Silver precursor inks

Abstract

The present invention relates to silver precursor inks by which a silver mirror having excellent conductivity and reflection properties after firing may be easily formed, and which have high stability. The present invention provides silver precursor inks comprising: a carboxylic acid silver precursor compound; an acetylene-based compound; a nitrogen atom-containing compound; and a solvent.

Description

silver precursor ink

[0001] The present invention relates to a silver precursor ink, and more specifically, to a silver precursor ink that can easily form a silver mirror with excellent conductivity and reflective properties after firing and has high stability.

[0002] Recently, as industries have become more advanced, there is an increasing preference for materials with metallic luster or good light reflectivity for products with luxurious surface gloss across the entire industry, such as home appliances like refrigerators, washing machines, air conditioners, and TVs, automotive interior and exterior parts like lamp reflectors, wheels, and dashboards, mobile phones, and monitors.

[0003] Generally, to manufacture products with high reflectivity in the form of mirrors, methods of applying metal directly to the product or indirectly are used.

[0004] The method of applying metal directly to a product involves applying a metal foil paint with a metallic texture directly to the product, or plating or depositing a metal with high reflectivity such as silver, aluminum, chrome, nickel, titanium, copper, etc. The indirect method involves attaching the above-mentioned metal or a product containing a metal component with high reflectivity to a substrate such as a film, sheet, or plate using a lamination, transfer, or lamination method, and then attaching the metal layer or the metal layer and the substrate to the product.

[0005] However, the coating method has the disadvantage of not having a very high reflectivity and having poor weather resistance. To improve this, a reflective film with high reflectivity can be manufactured by vacuum deposition using silver or aluminum as the main component, but vacuum deposition has limitations regarding the use of expensive vacuum equipment and the shape and size of the substrate, and in some cases, there is a problem of the coating thickness becoming uneven.

[0006] In addition, although a reflective film with a luxurious surface gloss and high reflectivity can be obtained by plating with metals such as silver (Ag) or chromium (Cr) on the substrate, there is a high defect rate during manufacturing, excessive costs for plating treatment, and problems such as air pollution and wastewater generation due to the emission of harmful substances during the plating process.

[0007] Meanwhile, silver mirrors are manufactured using the silver mirroring reaction with Tollens' reagent. Currently, they are used in silver mirrors for bathrooms or living rooms, as well as in vacuum flasks or Dewar bottles; however, since these mirrors primarily use the back surface rather than the silver-coated side, they are referred to as secondary mirrors. Korean Patent No. 10-2476608 discloses a method for manufacturing silver mirrors without using Tollens' reagent as a plating agent.

[0008] In addition, research has been conducted to manufacture primary mirrors that form a mirror on a coated surface. For example, Korean Patent No. 10-0727483 states that an ink manufactured using a special silver complex compound can form a reflective film with high reflectivity. However, in this case, there are limitations regarding the long-term storage stability of the silver ink, the unpleasant odor, and the adhesion to substrates such as glass. Above all, there are problems with compatibility with other solvents, binders, and additives, so there have been limitations in manufacturing mirrors using various printing equipment, such as inkjet, screen, offset (gravure offset, reverse offset, etc.), imprinting, dispensers, and electrohydrodynamics (EHD).

[0009] Therefore, there is a need for new silver precursor inks to overcome these existing limitations.

[0010] To solve the aforementioned problems, the present invention aims to provide a silver precursor ink with high stability that can easily form a silver mirror with excellent conductivity and reflective properties after firing.

[0011] To solve the above-mentioned problem, the present invention provides a silver precursor ink comprising a carboxylic acid silver precursor compound; an acetylene-based compound; a nitrogen atom-containing compound; and a solvent.

[0012] In one embodiment, the carboxylic acid silver precursor compound may include a compound of the following chemical formula 1.

[0013] [Chemical Formula 1]

[0014] R a R b R c C-COOAg

[0015] (In the above Chemical Formula 1, R a , R b and R c Each independently hydrogen, C1-C 20 alkyl groups, substituted or unsubstituted C1-C 28 Cycloalkyl groups, substituted or unsubstituted C1-C 28 aralkyl, substituted or unsubstituted C1-C 28 Heteroalkyl groups, substituted or unsubstituted C1-C 28 Heterocycloalkyl groups, or substituted or unsubstituted C1-C 28 heteroalkyl group)

[0016] In one embodiment, the silver carboxylic acid precursor compound is silver acetate, silver acetoacetate, silver 2-methylacetoacetate, silver trifluoroacetate, silver lactate, silver malonate, silver maleate, silver fumarate, silver pyruvate, silver succinate, silver picrate, silver citrate, silver tartrate, silver benzoate, silver cyclohexane carboxylate, and 2-ethylbutyric acid It may include silver (silver 2-ethylbutyrate), silver neoheptanoate, silver 2-ethylhexanoate, silver caprylate, silver isononanoate, silver neodecanoate, silver stearate, silver docosanoate, silver oleate, silver linoleate, silver naphthenate, silver behenate, silver abietate, silver neo acid 910, or silver neo acid 913. there is.

[0017] In one embodiment, the acetylene-based compound may include a compound of the following chemical formula 2.

[0018] [Chemical Formula 2]

[0019]

[0020] (In the above Chemical Formula 2, R1, R2, and R3 are each independently hydrogen, C1-C 20 alkyl groups, substituted or unsubstituted C1-C 28 Cycloalkyl groups, substituted or unsubstituted C1-C 28 Aralkyl, substituted or unsubstituted C1-C 28 Heteroalkyl groups, substituted or unsubstituted C1-C 28 Heterocycloalkyl groups, or substituted or unsubstituted C1-C 28 heteroalkyl group)

[0021] In one embodiment, the acetylene-based compound may be an acetylene-based alcohol compound.

[0022] In one embodiment, the acetylene-based compound is 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol, propargyl alcohol, butynol, hexynol, ethyloctinol, benzylbutynol, 3,5-dimethyl-1-hexyn-3-ol, 3,4-dimethyl-1-pentyn-3-ol, 3-butyn-2-ol, 1-ethynyl-1-cyclopentanol, 1-Ethynyl-1-cyclohexanol, 5-Methyl-1-hexyn-3-ol, 1-Hexyn-3-ol, 3-Methyl-1-penten-4-yn-3-ol, 3-Ethyl-1-pentyn-3-ol, 4-Methyl-1-pentyn-3-ol, 1-Pentyn-3-ol, 2-Phenyl-3-butyn-2-ol, It may include 1,1-diphenyl-2-propyn-1-ol, 3,7,11-trimethyl-1-dodecyn-3-ol, 2-butyne-1,4-diol, 2,5-dimethyl-3-hexyne-2,5-diol, or 2,4,7,9-tetramethyl-5-decindiol.

[0023] In one embodiment, the acetylene-based compound may be a mixture of two or more acetylene-based alcohols.

[0024] In one embodiment, the nitrogen atom-containing compound may be an amine compound, an ammonium compound, or a mixture thereof.

[0025] In one embodiment, the amine compound may be a primary amine, a secondary amine, a tertiary amine, or a polyamine.

[0026] In one embodiment, the ammonium compound may be an ammonium salt.

[0027] In one embodiment, the ammonium salt may be ammonium formate, ammonium acetate, ammonium nitrates, ammonium sulfate, ammonium sulfite, ammonium carbonate, ammonium bicarbonate, ammonium carbamate, ammonium phosphate, ammonium carbamate, ammonium carbonate, tetraethylammonium bicarbonate, tetraethylammonium bromide, or tetrabutylammonium hydroxide.

[0028] The present invention also provides a silver-plated product obtained by firing the silver precursor ink at 70 to 700°C.

[0029] The silver precursor ink according to the present invention has excellent compatibility with other solvents, binders, and additives, so it is easy to apply to existing silver plating processes.

[0030] In addition, the silver precursor ink according to the present invention can help improve the usage environment by reducing the generation of bad odors when used.

[0031] In addition, since the silver precursor ink according to the present invention has excellent conductivity and reflectivity after firing, it can provide high-quality silver-plated products as an alternative to the conventional silver plating method.

[0032] Figure 1 is a graph showing the reflectance of a film coated with a silver film on PET in Example 1 of the present invention.

[0033] FIG. 2 shows optical photographs of silver precursor inks prepared according to Examples 1 to 4 of the present invention.

[0034] Figure 3 shows an optical photograph of a film coated with a silver mirror on PET of Example 1 of the present invention.

[0035] Figure 4 shows a micrograph of the thickness of the silver mirror coated on the PET of Example 1 of the present invention.

[0036] Figure 5 shows an optical photograph of a film coated with a silver mirror on PET according to Example 2 of the present invention.

[0037] Figure 6 shows an AFM image of a silver mirror coated on glass of Example 8 of the present invention.

[0038] Figure 7 is a photograph showing the result of coating a ceramic with a brush using silver precursor ink prepared according to Example 9 of the present invention and then firing it.

[0039] Figure 8 is a photograph showing the results of an inkjet printing experiment using silver precursor ink prepared according to Example 10 of the present invention.

[0040] Figure 9 is an optical photograph of the surface of glass that has been coated on the entire surface using an inkjet printer with silver precursor ink prepared according to Example 10 of the present invention and then fired.

[0041] FIG. 10 is a thermogravimetric analysis (TGA) graph of a silver precursor ink prepared according to Example 15 of the present invention.

[0042] Preferred embodiments of the present invention are described in detail below. In describing the present invention, detailed descriptions of related prior art are omitted if it is determined that such detailed descriptions may obscure the essence of the invention. Throughout the specification, singular expressions should be understood to include plural expressions unless the context clearly indicates otherwise, and terms such as “comprising” or “having” are intended to specify the existence of the described features, numbers, steps, actions, components, parts, or combinations thereof, and should not be understood as precluding the existence or addition of one or more other features, numbers, steps, actions, components, parts, or combinations thereof. Furthermore, in carrying out the method or manufacturing method, each process constituting the method may occur differently from the specified order unless the context clearly indicates a specific order. That is, each process may occur in the same order as specified, may be performed substantially simultaneously, or may be performed in the reverse order.

[0043] The technology disclosed in this specification is not limited to the embodiments described herein and may be embodied in other forms. The embodiments introduced herein are provided merely to ensure that the disclosed content is thorough and complete, and to ensure that the technical concept of the technology is sufficiently conveyed to those skilled in the art. In the drawings, the dimensions, such as the width or thickness of each component, have been slightly enlarged to clearly represent the components of each device. The drawings are described from the perspective of an observer, and where one element is mentioned as being positioned above another element, this implies both that the element is positioned directly above the other element and that an additional element may be interposed between them. Furthermore, those skilled in the art may embody the concept of the invention in various other forms without departing from the technical concept of the invention. Also, in multiple drawings, the same reference numerals refer to substantially identical elements.

[0044] In this specification, the term "and / or" includes a combination of the plurality of described items or any one of the plurality of described items. In this specification, "A or B" may include "A," "B," or "both A and B."

[0045] The present invention relates to a silver precursor ink comprising a carboxylic acid silver precursor compound; an alcohol compound; a nitrogen atom-containing compound; and a solvent.

[0046] The above carboxylic acid silver precursor compound is a compound that performs a silver mirror reaction using a nitrogen atom-containing compound as a complexing agent and may have the structure of Chemical Formula 1 below.

[0047] [Chemical Formula 1]

[0048] R a R b R c C-COOAg

[0049] (In the above Chemical Formula 1, R a , R b and R c Each independently hydrogen, C1-C 20 alkyl groups, substituted or unsubstituted C1-C 28 Cycloalkyl groups, substituted or unsubstituted C1-C 28 aralkyl, substituted or unsubstituted C1-C 28 Heteroalkyl groups, substituted or unsubstituted C1-C 28 Heterocycloalkyl groups, or substituted or unsubstituted C1-C 28 heteroalkyl group)

[0050] In this specification, the term "alkyl" comprises straight-chain, branched-chain, or cyclic hydrocarbon radicals or combinations thereof, and may optionally include one or more double bonds, triple bonds, or combinations thereof within the chain. That is, "alkyl" includes alkenes or alkynes.

[0051] The term “heteroalkyl” means a stable straight-chain, branched-chain, or cyclic hydrocarbon radical or a combination thereof, consisting of one or more carbon atoms and one or more heteroatoms selected from the group consisting of O, N, P, Si, and S, either by itself or in combination with other terms, unless otherwise specified, and the nitrogen, phosphorus, and sulfur atoms may optionally be oxidized and the nitrogen heteroatom may optionally be quaternized.

[0052] The terms "cycloalkyl" and "heterocycloalkyl" refer to the cyclic versions of "alkyl" and "heteroalkyl," respectively, either by themselves or in combination with other terms, unless otherwise specified.

[0053] The term "aralkyl" refers to an alkyl group substituted with aryl and aryl, wherein the alkyl and aryl portions are independently and optionally substituted.

[0054] The term "aryl" means a polyunsaturated, aromatic, hydrocarbon substituent that may be a single ring or multiple rings (1 to 3 rings) fused or covalently bonded together, unless otherwise specified.

[0055] The term "heteroaryl" means an aryl group (or ring) comprising 1 to 4 heteroatoms selected from N, O, and S (in each separate ring in the case of a multi-ring), wherein the nitrogen and sulfur atoms are optionally oxidized, and the nitrogen atom(s) are optionally quaternized. The heteroaryl group may be bonded to the rest of the molecule through carbon or heteroatoms.

[0056] The term "heteroaralkyl" refers to an alkyl group substituted with an aryl and a heteroaryl, respectively, wherein the alkyl and heteroaryl portions are independently and optionally substituted.

[0057] In the expressions “substituted or unsubstituted” as used herein, “substitution” means that one or more hydrogen atoms in a hydrocarbon are each, independently of one another, replaced by the same or different substituents. Useful substituents include, but are not limited to, the following.

[0058] These substituents are C1-C6 substituted or unsubstituted with -F; -Cl; -Br; -CN; -NO2; -OH; =O; -F, -Cl, -Br, -CN, -NO2, -OH, or =O. 20 Alkyl group; C1-C substituted or unsubstituted with -F, -Cl, -Br, -CN, -NO2, -OH, or =O 20 Alkoxy group; C1-C 20 Alkyl group, C1-C 20 C6-C substituted or unsubstituted with alkoxy groups, -F, -Cl, -Br, -CN, -NO2, -OH, or =O 30 Aryl group; C1-C 20 Alkyl group, C1-C 20 C6-C substituted or unsubstituted with alkoxy groups, -F, -Cl, -Br, -CN, -NO2, -OH, or =O30 Heteroaryl group; C1-C 20 Alkyl group, C1-C 20 C5-C groups substituted or unsubstituted with alkoxy groups, -F, -Cl, -Br, -CN, -NO2, -OH, or =O 20 Cycloalkyl group; C1-C 20 Alkyl group, C1-C 20 C5-C groups substituted or unsubstituted with alkoxy groups, -F, -Cl, -Br, -CN, -NO2, -OH, or =O 30 Heterocycloalkyl group; C1-C substituted or unsubstituted with -F, -Cl, -Br, -CN, -NO2, -OH, or =O 20 It may be one or more selected from the group consisting of an alkoxysilane group; and a group represented by -N(G1)(G2). In this case, G1 and G2 are each independently hydrogen; C1-C 10 Alkyl group; or C1-C 10 C6-C substituted or unsubstituted with alkyl groups 30 It could be Arilgi.

[0059] "Derivative" of any substance described in this specification means that some of the hydrogen atoms of the substance are replaced with the substituents described above.

[0060] Specifically, the above-mentioned silver carboxylic acid precursor compounds are silver acetate, silver acetoacetate, silver 2-methylacetoacetate, silver trifluoroacetate, silver lactate, silver malonate, silver maleate, silver fumarate, silver pyruvate, silver succinate, silver picrate, silver citrate, silver tartrate, silver benzoate, silver cyclohexane carboxylate, and silver 2-ethylbutyrate. It may include 2-ethylbutyrate), silver neoheptanoate, silver 2-ethylhexanoate, silver caprylate, silver isononanoate, silver neodecanoate, silver stearate, silver docosanoate, silver oleate, silver linoleate, silver naphthenate, silver behenate, or silver abietate, and commercially available products include ExxonMobil's silver neo acid 910 or neo acid Silver 913 (Silver neo acid 913) can be used.These silver carboxylic acid compounds can preferably be silver alkanates such as silver 2-ethylhexanoate, silver isononanate, silver neodecanoate, silver naphthenate, silver abieticate, or silver neoate 913, more preferably silver neodecanoate, silver naphthenate, or silver neoate 913, and most preferably silver neodecanoate can be used in terms of economic feasibility, applicability, and solubility characteristics.

[0061] Acetylene-based compounds called alkynes are used to improve reflective properties while increasing the solubility and lowering the calcination temperature of the carboxylic acid silver precursor compound by forming a complex with the above-mentioned carboxylic acid silver precursor compound, and may have the structure of Chemical Formula 2 below.

[0062] [Chemical Formula 2]

[0063]

[0064] (In the above Chemical Formula 2, R1, R2, and R3 are each independently hydrogen, C1-C 20 alkyl groups, substituted or unsubstituted C1-C 28 Cycloalkyl groups, substituted or unsubstituted C1-C 28 Aralkyl, substituted or unsubstituted C1-C 28 Heteroalkyl groups, substituted or unsubstituted C1-C 28 Heterocycloalkyl groups, or substituted or unsubstituted C1-C 28 heteroalkyl group)

[0065] As specific examples of the above alcohol compounds, acetylene-based alcohol compounds may be used, preferably 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol, propagyl alcohol, butynol, hexynol, ethyloctinol, benzylbutynol, 3,5-dimethyl-1-hexyn-3-ol, 3,4-dimethyl-1-pentyn-3-ol, 3-butyn-2-ol, and 1-ethynyl-1-cyclopentanol. 1-Ethynyl-1-cyclohexanol, 5-Methyl-1-hexyn-3-ol, 1-Hexyn-3-ol, 3-Methyl-1-penten-4-yn-3-ol, 3-Ethyl-1-pentyn-3-ol, 4-Methyl-1-pentyn-3-ol, 1-Pentyn-3-ol, 2-Phenyl-3-butyn-2-ol, 1,1-diphenyl-2-propyn-1-ol, 3,7,11-trimethyl-1-dodecyn-3-ol, 2-butyne-1,4-diol, 2,5-dimethyl-3-hexyne-2,5-diol, or 2,4,7,9-tetramethyl-5-decindiol may be used.More preferably, 2-methyl-3-butyn-2-ol (MBO, Formula 3), 3-methyl-1-pentyn-3-ol (MPO, Formula 4), and 3,5-dimethyl-1-hexin-3-ol (DMHO, Formula 5) may be used.

[0066] [Chemical Formula 3]

[0067]

[0068] [Chemical Formula 4]

[0069]

[0070] [Chemical Formula 5]

[0071]

[0072] The above acetylene-based compound may be a mixture of two or more acetylene-based alcohols. In the case of such a mixture, it may serve to enhance the properties of the acetylene-based alcohols, particularly stability and reflectivity after calcination.

[0073] There is no need to specifically limit the amount of the above-mentioned acetylene-based compound used, but the above-mentioned carboxylic acid may be used in a molar ratio of 0.1 to 10.0 mol, preferably 0.3 to 5.0 mol, and more preferably 0.5 to 3.0 mol relative to the silver precursor compound. When used within the above range, the stability of the silver mirror ink is increased and the reflective properties after firing are excellent, but when used outside the above range, the mirror properties may deteriorate or problems with ink stability may occur.

[0074] The above nitrogen atom-containing compound may be an amine compound, an ammonium compound, or a mixture thereof. These amine or ammonium compounds primarily act as electron donors, complexing agents, or bases, and can exhibit catalytic effects in mirror formation, increase ink solubility, and lower the firing temperature. In addition, the above nitrogen atom-containing compound can act as a catalyst to produce a silver mirror quickly at low temperatures even when used in small amounts, and can simultaneously perform the role of a binder after firing.

[0075] Examples of the above amine compounds or ammonium compounds include primary, secondary, or tertiary amines or ammonium salts. These amine compounds may be of any form, such as linear, branched, comb, star-shaped or dendritic, and cyclic types, and may be multi-amines or amines or polyamines having functional groups such as hydroxy, alkoxy, ester, amide, or urethane.

[0076] Specific examples of the above amine compounds include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, tertiary-butylamine, n-pentylamine, iso-pentylamine, tertiary-amylamine, n-hexylamine, diethylamine, triethylamine, 2-ethylhexylamine, cyclohexylamine, allylamine, propagylamine, ethylenediamine, 1,3-propylenediamine, hexamethylenediamine, triethylenediamine, 1,2-diaminopropane, 1,4-butanediamine, monoethanolamine, diethanolamine, 1-amino-2-propanol, 3-amino-1-propanol, 2-amino-2-methyl-1-propanol (2-Amino-2-methyl-1-propanol), spermine, spermidine, diethylenetriamine, Triethylenetetraamine, 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, morpholin, imidazole, pyrrole, quinuclidine, benzylamine, phenethylamine, aminopropyltriethoxy silane, polyethyleneimine (PEI), poly(propylene imine), polyvinylamine (PVAm), poly(amidoamine) (PAMAM), or Jeffamines may be used, and derivatives of the above amine compounds or mixtures containing one or more of the above amine compounds may also be used.Considering the stability and mirror properties of the silver precursor ink of the present invention, it is preferable to use polyamines such as polyethyleneimine, polypropyleneimine, polyvinylamine, poly(amidoamine), and Jeffamines, and more preferably, polyethyleneimine can be used.

[0077] Specific examples of the above ammonium compounds include ammonium salts such as ammonium formate, ammonium acetate, ammonium nitrates, ammonium sulfate, ammonium sulfite, ammonium carbonate, ammonium bicarbonate, ammonium carbamate, ammonium phosphate, ammonium carbamate, ammonium carbonate, tetraethylammonium bicarbonate, tetraethylammonium bromide, or tetrabutylammonium hydroxide, and it is also possible to use ammonium-based ionic liquids such as ethylammonium nitrate.

[0078] The above amine-based compound may be used in an amount of 0.01 to 5.0% by weight relative to the total ink, preferably 0.03 to 3.0%, and more preferably 0.05 to 1.0%. Within this range, it is possible to produce a suitable silver precursor ink, but if it falls outside this range, the silver mirror reaction may not be performed, and stability problems such as the precipitation of insoluble compounds may occur.

[0079] The above ammonium compound may be used alone, but it is preferable to use it mixed with the above amine compound, and it may be used in a weight ratio of 20 to 80%, preferably 30 to 70%, and more preferably 40 to 60% with respect to the above amine compound.

[0080] In general, in the case of acetylene-based compounds, the hydrogen in the terminal acetylene group exhibits acidic protons, so when they come into contact with basic complexing agents such as basic amines or ammonium compounds, a dehydrogenation reaction occurs between them, and if silver ions are attached to this, insoluble silver acetylide compounds can be formed. Some substances of this type are known to be explosive, acting as detonators when subjected to impact. When acetylene-based alcohol compounds, which are the main compounds used in the present invention, are appropriately mixed and used, particularly compounds in which bulky groups are substituted on acetylene groups such as 2-methyl-3-butyn-2-ol (MBO), 3-methyl-1-pentyn-3-ol (MPO), and 3,5-dimethyl-1-hexin-3-ol (DMHO), the formation of such acetylide compounds can be significantly inhibited, and thus stability can be increased.

[0081] Generally, since silver acetylide compounds have low solubility and do not dissolve in common organic solvents, not only the amount of nitrogen-based complexing agent used but also its type can affect the stability of the ink. In the case of the present invention, by appropriately mixing and using the acetylene-based alcohol compounds, the formation of insoluble silver acetylide compounds can be suppressed as described above, and the resulting silver acetylide complex compounds are soluble, thereby ensuring the stability of the silver precursor ink.

[0082] The silver precursor ink according to the present invention may further include a solvent and a polymer-based viscosity modifier such as polyvinylpyrrolidone (PVP) to be suitable for a coating method or printing equipment, and may also further include one or more selected from resin, stabilizer, dispersant, reducing agent, coupling agent, leveling agent, surfactant, wetting agent, thickener, and thixotropic agent for smooth thin film formation.

[0083] The above solvents do not need to be specifically limited, but specific examples include hexane, cyclohexane, heptane, decane, dodecane, tetradecane, pentene, cyclopentene, cyclopentadiene, dipentene, dicyclopentadiene, hexene, cyclohexene, 1-octene, cyclooctene, 1,7-octadiene, cyclooctadiene, 1-decene, xylene, cumene, kerosene, petrolum, white spirit, terpentine, mineral spirit, decalin, naphtha, norvonane, myrcene, pinene, d-limonene, terpinene, terpinolene, 2-norbornene, and 2,5-norbornadiene. 5-Vinyl-2-norbornene, 5-Ethylidene-2-norbornene, isobornane, water, methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, tertiary-butanol, 1-methoxy-2-propanol, 2-methyl-3-butene-2-ol, benzyl alcohol, diacetone alcohol, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, ethylene glycol, propylene glycol, diethylene glycol, propylene glycol monomethyl ether, monoglyme, diglyme, butylcarbitol, linalool, Genariol, α-Terpineol, Glycerin, Ethyl Acetate, Butyl Acetate, Ethyl Lactate, Carbitol Acetate, Acetone, Methyl Ethyl Ketone, Methyl Isobutyl Ketone, Mesity Oxide, Iso-Amyl Ketone, Cyclohexanone, 2-Heptanone, 2-Octanone, 2-Dodecanone, 2-Undecanone, Dicyclohexyl Ketone, Dibutyl Ether, Tetrahydrofuran, Tetrahydrothiophene, Dioxane,Solvents such as cyclohexane oxide, acetonitrile, butyronitrile, isobutyronitrile, acrylonitrile, dimethylformamide, diethylformamide, dibutylformamide, dimethylacetamide, dimethyl sulfoxide, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, N-methylpyrrolidone, or N-ethylpyrrolidone may be used. Additionally, the above solvents may be used alone or as a mixture of two or more solvents.

[0084] The above viscosity modifier may be used to control the viscosity of the silver precursor ink of the present invention. At this time, the viscosity of the silver precursor ink may be selected and used as long as there are no problems with manufacturing thin films and patterns according to the coating and printing methods, but a range of 0.1 to 1,000,000 cps is preferred, and 1 to 100,000 cps is more preferred.

[0085] In particular, when performing thin film and pattern formation using an inkjet printing method, the viscosity may be in the range of 0.1 to 50 cps, preferably 1 to 20 cps, and more preferably 3 to 15 cps. If the viscosity is below the above range, there is a tendency for the conductivity to decrease due to bleeding during inkjet printing or insufficient thickness of the thin film after firing; if it exceeds the above range, it is difficult for the ink to be smoothly ejected through the inkjet nozzle.

[0086] The above resin may be a cellulose-based resin such as polyvinylpyrrolidone, poly(2-oxazoline), polyacrylamide, hydroxyethylcellulose, and carboxymethylcellulose; polyacrylic acid and its copolymer; polyester, polyamide, polyurethane, polybutadiene, polyisoprene and their copolymer; and a water-soluble and water-dispersible resin including latex and natural resin.

[0087] The above surfactant may be a nonionic, anionic, cationic, or amphoteric surfactant.

[0088] The above-mentioned humectant may be propylene glycol, 1,2-butanediol, pentanediol, 1,2-hexanediol, or polyethylene glycol, and may also be the Surfinol series from Air Products.

[0089] The above-mentioned thickener may be hydroxyethyl cellulose or benton, and the above-mentioned leveling agent may be the BYK series.

[0090] The above is a specific example of a coating or printing method for manufacturing a thin film by depositing a precursor ink, such as spin coating, pipetting, blade coating, brush, bar coating, rod coating, roll coating, gravure, flexography, screen, offset, nozzle, spray coating, curtain coating, dip coating, flow coating, comma coating, slot die coating, dispensing, casting, stamping, imprinting, pad printing, inkjet printing, aerosol jet, electrohydrodynamics (EHD), or Electrospray deposition (ESD) can be used.

[0091] The coating thin film or pattern film formed through the above-described application can be sintered using physical processing methods such as heat, visible light, plasma, infrared (IR), ultraviolet (UV), electron beam, laser, microwave, electrical, magnetic, or electromagnetic treatment. At this time, the sintering process may be performed as a single process, but it is also possible to use two or more processes to increase the sintering speed or improve mirror properties.

[0092] The above-described firing process may typically be performed under an inert gas atmosphere, but may also be performed under an atmosphere of air, nitrogen, carbon monoxide, hydrogen, or a mixture thereof if necessary. The firing process is generally preferably performed at 70 to 700°C, more preferably 100 to 300°C, and may be performed at an appropriate firing temperature depending on the type of substrate. Generally, firing is easily achieved at 120°C or higher, and for substrates with low surface roughness, mirror formation is easy regardless of their type or shape. Additionally, while there is no specific need to limit the firing process time, a silver mirror with excellent reflectivity is formed more quickly at higher temperatures; conversely, at temperatures below 100°C, complete firing does not occur, which may result in the formation of a black mirror with poor reflective properties. The firing process can be performed as either a batch or a continuous process.

[0093] When firing the silver precursor ink of the present invention, the coated surface (referred to as the front surface for convenience) may form a silver mirror (primary mirror) or a black mirror, although the reflectance may vary depending on the type and content of the additives or solvent used and the temperature. In this case, if fired at a temperature below 200°C, organic matter remains on the coated back surface (back surface) along with silver nanoparticles, so a black mirror may be formed on most of it regardless of the type. However, if a glass or transparent ceramic substrate is used and fired at a temperature of 200°C or higher, the organic matter on the back surface is removed by vaporization or sublimation, thereby forming a double-sided silver mirror in which both the front surface (primary mirror) and the back surface (secondary mirror) become mirrors.

[0094] The mirror produced through the silver precursor ink of the present invention can be easily manufactured into various shapes, such as front mirrors, back mirrors, and patterned mirrors, without being restricted by any shape or size. In addition, since a mirror (Mirror on Demand) can be formed on a desired location on various materials (glass, plastic, metal, ceramic, polymer, pottery, bottle, film, sheet, etc.) regardless of whether it is transparent or opaque, it is possible to significantly enhance brightness in various fields, such as various displays, lighting (LCD, OLED, QD-OLED, QLED, QNED, LED, etc.), and craft products.

[0095]

[0096] Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings so that those skilled in the art can easily implement them. Furthermore, in describing the present invention, if it is determined that a detailed description of related known functions or known configurations may unnecessarily obscure the essence of the invention, such detailed description will be omitted. Also, some features presented in the drawings have been enlarged, reduced, or simplified for ease of explanation, and the drawings and their components are not necessarily depicted in appropriate proportions. However, those skilled in the art will easily understand these details.

[0097] Unless otherwise noted in the manufacturing examples and embodiments below, all experiments were performed at an indoor temperature of 25°C. Hereinafter, unless otherwise noted, “%” represents “weight%”. In addition, the silver precursor used in the present invention, silver neodecanoic acid, was a product of 99.0% or higher.

[0098] In the following examples, the measurement and evaluation of experimental results were performed using the following equipment and methods.

[0099] 1) Conductivity evaluation: After spin-coating the prepared silver precursor ink and firing the sample, the resistance was measured at a distance of 1 cm using a HIOKI CARD HiTESTER 3244-60.

[0100] 2) Inkjet printing was performed at room temperature using a Dimatix DMP-2831 (10pl nozzle) machine.

[0101] 3) The viscosity of the ink was measured using Brookfield DV-II +PRO LV (Spindle# CPE-40).

[0102] 5) The surface tension of the ink was measured using Surface Tensiomat 21.

[0103] 6) The surface roughness (Rms) of the silver mirror was measured using an atomic force microscope (AFM) (Veeco D3100).

[0104] 7) Surface reflectance was measured using a Spectrophotometer (Konica Minolta, CM-3600d).

[0105] 8) The thickness of the fired silver film was measured using an electron microscope (Scanning Electron Microscopes, TESCAN product).

[0106]

[0107] Example 1

[0108] 2.0 g of 1-octene, 1.5 g of methylisobutylketone, 1.0 g of 2-methyl-3-butyn-2-ol (MBO), and 0.5 g of 3,5-dimethyl-1-hexine-3-ol (DMHO) were sequentially added to a 20 ml transparent container and mixed well. 3.5 g of neodecanoic acid was then added and shaken well to dissolve the solution until it became transparent. Next, 0.75 g of a solution prepared by mixing (1:1) 10% polyethyleneimine (PEI) dissolved in ethylene glycol (EG) and 5% ammonium nitrate (AMN) dissolved in EG as catalysts was added, and the mixture was shaken well until it was uniformly mixed and became transparent. The resulting mixed solution was purified using a 0.4 micron Teflon microfilter to produce a transparent, yellow silver precursor ink (Fig. 2 (c)). The viscosity of the obtained ink was 7.5 cps.

[0109] A silver mirror film was fabricated by spin-coating the silver precursor ink prepared as described above onto a PET film and firing it at 150°C for 15 minutes (see Fig. 3) (resistance: 1.0 Ω / cm, reflectance: 97.0% @550 nm, see Fig. 1).

[0110] In addition, a cross-section of the silver mirror formed on the PET film is shown in Fig. 4.

[0111]

[0112] Example 2

[0113] A no-catalyst system was prepared without using the ethylene glycol (EG), polyethyleneimine (PEI), and ammonium nitrate solution used as catalysts in Example 1 (Fig. 2(d)). After preparing the silver precursor ink under identical other conditions, coating and calcining were performed to obtain a reflective black mirror film. (See Fig. 5, resistance: 20.5 Ω / cm)

[0114]

[0115] Example 3

[0116] A silver precursor ink was prepared under the same conditions as in Example 1, except that 0.75 g of a 10% polyethyleneimine (PEI) solution was used instead of 0.75 g of a 1:1 mixed solution of 10% polyethyleneimine (PEI) and 5% ammonium nitrate, and then calcined, resulting in a film having black mirror properties. (Resistance: 1.2 MΩ / cm)

[0117]

[0118] Example 4

[0119] As a result of preparing a silver precursor ink under the same conditions as in Example 1, except that 0.75 g of a 5% ammonium nitrate (AMN) solution was used instead of 0.75 g of a 1:1 mixed solution of 10% polyethyleneimine (PEI) solution and 5% ammonium nitrate solution, a solid precipitated, and the calcination process of the ink could not be carried out further (Fig. 2 (b)).

[0120]

[0121] Example 5

[0122] Instead of calcining the silver precursor ink prepared in Example 1 at 150°C for 15 minutes, it was calcined at 130°C for 30 minutes. As a result of calcination, a film having silver mirror properties was obtained. (Resistance: 0.6 Ω / cm, Reflectance: 94.5% @550 nm)

[0123]

[0124] Example 6

[0125] A silver precursor ink was prepared in the same manner as in Example 1, except that norbornene was used instead of 1-octene. As a result of calcining the silver precursor ink prepared as described above, a conductive film having bright silver mirror properties was obtained. (Resistance: 0.9 Ω / cm, Reflectance: 97.3% @550 nm)

[0126]

[0127] Example 7

[0128] Instead of calcining the precursor ink prepared in Example 6 at 150°C for 15 minutes, it was calcined at 100°C for 12 hours. As a result of calcination, a film having silver mirror properties was obtained. (Resistance: 1.5 Ω / cm, Reflectance: 75.5% @550 nm)

[0129]

[0130] Example 8

[0131] A silver precursor ink was prepared under the same conditions as in Example 1, but a glass substrate was used instead of a PET substrate, and photonic sintering was performed instead of firing at 150°C for 15 minutes; as a result, a silver mirror film with excellent surface roughness, low resistance, and excellent reflectivity (see Fig. 6) was obtained. (Resistance: 0.3 Ω / cm, Reflectivity: 98.7% @550 nm)

[0132]

[0133] Example 9

[0134] A silver precursor ink was prepared under the same conditions as in Example 1, except that limonene (d-Limonene) and 2-heptanone were used instead of 1-octene and methylisobutylketone. After coating the prepared silver precursor ink onto a ceramic surface with a brush and firing it using an infrared (IR) lamp, it was confirmed that a silver mirror was formed as shown in Fig. 7.

[0135]

[0136] Example 10

[0137] 4.0 g of decalin, 4.0 g of dicyclohexyl ketone, 2.0 g of MBO, and 1.0 g of DMHO were sequentially added to a 30 ml transparent container and mixed well. 6.0 g of neodecanoic acid was then added, and the mixture was reacted while shaking well until it became transparent. After the reaction was complete, 1.5 g of a solution prepared by mixing 10% PEI dissolved in 1-methoxy-2-propanol (MPA) and 5% ethylammonium nitrate (EAN) dissolved in MPA in a 1:1 ratio was added and dissolved by shaking well for about 10 minutes. When this mixed solution was purified using a 0.4 micron Teflon microfilter, a yellow, transparent silver precursor ink for inkjet printing was produced. The viscosity of the obtained silver precursor ink for inkjet printing was 11.3 cps. This was uniformly inkjet printed onto a glass substrate and then fired at 150°C for 15 minutes to form a bright silver mirror film (see Fig. 9). The resistance of the silver mirror film formed on the substrate was 1.5 Ω / cm, and the reflectance was 96.5%. In addition, it was confirmed that the inkjet printing was performed well at 6000 Hz (see Fig. 8).

[0138]

[0139] Example 11

[0140] 4.0 g of white spirit, 4.0 g of methyl isobutyl ketone, 2.0 g of MBO, and 1.0 g of DMHO were sequentially added to a 30 mL transparent container and mixed well. Next, 8.0 g of neodecanoic acid was added, and the mixture was reacted while shaking well until it became transparent. After the reaction was finished, 1.5 g of a solution prepared by mixing 10% PEI dissolved in ethanol and 5% EAN dissolved in ethanol in a 1:1 ratio was added and dissolved by shaking well for about 10 minutes. When this mixed solution was purified using a 0.4 micron Teflon microfilter, a yellow and transparent silver precursor ink was produced. The viscosity of the obtained silver precursor ink was 7.8 cps. The silver precursor ink prepared as described above was spin-coated onto a PET film and heated and calcined at 150°C for 15 minutes to form a silver mirror film. The resistance value of the silver mirror film coated on the above PET film was 1.1 Ω / cm and the reflectance was 97.5% (@550 nm).

[0141]

[0142] Example 12

[0143] A yellow and transparent silver precursor ink was obtained by preparing it in the same manner as in Example 11, except that 1.0g of MBO and 1g of 3-methyl-1-penthen-3-ol (MPO) were used instead of 2.0g of MBO. The silver precursor ink was calcined in the same manner as in Example 11 to form a silver mirror film on a PET film, and the resistance value of the silver mirror film coated on the PET film was 1.2Ω / cm and the reflectance was 96.8%.

[0144]

[0145] Example 13

[0146] A silver precursor ink was prepared in the same manner as in Example 11, except that polyvinylamine was used instead of PEI. When fired on a PET film under the same conditions as in Example 11, the resistance value was 1.5 Ω / cm and the reflectance was 93.5%.

[0147]

[0148] Example 14

[0149] A silver precursor ink was prepared under the same conditions as in Example 11, except that 25.0% PEI dissolved in ethanol was used instead of 10.0% PEI dissolved in ethanol. When the silver precursor ink was calcined in the same manner as in Example 11, a black mirror was formed on the coated surface instead of a silver mirror, and it was confirmed that a black mirror was also formed on the back side of the coating. However, the resistance value was outside the measurement range (>MΩ / cm).

[0150]

[0151] Example 15

[0152] 4.0 g of 1-octene and 3.0 g of methylisobutylketone were sequentially added to a 30 mL clear container, followed by 0.6 g of MBO and 1.0 g of DMHO, and mixed thoroughly. Next, 7.0 g of neodecanoic acid was added, and the mixture was reacted while shaking well until it became transparent. After the reaction was complete, 1.5 g of a catalyst solution containing 5% PEI and 2.5% ammonium nitrate was added to the MBO, and the mixture was shaken well for about 10 minutes. When this mixture was filtered through a 0.4-micron Teflon microfilter, a transparent, pale yellow silver precursor ink was produced. The viscosity of the obtained ink was 8.1 cps, and thermal analysis (TGA) showed a solid content of 20.6% (see Fig. 10). When this is spin-coated onto a PET film and heated and fired at 130°C for 30 minutes, a bright silver mirror film is well formed, and the measured linear resistance value was 0.7 Ω / cm and the reflectance was 97.3% (@550 nm).

[0153]

[0154] Examples 16~19

[0155] Experiments were conducted to verify the action of various carboxylic acids instead of neodecanoic acid.

[0156] In the above Example 1, silver carboxylate was used instead of silver neodecanoate as shown in Table 1 below, and after manufacturing the silver mirror, the resistance (Ω / cm) and reflectance (% @550nm) were measured in the same way as in Example 1.

[0157] Carboxylic acid silver resistance reflectance Example 1 Neodecanate silver 1.097.0 Example 16 Propionic acid silver 35072.5 Example 17 Stearic acid silver 53067.3 Example 18 Malonic acid silver 70060.8 Example 19 Neoic acid silver 9105.393.4

[0158] As shown in Table 1, experiments were conducted under the same conditions with different silver carboxylates, and it was found that there was a difference from Example 1 because the silver content was relatively lower due to differences in solubility during ink manufacturing.

[0159]

[0160] Examples 20-25

[0161] An experiment was conducted to verify the effects according to the type of acetylene-based compound. In the above Example 1, an equal amount of the alcohol compound shown in Table 2 below was used instead of the mixture of MBO and DMHO, and a silver mirror was prepared in the same manner. After preparing the silver mirror, the resistance (Ω / cm²) and reflectance (% @550nm) were measured in the same way as in Example 1.

[0162] Resistance Reflectance of Alcohol Compounds Example 1: MBO 1.0g + DMHO 0.5g 1.097.0 Example 20: MBO 1.5g 1.991.3 Example 21: DMHO 1.5g 2.687.4 Example 22: MPO 1.0g + DMHO 0.5g 1.295.9 Example 23: MPO 1.5g 2.290.5 Example 24: 5-Methyl-1-hexine-3-ol 1.0g + DMHO 0.5g 1.693.2 Example 25: MBO 1.0g + 3,4-Dimethyl-1-penthen-3-ol 0.5g 1.295.9

[0163] As shown in Table 2, it was confirmed that resistance and reflectance decreased when different acetylene-based compounds were used. Therefore, it was confirmed that when using the same type of acetylene-based compound, mixing them provides a higher effect than using them alone. Furthermore, as in Examples 20, 21, and 23, it was confirmed that there were issues with ink storage stability when an acetylene-based compound was used alone, such as the occurrence of precipitation when the ink was stored at room temperature for 3 days after preparation.

[0164]

[0165] Examples 26~28

[0166] An experiment was conducted to verify the effects according to the type of nitrogen atom-containing compound. In the above Example 1, an equal amount of the nitrogen atom-containing compound shown in Table 3 below was used instead of polyethyleneimine, and a silver mirror was prepared in the same manner. After preparing the silver mirror, the resistance (Ω / cm²) and reflectance (% @550nm) were measured in the same way as in Example 1.

[0167] Resistance Reflectance of Nitrogen Atom-Containing Compounds Example 1 Polyethyleneimine 1.097.0 Example 26 Polypropyleneimine 1.795.3 Example 27 Polyvinylamine 1.593.5 Example 28 Polyamidoamine 1.492.6

[0168] Foregoing, specific parts of the present invention have been described in detail. It will be apparent to those skilled in the art that such specific descriptions are merely preferred embodiments and do not limit the scope of the invention. Accordingly, the actual scope of the invention is defined by the appended claims and their equivalents.

Claims

1. Carboxylic acid is a precursor compound; Acetylene-based compounds; Nitrogen atom-containing compounds; and menstruum; A precursor ink containing 2. In Paragraph 1, A silver precursor ink characterized in that the above-mentioned carboxylic acid silver precursor compound comprises a compound of the following chemical formula 1. [Chemical Formula 1] R a R b R c C-COOAg (In the above Chemical Formula 1, R a , R b and R c Each independently hydrogen, C1-C 20 alkyl groups, substituted or unsubstituted C1-C 28 Cycloalkyl groups, substituted or unsubstituted C1-C 28 aralkyl, substituted or unsubstituted C1-C 28 Heteroalkyl groups, substituted or unsubstituted C1-C 28 Heterocycloalkyl groups, or substituted or unsubstituted C1-C 28 heteroalkyl group) 3. In Paragraph 2, The above silver carboxylic acid precursor compounds are silver acetate, silver acetoacetate, silver 2-methylacetoacetate, silver trifluoroacetate, silver lactate, silver malonate, silver maleate, silver fumarate, silver pyruvate, silver succinate, silver picrate, silver citrate, silver tartrate, silver benzoate, silver cyclohexane carboxylate, and silver 2-ethylbutyrate. A silver precursor characterized by comprising 2-ethylbutyrate), silver neoheptanoate, silver 2-ethylhexanoate, silver caprylate, silver isononanoate, silver neodecanoate, silver stearate, silver docosanoate, silver oleate, silver linoleate, silver naphthenate, silver behenate, silver abietate, silver neo acid 910, or silver neo acid 913. Ink.

4. In Paragraph 1, A silver precursor ink characterized in that the above acetylene-based compound comprises a compound of the following chemical formula 2. [Chemical Formula 2] (In the above Chemical Formula 2, R1, R2, and R3 are each independently hydrogen, C1-C 20 alkyl groups, substituted or unsubstituted C1-C 28 Cycloalkyl groups, substituted or unsubstituted C1-C 28 aralkyl, substituted or unsubstituted C1-C 28 Heteroalkyl groups, substituted or unsubstituted C1-C 28 Heterocycloalkyl groups, or substituted or unsubstituted C1-C 28 heteroalkyl group) 5. In Paragraph 4, A silver precursor ink characterized in that the above acetylene-based compound is an acetylene-based alcohol compound.

6. In Paragraph 4, The above alcohol compounds are 2-methyl-3-butyn-2-ol, 3-methyl-1-pentyn-3-ol, propargyl alcohol, butynol, hexynol, ethyloctinol, benzylbutynol, 3,5-dimethyl-1-hexyn-3-ol, 3,4-dimethyl-1-pentyn-3-ol, 3-butyn-2-ol, and 1-ethynyl-1-cyclopentanol. 1-Ethynyl-1-cyclohexanol, 5-Methyl-1-hexyn-3-ol, 1-Hexyn-3-ol, 3-Methyl-1-penten-4-yn-3-ol, 3-Ethyl-1-pentyn-3-ol, 4-Methyl-1-pentyn-3-ol, 1-Pentyn-3-ol, 2-Phenyl-3-butyn-2-ol, A silver precursor ink characterized by comprising 1,1-diphenyl-2-propyn-1-ol, 3,7,11-trimethyl-1-dodecyn-3-ol, 2-butyne-1,4-diol, 2,5-dimethyl-3-hexyne-2,5-diol, or 2,4,7,9-tetramethyl-5-decindiol.

7. In Paragraph 4, A silver precursor ink characterized in that the above-mentioned acetylene-based compound is a mixture of two or more acetylene-based alcohols.

8. In Paragraph 1, A silver precursor ink characterized in that the above nitrogen atom-containing compound is an amine compound, an ammonium compound, or a mixture thereof.

9. In Paragraph 8, A silver precursor ink characterized in that the above amine compound is a primary amine, a secondary amine, a tertiary amine, or a polyamine.

10. In Paragraph 1, A silver precursor ink characterized in that the above ammonium compound is an ammonium salt.

11. In Paragraph 10, A silver precursor ink characterized in that the above ammonium salt is ammonium formate, ammonium acetate, ammonium nitrates, ethylammonium nitrate, ammonium sulfate, ammonium sulfite, ammonium carbonate, ammonium bicarbonate, ammonium carbamate, ammonium phosphate, ammonium carbamate, ammonium carbonate, tetraethylammonium bicarbonate, tetraethylammonium bromide, or tetrabutylammonium hydroxide.

12. A silver-plated product obtained by firing the silver precursor ink of any one of claims 1 to 11 at 70 to 700°C.

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