WO2023090964A1 - Silver plating solution - Google Patents

Silver plating solution Download PDF

Info

Publication number
WO2023090964A1
WO2023090964A1 PCT/KR2022/018390 KR2022018390W WO2023090964A1 WO 2023090964 A1 WO2023090964 A1 WO 2023090964A1 KR 2022018390 W KR2022018390 W KR 2022018390W WO 2023090964 A1 WO2023090964 A1 WO 2023090964A1
Authority
WO
WIPO (PCT)
Prior art keywords
silver
solution
silver plating
substituted
unsubstituted
Prior art date
Application number
PCT/KR2022/018390
Other languages
French (fr)
Korean (ko)
Inventor
조현남
김현주
조혜선
Original Assignee
(주)피이솔브
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by (주)피이솔브 filed Critical (주)피이솔브
Priority to EP22896161.1A priority Critical patent/EP4379092A1/en
Publication of WO2023090964A1 publication Critical patent/WO2023090964A1/en

Links

Images

Classifications

    • 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
    • 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
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals using reducing agents
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/46—Electroplating: Baths therefor from solutions of silver
    • 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

Definitions

  • the present invention relates to a silver plating solution capable of producing a high-quality silver-plated product simply and environmentally friendly, and silver plating using the same.
  • Silver which belongs to precious metals, has been used for high-end ornaments, tableware, and money since ancient times. It is widely used in various batteries including batteries, electrodes for various electronic products such as automobiles and semiconductors, electromagnetic wave shielding and heat dissipation products, and mechanical parts.
  • metals with high reflectivity such as silver, aluminum, chrome, nickel, titanium, and copper are painted, plated, or deposited to make products.
  • painting, coating, and printing methods are used for products that do not have high conductivity or reflectivity.
  • Plating methods can obtain a reflective film with high conductivity, high-quality surface gloss, and high reflectivity even in thin films, but the defect rate is high during manufacturing.
  • the cost of plating treatment is excessive, and there are problems of air pollution and wastewater generation due to the emission of harmful substances during the plating process. It is possible to manufacture a thin film electrode or a reflective film with high reflectivity by deposition or sputtering under vacuum, which is a dry method. However, in the case of deposition, there are restrictions on the use of expensive vacuum equipment and the shape or size of the base material, and there are problems in mass production of small quantity and various products. there is In this way, in manufacturing desired industrial electrical and electronic products or household items using silver, the plating method has many environmental problems to be solved, such as a process that cannot but be used or a wastewater treatment problem.
  • Silver plating is largely divided into electrolytic silver plating and electroless silver plating. It is common to use a silver precursor or silver complex, but electroless silver plating uses electricity to deposit silver. The difference is that reducing agents are used instead, and that it can be easily plated on plastics, textiles, and ceramic products that do not conduct electricity.
  • electrolytic silver plating has been carried out in alkali cyan solutions such as potassium cyanide and sodium cyanide using highly toxic silver cyanide for a long time.
  • alkali cyan solutions such as potassium cyanide and sodium cyanide using highly toxic silver cyanide for a long time.
  • a lot of research and development has been conducted over the past decades to replace silver compounds such as silver nitrate with cyan-free silver plating using various complexing agents and other additives, but silver plating using cyan compounds is still the mainstream in commercial product production.
  • cyan-free silver plating has disadvantages such as poor adhesion, difficulty in manufacturing a bright silver-plated product, and easy contamination of the plating solution.
  • U.S. Patent No. 5,322,553 discloses that a more stable plating solution can be provided by using silver thiosulfate or silver sulfite
  • U.S. Patent No. 6,620,304 It mentions the possibility of producing high-quality products with a plating solution that does not use harmful substances by using amino acids such as cysteine in silver methanesulfonate.
  • 8,608,932 discloses a differentiated electrolytic silver plating method using a silver complex of 5,5-dimethyl hydantoin.
  • a plating solution of excellent products has not yet been developed.
  • the development of a silver plating solution that does not use a cyanide compound remains an ongoing task.
  • a silver ammonium complex called Tollens' reagent meets a compound having an aldehyde group such as glucose, it is reduced to form a silver mirroring.
  • This is a kind of electroless silver plating that shows the oxidation-reduction reaction well, and is used in the manufacture of vacuum flasks or dewar bottles.
  • this silver plating solution is prepared in a strong base aqueous solution using silver nitrate and ammonia water as a complexing agent, there is an explosion risk due to the generation of silver nitride in the storage process. There is a problem that needs to be treated and disposed of.
  • a plating solution using silver nitrate and ammonia water as a complexing agent shows excellent properties in stability and quality of the plating solution in electrolytic silver plating or electroless silver plating, but is used extremely limitedly due to these problems. Therefore, when electroless silver plating is performed, selection of a type of complexing agent and a suitable reducing agent accordingly has become a very important matter.
  • An object of the present invention is to provide a silver plating solution that is environmentally friendly and has excellent stability and a high-quality silver-plated product using the same.
  • the silver plating complex solution is a solution containing a carboxylic acid silver salt of the following general formula 1, wherein the silver plating A silver plating solution capable of performing electroless silver plating by a silver mirror reaction between a complex solution and the reducing agent solution is provided.
  • R 1 is hydrogen, a substituted or unsubstituted C 1 -C 22 alkyl group, a substituted or unsubstituted C 3 -C 30 cycloalkyl group, a substituted or unsubstituted C 6 -C 30 aralkyl group, A substituted or unsubstituted C 1 -C 30 heteroalkyl group, a substituted or unsubstituted C 2 -C 30 heterocycloalkyl group, or a substituted or unsubstituted C 5 -C 30 heteroaralkyl group.
  • a silver-plated product obtained by reacting the above-described silver plating solution at 5 to 50° C. is provided.
  • the present invention not only is an environmentally friendly silver plating solution excellent in storage stability and performance, but also various high-quality silver-plated products are provided using the silver plating solution.
  • Example 2 is a photograph of a silver mirror product of a glass bottle prepared in Example 3.
  • Example 3 is a product photograph of a silver mirror of a PET bottle prepared in Example 8.
  • Example 4 is a product and conductivity photograph of the silver-plated coated nylon fabric prepared in Example 41.
  • Example 5 is a product and conductivity photograph of the silver-coated nylon fiber prepared in Example 42.
  • Example 6 is an electron microscope (SEM) photograph of the surface of silver-plated coated nylon fibers prepared in Example 42.
  • Example 7 is a photograph of a mirror-image polyimide film coated with silver plating prepared in Example 43.
  • Example 8 is a photograph of the silver-plated coated polyurethane foam prepared in Example 45.
  • Example 10 is a photograph of silver-plated copper foil prepared in Example 50.
  • Example 11 is a photograph of a silver-containing cotton fabric having antibacterial properties prepared in Example 51.
  • Figure 13 shows the solution state after storage for 6 months at room temperature as a reducing agent solution prepared in Preparation Example 8.
  • alkyl includes a straight-chain, branched-chain, or cyclic hydrocarbon radical or a combination thereof, and in some cases may include one or more double bonds, triple bonds, or combinations thereof in the chain. That is, “alkyl” includes alkene or alkyne.
  • heteroalkyl refers to one or more carbon atoms and one or more heteroatoms selected from the group consisting of O, N, P, Si, and S. means a stable straight or branched chain or cyclic hydrocarbon radical consisting of, or combinations thereof, wherein the nitrogen, phosphorus and sulfur atoms may optionally be oxidized and the nitrogen heteroatoms may optionally be quaternized.
  • cycloalkyl and “heterocycloalkyl” by themselves or in combination with other terms, unless otherwise specified, refer to cyclic versions of “alkyl” and “heteroalkyl”, respectively.
  • aryl refers to a polyunsaturated, aromatic, hydrocarbon substituent which may be a single ring or multiple rings (1 to 3 rings) fused or covalently bonded together.
  • heteroaryl means an aryl group (or ring) comprising (in each separate ring in the case of multiple rings) 1 to 4 heteroatoms selected from N, O and S, the nitrogen and sulfur atoms being optionally oxidized, and the nitrogen atom(s) are optionally quaternized.
  • a heteroaryl group can be attached to the rest of the molecule through a carbon or heteroatom.
  • aralkyl refers to aryl and aryl substituted alkyl groups, wherein the alkyl and aryl portions independently are optionally substituted.
  • heteroarylkyl refers to an alkyl group substituted with an aryl and heteroaryl, respectively, wherein the alkyl and heteroaryl portions independently are optionally substituted.
  • substitution in the expression “substituted or unsubstituted” means that one or more hydrogen atoms in a hydrocarbon are each, independently of one another, replaced with the same or different substituents.
  • Useful substituents include but are not limited to the following.
  • G1 and G2 are each independently hydrogen; C 1 -C 10 alkyl group; Alternatively, it may be a C 6 -C 30 aryl group unsubstituted or substituted with a C 1 -C 10 alkyl group.
  • a “derivative” of a substance described in this specification means a substance in which some of the hydrogen atoms of the substance are substituted with the substituents described above.
  • the present invention is a silver plating solution for electroless silver plating comprising a silver plating complex solution and a reducing agent solution, wherein the silver plating complex solution is a solution containing a carboxylic acid silver salt of the following general formula 1, the silver plating complex solution and the reducing agent
  • a silver plating solution capable of performing electroless silver plating by a silver mirror reaction between solutions is provided.
  • R 1 is hydrogen, a substituted or unsubstituted C 1 -C 22 alkyl group, a substituted or unsubstituted C 3 -C 30 cycloalkyl group, a substituted or unsubstituted C 6 -C 30 aralkyl group, A substituted or unsubstituted C 1 -C 30 heteroalkyl group, a substituted or unsubstituted C 2 -C 30 heterocycloalkyl group, or a substituted or unsubstituted C 5 -C 30 heteroaralkyl group.
  • the present invention provides a silver plating solution containing a silver carboxylate compound represented by [General Formula 1] and a complexing agent in the form of a nitrogen-containing compound as main components, and various conductive products and silver mirror products using the same.
  • R 1 is hydrogen, a substituted or unsubstituted C 1 -C 22 alkyl group, a substituted or unsubstituted C 3 -C 30 cycloalkyl group, or a substituted or unsubstituted C 6 -C 30 aralkyl ( aralkyl), a substituted or unsubstituted C 1 -C 30 heteroalkyl group, a substituted or unsubstituted C 2 -C 30 heterocycloalkyl group, or a substituted or unsubstituted C 5 -C 30 heteroaralkyl group.
  • R 1 is hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl, n-pentyl, iso-amyl, t-amyl, n-hexyl, 2- Ethylhexyl, n-heptyl, octyl, iso-octyl, nonyl, decyl, neodecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, docosanyl, oleyl, linoleyl, cyclopropyl, cyclopentyl, cyclohexyl, etc. can be heard
  • a silver precursor of [General Formula 1] for example, silver acetate, silver propionate, silver trifluoroacetate, silver lactate, silver malonate ( silver malonate, silver maleate, silver fumarate, silver pyruvate, silver succinate, silver picrate, silver citrate citrate), silver 2-ethylhexanoate, silver neodecanoate, silver stearate, silver docosanoate, silver oleate, silver linoleate ( silver linoleate) and silver cyclohexane carboxylate.
  • silver malonate silver malonate, silver maleate, silver fumarate, silver pyruvate, silver succinate, silver picrate, silver citrate citrate
  • silver 2-ethylhexanoate silver neodecanoate
  • silver stearate silver docosanoate
  • silver oleate silver linoleate ( silver linoleate) and silver cyclohexane
  • silver alkanoates such as silver acetate, silver propionate, and silver neodecanoate, among the various carboxylic acid silver salts of [General Formula 1] are the most advantageous in the present invention in terms of economic efficiency, stability, and dissolution characteristics. It matches.
  • the content of silver used does not need to be particularly limited if it conforms to the present invention, but may generally be 0.05 to 5.0% by weight relative to the final plating solution, preferably 0.1 to 3.0%, and more preferably 0.2 to 2.0%. do. If the amount used is less or more than this, there is a problem in that the economical efficiency and stability of the plating solution decrease or the quality of the product deteriorates.
  • the complexing agent combines with silver ions in the silver plating solution to form stable complex ions so that they can be easily dissolved in a solvent at a high concentration.
  • the complexing agent is mainly an electron donor, and is preferably a compound containing a nitrogen atom, a phosphorus atom, or a sulfur atom, but a compound containing a nitrogen atom is more preferable in terms of stability and economy.
  • the nitrogen atom-containing compound is, for example, selected from the group consisting of ammonia, amines (primary, secondary, or tertiary amines), quaternary ammonium salts, and polyamines. It may be one or more.
  • a substituted or unsubstituted alkyl, aryl, aralkyl group or the like having 1 to 20 (C 1 -C 20 ) carbon atoms may be bonded to the nitrogen atom of the nitrogen atom-containing compound.
  • the alkyl group may have any form such as a linear type, a branched type, a comb type, a star-shaped or dendritic type, and a cyclic type.
  • the nitrogen atom-containing compound may have a functional group such as hydroxy, alkoxy, ester, amide, or urethane.
  • ammonia or amine compound among the nitrogen atom-containing compounds may be represented by the following [General Formula 2]
  • the quaternary ammonium salt compound may be represented by the following [General Formula 3].
  • R 2 to R 8 may be the same as or different from each other, and are each hydrogen or a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, or a substituted or unsubstituted C 3 -C 30 Cycloalkyl group, substituted or unsubstituted C 6 -C 30 aralkyl group, substituted or unsubstituted C 1 -C 30 heteroalkyl group, substituted or unsubstituted C 2 -C 30 heterocycloalkyl group, substituted or unsubstituted a C 5 -C 30 heteroaryl group, or a substituted or unsubstituted C 5 -C 30 heteroaralkyl group.
  • X is F - , Cl - , Br - , I - , OH - , hydrogen sulfate, bicarbonate, carbamate or perchlorate.
  • the nitrogen atom-containing compound is ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, tertiary-butylamine, n-pentylamine, iso -pentylamine, tert-amylamine, n-hexylamine, diethylamine, triethylamine, 2-ethylhexylamine, cyclohexylamine, allylamine, propargylamine, ethylenediamine, 1,3-propylenediamine, Hexamethylenediamine, triethylenediamine, 1,2-diaminopropane, monoethanolamine, diethanolamine, 1-amino-2-propanol, 3-amino-1-propanol, 1,4-butanediamine, spermine ), spermidine, diethylenetriamine, triethylenetetramine, tris(
  • the plating solution in an alkaline aqueous solution may contain ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) compounds, such as disodium EDTA, trisodium EDTA, and tetrasodium.
  • EDTA Tetrasodium EDTA
  • Sodium NTA Trisodium NTA
  • Succinimide Maleimide, Phthalimide, Ethylenediamine, Hexamethylenetetraamine, Saccharin, Imidazole, Oxazoline
  • At least one selected from the group consisting of hydantoin and 5,5-dimethyl hydantoin may be selected and used.
  • alkylamines such as ammonia, methylamine, and ethylamine are most suitable for the present invention in terms of economic feasibility and characteristics.
  • the content of the complexing agent used does not need to be particularly limited if it conforms to the present invention, but in general, it may be 0.1 to 10.0, preferably 0.3 to 7.0, more preferably 0.5 in terms of molar ratio relative to the silver carboxylic acid salt used. ⁇ 5.0 is appropriate. If the amount used is less or more than this, there is a problem in that the stability of the plating solution or the reaction is not completed and the quality is deteriorated.
  • the silver plating solution of the present invention may use water, ethanol, ethylene glycol, glycerin, or a mixture thereof as a solvent. That is, as an alcohol or glycol-containing aqueous solution, wetting is very excellent. Therefore, metals and metal alloys such as copper, nickel, zinc, tin, antimony, molybdenum, platinum, bronze, and brass, as well as oxides and sulfides of these metals, silica, alumina, titanium oxide, mica, and clay , ceramics such as glass, plastics such as polyester, nylon, polyimide, polyurethane, acrylic, various carbon compounds such as carbon, carbon nanotubes, graphite, graphene, rubber, and non-woven fabrics , any kind of substrates such as paper, their particles, flakes, beads, sheets, foils, films, fibers, etc. It has the advantage that it can be easily plated by using it regardless of the shape or shape.
  • the silver plating solution of the present invention can prepare and store the silver solution in advance and use it whenever necessary. characteristic.
  • the hydrogen ion concentration (pH) of the present invention does not need to be particularly limited, but the present invention is different from general silver plating (including electroless silver plating) in a relatively strong acid (pH 3.0 or less) or strong alkali (pH 10.0 or more). Except for cases, most of them are characterized in that they proceed well in the neutral to slightly alkaline range of pH 7.0 ⁇ 9.0.
  • the silver solution of the present invention is environmentally friendly and has excellent ink storage stability, it has the advantage of being able to conveniently use the stored plating solution for a silver mirror whenever an experiment is desired.
  • it since it is simple and safe, it is characterized by being very useful for anyone to experiment with as an example of oxidation-reduction reaction at school or to manufacture silver mirror souvenirs or ornaments.
  • tin chloride since tin chloride is not used, it is possible to manufacture a mirror with excellent surface roughness, and above all, it can be used very usefully when manufacturing a high-quality optical mirror such as a telephoto lens.
  • a silver plating solution is prepared using the above-described silver carboxylate precursor compound and various complexing agents, and a stabilizer, a solvent, and an additive, and in particular, a reducing agent must be selected and used in the case of electroless silver plating or silver mirror reaction.
  • a stabilizer, a solvent, and an additive and in particular, a reducing agent must be selected and used in the case of electroless silver plating or silver mirror reaction.
  • the reducing agent serves to deposit silver on the surface of an object by transferring electrons emitted during oxidation to silver ions.
  • the reducing agent include acetol, acetoin, hydroxyacetone, hydroxyamine, diethylhydroxylamine, methylethylketoxime, and Alkyl aminoborane compounds such as Rochelle salt, erythobate, ammonia borane and methylamine borane, diethylamine borane, hydrazine, hydrated hydrazine (Hydrazine hydrate), Hydrazine sulfate, sodium hypophosphite, sodium sulfite, sodium thiosulfate, sodium borohydride, lithium aluminum hydride (Lithium aluminum hydride), sodium citrate, and alkylamine compounds such as butylamine, ethanolamine, ethylenediamine, and dodecylamine, ethylene glycol, thiodiglycol, and diethylene glycol , formalde
  • the reduction reaction can proceed more quickly through a process of proceeding alone or mixing with the above reducing agent.
  • the content of the reducing agent used does not need to be particularly limited in accordance with the present invention, but in general, it may be 0.1 to 5.0, preferably 0.3 to 3.0, more preferably 0.5 to 5.0 in terms of molar ratio relative to the silver carboxylic acid salt used. 2.0 is suitable. If the amount used is smaller or larger than this, the stability of the plating solution becomes a problem or the reaction proceeds too late or too fast, making it difficult to control the reaction and deteriorating product quality.
  • the reaction temperature during silver plating is not particularly limited in accordance with the present invention, but may be generally 5 to 50 ° C, preferably 10 to 40 ° C, and more preferably 15 to 30 ° C. If it is lower or higher than this, the reaction proceeds too late or too fast along with the stability of the plating solution, so that it is difficult to control the reaction and product quality deteriorates.
  • Stabilizers include long-chain mecaptan compounds such as dodecane thiol, fatty acid compounds such as oleic acid, amine compounds such as oleyl amine, polyvinylpyrrolidone, poly(2-ethyl-2-oxazoline), and polyvinyl alcohol.
  • Polymers such as polyethylene glycol and polystyrene sulfonic acid and their copolymers, synthetic or natural polymer compounds such as carboxymethyl cellulose, alginic acid, chitosan, dopamine, starch, polysaccharides, and various gums Using the same stabilizer can be expected to prevent change over time or to improve adhesion.
  • the surfactant is preferably a nonionic surfactant such as polyoxyethylene alkyl ether or ester, fatty acid sorbitan ester, or alkyl monoglyceryl ether
  • the discoloration inhibitor is selected from the group consisting of benzotriazole and derivatives. You can select and use one or more of them.
  • at least one selected from the group consisting of metal compounds such as ammonium molybdate, bismuth nitrate, selenic acid, and thallium nitrate can be selected and used. there is.
  • ammonium salts such as ammonium formate, ammonium acetate, ammonium nitrate, ammonium sulfate, sulfurous acid
  • ammonium salt additives such as ammonium sulfite, ammonium carbonate, ammonium bicarbonate, ammonium carbamate, and ammonium phosphate
  • the reaction rate is controlled and uniform. There are cases in which it is plated more carefully and the mirror characteristics or conductivity are increased.
  • the amount used does not need to be particularly limited in accordance with the present invention, but may generally be 0.01 to 10.0% by weight compared to the final plating solution, preferably 0.05 to 5.0%, and more preferably 0.1 to 3.0%. If the amount used is less or more than this, there is a problem that the stability of the plating solution is lowered or the quality of the product is lowered.
  • the solvent does not need to be particularly limited as long as it conforms to the present invention, but polar solvents such as water (deionized water), methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, 1-methoxy Alcohols such as 2-propanol (1-methoxy-2-propanol), diacetone alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol, diethylene glycol, propylene glycol, Glycols and glycol ethers such as glycerin, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, and ethylammonium nitrate, 1-ethyl-3-methyl imidazolium dicyanamide ( 1-Ethyl-3-methyl imidazolium dicyanamide) and at least one selected from the group consisting of ionic liquids.
  • the solvent most suitable for the present invention may include water, ethanol, ethylene glycol, glycerin, or a mixture thereof.
  • a mixed solvent of water and ethanol is most suitable.
  • silver electrolytic plating when the water content is minimized, the plating quality is excellent.
  • electroless plating including silver mirror reaction the higher the water content, the faster the reaction speed but the shorter the life of the plating solution. If there is a lot, the stability of the plating solution is low and the quality is not uniform, so it may be 1 to 80% by weight compared to the total solvent, more preferably 20 to 50%.
  • non-conductors such as glass, ceramics, and plastics are cleaned with nitric acid, surfactants, alcohol, etc., and mechanical polishing methods such as steam blasting or grinding using silicon carbide or chromic acid or sulfuric acid are used to increase adhesion.
  • mechanical polishing methods such as steam blasting or grinding using silicon carbide or chromic acid or sulfuric acid are used to increase adhesion.
  • an etching method using hydrofluoric acid, and a method of sensitization and activation with tin chloride (SnCl 2 ) and palladium chloride (PdCl 2 ) can be selected and utilized.
  • the silver plating solution of the present invention is mainly alcohol Since the solution is used and the silver ions themselves perform autocatalytic plating on their own, it is characterized in that the electroless plating, including the silver mirror reaction, proceeds well with some degree of adhesion even without the pretreatment process as described above. On the other hand, after electroless plating, electrolytic plating can be continuously performed using the electroless plated material as a cathode, which can increase the plating thickness or improve the appearance and physical properties.
  • the silver plating complex solution of the present invention may be used as an electrolyte to perform silver plating using electricity instead of a reducing agent.
  • compounds such as water-based polyurethane, water-based acrylic polymer, polyester polymer, silicone polymer, and fluorine-based polymer are applied by dipping, spray coating, or spin ( It can be used by wet coating in methods such as spin coating, bar coating, slit-die coating, and gravure coating, or by vacuum deposition or sputtering of inorganic compounds such as silica or titanium dioxide. there is.
  • An acid silver ammonia complex solution was prepared.
  • a silver complex solution was prepared by adding 2.0 g of ammonia aqueous solution to 100 g of the 0.5% colorless and transparent ammonia complex solution of silver neodecanoate prepared in Preparation Example 2.
  • a reducing agent solution was prepared by adding 1.5 g of hydroquinone to a mixed solution of 100 g of ethanol and 400 g of water.
  • a reducing agent solution was prepared by adding 1.5 g of hydroquinone to a mixture of 100 g of glycerin and 400 g of water.
  • a reducing agent solution was prepared by adding 1.5 g of hydroquinone to a mixture of 400 g of ethanol and 100 g of water.
  • a reducing agent solution was prepared by adding 3.0 g of 2,5-di-tert-butyl hydroquinone to a mixed solution of 250 g of ethanol and 250 g of water.
  • a reducing agent solution was prepared by adding 0.5 g of ammonium formate to 100 g of the reducing agent solution prepared in Preparation Example 5.
  • a reducing agent solution was prepared by adding 0.5 g of 80% hydrazine hydrate (80%) to 100 g of water.
  • a reducing agent solution was prepared by adding 5.0 g of glucose to 100 g of water.
  • a reducing agent solution was prepared by adding 0.5 g of 80% hydrazine hydrate (80%) to 50 g of water and 50 g of ethanol and adding 0.5 g of ammonium nitrate thereto.
  • a reducing agent solution was prepared by adding 0.5 g of 80% hydrazine hydrate to 100 g of water and adding 0.5 g of ammonium formate thereto.
  • a silver mirror manufacturing experiment was performed in the same manner as in Example 6, except that the silver complex solution prepared in Preparation Example 4 was used instead of the silver complex solution of Preparation Example 2, and as a result, a bright golden silver mirror was obtained on the inside and clean on the outside The silver mirror was well formed.
  • a photograph of the prepared sample is shown in FIG. 1 .
  • Example 2 As a result of the experiment in the same manner as in Example 1 using a transparent polyester container (PET bottle) instead of a transparent glass container with a cleanly prepared lid, a light gold mirror was formed on the inside and a clean silver mirror on the outside. A photograph of the prepared sample is shown in FIG. 3 .
  • PET bottle transparent polyester container
  • FIG. 3 A photograph of the prepared sample is shown in FIG. 3 .
  • Preparation Example 1 silver neodecanoate was dissolved using ammonia ethanol solution (Alcoholic ammonia) instead of aqueous ammonia solution, and then absolute ethanol was used as a diluent to finally obtain colorless alcoholic ammonia having a silver content of 0.5%.
  • a complex solution was prepared.
  • the prepared alcoholic ammonia complex solution was placed in a cleanly prepared transparent glass container with a lid and shaken well to sensitize and activate the inside of the container. Thereafter, the same amount of reducing agent solution in which 0.3% hydroquinone was dissolved in anhydrous ethanol prepared in advance was filled in the same amount by weight and reacted for 30 minutes. As a result, a dark silver mirror lower in quality than when using 95% ethanol was formed. .
  • the complex solution was placed in a cleanly prepared transparent glass container with a lid and shaken well to sensitize and activate the inside of the container. Thereafter, the reducing agent solution prepared in Preparation Example 5 was filled in the same amount by weight ratio, shaken well, left for 10 minutes, and then the contents were discarded and washed sequentially with water and ethanol to confirm whether the silver mirror reacted according to the final silver content.
  • Example 16 As a result of the experiment, it was confirmed that the most stable silver mirror reaction was performed in Example 16 and clean plating was performed, and it was confirmed that silver mirrors were formed even in Examples 14 and 15 having a low silver content. However, even in the case of Example 13 in which the silver content was 0.01%, the silver mirror reaction was performed, but it was confirmed that a semi-transparent silver mirror having weak mirror characteristics was formed.
  • Example 21 silver carboxylate Silver mirror response
  • Example 22 Silver 2-ethylhexanoate
  • Example 23 silver malonate
  • Example 24 Lactic acid is ⁇
  • Example 25 silver oleic acid
  • Example 26 silver nitrate ⁇
  • Silver Carboxylate (g) Ammonia aqueous solution (g) weight ratio Example 27 100 One 0.01 Example 28 100 4 0.04 Example 29 100 20 0.20 Example 30 100 40 0.40 Example 31 100 80 0.80 Example 32 100 120 1.20 Example 33 100 200 2.00
  • a silver mirror reaction was performed using the silver carboxylic acid salt and the complexing agent mixed in the same ratio as in Example 1.
  • Examples 27 and 28 having a low content of the complexing agent it was confirmed that there was a solubility problem and the silver mirror reaction was hardly performed.
  • Examples 29 to 32 it was confirmed that the silver mirror reaction was normally performed. However, it was confirmed that the best silver mirror was formed in Example 30.
  • Example 33 using an excessive amount of the complexing agent, the storage stability of the complex solution of the complexing agent and silver carboxylate was poor, and it was difficult to obtain a clean silver mirror.
  • Silver binding agent (g) reducing agent (g) weight ratio Example 34 100 5 0.05 Example 35 100 10 0.10 Example 36 50 20 0.40 Example 37 50 50 1.00 Example 38 40 80 2.00 Example 39 20 100 5.00 Example 40 20 120 6.00
  • a silver mirror reaction was performed by injecting the silver complex solution and the reducing agent solution mixed in the above ratio into a container.
  • the desired silver mirror reaction was normally performed, but it was confirmed that the silver mirror reaction was rapidly performed as the content of the reducing agent increased.
  • the time for performing the silver mirror reaction was long (about 50 to 80 minutes), making it difficult to use industrially, and in Example 40 using an excessive reducing agent, silver precipitation occurred At the same time, the silver content was relatively reduced, resulting in the formation of a semi-transparent silver mirror with weak mirror characteristics.
  • the silver ammonia complex solution of neodecanoate prepared in Preparation Example 1 was diluted with a mixed solution having a weight ratio of 4:1 of ethanol and water to obtain a final silver content of 1.0%.
  • An electroless silver plating solution was prepared by dissolving 0.5% ammonium formate therein.
  • the reducing agent solution was prepared by adding 3.0 grams of hydroquinone to a solution of 100 grams of glycerin and 400 grams of water.
  • a nylon fabric was first put into the silver plating solution and sufficiently wetted for 1 hour, and then a reducing agent solution was added thereto in a weight ratio of 1:1 to the silver plating solution and reacted while stirring for 3 hours. After the reaction was completed, it was filtered, washed sequentially with water and ethanol, and dried at 120° C. for 12 hours to prepare a silver-coated nylon fabric having excellent conductivity (see FIG. 4).
  • Example 41 As a result of the experiment in the same manner as in Example 41, except that nylon fibers were used instead of nylon fabrics, silver-coated nylon fibers having excellent conductivity were prepared. A photograph of the prepared sample and a drawing showing the conductivity are shown in FIG. 5, and an electron microscope (SEM) photograph of the fiber surface is shown in FIG. 6.
  • SEM electron microscope
  • Example 41 As a result of the experiment in the same manner as in Example 41, except that a 25 micron polyimide film was used instead of the nylon fabric, a silver-coated mirror-image polyimide film was prepared. A photograph of the prepared sample is shown in FIG. 7, the measured reflectance was 97.5% @ 550 nm, and the sheet resistance value was 120 m ⁇ / ⁇ .
  • Example 43 As a result of the experiment in the same manner as in Example 43, except that a 12 micron nylon film was used instead of the 25 micron polyimide film, a mirror image nylon film coated with silver was prepared. The measured sheet resistance value was 130 m ⁇ / ⁇ .
  • the silver ammonia neodecanoate solution prepared in Preparation Example 1 was diluted with a mixed solution of ethanol and water in a weight ratio of 1:1 to prepare an electroless silver plating solution so that the final silver content was 0.5%.
  • the solution of Preparation Example 12 was used as the reducing agent solution.
  • Polyurethane foam was first put into the silver plating solution and sufficiently wetted for 1 hour, and then a reducing agent solution was added thereto in a weight ratio of 1:1 to the silver plating solution and reacted with stirring for 2 hours. After the reaction was completed, it was taken out, washed sequentially with water and ethanol, and dried at 120 ° C for 30 minutes, resulting in silver-coated polyurethane foam.
  • As a result of measuring the surface resistance it was 0.3 ⁇ /cm, and pictures of the silver-coated sample and surface electron microscope (SEM) pictures are shown in FIGS. 8 and 9, respectively.
  • Silica beads having an average particle diameter of 12 ⁇ m surface-treated with 3-aminotriethoxysilane were added to the silver complex solution prepared in Preparation Example 3, sufficiently moistened with stirring, filtered, washed with ethanol, and dried.
  • the pretreated silica beads were added to a silver electroless plating solution in which the silver complex solution prepared in Preparation Example 4 and the reducing agent solution prepared in Preparation Example 9 were prepared in a weight ratio of 1:1, and reacted with stirring for 1 hour. After the reaction was completed, the mixture was filtered, washed sequentially with water and ethanol, and dried at 100° C. for 24 hours to obtain silver-coated silica beads.
  • Silver-coated copper particles were prepared as a result of the experiment in the same manner as in Example 46, except that copper particles having an average particle diameter of 4 ⁇ m were used instead of silica beads having an average particle diameter of 12 ⁇ m.
  • a silver complex solution having a concentration of 0.5% silver prepared in Preparation Example 3 was put into a polypropylene plating bath, and a silver plate was used as an anode and a copper foil having a smooth surface was used as a cathode.
  • electricity was applied by connecting 4.5 volts to which three 1.5 volt batteries were connected, and electroplating was performed for 1 minute and 30 seconds. After completion of the plating, it was washed well with water and ethanol and sufficiently dried at 80°C to obtain a copper product plated with bright mirror-like silver on the copper surface.
  • Example 48 Experiments were conducted in the same manner as in Example 48, except that a silver-coated PET film having a resistance of 1,5 ⁇ /cm was used instead of using a copper foil as the cathode. As a result of measuring the surface resistance after electroplating, a sample with improved conductivity of 0.4 ⁇ /cm was obtained.
  • the silver complex solution prepared in Preparation Example 3 having a concentration of 0.5% was diluted with ethanol to finally prepare a solution having a silver concentration of 50 ppm.
  • polyester microfiber cotton which is used as a heat-retaining material for blankets and pillows, was put into the silver solution to the extent that it was submerged, and it was sufficiently stirred and soaked.
  • the reducing agent solution prepared in Preparation Example 6 was diluted with ethanol, and the polyester microfiber cotton was added to the hydroquinone solution having a final silver concentration of 60 ppm and reacted with stirring for 1 hour. After the reaction was finished, it was filtered, washed sequentially with water and ethanol, and dried at 80° C. for 6 hours to obtain silver-treated polyester microfibers. As a result of testing the antibacterial properties of this microfiber, it showed 99.9% of antibacterial activity against E. coli.
  • Example 50 of the present invention Silver plating was performed on the surface of the copper-plated substrate using Example 50 of the present invention and Comparative Example 3 and Comparative Example 4.
  • the copper-plated substrate was put into a container, and then the same silver complex solution as in Example 50 was supplied, and after the plating reaction was completed, the surface was etched to remove the silver plating formed in a region other than the copper plating did
  • Example 1 of the present invention the same silver plating as the commercially available and used comparative example could be performed, and silver plating on the copper plating could be performed only by performing etching to remove excess silver. .
  • the thickness of silver on copper is thicker than the thickness of silver on insulator, although it is etched with the same thickness by applying the increase in the amount of silver deposited on the copper surface in the same way as the conventional plating method.
  • Comparative Examples 3 and 4 it was confirmed that the same silver plating was performed. That is, in the case of the present invention, it was confirmed that it can be used in the existing product production process only by slightly modifying the process.
  • Example 1 Comparative Example 3, and Comparative Example 4 were used in the same manner as in Experimental Example 1, and it was confirmed whether or not the surface of the polymer resin was plated.
  • a square bar having a size of 1 cm X 1 cm X 3 cm was installed inside the plating vessel. At this time, the material of the square bar was prepared as shown in Table 4 below.
  • Example 1 The plating solutions of Example 1, Comparative Example 3, and Comparative Example 4 were added to each container, and then the plating container was shaken and stirred. After 20 minutes, the square bar was taken out to check plating.
  • Example 1 polycarbonate O polyethylene O polypropylene O copper O aluminum O Comparative Example 3 polycarbonate X polyethylene X polypropylene X copper O aluminum O Comparative Example 4 polycarbonate X polyethylene X polypropylene X copper O aluminum O
  • Example 1 of the present invention it was confirmed that not only the metal material but also the metal surface of the polymer resin material was uniformly plated. However, in Comparative Examples 3 and 4, it was confirmed that silver was plated only on the surface of the metal, and it was confirmed that silver plating was not performed on the surface of the polymer resin.
  • FIG. 11 shows a solution state after storage for 6 months at room temperature as a silver complex solution prepared in Preparation Example 2.
  • Figure 12 shows the solution state after storage for 6 months at room temperature as a reducing agent solution prepared in Preparation Example 8.
  • Example 1 Silver nitrate concentration (M) Example 1 ⁇ 0.001 Example 2 ⁇ 0.001 Example 3 ⁇ 0.001 Example 4 ⁇ 0.001 Example 5 ⁇ 0.001 Comparative Example 3 0.7 Comparative Example 4 0.9 Comparative Example 5 4.5

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemically Coating (AREA)
  • Inorganic Chemistry (AREA)

Abstract

Provided is a silver plating solution for electroless silver plating comprising a silver-plated complex solution and a reducing agent solution, wherein the silver-plated complex solution is a solution comprising: a carboxylic acid silver salt of the following general formula 1; a complexing agent in the form of a nitrogen atom-containing compound; and a solvent, the reducing agent solution is a solution comprising: at least one reducing agent selected from the group consisting of glucose, hydrazine, hydroquinone, and derivatives thereof; and a solvent, and electroless silver plating by a silver mirror reaction between the silver-plated complex solution and the reducing agent solution is enabled. [General formula 1] R1-COOAg

Description

은도금액silver plating
본 발명은 친환경적이면서도 간단하게 고품질의 은도금 제품을 만들 수 있는 은 도금액 및 이를 이용한 은도금에 관한 것이다.The present invention relates to a silver plating solution capable of producing a high-quality silver-plated product simply and environmentally friendly, and silver plating using the same.
귀금속에 속하는 은(Silver)은 고대로부터 고급 장식품이나 식기, 화폐 등으로 사용되어 왔고, 근래 들어서는 금속 중에서 전기적, 열적, 광학적 및 마찰(Friction) 특성이 매우 우수할 뿐 아니라 항균 특성도 뛰어나 휴대폰이나 태양전지를 포함한 각종 전지, 자동차, 반도체 등 각종 전자제품 등의 전극이나 전자파 차폐 및 방열 제품, 기계부품 등으로 폭 넓게 사용되고 있으며, 각종 전기화학 반응의 촉매와 의료용 및 항균 제품 등에도 널리 응용되고 있다, 그리고 일반 가정의 거울이나 고급스러운 높은 반사율을 갖는 금속광택 제품이 필요할 때 은이나 알루미늄, 크롬, 니켈, 티타늄, 구리 등과 같이 반사율이 높은 금속을 도장하거나 도금, 또는 증착하여 제품화한다. 일반적으로 도장이나 코팅 및 프린팅 방식은 전도도나 반사율이 그리 높지 않은 제품에 사용하고 있으며 도금에 의한 방법은 박막에서도 전도도가 높고 고급스러운 표면 광택 및 높은 반사율을 가진 반사막을 얻을 수 있으나 제조 시 불량률이 높고 도금 처리에 의한 비용이 과다하게 소요되고 도금공정 중 유해 물질 배출로 인한 대기오염 및 폐수발생의 문제점이 있다. 건식방법인 진공 하에서 증착이나 스퍼터링을 하여 박막의 전극이나 반사율이 높은 반사막의 제조를 할 수 있으나 증착의 경우 고가의 진공 장비 사용 및 기재의 모양이나 크기에 제약이 있고 소량 다품종 제품을 대량 생산함에 문제점이 있다. 이처럼 은을 사용하여 원하는 산업용 전기 전자제품이나 가정용품을 제조하는데 도금 방식은 사용하지 않을 수 없는 공정이나 폐수처리 문제 등 환경적으로 해결해야 될 많은 문제점을 갖고 있는 실정이다.Silver, which belongs to precious metals, has been used for high-end ornaments, tableware, and money since ancient times. It is widely used in various batteries including batteries, electrodes for various electronic products such as automobiles and semiconductors, electromagnetic wave shielding and heat dissipation products, and mechanical parts. In addition, when mirrors for general households or high-quality metal luster products with high reflectivity are needed, metals with high reflectivity such as silver, aluminum, chrome, nickel, titanium, and copper are painted, plated, or deposited to make products. In general, painting, coating, and printing methods are used for products that do not have high conductivity or reflectivity. Plating methods can obtain a reflective film with high conductivity, high-quality surface gloss, and high reflectivity even in thin films, but the defect rate is high during manufacturing. The cost of plating treatment is excessive, and there are problems of air pollution and wastewater generation due to the emission of harmful substances during the plating process. It is possible to manufacture a thin film electrode or a reflective film with high reflectivity by deposition or sputtering under vacuum, which is a dry method. However, in the case of deposition, there are restrictions on the use of expensive vacuum equipment and the shape or size of the base material, and there are problems in mass production of small quantity and various products. there is In this way, in manufacturing desired industrial electrical and electronic products or household items using silver, the plating method has many environmental problems to be solved, such as a process that cannot but be used or a wastewater treatment problem.
은도금은 전해 은도금(Silver electroplating)과 무전해 은도금(Electroless silver plating)으로 크게 나누어지는데 은 전구체(Silver precursor) 또는 은 착체(Silver complex)를 사용하는 것은 공통이나 무전해 은도금은 은을 석출시키기 위해 전기 대신 환원제(Reducing agents)를 사용하는 것과 전기가 통하지 않는 플라스틱이나 섬유, 세라믹 제품 등에도 쉽게 도금할 수 있다는 것이 차이점이다. 특히 전해 은도금에는 오래전부터 독성이 강한 시안화 은을 사용하여 시안화 칼륨 및 시안화 나트륨과 같은 알칼리 시안 용액에서 진행되어왔다. 질산은과 같은 은 화합물에 다양한 착화제 및 기타 첨가제를 사용하여 시안-프리(Cyan-free) 은도금으로 대체하고자 지난 수십년 동안 많은 연구개발이 이루어지고 있으나 아직 상업적인 제품 생산에서 시안화합물을 사용한 은도금이 주류를 이루고 있다. 그 이유로는 시안-프리 은도금이 부착력이 떨어지고, 밝은(Bright) 은도금 제품 제조가 어려우며 도금액이 오염되기 쉬운 단점을 갖고 있기 때문이다. 시안-프리 은도금의 예로서, 미국특허 제5,322,553호에서는 은 티오설페이트 (Silver thiosulfate)나 은 설파이트(Silver sulfite)를 사용하여 보다 안정한 도금액을 제공할 수 있음을 개시하고 있고 미국특허 제6,620,304호에서는 메탄설폰산 은(Silver methanesulfonate)에 시스테인과 같은 아미노산을 사용하여 유해물질을 사용하지 않는 도금액으로 고품질 제품생산 가능성을 언급하고 있다. 또한 미국특허 제8,608,932호에서도 5,5-디메틸하이단토인(5,5-Dimethyl hydantoin)의 은 착체(Silver complex)를 사용한 차별화된 전해 은도금 방법 등이 개시되어 있으나 시안함유 도금처럼 값싸면서 품질이 우수한 제품의 도금액은 아직 개발되고 있지 못하다. 하지만 환경적인 측면을 고려할 때 시안화합물을 사용하지 않는 은 도금액 개발은 앞으로도 진행되어야할 과제로 남아 있다. 한편, 톨렌스 시약(Tollens' reagent)이라 불리는 은 암모늄 착체(Silver ammonium complex)는 글루코스와 같이 알데히드 기(Aldehyde group)를 갖는 화합물과 만나면 환원되어 은거울(Silver mirroring)을 형성한다. 이것은 산화 환원반응을 잘 보여주는 일종의 무전해 은도금으로, 보온용 진공 병(Vacuum flask 또는 Dewar bottle) 제조에 사용되고 있다. 하지만 이러한 은도금액은 질산은에 착화제로 암모니아수를 사용하여 강염기 수용액에서 제조하는데 보관하는 과정에서 은 나이트라이드(Silver nitride) 생성으로 인한 폭발 위험성이 있기 때문에 제조 후 바로 사용하고 사용 후에는 보관하지 않고 바로 산 처리하여 폐기처분해야하는 문제점이 있다. 질산은과 착화제로 암모니아수를 사용하는 도금액은 전해 은도금이나 무전해 은도금에서 도금액의 안정성 및 품질에서 우수한 특성을 보여주고 있으나 이러한 문제점으로 극히 제한적으로 사용되고 있다. 따라서 무전해 은도금을 진행할 때에 착화제 종류 및 이에 따른 적합한 환원제의 선택이 매우 중요한 사항이 되고 있다.Silver plating is largely divided into electrolytic silver plating and electroless silver plating. It is common to use a silver precursor or silver complex, but electroless silver plating uses electricity to deposit silver. The difference is that reducing agents are used instead, and that it can be easily plated on plastics, textiles, and ceramic products that do not conduct electricity. In particular, electrolytic silver plating has been carried out in alkali cyan solutions such as potassium cyanide and sodium cyanide using highly toxic silver cyanide for a long time. A lot of research and development has been conducted over the past decades to replace silver compounds such as silver nitrate with cyan-free silver plating using various complexing agents and other additives, but silver plating using cyan compounds is still the mainstream in commercial product production. is making up This is because the cyan-free silver plating has disadvantages such as poor adhesion, difficulty in manufacturing a bright silver-plated product, and easy contamination of the plating solution. As an example of cyanide-free silver plating, U.S. Patent No. 5,322,553 discloses that a more stable plating solution can be provided by using silver thiosulfate or silver sulfite, and U.S. Patent No. 6,620,304 It mentions the possibility of producing high-quality products with a plating solution that does not use harmful substances by using amino acids such as cysteine in silver methanesulfonate. In addition, U.S. Patent No. 8,608,932 discloses a differentiated electrolytic silver plating method using a silver complex of 5,5-dimethyl hydantoin. A plating solution of excellent products has not yet been developed. However, considering the environmental aspect, the development of a silver plating solution that does not use a cyanide compound remains an ongoing task. Meanwhile, when a silver ammonium complex called Tollens' reagent meets a compound having an aldehyde group such as glucose, it is reduced to form a silver mirroring. This is a kind of electroless silver plating that shows the oxidation-reduction reaction well, and is used in the manufacture of vacuum flasks or dewar bottles. However, since this silver plating solution is prepared in a strong base aqueous solution using silver nitrate and ammonia water as a complexing agent, there is an explosion risk due to the generation of silver nitride in the storage process. There is a problem that needs to be treated and disposed of. A plating solution using silver nitrate and ammonia water as a complexing agent shows excellent properties in stability and quality of the plating solution in electrolytic silver plating or electroless silver plating, but is used extremely limitedly due to these problems. Therefore, when electroless silver plating is performed, selection of a type of complexing agent and a suitable reducing agent accordingly has become a very important matter.
따라서 본 발명자들은 은도금에 있어서 이러한 여러 문제점을 해결하기 위하여 부단히 노력한 결과 본 발명에 도달하게 되었다.Therefore, the present inventors have reached the present invention as a result of constant efforts to solve these various problems in silver plating.
본 발명의 목적은, 친환경적이면서도 안정성이 뛰어난 은 도금액 및 이를 이용한 고품질의 은도금 제품을 제공하는 것이다.An object of the present invention is to provide a silver plating solution that is environmentally friendly and has excellent stability and a high-quality silver-plated product using the same.
본 발명의 일 측면에 의하면, 은도금 착체 용액 및 환원제 용액을 포함하는 무전해 은도금을 위한 은도금액에 있어서, 상기 은도금 착체 용액은, 하기 일반식 1의 카르복실산 은염을 포함하는 용액이고, 상기 은도금 착체 용액 및 상기 환원제 용액 간의 은거울 반응에 의한 무전해 은도금이 가능한 은도금액이 제공된다.According to one aspect of the present invention, in a silver plating solution for electroless silver plating comprising a silver plating complex solution and a reducing agent solution, the silver plating complex solution is a solution containing a carboxylic acid silver salt of the following general formula 1, wherein the silver plating A silver plating solution capable of performing electroless silver plating by a silver mirror reaction between a complex solution and the reducing agent solution is provided.
[일반식 1][Formula 1]
R1-COOAgR 1 -COOAg
상기 식에서, R1은 수소, 치환 또는 비치환된 C1-C22의 알킬기, 치환 또는 비치환된 C3-C30 시클로알킬기, 치환 또는 비치환된 C6-C30 아르알킬(aralkyl), 치환 또는 비치환된 C1-C30 헤테로알킬기, 치환 또는 비치환된 C2-C30 헤테로시클로알킬기, 또는 치환 또는 비치환된 C5-C30 헤테로아르알킬기이다. In the above formula, R 1 is hydrogen, a substituted or unsubstituted C 1 -C 22 alkyl group, a substituted or unsubstituted C 3 -C 30 cycloalkyl group, a substituted or unsubstituted C 6 -C 30 aralkyl group, A substituted or unsubstituted C 1 -C 30 heteroalkyl group, a substituted or unsubstituted C 2 -C 30 heterocycloalkyl group, or a substituted or unsubstituted C 5 -C 30 heteroaralkyl group.
본 발명의 또 다른 측면에 의하면, 상술한 은도금액을 5~50℃에서 반응시켜 얻은 은도금 제품이 제공된다.According to another aspect of the present invention, a silver-plated product obtained by reacting the above-described silver plating solution at 5 to 50° C. is provided.
본 발명에 따르면 친환경적이면서도 저장 안정성 및 성능이 뛰어난 은도금액이 제공될 뿐 아니라, 이를 이용하여 다양한 고품질의 은도금 제품이 제공된다. According to the present invention, not only is an environmentally friendly silver plating solution excellent in storage stability and performance, but also various high-quality silver-plated products are provided using the silver plating solution.
도 1은 실시 예 1 내지 실시 예 7에서 제조한 은거울 제품 사진이다.1 is a photograph of silver mirror products manufactured in Examples 1 to 7.
도 2는 실시 예 3에서 제조한 유리 병(Bottle)의 은거울 제품 사진이다.2 is a photograph of a silver mirror product of a glass bottle prepared in Example 3.
도 3은 실시 예 8에서 제조한 PET 병의 은거울 제품 사진이다.3 is a product photograph of a silver mirror of a PET bottle prepared in Example 8.
도 4는 실시 예 41에서 제조한 은도금 코팅된 나일론 직물의 제품 및 전도도 사진이다.4 is a product and conductivity photograph of the silver-plated coated nylon fabric prepared in Example 41.
도 5는 실시 예 42에서 제조한 은도금 코팅된 나일론 섬유의 제품 및 전도도 사진이다.5 is a product and conductivity photograph of the silver-coated nylon fiber prepared in Example 42.
도 6은 실시 예 42에서 제조한 은도금 코팅된 나일론 섬유 표면의 전자현미경(SEM) 사진이다.6 is an electron microscope (SEM) photograph of the surface of silver-plated coated nylon fibers prepared in Example 42.
도 7은 실시 예 43에서 제조한 은도금 코팅된 거울 상 폴리이미드 필름 사진이다.7 is a photograph of a mirror-image polyimide film coated with silver plating prepared in Example 43.
도 8은 실시 예 45에서 제조한 은도금 코팅된 폴리우레탄 폼 사진이다.8 is a photograph of the silver-plated coated polyurethane foam prepared in Example 45.
도 9는 실시 예 45에서 제조한 은도금 코팅된 폴리우레탄 폼 표면의 전자현미경(SEM) 사진이다.9 is an electron microscope (SEM) photograph of the surface of the polyurethane foam coated with silver plating prepared in Example 45.
도 10은 실시 예 50에서 제조한 은도금된 구리포일 사진이다.10 is a photograph of silver-plated copper foil prepared in Example 50.
도 11은 실시 예 51에서 제조한 항균 특성을 갖는 은 함유 면직물 사진이다.11 is a photograph of a silver-containing cotton fabric having antibacterial properties prepared in Example 51.
도 12는 제조예 2에서 제조한 은 착체용액으로서 상온에서 6개월간 보관한 후의 용액 상태를 나타낸다.12 shows the state of the silver complex solution prepared in Preparation Example 2 after being stored at room temperature for 6 months.
도 13은 제조예 8에서 제조한 환원제 용액으로서 상온에서 6개월간 보관한 후의 용액 상태를 나타낸다.Figure 13 shows the solution state after storage for 6 months at room temperature as a reducing agent solution prepared in Preparation Example 8.
본 명세서에서 용어 "알킬"은 직쇄, 분지쇄 또는 고리형의 탄화수소 라디칼 또는 이들의 조합을 포함하며, 경우에 따라 사슬 안에 이중 결합, 삼중 결합 또는 이들의 조합을 하나 이상 포함할 수도 있다. 즉 "알킬"은 알켄이나 알킨을 포함한다.In this specification, the term "alkyl" includes a straight-chain, branched-chain, or cyclic hydrocarbon radical or a combination thereof, and in some cases may include one or more double bonds, triple bonds, or combinations thereof in the chain. That is, "alkyl" includes alkene or alkyne.
용어 "헤테로알킬"은 그 자체로 또는 다른 용어와 조합되어, 다른 의미로 명시되지 않는 한, 1종 이상의 탄소 원자 및 O, N, P, Si 및 S로 이루어진 군으로부터 선택되는 1종 이상의 이종원자로 이루어지는 안정한 직쇄 또는 분지쇄 또는 고리형 탄화수소 라디칼 또는 이들의 조합을 의미하고, 질소, 인 및 황 원자는 임의로 산화될 수 있고, 질소 이종원자는 임의로 4차화될 수 있다.The term “heteroalkyl,” by itself or in combination with other terms, unless otherwise specified, refers to one or more carbon atoms and one or more heteroatoms selected from the group consisting of O, N, P, Si, and S. means a stable straight or branched chain or cyclic hydrocarbon radical consisting of, or combinations thereof, wherein the nitrogen, phosphorus and sulfur atoms may optionally be oxidized and the nitrogen heteroatoms may optionally be quaternized.
용어 "시클로알킬" 및 "헤테로시클로알킬"은 그 자체로 또는 다른 용어와 함께, 다른 의미로 명시하지 않는 한, 각각 "알킬" 및 "헤테로알킬"의 고리형 버전을 나타낸다.The terms "cycloalkyl" and "heterocycloalkyl" by themselves or in combination with other terms, unless otherwise specified, refer to cyclic versions of "alkyl" and "heteroalkyl", respectively.
용어 "아릴"은 다른 의미로 명시되지 않는 한, 함께 융합 또는 공유 결합된 단일 고리 또는 다중 고리(1개 내지 3개의 고리)일 수 있는 다중불포화, 방향족, 탄화수소 치환기를 의미한다. The term "aryl", unless otherwise specified, refers to a polyunsaturated, aromatic, hydrocarbon substituent which may be a single ring or multiple rings (1 to 3 rings) fused or covalently bonded together.
용어 "헤테로아릴"은 (다중 고리의 경우 각각의 별도의 고리에서) N, O 및 S로부터 선택되는 1 내지 4개의 이종원자를 포함하는 아릴 기(또는 고리)를 의미하고, 질소 및 황 원자는 임의로 산화되고, 질소 원자(들)은 임의로 4차화된다. 헤테로아릴 기는 탄소 또는 이종원자를 통해 분자의 나머지에 결합될 수 있다.The term "heteroaryl" means an aryl group (or ring) comprising (in each separate ring in the case of multiple rings) 1 to 4 heteroatoms selected from N, O and S, the nitrogen and sulfur atoms being optionally oxidized, and the nitrogen atom(s) are optionally quaternized. A heteroaryl group can be attached to the rest of the molecule through a carbon or heteroatom.
용어 "아르알킬"은 아릴 및 아릴로 치환된 알킬 그룹을 나타내며, 여기서, 알킬 및 아릴 부분은 독립적으로 임의로 치환된다.The term “aralkyl” refers to aryl and aryl substituted alkyl groups, wherein the alkyl and aryl portions independently are optionally substituted.
용어 "헤테로아르알킬"은 각각 아릴 및 헤테로아릴로 치환된 알킬 그룹을 나타내며, 여기서, 알킬 및 헤테로아릴 부분은 독립적으로 임의로 치환된다.The term "heteroaralkyl" refers to an alkyl group substituted with an aryl and heteroaryl, respectively, wherein the alkyl and heteroaryl portions independently are optionally substituted.
본 명세서에 기재된 "치환 또는 비치환된"이라는 표현에서 "치환"은 탄화수소 내의 수소 원자 하나 이상이 각각, 서로 독립적으로, 동일하거나 상이한 치환기로 대체되는 것을 의미한다. 유용한 치환기는 다음을 포함하지만 이에 제한되지 않는다.As used herein, “substitution” in the expression “substituted or unsubstituted” means that one or more hydrogen atoms in a hydrocarbon are each, independently of one another, replaced with the same or different substituents. Useful substituents include but are not limited to the following.
이러한 치환기는, -F; -Cl; -Br; -CN; -NO2; -OH; =O; -F, -Cl, -Br, -CN, -NO2, -OH 또는 =O로 치환되거나 비치환된 C1-C20 알킬기; -F, -Cl, -Br, -CN, -NO2, -OH 또는 =O로 치환되거나 비치환된 C1-C20 알콕시기; C1-C20 알킬기, C1-C20 알콕시기, -F, -Cl, -Br, -CN, -NO2, -OH 또는 =O로 치환되거나 비치환된 C6-C30 아릴기; C1-C20 알킬기, C1-C20 알콕시기, -F, -Cl, -Br, -CN, -NO2, -OH 또는 =O로 치환되거나 비치환된 C6-C30 헤테로아릴기; C1-C20 알킬기, C1-C20 알콕시기, -F, -Cl, -Br, -CN, -NO2, -OH 또는 =O로 치환되거나 비치환된 C5-C20 사이클로알킬기; C1-C20 알킬기, C1-C20 알콕시기, -F, -Cl, -Br, -CN, -NO2, -OH 또는 =O로 치환되거나 비치환된 C5-C30 헤테로사이클로알킬기; -F, -Cl, -Br, -CN, -NO2, -OH 또는 =O로 치환되거나 비치환된 C1-C20 알콕시실란기; 및 -N(G1)(G2)으로 표시되는 기로 이루어진 군으로부터 선택된 하나 이상일 수 있다. 이 때, 상기 G1 및 G2는 서로 독립적으로 각각 수소; C1-C10 알킬기; 또는 C1-C10 알킬기로 치환되거나 비치환된 C6-C30 아릴기일 수 있다.These substituents are -F; -Cl; -Br; -CN; -NO 2 ; -OH; =O; -F, -Cl, -Br, -CN, -NO 2 , -OH or =O substituted or unsubstituted C 1 -C 20 alkyl group; a C 1 -C 20 alkoxy group unsubstituted or substituted with -F, -Cl, -Br, -CN, -NO 2 , -OH or =O; a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 6 -C 30 aryl group unsubstituted or substituted with -F, -Cl, -Br, -CN, -NO 2 , -OH or =O; C 1 -C 20 alkyl group, C 1 -C 20 alkoxy group, -F, -Cl, -Br, -CN, -NO 2 , -OH or =O substituted or unsubstituted C 6 -C 30 heteroaryl group ; a C 1 -C 20 alkyl group, a C 1 -C 20 alkoxy group, a C 5 -C 20 cycloalkyl group unsubstituted or substituted with -F, -Cl, -Br, -CN, -NO 2 , -OH or =O; C 1 -C 20 alkyl group, C 1 -C 20 alkoxy group, -F, -Cl, -Br, -CN, -NO 2 , -OH or =O substituted or unsubstituted C 5 -C 30 heterocycloalkyl group ; a C 1 -C 20 alkoxysilane group unsubstituted or substituted with -F, -Cl, -Br, -CN, -NO 2 , -OH or =O; And it may be at least one selected from the group consisting of a group represented by -N(G1)(G2). At this time, G1 and G2 are each independently hydrogen; C 1 -C 10 alkyl group; Alternatively, it may be a C 6 -C 30 aryl group unsubstituted or substituted with a C 1 -C 10 alkyl group.
본 명세서에 기재된 어떤 물질의 "유도체"는 어떤 물질의 수소 원자 일부가 상술한 치환기로 치환된 것을 의미한다.A “derivative” of a substance described in this specification means a substance in which some of the hydrogen atoms of the substance are substituted with the substituents described above.
본 발명은 은도금 착체 용액 및 환원제 용액을 포함하는 무전해 은도금을 위한 은도금액에 있어서, 상기 은도금 착체 용액은, 하기 일반식 1의 카르복실산 은염을 포함하는 용액이고, 상기 은도금 착체 용액 및 상기 환원제 용액 간의 은거울 반응에 의한 무전해 은도금이 가능한 은도금액이 제공된다.The present invention is a silver plating solution for electroless silver plating comprising a silver plating complex solution and a reducing agent solution, wherein the silver plating complex solution is a solution containing a carboxylic acid silver salt of the following general formula 1, the silver plating complex solution and the reducing agent A silver plating solution capable of performing electroless silver plating by a silver mirror reaction between solutions is provided.
[일반식 1][Formula 1]
R1-COOAgR 1 -COOAg
상기 식에서, R1은 수소, 치환 또는 비치환된 C1-C22의 알킬기, 치환 또는 비치환된 C3-C30 시클로알킬기, 치환 또는 비치환된 C6-C30 아르알킬(aralkyl), 치환 또는 비치환된 C1-C30 헤테로알킬기, 치환 또는 비치환된 C2-C30 헤테로시클로알킬기, 또는 치환 또는 비치환된 C5-C30 헤테로아르알킬기이다. In the above formula, R 1 is hydrogen, a substituted or unsubstituted C 1 -C 22 alkyl group, a substituted or unsubstituted C 3 -C 30 cycloalkyl group, a substituted or unsubstituted C 6 -C 30 aralkyl group, A substituted or unsubstituted C 1 -C 30 heteroalkyl group, a substituted or unsubstituted C 2 -C 30 heterocycloalkyl group, or a substituted or unsubstituted C 5 -C 30 heteroaralkyl group.
구체적으로 본 발명은 [일반식 1]과 같이 표현되는 카르복실산 은염(silver carboxylate) 화합물과 질소함유 화합물 형태의 착화제를 주요 성분으로 하는 은도금액과 이를 이용하여 다양한 전도성 제품 및 은 거울제품 등을 제공한다.Specifically, the present invention provides a silver plating solution containing a silver carboxylate compound represented by [General Formula 1] and a complexing agent in the form of a nitrogen-containing compound as main components, and various conductive products and silver mirror products using the same. provides
[일반식 1][Formula 1]
R1-COOAgR 1 -COOAg
[일반식 1]에서 R1은 수소, 치환 또는 비치환된 C1-C22의 알킬기, 치환 또는 비치환된 C3-C30 시클로알킬기, 치환 또는 비치환된 C6-C30 아르알킬(aralkyl), 치환 또는 비치환된 C1-C30 헤테로알킬기, 치환 또는 비치환된 C2-C30 헤테로시클로알킬기, 또는 치환 또는 비치환된 C5-C30 헤테로아르알킬기이다. In [Formula 1], R 1 is hydrogen, a substituted or unsubstituted C 1 -C 22 alkyl group, a substituted or unsubstituted C 3 -C 30 cycloalkyl group, or a substituted or unsubstituted C 6 -C 30 aralkyl ( aralkyl), a substituted or unsubstituted C 1 -C 30 heteroalkyl group, a substituted or unsubstituted C 2 -C 30 heterocycloalkyl group, or a substituted or unsubstituted C 5 -C 30 heteroaralkyl group.
예를 들면 R1은 수소, 메틸, 에틸, n-프로필, iso-프로필, n-부틸, iso-부틸, t-부틸, n-펜틸, iso-아밀, t-아밀, n-헥실, 2-에틸헥실, n-헵틸, 옥틸, iso-옥틸, 노닐, 데실, 네오데실, 도데실, 테트라데실, 헥사데실, 옥타데실, 도코산일, 올레일, 리놀레일, 시클로프로필, 시클로펜틸, 시클로헥실 등을 들 수 있다.For example, R 1 is hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, t-butyl, n-pentyl, iso-amyl, t-amyl, n-hexyl, 2- Ethylhexyl, n-heptyl, octyl, iso-octyl, nonyl, decyl, neodecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, docosanyl, oleyl, linoleyl, cyclopropyl, cyclopentyl, cyclohexyl, etc. can be heard
한편, [일반식 1]의 은 전구체로서 구체적인 예를 들면 초산 은(Silver acetate), 프로피온산 은(Silver propionate), 트리플로로아세트산 은(silver trifluoroacetate), 락트산 은(silver lactate), 말론산 은(silver malonate), 말레산 은(silver maleate), 푸마릭산 은(silver fumarate), 피루빅산 은(silver pyruvate), 숙신산 은(silver succinate), 피크릭산 은(silver picrate), 시트릭산 은(silver citrate), 2-에틸헥사논산 은 (silver 2-ethylhexanoate), 네오데칸산 은(silver neodecanoate), 스테아린산 은(silver stearate), 도코산 은(silver docosanoate), 올레산 은(silver oleate), 리놀레산 은(silver linoleate), 시클로헥실산 은(silver cyclohexane carboxylate) 등이 여기에 해당된다. 이중에서도, 상기 [일반식 1]의 여러 카르복실산 은염 중에 바람직하게는 초산은, 프로피온산 은, 네오데칸산은 등과 같이 알칸산은이 경제성, 안정성 및 용해특성 등 여러 종합적인 측면에서 볼 때 본 발명에 가장 부합된다.On the other hand, as a silver precursor of [General Formula 1], for example, silver acetate, silver propionate, silver trifluoroacetate, silver lactate, silver malonate ( silver malonate, silver maleate, silver fumarate, silver pyruvate, silver succinate, silver picrate, silver citrate citrate), silver 2-ethylhexanoate, silver neodecanoate, silver stearate, silver docosanoate, silver oleate, silver linoleate ( silver linoleate) and silver cyclohexane carboxylate. Among these, silver alkanoates, such as silver acetate, silver propionate, and silver neodecanoate, among the various carboxylic acid silver salts of [General Formula 1], are the most advantageous in the present invention in terms of economic efficiency, stability, and dissolution characteristics. It matches.
사용되는 은의 함량은 본 발명에 부합되는 경우 특별히 제한할 필요는 없지만 일반적으로 최종 도금액 대비 중량비로 0.05~5.0%일 수 있으며, 바람직하게는 0.1~3.0%, 보다 바람직하게는 0.2~2.0%가 적당하다. 사용량이 이보다 적거나 많게 되면 도금액의 경제성 및 안정성이 떨어지거나 제품의 품질이 저하되는 문제점이 있다.The content of silver used does not need to be particularly limited if it conforms to the present invention, but may generally be 0.05 to 5.0% by weight relative to the final plating solution, preferably 0.1 to 3.0%, and more preferably 0.2 to 2.0%. do. If the amount used is less or more than this, there is a problem in that the economical efficiency and stability of the plating solution decrease or the quality of the product deteriorates.
착화제는 은도금액 중의 은 이온과 결합하여 안정한 착이온을 형성시켜 높은 농도로 용매에 쉽게 녹일 수 있게 한다. 이러한 착화제는 주로 전자 공여체(electron donor)로서, 질소원자 또는 인 원자, 또는 황원자 함유 화합물인 것이 바람직하나 안정성 및 경제적 측면에서 질소원자 함유 화합물이 더욱 바람직하다.The complexing agent combines with silver ions in the silver plating solution to form stable complex ions so that they can be easily dissolved in a solvent at a high concentration. The complexing agent is mainly an electron donor, and is preferably a compound containing a nitrogen atom, a phosphorus atom, or a sulfur atom, but a compound containing a nitrogen atom is more preferable in terms of stability and economy.
상기 질소원자 함유 화합물은 예를 들어 암모니아, 아민(1차(primary), 2차(secondary), 또는 3차(tertiary) 아민), 4차 암모늄 염(quaternary ammomium salts) 및 폴리아민으로 이루어진 군 중에서 선택된 1종 이상일 수 있다. 여기서 상기 질소원자 함유 화합물의 질소원자에는 치환 또는 비치환된 탄소 수 1∼20(C1-C20)을 갖는, 알킬, 아릴, 아르알킬 기 등이 결합되어도 좋다.The nitrogen atom-containing compound is, for example, selected from the group consisting of ammonia, amines (primary, secondary, or tertiary amines), quaternary ammonium salts, and polyamines. It may be one or more. Here, a substituted or unsubstituted alkyl, aryl, aralkyl group or the like having 1 to 20 (C 1 -C 20 ) carbon atoms may be bonded to the nitrogen atom of the nitrogen atom-containing compound.
여기서 알킬기는 선형(Linear type), 가지형(Branched type), 빗(Comb type), 별 또는 덴드리머 형(Star-shaped or Dendritic type), 그리고 환형(cyclic type) 등 어떠한 형태여도 무방하다. 또한 상기 질소원자 함유 화합물은 히드록시, 알콕시, 에스테르, 아미드, 우레탄 등 기능성 기(functional group)를 갖고 있을 수 있다.Here, the alkyl group may have any form such as a linear type, a branched type, a comb type, a star-shaped or dendritic type, and a cyclic type. In addition, the nitrogen atom-containing compound may have a functional group such as hydroxy, alkoxy, ester, amide, or urethane.
일 구현예에서, 상기 질소원자 함유 화합물 중 암모니아 또는 아민 화합물은 하기 [일반식 2]로 표현될 수 있으며, 4차 암모늄 염 화합물은 하기 [일반식 3]으로 표현될 수 있다. In one embodiment, the ammonia or amine compound among the nitrogen atom-containing compounds may be represented by the following [General Formula 2], and the quaternary ammonium salt compound may be represented by the following [General Formula 3].
[일반식 2][Formula 2]
(R2R3R4)N(R 2 R 3 R 4 )N
[일반식 3][Formula 3]
(R5R6R7R8)N+X(R 5 R 6 R 7 R 8 )N + X
상기 식에서, R2 내지 R8은 서로 동일하거나 상이할 수 있으며, 각각 수소 또는 치환 또는 비치환된 C1-C20의 알킬기, 치환 또는 비치환된 C6-C30 아릴기, 치환 또는 비치환된 C3-C30 시클로알킬기, 치환 또는 비치환된 C6-C30 아르알킬(aralkyl), 치환 또는 비치환된 C1-C30 헤테로알킬기, 치환 또는 비치환된 C2-C30 헤테로시클로알킬기, 치환 또는 비치환된 C5-C30 헤테로아릴기, 치환 또는 비치환된 C5-C30 헤테로아르알킬기이다. In the above formula, R 2 to R 8 may be the same as or different from each other, and are each hydrogen or a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, or a substituted or unsubstituted C 3 -C 30 Cycloalkyl group, substituted or unsubstituted C 6 -C 30 aralkyl group, substituted or unsubstituted C 1 -C 30 heteroalkyl group, substituted or unsubstituted C 2 -C 30 heterocycloalkyl group, substituted or unsubstituted a C 5 -C 30 heteroaryl group, or a substituted or unsubstituted C 5 -C 30 heteroaralkyl group.
X는 F-, Cl-, Br-, I-, OH-, 하이드로전 설페이트, 바이카르보네이트, 카바메이트 또는 퍼클로레이트이다. X is F - , Cl - , Br - , I - , OH - , hydrogen sulfate, bicarbonate, carbamate or perchlorate.
구체적으로 예를 들면, 상기 질소원자 함유 화합물은 암모니아, 메틸아민, 에틸아민, n-프로필아민, 이소프로필아민, n-부틸아민, 이소부틸아민, 터셔리-부틸아민, n-펜틸아민, 이소-펜틸아민, 터셔리-아밀아민, n-헥실아민, 디에틸아민, 트리에틸아민, 2-에틸헥실아민, 시클로헥실아민, 알릴아민, 프로파길아민, 에틸렌디아민, 1,3-프로필렌디아민, 헥사메틸렌디아민, 트리에틸렌디아민, 1,2-디아미노프로판, 모노에탄올아민, 디에탄올아민, 1-아미노-2-프로판올, 3-아미노-1-프로판올, 1,4-부탄디아민, 스퍼민(Spermine), 스퍼미딘(Spermidine), 디에틸렌트리아민, 트리에틸렌테트라아민, 트리스(2-아미노에틸)아민, 1,1,1-트리스(아미노메틸)에탄, N,N-디에틸히드록시아민, 메톡시에틸아민, N,N-디에틸에틸렌디아민, N,N,N',N'-테트라메틸에틸렌디아민, 피리딘, 피페리딘, 피페라진, 모폴린, 이미다졸, 피롤, 퀴누클리딘(Quinuclidine), 벤질아민, 페네틸아민(phenethylamine), 암모늄카바메이트, 암모늄카보네이트, 테트라에틸 암모늄 바이카보네이트(tetraethylammonium bicarbonate), 테트라에틸 암모늄 브로마이드, 테트라부틸암모늄 하이드록사이드, 아미노프로필 트리에톡시 실란(aminopropyltriethoxy silane), 폴리에틸렌이민(Polyethyleneimine, PEI), 폴리프로필렌이민(Poly(propylene imine), 폴리비닐아민(Polyvinylamine, PVAm), 폴리아미도아민(Poly(amidoamine), PAMAM)과 같은 화합물 및 그 유도체 등을 들 수 있다. 일 구현예에 있어서, 알칼리 수용액 상태의 도금용액에는 EDTA(Ethylenediaminetetraacetic acid)나 NTA(Nitrilotriacetic acid) 화합물, 예를 들면 디소디움 EDTA (Disodium EDTA), 트리소디움 EDTA (Trisodium EDTA), 테트라소디움 EDTA(Tetrasodium EDTA), 소디움 NTA(Sodium NTA), 트리소디움 NTA (Trisodium NTA), 숙신이미드(Succinimide), 말레이미드, 프탈이미드, 에틸렌디아민, 헥사메틸렌테트라아민, 사카린, 이미다졸, 옥사졸린, 하이단토인(Hydantoin) 및 5,5-디메틸 하이단토인(5,5-Dimethyl hydantoin)으로 이루어진 군 중에서 선택되는 1종 이상을 선택하여 사용할 수 있다. 상기 질소원자 함유 화합물로 특히, 대표적인 것으로는 암모니아나 메틸아민, 에틸아민과 같은 알킬아민이 경제성, 특성 등 여러 측면에서 볼 때 본 발명에 가장 부합된다.Specifically, for example, the nitrogen atom-containing compound is ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, tertiary-butylamine, n-pentylamine, iso -pentylamine, tert-amylamine, n-hexylamine, diethylamine, triethylamine, 2-ethylhexylamine, cyclohexylamine, allylamine, propargylamine, ethylenediamine, 1,3-propylenediamine, Hexamethylenediamine, triethylenediamine, 1,2-diaminopropane, monoethanolamine, diethanolamine, 1-amino-2-propanol, 3-amino-1-propanol, 1,4-butanediamine, spermine ), spermidine, diethylenetriamine, triethylenetetramine, tris(2-aminoethyl)amine, 1,1,1-tris(aminomethyl)ethane, N,N-diethylhydroxyamine, Methoxyethylamine, N,N-diethylethylenediamine, N,N,N',N'-tetramethylethylenediamine, pyridine, piperidine, piperazine, morpholine, imidazole, pyrrole, quinuclidine ( Quinuclidine), benzylamine, phenethylamine, ammonium carbamate, ammonium carbonate, tetraethylammonium bicarbonate, tetraethyl ammonium bromide, tetrabutylammonium hydroxide, aminopropyl triethoxy silane silane), polyethyleneimine (PEI), polypropylene imine (Poly (propylene imine), polyvinylamine (PVAm), polyamidoamine (Poly (amidoamine), PAMAM), and derivatives thereof. In one embodiment, the plating solution in an alkaline aqueous solution may contain ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) compounds, such as disodium EDTA, trisodium EDTA, and tetrasodium. EDTA (Tetrasodium EDTA), Sodium NTA, Trisodium NTA, Succinimide, Maleimide, Phthalimide, Ethylenediamine, Hexamethylenetetraamine, Saccharin, Imidazole, Oxazoline At least one selected from the group consisting of hydantoin and 5,5-dimethyl hydantoin may be selected and used. As the nitrogen atom-containing compound, especially representative examples, alkylamines such as ammonia, methylamine, and ethylamine are most suitable for the present invention in terms of economic feasibility and characteristics.
사용되는 착화제의 함량은 본 발명에 부합되는 경우 특별히 제한할 필요는 없지만 일반적으로, 사용하는 카르복실산 은염 대비 몰비로 0.1~10.0일 수 있으며, 바람직하게는 0.3~7.0, 보다 바람직하게는 0.5~5.0이 적당하다. 사용량이 이보다 적거나 많게 되면 도금액의 안정성이 문제되거나 반응이 완결되지 못하고 품질이 저하되는 문제점이 있다.The content of the complexing agent used does not need to be particularly limited if it conforms to the present invention, but in general, it may be 0.1 to 10.0, preferably 0.3 to 7.0, more preferably 0.5 in terms of molar ratio relative to the silver carboxylic acid salt used. ~5.0 is appropriate. If the amount used is less or more than this, there is a problem in that the stability of the plating solution or the reaction is not completed and the quality is deteriorated.
본 발명의 은도금액은 용매로서 물, 에탄올, 에틸렌글리콜, 글리세린 또는 이들의 혼합용액을 사용할 수 있다. 즉 알코올이나 글리콜 함유 수용액으로서 젖음 성(Wetting)이 매우 우수하다. 따라서 구리, 니켈, 아연, 주석, 안티몬, 몰리브덴, 백금, 청동, 황동과 같은 금속 및 금속합금 뿐 아니라 이들 금속의 산화물 및 황화물과, 실리카, 알루미나, 산화티탄, 마이카(Mica), 클레이(Clay), 유리와 같은 세라믹 류, 폴리에스테르, 나일론, 폴리이미드, 폴리우레탄, 아크릴과 같은 플라스틱류, 카본, 카본 나노튜브, 흑연(Graphite), 그래핀(Graphene)과 같은 각종 탄소 화합물, 그리고 고무, 부직포, 종이 등과 같은 어떠한 종류의 기재(Substrates)나 이들의 입자(Particles), 플레이크(Flakes), 비드(Beads), 시트(Sheets), 포일(Foils), 필름(Films), 섬유(Fibers) 등 어떠한 형태나 모양에도 무관하게 사용하여 쉽게 도금할 수 있다는 장점을 갖는다. The silver plating solution of the present invention may use water, ethanol, ethylene glycol, glycerin, or a mixture thereof as a solvent. That is, as an alcohol or glycol-containing aqueous solution, wetting is very excellent. Therefore, metals and metal alloys such as copper, nickel, zinc, tin, antimony, molybdenum, platinum, bronze, and brass, as well as oxides and sulfides of these metals, silica, alumina, titanium oxide, mica, and clay , ceramics such as glass, plastics such as polyester, nylon, polyimide, polyurethane, acrylic, various carbon compounds such as carbon, carbon nanotubes, graphite, graphene, rubber, and non-woven fabrics , any kind of substrates such as paper, their particles, flakes, beads, sheets, foils, films, fibers, etc. It has the advantage that it can be easily plated by using it regardless of the shape or shape.
톨렌스 시약으로 은거울 반응을 실험하는 경우에는 은거울 반응 시마다 새롭게 은 용액을 제조하여 사용해야 하는 번거로움이 있지만 본 발명의 은 도금액은 은 용액을 미리 제조하여 저장하였다가 필요할 때마다 사용할 수 있다는 것이 특징이다. 그리고 본 발명의 수소이온농도가(pH)는 특별히 제한할 필요는 없지만 본 발명은 일반적인 은도금(무전해 은도금 포함)이 비교적 강산(pH 3.0 이하)이나 강알칼리(pH 10.0 이상)에서 진행되는 것과는 달리 특수한 경우를 제외하고는 대부분이 pH 7.0~9.0의 중성내지는 약 알칼리성 범위에서도 잘 진행된다는 것이 특징이다. 즉, 본 발명의 은 용액은 친환경적이면서도 잉크 저장 안정성이 우수하기 때문에 언제든 실험하고 싶을 때 보관된 은거울용 도금 용액을 바로 편리하게 사용할 수 있는 장점이 있다. 또한 간단하면서도 안전하기 때문에 학교에서 산화-환원 반응의 예로서 실험할 경우나 은거울 기념품이나 장식품을 제조하고자 하는 경우 누구나 매우 유용하게 활용할 수 있다는 것이 특징이다. 또한 염화주석을 사용하지 않기에 표면 거칠기가 우수한 거울제조가 가능하여 무엇보다도 망원렌즈와 같은 고 품질의 광학용 거울 제조 시에도 매우 유용하게 사용할 수 있다.In the case of experimenting with the silver mirror reaction with Tollens reagent, it is inconvenient to prepare and use a new silver solution for each silver mirror reaction, but the silver plating solution of the present invention can prepare and store the silver solution in advance and use it whenever necessary. characteristic. In addition, the hydrogen ion concentration (pH) of the present invention does not need to be particularly limited, but the present invention is different from general silver plating (including electroless silver plating) in a relatively strong acid (pH 3.0 or less) or strong alkali (pH 10.0 or more). Except for cases, most of them are characterized in that they proceed well in the neutral to slightly alkaline range of pH 7.0 ~ 9.0. That is, since the silver solution of the present invention is environmentally friendly and has excellent ink storage stability, it has the advantage of being able to conveniently use the stored plating solution for a silver mirror whenever an experiment is desired. In addition, since it is simple and safe, it is characterized by being very useful for anyone to experiment with as an example of oxidation-reduction reaction at school or to manufacture silver mirror souvenirs or ornaments. In addition, since tin chloride is not used, it is possible to manufacture a mirror with excellent surface roughness, and above all, it can be used very usefully when manufacturing a high-quality optical mirror such as a telephoto lens.
한편, 상술한 카르복실산 은 전구체 화합물과 다양한 착화제를 이용하여 은도금액을 제조하고 여기에 안정제, 용매 및 첨가제, 그리고 특별히 무전해 은 도금 또는 은경반응할 경우에는 환원제를 필수적으로 선택하여 사용해야 하는 것으로 본 발명의 특징을 보다 더 잘 구현할 수 있다. On the other hand, a silver plating solution is prepared using the above-described silver carboxylate precursor compound and various complexing agents, and a stabilizer, a solvent, and an additive, and in particular, a reducing agent must be selected and used in the case of electroless silver plating or silver mirror reaction. As a result, the features of the present invention can be better implemented.
환원제는 그 자신이 산화되면서 방출되는 전자를 은 이온에 전이하여 은을 대상물 표면에 석출시키는 역할을 한다. 환원제로서 구체적인 예를 들면 아세톨(Acetol), 아세토인(Acetoin), 하이드록시아세톤(Hydroxyacetone), 하이드록시아민(Hydroxyamine), 디에틸하이드록실아민(diethylhydroxylamine), 메틸에틸케톡심(methylethylketoxime), 로셀염(Rochelle salt), 에리소베이트(erythobate), 암모니아 보란(Ammonia borane) 및 메틸아민보란(Methylamine borane), 디에틸아민보란(diethylamine borane)과 같은 알킬 아미노보란 화합물, 하이드라진(Hydrazine), 수화 하이드라진(Hydrazine hydrate), 하이드라진 설페이트(Hydrazine sulfate), 소디움 하이포 포스파이트(sodium hypophosphite), 소디움 설파이트(sodium sulfite), 소디움 티오설페이트(sodium thiosulfate), 소디움 보로하이드라이드(sodium borohydride), 리튬알루미늄하이드라이드(Lithium aluminum hydride), 소디움 시트레이트(Sodium citrate), 그리고 부틸아민, 에탄올아민, 에틸렌디아민, 도데실아민(Dodecyl amine)과 같은 알킬아민 화합물, 에틸렌글리콜, 티오디글리콜(Thiodiglycol), 디에틸렌글리콜, 포름알데히드, 글루코스, 솔비톨, 설탕(Sugars), 포름산, 포름산 암모늄(ammonium formate), 트리에틸암모늄(triethylammonium formate), 테트라메틸암모늄(tetramethylammonium formate), 시트릭산(Citric acid), 아스코빅산(Ascobic acid), 타타르산(Tartric acid), 페니돈(phenidone), 2-[(4-아미노-3-메틸페닐)에틸아미노]에틸 설페이트(2-[(4-Amino-3-methylphenyl)ethylamino]ethyl sulfate), N-[2-[(4-아미노-3-메틸페닐)에틸아미노]에틸]메탄설폰아미드(N-[2-[(4-amino-3-methylphenyl) ethylamino]ethyl] methanesulfonamide) 및 4-(N-에틸-N-2-히드록시에틸)-2-메틸페닐렌디아민설페이트(4-(N-ethyl-N-2-hydroxy ethyl)-2-methylphenylenediamine sulfate), 그리고 하이드로퀴논(Hydroquinone) 메틸 하이드로퀴논, 메톡시하이드로퀴논, t-부틸 하이드로퀴논, 2,5-디-t-부틸 하이드로퀴논, 2,5-비스(1,1-디메틸부틸) 하이드로퀴논, 2,5-비스(1,1,3,3-테트라메틸부틸) 하이드로퀴논, 4-메톡시페놀, 2,6-디-t-부틸-4-메틸페놀, 퀸히드론(quinhydrone), 파라-메틸아미노페놀 설페이트(p-methylaminophenol sulfate), 파라-아미노페놀(p-aminophenol), 디아미노페놀(diaminophenol), 2-나프톨, 카테콜(Catechol), t-부틸 카테콜, 레소시놀(Resorcinol), 플로로글루시놀(Phloroglucinol), 하이드록시퀴놀(Hydroxyquinol), 피로갈롤(Pyrogallol), 탄닌(Tannin), 탄닌산(Tannic acid), 도파민, 카다놀, 우루시올, 갈릭산 (Gallic acid) 및 그 유도체, 탄닌, 탄닌산, 플라보노이드, 이소플라본, 안토시아닌과 같은 페놀계 및 폴리페놀 화합물로 이루어진 군 중에서 선택되는 1종 이상 선택하여 사용할 수 있다. 이들 중 대표적으로 것으로는 글루코스, 하이드라진과 하이드로퀴논 및 그 유도체들을 들 수 있으나 글루코스는 반응시간이 너무 길고, 하이드라진은 반응시간은 빠르나 인체에 유해하기 때문에 이들 중에서도 특히, 하이드로퀴논이 반응속도와, 친환경과 안전 등 여러 측면에서 볼 때 본 발명에 가장 부합된다. 이들 환원제와 별도로 열(Heat), 햇빛(Light), 플라즈마(Plasma), 적외선(IR), 자외선(UV), 전자 선(electron beam), 포토닉(photonic), 레이저(laser), 마이크로웨이브(microwave), 전기적(electrical), 자기적(magnetic) 처리 등도 환원제 역할을 하기 때문에 단독으로 진행하거나 상기의 환원제와 혼합한 공정을 통하면 보다 빠르게 환원 반응을 진행 시킬 수 있다. 사용되는 환원제의 함량은 본 발명에 부합되는 경우 특별히 제한할 필요는 없지만 일반적으로, 사용되는 카르복실산 은염 대비 몰비로 0.1~5.0일 수 있으며, 바람직하게는 0.3~3.0, 보다 바람직하게는 0.5~2.0이 적당하다. 사용량이 이보다 적거나 많게 되면 도금액의 안정성이 문제되거나 반응이 너무 늦거나 빠르게 진행되어 반응을 제어하기 힘들 뿐 아니라 제품 품질이 저하되는 문제점이 있다.The reducing agent serves to deposit silver on the surface of an object by transferring electrons emitted during oxidation to silver ions. Specific examples of the reducing agent include acetol, acetoin, hydroxyacetone, hydroxyamine, diethylhydroxylamine, methylethylketoxime, and Alkyl aminoborane compounds such as Rochelle salt, erythobate, ammonia borane and methylamine borane, diethylamine borane, hydrazine, hydrated hydrazine (Hydrazine hydrate), Hydrazine sulfate, sodium hypophosphite, sodium sulfite, sodium thiosulfate, sodium borohydride, lithium aluminum hydride (Lithium aluminum hydride), sodium citrate, and alkylamine compounds such as butylamine, ethanolamine, ethylenediamine, and dodecylamine, ethylene glycol, thiodiglycol, and diethylene glycol , formaldehyde, glucose, sorbitol, sugars, formic acid, ammonium formate, triethylammonium formate, tetramethylammonium formate, citric acid, ascorbic acid ), Tartric acid, phenidone, 2-[(4-amino-3-methylphenyl)ethylamino]ethyl sulfate (2-[(4-Amino-3-methylphenyl)ethylamino]ethyl sulfate) , N-[2-[(4-amino-3-methylphenyl)ethylamino]ethyl]methanesulfonamide (N-[2-[(4-amino-3-methylphenyl) ethylamino]ethyl] methanesulfonamide) and 4-( N-ethyl-N-2-hydroxyethyl)-2-methylphenylenediamine sulfate (4-(N-ethyl-N-2-hydroxy ethyl)-2-methylphenylenediamine sulfate), and Hydroquinone Methyl Hydroquinone , methoxyhydroquinone, t-butyl hydroquinone, 2,5-di-t-butyl hydroquinone, 2,5-bis(1,1-dimethylbutyl) hydroquinone, 2,5-bis(1,1, 3,3-tetramethylbutyl) hydroquinone, 4-methoxyphenol, 2,6-di-t-butyl-4-methylphenol, quinhydrone, p-methylaminophenol sulfate , p-aminophenol, diaminophenol, 2-naphthol, catechol, t-butyl catechol, resorcinol, phloroglucinol, hydroxy Hydroxyquinol, Pyrogallol, Tannin, Tannic acid, Dopamine, Cardanol, Urushiol, Gallic acid and its derivatives, Tannin, Tannic acid, Flavonoids, Isoflavones, Anthocyanins It may be used by selecting one or more selected from the group consisting of phenolic and polyphenolic compounds such as Representative examples of these include glucose, hydrazine, hydroquinone and their derivatives, but glucose has a too long reaction time, and hydrazine has a fast reaction time but is harmful to the human body. and safety are most suitable for the present invention in view of various aspects. Apart from these reducing agents, heat, sunlight, plasma, infrared (IR), ultraviolet (UV), electron beam, photonic, laser, microwave ( Since microwave, electrical, and magnetic treatment also act as a reducing agent, the reduction reaction can proceed more quickly through a process of proceeding alone or mixing with the above reducing agent. The content of the reducing agent used does not need to be particularly limited in accordance with the present invention, but in general, it may be 0.1 to 5.0, preferably 0.3 to 3.0, more preferably 0.5 to 5.0 in terms of molar ratio relative to the silver carboxylic acid salt used. 2.0 is suitable. If the amount used is smaller or larger than this, the stability of the plating solution becomes a problem or the reaction proceeds too late or too fast, making it difficult to control the reaction and deteriorating product quality.
은도금 진행시 반응 온도는 본 발명에 부합되는 경우 특별히 제한할 필요는 없지만 일반적으로 5~50℃일 수 있으며, 바람직하게는 10~40℃, 보다 바람직하게는 15~30℃이 적당하다. 이보다 낮거나 높으면 도금액의 안정성과 함께 반응이 너무 늦거나 빠르게 진행되어 반응을 제어하기 힘들 뿐 아니라 제품 품질이 저하되는 문제점이 있다.The reaction temperature during silver plating is not particularly limited in accordance with the present invention, but may be generally 5 to 50 ° C, preferably 10 to 40 ° C, and more preferably 15 to 30 ° C. If it is lower or higher than this, the reaction proceeds too late or too fast along with the stability of the plating solution, so that it is difficult to control the reaction and product quality deteriorates.
그리고 안정제로는 도데칸 티올과 같은 긴 사슬의 메켑탄 화합물, 올레산과 같은 지방산 화합물, 올레일 아민 같은 아민 화합물, 폴리비닐피롤리돈, 폴리(2-에틸-2-옥사졸린), 폴리비닐알코올, 폴리에틸렌글리콜, 폴리스티렌술폰산과 같은 중합체 및 이들의 공중합체, 카르복시메틸 셀룰로스, 알긴산, 키토산, 도파민, 전분(Starch), 폴리사카라이드(Polysaccharide), 각종 검(Gums)과 같은 합성 또는 천연고분자 화합물과 같은 안정제를 사용하여 경시변화를 방지하거나 부착력 개선효과 등을 기대해 볼 수 있다. 그리고 첨가제로서 계면활성제는 폴리옥시에틸렌알킬에테르나 에스테르, 지방산 솔비탄에스테르, 알킬모노글리세릴에테르와 같은 주로 비이온계 계면활성제가 바람직하며, 변색방지제로는 벤조트리아졸 및 유도체로 이루어진 군 중에서 선택되는 1종 이상 선택하여 사용할 수 있다. 기타 첨가제로서 몰리브덴산암모늄(Ammonium molybdate), 비스무스 나이트레이트(Bismuth nitrate), 셀렌산(Selenic acid), 탈륨 나이트레이트(Tallium nitrate)와 같은 금속화합물로 이루어진 군 중에서 선택되는 1종 이상 선택하여 사용할 수 있다.Stabilizers include long-chain mecaptan compounds such as dodecane thiol, fatty acid compounds such as oleic acid, amine compounds such as oleyl amine, polyvinylpyrrolidone, poly(2-ethyl-2-oxazoline), and polyvinyl alcohol. Polymers such as polyethylene glycol and polystyrene sulfonic acid and their copolymers, synthetic or natural polymer compounds such as carboxymethyl cellulose, alginic acid, chitosan, dopamine, starch, polysaccharides, and various gums Using the same stabilizer can be expected to prevent change over time or to improve adhesion. As the additive, the surfactant is preferably a nonionic surfactant such as polyoxyethylene alkyl ether or ester, fatty acid sorbitan ester, or alkyl monoglyceryl ether, and the discoloration inhibitor is selected from the group consisting of benzotriazole and derivatives. You can select and use one or more of them. As other additives, at least one selected from the group consisting of metal compounds such as ammonium molybdate, bismuth nitrate, selenic acid, and thallium nitrate can be selected and used. there is.
특히 본 발명의 은거울 반응을 포함한 은 무전해 도금하는 경우 암모늄 염, 예를 들면 포름산암모늄(Ammonium formate), 초산암모늄(Ammonium acetate), 질산암모늄(Ammonium nitrate), 황산암모늄(Ammonium sulfate), 아황산암모늄(Ammonium sulfite), 탄산암모늄(Ammonium carbonate), 암모늄바이카보네이트(Ammonium bicarbonate), 카밤산암모늄(Ammonium carbamate), 인산암모늄(Ammonium phosphate) 등과 같은 암모늄염 첨가제를 적절히 사용하는 경우 반응 속도가 조절되어 균일하게 도금되고 거울특성이나 전도도가 높아지는 경우가 있다. 사용량은 본 발명에 부합되는 경우 특별히 제한할 필요는 없지만 일반적으로 최종 도금액 대비 중량비로 0.01~10.0%일 수 있으며, 바람직하게는 0.05~5.0%, 보다 바람직하게는 0.1~3.0%가 적당하다. 사용량이 이보다 적거나 많게 되면 도금액의 안정성이 떨어지거나 제품의 품질이 저하되는 문제점이 있다.In particular, in the case of silver electroless plating including the silver mirror reaction of the present invention, ammonium salts such as ammonium formate, ammonium acetate, ammonium nitrate, ammonium sulfate, sulfurous acid When ammonium salt additives such as ammonium sulfite, ammonium carbonate, ammonium bicarbonate, ammonium carbamate, and ammonium phosphate are appropriately used, the reaction rate is controlled and uniform. There are cases in which it is plated more carefully and the mirror characteristics or conductivity are increased. The amount used does not need to be particularly limited in accordance with the present invention, but may generally be 0.01 to 10.0% by weight compared to the final plating solution, preferably 0.05 to 5.0%, and more preferably 0.1 to 3.0%. If the amount used is less or more than this, there is a problem that the stability of the plating solution is lowered or the quality of the product is lowered.
용매는 본 발명에 부합하다면 특별히 제한할 필요는 없으나, 극성 용매, 예를 들면 물(탈 이온수), 메탄올, 에탄올, n-프로판올, 이소-프로판올, n-부탄올, 이소-부탄올, 1-메톡시-2-프로판올(1-methoxy-2-propanol), 디아세톤알코올, 2-메톡시에탄올, 2-에톡시에탄올, 2-부톡시에탄올과 같은 알코올 류, 에틸렌글리콜, 디에티렌글리콜, 프로필렌글리콜, 글리세린, 에틸렌글리콜 모노부틸에테르, 프로필렌글리콜 모노메틸에테르, 디에틸렌글리콜 모노에틸에테르과 같은 글리콜 및 글리콜에테르, 그리고 에틸암모늄 나이트레이트(Ethylammonium nitrate), 1-에틸-3-메틸 이미다졸리움 디시안아미드 (1-Ethyl-3-methyl imidazolium dicyanamide)와 같은 이온성 액체로 이루어진 군 중에서 선택되는 1종 이상 선택하여 사용할 수 있다. 본 발명에 가장 부합되는 용매로는 물, 에탄올, 에틸렌글리콜, 글리세린 또는 이들의 혼합용액을 들 수 있다. 특히 물과 에탄올 혼합용매가 가장 적합하며 은 전해 도금 때에는 물의 함량을 최소화한 경우 도금 품질이 우수하고, 은거울 반응을 포함한 무전해 도금 시에는 물의 함량이 많을수록 반응속도는 빠르나 도금액 수명이 짧고, 너무 많으면 도금액의 안정성이 떨어지고 품질이 균일하지 못하기에 전체 용매대비 중량으로 1~80%일 수 있고, 보다 바람직하게는 20~50%가 바람직하다.The solvent does not need to be particularly limited as long as it conforms to the present invention, but polar solvents such as water (deionized water), methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, 1-methoxy Alcohols such as 2-propanol (1-methoxy-2-propanol), diacetone alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol, diethylene glycol, propylene glycol, Glycols and glycol ethers such as glycerin, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, and ethylammonium nitrate, 1-ethyl-3-methyl imidazolium dicyanamide ( 1-Ethyl-3-methyl imidazolium dicyanamide) and at least one selected from the group consisting of ionic liquids. The solvent most suitable for the present invention may include water, ethanol, ethylene glycol, glycerin, or a mixture thereof. In particular, a mixed solvent of water and ethanol is most suitable. In case of silver electrolytic plating, when the water content is minimized, the plating quality is excellent. In case of electroless plating including silver mirror reaction, the higher the water content, the faster the reaction speed but the shorter the life of the plating solution. If there is a lot, the stability of the plating solution is low and the quality is not uniform, so it may be 1 to 80% by weight compared to the total solvent, more preferably 20 to 50%.
한편, 무전해 은도금을 진행하기 전에 유리나 세라믹, 플라스틱과 같은 부도체에 질산이나 계면활성제, 알코올 등을 사용하여 세정한 후에 부착력을 높이기 위하여 증기 블라스팅이나 실리콘 카바이드사용한 그라인딩과 같은 기계적 연마 방법이나 크롬산, 황산, 불산을 이용한 에칭법, 그리고 염화주석(SnCl2)과 염화 팔라듐(PdCl2)으로 민감화(Sensitization) 및 활성화(Activation) 시키는 방법 등을 선택하여 활용할 수 있다, 그러나 본 발명의 은 도금액은 주로 알코올 용액을 사용하고 은 이온 자체가 스스로 자동촉매 도금(Autocatalytic plating)을 하기 때문에 특별히 상기와 같은 전처리 공정이 없어도 은거울 반응을 포함한 무전해 도금이 어느정도 부착력을 가지면서 잘 진행되는 것이 특징이다. 한편 무전해 도금 후 연속해서 무전해 도금된 소재를 음극으로 하여 전해도금을 행할 수 있는데 이는 도금 두께를 높이거나 외관 및 물성향상을 꾀할 수 있다.On the other hand, before electroless silver plating, non-conductors such as glass, ceramics, and plastics are cleaned with nitric acid, surfactants, alcohol, etc., and mechanical polishing methods such as steam blasting or grinding using silicon carbide or chromic acid or sulfuric acid are used to increase adhesion. , an etching method using hydrofluoric acid, and a method of sensitization and activation with tin chloride (SnCl 2 ) and palladium chloride (PdCl 2 ) can be selected and utilized. However, the silver plating solution of the present invention is mainly alcohol Since the solution is used and the silver ions themselves perform autocatalytic plating on their own, it is characterized in that the electroless plating, including the silver mirror reaction, proceeds well with some degree of adhesion even without the pretreatment process as described above. On the other hand, after electroless plating, electrolytic plating can be continuously performed using the electroless plated material as a cathode, which can increase the plating thickness or improve the appearance and physical properties.
한편, 구리를 기재로 사용하여 도금하는 경우는 환원제 용액을 포함하지 않고도 치환도금이 쉽게 일어나기에 본 발명의 은도금 착체용액 사용만으로 무전해 도금이 가능하며 전해도금을 하는 경우는 본 발명의 은도금 착체용액을 전해질로 사용하여 환원제 대신 전기를 사용하여 은도금을 진행할 수 있다. On the other hand, in the case of plating using copper as a base material, since substitution plating easily occurs without including a reducing agent solution, electroless plating is possible only by using the silver plating complex solution of the present invention, and in the case of electrolytic plating, the silver plating complex solution of the present invention may be used as an electrolyte to perform silver plating using electricity instead of a reducing agent.
은도금이 완료되면 일반적으로 은 및 은 합금이 변색되는 것을 방지하기 위하여 타니반(Tarniban)과 같은 시판되고 있는 여러 변색 방지(Anti-tarnish) 제품들을 사용하거나 티올 또는 설파이드 같은 황 화합물로 표면을 코팅하거나 무수크롬산 용액에 침적시키거나 알칼리 크롬산용액에서 음극처리하는 방식으로 변색방지를 꾀할 수 있다. 또한 제품에 따라 품질 안정화 및 이물 제거를 위하여 50~150℃ 범위에서 열처리 공정을 더 할 수 있다. 열처리 공정이 끝난 제품은 제품에 따라 수계(Water-based) 폴리우레탄, 수계 아크릴계 고분자, 폴리에스테르계 고분자, 실리콘계 고분자, 및 불소계 고분자 등과 같은 화합물을 침적(Dipping)이나 스프레이(Spray) 코팅, 스핀(Spin) 코팅, 바(Bar) 코팅 및 슬릿다이(Slit-die) 코팅, 그라비아(Gravure) 코팅과 같은 방식으로 습식 코팅하거나 실리카나 이산화티타늄 등의 무기계 화합물을 진공증착하거나 스퍼터링(Sputtering)하여 사용할 수 있다.When silver plating is completed, in order to prevent discoloration of silver and silver alloys, various commercially available anti-tarnish products such as Tarniban are generally used, or the surface is coated with a sulfur compound such as thiol or sulfide, or Discoloration can be prevented by immersion in an anhydrous chromic acid solution or cathodic treatment in an alkali chromic acid solution. In addition, depending on the product, a heat treatment process may be added in the range of 50 to 150 ° C for quality stabilization and foreign matter removal. After the heat treatment process, depending on the product, compounds such as water-based polyurethane, water-based acrylic polymer, polyester polymer, silicone polymer, and fluorine-based polymer are applied by dipping, spray coating, or spin ( It can be used by wet coating in methods such as spin coating, bar coating, slit-die coating, and gravure coating, or by vacuum deposition or sputtering of inorganic compounds such as silica or titanium dioxide. there is.
이하에서는, 실시 예를 통해 본 발명에 대해 더욱 상세히 설명하기로 하나, 이는 본 발명의 예시로서 본 발명의 범위가 실시 예에 의하여 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail through examples, but this is an example of the present invention and the scope of the present invention is not limited by the examples.
[실시 예][Example]
아래의 제조 예 및 실시 예에서 별도의 언급이 없는 한 모든 실험은 실내온도 25℃에서 수행하였다. 이하, 특별한 언급이 없는 한 "%"는 모두 "중량%"를 나타낸다.In the preparation examples and examples below, all experiments were conducted at room temperature of 25° C. unless otherwise noted. Hereinafter, "%" represents "% by weight" unless otherwise specified.
은도금용 은 착체 용액의 제조Preparation of silver complex solution for silver plating
제조 예 1.Manufacturing example 1.
네오데칸산 은 (Silver neodecanoate) 100그램에 암모니아 수용액(Aqueous ammonia, 28~30%) 40그램을 서서히 첨가하여 완전히 녹였다. 여기에 에탄올(Ethanol, 95%) 70그램을 첨가한 후 여과하여 최종적으로 은 함량이 약 18.0%인 네오데칸산 은의 암모니아 착체 용액을 제조하였다.40 grams of aqueous ammonia (28-30%) was slowly added to 100 grams of silver neodecanoate to completely dissolve them. After adding 70 grams of ethanol (Ethanol, 95%) thereto, it was filtered to finally prepare an ammonia complex solution of silver neodecanoate having a silver content of about 18.0%.
제조 예 2.Manufacturing example 2.
제조 예 1에서 제조한 네오데칸산 은 암모니아 착체 용액 10그램에 에탄올 280그램과 탈 이온 수(이하, 물) 70그램이 혼합된 용액을 첨가하여 최종적으로 은 함량이 0.5%인 무색의 투명한 네오데칸산 은의 암모니아 착체 용액을 제조하였다.A solution of 280 grams of ethanol and 70 grams of deionized water (hereinafter referred to as water) was added to 10 grams of the silver ammonia complex solution of neodecanoate prepared in Preparation Example 1 to finally obtain colorless and transparent neodecane having a silver content of 0.5%. An acid silver ammonia complex solution was prepared.
제조 예 3.Manufacturing example 3.
제조 예 1에서 제조한 네오데칸산 은 암모니아 착체 용액 10그램에 에탄올 350그램을 첨가하여 최종적으로 은 함량이 0.5%인 네오데칸산 은의 암모니아 착체 용액을 제조하였다.350 g of ethanol was added to 10 g of the silver neodecanoate ammonia complex solution prepared in Preparation Example 1 to finally prepare a silver neodecanoate ammonia complex solution having a silver content of 0.5%.
제조 예 4.Manufacturing example 4.
제조 예 2에서 제조한 0.5%인 무색의 투명한 네오데칸산 은의 암모니아 착체 용액 100그램에 2.0그램의 암모니아 수용액을 첨가하여 은 착체 용액을 제조하였다.A silver complex solution was prepared by adding 2.0 g of ammonia aqueous solution to 100 g of the 0.5% colorless and transparent ammonia complex solution of silver neodecanoate prepared in Preparation Example 2.
환원제 용액의 제조Preparation of reducing agent solution
제조 예 5.Manufacturing example 5.
에탄올 100그램과 물 400그램이 혼합된 용액에 하이드로퀴논(Hydroquinone) 1.5그램을 첨가하여 환원제 용액을 제조하였다.A reducing agent solution was prepared by adding 1.5 g of hydroquinone to a mixed solution of 100 g of ethanol and 400 g of water.
제조 예 6.Manufacturing example 6.
글리세린 100그램과 물 400그램이 혼합된 용액에 하이드로퀴논(Hydroquinone) 1.5그램을 첨가하여 환원제 용액을 제조하였다.A reducing agent solution was prepared by adding 1.5 g of hydroquinone to a mixture of 100 g of glycerin and 400 g of water.
제조 예 7.Manufacturing example 7.
에탄올 400그램과 물 100그램이 혼합된 용액에 하이드로퀴논(Hydroquinone) 1.5그램을 첨가하여 환원제 용액을 제조하였다.A reducing agent solution was prepared by adding 1.5 g of hydroquinone to a mixture of 400 g of ethanol and 100 g of water.
제조 예 8.Manufacturing example 8.
에탄올 250그램과 물 250그램이 혼합된 용액에 2,5-디-터셔리-부틸 하이드로퀴논(2,5-Di-tert-butyl hydroquinone) 3.0그램을 첨가하여 환원제 용액을 제조하였다.A reducing agent solution was prepared by adding 3.0 g of 2,5-di-tert-butyl hydroquinone to a mixed solution of 250 g of ethanol and 250 g of water.
제조 예 9.Manufacturing example 9.
제조 예 5에서 제조한 환원제 용액 100그램에 포름산 암모늄(Ammonium formate) 0.5그램을 첨가하여 환원제 용액을 제조하였다.A reducing agent solution was prepared by adding 0.5 g of ammonium formate to 100 g of the reducing agent solution prepared in Preparation Example 5.
제조 예 10.Manufacturing example 10.
물 100그램에 80% 하이드라진 하이드레이트(Hydrazine hydrate, 80%) 0.5그램을 첨가하여 환원제 용액을 제조하였다.A reducing agent solution was prepared by adding 0.5 g of 80% hydrazine hydrate (80%) to 100 g of water.
제조 예 11.Manufacturing example 11.
물 100그램에 글루코스(Glucose) 5.0그램을 첨가하여 환원제 용액을 제조하였다.A reducing agent solution was prepared by adding 5.0 g of glucose to 100 g of water.
제조 예 12.Manufacturing example 12.
물 50그램과 에탄올 50그램에 80% 하이드라진 하이드레이트(Hydrazine hydrate, 80%) 0.5그램을 첨가하고 여기에 질산암모늄(Ammonium nitrate) 0.5그램을 더하여 환원제 용액을 제조하였다.A reducing agent solution was prepared by adding 0.5 g of 80% hydrazine hydrate (80%) to 50 g of water and 50 g of ethanol and adding 0.5 g of ammonium nitrate thereto.
제조 예 13.Manufacturing example 13.
물 100그램에 80% 하이드라진 하이드레이트 0.5그램을 첨가하고 여기에 포름산암모늄(Ammonium formate) 0.5그램을 더하여 환원제 용액을 제조하였다.A reducing agent solution was prepared by adding 0.5 g of 80% hydrazine hydrate to 100 g of water and adding 0.5 g of ammonium formate thereto.
은거울의 제조manufacture of silver mirrors
실시 예 1. Example 1.
깨끗하게 준비된 뚜껑이 있는 투명한 유리 용기에 먼저 제조 예 2의 은 착체용액을 용기 부피의 절반 정도 넣고 잘 흔들어 용기 내부를 민감화 및 활성화시켰다. 이후 제조 예 5에서 제조한 환원제용액으로 나머지 절반을 채워 잘 흔들어 준 다음 그대로 30분 정도 방치해 둔 후에 내용물을 버리고 에탄올로 잘 씻었더니 내부에는 연한 금색의 거울이, 외부에는 깨끗한 은거울이 형성되었다. 변색방지를 위하여 내부를 수계 폴리우레탄으로 코팅하였다. 제조한 샘플의 사진을 도 1에 나타내었다.First, about half the volume of the silver complex solution of Preparation Example 2 was put into a cleanly prepared transparent glass container with a lid, and shaken well to sensitize and activate the inside of the container. Thereafter, the other half was filled with the reducing agent solution prepared in Preparation Example 5, shaken well, left as it is for about 30 minutes, then the contents were discarded and washed with ethanol. A light golden mirror was formed on the inside and a clean silver mirror on the outside. . To prevent discoloration, the inside was coated with water-based polyurethane. A photograph of the prepared sample is shown in FIG. 1 .
실시 예 2. Example 2.
제조 예 5의 환원제용액 대신에 제조 예 6에서 제조한 환원제용액을 사용한 것을 제외하고는 실시 예 1과 같은 방법으로 은거울 제조실험을 한 결과 실시 예 1보다는 반응속도가 조금 늦은 대신 내부에는 연한 검정색의 거울이, 외부에는 깨끗한 은거울이 잘 형성되었다. 내부를 수계 아크릴계 고분자로 코팅하였다. 제조한 샘플의 사진을 도 1에 나타내었다.Except for using the reducing agent solution prepared in Preparation Example 6 instead of the reducing agent solution of Preparation Example 5, a silver mirror manufacturing experiment was performed in the same manner as in Example 1, and the reaction rate was slightly slower than in Example 1, but the inside was light black The mirror of the outside was well formed with a clean silver mirror. The inside was coated with a water-based acrylic polymer. A photograph of the prepared sample is shown in FIG. 1 .
실시 예 3. Example 3.
제조 예 5의 환원제용액 대신에 제조 예 7에서 제조한 환원제용액을 사용한 것을 제외하고는 실시 예 1과 같은 방법으로 은거울 제조실험을 한 결과 실시 예 1보다는 반응속도가 조금 늦은 대신 내부 및 외부 모두에 깨끗한 은거울이 잘 형성되었다. 제조한 샘플의 사진을 도 1에 나타내었다.Except for using the reducing agent solution prepared in Preparation Example 7 instead of the reducing agent solution of Preparation Example 5, a silver mirror manufacturing experiment was performed in the same manner as in Example 1, and the reaction rate was slightly slower than in Example 1, but both internal and external A clean silver mirror was well formed. A photograph of the prepared sample is shown in FIG. 1 .
실시 예 4. Example 4.
제조 예 5의 환원제용액 대신에 제조 예 8에서 제조한 환원제용액을 사용한 것을 제외하고는 실시 예 1과 같은 방법으로 은거울 제조실험을 한 결과 1시간 안에 내부 및 외부 모두에 깨끗한 은거울이 잘 형성되었다. 제조한 샘플의 사진을 도 1에 나타내었다.Except for using the reducing agent solution prepared in Preparation Example 8 instead of the reducing agent solution of Preparation Example 5, a silver mirror manufacturing experiment was conducted in the same manner as in Example 1, and as a result, clean silver mirrors were well formed on both the inside and outside within 1 hour It became. A photograph of the prepared sample is shown in FIG. 1 .
실시 예 5. Example 5.
깨끗하게 준비된 뚜껑이 있는 투명한 유리 용기에 먼저 제조 예 3의 은 착체용액을 용기 부피 절반 정도 넣고 잘 흔들어 용기 내부를 민감화 및 활성화시켰다. 이후 제조 예 6에서 제조한 환원제용액으로 나머지 절반을 채워 잘 흔들어 준 다음 그대로 1시간 정도 방치해 둔 후 내용물을 버리고 에탄올로 잘 씻었더니 내부에는 금빛 거울이, 외부에는 깨끗한 은거울이 잘 형성되었다. 변색방지를 위하여 내부를 실리콘계 고분자로 코팅하였다. 제조한 샘플의 사진을 도 1 및 도 2에 나타내었다.First, about half the volume of the silver complex solution of Preparation Example 3 was placed in a cleanly prepared transparent glass container with a lid, and shaken well to sensitize and activate the inside of the container. Thereafter, the other half was filled with the reducing agent solution prepared in Preparation Example 6, shaken well, left as it is for about 1 hour, then the contents were discarded and washed well with ethanol. A golden mirror was formed on the inside and a clean silver mirror on the outside. To prevent discoloration, the inside was coated with a silicone-based polymer. Photographs of the prepared samples are shown in FIGS. 1 and 2 .
실시 예 6. Example 6.
깨끗하게 준비된 뚜껑이 있는 투명한 유리 용기에 먼저 제조 예 2의 은 착체용액을 용기 부피 절반 정도 넣고 잘 흔들어 용기 내부를 민감화 및 활성화시켰다. 이후 제조 예 9에서 제조한 환원제용액으로 나머지 절반을 채워 잘 흔들어 준 다음 그대로 1시간 정도 방치해 둔 후 내용물을 버리고 에탄올로 잘 씻었더니 내부에는 검은색이 외부에는 깨끗한 은거울이 잘 형성되었다. 제조한 샘플의 사진을 도 1에 나타내었다.First, about half the volume of the silver complex solution of Preparation Example 2 was put into a cleanly prepared transparent glass container with a lid, and shaken well to sensitize and activate the inside of the container. Thereafter, the remaining half was filled with the reducing agent solution prepared in Preparation Example 9, shaken well, left as it is for about 1 hour, and then the contents were discarded and washed well with ethanol. A black mirror was formed on the inside and a clean silver mirror on the outside. A photograph of the prepared sample is shown in FIG. 1 .
실시 예 7. Example 7.
제조 예 2의 은 착체용액 대신에 제조 예 4에서 제조한 은 착체용액을 사용한 것을 제외하고는 실시 예 6과 같은 방법으로 은거울 제조실험을 한 결과 내부에는 밝은 금빛의 은색 거울이, 외부에는 깨끗한 은거울이 잘 형성되었다. 제조한 샘플의 사진을 도 1에 나타내었다.A silver mirror manufacturing experiment was performed in the same manner as in Example 6, except that the silver complex solution prepared in Preparation Example 4 was used instead of the silver complex solution of Preparation Example 2, and as a result, a bright golden silver mirror was obtained on the inside and clean on the outside The silver mirror was well formed. A photograph of the prepared sample is shown in FIG. 1 .
실시 예 8. Example 8.
깨끗하게 준비된 뚜껑이 있는 투명한 유리 용기 대신에 투명한 폴리에스테르 용기(PET bottle)를 사용하여 실시 예 1과 같은 방법으로 실험한 결과 내부에는 연한 금색의 거울이, 외부에는 깨끗한 은거울이 형성되었다. 제조한 샘플의 사진을 도 3에 나타내었다.As a result of the experiment in the same manner as in Example 1 using a transparent polyester container (PET bottle) instead of a transparent glass container with a cleanly prepared lid, a light gold mirror was formed on the inside and a clean silver mirror on the outside. A photograph of the prepared sample is shown in FIG. 3 .
실시 예 9. Example 9.
깨끗하게 준비된 뚜껑이 있는 투명한 유리 용기에 먼저 제조 예 3의 은 착체용액을 용기 부피 절반 정도 넣고 잘 흔들어 용기 내부를 민감화 및 활성화시켰다. 이후 제조 예 10에서 제조한 환원제용액으로 나머지 절반을 채워 잘 흔들어 준 다음 그대로 10분 정도 방치해 둔 후 내용물을 버리고 물로 잘 씻었더니 내부에는 밝은 연한 금색의 거울이, 외부에는 은거울이 하이드로퀴논 환원제를 사용한 경우보다는 얇게 형성되었다.First, about half the volume of the silver complex solution of Preparation Example 3 was placed in a cleanly prepared transparent glass container with a lid, and shaken well to sensitize and activate the inside of the container. Thereafter, the other half was filled with the reducing agent solution prepared in Preparation Example 10, shaken well, left as it is for about 10 minutes, then the contents were discarded and washed well with water. was formed thinner than in the case of using
실시 예 10. Example 10.
깨끗하게 준비된 뚜껑이 있는 투명한 유리 용기에 먼저 제조 예 3의 은 착체용액을 용기 부피 절반 정도 넣고 잘 흔들어 용기 내부를 민감화 및 활성화시켰다. 이후 제조 예 11에서 제조한 환원제용액으로 나머지 절반을 채워 잘 흔들어준 다음 그대로 6시간 정도 방치해 둔 후 내용물을 버리고 물과 에탄올로 순차적으로 잘 씻었더니 내부에는 밝은 금색의 거울이, 외부에는 은거울이 하이드로퀴논 환원제보다는 얇게 형성되었다.First, about half the volume of the silver complex solution of Preparation Example 3 was placed in a cleanly prepared transparent glass container with a lid, and shaken well to sensitize and activate the inside of the container. Thereafter, the other half was filled with the reducing agent solution prepared in Preparation Example 11, shaken well, left as it is for about 6 hours, then the contents were discarded and washed sequentially with water and ethanol. It was formed thinner than this hydroquinone reducing agent.
실시 예 11. Example 11.
제조 예 1에서 착화제로서 암모니아 수용액 대신에 메틸아민 수용액(40%)을 60그램 사용하고 완전히 녹였다. 여기에 에탄올 80그램을 첨가한 후 여과하여 보라색(Purple)을 나타내는 네오데칸산은의 메틸아민 착체 용액을 얻었다. 이 착체용액 10그램에 에탄올 300그램을 추가하여 최종적으로 은 함량이 약 0.5%인 무색의 착체 용액을 제조하였다. 깨끗하게 준비된 뚜껑이 있는 투명한 유리 용기에 이 착체 용액을 넣고 잘 흔들어 용기 내부를 민감화 및 활성화시켰다. 이후 제조 예 13에서 제조한 환원제 용액을 무게비로 같은 양을 채워 잘 흔들어 섞고 10분 간 방치한 후 내용물을 버리고 물과 에탄올로 순차적으로 잘 씻었더니 내부에는 검고 어두운 금색 거울이, 외부에는 밝은 은거울이 잘 형성되었다.In Production Example 1, 60 grams of methylamine aqueous solution (40%) was used instead of aqueous ammonia as a complexing agent and completely dissolved. After adding 80 grams of ethanol thereto, the solution was filtered to obtain a purple neodecanoate methylamine complex solution. 300 g of ethanol was added to 10 g of the complex solution to finally prepare a colorless complex solution having a silver content of about 0.5%. The complex solution was placed in a cleanly prepared transparent glass container with a lid and shaken well to sensitize and activate the inside of the container. Thereafter, the reducing agent solution prepared in Preparation Example 13 was filled in equal amounts in weight ratio, shaken well, left for 10 minutes, then the contents were discarded and washed sequentially with water and ethanol. this is well formed
실시 예 12. Example 12.
실시 예 11에서 사용한 제조 예 13의 환원제 용액 대신에 제조 예 11에서 제조한 환원제 용액을 사용한 결과 1시간 경과 후에 내부에는 밝고 은색의 거울이, 그리고 외부에는 밝은 은거울이 잘 형성되었다.As a result of using the reducing agent solution prepared in Preparation Example 11 instead of the reducing agent solution of Preparation Example 13 used in Example 11, a bright silver mirror was formed well on the inside and a bright silver mirror on the outside after 1 hour.
비교실시 예 1. Comparative Example 1.
제조 예 1에서 암모니아 수용액 대신에 암모니아 에탄올 용액(Alcoholic ammonia)을 사용하여 네오데칸산 은을 녹인 후 여기에 무수 에탄올(Absolute ethanol)을 희석제로 사용하여 최종적으로 은 함량이 0.5%인 무색의 알코올성 암모니아 착체 용액을 제조하였다. 깨끗하게 준비된 뚜껑이 있는 투명한 유리 용기에 제조한 알코올성 암모니아 착체 용액을 넣고 잘 흔들어 용기 내부를 민감화 및 활성화시켰다. 이후, 여기에 미리 제조한 무수 에탄올에 0.3%의 하이드로퀴논이 용해된 환원제 용액을 무게비로 같은 양을 채워 30분 동안 반응시킨 결과 95% 에탄올을 사용했을 때보다 품질이 떨어지는 어두운 은거울이 형성되었다.In Preparation Example 1, silver neodecanoate was dissolved using ammonia ethanol solution (Alcoholic ammonia) instead of aqueous ammonia solution, and then absolute ethanol was used as a diluent to finally obtain colorless alcoholic ammonia having a silver content of 0.5%. A complex solution was prepared. The prepared alcoholic ammonia complex solution was placed in a cleanly prepared transparent glass container with a lid and shaken well to sensitize and activate the inside of the container. Thereafter, the same amount of reducing agent solution in which 0.3% hydroquinone was dissolved in anhydrous ethanol prepared in advance was filled in the same amount by weight and reacted for 30 minutes. As a result, a dark silver mirror lower in quality than when using 95% ethanol was formed. .
비교실시 예 2. Comparative Example 2.
제조 예 1에서 에탄올을 첨가하는 대신에 물을 첨가하고 계속해서 물을 첨가하여 최종적으로 은 함량이 0.5%인 네오데칸산 은의 암모니아 착체 수용액을 제조하려 하였으나 흰 고체가 석출되어 더 이상 은거울 반응을 진행하지 못하였다.In Production Example 1, instead of adding ethanol, water was added and then water was added to finally prepare an aqueous solution of silver neodecanoate ammonia complex having a silver content of 0.5%, but a white solid was precipitated and the silver mirror reaction was no longer possible. couldn't proceed
실시예 13~19Examples 13-19
은 함량에 따른 도금여부를 확인하기 위한 실험을 실시하였다. 실시예 1과 동일하게 제조하되 하기의 표 1에 나타난 바와 같은 은 함량을 가질 수 있도록 착체 용액과 혼합되는 에탄올의 양을 조절하였다. 이때 물의 함량은 제조예 2에서와 같이70g으로 동일하게 고정하여 사용하였다.An experiment was conducted to check the plating according to the silver content. It was prepared in the same manner as in Example 1, but the amount of ethanol mixed with the complex solution was adjusted so as to have a silver content as shown in Table 1 below. At this time, the water content was used with the same fixation as 70 g as in Preparation Example 2.
착체용액(g)Complex solution (g) 에탄올(g)Ethanol (g) 최종 은 함량(%)Final silver content (%)
실시예 13Example 13 22 35283528 0.010.01
실시예 14Example 14 1010 35203520 0.050.05
실시예 15Example 15 2020 35103510 0.10.1
실시예 16Example 16 1010 280280 0.50.5
실시예 17Example 17 2020 270270 1One
실시예 18Example 18 1010 2828 55
실시예 19Example 19 7575 3535 7.57.5
깨끗하게 준비된 뚜껑이 있는 투명한 유리 용기에 이 착체 용액을 넣고 잘 흔들어 용기 내부를 민감화 및 활성화시켰다. 이후 제조 예 5에서 제조한 환원제 용액을 무게비로 같은 양을 채워 잘 흔들어 섞고 10분 간 방치한 후 내용물을 버리고 물과 에탄올로 순차적으로 잘 세척하여 최종 은함량에 따른 은거울 반응여부를 확인하였다.The complex solution was placed in a cleanly prepared transparent glass container with a lid and shaken well to sensitize and activate the inside of the container. Thereafter, the reducing agent solution prepared in Preparation Example 5 was filled in the same amount by weight ratio, shaken well, left for 10 minutes, and then the contents were discarded and washed sequentially with water and ethanol to confirm whether the silver mirror reacted according to the final silver content.
실험결과 실시예 16에서 가장 안정적인 은거울 반응이 수행되어 깨끗하게 도금되는 것을 확인하였으며, 은함량이 낮은 실시예 14, 15의 경우에도 은거울이 형성되는 것을 확인하였다. 하지만 은 함량이 0.01%인 실시예 13의 경우도 은거울 반응은 수행되나 거울 특성이 미약한 반투명 상태의 은거울이 형성되는 것을 확인하였다.As a result of the experiment, it was confirmed that the most stable silver mirror reaction was performed in Example 16 and clean plating was performed, and it was confirmed that silver mirrors were formed even in Examples 14 and 15 having a low silver content. However, even in the case of Example 13 in which the silver content was 0.01%, the silver mirror reaction was performed, but it was confirmed that a semi-transparent silver mirror having weak mirror characteristics was formed.
또한 이와는 반대로 높은 함량의 은을 가지는 실시예 17 및 18의 경우 함량이 높아질수록 은거울의 색상이 진해지는 것을 확인할 수 있었으며, 7.5%의 은 함량을 가지는 실시예 19의 경우 어두운색의 은거울을 형성함과 동시에 바닥에 은 침전물이 발생하는 것을 확인할 수 있었다.In contrast, in the case of Examples 17 and 18 having a high silver content, it was confirmed that the color of the silver mirror became darker as the content increased, and in the case of Example 19 having a silver content of 7.5%, a dark silver mirror was obtained. It was confirmed that a silver precipitate was generated on the bottom at the same time as the formation.
실시 예 20. Example 20.
제조 예 1에서 네오데칸산은 대신에 초산은 20그램에 암모니아 수용액 15그램을 서서히 첨가하여 완전히 녹였다. 여기에 에탄올 15그램을 첨가한 후 여과하여 무색의 초산은의 암모니아 착체 용액을 얻었다. 이 착체용액 10그램에 에탄올 500그램을 추가하여 최종적으로 은 함량이 약 0.5%인 무색의 착체 용액을 제조하였다. 깨끗하게 준비된 뚜껑이 있는 투명한 유리 용기에 이 초산은 용액을 넣고 잘 흔들어 용기 내부를 민감화 및 활성화시켰다. 이후 제조 예 13에서 제조한 환원제용액을 무게비로 같은 양을 채워 계속해서 잘 흔들어 준 결과 5분 이내에 밝은 은거울이 잘 형성되었다. 내용물을 버리고 물과 에탄올로 순차적으로 잘 씻었더니 내부는 금색의 거울이, 외부는 밝은 은거울이 잘 형성되었다.In Production Example 1, instead of silver neodecanoate, 15 grams of ammonia aqueous solution was slowly added to 20 grams of silver acetate to completely dissolve them. After adding 15 grams of ethanol thereto, the mixture was filtered to obtain a colorless silver acetate ammonia complex solution. 500 g of ethanol was added to 10 g of the complex solution to finally prepare a colorless complex solution having a silver content of about 0.5%. The silver acetate solution was placed in a cleanly prepared transparent glass container with a lid and shaken well to sensitize and activate the inside of the container. Thereafter, the same amount of the reducing agent solution prepared in Preparation Example 13 was filled and shaken well, and as a result, a bright silver mirror was well formed within 5 minutes. The contents were discarded and washed sequentially with water and ethanol, and a golden mirror was formed on the inside and a bright silver mirror on the outside.
실시예 21~26Examples 21-26
카르복실산 은의 종류에 따른 은거울 반응 여부를 확인하기 위한 실험을 실시하였다. 상기 실시예 20과 동일하게 실험을 실시하되, 하기의 표 2와 같이 카르복실산 은을 사용하였다.An experiment was conducted to determine whether a silver mirror reaction occurred according to the type of silver carboxylate. The experiment was conducted in the same manner as in Example 20, but silver carboxylate was used as shown in Table 2 below.
카르복실산 은silver carboxylate 은거울 반응 여부Silver mirror response
실시예 21Example 21 프로피온산 은silver propionate OO
실시예 22Example 22 2-에틸헥사논산 은Silver 2-ethylhexanoate OO
실시예 23Example 23 말론산 은silver malonate △△
실시예 24Example 24 락트산은Lactic acid is △△
실시예 25Example 25 올레산 은silver oleic acid △△
실시예 26Example 26 질산 은silver nitrate △△
표 2에 나타난 바와 같이, 프로피온산 은 또는 2-에틸헥사논산 은을 사용하는 경우 적절한 반응조건에 따라 실시예 1~20의 네오데칸산 은과 초산 은 같이 은거울 반응이 비교적 원활하게 진행되는 것을 확인할 수 있었다. 또한 다른 종류의 카르복실산 은을 사용한 경우에도 은거울 반응이 수행되기는 하였지만, 일반적인 조건에서는 반응성이 떨어져 은거울 반응이 약하게 일어나는 것을 확인하였다. 다만 다른 종류의 카르복실산 은도 기존에 많이 사용하는 질산은과 비교시 동등 또는 그 이상의 은거울 반응이 가능함을 확인할 수 있었다.As shown in Table 2, when silver propionate or silver 2-ethylhexanoate was used, it was confirmed that the silver mirror reaction proceeded relatively smoothly, as in the case of the silver neodecanoate and silver acetate of Examples 1 to 20, depending on the appropriate reaction conditions. could In addition, it was confirmed that the silver mirror reaction was performed even when a different type of silver carboxylate was used, but the silver mirror reaction was weak under normal conditions due to low reactivity. However, it was confirmed that other types of silver carboxylate can have the same or better silver mirror reaction compared to silver nitrate, which is widely used in the past.
실시예 27~33Examples 27-33
착화제의 함량에 따른 도금여부를 확인하기 위한 실험을 실시하였다. 제조예 1 및 실시예 1과 동일하게 제조하되 하기의 표 3에 나타난 바와 같은 착화제의 함량을 가질 수 있도록 착체 용액에 카르복실산 은염(네오데칸산 은)과 혼합되는 착화제(암모니아 수용액)의 양을 조절하였다.An experiment was conducted to determine whether plating was performed according to the content of the complexing agent. A complexing agent (aqueous ammonia solution) mixed with a silver carboxylic acid salt (silver neodecanoate) in a complex solution to be prepared in the same manner as in Preparation Example 1 and Example 1, but to have the content of the complexing agent as shown in Table 3 below The amount of was adjusted.
카르복실산 은(g)Silver Carboxylate (g) 암모니아 수용액(g)Ammonia aqueous solution (g) 중량비weight ratio
실시예 27Example 27 100100 1One 0.010.01
실시예 28Example 28 100100 44 0.040.04
실시예 29Example 29 100100 2020 0.200.20
실시예 30Example 30 100100 4040 0.400.40
실시예 31Example 31 100100 8080 0.800.80
실시예 32Example 32 100100 120120 1.201.20
실시예 33Example 33 100100 200200 2.002.00
상기와 같은 비율로 혼합된 카르복실산 은 염과 착화제를 실시예 1과 동일한 방법으로 은거울 반응을 수행하였다. 착화제의 함량이 낮은 실시예 27~28의 경우 용해도 문제가 있으며 은거울반응이 거의 수행되지 않은 것을 확인하였다. 실시예 29~32의 경우에는 정상적으로 은거울 반응이 수행되는 것을 확인할 수 있었다. 다만 실시예 30에서 가장 우수한 은거울이 형성되는 것을 확인 할 수 있었다. A silver mirror reaction was performed using the silver carboxylic acid salt and the complexing agent mixed in the same ratio as in Example 1. In the case of Examples 27 and 28 having a low content of the complexing agent, it was confirmed that there was a solubility problem and the silver mirror reaction was hardly performed. In the case of Examples 29 to 32, it was confirmed that the silver mirror reaction was normally performed. However, it was confirmed that the best silver mirror was formed in Example 30.
또한 과량의 착화제를 사용한 실시예 33의 경우 착화제와 카르복실산 은의착체용액이 저장 안정성이 떨어지고 깨끗한 은거울을 얻기가 힘들었다.Also, in the case of Example 33 using an excessive amount of the complexing agent, the storage stability of the complex solution of the complexing agent and silver carboxylate was poor, and it was difficult to obtain a clean silver mirror.
실시예 34~40Examples 34-40
환원제의 함량에 따른 도금여부를 확인하기 위한 실험을 실시하였다. 실시예 1과 동일하게 제조하되 하기의 표 4에 나타난 바와 같이 은 착체와 환원제의 양을 각기 달리하여 혼합한 다음, 동량(10g)을 용기에 주입하여 실험을 실시하였다.An experiment was conducted to determine whether plating was performed according to the content of the reducing agent. It was prepared in the same manner as in Example 1, but as shown in Table 4 below, the silver complex and the reducing agent were mixed in different amounts, and then the same amount (10 g) was injected into a container to conduct an experiment.
은착제(g)Silver binding agent (g) 환원제(g)reducing agent (g) 중량비weight ratio
실시예 34Example 34 100100 55 0.050.05
실시예 35Example 35 100100 1010 0.100.10
실시예 36Example 36 5050 2020 0.400.40
실시예 37Example 37 5050 5050 1.001.00
실시예 38Example 38 4040 8080 2.002.00
실시예 39Example 39 2020 100100 5.005.00
실시예 40Example 40 2020 120120 6.006.00
상기와 같은 비율로 혼합된 은 착체용액과 환원제 용액을 용기에 주입하여 은거울 반응을 수행하였다. 상기 실시예 중 35~39의 경우 원하는 은거울 반응이 정상적으로 수행되는 것을 확인하였지만, 환원제의 함량이 높아질수록 은거울 반응이 빠르게 수행되는 것을 확인하였다. 다만 환원제의 함량이 낮은 실시예 34의 경우 은거울 반응이 수행되는 시간이 길어져(약 50~80분)공업적으로 사용이 어려운 것을 확인하였으며, 과도한 환원제를 사용한 실시예 40의 경우 은 침전이 발생함과 동시에 상대적으로 은의 함량이 줄어들어 거울 특성이 미약한 반투명 상태의 은거울이 형성되는 것으로 나타났다.A silver mirror reaction was performed by injecting the silver complex solution and the reducing agent solution mixed in the above ratio into a container. In the case of Examples 35 to 39, it was confirmed that the desired silver mirror reaction was normally performed, but it was confirmed that the silver mirror reaction was rapidly performed as the content of the reducing agent increased. However, in the case of Example 34 with a low content of reducing agent, it was confirmed that the time for performing the silver mirror reaction was long (about 50 to 80 minutes), making it difficult to use industrially, and in Example 40 using an excessive reducing agent, silver precipitation occurred At the same time, the silver content was relatively reduced, resulting in the formation of a semi-transparent silver mirror with weak mirror characteristics.
전도성 제품의 제조Manufacture of conductive products
실시 예 41. Example 41.
제조 예 1에서 제조한 네오데칸산 은 암모니아 착체 용액 (은 함량 18.0%) 에탄올과 물의 중량비가 4:1인 혼합용액으로 희석하여 최종 은 함량이 1.0% 되도록 하였다. 여기에 0.5%의 포름산 암모늄을 녹여 무전해 은 도금용액을 제조하였다. 환원제 용액은 글리세린 100그램과 물 400그램이 혼합된 용액에 하이드로퀴논(Hydroquinone) 3.0그램을 첨가하여 제조하였다. 나일론 직물(Fabric)을 먼저 은 도금용액에 넣고 1시간 동안 충분히 적신 다음 여기에 환원제 용액을 은 도금용액과 무게비로 1:1비율로 넣고 3시간동안 교반하면서 반응 시켰다. 반응이 끝나면 여과하고 물과 에탄올로 순차적으로 씻은 후 120℃에서 12시간 건조시켜 은이 코팅된 전도도가 우수한 나일론 직물을 제조하였다(도 4 참조).The silver ammonia complex solution of neodecanoate prepared in Preparation Example 1 (silver content: 18.0%) was diluted with a mixed solution having a weight ratio of 4:1 of ethanol and water to obtain a final silver content of 1.0%. An electroless silver plating solution was prepared by dissolving 0.5% ammonium formate therein. The reducing agent solution was prepared by adding 3.0 grams of hydroquinone to a solution of 100 grams of glycerin and 400 grams of water. A nylon fabric was first put into the silver plating solution and sufficiently wetted for 1 hour, and then a reducing agent solution was added thereto in a weight ratio of 1:1 to the silver plating solution and reacted while stirring for 3 hours. After the reaction was completed, it was filtered, washed sequentially with water and ethanol, and dried at 120° C. for 12 hours to prepare a silver-coated nylon fabric having excellent conductivity (see FIG. 4).
실시 예 42. Example 42.
실시 예 41에서 나일론 직물 대신에 나일론 섬유(Fiber)를 사용하는 것을 제외하고는 같은 방법으로 실험을 진행한 결과 은이 코팅된 전도도가 우수한 나일론 섬유가 제조되었다. 제조한 샘플의 사진과 전도도가 표기된 그림을 도 5에 나타내었으며 섬유 표면의 전자현미경(SEM) 사진은 도 6에 나타내었다.As a result of the experiment in the same manner as in Example 41, except that nylon fibers were used instead of nylon fabrics, silver-coated nylon fibers having excellent conductivity were prepared. A photograph of the prepared sample and a drawing showing the conductivity are shown in FIG. 5, and an electron microscope (SEM) photograph of the fiber surface is shown in FIG. 6.
실시 예 43. Example 43.
실시 예 41에서 나일론 직물 대신에 25미크론의 폴리이미드 필름(Polyimide film)을 사용하는 것을 제외하고는 같은 방법으로 실험을 진행한 결과 은이 코팅된 거울 상 폴리이미드 필름이 제조되었다. 제조한 샘플의 사진을 도 7에 나타내었으며 측정된 반사율은 97.5% @550nm, 면 저항 값은 120mΩ/□이었다.As a result of the experiment in the same manner as in Example 41, except that a 25 micron polyimide film was used instead of the nylon fabric, a silver-coated mirror-image polyimide film was prepared. A photograph of the prepared sample is shown in FIG. 7, the measured reflectance was 97.5% @ 550 nm, and the sheet resistance value was 120 mΩ/□.
실시 예 44. Example 44.
실시 예 43에서 25미크론의 폴리이미드 필름 대신에 12미크론의 나일론 필름(Nylon film)을 사용하는 것을 제외하고는 같은 방법으로 실험을 진행한 결과 은이 코팅된 거울 상 나일론 필름이 제조되었다. 측정된 면 저항 값은 130mΩ/□이었다.As a result of the experiment in the same manner as in Example 43, except that a 12 micron nylon film was used instead of the 25 micron polyimide film, a mirror image nylon film coated with silver was prepared. The measured sheet resistance value was 130 mΩ/□.
실시 예 45. Example 45.
제조 예 1에서 제조한 네오데칸산 은 암모니아 착체 용액 (은 함량 18.0%) 에탄올과 물의 중량비가 1:1인 혼합용액으로 희석하여 최종 은 함량이 0.5% 되도록 무전해 은 도금용액을 제조하였다. 환원제 용액으로는 제조 예 12의 용액을 사용하였다. 폴리우레탄 폼(Polyurethane foam)을 먼저 은 도금용액에 넣고 1시간 동안 충분히 적신 다음 여기에 환원제 용액을 은 도금용액 대비 무게비로 1:1비율로 넣고 2시간동안 교반하면서 반응시켰다. 반응이 끝난 후 건져내어 물과 에탄올로 순차적으로 씻은 다음 120℃에서 30분간 건조시킨 결과 은이 코팅된 폴리우레탄 폼이 만들어졌다. 표면 저항의 측정결과 0.3Ω/cm이었으며 은 코팅 샘플의 사진과 표면 전자현미경(SEM) 사진을 도 8 및 도 9에 각각 나타내었다.The silver ammonia neodecanoate solution prepared in Preparation Example 1 (silver content: 18.0%) was diluted with a mixed solution of ethanol and water in a weight ratio of 1:1 to prepare an electroless silver plating solution so that the final silver content was 0.5%. The solution of Preparation Example 12 was used as the reducing agent solution. Polyurethane foam was first put into the silver plating solution and sufficiently wetted for 1 hour, and then a reducing agent solution was added thereto in a weight ratio of 1:1 to the silver plating solution and reacted with stirring for 2 hours. After the reaction was completed, it was taken out, washed sequentially with water and ethanol, and dried at 120 ° C for 30 minutes, resulting in silver-coated polyurethane foam. As a result of measuring the surface resistance, it was 0.3 Ω/cm, and pictures of the silver-coated sample and surface electron microscope (SEM) pictures are shown in FIGS. 8 and 9, respectively.
실시 예 46. Example 46.
제조 예 3에서 제조한 은 착체용액에 3-아미노트리에톡시실란으로 표면 처리된 평균 입자직경 12μm 크기의 실리카 비드를 넣고 교반하며 충분히 적신 다음 여과하고 에탄올로 씻어 건조하였다. 이같이 전처리가 끝난 실리카 비드를 제조 예 4에서 제조한 은 착체용액과 제조 예 9에서 제조한 환원제 용액이 무게비로 1:1비율로 된 은 무전해 도금용액에 넣고 1시간 동안 교반하면서 반응시켰다. 반응이 끝난 후 여과하고 물과 에탄올로 순차적으로 씻은 후 100℃에서 24시간 건조시켜 은이 코팅된 실리카 비드를 얻었다.Silica beads having an average particle diameter of 12 μm surface-treated with 3-aminotriethoxysilane were added to the silver complex solution prepared in Preparation Example 3, sufficiently moistened with stirring, filtered, washed with ethanol, and dried. The pretreated silica beads were added to a silver electroless plating solution in which the silver complex solution prepared in Preparation Example 4 and the reducing agent solution prepared in Preparation Example 9 were prepared in a weight ratio of 1:1, and reacted with stirring for 1 hour. After the reaction was completed, the mixture was filtered, washed sequentially with water and ethanol, and dried at 100° C. for 24 hours to obtain silver-coated silica beads.
실시 예 47. Example 47.
실시 예 46에서 평균 입자직경 12μm의 실리카 비드 대신에 평균입자 직경 4μm의 구리 입자를 사용하는 것을 제외하고는 같은 방법으로 실험을 진행한 결과 은이 코팅된 구리 입자가 제조되었다.Silver-coated copper particles were prepared as a result of the experiment in the same manner as in Example 46, except that copper particles having an average particle diameter of 4 μm were used instead of silica beads having an average particle diameter of 12 μm.
실시 예 48. Example 48.
폴리프로필렌 도금 조(Plating bath)에 제조 예 3에서 제조한 은이 0.5%의 농도를 갖는 은 착체 용액을 넣고 양극으로 은 플레이트(Silver plate)를 그리고 음극으로는 표면이 매끈한 구리박편을 사용하였다. 여기에 1.5볼트 건전지 3개가 연결된 4.5볼트를 연결하여 전기를 가하고 1분30초 동안 전해도금을 실시하였다. 도금완료 후 물과 에탄올로 잘 씻고 80℃에서 충분히 건조시키면 구리표면 위에 밝은(Bright) 거울상의 은이 도금된 구리제품이 얻어 졌다. A silver complex solution having a concentration of 0.5% silver prepared in Preparation Example 3 was put into a polypropylene plating bath, and a silver plate was used as an anode and a copper foil having a smooth surface was used as a cathode. Here, electricity was applied by connecting 4.5 volts to which three 1.5 volt batteries were connected, and electroplating was performed for 1 minute and 30 seconds. After completion of the plating, it was washed well with water and ethanol and sufficiently dried at 80℃ to obtain a copper product plated with bright mirror-like silver on the copper surface.
실시 예 49 Example 49
실시 예 48에서 음극으로 구리박편을 사용하는 대신에 저항 1,5Ω/cm의 은 코팅 PET 필름을 사용한 것을 제외하고는 같은 방법으로 실험하였다. 전해도금 후 표면 저항을 측정한 결과 0.4Ω/cm으로 전도도가 좋아진 샘플이 얻어졌다.Experiments were conducted in the same manner as in Example 48, except that a silver-coated PET film having a resistance of 1,5 Ω/cm was used instead of using a copper foil as the cathode. As a result of measuring the surface resistance after electroplating, a sample with improved conductivity of 0.4 Ω/cm was obtained.
실시 예 50.Example 50.
환원제 용액 없이 제조 예 4에서 제조한 은이 0.5%의 농도를 갖는 착체 용액 100그램만을 비이커에 담아 여기에 구리포일(copper foil)을 넣고 상온에서 15분간 치환도금을 실시하여 거울상의 밝은 은 코팅된 구리포일을 얻을 수 있었다(도 10 참조).Put only 100 grams of the complex solution having a concentration of 0.5% silver prepared in Preparation Example 4 without a reducing agent solution into a beaker, put copper foil therein, and perform substitution plating at room temperature for 15 minutes to obtain mirror-image bright silver-coated copper A foil was obtained (see Fig. 10).
항균 제품의 제조Manufacture of antibacterial products
실시 예 51.Example 51.
제조 예 2에서 제조한 은이 0.5%의 농도를 갖는 착체 용액 100그램을 에탄올 80%와 물 20%로 구성된 혼합용액 4.9 킬로그램에 희석하여 최종적으로 100ppm 농도의 은 함유 혼합용액을 제조하였다. 여기에 황산암모늄 100ppm과 흰색의 면(Cotton) 원단을 넣고 3시간 동안 휘저으며 은 용액이 충분히 적혀지도록 하였다. 적셔진 원단을 짜서 용매를 충분히 제거한 후 햇빛에 장시간 노출시켜 은 이온을 환원시켰다. 환원 정도에 따라 색상이 갈색으로 변하였다. 세탁기를 이용하여 세탁한 후 건조시킨 이 원단의 항균특성을 시험한 결과 대장균(E. coli)에 대하여 99.9%의 항균력을 나타내었다(도 11 참조).100 g of the complex solution having a concentration of 0.5% silver prepared in Preparation Example 2 was diluted with 4.9 kg of a mixed solution composed of 80% ethanol and 20% water to finally prepare a silver-containing mixed solution having a concentration of 100 ppm. Here, 100 ppm of ammonium sulfate and white cotton fabric were added and stirred for 3 hours so that the silver solution was sufficiently written. After sufficiently removing the solvent by squeezing the wet fabric, silver ions were reduced by exposure to sunlight for a long time. The color changed to brown depending on the degree of reduction. As a result of testing the antibacterial properties of this fabric, which was washed and dried using a washing machine, it showed 99.9% antimicrobial activity against E. coli (see FIG. 11).
실시 예 52.Example 52.
제조 예 3에서 제조한 은이 0.5%의 농도를 갖는 착체 용액에 에탄올로 희석하여 최종적으로 50ppm의 은 농도를 갖는 용액을 제조하였다. 여기에 이불이나 베게 등에 보온재 등으로 쓰이고 있는 폴리에스테르 극세사 솜을 은 용액에 잠길 정도로 넣고 충분히 휘저으며 적셨다. 다음 제조 예 6에서 제조한 환원제 용액을 에탄올로 희석하여 하이드로퀴논이 최종적으로 60ppm의 은 농도를 갖는 용액에 앞서의 폴리에스테르 극세사 솜을 넣고 1시간동안 교반하면서 반응시켰다. 반응이 끝난 후 여과하고 물과 에탄올로 순차적으로 씻은 후 80℃에서 6시간 건조시켜 은이 처리된 폴리에스테르 극세사를 얻었다. 이 극세사의 항균특성을 시험한 결과 대장균(E. coli)에 대하여 99.9%의 항균력을 나타내었다.The silver complex solution prepared in Preparation Example 3 having a concentration of 0.5% was diluted with ethanol to finally prepare a solution having a silver concentration of 50 ppm. Here, polyester microfiber cotton, which is used as a heat-retaining material for blankets and pillows, was put into the silver solution to the extent that it was submerged, and it was sufficiently stirred and soaked. The reducing agent solution prepared in Preparation Example 6 was diluted with ethanol, and the polyester microfiber cotton was added to the hydroquinone solution having a final silver concentration of 60 ppm and reacted with stirring for 1 hour. After the reaction was finished, it was filtered, washed sequentially with water and ethanol, and dried at 80° C. for 6 hours to obtain silver-treated polyester microfibers. As a result of testing the antibacterial properties of this microfiber, it showed 99.9% of antibacterial activity against E. coli.
실험예 1Experimental Example 1
기존의 1액형 무전해 은도금약품과의 비교를 실시하였다. 비교실시예 3으로서 한빛케미컬의 무전해 은도금약품(AG-10)을 사용하였으며, 비교실시예 4로서 ㈜MSC의 MS-AG100을 사용하였다.A comparison with existing one-component electroless silver plating chemicals was conducted. As Comparative Example 3, Hanbit Chemical's electroless silver plating chemical (AG-10) was used, and as Comparative Example 4, MSC's MS-AG100 was used.
본 발명의 실시예 50 및 상기 비교실시예 3 및 비교실시예 4를 이용하여 구리도금된 기판의 표면에 은 도금을 실시하였다. 본 발명의 실시예 50의 경우 구리도금된 기판을 용기에 투입한 다음, 실시예 50과 동일한 은 착체용액 용액을 공급하였으며, 도금 반응이 완료된 이후 표면을 식각하여 구리도금 이외부위에 형성된 은도금을 제거하였다.Silver plating was performed on the surface of the copper-plated substrate using Example 50 of the present invention and Comparative Example 3 and Comparative Example 4. In the case of Example 50 of the present invention, the copper-plated substrate was put into a container, and then the same silver complex solution as in Example 50 was supplied, and after the plating reaction was completed, the surface was etched to remove the silver plating formed in a region other than the copper plating did
비교실시예 3 및 4의 경우 용기에 각 용액을 주입한 다음, 구리도금된 기판을 침지하여 은도금을 실시하였다.In the case of Comparative Examples 3 and 4, after each solution was injected into the container, silver plating was performed by dipping the copper-plated substrate.
은도금의 결과 본 발명의 실시예 1의 경우에도 시판되어 사용되는 비교실시예와 동일한 은도금을 수행할 수 있었으며, 여분의 은을 제거하기 위한 식각을 수행하는 것 만으로도 구리도금 상의 은도금을 실시할 수 있었다. 이는 기존의 도금법과 동일하게 구리표면에 은의 석출량이 많아지는 것을 응용한 것으로 동일한 두께로 식각되지만 구리상의 은 두께가 절연체 상의 은의 두께에 비하여 두껍게 형성되기 때문이다. 비교실시예 3 및 4의 경우에도 동일한 은 도금이 되는 것으로 확인되었다. 즉 본 발명의 경우 공정을 약간 수정하는 것만으로도 기존의 제품 생산공정에 사용할 수 있음을 확인하였다.As a result of the silver plating, even in the case of Example 1 of the present invention, the same silver plating as the commercially available and used comparative example could be performed, and silver plating on the copper plating could be performed only by performing etching to remove excess silver. . This is because the thickness of silver on copper is thicker than the thickness of silver on insulator, although it is etched with the same thickness by applying the increase in the amount of silver deposited on the copper surface in the same way as the conventional plating method. In the case of Comparative Examples 3 and 4, it was confirmed that the same silver plating was performed. That is, in the case of the present invention, it was confirmed that it can be used in the existing product production process only by slightly modifying the process.
실험예 2Experimental Example 2
상기 실험예 1과 동일하게 실시예 1, 비교실시예 3, 비교실시예 4를 사용하였으며, 고분자수지의 표면에 도금여부를 확인하였다.Example 1, Comparative Example 3, and Comparative Example 4 were used in the same manner as in Experimental Example 1, and it was confirmed whether or not the surface of the polymer resin was plated.
도금용 용기의 내부에 1cm X 1cm X 3cm크기의 사각바를 설치하였다. 이때 상기 사각바의 재질은 하기의 표 4와 같이 준비하였다.A square bar having a size of 1 cm X 1 cm X 3 cm was installed inside the plating vessel. At this time, the material of the square bar was prepared as shown in Table 4 below.
각 용기에 상기 실시예 1, 비교실시예 3 및 비교실시예 4의 도금액을 조입한 다음, 도금용 용기를 흔들어 교반하였으며, 20분후 상기 사각바를 꺼내어 도금여부를 확인하였다.The plating solutions of Example 1, Comparative Example 3, and Comparative Example 4 were added to each container, and then the plating container was shaken and stirred. After 20 minutes, the square bar was taken out to check plating.
사각바 재질square bar material 도금여부plating
실시예 1Example 1 폴리카보네이트polycarbonate OO
폴리에틸렌polyethylene OO
폴리프로필렌polypropylene OO
구리copper OO
알루미늄aluminum OO
비교실시예 3Comparative Example 3 폴리카보네이트polycarbonate XX
폴리에틸렌polyethylene XX
폴리프로필렌polypropylene XX
구리copper OO
알루미늄aluminum OO
비교실시예 4Comparative Example 4 폴리카보네이트polycarbonate XX
폴리에틸렌polyethylene XX
폴리프로필렌polypropylene XX
구리copper OO
알루미늄aluminum OO
표 5에 나타난 바와 같이 본 발명의 실시예 1의 경우 금속재질 뿐만 아니라 고분자수지재질의 금속표면에도 균일하게 도금이 되는 것을 확인할 수 있었다. 하지만 비교실시예 3 및 4의 경우 금속의 표면에만 은이 도금되는 것을 확인할 수 있었으며, 고분자수지의 표면에는 은 도금이 수행되지 않는 것으로 확인되었다.As shown in Table 5, in the case of Example 1 of the present invention, it was confirmed that not only the metal material but also the metal surface of the polymer resin material was uniformly plated. However, in Comparative Examples 3 and 4, it was confirmed that silver was plated only on the surface of the metal, and it was confirmed that silver plating was not performed on the surface of the polymer resin.
실험예 3Experimental Example 3
6개월 상온 보관 후의 은 착체용액 및 환원제의 저장안정성을 시험하였다. 도 11은 제조예 2에서 제조한 은 착체용액으로서 상온에서 6개월간 보관한 후의 용액 상태를 나타낸다. 또한 도 12는 제조예 8에서 제조한 환원제 용액으로서 상온에서 6개월간 보관한 후의 용액 상태를 나타낸다.The storage stability of the silver complex solution and the reducing agent after storage at room temperature for 6 months was tested. 11 shows a solution state after storage for 6 months at room temperature as a silver complex solution prepared in Preparation Example 2. In addition, Figure 12 shows the solution state after storage for 6 months at room temperature as a reducing agent solution prepared in Preparation Example 8.
도 12 및 도 13에 나타난 바와 같이, 어떠한 침전없이 상온 6개월 보관 후에도 용액 안정성이 우수한 것을 관찰할 수 있었으며, 수 년 지나도 안정할 것으로 판단된다.As shown in FIGS. 12 and 13, it was observed that the solution stability was excellent even after storage for 6 months at room temperature without any precipitation, and it was judged to be stable even after several years.
다만 동일한 기간동안 보관한 비교실시예 3 및 비교실시예 4의 경우 침전이 형성되는 것을 확인할 수 있었으며, 이는 본 발명의 2액형 은도금액은 기존의 1액형 무전해도금액과 동등이상의 안정성을 가지는 것으로 판단할 수 있다.However, in the case of Comparative Example 3 and Comparative Example 4, which were stored for the same period, it was confirmed that precipitate was formed, which indicates that the two-component silver plating solution of the present invention has stability equivalent to or higher than that of the existing one-component electroless plating solution. can do.
실험예 4Experimental Example 4
본 발명의 질산은 생성을 확인하기 위한 실험을 실시하였다. 본발명의 실시예 1~5 및 비교실시예 3, 4의 질산은 함량을 측정하였다.An experiment was conducted to confirm the generation of silver nitrate according to the present invention. The silver nitrate content of Examples 1 to 5 and Comparative Examples 3 and 4 of the present invention was measured.
일반적으로 질산은의 함량을 측정하는 방법은 존재하지 않으므로 질산은을 이용한 염소이온 측정법을 역으로 적용하여 이를 적용하였다.In general, since there is no method for measuring the content of silver nitrate, the method for measuring chlorine ions using silver nitrate was reversely applied and applied.
0.01N 염산을 이용하여 기존의 염소이온 측정방법과 동일하게 실시하였으며, 다만 염소이온의 농도를 측정하는 대신 염소이온 농도를 고정하여 질산은의 함량을 간접적으로 측정하였다. 또한 비교실시예 5로서 은거울 반응 실험에 사용되는 실험키트(오피스안)를 사용하였다.Using 0.01N hydrochloric acid, it was carried out in the same way as the conventional method for measuring chlorine ions, except that instead of measuring the concentration of chlorine ions, the concentration of chlorine ions was fixed and the content of silver nitrate was indirectly measured. In addition, as Comparative Example 5, an experiment kit (Office An) used for a silver mirror reaction experiment was used.
질산은 농도(M)Silver nitrate concentration (M)
실시예 1Example 1 <0.001<0.001
실시예 2Example 2 <0.001<0.001
실시예 3Example 3 <0.001<0.001
실시예 4Example 4 <0.001<0.001
실시예 5Example 5 <0.001<0.001
비교실시예 3Comparative Example 3 0.70.7
비교실시예 4Comparative Example 4 0.90.9
비교실시예 5Comparative Example 5 4.54.5
표 6에 나타난 바와 같이 본 발명의 경우 질산은을 거의 생성하지 않아 측정치 미만의 결과를 가지는 것으로 나타났다. 위에서 살펴본 바와 같이 질산은은 폭발성을 가지는 물질이므로 본 발명의 경우 사용이전 또는 사용이후 장기 보관을 하더라도 질산은의 발생이 없어 안정성이 높은 것으로 나타났다. 하지만 기존에 은 도금에 사용되는 비교실시예 3 및 4의 경우 질산은이 생성되고 있으며, 이는 장기간에 걸쳐 농축되거나 보관하는 경우 질산은의 농도가 높아질 수 있음을 의미한다. 마지막으로 은거울반응 실험에 사용되는 키트의 경우 질산은을 직접 사용하고 있으므로, 다량의 질산은이 검출되는 것을 확인할 수 있었다.As shown in Table 6, in the case of the present invention, silver nitrate was hardly produced, resulting in less than the measured value. As described above, since silver nitrate is an explosive material, in the case of the present invention, even if stored for a long time before or after use, silver nitrate is not generated, so the stability is high. However, in Comparative Examples 3 and 4, which are conventionally used for silver plating, silver nitrate is produced, which means that the concentration of silver nitrate may increase when concentrated or stored for a long period of time. Finally, since silver nitrate was directly used in the kit used for the silver mirror reaction experiment, it was confirmed that a large amount of silver nitrate was detected.

Claims (17)

  1. 은도금 착체 용액 및 환원제 용액을 포함하는 무전해 은도금을 위한 은도금액에 있어서,A silver plating solution for electroless silver plating comprising a silver plating complex solution and a reducing agent solution,
    상기 은도금 착체 용액은, 하기 일반식 1의 카르복실산 은염을 포함하는 용액이고,The silver plating complex solution is a solution containing a carboxylic acid silver salt of the following general formula 1,
    상기 은도금 착체 용액 및 상기 환원제 용액 간의 은거울 반응에 의한 무전해 은도금이 가능한 은도금액:A silver plating solution capable of electroless silver plating by a silver mirror reaction between the silver plating complex solution and the reducing agent solution:
    [일반식 1][Formula 1]
    R1-COOAgR 1 -COOAg
    상기 식에서, R1은 수소, 치환 또는 비치환된 C1-C22의 알킬기, 치환 또는 비치환된 C3-C30 시클로알킬기, 치환 또는 비치환된 C6-C30 아르알킬(aralkyl), 치환 또는 비치환된 C1-C30 헤테로알킬기, 치환 또는 비치환된 C2-C30 헤테로시클로알킬기, 또는 치환 또는 비치환된 C5-C30 헤테로아르알킬기이다. In the above formula, R 1 is hydrogen, a substituted or unsubstituted C 1 -C 22 alkyl group, a substituted or unsubstituted C 3 -C 30 cycloalkyl group, a substituted or unsubstituted C 6 -C 30 aralkyl group, A substituted or unsubstituted C 1 -C 30 heteroalkyl group, a substituted or unsubstituted C 2 -C 30 heterocycloalkyl group, or a substituted or unsubstituted C 5 -C 30 heteroaralkyl group.
  2. 청구항 1에 있어서,The method of claim 1,
    상기 은도금 착체 용액은 질소원자 함유 화합물 형태의 착화제; 및 용매를 더 포함하는 은도금액The silver plating complex solution includes a nitrogen atom-containing compound type complexing agent; And a silver plating solution further comprising a solvent
  3. 청구항 2에 있어서,The method of claim 2,
    상기 질소원자 함유 화합물은 암모니아, 아민, 4차 암모늄 염(quaternary ammomium salts) 및 폴리아민으로 이루어진 군 중에서 선택된 1종 이상인 것인 은도금액.The silver plating solution of claim 1 , wherein the nitrogen atom-containing compound is at least one selected from the group consisting of ammonia, amines, quaternary ammonium salts, and polyamines.
  4. 청구항 3에 있어서,The method of claim 3,
    상기 아민 또는 4차 암모늄 염은 각각 하기 [일반식 2] 및 [일반식 3]으로 표현되는 것인 은도금액: A silver plating solution wherein the amine or quaternary ammonium salt is represented by the following [General Formula 2] and [General Formula 3], respectively:
    [일반식 2][Formula 2]
    (R2R3R4)N(R 2 R 3 R 4 )N
    [일반식 3][Formula 3]
    (R5R6R7R8)N+X(R 5 R 6 R 7 R 8 )N + X
    상기 식에서, R2 내지 R8은 서로 동일하거나 상이할 수 있으며, 각각 수소 또는 치환 또는 비치환된 C1-C20의 알킬기, 치환 또는 비치환된 C6-C30 아릴기, 치환 또는 비치환된 C3-C30 시클로알킬기, 치환 또는 비치환된 C6-C30 아르알킬(aralkyl), 치환 또는 비치환된 C1-C30 헤테로알킬기, 치환 또는 비치환된 C2-C30 헤테로시클로알킬기, 치환 또는 비치환된 C5-C30 헤테로아릴기, 치환 또는 비치환된 C5-C30 헤테로아르알킬기이고,In the above formula, R 2 to R 8 may be the same as or different from each other, and are each hydrogen or a substituted or unsubstituted C 1 -C 20 alkyl group, a substituted or unsubstituted C 6 -C 30 aryl group, or a substituted or unsubstituted C 3 -C 30 Cycloalkyl group, substituted or unsubstituted C 6 -C 30 aralkyl group, substituted or unsubstituted C 1 -C 30 heteroalkyl group, substituted or unsubstituted C 2 -C 30 heterocycloalkyl group, substituted or unsubstituted A C 5 -C 30 heteroaryl group, a substituted or unsubstituted C 5 -C 30 heteroaralkyl group,
    X는 F-, Cl-, Br-, I-, OH-, 하이드로전 설페이트, 바이카르보네이트, 카바메이트 또는 퍼클로레이트이다. X is F - , Cl - , Br - , I - , OH - , hydrogen sulfate, bicarbonate, carbamate or perchlorate.
  5. 청구항 2에 있어서,The method of claim 2,
    상기 질소원자 함유 화합물은 암모니아 또는 알킬아민인 것인 은도금액.The silver plating solution, wherein the nitrogen atom-containing compound is ammonia or alkylamine.
  6. 청구항 2에 있어서,The method of claim 2,
    상기 용매는 물, 에탄올, 에틸렌글리콜, 글리세린 또는 이들의 혼합용매인 은도금액.The silver plating solution in which the solvent is water, ethanol, ethylene glycol, glycerin, or a mixed solvent thereof.
  7. 청구항 2에 있어서,The method of claim 2,
    상기 착화제의 함량이 상기 카르복실산 은염 대비 몰비로 0.1~10.0인 것인 은도금액.A silver plating solution in which the content of the complexing agent is 0.1 to 10.0 in a molar ratio relative to the carboxylic acid silver salt.
  8. 청구항 2에 있어서,The method of claim 2,
    상기 질소원자 함유 화합물 형태의 착화제는 상기 카르복실산 은염의 은이온과 결합하여 착이온을 형성하는 것인 은도금액.The silver plating solution of claim 1 , wherein the complexing agent in the form of a nitrogen atom-containing compound combines with silver ions of the silver carboxylic acid salt to form complex ions.
  9. 청구항 1에 있어서,The method of claim 1,
    상기 환원제 용액은,The reducing agent solution,
    글루코스, 하이드라진, 하이드로퀴논 및 그 유도체로 이루어진 군으로부터 선택되는 1종 이상의 환원제; 및 용매를 포함하는 용액인 은도금액.at least one reducing agent selected from the group consisting of glucose, hydrazine, hydroquinone, and derivatives thereof; and a silver plating solution comprising a solvent.
  10. 청구항 9에 있어서,The method of claim 9,
    상기 용매는 물, 에탄올, 에틸렌글리콜, 글리세린 또는 이들의 혼합용매인 은도금액.The silver plating solution in which the solvent is water, ethanol, ethylene glycol, glycerin, or a mixed solvent thereof.
  11. 청구항 10에 있어서,The method of claim 10,
    상기 용매 중 물의 함량이 중량비로 1~80%인 것인 은도금액.A silver plating solution in which the content of water in the solvent is 1 to 80% by weight.
  12. 청구항 9에 있어서,The method of claim 9,
    상기 환원제 용액은 암모늄 염을 포함하는 첨가제가 더 포함된 것인 은도금액.The silver plating solution of claim 1 , wherein the reducing agent solution further includes an additive containing an ammonium salt.
  13. 청구항 12에 있어서,The method of claim 12,
    상기 암모늄 염이 최종 도금액 대비 중량비로 0.01~10.0% 포함된 것인 은도금액.A silver plating solution containing 0.01 to 10.0% of the ammonium salt in a weight ratio relative to the final plating solution.
  14. 청구항 1에 있어서,The method of claim 1,
    상기 카르복실산 은염은 알칸산 은인 것인 은도금액.The silver plating solution of claim 1, wherein the silver carboxylic acid salt is silver alkanoate.
  15. 청구항 1에 있어서,The method of claim 1,
    은의 함량이 최종 도금액 대비 중량비로 0.05~5.0%인 것인 은도금액.A silver plating solution in which the content of silver is 0.05 to 5.0% by weight compared to the final plating solution.
  16. 청구항 1에 있어서,The method of claim 1,
    상기 환원제의 함량이 상기 카르복실산 은염 대비 몰비로 0.1~5.0인 것인 은도금액.The silver plating solution, wherein the reducing agent has a molar ratio of 0.1 to 5.0 relative to the carboxylic acid silver salt.
  17. 청구항 1 내지 16 중 어느 한 항에 따른 은도금액을 5~50℃에서 반응시켜 얻은 은도금 제품.A silver-plated product obtained by reacting the silver plating solution according to any one of claims 1 to 16 at 5 to 50 ° C.
PCT/KR2022/018390 2021-11-19 2022-11-21 Silver plating solution WO2023090964A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP22896161.1A EP4379092A1 (en) 2021-11-19 2022-11-21 Silver plating solution

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020210160238A KR102476608B1 (en) 2021-11-19 2021-11-19 Silver Plating Solution
KR10-2021-0160238 2021-11-19

Publications (1)

Publication Number Publication Date
WO2023090964A1 true WO2023090964A1 (en) 2023-05-25

Family

ID=84439261

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2022/018390 WO2023090964A1 (en) 2021-11-19 2022-11-21 Silver plating solution

Country Status (3)

Country Link
EP (1) EP4379092A1 (en)
KR (1) KR102476608B1 (en)
WO (1) WO2023090964A1 (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5322553A (en) 1993-02-22 1994-06-21 Applied Electroless Concepts Electroless silver plating composition
US6620304B1 (en) 1999-06-19 2003-09-16 Gerhard Hoffacker Bath system for galvanic deposition of metals
KR20060093789A (en) * 2005-02-22 2006-08-25 주식회사 에이엔씨아이 Preparation of a high functional active carbon/fibers by electroless silver/iodine plating methods
JP2012082444A (en) * 2010-10-06 2012-04-26 C Uyemura & Co Ltd Reducing type electroless silver plating solution
KR20120118886A (en) * 2011-04-20 2012-10-30 주식회사 잉크테크 Silver ink composition
US8608932B2 (en) 2010-09-21 2013-12-17 Rohm And Haas Electronic Materials Llc Cyanide-free silver electroplating solutions
KR20140113681A (en) * 2011-12-15 2014-09-24 헨켈 아이피 앤드 홀딩 게엠베하 Electroless plating of silver onto graphite
KR20150063042A (en) * 2012-09-28 2015-06-08 돗빤호무즈가부시기가이샤 Silver ink composition, conductor and communication device

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5322553A (en) 1993-02-22 1994-06-21 Applied Electroless Concepts Electroless silver plating composition
US6620304B1 (en) 1999-06-19 2003-09-16 Gerhard Hoffacker Bath system for galvanic deposition of metals
KR20060093789A (en) * 2005-02-22 2006-08-25 주식회사 에이엔씨아이 Preparation of a high functional active carbon/fibers by electroless silver/iodine plating methods
US8608932B2 (en) 2010-09-21 2013-12-17 Rohm And Haas Electronic Materials Llc Cyanide-free silver electroplating solutions
JP2012082444A (en) * 2010-10-06 2012-04-26 C Uyemura & Co Ltd Reducing type electroless silver plating solution
KR20120118886A (en) * 2011-04-20 2012-10-30 주식회사 잉크테크 Silver ink composition
KR20140113681A (en) * 2011-12-15 2014-09-24 헨켈 아이피 앤드 홀딩 게엠베하 Electroless plating of silver onto graphite
KR20150063042A (en) * 2012-09-28 2015-06-08 돗빤호무즈가부시기가이샤 Silver ink composition, conductor and communication device

Also Published As

Publication number Publication date
KR102476608B1 (en) 2022-12-13
EP4379092A1 (en) 2024-06-05

Similar Documents

Publication Publication Date Title
WO2017209474A1 (en) Method for manufacturing silver-coated copper nanowire having core-shell structure by using chemical reduction method
CN105274591B (en) Electrodeless copper electroplating composition
US5846615A (en) Direct deposition of a gold layer
KR100733748B1 (en) Colloidal metal solution, process for producing the same, and coating material containing the same
WO2010024564A2 (en) Method for manufacturing metal flakes
WO2016017836A1 (en) Conductive ink
JP2009527076A (en) Silver organosol ink for conductive line pattern formation
CN108342718A (en) Electrodeless copper electroplating composition
WO2011065709A2 (en) Conductive ink composition that does not form particles, and method for manufacturing same
EP3256620B1 (en) Method for producing metal patterns on a substrate for decorative and/or functional purposes, manufacture of objects incorporating said method and set of consumables used
EP1538237A1 (en) Method for metal plating and pre-treating agent
KR20110027487A (en) Composition for metal pattern and method of forming metal pattern using the same
WO2023090964A1 (en) Silver plating solution
WO2015099498A1 (en) Color-treated base material and base material color treatment method therefor
TWI638821B (en) Metal catalyst, manufacturing method and applications thereof
CN109790622B (en) Method for providing a multilayer coating on a substrate surface
US20180057945A1 (en) Metal catalyst, manufacturing method and application thereof
WO2017073956A1 (en) Ink composition for photonic sintering and method for producing same
KR100357427B1 (en) Reduction Method of Copper Oxide
CN109399961B (en) Deplating solution and deplating process for removing NCVM (non-volatile memory) film layer of glass
CN102866601A (en) Stripping liquid for plasma display screen as well as preparation method and application of stripping liquid
CN118159687A (en) Silver plating solution
TWI839818B (en) Manufacturing method, kit, and system for structure with conductive pattern
US9269478B2 (en) Transparent conductive film-preparing method and transparent film prepared therefrom
KR101199969B1 (en) silver organo-sol ink for forming conductive patterns

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22896161

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2022896161

Country of ref document: EP

Effective date: 20240229