Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/20—Conductive material dispersed in non-conductive organic material
  • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/52—Electrically conductive inks
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/24—Electrically-conducting paints

Definitions

• the present invention was obtained by heating a silver-containing composition capable of producing a silver element such as a metal silver film or metal silver wire excellent in adhesion and conductivity by low-temperature sintering, and the composition on the surface of the substrate.
• the present invention relates to a silver element forming substrate.
• a method for producing a metal thin film or wire there is known a method in which a metal is made into a liquid ink or paste ink and heated after being applied or printed on a substrate.
• Gold, silver, copper, and aluminum are used as metals, and silver is widely used as a material for wiring materials.
• ink using silver generally, an ink in which metallic silver is dispersed in a dispersion solvent is used, a pattern is formed on a wiring board, and metallic silver in the ink is sintered to form a wiring.
• metallic silver as a conductive material
• a method of sintering at a low temperature using a melting point drop due to refinement of dispersed metallic silver is known.
• a transparent resin substrate generally has a softening point lower than that of glass or the like, a low-temperature sinterable silver-forming material capable of producing metallic silver by heating at less than 150 ° C. is desired.
• silver capable of forming a silver element such as a metallic silver film or wire that exhibits good conductivity by low-temperature sintering at 120 ° C. or lower, or sintering at 150 ° C. or higher for a very short time.
• a containing composition is required.
• Patent Document 2 As a silver material that can be sintered at low temperature, a method for forming metallic silver using a silver salt using an organic acid has been reported (Patent Document 2). Since the organic silver salt is a silver salt composed of a monofunctional carboxylic acid and silver, the silver content in the compound is low, and the organic components remaining during sintering increase. In order to decompose and evaporate the organic component, it is necessary to lengthen the sintering time. In addition, the organic silver salt that exhibits low-temperature sinterability is unstable with respect to heat, and the storage stability of the silver-containing composition is problematic.
• the object of the present invention is to obtain a silver element such as a metallic silver film or wire excellent in conductivity and adhesion by sintering at a low temperature of 120 ° C. or lower and for a short time, or by sintering for a short time at 150 ° C. or higher.
• the object is to provide a silver-containing composition having high storage stability.
• Another object of the present invention is to provide a silver element-forming substrate provided with a silver element such as a metallic silver film or wire excellent in conductivity and adhesion.
• a composition comprising a silver compound (A) represented by formula (1), an amine compound (B) represented by formula (2), and a silane coupling agent (C), 10 to 50% by mass of silver compound (A) and 50 to 90% by mass of amine compound (B) with respect to 100% by mass in total of silver compound (A), amine compound (B) and silane coupling agent (C) %, And a silver-containing composition containing 0.1 to 5% by mass of the silane coupling agent (C).
• R 1 represents a hydrogen atom, — (CY 1 Y 2 ) a—CH 3 or — ((CH 2 ) b—O—CHZ) c—CH 3
• R 2 represents — (CY 1 Y 2 ) d—CH 3 or — ((CH 2 ) e—O—CHZ) f—CH 3
• Y 1 and Y 2 each independently represent a hydrogen atom or — (CH 2 ) g—CH 3 .
• Z represents a hydrogen atom or — (CH 2 ) h—CH 3 , a is an integer of 0 to 8, b is an integer of 1 to 4, c is an integer of 1 to 3, and d is 0 to 8, preferably Is an integer from 1 to 8, e is an integer from 1 to 4, f is an integer from 1 to 3, g is an integer from 0 to 3, preferably from 1 to 3, and h is an integer from 0 to 2, preferably from 1 to 2. .) Moreover, according to this invention, the said silver containing composition is apply
• the silver-containing composition of the present invention contains the silver compound (A), the amine compound (B), and the silane coupling agent (C) at a specific ratio, it is excellent in sintering at a low temperature of 120 ° C. or lower and for a short time.
• the silver element which has electroconductivity and the outstanding adhesiveness with respect to various base materials, such as glass, a silicon
• the silver concentration in the composition can be increased, and a silver element can be obtained quickly at a low temperature of 120 ° C. or less in the absence of a catalyst.
• silver elements can be formed on a resin base material having low heat resistance in a short time. Furthermore, since a metallic silver element can be formed in a shorter time at a high temperature of 150 ° C. or higher, an improvement in productivity can be expected. Since the silver element obtained in this way has high adhesion to various substrates, the silver element obtained by applying this composition and heating it after printing can be used in various fields such as wiring materials and reflectors. Can be expected.
• the silver-containing composition of the present invention (hereinafter sometimes simply referred to as a composition) includes a silver compound (A) represented by the above formula (1), an amine compound (B) represented by the above formula (2), And a silane coupling agent (C) in a specific ratio.
• the silver compound (A) is acetone dicarboxylate, and its form is usually a powder. It is known that the silver compound (A) has a high viscosity when diluted in a solvent and is difficult to pattern such as printing.
• the viscosity when combined with the amine compound (B), the viscosity can be set low even in a composition having a high silver content, and metallic silver can be produced by sintering at a low temperature of 120 ° C. or lower for a short time. It becomes possible.
• silver elements such as metallic silver films and wires obtained from a silver-containing composition obtained by combining a silver compound (A) and an amine compound (B) are adhesive to various substrates such as glass, silicon, ITO, and polyester. It is scarce. Therefore, by adding a silane coupling agent (C) at a specific ratio to the silver compound (A) and the amine compound (B), a silver element formed even at a low temperature of 120 ° C. or lower and for a short time of sintering. Can significantly improve the adhesion to various substrates while maintaining good electrical conductivity.
• the silver compound (A), the amine compound (B), and the silane coupling agent (C) have a total content of 100 to 50% by mass, the silver compound (A) content is 10 to 50% by mass, and the amine
• the content of the compound (B) is 50 to 90% by mass, and the content of the silane coupling agent (C) is 0.1 to 5% by mass. If the content rate of an amine compound (B) is less than 50 mass%, the solubility of a silver compound (A) will fall remarkably.
• the content rate of a silane coupling agent (C) is less than 0.1 mass%, sufficient adhesiveness to the base material of the obtained silver element is not acquired, and on the other hand, when more than 5 mass%, it adheres However, the conductivity is deteriorated.
• the content of the silane coupling agent (C) is preferably 0.3 to 5% by mass.
• the manufacturing method of the silver compound (A) used for this invention is not restrict
• the amine compound (B) used in the present invention is a compound represented by the above formula (2), wherein R 1 is a hydrogen atom,-(CY 1 Y 2 ) a-CH 3 or-((CH 2 ) b—O—CHZ) c—CH 3 and R 2 represents — (CY 1 Y 2 ) d—CH 3 or — ((CH 2 ) e—O—CHZ) f—CH 3 .
• Y 1 and Y 2 each independently represent a hydrogen atom or — (CH 2 ) g—CH 3
• Z represents a hydrogen atom or — (CH 2 ) h—CH 3 .
• a is an integer from 0 to 8
• b is an integer from 1 to 4
• c is an integer from 1 to 3
• d is an integer from 0 to 8
• e is an integer from 1 to 4
• f is an integer from 1 to 3
• g is An integer from 0 to 3
• h is an integer from 0 to 2.
• the amine compound (B) include ethylamine, 1-propylamine, 1-butylamine, 1-pentylamine, 1-hexylamine, 1-heptylamine, 1-octylamine, 2-ethylhexylamine, isopropylamine, isobutyl.
• amine isopentylamine, sec-butylamine, tert-butylamine, tert-amylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-isopropoxypropylamine, diisopropylamine, dibutylamine Can be mentioned.
• examples of such amine compound (B) include 1-propylamine, 1-butylamine, 1-pentylamine, 1-hexylamine, 1-heptylamine, 1-octylamine, isopropylamine, isobutylamine, isopentyl.
• Preferable examples include one or more of amine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-isopropoxypropylamine, diisopropylamine, and dibutylamine.
• the silane coupling agent (C) is a compound having two different functional groups, an organic functional group and an alkoxy group, in one molecule.
• the organic functional group include vinyl group, allyl group, styryl group, epoxy group, (meth) acryl group, amino group, ureido group, mercapto group, sulfide group, and isocyanate group.
• the compound represented by Formula (3) is mentioned, for example.
• R 3 represents — (CH 2 ) i—CH ⁇ CH 2 , — (CH 2 ) j—R 6 , —C 6 H 4 —CH ⁇ CH 2 , — (CH 2 ) 3 —O— (C ⁇ O) —CR 7 ⁇ CH 2 , — (CH 2 ) 3 —NHR 8 , — (CH 2 ) 3 —R 9 , — (CH 2 ) 3 —SR 10 or — (CH 2 ) 3 —N ⁇ C ⁇ O, wherein R 6 is an organic functional group represented by formula (4) or formula (5), R 7 represents a hydrogen atom or CH 3 , R 8 represents a hydrogen atom, — (CH 2 ) 2 —NH 2 , —C 6 H 5 or — (C ⁇ O) —NH 2 , R 9 represents an organic functional group represented by the formula (6), and R 10 represents a hydrogen atom or —S —S—S— (CH 2 ) 3 —S
• R 4 represents a methyl group, a methoxy group, an ethoxy group or an acetoxy group
• R 5 represents a methyl group, an ethyl group or an acetyl group.
• silane coupling agent (C) represented by the above formula (3) examples include vinyltrimethoxysilane, vinylethoxysilane, vinyltriacetoxysilane, allyltrimethoxysilane, p-styryltrimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxy Silane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropylto Methoxysilane, N-2- (aminoethyl) -3
• R 3 in the formula (3) is — (CH 2 ) 3 —NHR 8 or (CH 2 ) 3 —R 9 .
• R 8 represents a hydrogen atom, — (CH 2 ) 2 —NH 2 , —C 6 H 5 or (C ⁇ O) —NH 2
• R 9 represents an organic functional group represented by the formula (6). Represents.
• silane coupling agent having an amino group examples include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-amino Examples thereof include propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene) propylamine, and N-phenyl-3-aminopropyltrimethoxysilane.
• the mixing order of the silver compound (A), the amine compound (B), and the silane coupling agent (C) is not particularly limited.
• the composition of the present invention contains a solvent in addition to the silver compound (A), the amine compound (B), and the silane coupling agent (C) for the purpose of improving the coating property to the substrate and adjusting the viscosity. It can be added as appropriate.
• the amount of the solvent used is preferably 20 to 80% by mass with respect to 100% by mass in total of the silver compound (A), the amine compound (B), the silane coupling agent (C) and the solvent. If the amount of solvent exceeds 80% by mass, a uniform silver film may not be obtained due to a decrease in silver content.
• the type of the solvent is not particularly limited, but is preferably a solvent that can be easily removed during production of the silver element, and the solvents can be used alone or in combination depending on the application.
• the solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, and 2-pen.
• Solvents that further improve the flatness and low-temperature sinterability of the silver element formed include, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and 2-methyl-1-propanol.
• 2-methyl-2-propanol 1-pentanol, 2-pentanol, 3-pentanol, 3-methyl-1-butanol, 2-methyl-1-butanol, 2,2-dimethyl-1-propanol, 3-methyl-2-butanol, 2-methyl-2-butanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 4-methyl- 1-pentanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, 4-methyl-2-pentanol, -Methyl-3-pentanol, 3-methyl-3-pentanol, 2,2-dimethyl-1-butanol, 2,3-dimethyl-1-butanol, 3,3-dimethyl-1-butanol, 2,3 -Dimethyl-2-butanol, 3,3-dimethyl-2-butanol, 2-ethyl-1-
• the mixing order of the silver compound (A), the amine compound (B), the silane coupling agent (C) and the solvent is not particularly limited.
• a method of adding a solvent to a mixture of a silver compound (A), an amine compound (B), and a silane coupling agent (C), a silver compound (A) and a silane in a mixture of an amine compound (B) and a solvent Method of adding coupling agent (C), method of adding amine compound (B) and silane coupling agent (C) to a mixture of silver compound (A) and solvent, silane coupling agent (C) and solvent And a method of adding the silver compound (A) and the amine compound (B) to the mixture.
• composition of the present invention if necessary, for example, a hydrocarbon, acetylene alcohol, or silicone oil is used to adjust the leveling property with respect to the substrate, and, for example, a resin is used to adjust the viscosity characteristics of the composition. Or a plasticizer can be appropriately blended. Furthermore, if necessary, for example, other conductor powders, glass powders, surfactants, metal salts, and other additives generally used in silver-containing compositions may be appropriately blended.
• the composition of the present invention comprises a silver colloid dispersion liquid in which the composition is pre-heated and a generally known reducing agent is allowed to act to form silver clusters and nanoparticles.
• a generally known reducing agent include borohydride compounds, tertiary amines, thiol compounds, phosphorus compounds, ascorbic acid, quinones, and phenols.
• the amount of the reducing agent used can be appropriately selected as long as the conductivity and flatness of the resulting silver element are not lost.
• the silver element-forming base material of the present invention is a silver element in which the silver-containing composition of the present invention is applied on a base material such as a substrate, and the base material is heated to form metallic silver in a film or line shape. It is a base material provided.
• the material of the base material to which the composition of the present invention is applied is not particularly limited, and examples thereof include glass, silicon, silicon nitride, ITO, copper, aluminum, polyimide, polyester, and polycarbonate. From the viewpoint of productivity, a resin base material such as flexible polyester suitable for various printing methods is preferable.
• composition of the present invention to a substrate can be performed by printing or the like.
• the heating temperature at the time of heat-treating the substrate is not particularly limited as long as it is room temperature or higher. However, in consideration of productivity, heating at 80 ° C. or higher is preferable for firing in a short time.
• heat treatment is preferably performed at a temperature of 80 ° C. or higher and lower than 150 ° C.
• the heat processing of 120 to 170 degreeC is preferable from the point of productivity.
• Example 1-1 In a light-shielding bottle, 100 mg of the silver salt (A) prepared in Synthesis Example 1 as the silver compound (A) is dissolved in 896 mg of hexylamine (HA) as the amine compound (B), and the silane coupling agent (C) 4 mg of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was added and mixed to obtain 1000 mg of a silver-containing composition.
• Table 1 shows the amount of the silver compound (A), the amount of the amine compound (B) and the substituent in the above formula (2), and the amount of the silane coupling agent (C) and the substituent in the above formula (3). Show.
• Examples 1-2 to 1-5 A silver-containing composition was prepared in the same manner as in Example 1-1 except that the amounts of silver salt (A), HA and N-2- (aminoethyl) -3-aminopropyltrimethoxysilane were changed as shown in Table 1. Obtained.
• Example 1-6 In a light-shielding bottle, 398 mg of the silver salt (A) prepared in Synthesis Example 1 as the silver compound (A) is dissolved in 597 mg of HA as the amine compound (B), and vinyltril as the silane coupling agent (C) is dissolved. 5 mg of acetoxysilane was added to obtain 1000 mg of a silver-containing composition.
• Table 1 shows the amount of the silver compound (A), the amount of the amine compound (B) and the substituent in the above formula (2), and the amount of the silane coupling agent (C) and the substituent in the above formula (3). Show.
• Examples 1-7 to 1-21 The silane coupling agent (C) was changed to allyltrimethoxysilane in Example 1-7, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane in Example 1-8, and 3 in Example 1-9.
• Example 1-16 3-triethoxysilyl-N- (1, -Dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane in Example 1-17, 3-ureidopropyltriethoxysilane in Example 1-18, 3 in Example 1-19 -Same as Example 1-6 except that mercaptopropyltrimethoxysilane was changed to bis (triethoxysilylpropyl) tetrasulfide in Example 1-20 and 3-isocyanatopropyltriethoxysilane in Example 1-21. A silver-containing composition was obtained. The results are shown in Table 1.
• Example 1-22 In a light-shielding bottle, 398 mg of the silver salt (A) prepared in Synthesis Example 1 as the silver compound (A) is dissolved in 597 mg of butylamine (BA) as the amine compound (B), and used as the silane coupling agent (C). 5 mg of N-2- (aminoethyl) -3-aminopropyltrimethoxysilane was added to obtain a silver-containing composition.
• Table 1 shows the amount of the silver compound (A), the amount of the amine compound (B) and the substituent in the above formula (2), and the amount of the silane coupling agent (C) and the substituent in the above formula (3). Show.
• Examples 1-23 to 1-28 The amine compound (B) is propylamine (PA) in Example 1-23, dibutylamine (DBA) in Example 1-24, 2-ethoxyethylamine (2-EOEA) in Example 1-25, Example 1-26 was changed to 2-ethylhexylamine (2-EHA), Example 1-27 was changed to isopentylamine (IAA), and Example 1-28 was changed to 2-EHA 199 mg and 2-EOEA 398 mg. Obtained a silver-containing composition in the same manner as in Example 1-22. The results are shown in Table 1.
• Comparative Example 1-1 In a light-shielding bottle, 100 mg of the silver salt (A) prepared in Synthesis Example 1 as the silver compound (A) was dissolved in 900 mg of HA as the amine compound (B) to obtain a silver-containing composition. Table 1 shows the amount of the silver compound (A), the amount of the amine compound (B), and the substituent in the above formula (2). Comparative Example 1-2 A silver-containing composition was obtained in the same manner as in Comparative Example 1 except that the amount of silver salt (A) and the amount of HA prepared in Synthesis Example 1 were changed as shown in Table 1.
• Examples 2-1 to 2-32 and Comparative Examples 2-1 to 2-4 In a light-shielding bottle, the silver-containing composition obtained in any of Examples 1-1 to 1-28 and Comparative Examples 1-1 and 1-2 in the amount shown in Table 2 was used in the amount of solvent shown in Table 2.
• IPA isopropyl alcohol
• MeOH represents methanol
• PGM represents propylene glycol monomethyl ether
• n-HA represents 1-hexanol
• TAA represents tert-amyl alcohol.
• Examples 3-1 to 3-32, Comparative Examples 3-1 and 3-2 The solutions prepared in Examples 1-1 to 1-28 and Comparative Examples 1-1 and 1-2 were applied to various substrates shown in Table 3 with a spin coater (Mikasa Co., Ltd.). A heat treatment was performed under the heating conditions shown to obtain a silver film. About the obtained silver film, the electrical conductivity shown below, adhesiveness, and the storage stability of a silver containing composition were evaluated. The results are shown in Table 3.
• ⁇ Electrical conductivity evaluation> The measurement was performed using a four-end needle type low resistivity meter (Lorestar GP: manufactured by Mitsubishi Chemical Corporation).
• the volume resistivity is a value when glass is used for the substrate, and those having a volume resistivity of 5.0 ⁇ 10 ⁇ 5 ⁇ ⁇ cm or less are represented by “ ⁇ ”, and “ ⁇ ” evaluation is the effect of the present invention. It was supposed to satisfy.
• ⁇ Adhesion evaluation> The cellophane tape was adhered to and peeled from the obtained silver film to evaluate the adhesion to the substrate. The evaluation was performed by the mechanical property-adhesion (cross-cut method) test method of the coating film specified in JIS K5600-5-6.
• the copper base material is abbreviated as Cu
• the polyester base material as PET
• the polycarbonate base material as PC
• the silicon base material as Si
• the silicon nitride base material as SiN.
• Examples 4-1 to 4-36, Comparative examples 4-1 to 4-4 The solutions prepared in Examples 2-1 to 2-32 and Comparative Examples 2-1 to 2-4 were applied to various substrates shown in Table 4 with a spin coater (Mikasa Co., Ltd.). Heat treatment was performed under the heating conditions shown to obtain a silver film. The conductivity, adhesion, and storage stability of the resulting silver film were evaluated in the same manner as in Examples 3-1 to 3-30 and Comparative Examples 3-1 and 3-2. The results are shown in Table 4.

Landscapes

• Chemical & Material Sciences (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Wood Science & Technology (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Physics & Mathematics (AREA)
• Dispersion Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Conductive Materials (AREA)
• Paints Or Removers (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=49916003

Family Applications (1)

Country Status (4)

Cited By (2)

Citations (2)

Family Cites Families (6)

• 2013
  • 2013-07-08 WO PCT/JP2013/068631 patent/WO2014010549A1/ja active Application Filing
  • 2013-07-08 JP JP2014524793A patent/JP6146414B2/ja active Active
  • 2013-07-08 KR KR1020147036068A patent/KR102021636B1/ko active IP Right Grant
  • 2013-07-10 TW TW102124649A patent/TWI594270B/zh active

Patent Citations (2)

Also Published As

Similar Documents

Legal Events