required, and there is a problem in adhesion between plating and coating.

  In addition, there is a method of expressing partial plating by performing masking by a method such as painting on the unplated portion after molding, then plating the unmasked portion, and then peeling off the masking. This process also requires a process such as masking, which increases man-hours and thus requires more manufacturing costs. In addition, coating on the plating is required, and there is a problem in adhesion between plating and coating.

  In the plating of a resin molded product, excellent adhesion is required between the resin molded product and the plating. Therefore, the anchor effect (throwing effect) can be imparted by performing etching (roughening) to form fine irregularities on the surface of the resin molded product. However, this etching requires a complicated process, and it is necessary to use a chemical with a high environmental load such as chromic acid.

  In order to solve these problems, the following techniques have been proposed.

  In Patent Document 1, the substrate is patterned by a general-purpose printing method using a base coating material containing conductive or reducing polymer fine particles, a binder, and an inorganic filler and having a viscosity of 50 cps or more. A method of forming a metal film and performing electroless plating has been proposed. Moreover, in patent document 2, the method of irradiating a part which wants to form the pattern of plating with a laser beam, roughening the surface, and giving a catalyst after that is proposed, and the method of giving electroless plating partially is proposed. .

  However, in patent document 1, the catalyst provision process of performing water washing etc. is required after being immersed in the catalyst liquid for making a catalyst metal, such as palladium chloride, adhere between electroless-plating processes. In Patent Document 2, a step of immersing in a mixed catalyst solution such as tin or palladium before the electroless plating step and then activating with an acid such as hydrochloric acid or sulfuric acid to deposit palladium on the surface, or stannous chloride A process of adsorbing a relatively strong reducing agent, such as, on the surface and immersing in a catalyst solution containing noble metal ions is required. That is, in Patent Document 2, the number of steps is not different from the conventional etching with chromic acid, and the steps are complicated.

  Patent Document 3 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, Patent Document 3 requires a catalyst application step of immersing in a catalyst solution for adhering a catalytic metal such as palladium chloride between the electroless plating step and then washing with water, which is complicated. is there. Moreover, since the silica particles are contained in the polyimide film serving as the substrate, the original properties of the substrate are impaired.

  Moreover, in patent document 4, the coating composition for electroless plating containing the composite of a palladium particle | grain and a dispersing agent, a solvent, and binder resin is used by an inkjet printing system, a gravure offset printing system, or a flexographic printing system, A method of performing electroless plating partially by pattern printing has been proposed. In patent document 4, a pattern can be formed by various printing methods and partial plating is possible, and a complicated catalyst provision process is not required before an electroless-plating process.

  In Patent Document 4, the solvent inside the Pd complex present in the coating film is dried, and a plating film is formed on the crater-like irregularities on the coating film surface. As a result, an anchor effect occurs between the coating film and the plating film. Here, a better adhesion strength is required for a multilayer plating process generally used as a decorative plating. The “multilayer plating” indicates that after electroless plating, electrolytic copper plating having a thickness of about several μm, semi-bright nickel plating, bright nickel plating, and submicron chromium plating having the same thickness are applied. This multilayer plating is widely used as a plastic inner / outer part used in automobiles.

JP 2010-95776 JP 2011-17069 A JP 2005-325147 A JP 2013-1955 Gazette

  In electroless plating for pattern plating on plastic, the electroless plating has high reactivity, excellent adhesion that can withstand multilayer plating up to chromium plating, and excellent smoothness that can withstand decorative plating It is an object of the present invention to provide an electroless plating pretreatment ink composition capable of expressing

  Another object of the present invention is to provide a partial plating method using the ink composition to suppress the spread of a pattern.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used coating treatment, curing treatment, alkali treatment, and electroless plating by using a specific electroless plating pretreatment ink composition for pattern plating. When processing, it is possible to form a plating film with high electroless plating reactivity, excellent adhesion that can withstand chrome plating, and excellent smoothness that can withstand decorative plating I found.

  The present inventors have further found that by using an ink composition, it is possible to form a partial plating while suppressing the spread of the pattern on the substrate.

  That is, the present invention is the following electroless plating pretreatment ink composition for pattern plating.

Item 1.
The following (1) to (4):
(1) Composite of palladium particles and dispersant
(2) Solvent
(3) Binder
(4) An electroless plating pretreatment ink composition for pattern plating containing nanoparticles.

Item 2.
Item 2. The ink composition according to Item 1, wherein the nanoparticles are inorganic oxides.

Item 3.
Item 3. The ink composition according to Item 1 or 2, wherein the average particle size of the nanoparticles is in the range of 10 to 1,000 nm.

Item 4.
Item 4. The ink composition according to any one of Items 1 to 3, wherein the nanoparticles are silicon dioxide.

Item 5.
Item 5. The ink composition according to any one of Items 1 to 4, wherein the nanoparticles are surface-treated.

Item 6.
Item 6. The ink composition according to any one of Items 1 to 5, wherein the amount of the nanoparticles added is in the range of 0.01 to 100 parts by weight with respect to 1 part by weight of (3) the binder.

Item 7.
The method of forming pattern plating on a base material by performing a coating process, a hardening process, an alkali treatment, and an electroless-plating process using the ink composition in any one of said items 1-6.

Item 8.
An electroless plating film formed by the method according to Item 7.

Item 9.
A molded article on which the electroless plating film according to Item 8 is mounted.

  Using the electroless plating pretreatment ink composition for pattern plating of the present invention (hereinafter also referred to as “ink composition”), coating treatment, curing treatment, alkali treatment, and then electroless plating treatment are performed by a predetermined method. Thus, it is possible to form a film that 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 a partial plating while suppressing the spread of the pattern on the substrate.

  Moreover, the film | membrane formed using the ink composition of this invention is excellent in the effect which relieve | moderates the stress which arises between the base material and plating film by a temperature difference. Usually, when a temperature difference occurs between the resin base material and the plating film, the adhesiveness is reduced due to the stress generated from the difference between the expansion coefficients of the two. However, since the film made of the ink composition of the present invention exists between the base material and the plating film, the stress can be relieved and a decrease in adhesion can be prevented.

  Therefore, the plating film formed using the ink composition of the present invention can maintain high adhesion even when exposed to an environment with a large temperature difference for a long time.

  When the ink composition of the present invention is used, for the purpose of improving the reactivity of electroless plating, treatment such as increasing the reducing agent concentration of electroless plating or raising the reaction temperature is not required. Therefore, the stability of the electroless plating solution can be improved and the plating bath management can be facilitated. When the ink composition is used, an etching process using a harmful substance, a complicated catalyst application process, and the like are not required.

It is a cross-sectional TEM photograph of what carried out the hardening process, the alkali treatment, and the electroless-plating process after masking spray-coating the electroless-plating pretreatment ink composition for pattern plating on the base material. It is a figure which shows the distribution state of the palladium element (Pd particle | grains) in the visual field of FIG. It is a figure which shows the distribution state of the copper element (Cu particle) in the visual field of FIG.

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

[1] Electroless plating pretreatment ink composition for pattern plating The electroless plating pretreatment ink composition for pattern plating of the present invention includes the following (1) to (4):
(1) Composite of palladium particles and dispersant
(2) Solvent
(3) Binder
(4) It contains nanoparticles.

  The “electroless plating pretreatment ink composition for pattern plating” of the present invention is an ink composition comprising the above (1) to (4), and in order to perform pattern plating or partial plating treatment, It is an ink composition used in the pretreatment.

(1) Complex of palladium particles and dispersant The ink composition of the present invention comprises a complex of palladium particles (hereinafter also referred to as “Pd particles”) and a dispersant (hereinafter referred to as “palladium complex”, “Pd complex”). ”).

  The Pd complex can be produced by the following method.

  Palladium ions (hereinafter also referred to as “Pd ions”) supplied from palladium compounds such as palladium chloride (hereinafter also referred to as “Pd compounds”) in the presence of dispersants such as polycarboxylic acid-based polymers, hydrazine hydrates, etc. Can be obtained by reduction with a secondary or tertiary amine.

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

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

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

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

Pd particles The Pd particles can be obtained by reducing Pd ions supplied from a Pd compound using a reducing agent in the presence of a dispersant.

  As the Pd compound for supplying the Pd ions, it is preferable to use palladium chloride, palladium sulfate, palladium nitrate, palladium acetate, palladium benzoate, palladium salicylate, palladium paratoluenesulfonate, palladium perchlorate, palladium benzenesulfonate, or the like. .

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

  As the reducing agent, it is preferable to use secondary or tertiary amines such as hydrazine hydrate (hydrazine monohydrate), sodium borohydride, N, N dimethylethanolamine, diethanolamine and the like.

  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 between the Pd particles and the dispersant in the Pd composite is preferably about Pd particles: dispersant = 35: 65 to 85:15, more preferably about Pd particles: dispersant = 50: 50 to 75:25. .

  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 diameter of the Pd complex is not particularly limited, and as a whole, it preferably has a spherical structure with an average particle diameter of about 10 to 300 nm, more preferably 10 to 100 nm. 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).

(2) Solvent The ink composition of the present invention contains a solvent.

  The solvent (dispersion medium) can disperse the Pd complex. Moreover, the solvent is excellent in affinity with the binder. From the viewpoint that the dispersibility of the Pd complex in the coating composition for electroless plating can be imparted, at least one selected from the group consisting of water and an aprotic polar solvent such as N-methylpyrrolidone is preferred.

  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 Pd ions. For example, the solvent can be converted from water to NMP.

The content of the dispersion solvent of the Pd complex is not particularly limited, and is preferably about 1 × 10 ² to 1 × 10 ⁶ parts by weight with respect to 100 parts by weight of the Pd complex. When the solvent is water, it is preferably 5 × 10 ^{3 to} 3 × 10 ⁵ parts by weight, more preferably 1 × 10 ⁴ to 2 × 10 ⁵ parts by weight with respect to 100 parts by weight of the Pd complex. When the solvent is an aprotic polar solvent, it is preferably 5 × 10 ^{2 to} 5 × 10 ³ parts by weight, more preferably 1 × 10 ^{3 to} 3 × 10 ³ parts by weight with respect to 100 parts by weight of the Pd complex. .

  The solvent further considers the dispersibility of the complex of (1) palladium particles and a dispersant contained in the ink composition, (3) solubility of the binder, and (4) dispersibility of the nanoparticles, etc. Furthermore, it is preferable to select from the viewpoint of the viscosity of the ink composition, the evaporation rate, and the adhesion between the ink composition and the substrate (ABS resin, glass plate, etc.). In order to satisfy these viewpoints, in addition to the solvent used for the dispersion of the Pd complex, another type of solvent can be additionally used.

  Specifically, alcohols such as methanol, ethanol, isopropyl alcohol (IPA), 1-butyl alcohol, isobutyl alcohol; acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, 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, xylene and the like Aromatic hydrocarbons; aliphatic hydrocarbons such as n-hexane, n-heptane, mineral spirit; methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, methyl carbitol acetate, buty Glycol ether esters such as carbitol acetate; ethyl acetate, alkanol esters such as ethyl acetate and butyl acetate; it is preferable to use a 2-phenoxyethanol (ethylene glycol phenyl ether), etc. in addition.

  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 can be used as dilution solvents.

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

(3) Binder The ink composition of the present invention contains a binder.

  The binder is selected so that the electroless plating can be satisfactorily obtained from the viewpoints of the viscosity of the ink composition, the adhesion between the ink composition and the substrate (ABS resin, glass plate, etc.), and the curing conditions. It is preferable. The binder is dispersed or dissolved in the solvent.

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

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

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

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

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

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 Pd composite.

(4) Nanoparticles The ink composition of the present invention contains nanoparticles.

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

  As the nanoparticles, it is preferable to use an inorganic oxide.

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

Among inorganic oxides, it is preferable to use nanoparticles mainly composed of silicon dioxide. Silica is a nanoparticle mainly composed of silicon dioxide (SiO ₂ ). Silica is called silicic anhydride, silicic acid, and silicon oxide in addition to silicon dioxide. Nanoparticles mainly composed of silicon dioxide have high reactivity and adhesion of electroless plating because the nanoparticles themselves are dissolved by alkali treatment.

  Even if the nanoparticles are not dissolved by the alkali treatment, the binder resin swells and dissolves by the alkali treatment by using the binder resin, resulting in a gap between the nanoparticles and the binder. Drops off, so that the same effect as that of nanoparticles dissolved by alkali treatment can be obtained.

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

  The shape of the nanoparticles is not particularly limited. The shape of the nanoparticles is preferably a sphere, a polygon or the like.

  The added amount of nanoparticles is preferably about 0.01 to 100 parts by weight, more preferably about 0.05 to 20 parts by weight, and still more preferably about 0.1 to 3 parts by weight with respect to 1 part by weight of the binder. When the addition amount of the nanoparticles is within the above range, the viscosity of the ink composition is well maintained and the ink composition is easy to apply. Moreover, the adhesiveness of an ink composition and a base material is favorable, and an electroless plating film | membrane is not peeled easily.

  In other words, if the amount of nanoparticles added is too large, the increase in viscosity tends to be too large, making it difficult to apply. In addition, the adhesion between the ink composition and the substrate is lowered, and there is a tendency that the electroless plating film is easily peeled off with a tape. If it is less, the effect of addition cannot 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 particles that do not satisfy the range of the average particle diameter defined in the nanoparticles are included, there is no particular limitation as long as the effects of the present invention are not impaired.

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

  The particle diameter of the nanoparticles can be determined by a dynamic light scattering method or observation with an electron microscope as long as it is approximately 0.1 μm or less depending on the particle diameter range. The particle diameter of the nanoparticles can be determined by a laser diffraction / scattering method if it is approximately 0.1 μm or more.

  The average particle diameter of the nanoparticles measured by the dynamic light scattering method is the harmonic average particle diameter (diameter) based on 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 hardly aggregated, the dispersibility is good, and the handleability of the ink composition is good. Moreover, when the ink composition containing nanoparticles is used, the appearance after plating is good. In other words, particles having an average particle diameter of less than 10 nm have a strong cohesive force and are difficult to disperse, and thus there is a tendency that good handleability of the ink composition cannot be obtained. Further, when nanoparticles having an average particle diameter exceeding 1,000 nm are used in the ink composition, the appearance tends to be inferior when plating is performed using the ink composition.

Surface treatment of nanoparticles The nanoparticles are preferably surface-treated. That is, it is preferable that the ink composition of the present invention contains nanoparticles, which are surface-treated nanoparticles (surface-treated nanoparticles).

  Since the nanoparticles are surface-treated, the nanoparticles are well dispersed and re-aggregation does not occur, and uniform plating can be obtained using the ink composition. In other words, if there is no surface treatment, poor dispersion of particles and reaggregation tend to occur, and there is a tendency that uniform plating is not achieved.

  As the surface treatment of the nanoparticles, both hydrophilic treatment and hydrophobic treatment can be used. The surface treatment of the nanoparticles can be appropriately selected depending on the kind of the solvent and binder contained in the ink composition.

  The surface treatment of the nanoparticles is preferably a hydrophobic treatment since the binder and the solvent are often hydrophobic. As the hydrophobic treatment, a surface treatment using a silane coupling agent is preferable.

  Silane coupling agents used for surface treatment include phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycol. Sidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like are preferably used.

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

  The surface treatment of the nanoparticles (inorganic oxide) can be performed, for example, by adding and spraying the silane coupling agent and stirring for 5 to 15 minutes while stirring and dispersing the untreated inorganic filler at room temperature with a mixer. Can be done. As the mixer, a known mixer can be used. For example, a blender such as a V blender, a ribbon blender or a bubble cone blender, a mixer such as a Henschel mixer or a concrete mixer, a ball mill or the like is preferably used, and a mixer is used. Is 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 This surface can be treated with phenylsilane. The ink composition of the present invention preferably contains nanoparticles whose surfaces are treated with phenylsilane, in other words, nanoparticles whose surfaces are surface-modified with phenylsilane groups and phenylsilane surface-treated nanoparticles.

  The treatment 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 (hydrophobic treatment) with a silane coupling agent.

  The ink composition of the present invention includes nanoparticles (such as silicon dioxide) and surface-treated nanoparticles (such as phenylsilane-treated silica). Using this, by performing a coating process, a curing process, an alkali process, and then an electroless plating process in a predetermined method, the electroless plating has high reactivity, 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 a partial plating while suppressing the spread of the pattern on the substrate.

  Since the ink composition of the present invention contains nanoparticles and surface-treated nanoparticles, a film formed using the ink composition is excellent in reducing the stress generated between the substrate and the plating film due to a temperature difference. . The film is present between the base material and the plating film, so that the stress can be relaxed and a decrease in adhesion can be prevented.

  The plating film formed using the ink composition of the present invention can maintain high adhesion even when exposed to an environment with a large temperature difference for a long time.

[2] Method for producing electroless plating pretreatment ink composition for pattern plating The above (1) composite of Pd particles and dispersant of the present invention, (2) solvent, (3) binder and (4) nanoparticles The ink composition to be contained can be produced by the following method. As described above, Pd particles can be obtained by reducing Pd ions supplied from a Pd compound using a reducing agent in the presence of a dispersant.

That is, the ink composition of the present invention is
(i) (2) In the solvent, Pd ions and a dispersant are present, and the Pd ions are reduced using a reducing agent, (1) a step of producing a complex of Pd particles and a dispersant,
(ii) (2) (4) dispersing nanoparticles in a solvent, then (3) mixing the binder to make a mixture, and
(iii) (2) the solvent obtained in the step (ii), the mixture of the complex of (2) the solvent obtained in the step (i) and (1) the Pd particles and the dispersant, (4) Mixing the nanoparticles and (3) a mixture of binders;
It is preferable to manufacture by the manufacturing method containing.

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

  According to the said manufacturing method, in order to perform pattern plating or partial plating processing, the ink composition used by the pre-processing of electroless plating can be manufactured.

  When the ink composition of the present invention is used, it is possible to form a film that exhibits high electroless plating reactivity, excellent adhesion that can withstand chromium plating, and excellent smoothness that can withstand decorative plating. is there. When the ink composition is used, it is possible to form a partial plating while suppressing the spread of the pattern on the substrate.

  When the ink composition is used, it is not necessary to increase the reducing agent concentration of the electroless plating or increase the reaction temperature in order to improve the reactivity of the electroless plating. When the ink composition is used, an etching process using a harmful substance, a complicated catalyst application process, and the like are not required.

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

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

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

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

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

  Next, Pd ions are reduced by the reducing agent by reacting the Pd ions with the reducing agent. That is, a reduction reaction of Pd ions occurs, and as a result, (1) a complex (Pd complex) of Pd particles and a dispersant can be obtained. As the reducing agent, a reducing agent used for producing the Pd complex 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 Pd compound.

  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 Pd ions (Pd compound), a dispersant and a reducing agent with a bladed stir bar.

  It is preferable that the mixture (Pd complex-containing liquid) containing a complex of a solvent and Pd particles and a dispersant is ultrafiltered to separate the complex of the Pd particles and the dispersant. By this operation, it is possible to remove inorganic salts, excess dispersants, and the like contained in the Pd complex-containing liquid. For example, it is possible to filter the Pd complex-containing liquid and supplement a solvent such as water or NMP. This process can be repeated.

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

Step (ii)
(2) (4) Disperse the nanoparticles in the solvent, and then (3) mix the binder to make a mixture.

  The nanoparticles are dispersed in a solvent (dispersion medium). As the nanoparticles, the aforementioned nanoparticles can be used, and surface-treated nanoparticles are preferably used. 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 (hydrophobic treatment) with a silane coupling agent.

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

  As the binder, the above (3) binder can be used. The binder is used in an amount of 1 to 10,000 with respect to 100 parts by weight of the nanoparticles from the viewpoints of the viscosity of the ink composition, the adhesion between the ink composition and the substrate (ABS resin, glass plate, etc.), and curing conditions. About part by weight is preferred, about 5 to 2,000 parts by weight is more preferred, and about 33 to 1000 parts by weight is even more preferred.

  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 a mixture containing a solvent, nanoparticles and a binder with a bladed stir bar.

Step (iii)
In the mixture of (2) the solvent obtained in the step (i) and (1) the complex of the Pd particles and the dispersant, the (2) solvent obtained in the step (ii), (4) the nanoparticles and (3) Mix the binder mixture.

[3] Method of Forming Pattern Plating Pattern plating can be formed on the substrate by performing coating treatment, curing treatment, alkali treatment and electroless plating treatment using the ink composition of the present invention. Using the ink composition of the present invention, (i) coating the ink composition on the substrate, (ii) volatilizing and / or drying the solvent contained in the ink composition, and (iii) the ink It is preferable that (3) the binder contained in the composition is cured, (iv) the substrate coated with the ink composition is alkali-treated, and (v) the substrate is electrolessly plated.

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

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

  Polyethylene such as polyethylene (PE), polypropylene (PP), polystyrene (PS), polybutadiene, polybutene, polyisoprene, polychloroprene, polyisobutylene, polyisoprene, polymethylpentene (TPX), etc. should be used as the plastic (resin). Is preferred.

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

  As plastic (resin), polyester such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polylactic acid ester; acrylic resin such as polymethyl methacrylate (PMMA); polycarbonate (PC) PC / ABS; Polyvinyl chloride; Polyamide; Polyimide; Polyamideimide; Polyetherimide; Polyacetal; Polyetheretherketone; Cyclic polyolefin having a norbornene skeleton; Polyphenylene sulfide (PPS); It is preferable to use ether; polysulfone; polyethersulfone (PES); phenol; polyphthalamide (PPA); polyarylate.

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

  The shape of the 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, a solvent, a binder, and the like contained in the ink composition can be appropriately selected.

The method for applying the ink composition of the present invention to the application-treated substrate 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 inkjet printing machine, a dispenser, dipping, spraying, a spin coater, a roll coater, a reverse coater, a screen printing machine, and the like. From the viewpoint of masking-less and production efficiency, gravure offset printing, pad printing, and 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 coating method.

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

  When coating with a dispenser, or when spraying 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 intended use, and depends on the viscosity of the ink composition. The film thickness is preferably about 1 to 120 μm, more preferably about 10 to 100 μm, from the viewpoint of satisfactorily applying the ink composition. When the film thickness exceeds 120 μm, the ink composition tends to cause dripping.

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 a curing process is performed. The binder is cured by the curing process.

  A drying process can be performed after apply | coating an ink composition to a base material. 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 ink composition. The temperature of the curing treatment is preferably about 40 to 400 ° C. Moreover, when using a plastic as a base material, it is preferable to set the temperature of a hardening process to about 40-200 degreeC in consideration of the softening temperature of a plastic raw material.

  The film thickness of the 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, 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, the electroless plating reactivity can be obtained, but the plating adhesion tends not to be sufficiently exhibited. When the film thickness exceeds 20 μm, the reaction rate of electroless plating tends to be inferior.

After the solvent contained in the alkali-treated ink composition is volatilized and / or dried and the binder contained in the ink composition is cured, the substrate on which the ink composition is applied is subjected to alkali treatment.

  The outermost nanoparticles that are not coated with the binder component can be dissolved and / or dropped off by alkali treatment. As a result, the nanoparticle layer covered 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 process.

  An ink film can be formed on a substrate by performing a series of treatments using the ink composition of the present invention. The ink film contains a Pd complex. The Pd complex exists in a state of being uniformly dispersed in the coating film. Therefore, electroless plating can be performed more efficiently on the ink film.

Pattern washing can be formed on a substrate by performing electroless plating after washing the ink (composition) film after the electroless plating treatment alkali treatment. The base material on which the ink film is formed comes into contact with a plating solution for depositing a metal, thereby forming an electroless plating film. The ink film formed by the ink composition of the present invention 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. As the 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 from the relationship with the ink film formed by the ink composition of the present invention.

  The plating conditions can follow a conventional method. Since the ink film of the present invention 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 ink pattern. That is, the ink film formed from the ink composition of the present invention 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 treatment, 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 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 a substrate using the ink composition of the present invention is preferably for pattern plating. However, in the present invention, the ink composition of the present invention may be used for entire plating.

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

When an electrolytic copper plating bath is used 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 preferably about 10 to 60 minutes. By this decorating treatment, a deposited film thickness of about 5 to 40 μm can be formed.

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 decorating treatment, a deposited film thickness of about 5 to 20 μm is obtained.

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 decorating treatment, a deposited film thickness of about 5 to 20 μm is obtained.

When a chromium plating bath is used in the decorating 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 decorating treatment, a deposited film thickness of about 0.1 to 0.3 μm is obtained.

[3] Electroless plating film and molded article on which the film is mounted The ink composition of the present invention is applied to a substrate to form an ink film, 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. A molded product (to-be-plated object) on which an electroless plating film is placed has excellent adhesion of the plating film.

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

  When the electroless plating pretreatment ink composition for pattern plating of the present invention is used, in electroless plating for pattern plating on a substrate (plastic (resin) or the like), the electroless plating has high reactivity, and chromium plating Excellent adhesion that can withstand multilayer plating up to the above and excellent smoothness that can withstand decorative plating can be exhibited. In the electroless plating, it is possible to suppress the spread of the pattern and to perform partial plating satisfactorily.

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

  The reason why the ink composition of the present invention has high reactivity of electroless plating and can realize good adhesion that can withstand multilayer plating up to chromium plating is considered to be due to the following principle.

  First, the adhesion mechanism between the base material (plastic or the like) and the ink composition is as follows. The surface of the base material is eroded by the solvent (solvent) component contained in the ink composition of the present invention, the binder component of the ink composition enters the base material, and is mixed with the base material to form a hybrid layer. For example, in the case of an ABS resin, the butadiene rubber contained in the ABS resin dissolves and swells, so that the binder component of the ink composition enters the substrate.

  The mechanism for improving the reactivity and adhesion of electroless plating is as follows. By subjecting the substrate coated with the ink composition of the present invention to an alkali treatment, nanoparticles on the outermost layer not coated with the binder component dissolve and / or fall off. Thereby, the nanoparticle layer thinly covered with the binder component of the surface layer (lower layer of the outermost layer) next to the outermost layer is exposed. As a result, the contact frequency between the electroless plating solution and the Pd particles having a catalytic action of electroless plating contained in the thin binder coating covering the nanoparticle layer increases.

  In addition, due to the alkali treatment, a gap is formed between the nanoparticles and the binder component, a capillary phenomenon occurs in the gap, and the penetration of the plating solution into the ink film is improved, and the Pd particles and the electroless plating solution The frequency of contact increases. Because of this phenomenon, the metal ions in the electroless plating solution are reduced by Pd particles existing deep inside the film from the surface of the ink film, and the reduced metal is deposited from inside the film so as to be rooted. High adhesion between the ink film and the plating film is obtained.

  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) Preparation of a composite of palladium particles (Pd particles) and a dispersant
To a 3 L flask, 944.5 g of ion exchange water and 5.0 g of palladium nitrate were added and stirred to prepare an aqueous solution of palladium nitrate. To the aqueous solution, 3.8 g of a block copolymer type polymer dispersant having a carboxyl group (DISPERBYK194, manufactured by Big Chemie Japan, non-volatile content 53 wt%) was further added and dissolved.

  The solution was heated to 42 ° C., and 10.0 g of hydrazine monohydrate was added with stirring. Thereafter, the solution was stirred at room temperature (23 ° C.) for 1 hour. The temperature of the solution rose to 53 ° C. after the addition of hydrazine monohydrate, but the temperature of the solution after stirring for 1 hour was 40 ° C.

  By this operation, palladium ions (Pd ions) in the aqueous solution were reduced. This solution is separated by ultrafiltration filter AHP-1010 (manufactured by Asahi Kasei Co., Ltd.), and the reduced Pd complex-containing liquid and the inorganic salt-containing liquid are separated, and the Pd complex (composite of Pd particles and dispersant) is separated. Body) -containing liquid was obtained.

  The Pd complex-containing liquid was rotated with a centrifuge at a rotation speed of 13,000 G load for 16 hours to precipitate the solid content. After removing the supernatant by decantation, N-methylpyrrolidone (NMP) in the same weight as the removed supernatant was added. This operation was repeated several times to obtain a composite of Pd particles and a dispersing agent using NMP as a dispersion medium.

(2) Examples and comparative examples
Example 1: Preparation of electroless plating pretreatment ink composition 1
To 14 parts by weight of 2-phenoxyethanol, 1.9 parts by weight of silica having an average particle diameter of 50 nm (Admanex Admanano YA050C-SP3) treated with phenylsilane as nanoparticles was added, and stirred and dispersed with a spoon (small).

  Add 5 parts by weight of the epoxy resin solution (solid content: 22% by weight) as a binder component and 1 part by weight of the composite of the Pd particles and the dispersant to the nanoparticle dispersion solution, and shaken and stir before electroless plating. A treated ink composition was prepared. This ink composition was used for gravure offset printing.

Gravure offset printing
The electroless plating pretreatment ink composition was subjected to gravure offset printing on a flat plate produced by injection molding using ABS resin (UMG ABS 3001M) as a raw material. For gravure offset printing, a small printing tester (F1 made by IGT) was used, and four strip-shaped patterns having a width of 10 mm and a length of 120 mm were printed on the flat plate. Thus, an electroless plating pretreatment ink application sample 1 was obtained.

Example 2: Preparation of electroless plating pre-treatment ink composition 2 Silica with an average particle diameter of 50 nm treated with vinylsilane as nanoparticles (Admanano YA050C-SV2 manufactured by Admatechs) 1.9 wt. Part was added and steered with a spoon (small) to disperse.

  To the nanoparticle dispersion solution, 5 parts by weight of an epoxy resin solution (solid content: 22% by weight) as a binder component and 1 part by weight of a composite of the Pd particles and a dispersant are added, and the mixture is shaken and stirred, and electroless plating pretreatment An ink composition was prepared. This ink composition was used for gravure offset printing.

Gravure offset printing Sample 2 for electroless plating pretreatment ink application was obtained in the same manner as in Example 1.

Example 3: Preparation of electroless plating pre-treatment ink composition 3 Silica with an average particle diameter of 50 nm treated with phenylsilane as nanoparticles (Admanano YA050C-SP3 manufactured by Admatechs) 1.9 in 14 parts by weight of diacetone alcohol (DAA) A part by weight was added and steered with a spoon (small) to disperse.

  Add 5 parts by weight of the epoxy resin solution (solid content 22% by weight) as a binder component and 1 part by weight of the composite of the Pd particles and the dispersant to the nanoparticle dispersion solution, and shaken and stir. A treated ink composition was prepared. To this ink composition, diacetone alcohol was additionally added to reduce the viscosity of the ink composition, which was used for spray coating.

Masking spray painting
The electroless plating pretreatment ink was spray-coated on a flat plate made by injection molding using ABS resin (UMG ABS 3001M) as a raw material. For spray coating, a commercially available air spray gun was used to coat the sample that had been masked so that four strip-shaped patterns having a width of 10 mm and a length of 120 mm were obtained on the flat plate. Thus, an electroless plating pretreatment ink application sample 3 was obtained.

Comparative Example 1: Preparation of electroless plating pretreatment ink composition
To 14 parts by weight of 2-phenoxyethanol, add 5 parts by weight of an epoxy resin solution (solid content of 22% by weight) as a binder component and 1 part by weight of a composite of the above Pd particles and a dispersing agent. A plating pretreatment ink composition was prepared. This ink composition was used for gravure offset printing.

Gravure offset printing Sample 4 for electroless plating pretreatment ink application was obtained in the same manner as in Example 1.

  Sample 4 does not contain nanoparticles.

Comparative Example 2: Preparation of electroless plating pretreatment ink composition 14 parts by weight of diacetone alcohol (DAA), 5 parts by weight of an epoxy resin solution (solid content 22% by weight) as a binder component, the Pd particles and the dispersant 1 part by weight of the above composite was added and shaken and stirred to prepare an electroless plating pretreatment ink composition. To this ink composition, diacetone alcohol was additionally added to reduce the viscosity of the ink composition, which was used for spray coating.

Masking spray coating Sample 5 for electroless plating pretreatment ink application was obtained in the same manner as in Example 3.

  Sample 5 does not contain nanoparticles.

Example 4: Preparation of electroless plating pretreatment ink composition 4
To 14 parts by weight of 2-phenoxyethanol, 1.9 parts by weight of silica having an average particle diameter of 10 nm (Admanex Admanano YA010C-SP3) treated with phenylsilane as nanoparticles was added and stirred and dispersed with a spoon (small).

  Add 5 parts by weight of the epoxy resin solution (solid content: 22% by weight) as a binder component and 1 part by weight of the composite of the Pd particles and the dispersant to the nanoparticle dispersion solution, and shaken and stir before electroless plating. A treated ink composition was prepared. This ink composition was used for gravure offset printing.

Gravure offset printing Sample 6 for electroless plating pretreatment ink application was obtained in the same manner as in Example 1.

Example 5: Preparation of electroless plating pretreatment ink composition 5
To 14 parts by weight of 2-phenoxyethanol, 1.9 parts by weight of silica having an average particle diameter of 100 nm (Admanex Admanano YA100C-SP3) treated with phenylsilane as nanoparticles was added and stirred and dispersed with a spoon (small).

  Add 5 parts by weight of the epoxy resin solution (solid content: 22% by weight) as a binder component and 1 part by weight of the composite of the Pd particles and the dispersant to the nanoparticle dispersion solution, and shaken and stir before electroless plating. A treated ink composition was prepared. This ink composition was used for gravure offset printing.

Gravure offset printing Sample 7 for electroless plating pretreatment ink application was obtained in the same manner as in Example 1.

Example 6: Preparation of electroless plating pretreatment ink composition 6
To 14 parts by weight of 2-phenoxyethanol, 1.9 parts by weight of silica treated with phenylsilane as an average particle diameter of 0.5 μm (Admafine SC2500-SPJ manufactured by Admatechs) was added and stirred and dispersed with a small spoon. .

  Add 5 parts by weight of the epoxy resin solution (solid content: 22% by weight) as a binder component and 1 part by weight of the composite of the Pd particles and the dispersant to the nanoparticle dispersion solution, and shaken and stir before electroless plating. A treated ink composition was prepared. This ink composition was used for gravure offset printing.

Gravure offset printing Sample 8 for electroless plating pretreatment ink application was obtained in the same manner as in Example 1.

Example 7: Preparation of electroless plating pretreatment ink composition 7
To 14 parts by weight of 2-phenoxyethanol, 1.9 parts by weight of alumina treated with phenylsilane as an average particle diameter of 0.6 μm (Admatech Admafine AC2500-SPM) was added, and the mixture was stirred and dispersed with a small spoon. .

  Add 5 parts by weight of the epoxy resin solution (solid content: 22% by weight) as a binder component and 1 part by weight of the composite of the Pd particles and the dispersant to the nanoparticle dispersion solution, and shaken and stir before electroless plating. A treated ink composition was prepared. This ink composition was used for gravure offset printing.

Gravure offset printing In the same manner as in Example 1, an electroless plating pretreatment ink application sample 9 was obtained.

Example 8: Preparation of electroless plating pretreatment ink composition 8 To the ink composition of Example 3, additional diacetone alcohol was added to reduce the viscosity of the ink composition, which was used for spray coating.

Masking spray coating A commercially available glass plate was spray-coated with the electroless plating pretreatment ink. For spray coating, a commercially available air spray gun was used to coat a sample that had been masked so that four strip-shaped patterns having a width of 10 mm and a length of 120 mm were obtained on the glass plate. Thus, an electroless plating pretreatment ink application sample 10 was obtained.

Example 9: Preparation of electroless plating pretreatment ink composition 9 To 14 parts by weight of cyclohexanone, 1.9 parts by weight of silica having an average particle size of 50 nm treated with phenylsilane as nanoparticles (Admanex ADM050 Nano-YA050C-SP3) was added, Stir with a spoon (small) and disperse.

  To the nanoparticle dispersion solution, 5 parts by weight of a polyolefin resin (solid content 35 wt%) as a binder component and 1 part by weight of a composite of the Pd particles and a dispersant are added, and the mixture is shaken and stirred, and electroless plating pretreatment ink composition A product was made. To this ink composition, cyclohexanone was additionally added to reduce the viscosity of the ink composition, which was used for spray coating.

Masking spray painting
The electroless plating pretreatment ink was spray-coated on a flat plate produced by injection molding using TSOP resin (manufactured by Nippon Polypro and Prime Polymer) as a raw material. For spray coating, a commercially available air spray gun was used to coat the sample that had been masked so that four strip-shaped patterns having a width of 10 mm and a length of 120 mm were obtained on the flat plate. Thus, an electroless plating pretreatment ink application sample 11 was obtained.

  TSOP resin: Toyota Super Olefin Polymer. Thermoplastic resin with improved recyclability compared to conventional composite PP (polypropylene).

Example 10: Preparation of electroless plating pretreatment ink composition 10 Addition of diacetone alcohol (DAA) to the electroless plating pretreatment ink for gravure offset printing in Example 7 to reduce the viscosity of the ink composition Used for spray coating.

Masking spray coating Sample 12 for electroless plating pretreatment ink application was obtained in the same manner as in Example 3.

Example 11: Preparation of electroless plating pretreatment ink composition 11 Silica with an average particle diameter of 50 nm treated with phenylsilane as nanoparticles (Admanano YA050C-SP3 manufactured by ADMATEX) 0.9 in 14 parts by weight of diacetone alcohol (DAA) A weight part was added, and it stirs and disperses with a spoonful (small).

  Add 5 parts by weight of the epoxy resin solution (solid content 22% by weight) as a binder component and 1 part by weight of a composite of Pd particles and a dispersant to the nanoparticle dispersion solution, and shake and agitate to prepare a pretreatment for electroless plating. An ink composition was prepared. To this ink composition, diacetone alcohol was additionally added to reduce the viscosity of the ink composition, which was used for spray coating.

Masking spray coating In the same manner as in Example 3, an electroless plating pretreatment ink application sample 13 was obtained.

Example 12: Preparation of electroless plating pretreatment ink composition 12 Silica with an average particle size of 50 nm treated with phenylsilane as nanoparticles (Admanano YA050C-SP3 manufactured by ADMATEX) 3.8 in 14 parts by weight of diacetone alcohol (DAA) A weight part was added, and it stirs and disperses with a spoonful (small).

  Add 5 parts by weight of the epoxy resin solution (solid content 22% by weight) as a binder component and 1 part by weight of a composite of Pd particles and a dispersant to the nanoparticle dispersion solution, and shake and agitate to prepare a pretreatment for electroless plating. An ink composition was prepared. To this ink composition, diacetone alcohol was additionally added to reduce the viscosity of the ink composition, which was used for spray coating.

Masking spray coating Sample 14 for electroless plating pretreatment ink application was obtained in the same manner as in Example 3.

Example 13: Preparation of electroless plating pretreatment ink composition 13 The electroless plating pretreatment ink for gravure offset printing of Example 1 was used.

Pad printing
The electroless plating pretreatment ink was pad printed on a flat plate produced by injection molding using ABS resin (UMG ABS 3001M) as a raw material. For pad printing, a pad printing machine (Navitas T-5) was used, and four strip-shaped patterns having a width of 10 mm and a length of 120 mm were transferred to the flat plate. Thus, an electroless plating pretreatment ink application sample 15 was obtained.

Example 14: Preparation of electroless plating pretreatment ink composition 14 The electroless plating pretreatment ink for gravure offset printing of Example 1 was used.

Gravure offset printing In the same manner as in Example 1, an electroless plating pretreatment ink application sample 16 was obtained.

Example 15: Preparation of electroless plating pretreatment ink composition 15 To the ink composition of Example 3, additional diacetone alcohol was added to reduce the viscosity of the ink composition, which was used for spray coating.

Masking spray coating In the same manner as in Example 3, an electroless plating pretreatment ink application sample 17 was obtained.

Example 16: Preparation of electroless plating pretreatment ink composition 16 The electroless plating pretreatment ink for gravure offset printing of Example 1 was used.

Dispenser painting
The electroless plating pretreatment ink composition was drawn by a dispenser on a flat plate produced by injection molding using ABS resin (UMG ABS 3001M) as a raw material. The dispenser used a small tester (manufactured by Musashi Engineering Co., Ltd.) and drawn four strip-shaped patterns with a width of 10 mm and a length of 100 mm on the flat plate. Thus, an electroless plating pretreatment ink application sample 18 was obtained.

Example 17: Preparation of electroless plating pretreatment ink composition 17 The electroless plating pretreatment ink for gravure offset printing of Example 1 was used.

Dispenser painting
The electroless plating pretreatment ink composition was drawn by a dispenser on a flat plate produced by injection molding using ABS resin (UMG ABS 3001M) as a raw material. The dispenser used a small tester (manufactured by Musashi Engineering Co., Ltd.) and drawn four strip-shaped patterns with a width of 10 mm and a length of 100 mm on the flat plate. Thus, an electroless plating pretreatment ink application sample 19 was obtained.

Example 18: Preparation of electroless plating pretreatment ink composition 18 The electroless plating pretreatment ink for gravure offset printing of Example 1 was used.

Pad printing
The electroless plating pretreatment ink was pad-printed on a flat plate produced by injection molding using ABS resin (TM-25M manufactured by UMG ABS) as a raw material. For pad printing, a pad printing machine (Navitas T-5) was used, and four strip-shaped patterns having a width of 10 mm and a length of 120 mm were transferred to the flat plate. Thus, an electroless plating pretreatment ink application sample 20 was obtained.

Example 19: Preparation of electroless plating pretreatment ink composition 19 The electroless plating pretreatment ink for gravure offset printing of Example 1 was used.

The electroless plating pretreatment ink was pad-printed on a flat plate produced by injection molding using a pad-printed polyetherimide resin (ULTEM1010 manufactured by SABIC) as a raw material. For pad printing, a pad printing machine (Navitas T-5) was used, and four strip-shaped patterns having a width of 10 mm and a length of 120 mm were transferred to the flat plate. Thus, an electroless plating pretreatment ink application sample 21 was obtained.

Example 20: Preparation of electroless plating pretreatment ink composition 20 The electroless plating pretreatment ink for gravure offset printing of Example 1 was used.

Pad printing
The electroless plating pretreatment ink was pad-printed on a flat plate produced by injection molding using PC / ABS resin (Iupilon PL-2010 manufactured by Mitsubishi Engineering Plastics) as a raw material. For pad printing, a pad printing machine (Navitas T-5) was used, and four strip-shaped patterns having a width of 10 mm and a length of 120 mm were transferred to the flat plate. Thus, an electroless plating pretreatment ink application sample 22 was obtained.

Example 21: Preparation of electroless plating pretreatment ink composition 21 The electroless plating pretreatment ink for gravure offset printing of Example 1 was used.

The electroless plating pretreatment ink was pad printed on a flat plate produced by injection molding using a pad printing polycarbonate resin (Carboglass manufactured by Asahi Glass Co., Ltd.) as a raw material. For pad printing, a pad printing machine (Navitas T-5) was used, and four strip-shaped patterns having a width of 10 mm and a length of 120 mm were transferred to the flat plate. Thus, an electroless plating pretreatment ink application sample 23 was obtained.

Example 22: Preparation of electroless plating pretreatment ink composition 22 The electroless plating pretreatment ink for gravure offset printing of Example 1 was used.

Pad printing
The electroless plating pretreatment ink was pad printed on a flat plate produced by injection molding using AES resin (HATGABS HAT550) as a raw material. For pad printing, a pad printing machine (Navitas T-5) was used, and four strip-shaped patterns having a width of 10 mm and a length of 120 mm were transferred to the flat plate. Thus, an electroless plating pretreatment ink application sample 24 was obtained.

(3) Evaluation item 1: Evaluation of electroless plating reactivity (plating film formation)
The obtained electroless plating pretreatment ink application samples of Examples 1, 2, 4-7, 13-15, 16-22, and Comparative Example 1 were put into a shelf dryer, and dried at 80 ° C. for 60 minutes. And a curing treatment was performed.

  The obtained electroless plating pretreatment ink coating samples of Examples 3, 8 to 12 and Comparative Example 2 were set at room temperature for 5 minutes, and then placed in a shelf-type dryer, followed by drying treatment and curing treatment at 80 ° C. for 60 minutes. Went.

  Thereafter, the electroless plating pretreatment ink application sample was immersed in an alkali treatment liquid adjusted to pH 11 to 14 and heated to 60 ° C. for 3 minutes. Thereafter, it was washed with city water and replaced with ion-exchanged water.

  Next, whether or not the plating film is deposited by immersing the electroless plating pretreatment ink coating samples of Examples 1 to 13, 16, 18 to 22, and Comparative Examples 1 to 4 in an electroless copper plating bath Evaluated.

  Whether or not the plating film was deposited was evaluated by immersing the electroless plating pretreatment ink-coated samples of Examples 14, 15, and 17 in an electroless nickel plating bath.

  As the electroless copper plating bath, OPC Copper HFS manufactured by Okuno Pharmaceutical Co., Ltd. (initial Cu concentration 2.5 g / L, bath volume 500 mL, 40 ° C., 20 minutes) was used.

  As the electroless nickel plating bath, chemical nickel EXC manufactured by Okuno Pharmaceutical Co., Ltd. (initial Ni concentration 5.0 g / L, bath volume 500 mL, 40 ° C., 5 minutes) was used.

The evaluation criteria for electroless plating reactivity are as follows.
○: Plating is deposited on the entire coating pattern within 3 minutes after immersion.
(Triangle | delta): It is what the plating deposited on the coating pattern partially.
X: Those that did not react at all, or those that stopped after plating deposition of 1/10 or less of the coating pattern area.

  In Comparative Example 3, the electroless plating pretreatment ink application sample 1 was subjected to the same treatment as the drying step, and the electroless plating treatment was performed without performing the alkali treatment.

  FIG. 1 is a cross-sectional TEM photograph of a substrate subjected to an electroless plating pretreatment ink composition for pattern plating after masking spray coating, followed by curing treatment, alkali treatment and electroless plating treatment.

  FIG. 2 is a diagram showing a distribution state of palladium element (Pd particles) in the visual field of FIG.

  FIG. 3 is a diagram showing a distribution state of copper elements (Cu particles) in the visual field of FIG.

  1 to 3, it was confirmed that the metal ions of the electroless plating solution were reduced by the Pd particles existing deep from the surface of the ink film, and the metal ions were deposited so as to be rooted.

(4) Evaluation item 2: Evaluation of pattern forming ability The evaluation standard of pattern forming ability is as follows.
○: For gravure offset printing or pad printing, the width dimension accuracy of the electroless plating film is ± 0.1 mm (accuracy of 1/100 of the plate pattern) with respect to the width dimension of the plate pattern.
Δ: For gravure offset printing or pad printing, the width dimension accuracy of the electroless plating film is ± 0.5 mm (accuracy 1/20 of the plate pattern) with respect to the width dimension of the plate pattern.
X: In the case of gravure offset printing or pad printing, the width dimension accuracy of the electroless plating film exceeds the range with respect to the width dimension of the plate pattern.

  About what was (triangle | delta) by evaluation of the said pattern formation ability, it evaluated using the location where a width pattern is observed firmly. A KEYENCE microscope (KEYENCE VHX-1000) was used to check the dimensions.

  Comparative Example 4 uses the electroless plating pretreatment ink application sample 4 (Comparative Example 1 sample), performs the drying step and the alkali treatment, and adds the reducing agent to the electroless copper plating bath twice the predetermined concentration. The electroless plating treatment was added in an amount. Sample 4 does not contain nanoparticles.

(5) Evaluation item 3: Whether or not to achieve chrome plating After electroless plating treatment, if it is electroless copper plating, electrolytic copper (Cu) plating, semi-bright nickel, bright nickel, and chromium (Cr) plating are sequentially performed. In which process the plating was peeled off.

  In the case of electroless nickel plating, after strike copper plating, chrome plating was sequentially performed in the same process as electroless copper plating, and it was evaluated in which process the plating was peeled off.

The evaluation criteria for the achievement up to chromium (Cr) plating are as follows.
○: Reached chrome plating.
X: Detachment with electrolytic copper or nickel in the middle.

  As the electroless copper plating bath, OPC Copper HFS manufactured by Okuno Pharmaceutical Co., Ltd. (initial Cu concentration 2.5 g / L, bath volume 500 mL, 40 ° C., 20 minutes) was used.

  As the electroless nickel bath, Okuno Pharmaceutical Co., Ltd. Chemical Nickel EXC (initial Ni concentration 5.0 g / L, bath volume 500 mL, 40 ° C., 20 minutes) was used.

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

As the electrolytic copper (Cu) plating bath, a bath temperature of 30 ° C. and a current density of 1.5 A / dm ² were used.

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

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

As the chromium plating bath, a bath temperature of 45 ° C. and 12 A / dm ² was used.

(6) Evaluation item 4: Peel strength of multilayer plating film up to chrome plating The sample reaching the chromium (Cr) plating in the above evaluation item 3 was evaluated for peel strength by the 180 ° peel test method.

  The pattern-plated multilayer plating film having a width of 10 mm was peeled off, and one end thereof was held by a tension jig of a tensile tester (Strograph V10-C manufactured by Toyo Seiki Seisakusho). A tensile test was conducted at a test speed of 5 mm / min, with the other side of the pattern-plated multilayer plating film held on another tensile jig. The maximum load was defined as peel strength.

  In addition, all the samples that reached the chrome plating had the same luster as the pretreatment method in which the conventional chromic acid etching was performed, and no cloudiness was observed.

(7) Evaluation item 5: Peel strength before and after heat treatment of the electric Cu plating film The sample that reached the electric Cu plating in the evaluation item 3 was evaluated for peel strength by the 90 ° peel test method. Further, the sample after measurement was left at 80 ° C. for 5 hours, and the peel strength was evaluated again. This test evaluated the adhesion before and after the heat treatment.

○: No decrease in adhesion is observed after heat treatment.
X: Decrease in adhesion is observed after heat treatment. Or peeling occurs.

  The results are shown in Tables 1 to 3 below.

Claims (5)

The following (1) to (4):
(1) Composite of palladium particles and dispersant
(2) Solvent
(3) Binder
(4) Nanoparticles are contained, the nanoparticles are surface-treated, and the amount of the nanoparticles added is in the range of 0.01 to 100 parts by weight with respect to 1 part by weight of the binder (3) ,
Electroless plating pretreatment ink composition for pattern plating.   The ink composition according to claim 1, wherein the nanoparticles are inorganic oxides.   The ink composition according to claim 1 or 2, wherein the average particle diameter of the nanoparticles is in the range of 10 to 1,000 nm.   The ink composition according to claim 1, wherein the nanoparticles are silicon dioxide. The method of forming pattern plating on a base material by performing an application | coating process, a hardening process, an alkali treatment, and an electroless-plating process using the ink composition in any one of Claims 1-4 .