Classifications

• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
  • C25D5/54—Electroplating of non-metallic surfaces
  • C25D5/56—Electroplating of non-metallic surfaces of plastics
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/24—Electrically-conducting paints

Definitions

• the present invention relates to a primer composition for electrolytic plating, a method for producing a plated product using the primer composition for electrolytic plating, and a plated product produced by this production method.
• circuit component As a circuit component constituting an electronic component, a circuit component in which a conductor layer (circuit) made of copper or the like is formed on the surface of an insulating base made of resin or ceramic is widely known. At the time of manufacture, a conductor layer is formed by using an electrolytic plating method.
• a conductor layer when a conductor layer is formed by using an electrolytic plating method, the conductor layer cannot be formed directly on the surface of the insulating base material.
• a thin conductor film is formed using an electroless plating method, and then a conductor layer is formed using an electrolytic plating method.
• a metal catalyst such as palladium is supported on the insulating base material on the surface of the insulating base material that has been previously roughened, and the access is made. It is necessary to perform electroless plating after activating the metal catalyst supported on the surface of the insulating base material by a radiator or the like. For this reason, the method of forming a conductive layer by electroless plating on an insulating substrate requires many processing steps, and there are problems such as a limited number of substrates on which the catalyst can be supported.
• a conductive polymer layer is formed on the surface of the base material to impart conductivity to the base material surface, and an electroplating process is performed directly on the conductive polymer layer, thereby A method of forming an electrolytic plating layer on the material surface has been proposed (see, for example, Patent Documents 1 and 2).
• Patent Documents 1 and 2 have poor adhesion between the base material and the electrolytic plating layer, and there is a problem that peeling easily occurs between the two.
• the present invention provides a primer composition for electroplating for forming a substrate and a conductive primer layer having excellent adhesion to the electroplating layer, and uses the primer composition for electroplating. It is an object to provide a method for producing a plated product and a plated product.
• a composition containing a conductive polymer and a specific component is extremely suitable as a primer for electrolytic plating.
• a conductive primer layer is formed on the surface of the substrate using the composition having the above-described structure, and an electrolytic plating layer is formed starting from this conductive primer layer, the substrate, the conductive primer layer, and Since the adhesiveness of each layer of the electroplating layer is excellent, the above composition was found to be extremely suitable as a primer for electroplating, and the present invention was completed.
• the primer composition for electrolytic plating of the present invention is (A) a conductive polymer; (B) It contains at least one component selected from the group consisting of acrylic monomers, acrylic oligomers, acrylic resins, epoxy resins, urethane resins and ester resins.
• the component (b) is preferably a compound containing two or more acrylic groups or epoxy groups in the molecule.
• the blending amount of the component (b) is preferably 10 to 1500 parts by mass with respect to 100 parts by mass of the conductive polymer (a).
• the (a) conductive polymer is preferably a conductive polymer containing at least one thiophene ring in the molecule, poly (3,4-disubstituted thiophene), Alternatively, a complex of poly (3,4-disubstituted thiophene) and a polyanion is more preferable. Furthermore, the poly (3,4-disubstituted thiophene) is particularly preferably polyethylene dioxythiophene.
• the manufacturing method of the plated product of the present invention includes: (1) A step of forming a conductive primer layer (B) on part or all of the surface of the substrate (A) using the primer composition for electrolytic plating of the present invention, and (2) forming an electroplating layer (C) by electroplating on the conductive primer layer (B); It is characterized by going through.
• the substrate (A) is preferably a resin substrate, a glass substrate, or a ceramic substrate.
• the material resin of the resin base is epoxy resin, polyacetal, polyamide, polyphthalamide, polycarbonate, modified polyphenylene ether, polybutylene terephthalate, syndiotactic polystyrene, polyacrylate, polysulfone, polyethersulfone, polyphenylene sulfide.
• the method further includes a step of pre-treating the substrate (A).
• the plated product of the present invention is manufactured using the method for manufacturing a plated product of the present invention, and the plated product is preferably a circuit component, an electromagnetic wave shielding member, or a decorative product.
• the primer composition for electrolytic plating of the present invention contains at least (a) a conductive polymer and (b) a specific component, an electrolytic plating layer having excellent adhesion to the substrate is formed on the surface of the substrate. Therefore, it is suitable as a primer for electrolytic plating. Further, in the method for producing a plated product of the present invention, a conductive primer layer is formed using the primer composition for electrolytic plating of the present invention, so that a plated product having an electrolytic plated layer with excellent adhesion on the substrate surface is formed. Can be manufactured. Furthermore, since the plated product of the present invention is manufactured using the method for manufacturing a plated product of the present invention, the adhesion of each layer of the conductive primer layer, the substrate and the electrolytic plating layer is excellent.
• the primer composition for electrolytic plating of the present invention is (A) a conductive polymer; (B) It contains at least one component selected from the group consisting of acrylic monomers, acrylic oligomers, acrylic resins, epoxy resins, urethane resins and ester resins.
• the primer composition for electrolytic plating of the present invention comprises (a) a conductive polymer and (b) component as essential components, and in particular, it is important to contain a specific compound as component (b). Therefore, first, the component (b) will be described among the constituent components of the electrolytic plating primer composition.
• the component (b) is a component that functions as a binder when the conductive primer layer is formed using the primer composition for electrolytic plating of the present invention. May function as a binder as it is, or may function as a binder after undergoing a polymerization reaction or a crosslinking reaction (curing reaction).
• the component (b) is at least one selected from the group consisting of acrylic monomers, acrylic oligomers, acrylic resins, epoxy resins, urethane resins and ester resins. Since the above-mentioned primer composition for electrolytic plating contains such a specific component, it has excellent characteristics when used as a primer for electrolytic plating, that is, excellent adhesion to the substrate and the electrolytic plating layer. .
• (B-1) Acrylic monomer, acrylic oligomer, acrylic resin
• the above-mentioned acrylic monomer refers to a monomer component that is polymerized to become an acrylic resin described later. If it does not specifically limit.
• the acrylic oligomer is not particularly limited as long as it is a polymer obtained by polymerizing the acrylic monomer and further polymerizes to become an acrylic resin described later.
• the acrylic oligomer is one having a relatively low molecular weight, but the molecular weight is not limited.
• acrylic resins examples include (meth) acrylic resins and vinyl ester resins.
• acrylic resins for example, a polymer containing a polymerizable monomer having an acid group such as a carboxyl group, an acid anhydride group, a sulfonic acid group, or a phosphoric acid group as a constituent monomer may be used.
• examples thereof include a single or copolymer of a polymerizable monomer having a group, a copolymer of a polymerizable monomer having a acid group and a copolymerizable monomer, and the like.
• the (meth) acrylic resin may contain a (meth) acrylic monomer as a main constituent monomer (for example, 50 mol% or more). It is sufficient that at least one of the monomers has an acid group.
• a (meth) acrylic resin for example, a (meth) acrylic monomer having the above acid group [(meth) acrylic acid, sulfoalkyl (meth) acrylate, sulfonic acid group-containing (meth) acrylamide, etc.) alone Or a copolymer, the (meth) acrylic monomer optionally having an acid group and another polymerizable monomer having an acid group [other polymerizable carboxylic acid, polymerizable polyvalent carboxylic acid or Anhydride, vinyl aromatic sulfonic acid, etc.] and / or the above copolymerizable monomers [e.g., (meth) acrylic acid alkyl ester, glycidyl (meth) acrylate, (meth) acrylonitrile, aromatic vinyl
• a polymer containing at least (meth) acrylic acid for example, (meth) acrylic acid- (meth) acrylic acid ester polymer (acrylic acid-methyl methacrylate copolymer, etc.) (Meth) acrylic acid- (meth) acrylic acid ester-styrene copolymer (acrylic acid-methyl methacrylate-styrene copolymer, etc.) and the like are preferable.
• Epoxy resin may be a compound having two or more epoxy groups in the molecule.
• an epoxy resin that is water-soluble and soluble in a mixed solvent of alcohol can be suitably used.
• sorbitol glycidyl ether polyglycerol glycidyl ether, pentaerythritol glycidyl ether, diglycerol glycidyl ether, trimethylolpropane glycidyl ether, Resorcinol glycidyl ether, neopentyl glycidyl ether, hexanediol diglycidyl ether, ethylene glycidyl ether, propylene glycidyl ether, allyl glycidyl ether, ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol glycidyl ether, tert-butyl glycidyl ether, lauryl alcohol glycidyl
• the urethane resin is a polymer compound obtained by copolymerizing a compound having an isocyanate group and a compound having a hydroxyl group.
• a compound having an isocyanate group for example, an ester / ether polyurethane, an ether polyurethane, a polyester polyurethane, Carbonate polyurethane, acrylic polyurethane and the like are preferably used.
• ester resin is a polymer compound obtained by polycondensation of a compound having two or more carboxyl groups in the molecule and a compound having two or more hydroxyl groups, such as polyethylene terephthalate.
• polyethylene terephthalate Polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate and the like are preferably used.
• the primer composition for electrolytic plating of this invention may contain these (b) components independently, and may contain 2 or more types.
• a compound containing two or more acrylic groups or epoxy groups in the molecule is particularly preferable.
• a compound having two or more acrylic groups or epoxy groups in the molecule is blended in the primer composition for electrolytic plating, and then a layer made of the primer composition for electrolytic plating is formed.
• a conductive primer layer having a crosslinked structure in the molecule can be formed.
• the electrolytic plating layer is formed on the conductive primer layer by electrolytic plating, the conductive primer layer is in a state where the plating metal and the primer composition for electrolytic plating are mixed.
• the film strength of the conductive primer layer is weak, the plating metal aggregates in the conductive primer layer during electrolytic plating, and the conductive primer layer is destroyed. If it grows to the point, the conductive primer layer itself is destroyed, and the electrolytic plating layer and the substrate cannot be adhered.
• the conductive primer layer has a cross-linked structure, aggregation of the plating metal is suppressed, abnormal growth does not occur, and the plating metal and the primer composition for electrolytic plating are mixed appropriately in the conductive primer layer. As a result, the electroplating layer and the conductive primer layer can be adhered, and therefore the electroplating layer and the substrate can be adhered.
• the compound containing two or more acrylic groups or epoxy groups in the molecule may itself be crosslinked to function as a binder, or may be crosslinked and function as a binder after polymerization or with polymerization. It may be.
• the compound having two or more acrylic groups or epoxy groups in the molecule include, for example, U-4HA (manufactured by Shin-Nakamura Chemical Co., Ltd.), U-6HA (manufactured by Shin-Nakamura Chemical Co., Ltd.) U-6LPA ( Shin-Nakamura Chemical Co., Ltd.), UA-1100 (Shin-Nakamura Chemical Co., Ltd.), UA-53H (Shin-Nakamura Chemical Co., Ltd.), U-33H (Shin-Nakamura Chemical Co., Ltd.), U-2000 (Shin Nakamura) Chemical Industry Co., Ltd.), UA-4200 (Shin Nakamura Chemical Co., Ltd.), U-122P (Shin Nakamura Chemical Co., Ltd.), UA-7100 (Shin Nakamura Chemical Co., Ltd.), UA-7200 (Shin Nakamura Chemical Co., Ltd.) NK OLIGO UA-W2A (Shin Nakamura Chemical Co.
• the conductive property is within a range that does not impair the characteristics of the present invention. It may further contain other components that improve the adhesion between the adhesive primer layer and the substrate and / or the electrolytic plating layer.
• other components include compounds having one epoxy group, homopolymers such as polyvinyl acetate, polyvinylidene chloride, polyamide, and polyimide; and obtained by copolymerizing monomers such as styrene, vinylidene chloride, and vinyl chloride.
• Copolymers include alkoxysilane compounds such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
• the content of the component (b) is not particularly limited, but is preferably 10 to 1500 parts by mass with respect to 100 parts by mass of the conductive polymer (a) in terms of solid content.
• the strength of the conductive primer layer (B) becomes weak and may cause the detachment of the conductive polymer when immersed in the plating solution, whereas 1500 parts by mass. If it exceeds 1, the abundance ratio of the conductive polymer (a) in the conductive primer layer (B) decreases, and the deposition rate of the metal by plating becomes slow, which may be disadvantageous in the process.
• the conductive polymer is a compound for imparting conductivity to a layer (conductive primer layer) formed using the primer composition for electrolytic plating.
• the conductive polymer is not particularly limited, and a conventionally known conductive polymer can be used. Specific examples include, for example, polythiophene, polypyrrole, polyaniline, polyacetylene, polyphenylene vinylene, polynaphthalene, derivatives thereof, and A complex of these and a dopant is exemplified. These may be used alone or in combination of two or more.
• the conductive polymer is preferably a conductive polymer containing at least one thiophene ring in the molecule. The reason is that a molecule having high conductivity is easily formed by including a thiophene ring in the molecule.
• the conductive polymer poly (3,4-disubstituted thiophene) or a complex of poly (3,4-disubstituted thiophene) and polyanion is more preferable. This is because it is extremely excellent in conductivity and chemical stability. Further, when the primer composition for electrolytic plating contains poly (3,4-disubstituted thiophene) or a complex of poly (3,4-disubstituted thiophene) and polyanion, this electrolytic plating By using the primer composition for electroconductivity, the conductive primer layer can be formed at a low temperature in a short time, and the productivity will be excellent.
• poly (3,4-disubstituted thiophene) poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene) is particularly preferable.
• poly (3,4-dialkoxythiophene) or poly (3,4-alkylenedioxythiophene) include the following formula (I):
• R 1 and R 2 each independently represent a hydrogen atom or a C 1-4 alkyl group, or a C 1-4 alkylene group which may be substituted together.
• the C 1-4 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group.
• the optionally substituted C 1-4 alkylene group formed by combining R 1 and R 2 include a methylene group, a 1,2-ethylene group, and a 1,3-propylene group.
• 1,4-butylene group 1-methyl-1,2-ethylene group, 1-ethyl-1,2-ethylene group, 1-methyl-1,3-propylene group, 2-methyl-1,3-propylene Groups and the like.
• Preferred are a methylene group, 1,2-ethylene group and 1,3-propylene group, and a 1,2-ethylene group is particularly preferred.
• polythiophene having an alkylene group poly (3,4-ethylenedioxythiophene) is particularly preferable.
• the poly anion forms a complex by forming an ion pair with the polythiophene (derivative), and the polythiophene (derivative) can be stably dispersed in water.
• the poly anion include carboxylic acid polymers (eg, polyacrylic acid, polymaleic acid, polymethacrylic acid, etc.), sulfonic acid polymers (eg, polystyrene sulfonic acid, polyvinyl sulfonic acid, polyisoprene sulfonic acid, etc.) Etc.
• carboxylic acid polymers and sulfonic acid polymers are also copolymers of vinyl carboxylic acids and vinyl sulfonic acids with other polymerizable monomers such as aromatic vinyl compounds such as acrylates, styrene, vinyl naphthalene, etc. It may be. Among these, polystyrene sulfonic acid is particularly preferable.
• the polystyrene sulfonic acid preferably has a weight average molecular weight of more than 20000 and 500,000 or less. More preferably, it is 40,000 to 200,000. If polystyrene sulfonic acid having a molecular weight outside this range is used, the dispersion stability of the polythiophene-based conductive polymer in water may decrease.
• the weight average molecular weight of the polymer is a value measured by gel permeation chromatography (GPC). For the measurement, an ultrahydrogel 500 column manufactured by Waters was used.
• the content of the polythiophene conductive polymer in the electrolytic plating primer composition is not particularly limited, but is preferably 0.01 to 50.0 mg / m 2 when the conductive primer layer is formed. An amount of 1 to 10.0 mg / m 2 is more preferable. If it is less than 0.01 mg / m 2 , the proportion of the conductive polymer in the conductive primer layer decreases, the metal deposition rate is slow, and the function as a primer layer for electrolytic plating may be insufficient. If it exceeds 50.0 mg / m 2 , the proportion of the conductive polymer in the conductive primer layer will increase, and it will be difficult to control the thickness of the electrolytic plating layer to be formed because the metal deposition rate will be too high. Because it becomes.
• the primer composition for electrolytic plating may contain other components in addition to (a) the conductive polymer and (b) component described so far.
• a water-soluble antioxidant may contain d) a crosslinking agent, (e) a surfactant or leveling agent, (f) a solvent, (g) a conductivity improver, (h) a catalyst, and the like.
• a crosslinking agent may contain d) a crosslinking agent, (e) a surfactant or leveling agent, (f) a solvent, (g) a conductivity improver, (h) a catalyst, and the like.
• the water-soluble antioxidant When the water-soluble antioxidant is contained, it is possible to improve the heat resistance and moist heat resistance of the layer formed using the primer composition for electrolytic plating.
• the water-soluble antioxidant is not particularly limited, and examples thereof include reducing or non-reducing water-soluble antioxidants. Examples of the water-soluble antioxidant having reducing properties include L-ascorbic acid, sodium L-ascorbate, potassium L-ascorbate, D ( ⁇ )-isoascorbic acid (erythorbic acid), sodium erythorbate, and erythorbic acid.
• Compounds having a lactone ring substituted with two hydroxyl groups such as potassium; monosaccharides or disaccharides (excluding sucrose) such as maltose, lactose, cellobiose, xylose, arabinose, glucose, fructose, galactose, mannose; , Flavonoids such as rutin, myricetin, quercetin, kaempferol, sanmerin (registered trademark) Y-AF; two phenolic hydroxyl groups such as curcumin, rosmarinic acid, chlorogenic acid, hydroquinone, 3,4,5-trihydroxybenzoic acid more than Compounds; cysteine, glutathione, a compound having a pentaerythritol tetrakis (3-mercapto butyrate) thiol groups, such as and the like.
• monosaccharides or disaccharides excluding sucrose
• maltose lactose
• lactose cellobio
• Non-reducing water-soluble antioxidants include, for example, oxidative degradation such as phenylimidazolesulfonic acid, phenyltriazolesulfonic acid, 2-hydroxypyrimidine, phenyl salicylate, sodium 2-hydroxy-4-methoxybenzophenone-5-sulfonate.
• oxidative degradation such as phenylimidazolesulfonic acid, phenyltriazolesulfonic acid, 2-hydroxypyrimidine, phenyl salicylate, sodium 2-hydroxy-4-methoxybenzophenone-5-sulfonate.
• the compound which absorbs the ultraviolet-ray which causes this is mentioned. These may be used alone or in combination of two or more.
• At least one compound selected from the group consisting of a compound having a lactone ring substituted with two hydroxyl groups and a compound having two or more phenolic hydroxyl groups is preferable.
• -Isoascorbic acid or Sanmerin (registered trademark) Y-AF is more preferred.
• the content of the water-soluble antioxidant is preferably 0.001 to 500 parts by mass, more preferably 0.01 to 250 parts by mass, and more preferably 0.05 to 100 parts per 100 parts by mass of the conductive polymer (a). Part by mass is particularly preferred.
• the content is less than 0.001 part by mass, the heat resistance and heat-and-moisture resistance of the layer formed using the electrolytic plating primer composition may not be sufficiently improved.
• the content exceeds 500 parts by mass.
• the proportion of the conductive polymer in the layer formed using the primer composition for electrolytic plating decreases, the metal deposition rate by electrolytic plating becomes slow, and the strength of the formed layer may decrease. .
• (D) Crosslinking agent
• the strength of the layer formed using the electrolytic plating primer composition can be further improved. This is because the component (b) can be crosslinked by using in combination with the component (b).
• crosslinking agent examples include melamine-based, polycarbodiimide-based, polyoxazoline-based, polyepoxy-based, and polyisocyanate-based crosslinking agents. These crosslinking agents may be used independently and may use 2 or more types together.
• the content of the cross-linking agent is not particularly limited, but is preferably 0.1 to 17000 parts by mass and preferably 1 to 1000 parts by mass with respect to 100 parts by mass of the solid content of the conductive polymer (a) in terms of solids More preferred.
• the content is less than 0.1 parts by mass, the strength of the conductive primer layer (B) may be insufficient.
• the content exceeds 17000 parts by mass, (a ) The proportion of the conductive polymer is reduced, and the deposition rate of the metal by plating is slow, which may be disadvantageous in terms of the process.
• an acidic group of the dopant may be used, or an organic acid or an inorganic acid may be newly added.
• (E) Surfactant / Leveling Agent When the surfactant or the leveling agent is contained, the leveling property of the layer formed using the primer composition for electrolytic plating can be improved and a uniform layer can be obtained.
• the same compound may be equivalent to both a surfactant and a leveling agent.
• the surfactant is not particularly limited as long as it can exhibit such a function.
• Specific examples thereof include polyether-modified polydimethylsiloxane, polyether-modified siloxane, and polyetherester-modified hydroxyl group. -Containing polydimethylsiloxane, polyether-modified acrylic group-containing polydimethylsiloxane, polyester-modified acrylic group-containing polydimethylsiloxane, perfluoropolydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, perfluoropolyester-modified polydimethylsiloxane, etc.
• Fluorine-containing organic compound such as perfluoroalkyl carboxylic acid and perfluoroalkyl polyoxyethylene ethanol; polyoxyethylene alkyl phenyl ether, propylene Polyether compounds such as oxide polymers and ethylene oxide polymers; carboxylic acids such as coconut oil fatty acid amine salts and gum rosins; castor oil sulfates, phosphate esters, alkyl ether sulfates, sorbitan fatty acid esters, sulfonate esters, succinates Ester compounds such as acid esters; sulfonate compounds such as alkyl aryl sulfonate amine salts and dioctyl sodium sulfosuccinate; phosphate compounds such as sodium lauryl phosphate; amide compounds such as coconut oil fatty acid ethanol amide; And the like, and the like.
• siloxane compounds and fluorine-containing organic compounds are preferable from the viewpoint of leveling properties, and
• Specific product names of the above surfactants include, for example, BYK-301 (manufactured by BYK Japan), BYK-302 (manufactured by BYK Japan), and BYK-307 (manufactured by BYK Japan).
• BYK-331 (manufactured by BYK Japan), BYK-333 (manufactured by BYK Japan), BYK-337 (manufactured by BYK Japan), BYK-341 (manufactured by BYK Japan), BYK -375 (manufactured by BYK Japan), BYK-378 (manufactured by BYK Japan), BYK-380N (manufactured by BYK Japan), BYK-340 (manufactured by BYK Japan), BYK-DYNWET800 (Big Chemie Ji Pan Corporation), NIKKOL AM-101 (Nihon Surfactant Industries, Ltd.), NIKKOL AM-301 (Nihon Surfactant Industries, Ltd.), NIKKOL AM-3130N (Nihon Surfactant Industries, Ltd.), Asahi Guard AG-8025 (Manufactured by Meisei Chemical Co., Ltd.), Asahi Guard MA-91 (manu
• the content of the surfactant is not particularly limited, but is preferably 0.001 to 2300 parts by mass, preferably 0.01 to 500 parts per 100 parts by mass of the solid content of the conductive polymer (a) in terms of solids. Part by mass is more preferable. When the content is less than 0.001 part by mass, it may be difficult to form a uniform film thickness. On the other hand, when the content exceeds 2300 parts by mass, (a) conductivity in the layer to be formed In some cases, the polymer content is reduced, the metal deposition rate by electrolytic plating is slowed, and the strength of the layer to be formed is lowered.
• leveling agent examples include polyether-modified polydimethylsiloxane, polyether-modified siloxane, polyetherester-modified hydroxyl group-containing polydimethylsiloxane, polyether-modified acrylic group-containing polydimethylsiloxane, polyester-modified acrylic group-containing polydimethylsiloxane, Siloxane compounds such as fluoropolydimethylsiloxane, perfluoropolyether-modified polydimethylsiloxane, and perfluoropolyester-modified polydimethylsiloxane; fluorine-containing organic compounds such as perfluoroalkylcarboxylic acid and perfluoroalkylpolyoxyethyleneethanol; polyoxyethylenealkyl Polyether compounds such as phenyl ether, propylene oxide polymer, ethylene oxide polymer; coconut oil fatty acid polymer Carboxylic acids such as salt and gum rosin; castor oil sulfates, phosphate esters
• Specific product names of the above leveling agents include, for example, BYK-325 (manufactured by Big Chemie Japan Co., Ltd.), BYK-345 (manufactured by Big Chemie Japan Co., Ltd.), BYK-346 (manufactured by Big Chemie Japan Co., Ltd.), BYK-347 (manufactured by BYK Japan), BYK-348 (manufactured by BYK Japan), BYK-349 (manufactured by BYK Japan), BYK-UV3500 (manufactured by BYK Japan), BYK- 381 (manufactured by Big Chemie Japan Co., Ltd.), BYKETOL-AQ (manufactured by BYK Chemie Japan Co., Ltd.), BYKETOL-WS (manufactured by Big Chemie Japan Co., Ltd.), Polyflow WS (manufactured by Kyoeisha Chemical Industry Co., Ltd.), Polyflow WS-30 ( Kyoe
• the content of the leveling agent is not particularly limited, but is preferably 0.001 to 2300 parts by mass, and 0.01 to 500 parts by mass in terms of solid content with respect to 100 parts by mass of the solid content of the conductive polymer (a). Part is more preferred.
• the content is less than 0.001 part by mass, it may be difficult to form a uniform film thickness.
• the content exceeds 2300 parts by mass, (a) conductivity in the layer to be formed In some cases, the polymer content is reduced, the metal deposition rate by electrolytic plating is slowed, and the strength of the layer to be formed is lowered.
• the primer composition for electrolytic plating may contain a solvent. It is preferable that the solvent does not remain in the layer formed using the electrolytic plating primer composition. In addition, what completely dissolves all the components of the primer composition for electrolytic plating is called “solvent”, and what disperses insoluble components is called “dispersion medium”. Is also described as “solvent”.
• the solvent examples include alcohols such as water, methanol, ethanol, 2-propanol, and 1-propanol; ethylene glycols such as ethylene glycol, diethylene glycol, triethylene glycol, and tetraethylene glycol; ethylene glycol monomethyl ether and diethylene glycol monomethyl.
• Glycol ethers such as ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether;
• Glycol ether acetates such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate; Propylene glycol, dipropylene glycol, tripropylene glycol, etc.
• Propylene rubber Coles propylene glycol such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether, dipropylene glycol diethyl ether Ethers: propylene glycol ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate; tetrahydrofuran; acetone; acetonitrile and the like It is. These may be used alone or in combination of two or more.
• water or a mixture of water and an organic solvent is preferable.
• the water content is preferably 20 to 1,000,000 parts by mass, more preferably 200 to 500,000 parts by mass with respect to 100 parts by mass of the solid content of the conductive polymer (a). The reason is that when the amount is less than 20 parts by mass, the viscosity becomes high and handling may be difficult. When the amount exceeds 1000000 parts by mass, it becomes a dilute solution and it is difficult to adjust the thickness of the layer to be formed. Because there are things.
• the organic solvent is preferably methanol, ethanol, or 2-propanol.
• the content of the organic solvent is not particularly limited, and is preferably 20 to 700000 parts by mass and more preferably 200 to 350,000 parts by mass with respect to 100 parts by mass of the solid content of the conductive polymer (a).
• the ratio between the two is preferably 100: 0 to 5:95, and more preferably 100: 0 to 30:70.
• the conductivity improver is added for the purpose of improving the conductivity of the conductive primer layer formed by applying the primer composition for electrolytic plating.
• the conductivity improver evaporates by heating when forming the conductive primer layer, and it is presumed that the conductivity of the conductive primer layer is improved by controlling the orientation of the conductive polymer at that time.
• the primer composition for electrolytic plating of the present invention preferably contains a conductivity improver composed of at least one compound selected from the group consisting of: (1) A compound having a boiling point of 60 ° C. or higher and having at least one ketone group in the molecule (2) A compound having a boiling point of 100 ° C. or higher and having at least one ether group in the molecule (3) A molecule having a boiling point of 100 ° C. or higher Compound (4) having at least one sulfinyl group in it (4) Compound having a boiling point of 100 ° C. or more and at least one amide group in the molecule (5) Compound having a boiling point of 50 ° C.
• a conductivity improver composed of at least one compound selected from the group consisting of: (1) A compound having a boiling point of 60 ° C. or higher and having at least one ketone group in the molecule (2) A compound having a boiling point of 100 ° C. or higher and having at least one ether group in the molecule (3) A molecule having
• Examples of the compound (1) having a boiling point of 60 ° C. or higher and having at least one ketone group in the molecule include isophorone, propylene carbonate, ⁇ -butyrolactone, ⁇ -butyllactone, 1,3-dimethyl-2-imidazolidinone. Etc.
• Examples of the compound (2) having a boiling point of 100 ° C. or more and having at least one ether group in the molecule include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, 2-phenoxyethanol, dioxane, morpholine, 4-acryloylmorpholine, N-methylmorpholine N-oxide, 4-ethylmorpholine, oxetane, THF, THP and the like can be mentioned.
• Examples of the compound (3) having a boiling point of 100 ° C. or higher and having at least one sulfinyl group in the molecule include dimethyl sulfoxide and the like.
• Examples of the compound (4) having a boiling point of 100 ° C. or higher and having at least one amide group in the molecule include N, N-dimethylacetamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-ethylacetamide N-phenyl-N-propylacetamide, benzamide and the like.
• Examples of the compound (5) having a boiling point of 50 ° C. or more and having at least one carboxyl group in the molecule include acrylic acid, methacrylic acid, methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, and octane.
• Acid decanoic acid, dodecanoic acid, benzoic acid, p-toluic acid, p-chlorobenzoic acid, p-nitrobenzoic acid, 1-naphthoic acid, 2-naphthoic acid, phthalic acid, isophthalic acid, oxalic acid, malonic acid,
• succinic acid adipic acid, maleic acid, fumaric acid and the like.
• Examples of the compound (6) having a boiling point of 100 ° C. or more and having two or more hydroxyl groups in the molecule include ethylene glycol, diethylene glycol, propylene glycol, trimethylene glycol, ⁇ -thiodiglycol, triethylene glycol, and tripropylene.
• Glycol 1,4-butanediol, 1,5-pentanediol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, catechol, cyclohexanediol, cyclohexanedimethanol, glycerin, erythritol, glycerin, immutol , Lactitol, maltitol, mannitol, sorbitol, xylitol, sucrose and the like.
• Examples of the compound (7) having a boiling point of 100 ° C. or more and having at least one lactam group in the molecule include N-methylpyrrolidone, ⁇ -lactam, ⁇ -lactam, ⁇ -lactam, ⁇ -caprolactam, laurolactam and the like. Can be mentioned.
• the conductivity improver If the boiling point of the conductivity improver is above a specific temperature, the conductivity improver gradually volatilizes due to heating during the formation of the conductive primer layer. In the process, the orientation of the conductive polymer is changed. It is considered that the orientation is controlled to be advantageous for the conductivity, and as a result, the conductivity is improved. On the other hand, if the boiling point of the conductivity improver is less than a specific temperature, the conductivity improver will rapidly evaporate, so that the orientation of the conductive polymer is not sufficiently controlled and the conductivity is not improved. it is conceivable that.
• the blending amount of the conductivity improver is preferably 5 to 2000 parts by mass and more preferably 10 to 1500 parts by mass with respect to 100 parts by mass of the conductive polymer (a). If the amount is less than 5 parts by mass, the effect of improving the heat generation characteristics due to the addition of the conductivity improver cannot be achieved. If the amount exceeds 2000 parts by mass, the conductivity improver component in the primer composition for electrolytic plating becomes dilute, and sufficient conductivity cannot be obtained when the conductive primer layer is formed. It becomes difficult to obtain the plating layer within a predetermined time.
• the conductive primer layer formed using the electrolytic plating primer composition preferably has a surface resistivity of 100,000 ⁇ / ⁇ or less.
• the surface resistivity is more preferably 50,000 ⁇ / ⁇ or less, further preferably 10,000 ⁇ / ⁇ or less, and particularly preferably 5,000 ⁇ / ⁇ or less.
• the said surface resistivity is so preferable that it is small.
• the catalyst examples include a photopolymerization initiator and a thermal polymerization initiator.
• a photopolymerization initiator When the compound containing two or more acrylic groups in the molecule is used as the component (b), light is used. It is preferable to use a polymerization initiator, and when using a compound containing two or more epoxy groups in the molecule, it is preferable to use a thermal polymerization initiator.
• the photopolymerization initiator examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, and 2-hydroxy-2-methyl-1-phenyl-propane.
• thermal polymerization initiator examples include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2 -Phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2 -Ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino- 6- [2'-Me Louisimidazolyl- (1
• the method for producing a plated product of the present invention includes at least (1) A step of forming a conductive primer layer (B) on part or all of the surface of the substrate (A) using the primer composition for electrolytic plating of the present invention, and (2) forming an electroplating layer (C) by electroplating on the conductive primer layer (B); It is characterized by going through.
• the conductive primer layer is formed using the primer composition for electrolytic plating of the present invention, the adhesion of each layer of the substrate, the conductive primer layer, and the electrolytic plated layer is mutual. An excellent plating product can be produced.
• the manufacturing method of the said plated material is demonstrated in order of a process.
• a step of forming a conductive primer layer (B) on a part or all of the surface of the substrate (A) using the primer composition for electrolytic plating of the present invention (hereinafter referred to as “a”).
• a primer layer forming step a part or all of the surface of the substrate (A) is coated with the above-mentioned primer composition for electrolytic plating, and then drying treatment, heat treatment, light irradiation treatment, electron beam (EB) irradiation treatment as necessary. Etc. to form a conductive primer layer (B).
• the position where the conductive primer layer (B) is formed coincides with the position where the electrolytic plating layer (C) is formed by electrolytic plating in the subsequent step (2).
• the substrate (A) is not particularly limited, and examples thereof include a resin substrate, a glass substrate, and a ceramic substrate.
• the method for producing a plated product according to the present invention is advantageous in that the range of selection of the material of the substrate is wide.
• the resin material for the resin substrate include epoxy resin, polyacetal, polyamide, polyphthalamide, polycarbonate, modified polyphenylene ether, polybutylene terephthalate, syndiotactic polystyrene, polyacrylate, polysulfone, polyethersulfone, and polyphenylene sulfide.
• Polyether ketone, polyimide, polyether imide, fluororesin, liquid crystal polymer, polyethylene terephthalate, ABS resin, and a resin alloy containing at least one selected from the group consisting of these resins are preferably used in the present invention.
• a known coating method or printing method can be used as a method for coating a part or all of the surface of the substrate (A) with the primer composition for electrolytic plating of the present invention.
• the coating method include spin coating, gravure coating, bar coating, dip coating, curtain coating, die coating, and spray coating.
• printing methods such as screen printing, spray printing, ink jet printing, relief printing, intaglio printing, and lithographic printing can also be applied. What is necessary is just to select suitably from these methods according to the objective.
• a drying treatment or a heat treatment may be performed as necessary.
• the method is not particularly limited, and may be performed using, for example, a dryer such as an air dryer, a hot air dryer, or an infrared dryer. Further, when a dryer having a heating means (hot air dryer, infrared dryer, etc.) is used, drying and heating can be performed simultaneously. Further, in addition to these dryers, a heating / pressurizing roll having a heating / pressurizing function, a press machine, or the like may be used. Further, the drying conditions are not particularly limited, but conditions of 50 to 250 ° C. for about 10 seconds to 2 hours are preferable, and conditions of 70 to 200 ° C. for about 30 seconds to 1 hour are more preferable.
• the light source may be a metal halide lamp, a low-pressure mercury lamp, a high-pressure UV lamp, or the like that can irradiate UV light.
• the amount of light irradiation is not particularly limited, but is preferably 10 ⁇ 10,000mJ / cm 2, more preferably 100 ⁇ 5,000mJ / cm 2.
• the amount of electron beam (EB) irradiation is not particularly limited, but is preferably 1 to 1,000 kGy ⁇ m / min, and particularly preferably 5 to 500 kGy ⁇ m / min.
• the thickness of the conductive primer layer formed in this step is preferably 0.01 to 10 ⁇ m. If the thickness is less than 0.01 ⁇ m, the surface resistivity of the electrolytic plating layer becomes too large in the subsequent process, and it may be difficult to form the electrolytic plating layer by electrolytic plating. This is because there is a possibility that the process is not improved, and it may be disadvantageous in terms of productivity and cost.
• a step of pretreating the substrate (A) (hereinafter also referred to as a pretreatment step) before performing the primer layer forming step.
• a pretreatment step By performing this pretreatment step, the wettability of the substrate (A) with respect to the electrolytic plating primer composition can be improved, and as a result, the adhesion between the substrate (A) and the conductive primer layer (B). This is because is better.
• the pretreatment performed in the pretreatment step is not particularly limited as long as the wettability can be improved.
• a method of physically roughing the surface plasma treatment, ozone treatment, corona treatment, low pressure UV
• dry chemical treatment methods such as treatment, high-pressure UV treatment, and intro treatment
• a method of immersing in a mixed solution of chromic acid, concentrated sulfuric acid and concentrated hydrochloric acid a wet chemical treatment with a silane coupling agent or a titanate coupling agent. These methods may be used independently and 2 or more types may be used together.
• an easy adhesion layer (B ′) may be provided between the substrate (A) and the conductive primer layer (B).
• the adhesion between the substrate (A) and the conductive primer layer (B) is further improved.
• the substrate (A) and the electroplating layer (C) It is possible to further improve the adhesion.
• the easy-adhesion layer (B ′) is not particularly limited, but is preferably formed using an organic-inorganic hybrid resin or a composition containing an organic resin.
• the substrate (A) is a glass substrate or a ceramic substrate
• the substrate (A) is an epoxy resin, polyacetal, polyamide, polyphthalamide, polycarbonate, modified polyphenylene ether, polybutylene terephthalate, syndiotactic polystyrene, polyacrylate, polysulfone, polyethersulfone, polyphenylene sulfide, poly When it is at least one selected from the group consisting of ether ketone, polyimide, polyether imide, fluororesin, liquid crystal polymer, polyethylene terephthalate, and ABS resin, acrylic monomer, acrylic oligomer, acrylic resin, epoxy resin, urethane
• the easy-adhesion layer (B ′) is preferably formed using a composition containing at least one selected from the group consisting of resins and ester resins.
• the composition used for forming the easy-adhesion layer (B ′) may contain other components as long as it does not hinder the function of improving the adhesion between the substrate (A) and the conductive primer layer (B). Good.
• the adhesive layer (B ′) is provided between the substrate (A) and the conductive primer layer (B)
• the substrate (A) is coated with the composition, and then, if necessary, drying treatment, heat treatment, light What is necessary is just to form an electroconductive primer layer (B) on the easily bonding layer (B ') obtained by performing irradiation treatment, electron beam (EB) irradiation treatment, etc.
• the thickness of the easily adhesive layer (B ′) is not particularly limited, but is preferably 0.01 to 50 ⁇ m. When the thickness of the easy adhesion layer (B ′) is 0.01 ⁇ m or less, the function as the easy adhesion layer is remarkably reduced, and when it is 50 ⁇ m or more, the performance of the substrate (A) may be reduced.
• the method of electrolytic plating performed in the present electrolytic plating layer forming step is not particularly limited, and a conventionally known method can be used. Specifically, for example, the following electrolytic plating method can be used.
• a direct current electrolytic plating method (DC plating method), which is a general electrolytic plating method, and a method of controlling the current to a rectangular wave pulse current by alternately repeating supply and interruption of the cathode current (PC plating method)
• the cathode current supply and the anode current supply are alternately reversed and repeated to control the current using a periodic reversal wave.
• the pulse-reverse electroplating method PR plating method
• a method of alternately applying a density current pulse and a low density current pulse can be used.
• the direct current electrolytic plating method (DC plating method) is preferable from the viewpoint that an expensive power supply device and control device are not required.
• the electrolytic plating may be performed a plurality of times, and in that case, an electrolytic plating layer in which different metals are laminated can be formed.
• the thickness of the electrolytic plating layer (C) formed in this step is not particularly limited, and may be appropriately selected according to the design of the plated product to be manufactured. Usually, about 0.1 to 100 ⁇ m is preferable. The reason is that the thickness of the metal layer is necessary for applications such as circuits, wiring, electromagnetic shielding, and decoration.
• the thickness of the electrolytic plating layer (C) can be controlled, for example, by appropriately setting the electrolytic plating treatment time.
• a plated product in which the electrolytic plating layer (C) is formed on a part or all of the surface of the substrate (A) can be produced.
• an electrolytic plating layer (C) is previously formed in a range wider than a desired range, and then unnecessary portions of the electrolytic plating layer (C) are removed by etching. May be.
• An electrolytic plating layer (C) may be formed only on a necessary portion on the substrate (A) by forming an etching resist on the plating layer (C) and further performing an etching process.
• patterning method applicable to the present invention includes the following methods: Forming a conductive primer layer (B) having a predetermined patterning image on the substrate (A), and obtaining an electrolytic plating layer (C) patterned by electrolytic plating; A conductive primer layer (B) is uniformly formed on the substrate (A), and then a mask (plating resist) having a predetermined pattern image is pasted on the conductive primer layer (B) without any gap, and patterned by electrolytic plating.
• the conductive primer layer (B) is uniformly formed on the substrate (A), and the conductive primer layer (B) is formed into a conductive primer layer (B) patterned by a known technique such as etching or a lift-off method.
• a negative or positive resist conductive primer layer (B) is formed on the substrate (A), light is irradiated through a mask having a predetermined patterning image, unnecessary portions are peeled off, and patterned conductive
• a plated product in which the electrolytic plating layer (C) is formed on the surface of the substrate (A) can be suitably produced.
• the method for producing a plated product of the present invention is extremely useful in that an electrolytic plating layer can be formed on the surface of a base made of an insulating material without performing electroless plating.
• a plated product produced using the method for producing a plated product of the present invention is also one aspect of the present invention.
• Examples of the plated product include circuit components, electromagnetic wave shielding members, and ornaments.
• Examples of the circuit components include printed circuit boards such as single-sided boards, double-sided boards, multilayer boards, and build-up boards, and molded circuit parts (MID) such as antennas, optical pickups, and board-to-board connecting parts.
• a molded circuit component (MID) can be preferably manufactured.
• Examples of the electromagnetic wave shielding member include those in which a metal layer is formed on the surface of a flexible film, and those in which a metal layer is formed on the surface of a box-shaped substrate.
• the conductive polymer (commercially available from HC Starck Co., Ltd .: CleviosPH1000, solid content 1.0%) composed of a complex of poly (3,4-ethylenedioxythiophene) and polystyrenesulfonic acid is shown in Table 1 below ( b) Component, conductivity improver, surfactant, leveling agent, water, ethanol and catalyst were added and stirred for 1 hour. This was filtered through a 400 mesh SUS sieve to obtain primer compositions A to W for electrolytic plating. The amount of each component is as shown in Table 1 below.
• the component (b) shown in Table 1 is as follows.
• U-4HA (manufactured by Shin-Nakamura Chemical Co., Ltd., solid content 100%)
• EBECRYL11 (Daicel Cytec, 100% solid content)
• Nicazole RX-7108 (Nippon Carbide Industries, solid content 100%)
• Denacol EX-314 (manufactured by Nagase ChemteX Corporation, solid content 100%)
• Denacol EX-821 manufactured by Nagase ChemteX Corporation, solid content 100%
• Gabsen ES-210 (manufactured by Nagase ChemteX Corporation, solid content 100%)
• Hydran WLS-213 (manufactured by DIC, solid content 100%)
• XC96-B0446 (Tanak Co., Ltd., 100% solid content)
• Epocros WS-300 (Nippon Shokubai Co., Ltd., 100% solid content)
• Carbodilite V-02 (N
• the conductivity improvers shown in Table 1 are as follows. Dimethyl sulfoxide (manufactured by Kanto Chemical Co., Inc.)
• the catalysts shown in Table 1 are as follows. IRGACURE 500 (BASF), (1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone mixed system) Cureazole 2MZ-H (manufactured by Shikoku Chemicals), (imidazole)
• Example 1 (1) Primer layer forming step 5 ⁇ 5 ⁇ 5 cm polycarbonate / ABS resin alloy substrate (manufactured by Daicel Polymer Co., Ltd., Novalloy S) is coated with a primer composition A for electrolytic plating on a wire bar No. 8 (wet film thickness 18 ⁇ m) was applied by a bar coating method, dried at 130 ° C. for 30 minutes, then subjected to a light irradiation treatment of 2500 mJ / cm 2 to form a conductive primer layer, and polycarbonate / ABS resin A laminate in which a conductive primer layer was formed on an alloy substrate was obtained.
• a primer composition A for electrolytic plating on a wire bar No. 8 wet film thickness 18 ⁇ m
• Electroplating layer forming step Electrolytic plating was performed by the following method to produce an electroplating layer having a thickness of 20 ⁇ m on the surface of the laminate, followed by washing with water and drying to produce a plated product.
• the thickness of the electrolytic plating layer was measured by DIGIMATIC MICROMETER (manufactured by Mitutoyo, MDC-25M).
• DIGIMATIC MICROMETER manufactured by Mitutoyo, MDC-25M.
• a predetermined amount of a plating solution for copper plating (Okuno Pharmaceutical Co., Ltd., Elecapper 25) was placed in a plating bath (Yamamoto Metal Testing Machine Co., Ltd., Hull Cell Model 3).
• a DC power supply (P4K-80M, manufactured by Matsusada Precision Co., Ltd.) as a power source
• a copper plate manufactured by Yamamoto Metal Testing Machine Co., Ltd., Hull Cell anode plate-containing phosphorous copper
• a conductive primer on the substrate (A) as the cathode The laminate on which the layer (B) was formed was attached, and electrolytic copper plating was performed in a plating bath.
• the set current of the DC power supply was 1 A, and the laminated substrate was taken out after 300 seconds. Thereafter, the laminate was washed with water and dried at 100 ° C. for 60 minutes to obtain a plated product on which copper was plated.
• Examples 2 to 28, Comparative Examples 1 to 7 A substrate made of the material shown in Table 2 below was used as the substrate, and any one of the above-described primer compositions A to W for electrolytic plating was used in a combination shown in Table 2 below as the primer composition for electrolytic plating. In the same manner as in Example 1, a plated product was obtained. In addition, when the primer composition C, E, J, and L for electroplating containing an acrylic oligomer is used among the primer compositions for electroplating, the light is applied to the substrate and dried after the same treatment as in Example 1. Although irradiation treatment was performed, light irradiation treatment was not performed when other primer compositions for electrolytic plating were used.
• Each substrate shown in Table 2 is as follows.
• Polycarbonate / ABS resin alloy substrate (Daicel Polymer, Novalloy S)
• Polyamide substrate manufactured by Kuraray, PA9T G1300A
• Syndiotactic polystyrene substrate made by Idemitsu Kosan Co., Ltd., Zalek S131
• Liquid crystal polymer substrate (Toray Industries, Siberus LX70G35F)
• Polyphenylene sulfide substrate manufactured by Polyplastics, Fortron 1140A64
• Polybutylene terephthalate substrate Polybutylene terephthalate substrate
• Polyethylene terephthalate substrate Toray Industries, Lumirror T60
• Polycarbonate substrate Mitsubishi Engineering Plastics, Iupilon H-4000
• the peel strength was measured using a handy force gauge (manufactured by Nippon Measurement System Co., Ltd., HF-10) according to the following criteria. ⁇ : 1.0 N / cm or more ⁇ : 0.5 N / cm or more, less than 1.0 N / cm x: less than 0.5 N / cm
• the primer composition for electrolytic plating containing, as component (b), an acrylic monomer, an acrylic oligomer, an acrylic resin, an epoxy resin, a urethane resin, or an ester resin It has been clarified that a plated product having excellent adhesion between the substrate, the conductive primer layer and the electrolytic plating layer can be produced by using the product.
• the present invention is used for the manufacture of plated products such as circuit components, electromagnetic wave shielding members, and ornaments.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Electrochemistry (AREA)
• Metallurgy (AREA)
• Life Sciences & Earth Sciences (AREA)
• Wood Science & Technology (AREA)
• Electroplating Methods And Accessories (AREA)
• Manufacturing Of Printed Wiring (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=48799139

Family Applications (1)

Country Status (3)

Families Citing this family (2)

Citations (7)

Family Cites Families (3)

• 2012
  • 2012-01-19 JP JP2012009423A patent/JP2013147707A/ja active Pending
• 2013
  • 2013-01-11 WO PCT/JP2013/050378 patent/WO2013108713A1/ja not_active Ceased
  • 2013-01-15 TW TW102101451A patent/TW201339376A/zh unknown

Patent Citations (7)

Also Published As

Similar Documents

Legal Events