WO2022097487A1 - 金属皮膜形成方法 - Google Patents

金属皮膜形成方法 Download PDF

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Publication number
WO2022097487A1
WO2022097487A1 PCT/JP2021/038875 JP2021038875W WO2022097487A1 WO 2022097487 A1 WO2022097487 A1 WO 2022097487A1 JP 2021038875 W JP2021038875 W JP 2021038875W WO 2022097487 A1 WO2022097487 A1 WO 2022097487A1
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Prior art keywords
metal film
metal
group
forming
plating
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PCT/JP2021/038875
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English (en)
French (fr)
Japanese (ja)
Inventor
憲正 深澤
潤 白髪
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Dic株式会社
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Priority to JP2022540727A priority Critical patent/JPWO2022097487A1/ja
Publication of WO2022097487A1 publication Critical patent/WO2022097487A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
    • 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

Definitions

  • the present invention relates to a metal film forming method capable of forming a metal film on an insulating base material having a three-dimensional three-dimensional structure with high adhesion.
  • the surface of the base material is roughened and the adhesion between the base material and the plating film is ensured by the anchor effect.
  • chemical solutions having a large environmental load such as chromic acid and permanganate are used, and an alternative method that does not use these chemical solutions is required.
  • the method of roughening the surface is used for a base material in which transparency is important, or a base material in which it is difficult to roughen the surface due to low chemical resistance or, conversely, too high chemical resistance.
  • Patent Document 1 describes a first step of performing plasma treatment or electron beam irradiation on a filament bundle, and the filament bundle.
  • a method for producing a conductive fiber yarn which comprises a fourth step of forming a metal plating layer by immersing and performing a electroless plating treatment.
  • a step of fixing a silane coupling agent to the fiber surface of an organic polymer fiber, a metallizing treatment of the silane coupling agent fixed to the fiber surface, and metal particles via the silane coupling agent is characterized by including a step of producing an organic polymer fiber adhered to the fiber surface and a step of electrolyzing the metallized organic polymer fiber using a compound of a metal having a larger ionization tendency than the above metal.
  • a method for producing an organic polymer fiber for carrying out metal plating is disclosed.
  • Patent Document 3 an organic metal complex is dissolved in a carbon dioxide fluid in a supercritical state, impregnated into a polymer fiber material, and then the impregnated organic metal complex is reduced by setting the reduction temperature with a heater.
  • Disclosed is a technique of precipitating a metal catalyst for plating on the surface of a material and using this as the core of plating for plating.
  • the adhesion between the fiber and the metal film is poor, the metal film may be easily peeled off, or the strength of the fiber itself may decrease, and improvement has been sought.
  • Patent Document 4 as a method of performing electroless plating having excellent adhesion between the fiber and the metal film without lowering the strength of the polymer fiber material, the organic polymer fiber is subjected to electron beam irradiation treatment.
  • a method for producing a plated fiber characterized by the above is disclosed.
  • the plating catalyst is held by the polymer of the nitrogen-containing monomer grafted on the fiber surface, which serves as the starting point of plating precipitation, so that the strength of the fiber itself is not reduced and the fiber and the metal film adhere to each other. It is said that sex can be secured.
  • Japanese Unexamined Patent Publication No. 2010-100934 Japanese Patent Application Laid-Open No. 2003-171869 Japanese Unexamined Patent Publication No. 2007-56287 Japanese Unexamined Patent Publication No. 2015-214735
  • the problem to be solved by the present invention does not require surface roughening with chromic acid or permanganic acid, surface modified layer formation with supercritical fluid, etc., and does not use an expensive vacuum device or electron beam irradiation device. It is a simple method to provide a method for forming a metal film on a three-dimensional molded body having high adhesion between a base material and a metal film.
  • the present inventors have formed a primer layer (B) so as to cover at least a continuous series of surfaces of the three-dimensional insulating molded base material (A). Therefore, they have found that a metal film having high adhesion can be formed on a three-dimensional molded body base material, and have completed the present invention.
  • the present invention 1.
  • a method for forming a metal film on a three-dimensional molded body which comprises laminating a primer layer (B) and a metal film (M) formed so as to cover the surface in this order.
  • 2. The method for forming a metal film on a three-dimensional molded body according to 1, wherein the three-dimensional insulating base material (A) has a rod-like or fibrous shape having a diameter of 0.5 ⁇ m to 5 mm. 3. 3.
  • the metal film (M) is one of 1 to 3 characterized in that the plated metal film (M2) is further laminated on the metal particle film (M1) formed from the metal particles.
  • a resin having a reactive functional group [X] is used for the primer layer (B), a resin having a reactive functional group [Y] is used for the polymer dispersant, and the reaction with the reactive functional group [X].
  • the polymer dispersant having the reactive functional group [Y] is at least one selected from the group consisting of polyalkyleneimine and polyalkyleneimine having a polyoxyalkylene structure containing an oxyethylene unit. Film forming method. 11.
  • the reactive functional group [X] is selected from the group consisting of a keto group, an acetoacetyl group, an epoxy group, a carboxyl group, an N-alkyrole group, an isocyanate group, a vinyl group, a (meth) acryloyl group and an allyl group1
  • a base material in which transparency is important and chemical resistance is low without using a chemical solution having a large environmental load such as chromic acid and permanganic acid.
  • a chemical solution having a large environmental load such as chromic acid and permanganic acid.
  • Highly high-quality metal plating can be performed.
  • the surface of the base material is not roughened, the surface of the metal film formed by plating becomes a glossy surface that reflects the smooth surface of the surface of the base material, so that the plating film thickness can be reduced, and the plating time can be shortened. Not only contributes to the improvement of productivity, but also contributes to the weight reduction of the base material. In addition, since it is a simple method that does not use an expensive vacuum device or electron beam irradiation device, it is possible to manufacture a product with high production efficiency and low cost.
  • the insulating base material (A) used in the present invention is a molded base material having a three-dimensional structure in which at least one dimension of the base material has a size of 0.5 ⁇ m to 5 mm.
  • Examples of the material of the insulating base material (A) used in the present invention include polyimide resin, polyamideimide resin, polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polycarbonate resin, and acrylonitrile-butadiene-. Grafted styrene (ABS) resin, polyarylate resin, polyacetal resin, acrylic resin such as poly (meth) methyl acrylate, polyfluorovinylidene resin, polytetrafluoroethylene resin, polyvinyl chloride resin, polyvinylidene chloride resin, acrylic resin.
  • ABS Grafted styrene
  • Copolymerized vinyl chloride resin polyvinyl alcohol resin, polyethylene resin, polypropylene resin, urethane resin, cycloolefin resin, polystyrene, liquid crystal polymer (LCP), polyether ether ketone (PEEK) resin, polyphenylene sulfide (PPS), polyphenylene sulfone (PPSU), cellulose nanofibers, silicon, silicon carbide, gallium nitride, sapphire, ceramics, glass, diamond-like carbon (DLC), alumina and the like.
  • LCP liquid crystal polymer
  • PEEK polyether ether ketone
  • PPS polyphenylene sulfide
  • PPSU polyphenylene sulfone
  • cellulose nanofibers silicon, silicon carbide, gallium nitride, sapphire, ceramics, glass, diamond-like carbon (DLC), alumina and the like.
  • thermosetting resin examples include epoxy resin, phenol resin, unsaturated imide resin, cyanate resin, isocyanate resin, benzoxazine resin, oxetane resin, amino resin, unsaturated polyester resin, allyl resin, and dicyclopentadiene resin.
  • examples thereof include silicone resin, triazine resin, and melamine resin.
  • examples of the inorganic filler include silica, alumina, talc, mica, aluminum hydroxide, magnesium hydroxide, calcium carbonate, aluminum borate, and glass borate.
  • the form of the insulating base material (A) is not particularly limited as long as it has a three-dimensional structure having at least one dimension having a size of 0.5 ⁇ m to 5 mm, and is a flexible material, a rigid material, or a rigid flexible material. Any of the above can be used. More specifically, as the insulating base material (A), a commercially available material molded into powder, granular, fibrous, thread-like, rod-like, film-like, sheet-like, or plate-like may be used. A material formed into an arbitrary shape from the above-mentioned resin solution, melt liquid, and dispersion liquid may be used. Further, the insulating base material (A) may be a base material obtained by forming the above-mentioned resin material on a conductive material such as metal.
  • the powder or granular material may be spherical, polygonal, or amorphous.
  • the cross-sectional shape thereof may be a perfect circle or an ellipse, and there are many cases. It may be rectangular or amorphous.
  • the form of the insulating base material (A) may be an aggregate of three-dimensional molded bodies having a three-dimensional structure having a size of at least one dimension of 0.5 ⁇ m to 5 mm.
  • it may be a colloidal crystal in which a large number of particles of the size are aggregated, and paper in which fibers having the size are aggregated, a woven fabric in which threads having the size are aggregated, a non-woven fabric, a web, a net, a mesh, and the like are also preferably used. be able to.
  • the insulating base material may have through holes in the base material, and when the insulating base material is a film or a plate, through holes may be formed, and the insulating material may be formed.
  • the base material (A) When the base material (A) has a rod shape, it may have a macaroni-like structure due to the presence of through holes.
  • the insulating base material (A) when the insulating base material (A) is in the form of particles, it may have a donut-like structure due to the presence of through holes. There may be one through hole, a large number of through holes, and the insulating base material (A) may have a porous structure.
  • the pillar portion forming the porous structure When the insulating base material (A) has a porous structure, the pillar portion forming the porous structure may have a size of 0.5 ⁇ m to 5 mm.
  • the primer layer (B) is formed so as to cover at least a continuous series of surfaces on the three-dimensional insulating molded base material (A). At least a continuous series of surfaces on the three-dimensional insulating molded substrate (A) is a cross section of a three-dimensional molded body formed in a direction orthogonal to the surface covered by the primer layer, as illustrated in FIG. In, it means that the primer layer has a continuous structure without a break (FIG. 1).
  • the primer layer (B) is formed so as to cover at least a continuous series of surfaces on the insulating molded substrate (A), that is, orthogonal to the surface covered by the primer layer.
  • a primer is placed on the continuous series of surfaces of the insulating base material (A). It can be formed by coating and removing a solvent such as an aqueous medium and an organic solvent contained in the primer.
  • the primer is a liquid composition in which various resins described later are dissolved or dispersed in a solvent.
  • the method of applying the primer to the insulating base material (A) is not particularly limited as long as the primer layer (B) can be formed so as to cover a continuous series of surfaces of the insulating base material (A).
  • Various coating methods may be appropriately selected depending on the shape, size, degree of flexibility and the like of the insulating base material (A) to be used. Specific coating methods include, for example, a gravure method, an offset method, a flexographic method, a pad printing method, a gravure offset method, a letterpress method, a letterpress inversion method, a screen method, a microcontact method, a reverse method, and an air doctor coater method.
  • Blade coater method air knife coater method, squeeze coater method, impregnation coater method, transfer roll coater method, kiss coater method, cast coater method, spray coater method, inkjet method, die coater method, spin coater method, bar coater method, dip coater method. And so on.
  • a spray coater method, a dip coater method, or the like can be preferably used for the purpose of efficiently forming the primer layer (B) so as to cover a continuous series of surfaces of the three-dimensional molded body. ..
  • the method of applying the primer to the surface of the insulating base material (A) is to unwind the fiber, thread, woven fabric, roll film or roll sheet in which the insulating base material (A) is a continuum.
  • the coating may be performed by a roll-to-roll equipped with a take-up mechanism or a reel-to-reel type device.
  • the insulating base material (A) may be surface-treated before the primer is applied for the purpose of improving the coatability of the primer.
  • the surface treatment method for the insulating base material (A) is not particularly limited as long as the characteristics of the insulating base material (A) itself are not deteriorated, and various methods may be appropriately selected. Examples of such a surface treatment method include UV treatment, vapor phase ozone treatment, liquid layer ozone treatment, corona treatment, plasma treatment and the like. These surface treatment methods may be carried out by one kind of method or a combination of two or more kinds of methods.
  • drying using a dryer As a method of applying the primer to the surface of the insulating base material (A) and then removing the solvent contained in the coating layer to form the primer layer (B), for example, drying using a dryer is used.
  • the method of volatilizing the solvent is common.
  • the drying temperature may be set to a temperature within a range in which the solvent can be volatilized and does not adversely affect the insulating base material (A), and may be room temperature drying or heat drying.
  • the specific drying temperature is preferably in the range of 20 to 350 ° C, more preferably in the range of 60 to 300 ° C.
  • the drying time is preferably in the range of 1 to 200 minutes, more preferably in the range of 1 to 60 minutes.
  • the above drying may be performed by blowing air, or may not be blown in particular. Further, the drying may be carried out in the atmosphere, in a substitution atmosphere such as nitrogen or argon, in an air flow, or in a vacuum.
  • a substitution atmosphere such as nitrogen or argon
  • the insulating base material (A) is a fiber, a thread, a woven fabric, a sheet-fed film, a sheet, a board, etc., which are three-dimensional molded bodies that are individualized, they are naturally dried at the coating site. In addition, it can be performed in a dryer such as a blower or a constant temperature dryer. Further, when the insulating base material (A) is a continuous fiber, thread, woven fabric, roll film or roll sheet, the insulating base material (A) is rolled in an installed non-heated or heated space following the coating process. Drying can be performed by continuously moving the material.
  • the film thickness of the primer layer (B) may be appropriately selected depending on the intended use of the plated product manufactured using the present invention, but the insulating substrate (A) and the above are described because the primer layer is a continuous film. Since the adhesion to the metal film (M) can be further improved, the range of 10 nm to 30 ⁇ m is preferable, the range of 30 nm to 5 ⁇ m is more preferable, and the range of 50 nm to 1 ⁇ m is further preferable.
  • the resin forming the primer layer (B) is solid in the temperature range in which the product manufactured by the technique of the present invention is used, and is particularly limited as long as a continuous film can be formed on the insulating base material (A).
  • a dispersant for metal particles which will be described later, is used in the step of forming a metal film (M) on the primer layer (B) and has a reactive functional group [Y]
  • the reactive functional group is used.
  • a resin having a reactive functional group [X] having reactivity with [Y] is preferable.
  • Examples of the reactive functional group [X] include an amino group, an amide group, an alkyrole amide group, a keto group, a carboxyl group, an anhydrous carboxyl group, a carbonyl group, an acetoacetyl group, an epoxy group, an alicyclic epoxy group and an oxetane.
  • Examples thereof include a ring, a vinyl group, an allyl group, a (meth) acryloyl group, a (blocked) isocyanate group, and a (alkoxy) silyl group.
  • a silsesquioxane compound can also be used as the compound forming the primer layer (B).
  • the adhesion of the metal film (M) on the insulating substrate (A) can be further improved.
  • the resin forming the primer layer (B) has a keto group, a carboxyl group, a carbonyl group, an acetoacetyl group, an epoxy group, an alicyclic epoxy group, an alkylolamide group, an isocyanate group and vinyl as the reactive functional group [X]. Those having a group, a (meth) acryloyl group, and an allyl group are preferable.
  • Examples of the resin forming the primer layer (B) include a urethane resin, an acrylic resin, a core-shell type composite resin having a urethane resin as a shell and an acrylic resin as a core, an epoxy resin, an imide resin, an amide resin, and a melamine resin. , Phenolic resin, urea formaldehyde resin, blocked isocyanate obtained by reacting polyisocyanate with a blocking agent such as phenol, polyvinyl alcohol, polyvinylpyrrolidone and the like.
  • the core-shell type composite resin having a urethane resin as a shell and an acrylic resin as a core can be obtained, for example, by polymerizing an acrylic monomer in the presence of a urethane resin. Further, these resins can be used alone or in combination of two or more.
  • a resin that produces a reducing compound by heating is preferable because the adhesion of the metal film (M) to the insulating substrate (A) can be further improved.
  • the reducing compound include phenol compounds, aromatic amine compounds, sulfur compounds, phosphoric acid compounds, aldehyde compounds and the like. Among these reducing compounds, phenol compounds and aldehyde compounds are preferable.
  • a reducing compound such as formaldehyde or phenol is produced in the heating and drying step when forming the primer layer (B).
  • the resin that produces a reducing compound by heating include a resin obtained by polymerizing a monomer containing N-alkyrole (meth) acrylamide, and N-alkyrole (meth) acrylamide using a urethane resin as a shell.
  • Core-shell type composite resin with a polymer polymer resin as the core urea-formaldehyde-methanol condensate, urea-melamine-formaldehyde-methanol condensate, poly N-alkoxymethylol (meth) acrylamide, poly (meth)
  • examples thereof include a formaldehyde adduct of acrylamide, a resin that produces formaldehyde by heating a melamine resin, and the like; a resin that produces a phenol compound by heating a phenol resin, a phenol block isocyanate, and the like.
  • a core-shell type composite resin having a urethane resin as a shell and a resin obtained by polymerizing a monomer containing N-alkyrole (meth) acrylamide as a core, a melamine resin, and a phenol Blocked isocyanate is preferred.
  • (meth) acrylamide refers to one or both of “methacrylamide” and “acrylamide”
  • (meth) acrylic acid refers to "methacrylic acid” and "acrylic acid”. Refers to one or both.
  • the resin that produces a reducing compound by heating is obtained by polymerizing a monomer having a functional group that produces a reducing compound by heating by a polymerization method such as radical polymerization, anionic polymerization, or cationic polymerization.
  • Examples of the monomer having a functional group that produces a reducing compound by heating include N-alkyrole vinyl monomer, and specific examples thereof include N-methylol (meth) acrylamide and N-methoxymethyl (N-methoxymethyl). Meta) acrylamide, N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-isopropoxymethyl (meth) acrylamide, Nn-butoxymethyl (meth) acrylamide, N-isobutoxymethyl (meth) ) Acrylamide, N-pentoxymethyl (meth) acrylamide, N-ethanol (meth) acrylamide, N-propanol (meth) acrylamide and the like.
  • a monomer having a functional group that produces a reducing compound by heating when producing a resin that produces a reducing compound by heating, a monomer having a functional group that produces a reducing compound by heating, and various other types such as (meth) acrylic acid alkyl ester are used.
  • the monomers can also be copolymerized.
  • a uretdione bond is formed by self-reacting between the isocyanate groups, or the isocyanate group and the functional group of other components are used.
  • the bond formed at this time may be formed before the silver particle dispersion liquid is applied, or is not formed before the silver particle dispersion liquid is applied, and the silver particle dispersion liquid is not formed. May be formed by heating after coating.
  • Examples of the blocked isocyanate include those having a functional group formed by blocking the isocyanate group with a blocking agent.
  • the blocked isocyanate is preferably one having the functional group in the range of 350 to 600 g / mol per 1 mol of the blocked isocyanate.
  • the functional group preferably has 1 to 10 in one molecule of the blocked isocyanate, and more preferably 2 to 5.
  • the number average molecular weight of the blocked isocyanate is preferably in the range of 1,500 to 5,000, more preferably in the range of 1,500 to 3,000, from the viewpoint of improving adhesion.
  • the blocked isocyanate one having an aromatic ring is preferable from the viewpoint of further improving the adhesion.
  • the aromatic ring include a phenyl group and a naphthyl group.
  • the blocked isocyanate can be produced by reacting a part or all of the isocyanate groups of the isocyanate compound with the blocking agent.
  • Examples of the isocyanate compound as a raw material of the blocked isocyanate include 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylenediocyanate, tolylene diisocyanate, naphthalenedi isocyanate and the like.
  • Polyisocyanate compound having an aromatic ring an aliphatic polyisocyanate compound such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexanediisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, or polyisocyanate having an alicyclic structure.
  • Examples include compounds.
  • those burette form, isocyanurate form, adduct form and the like of the said polyisocyanate compound are also mentioned.
  • examples of the isocyanate compound include those obtained by reacting the polyisocyanate compound exemplified above with a compound having a hydroxyl group or an amino group.
  • polyisocyanate compound having an aromatic ring When introducing an aromatic ring into the blocked isocyanate, it is preferable to use a polyisocyanate compound having an aromatic ring.
  • polyisocyanate compounds having an aromatic ring 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, isocyanurate of 4,4'-diphenylmethane diisocyanate, and isocyanurate of tolylene diisocyanate are preferable.
  • Examples of the blocking agent used for producing the blocked isocyanate include phenol compounds such as phenol and cresol; lactam compounds such as ⁇ -caprolactam, ⁇ -valerolactam and ⁇ -butyrolactam; Oxime compounds such as methyl ethyl keto oxime, methyl isobutyl keto oxime, cyclohexanone oxime; 2-hydroxypyridine, butyl cellosolve, propylene glycol monomethyl ether, benzyl alcohol, methanol, ethanol, n-butanol, isobutanol, dimethyl malonate, diethyl malonate, acet Methyl acetate, ethyl acetoacetate, acetylacetone, butyl mercaptan, dodecyl mercaptan, acetoanilide, acetate amide, succinate imide, maleate imide, imidazole, 2-methyl imidazole, urea, thiour
  • a blocking agent capable of dissociating to generate an isocyanate group by heating in the range of 70 to 200 ° C. is preferable, and a block capable of producing an isocyanate group dissociating by heating in the range of 110 to 180 ° C. is preferable.
  • Agents are more preferred. Specifically, a phenol compound, a lactam compound, and an oxime compound are preferable, and a phenol compound is more preferable because it becomes a reducing compound when the blocking agent is desorbed by heating.
  • Examples of the method for producing the blocked isocyanate include a method of mixing and reacting the isocyanate compound produced in advance with the blocking agent, a method of mixing and reacting the blocking agent with a raw material used for producing the isocyanate compound, and the like. Can be mentioned.
  • the blocked isocyanate produces an isocyanate compound having an isocyanate group at the terminal by reacting the polyisocyanate compound with a compound having a hydroxyl group or an amino group, and then the isocyanate compound and the block. It can be produced by mixing and reacting with an agent.
  • the content ratio of the blocked isocyanate obtained by the above method in the resin forming the primer layer (B) is preferably in the range of 50 to 100% by mass, more preferably in the range of 70 to 100% by mass.
  • the melamine resin examples include mono or polymethylol melamine in which 1 to 6 mol of formaldehyde is added to 1 mol of melamine; (poly) methylol melamine such as trimethoxymethylol melamine, tributoxymethylol melamine, and hexamethoxymethylol melamine. Ethereate (arbitrary degree of etherification); urea-melamine-formaldehyde-methanol condensate and the like.
  • a method of adding a reducing compound to the resin can also be mentioned.
  • the reducing compound to be added include phenol-based antioxidants, aromatic amine-based antioxidants, sulfur-based antioxidants, phosphoric acid-based antioxidants, vitamin C, vitamin E, and ethylenediamine tetraacetic acid. Examples thereof include sodium, sulfite, hypophosphoric acid, hypophosphite, hydrazine, formaldehyde, sodium hydride, dimethylamine borane, phenol and the like.
  • the method of adding a reducing compound to a resin may result in deterioration of electrical properties due to the residual low molecular weight component or ionic compound. Therefore, a resin that produces a reducing compound by heating. Is more preferable.
  • the primer used to form the primer layer (B) preferably contains 1 to 70% by mass of the resin in the primer from the viewpoint of coatability and film forming property, and contains 1 to 20% by mass. The one is more preferable.
  • examples of the solvent that can be used for the primer include various organic solvents and aqueous media.
  • examples of the organic solvent include toluene, ethyl acetate, methyl ethyl ketone, cyclohexanone and the like
  • examples of the aqueous medium include water, an organic solvent miscible with water, and a mixture thereof.
  • organic solvent to be mixed with water examples include alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, ethyl carbitol, ethyl cellosolve and butyl cellosolve; ketone solvents such as acetone and methyl ethyl ketone; ethylene glycol, diethylene glycol and propylene.
  • alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, ethyl carbitol, ethyl cellosolve and butyl cellosolve
  • ketone solvents such as acetone and methyl ethyl ketone
  • ethylene glycol diethylene glycol and propylene.
  • alkylene glycol solvent such as glycol
  • a polyalkylene glycol solvent such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol
  • lactam solvent such as N-methyl-2-pyrrol
  • the resin forming the primer layer (B) may have a functional group that contributes to the crosslinking reaction, such as an alkoxysilyl group, a silanol group, a hydroxyl group, or an amino group, if necessary.
  • the crosslinked structure formed by utilizing these functional groups may have already formed the crosslinked structure before the step of forming the metal film (M1) formed from the metal particles in the subsequent step, or the metal.
  • a crosslinked structure may be formed after the step of forming the metal film (M1) formed from the particles.
  • a crosslinked structure is formed on the primer layer (B) before forming the metal film (M2).
  • a crosslinked structure may be formed in the primer layer (B) by, for example, aging after forming the metal film (M2).
  • a known substance such as a cross-linking agent, a pH adjuster, a film forming aid, a leveling agent, a thickener, a water repellent agent, and an antifoaming agent is appropriately added to the primer layer (B). May be used.
  • the cross-linking agent examples include a metal chelate compound, a polyamine compound, an aziridine compound, a metal salt compound, an isocyanate compound and the like, and a thermal cross-linking agent that reacts at a relatively low temperature of about 25 to 100 ° C. to form a cross-linking structure.
  • thermal cross-linking agents such as melamine-based compounds, epoxy-based compounds, oxazoline compounds, carbodiimide compounds, and blocked isocyanate compounds that react at a relatively high temperature of 100 ° C. or higher to form a cross-linking structure, and various photocross-linking agents.
  • the amount of the cross-linking agent used varies depending on the type, from the viewpoint of improving the adhesion of the metal film (M) of the insulating base material, 0.01 to 0.01 to 100 parts by mass of the resin contained in the primer.
  • the range of 60 parts by mass is preferable, the range of 0.1 to 10 parts by mass is more preferable, and the range of 0.1 to 5 parts by mass is further preferable.
  • the cross-linking structure may already be formed before the step of forming the metal particle layer (M1) containing the metal particles in the subsequent step, or the metal particles formed from the metal particles.
  • a crosslinked structure may be formed after the step of forming the layer (M1).
  • the crosslinked structure may be formed on the primer layer (B) before the metal film (M2) is formed.
  • a crosslinked structure may be formed in the primer layer (B) by, for example, aging after forming the metal film (M2).
  • a metal film (M) is formed on the primer layer (B) formed on the insulating base material (A).
  • One of the preferable modes in the method for forming a metal film on a three-dimensional molded body of the present invention is a metal particle film (M1) in which the metal film (M) formed on the primer layer (B) is formed from metal particles. ).
  • the metal particles forming the metal particle layer (M1) are selected from the group consisting of silver, copper, nickel, gold, platinum, palladium, ruthenium, tin, iron, cobalt, titanium, indium, iridium and the like.
  • One or more kinds of metals can be preferably used.
  • silver or copper particles are preferably used as the main component because they are relatively inexpensive and have a sufficiently low electrical resistance as a conductive metal layer, and are stored in the atmosphere.
  • silver particles it is particularly preferable to use silver particles as a main component because the surface is not easily oxidized.
  • the metal particles When silver particles are used as the main component of the metal particles, the metal particles may contain a metal other than silver, and when a metal other than silver is contained, the proportion of the metal other than silver is described later. As long as the plating in No. 3 can be carried out without any problem, there is no particular limitation, but 5 parts by mass or less is preferable with respect to 100 parts by mass of silver, and 2 parts by mass or less is more preferable.
  • the metal other than silver may contain a component other than silver in the individual metal particles, or may contain particles of a metal other than silver. good.
  • the metal substituted or mixed with silver include one or more metal elements selected from the group consisting of gold, platinum, palladium, ruthenium, tin, copper, nickel, iron, cobalt, titanium, indium and iridium.
  • the metal is placed on a primer layer (B) formed so as to cover at least a continuous series of surfaces on the insulating base material (A).
  • a metal particle layer (M1) is formed on the primer layer (B).
  • the coating method of the metal particle dispersion liquid is not particularly limited, and various coating methods mentioned in the primer coating may be appropriately selected.
  • the method of applying the dispersion liquid of the metal particles may be the same as the method of applying the primer, or a different method may be used.
  • the primer layer (B) has the same purpose as the insulating base material (A) for improving the coatability of the metal particle dispersion and improving the adhesion of the metal film (M) to the primer layer. Therefore, the surface treatment may be performed before applying the metal particle dispersion liquid. As the surface treatment method, various surface treatment methods mentioned in the primer coating may be appropriately selected.
  • the coating film is dried and fired to volatilize the solvent contained in the metal particle dispersion liquid, and the insulating base material (the insulating base material (A)).
  • a metal particle layer (M1) is formed on A).
  • drying mainly means a process of volatilizing a solvent from the dispersion liquid of the metal particles
  • firing mainly means a process of joining metal particles to each other.
  • the above drying and firing may be performed at the same time, or the coating film may be dried once and then fired if necessary before use.
  • the drying temperature and time may be appropriately selected depending on the body heat temperature of the insulating base material (A) to be used and the type of solvent used for the metal particle dispersion liquid described later, and may be 20 ° C. to 250 ° C.
  • the time is preferably in the range of 1 to 200 minutes.
  • the firing temperature and time may be appropriately selected according to the conductivity required for the metal particle layer (M1), but the temperature is in the range of 80 to 350 ° C. and the time is in the range of 1 to 200 minutes. Is preferable.
  • the above drying / firing may be performed by blowing air, or may not be blown in particular. Further, the drying / firing may be performed in the atmosphere, under a substitution atmosphere of an inert gas such as nitrogen or argon, under an air flow, or under a vacuum.
  • an inert gas such as nitrogen or argon
  • the metal particle layer (M1) contains metal particles in the range of 80 to 99.9% by mass, and contains a polymer dispersant component described later in the range of 0.1 to 20% by mass. Is preferable.
  • the thickness of the metal particle layer (M1) is preferably in the range of 30 to 500 nm.
  • the metal film (M) is a metal particle film (M1) formed of metal particles and a plated metal film (M2) laminated on the metal particle film (M1)
  • the metal particle layer (M1) is a plated metal film (M2).
  • the thickness of the metal particle layer (M1) is preferably 50 to 500 nm.
  • the thickness of the metal particle layer (M1) can be estimated by various known and commonly used methods. For example, a cross-sectional observation method using an electron microscope or a method using fluorescent X-rays can be used. It is convenient and preferable to use the linear method.
  • the metal particle dispersion used in the present invention for forming the metal particle layer (M1) is one in which metal particles are dispersed in a solvent.
  • the shape of the metal particles is not particularly limited as long as it can form the metal particle layer (M1) satisfactorily, and has various shapes such as spherical, lenticular, polyhedral, flat plate, rod, and wire.
  • Metal particles can be used. These metal particles may be used as one type having a single shape, or may be used in combination with two or more types having different shapes.
  • the average particle diameter thereof is preferably in the range of 1 to 20,000 nm. Further, when used for the purpose of forming a fine circuit pattern, the homogeneity of the metal particle layer (M1) can be further improved, and the removability by an etching solution can be further improved. Therefore, the average particle diameter thereof is 1 to 200 nm. Those in the range of 1 to 50 nm are more preferable.
  • the "average particle size" of the nanometer-sized particles is a volume average value measured by a dynamic light scattering method obtained by diluting the silver particles with a good dispersion solvent. "Nanotrack UPA-150" manufactured by Microtrack Co., Ltd. can be used for this measurement.
  • the metal particles have a shape such as a lens shape, a rod shape, or a wire shape
  • those having a minor axis in the range of 1 to 200 nm are preferable, those having a minor axis in the range of 2 to 100 nm are more preferable, and those having a minor axis in the range of 5 to 50 nm are more preferable. Those in the range of are more preferable.
  • the metal particle dispersion used to form the metal particle layer (M1) is one in which metal particles are dispersed in various solvents, and the particle size distribution of the metal particles in the dispersion is uniform in a single dispersion. It may be a mixture of particles within the above average particle size range.
  • an aqueous medium or an organic solvent can be used as the solvent used for the dispersion liquid of the metal particles.
  • the aqueous medium include distilled water, ion-exchanged water, pure water, ultrapure water, and a mixture of the water and an organic solvent to be mixed with the water.
  • Examples of the organic solvent to be mixed with water include alcohol solvents such as methanol, ethanol, n-propanol, isopropanol, ethyl carbitol, ethyl cellosolve and butyl cellosolve; ketone solvents such as acetone and methyl ethyl ketone; ethylene glycol, diethylene glycol and propylene.
  • Examples thereof include an alkylene glycol solvent such as glycol; a polyalkylene glycol solvent such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol; and a lactam solvent such as N-methyl-2-pyrrolidone.
  • examples of the organic solvent when the organic solvent is used alone include alcohol compounds, ether compounds, ester compounds, and ketone compounds.
  • Examples of the alcohol solvent or ether solvent include methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, sec-butanol, tert-butanol, heptanol, hexanol, octanol, nonanol, decanol, undecanol, and dodecanol.
  • Tridecanol Tetradecanol, Pentadecanol, Stearyl Alcohol, Allyl Alcohol, Cyclohexanol, Terpineol, Tarpineol, Dihydroterpineol, 2-Ethyl-1,3-hexanediol, Ethylene Glycol, Diethylene Glycol, Triethylene Glycol, Polyethylene Glycol, Propylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Monobutyl Ether, Diethylene Glycol Monoethyl Ether, Diethylene Glycol Monomethyl Ether, Diethylene Glycol Monobutyl Ether, Tetraethylene Glycol Monobutyl Ether, Propylene Glycol Monomethyl
  • Examples of the ketone solvent include acetone, cyclohexanone, methyl ethyl ketone and the like.
  • Examples of the ester solvent include ethyl acetate, butyl acetate, 3-methoxybutyl acetate, 3-methoxy-3-methyl-butyl acetate and the like.
  • a hydrocarbon solvent such as toluene, particularly a hydrocarbon solvent having 8 or more carbon atoms can be mentioned.
  • hydrocarbon solvent having 8 or more carbon atoms examples include non-polar solvents such as octane, nonane, decane, dodecane, tridecane, tetradecane, cyclooctane, xylene, mesitylene, ethylbenzene, dodecylbenzene, tetraline, and trimethylbenzenecyclohexane. It can be used in combination with other solvents as needed. Further, a solvent such as mineral spirit or solvent naphtha which is a mixed solvent can be used in combination.
  • non-polar solvents such as octane, nonane, decane, dodecane, tridecane, tetradecane, cyclooctane, xylene, mesitylene, ethylbenzene, dodecylbenzene, tetraline, and trimethylbenzenecyclohexane. It can be used in combination with other solvent
  • the solvent is particularly limited as long as the metal particles are stably dispersed and the metal particle layer (M1) is satisfactorily formed on the primer layer (B) formed on the insulating base material (A). There is no limit. Further, the solvent may be used alone or in combination of two or more.
  • the content of the metal particles in the metal particle dispersion is adjusted so as to have a viscosity having optimum coating suitability according to the above coating method, but is preferably in the range of 0.5 to 90% by mass.
  • the range of 1 to 60% by mass is more preferable, and the range of 2 to 10% by mass is more preferable.
  • the metal particles do not aggregate, fuse, or precipitate in the various solvent media, and the dispersion stability is maintained for a long period of time. It is coated with a polymer dispersant for dispersion.
  • a polymer dispersant for dispersion, a dispersant having a functional group that coordinates with the metal particles is preferable, and for example, a carboxyl group, an amino group, a cyano group, an acetoacetyl group, a phosphorus atom-containing group, a thiol group, and a thiocyanato group.
  • Dispersants having a functional group such as a glycinato group can be mentioned.
  • the dispersant a commercially available or independently synthesized low molecular weight or high molecular weight dispersant can be used, and the insulating molded body coated with a solvent for dispersing silver particles or a dispersion liquid of silver particles is applied. It may be appropriately selected according to the purpose such as the type of (A).
  • a polycyclic hydrocarbon compound having a carboxyl group of the above is preferably used, but a reactive functional group [Y] capable of forming a bond with the reactive functional group [X] of the resin used for the primer layer (B). It is preferable to use a compound having.
  • Examples of the compound having a reactive functional group [Y] include an amino group, an amide group, an alkyrole amide group, a carboxyl group, an anhydrous carboxyl group, a carbonyl group, an acetoacetyl group, an epoxy group, an alicyclic epoxy group and an oxetan ring. , Vinyl group, allyl group, (meth) acryloyl group, (blocked) isocyanate group, (alkoxy) silyl group and the like, silsesquioxane compound and the like.
  • the reactive functional group [Y] is preferably a basic nitrogen atom-containing group because the adhesion between the primer layer (B) and the conductive metal layer (M1) can be further improved.
  • Examples of the basic nitrogen atom-containing group include an imino group, a primary amino group, a secondary amino group and the like.
  • the basic nitrogen atom-containing group may be singular or plural in one molecule of the dispersant. By containing a plurality of basic nitrogen atoms in the dispersant, some of the basic nitrogen atom-containing groups contribute to the dispersion stability of the metal particles by interacting with the silver particles, and the remaining basic nitrogen. The atom-containing group contributes to improving the adhesion to the insulating base material (A). Further, when a resin having a reactive functional group [X] is used for the primer layer (B) described later, the basic nitrogen atom-containing group in the dispersant is between the reactive functional group [X]. It is preferable because a bond can be formed with the metal film (M) and the adhesion of the metal film (M) to the insulating base material (A) can be further improved.
  • the polymer dispersant can form a metal particle layer (M1) showing stability, coatability, and good adhesion on the primer layer (B) of the dispersion liquid of metal particles, polyethyleneimine, Polyalkylene imine such as polypropylene imine, a compound obtained by adding polyoxyalkylene to the polyalkylene imine, and the like are preferable.
  • the compound to which polyoxyalkylene is added to the polyalkyleneimine may be a compound in which polyethyleneimine and polyoxyalkylene are bonded in a linear manner, and the side of the main chain made of polyethyleneimine is the side thereof.
  • the chain may be grafted with polyoxyalkylene.
  • the compound in which polyoxyalkylene is added to the polyalkyleneimine include a block copolymer of polyethyleneimine and polyoxyethylene, and ethylene oxide in a part of the imino group present in the main chain of polyethyleneimine.
  • examples thereof include those in which a polyoxyethylene structure is introduced by an addition reaction, and those in which an amino group possessed by polyalkyleneimine, a hydroxyl group possessed by polyoxyethylene glycol, and an epoxy group possessed by an epoxy resin are reacted.
  • Examples of the commercially available product of the polyalkyleneimine include “PAO2006W”, “PAO306”, “PAO318” and “PAO718” of "Epomin (registered trademark) PAO series” manufactured by Nippon Shokubai Co., Ltd.
  • the number average molecular weight of the polyalkyleneimine is preferably in the range of 3,000 to 30,000.
  • the amount of the dispersant required to disperse the metal particles is preferably in the range of 0.01 to 50 parts by mass with respect to 100 parts by mass of the metal particles, and on the primer layer (B). Since a metal particle layer (M1) exhibiting good adhesion can be formed, the range of 0.1 to 10 parts by mass is preferable with respect to 100 parts by mass of the metal particles, and the metal particle layer (M1) is more conductive. When used as a plating seed, the range of 0.1 to 5 parts by mass is more preferable because the conductivity of the metal particle layer (M1) can be improved.
  • the method for producing the dispersion liquid of the metal particles is not particularly limited and can be produced by using various methods.
  • the metal particles produced by a vapor phase method such as an evaporation method in a low vacuum gas can be used as a solvent. It may be dispersed therein, or the metal compound may be reduced in the liquid phase to directly prepare a dispersion of metal particles.
  • the solvent composition of the dispersion liquid at the time of production and the dispersion liquid at the time of coating can be changed as appropriate by exchanging the solvent or adding a solvent.
  • the liquid phase method can be particularly preferably used because of the stability of the dispersion liquid and the simplicity of the manufacturing process.
  • a liquid phase method for example, it can be produced by reducing metal ions in the presence of the polymer dispersant.
  • the dispersion liquid of the metal particles may further contain an organic compound such as a surfactant, a leveling agent, a viscosity modifier, a film forming aid, an antifoaming agent, and an antiseptic.
  • an organic compound such as a surfactant, a leveling agent, a viscosity modifier, a film forming aid, an antifoaming agent, and an antiseptic.
  • surfactant examples include nonions such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene / polyoxypropylene copolymer.
  • fatty acid salts such as sodium oleate, alkyl sulfate ester salts, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, sodium alkyldiphenyl ether sulfonates
  • Anionic surfactants such as salts
  • cationic surfactants such as alkylamine salts, alkyltrimethylammonium salts, and alkyldimethylbenzylammonium salts can be mentioned.
  • leveling agent a general leveling agent can be used, and examples thereof include silicone-based compounds, acetylenediol-based compounds, and fluorine-based compounds.
  • a general thickener can be used as the viscosity modifier.
  • an acrylic polymer that can be thickened by adjusting it to alkaline, a synthetic rubber latex, and a thickening agent by associating molecules can be used.
  • examples thereof include urethane resin, hydroxyethyl cellulose, carboxymethyl cellulose, methyl cellulose, polyvinyl alcohol, water-added castor oil, amido wax, polyethylene oxide, metal soap, and dibenzylidene sorbitol.
  • a general film-forming auxiliary can be used.
  • an anionic surfactant such as dioctyl sulfosuccinate sodium salt, a hydrophobic nonionic surfactant such as sorbitan monooleate, etc. can be used.
  • a general defoaming agent can be used, and examples thereof include silicone-based defoaming agents, nonionic-based surfactants, polyethers, higher alcohols, and polymer-based surfactants.
  • a general preservative can be used, for example, an isothiazoline-based preservative, a triazine-based preservative, an imidazole-based preservative, a pyridine-based preservative, an azole-based preservative, a pyrithione-based preservative, and the like. Can be mentioned.
  • a more preferable uniform of the method for forming a metal film on a three-dimensional molded body of the present invention is that the metal film (M) is further plated on a metal particle film (M1) formed of metal particles (M2). ) Are laminated.
  • Examples of the plating method for forming the plated metal film (M2) on the metal particle layer (M1) include electroless plating, electrolytic plating, and a method in which electroless plating and electrolytic plating are combined.
  • the metal particle layer (M1) can be used as a catalyst seed.
  • the plating layer (M2) may be formed by forming a thick film only by electrolytic plating, or by further performing electrolytic plating using the electrolytic plating layer formed by electrolytic plating as a conductive seed.
  • the plating layer (M2) may be thickened.
  • the plating layer (M2) may be formed by performing electrolytic plating after electroless plating.
  • the plating precipitation rate can be increased, which is advantageous because the production efficiency is high.
  • the metal plating layer (M2) When the metal plating layer (M2) is formed by electroless plating, examples of the plating metal include copper, nickel, chromium, cobalt, cobalt-tungsten, cobalt-tungsten-boron, tin and the like. When the metal plating layer (M2) has a conductor circuit pattern, it is preferable to use copper among these metals because the electric resistance value is low. Further, as described above, the metal plating layer (M2) can be formed by performing electrolytic plating after electroless plating. When electrolytic plating is used in combination, the plating precipitation rate can be increased, which is advantageous because the production efficiency is high.
  • the metal plating layer (M2) is formed by using electrolytic plating and electrolytic plating in combination
  • the deposited metal of the electrolytic plating and the electrolytic plating is the same. May be different.
  • electroless copper plating followed by electrolytic copper plating, electroless nickel plating followed by electrolytic copper plating, electroless nickel plating followed by electrolytic nickel plating, electroless cobalt plating followed by electrolytic copper plating, and the like can be mentioned.
  • the metal plating layer (M2) has a circuit pattern
  • copper is preferably used as the main metal constituting the metal plating layer (M2) because the electric resistance value is low, and electroless nickel or electroless nickel or electroless electrolysis is preferable.
  • the metal constituting the metal plating layer (M2) preferably contains a magnetic material, and nickel, iron-nickel alloy, or the like is preferably used.
  • the thickness of the electrolytic plating layer is appropriately selected as necessary.
  • the range is 0.1 ⁇ m to 2 ⁇ m in order to secure conductivity for proper electrolytic plating, and the range is 0.15 ⁇ m to 1 ⁇ m from the viewpoint of improving productivity. Is more preferable.
  • the plating metal constituting the metal plating layer (M2) may be, for example, copper.
  • the plating metal constituting the metal plating layer (M2) may be, for example, copper.
  • examples thereof include nickel, chromium, zinc, tin, gold, silver, rhodium, palladium, platinum and the like.
  • copper is preferable because it is inexpensive and has a low electric resistance value as described above, and the metal plating layer (M2) is plated with electrolytic copper. It is preferable to form.
  • the electrolytic copper plating may be performed by using a known and commonly used method, but a copper sulfate plating method using a copper sulfate bath is preferable.
  • a copper sulfate plating method using a copper sulfate bath is preferable.
  • the metal film (M) is used as an electromagnetic wave shield, it is preferable to contain a magnetic metal such as nickel or nickel-iron alloy as described above.
  • These electrolytic platings may be performed by a known and commonly used method, and commercially available plating additives can be preferably used.
  • the plating metal constituting the metal plating layer (M2) may be used alone or in combination of a plurality of the above-mentioned various metals.
  • the metal plating layer (M2) to be formed is for decorative purposes, copper plating is performed on the lower layer of the outermost nickel-chromium plating for the purpose of stress relief of the plated metal.
  • the copper plating carried out at this time may be carried out by subjecting the metal particle layer (M1) to electrolytic nickel plating, then electrolytic copper plating, and further electrolytic nickel and electrolytic chrome plating, or the metal particles. Electrolytic copper plating may be performed on the layer (PM1), followed by electrolytic nickel or electrolytic chrome plating. Further, the metal particle layer (M1) may be subjected to electrolytic copper plating and then electrolytic nickel plating or electrolytic nickel-iron alloy plating.
  • the metal film (M) formed on the insulating base material (A) may be patterned.
  • the unnecessary portion may be removed and patterned, or the metal particle layer may be patterned.
  • a method is used in which a pattern resist is formed on (M1), a plated metal layer (M2) is formed only on a necessary pattern portion, the resist is peeled off, and the metal particle layer (M1) on an unnecessary portion is removed by etching. May be.
  • the non-pattern forming portion of the metal particle layer (M1) is removed by a mechanical method such as marking or laser irradiation to leave the metal particle layer (M1) of the pattern portion, and the metal particle layer (M1) is seeded. As a result, plating of the pattern portion may be formed.
  • a base material in which transparency is important and resistance to a base material such as chromic acid and permanganic acid, which have a large environmental load are not used.
  • a base material in which transparency is important and resistance to a base material such as chromic acid and permanganic acid, which have a large environmental load are not used.
  • difficult-to-plating materials with a three-dimensional structure that makes it difficult to roughen the surface such as low chemical resistance, or conversely too high chemical resistance, and the roughening treatment causes deterioration of the strength and function of the base material.
  • metal plating with high adhesion can be performed.
  • the surface of the base material is not roughened, the surface of the metal film formed by plating becomes a glossy surface that reflects the smooth surface of the surface of the base material, so that the plating film thickness can be reduced, and the plating time can be shortened. Not only contributes to the improvement of productivity, but also contributes to the weight reduction of the base material.
  • it is a simple method that does not use an expensive vacuum device or electron beam irradiation device, it is possible to manufacture a product with high production efficiency and low cost.
  • in printed wiring board applications where high density and high frequency compatibility are advancing, if unevenness is formed on the surface by roughening processing, it becomes difficult to form a narrow pitch circuit and signal delay occurs.
  • the metal film forming method of the present invention not only a printed wiring board but also various members having a patterned metal layer on the surface of a base material, for example, a connector, an electromagnetic wave shield, an antenna such as RFID, a film capacitor and the like can be obtained. Can be manufactured. Furthermore, the metal film forming method of the present invention can also be suitably used in decorative plating applications in which a metal film is provided on a substrate having various shapes and sizes.
  • Polyester polyol (polyolpolyol obtained by reacting 1,4-cyclohexanedimethanol, neopentylglycol, and adipic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer) 100 By mass, 17.6 parts by mass of 2,2-dimethylolpropionic acid, 21.7 parts by mass of 1,4-cyclohexanedimethanol, 106.2 parts by mass of dicyclohexylmethane-4,4'-diisocyanate, and 178 parts by mass of methylethylketone. By reacting in the mixed solvent of the above, a urethane prepolymer solution having an isocyanate group at the terminal was obtained.
  • a monomer mixture consisting of 60 parts by mass of methyl methacrylate, 30 parts by mass of n-butyl acrylate and 10 parts by mass of Nn-butoxymethylacrylamide, and 20 parts by mass of a 0.5% by mass ammonium persulfate aqueous solution were added.
  • the parts were dropped from a separate dropping funnel over 120 minutes while keeping the temperature inside the reaction vessel at 80 ° C.
  • aqueous dispersion of a resin composition for a primer layer which is a core-shell type composite resin having the urethane resin as a shell layer and an acrylic resin made of methyl methacrylate or the like as a core layer, was obtained. ..
  • Preparation Example 1 Preparation of silver particle dispersion
  • a dispersion containing the agent was prepared.
  • ion-exchanged water, ethanol and a surfactant were added to the obtained dispersion to prepare a 5% by mass silver particle dispersion.
  • Preparation Example 2 Preparation of Primer (B-1)]
  • the mass ratio of isopropanol and water is 7/3, and the non-volatile content is 2% by mass.
  • Isoppil alcohol and deionized water were added to the dispersion and mixed to obtain a primer (B-1).
  • Example 1 A nylon thread (fishing line) of No. 0.1 (53 ⁇ m diameter) was used as the insulating base material (A), immersed in the primer prepared in Preparation Example 2 for 10 seconds, pulled up, and dried at 80 ° C. for 5 minutes. A primer layer having a thickness of 100 nm was formed on the entire surface of the nylon thread. Next, the nylon thread having the primer layer formed on the surface was immersed in the silver particle dispersion prepared in Preparation Example 1 for 10 seconds, then pulled up and dried at 120 ° C. for 5 minutes to obtain a 120 nm thick silver particle film (M1). A metal film (M) of a silver particle layer was formed on a nylon thread having a diameter of 53 ⁇ m, which is an insulating base material, via a primer layer (B-1).
  • a metal film (M) of a silver particle layer was formed on a nylon thread having a diameter of 53 ⁇ m, which is an insulating base material, via a primer layer (B-1).
  • the nylon thread having the metal film of the silver particle layer prepared by fixing it on the desk so that the adhesive side of Nichiban Cello Tape (registered trademark) faces up is attached to the tape surface and then strongly peeled off to form the nylon thread.
  • Nichiban Cello Tape registered trademark
  • Example 2 The nylon thread having the metal film of the silver particle layer (M1) obtained in Example 1 was placed in a non-electrolytic copper plating solution (“Circuposit 6550” manufactured by Roam & Haas Electronic Materials Co., Ltd.) at 35 ° C. , By immersing for 22 minutes to form an electrolytic copper plating film (thickness 0.5 ⁇ m) on the surface of silver particles, a primer layer (B-1) was placed on a 53 ⁇ m diameter nylon thread which is an insulating base material. A silver particle layer (M1) and a metal film (M) of a copper plating film (M2) were formed therethrough.
  • a non-electrolytic copper plating solution (“Circuposit 6550” manufactured by Roam & Haas Electronic Materials Co., Ltd.)
  • a primer layer (B-1) was placed on a 53 ⁇ m diameter nylon thread which is an insulating base material.
  • Example 3 In Example 2, the primer was changed from (B-1) of Preparation Example 2 to (B-2) of Preparation Example 3, the drying temperature was set to 120 ° C. for 5 minutes, a primer layer of 80 nm was formed, and silver particles were formed. In the same manner as in Example 2, a primer layer (B- A silver particle layer (M1) and a metal film (M) of a copper plating film (M2) were formed via 2).
  • Example 4 On the 97 ⁇ m diameter polyester yarn which is the insulating base material in the same manner as in Example 1 except that the polyester yarn (fishing line) of No. 0.35 (97 ⁇ m diameter) was used as the insulating base material (A). A metal film (M) of a silver particle layer was formed in the primer layer (B-2).
  • the obtained polyester yarn having a silver particle layer (M1) is treated with electroless nickel-boron plating (“Top Chemialoy 66-LF” manufactured by Okuno Pharmaceutical Co., Ltd.) at 65 ° C. for 2 minutes.
  • a nickel-boron plated layer having a thickness of 0.2 ⁇ m is formed on the silver particle layer (M1), and a primer layer (B-2) and silver are formed on a 97 ⁇ m diameter polyester yarn which is an insulating base material.
  • a particle layer (M1) and a nickel-boron plated layer (M2) were formed.
  • Example 5 An LCP monofilament (manufactured by Toray Industries, Inc.) having a diameter of 20 ⁇ m was used as the insulating base material (A), immersed in the primer prepared in Preparation Example 2 for 10 seconds, then pulled up and dried at 120 ° C. for 5 minutes to form a nylon thread. A primer layer having a thickness of 100 nm was formed on the entire surface. Next, the polyester yarn having the primer layer formed on the surface was immersed in the silver particle dispersion prepared in Preparation Example 1 for 10 seconds, then pulled up and dried at 120 ° C. for 5 minutes to obtain a 120 nm thick silver particle film (M1). A metal film (M) of a silver particle layer was formed on an LCP monofilament having a diameter of 20 ⁇ m, which is an insulating base material, via a primer layer (B-1).
  • a metal film (M) of a silver particle layer was formed on an LCP monofilament having a diameter of 20 ⁇ m, which is an insulating base
  • the LCP monofilament having the obtained silver particle layer (M1) was placed in an electroless copper plating solution (“Circuposit 6550” manufactured by Roam & Haas Electronic Materials Co., Ltd.) at 35 ° C. in the same manner as in Example 2. It was immersed for 10 minutes to form an electroless copper plating film (thickness 0.2 ⁇ m) on the surface of silver particles.
  • an electroless copper plating solution (“Circuposit 6550” manufactured by Roam & Haas Electronic Materials Co., Ltd.) at 35 ° C.
  • Example 6 A part of the LCP monofilament having a copper-plated layer (M2) obtained in Example 5 was immersed in a 38 mass% ferric chloride aqueous solution set at 40 ° C. for 20 seconds, and the silver particle layer (immersed portion). M1) and the copper plating layer (M2) were removed by etching to perform patterning. The primer layer (B) was not removed with the ferric chloride aqueous solution.
  • Example 7 As the insulating base material (A), a 100 ⁇ m pore net filter (manufactured by Millipore, NY1H04700, 47 mm ⁇ ; FIG. 2) made of nylon thread having a diameter of 50 ⁇ m was used, immersed in the primer prepared in Preparation Example 2 for 10 seconds, and then pulled up. After drying at 70 ° C. for 5 minutes, a primer layer having a thickness of 100 nm was formed on the entire surface of the nylon yarn. Next, the nylon thread having the primer layer formed on the surface was immersed in the silver particle dispersion prepared in Preparation Example 1 for 10 seconds, then pulled up and dried at 70 ° C. for 5 minutes to obtain a 120 nm thick silver particle film (M1).
  • M1 120 nm thick silver particle film
  • Example 2 After forming the primer layer (B) and the silver particle layer (M1) on the nylon thread of the net filter, which is the insulating base material (A), 0 was formed in the same manner as in Example 1. An electroless copper plating layer (M2) having a thickness of .5 ⁇ m was formed. Next, the net filter is fixed to a stainless steel frame, an electrolytically-free copper plating layer is placed on the cathode, and an electrolytic plating solution containing copper sulfate (copper sulfate 60 g / L, sulfuric acid 190 g / L, using phosphorus-containing copper as an anode).
  • copper sulfate copper sulfate 60 g / L, sulfuric acid 190 g / L, using phosphorus-containing copper as an anode.
  • Example 8 On the copper plating layer on the ⁇ 47 mm nylon net filter having the copper plating layer (M2) obtained in Example 7, a cover tape having a width of 5 mm (Macu Tape P-3, manufactured by McDermid) was applied to both sides of the filter. A silver particle layer in the part without the cover tape with a 38 mass% ferric chloride aqueous solution set at 40 ° C. using an etching machine (San Hayato Co., Ltd., ES-800M) and pasted in the same position in a grid pattern. (M1) and the copper plating layer (M2) were removed by etching to perform patterning. The primer layer (B) was not removed by the ferric chloride aqueous solution, and a 0.5 cm square arranged copper pattern was formed on the nylon net filter.
  • an etching machine San Hayato Co., Ltd., ES-800M
  • cellophane tape (registered trademark) was attached to the net filter on which the electrolytic copper plating layer (M2') pattern was formed, and the copper plating layer was peeled off when the surface of the net filter was observed. It was retained on the net substrate.
  • Example 9 In the same manner as in Example 7, after forming the primer layer (B) and the silver particle layer (M1) on the nylon thread of the net filter which is the insulating base material (A), the silver particle layer (M1) is formed. A 5 mm wide cover tape (MacDermid Co., Ltd., Macu Tape P-3) was attached in a striped manner at the same positions on the front and back of the formed net filter. This nylon net filter is subjected to electrolytically electrolytic copper plating in the same manner as in Example 7 to form a 0.5 ⁇ m thick electrolytically electrolytic copper plating layer (M2), and then the net filter is fixed to a stainless steel frame to be absent.
  • a 5 mm wide cover tape MacDermid Co., Ltd., Macu Tape P-3
  • An electrolytic copper plating layer is placed on the cathode, and a phosphorus-containing copper is used as an anode, and an electrolytic plating solution containing copper sulfate (copper sulfate 60 g / L, sulfate 190 g / L, chlorine ion 50 mg / L, additive (Roam and).
  • a copper plating layer (M2') having a thickness of 5 ⁇ m was formed in stripes by performing electrolytic plating at a current density of 2 A / dm 2 for 10 minutes using Copper Glyme ST-901 ”manufactured by Haas Electronic Materials Co., Ltd. ..
  • cellophane tape (registered trademark) was attached to the net filter on which the electrolytic copper plating layer (M2') pattern was formed, peeled off strongly, and the surface of the net filter was observed. The layer did not peel off and was retained on the net substrate.
  • Example 7 (Example 10) In Example 7, instead of performing electrolytic copper plating, an electrolytic nickel plating solution (sulfamic acid bath: nickel sulfamate / tetrahydrate 350 g / L, nickel chloride / hexahydrate 5 g / L, boric acid 60 g / L). On the nylon thread of the net filter, which is the insulating base material (A), in the same manner as in Example 5 except that plating was performed at 60 ° C., 8A / dm 2 , 8 minutes and 40 seconds using L).
  • a primer layer (B), a silver particle layer (M1), an electroless copper plating layer (M2) having a thickness of 0.5 ⁇ m, and a nickel plating layer (M2') having a thickness of 15 ⁇ m were formed on the surface.
  • M1 silver particle layer
  • M2 electroless copper plating layer
  • M2' nickel plating layer
  • Example 11 Amorphous polyester (Byron 200, manufactured by Toyobo Co., Ltd.) having an average size of 3 mm diameter x 5 mm length is immersed in the primer prepared in Preparation Example 2 for 10 seconds, and then the primer is filtered to remove the pellet. , A primer layer having a thickness of 100 nm was formed on the entire surface of the polyester pellet by drying at 80 ° C. for 5 minutes. Next, the polyester pellet having the primer layer formed therein is immersed in the silver particle dispersion prepared in Preparation Example 1 for 10 seconds, the silver particle dispersion is filtered, the pellet is taken out, and dried at 80 ° C. for 5 minutes. A silver particle layer (M1) having a thickness of 120 nm was formed.
  • Byron 200 manufactured by Toyobo Co., Ltd.
  • the pellets on which the silver particle layer (M1) was formed were placed in a stainless steel basket, and 35 were placed in an electroless copper plating solution (“Circuposit 6550” manufactured by Roam & Haas Electronic Materials Co., Ltd.) in the same manner as in Example 2. It was immersed at ° C. for 22 minutes to form a copper plating film having a thickness of 0.5 ⁇ m on the pellets. That is, a metal film (M) of a silver particle layer (M1) and a copper plating film (M2) is formed on an amorphous polyester pellet which is an insulating base material via a primer layer (B-1). bottom.
  • an electroless copper plating solution (“Circuposit 6550” manufactured by Roam & Haas Electronic Materials Co., Ltd.)
  • Example 12 A glass cloth (Nitto Boseki, WEA116E 2116 standard, 95 ⁇ m thickness) was immersed in the primer prepared in Preparation Example 3 for 10 seconds, then taken out and dried at 120 ° C. for 5 minutes to cover the entire surface of the glass fiber of the glass cloth. A 100 nm thick primer layer was formed. Next, the glass cloth having the primer layer formed was immersed in the silver particle dispersion prepared in Preparation Example 1 for 10 seconds, then taken out and dried at 200 ° C. for 5 minutes to obtain a 120 nm thick silver particle layer (M1). Formed.
  • M1 120 nm thick silver particle layer
  • the glass cloth on which the silver particle layer (M1) is formed is fixed to a stainless steel frame, the silver particle layer (M1) is placed on the cathode, and an electrolytic plating solution (copper sulfate) containing copper sulfate is used as an anode with phosphorus-containing copper as an anode.
  • Electrolytic plating at a current density of 2 A / dm 2 for 10 minutes using 60 g / L, 190 g / L sulfuric acid, 50 mg / L chlorine ion, and an additive (Copper Grim ST-901 manufactured by Roam & Haas Electronic Materials Co., Ltd.).
  • a copper-plated layer (M2') having a thickness of 5 ⁇ m was formed.
  • a silver particle layer was formed on the entire surface of the glass fiber of the glass cloth, which is an insulating base material, via a primer layer (B-1).
  • a metal film (M) of (M1) and a copper plating film (M2) was formed.
  • Cellotape (registered trademark) was attached to the glass cloth on which the electrolytic copper plating layer (M2') was formed, and it was strongly peeled off. When the surface of the glass cloth was observed, the copper plating layer did not peel off and was retained on the glass cloth substrate. Was done.
  • a silver particle layer (M1) was formed on the LCP monofilament and an electroless copper plating film (thickness 0.2 ⁇ m) was formed on the surface of the silver particles in the same manner as in Example 5 except that the primer layer was not formed. ..
  • Example 2 In Example 1, a process of forming electroless copper plating on nylon yarn was carried out based on a conventional method without forming a primer layer and a silver particle layer.
  • a predip solution for electroless plating (“OPC-SAL-M”, manufactured by Okuno Pharmaceutical Industry Co., Ltd.) was diluted with water to a ratio of 260 g / L and maintained at 25 ° C.
  • the nylon thread used in Example 1 was immersed in this liquid for 1 minute.
  • Pre-dilution liquid OPC-SAL-M, manufactured by Okuno Pharmaceutical Industry Co., Ltd.
  • Sn-Pd colloidal catalyst liquid OPC-90 catalystist, manufactured by Okuno Pharmaceutical Industry Co., Ltd.
  • OPC-SAL-M Sn-Pd colloidal catalyst liquid
  • OPC-90 catalystist manufactured by Okuno Pharmaceutical Industry Co., Ltd.
  • the activation solution (“OPC-505 Accelerator A”, manufactured by Okuno Pharmaceutical Industry Co., Ltd.) and the activation solution (“OPC-505 Accelerator B”, manufactured by Okuno Pharmaceutical Industry Co., Ltd.) were 100 mL / L, respectively. It was mixed and diluted with water to 8 mL / L and kept at 30 ° C. The nylon thread after the step of applying the catalyst compound was immersed in this for 5 minutes, then washed with running water for 2 minutes to apply a palladium catalyst to the inner wall of the through hole and the surfaces of both coppers, and then used in Example 2. When immersed in the electrolytic copper plating solution for 10 minutes, the plating film was peeled off during electroless plating.
  • Example 4 (Comparative Example 3)
  • the primer layer and the silver particle layer were not formed on the polyester yarn, and the plating process based on the conventional method was carried out in the same manner as in Comparative Example 2. It peeled off from the polyester thread.
  • Example 5 (Comparative Example 4)
  • the primer layer and the silver particle layer were not formed on the LCP monofilament, and the plating process based on the conventional method was carried out in the same manner as in Comparative Example 2. It was deposited only on the part, and the deposited plating film was easily peeled off.
  • Example 7 (Comparative Example 5) In Example 7, a cover film is attached to one side of a part of the nylon net filter and immersed in the primer layer, and in the cover film attached portion, the primer layer forms a structure that does not cover the entire fiber surface constituting the net. bottom. The cover film was removed, and thereafter, a silver particle layer (M1), an electroless copper plating layer (M2), and an electrolytic copper plating layer (M2') were formed in the same manner as in Example 7.
  • M1 silver particle layer
  • M2 an electroless copper plating layer
  • M2' electrolytic copper plating layer
  • cellophane tape (registered trademark) was attached to the net filter on which the electrolytic copper plating layer (M2') was formed, peeled off strongly, and the surface of the net filter was observed. The copper-plated layer at the position where the layer was not formed was peeled off.
  • Example 9 (Comparative Example 5)
  • the primer layer and the silver particle layer were not formed on the glass cloth, and the plating process based on the conventional method was carried out in the same manner as in Comparative Example 2. It was deposited only on the part, and the deposited plating film was easily peeled off.

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001107257A (ja) * 1999-10-07 2001-04-17 Inoac Corp 電気的不導体への金属メッキ方法
WO2017154879A1 (ja) * 2016-03-11 2017-09-14 Dic株式会社 積層体の製造方法
JP2019123909A (ja) * 2018-01-17 2019-07-25 日本エレクトロプレイテイング・エンジニヤース株式会社 無電解メッキ用被メッキ構造体および電気回路の構造体、並びに、無電解メッキの前処理方法および無電解メッキ方法
JP2019157158A (ja) * 2018-03-08 2019-09-19 三菱重工業株式会社 めっき層を有する成形品の製造方法

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JP4897165B2 (ja) * 2000-09-27 2012-03-14 名古屋メッキ工業株式会社 金属めっきされた有機高分子繊維の製造方法
JP2016160480A (ja) * 2015-02-28 2016-09-05 住江織物株式会社 めっき繊維及びその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001107257A (ja) * 1999-10-07 2001-04-17 Inoac Corp 電気的不導体への金属メッキ方法
WO2017154879A1 (ja) * 2016-03-11 2017-09-14 Dic株式会社 積層体の製造方法
JP2019123909A (ja) * 2018-01-17 2019-07-25 日本エレクトロプレイテイング・エンジニヤース株式会社 無電解メッキ用被メッキ構造体および電気回路の構造体、並びに、無電解メッキの前処理方法および無電解メッキ方法
JP2019157158A (ja) * 2018-03-08 2019-09-19 三菱重工業株式会社 めっき層を有する成形品の製造方法

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