WO2018150697A1 - Pâte conductrice pour impression offset par gravure, procédé de formation d'un motif conducteur, et procédé de fabrication d'un substrat conducteur - Google Patents

Pâte conductrice pour impression offset par gravure, procédé de formation d'un motif conducteur, et procédé de fabrication d'un substrat conducteur Download PDF

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Publication number
WO2018150697A1
WO2018150697A1 PCT/JP2017/044157 JP2017044157W WO2018150697A1 WO 2018150697 A1 WO2018150697 A1 WO 2018150697A1 JP 2017044157 W JP2017044157 W JP 2017044157W WO 2018150697 A1 WO2018150697 A1 WO 2018150697A1
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conductive paste
offset printing
conductive
gravure offset
fine particles
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PCT/JP2017/044157
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English (en)
Japanese (ja)
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祐樹 新谷
外村　卓也
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バンドー化学株式会社
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Priority to JP2017565327A priority Critical patent/JP6348241B1/ja
Publication of WO2018150697A1 publication Critical patent/WO2018150697A1/fr

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    • 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
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns

Definitions

  • the present invention relates to a conductive paste for gravure offset printing, a method for forming a conductive pattern using the conductive paste for gravure offset printing, and a method for manufacturing a conductive substrate using the method for forming the conductive pattern.
  • Patent Document 1 a conductive metal particle (A), an organic compound (B) that is solid at 50 ° C. and has a boiling point at normal pressure exceeding 300 ° C., and a liquid that is liquid at 50 ° C. and has a boiling point at normal pressure.
  • a conductive paste for bezel pattern printing by a gravure offset printing method containing (B) a non-volatile content of 1.0 to 3.0% in terms of mass with respect to the total of (A) to (D) And, in terms of the mass of the non-volatile content, the total use amount of the organic compound (B) and the organic compound (C) is R and the use amount of the conductive metal particles (A) is P. / P is set to 0.07 to 0.15 It discloses conductive paste.
  • Patent Document 2 discloses a method for producing a conductive film using a conductive copper paste that does not contain a thermosetting resin component or glass frit, and the conductive copper paste has an average particle diameter. Selected from the range of 2 ⁇ m to 10 ⁇ m, fine copper powder selected from the average particle size of 0.2 ⁇ m to 1.0 ⁇ m, a copper salt of a specific aliphatic monocarboxylic acid, a specific (dialkylamino ) Using the conductive copper paste containing a specific amount of alkylamine, a polymer binder having a thermal decomposition temperature in a specific range, and a first organic solvent having a specific functional group having a boiling point in a specific range, Production of a conductive film, characterized in that after applying a copper paste on a resin substrate, light irradiation is performed in a state where the residual amount of the first organic solvent is 0.1 to 5% by mass. A method is disclosed There.
  • gravure offset printing which is a kind of the intaglio printing method, is suitably used because it is suitable for fine line printing.
  • a conductive paste is filled in a recess formed on the surface of a gravure plate, the conductive paste is temporarily transferred to a blanket, and the conductive paste transferred to the blanket is transferred to an adherend.
  • the print pattern formed on the surface of the gravure plate is printed on the adherend. Therefore, the conductive paste for gravure offset printing has an appropriate viscosity so that it can be easily filled in the concave portion of the gravure plate, and the transfer from the gravure plate to the blanket and the transfer from the blanket to the adherend are good. In order to achieve this, it is required to have a degree of tackiness (tack) in a semisolid / semiliquid state.
  • Patent Document 1 The conductive paste described in Patent Document 1 is designed for printing a bezel pattern, and there is room for further study in order to cope with the thinning of the conductive pattern in recent years. Moreover, in the said patent document 2, it is not examined about the thinning of the conductive pattern formed by gravure offset printing.
  • the present invention has been made in view of the above problems, and has a sufficient conductivity and good adhesion to a substrate and can form a fine conductive pattern, a conductive paste for gravure offset printing, and a conductive material.
  • a method for forming a conductive pattern and a method for manufacturing a conductive substrate are provided.
  • the present inventors have added a water-soluble polymer to the conductive paste in order to thin the conductive pattern formed by the gravure offset printing method.
  • the present inventors have found that the adhesiveness in a semi-solid / semi-liquid state is improved and fine line printing is possible by gravure offset printing, and the present invention has been achieved.
  • the conductive paste for gravure offset printing of the present invention contains silver fine particles, an organic solvent, and a water-soluble polymer, and the average particle size of the silver fine particles is 1 ⁇ m or less.
  • the water-soluble polymer preferably contains a polymerizable compound having a cyclic structure.
  • the water-soluble polymer preferably contains polyvinyl pyrrolidone.
  • the content of the water-soluble polymer is preferably 3 to 8% by weight with respect to the entire conductive paste.
  • the organic solvent preferably contains a first organic solvent containing a hydroxyl group and having a boiling point of 200 ° C. or higher at normal pressure.
  • the organic solvent preferably contains 3.0 to 30% by weight of a second organic solvent having a blanket swelling ratio of 2.0% or less based on the entire conductive paste.
  • the method for forming a conductive pattern of the present invention uses a gravure offset printing method using a gravure plate, and the gravure plate has a recess filled with a conductive paste for gravure offset printing on the printing surface,
  • the width is 10 ⁇ m or less
  • the gravure offset printing conductive paste is the gravure offset printing conductive paste of the present invention.
  • the method for producing a conductive substrate of the present invention is characterized in that a conductive pattern is drawn on a substrate using the method for forming a conductive pattern of the present invention.
  • the conductive paste for gravure offset printing of the present invention has sufficient conductivity and good adhesion to a substrate, fine line printing by gravure offset printing is possible. Moreover, according to the method for forming a conductive pattern of the present invention, a conductive pattern having a line width of 10 ⁇ m or less can be formed, and even a conductive pattern having a line width of 3 ⁇ m or less is formed without disconnection. be able to. According to the method for manufacturing a conductive substrate of the present invention, a conductive substrate on which a precise conductive pattern is printed can be manufactured.
  • the conductive paste for gravure offset printing of the present invention contains silver fine particles, an organic solvent, and a water-soluble polymer, and the average particle size of the silver fine particles is 1 ⁇ m or less. Since the conductive paste for gravure offset printing of the present invention contains an organic solvent and a water-soluble polymer, it is difficult to dry and has a degree of adhesiveness in a semi-solid / semi-liquid state. Suitable for fine line printing.
  • the average particle diameter of the silver fine particles is 1 ⁇ m or less.
  • a fine conductive pattern having a line width of 3 ⁇ m or less can be formed using a gravure offset printing method.
  • the shape of the silver fine particles is not particularly limited as long as the effects of the present invention are not impaired.
  • coarse silver particles having an average particle diameter exceeding 1 ⁇ m are used, for example, when the width of the recess formed on the surface of the gravure plate is 3 ⁇ m, only a few silver particles can be filled. It is difficult to form a fine conductive pattern.
  • the particle diameter of the silver particles there may be a case where the silver particles cannot be filled at all in the 3 ⁇ m-wide recess.
  • the silver fine particles preferably have an average particle size that causes a melting point drop.
  • the gravure plate can be densely filled with a large number of silver fine particles, and the silver fine particles can be arranged so as to overlap each other, so that the silver fine particles are sintered (necking). It is easy to make.
  • the particle diameter is extremely small, the influence of one silver fine particle on the print quality can be further reduced.
  • the average particle diameter of the silver fine particles is 1 nm or more, the silver fine particles have good low-temperature sinterability, and the production cost of the silver fine particles can be suppressed, which is practical. Further, when the average particle size of the silver fine particles is 200 nm or less, the dispersibility of the silver fine particles hardly changes over time.
  • the more preferable lower limit of the average particle diameter of the silver fine particles is 2 nm, and the more preferable upper limit is 100 nm.
  • the silver fine particles may contain submicron-sized silver fine particles having an average particle diameter of more than 200 nm and 1 ⁇ m or less. When submicron-sized silver fine particles are used, the silver fine particles have a large particle diameter, so that the sinterability between the silver fine particles is slightly lowered, but sufficient thin line printing is possible.
  • the silver fine particles may contain nanometer-sized silver fine particles having an average particle diameter of 1 to 200 nm and submicron-sized silver fine particles having an average particle diameter of more than 200 nm and not more than 1 ⁇ m.
  • nanometer-sized silver fine particles and submicron-sized silver fine particles in combination, the nanometer-sized silver fine particles drop in melting point around the submicron-sized silver fine particles, so that only the submicron-sized silver fine particles are obtained. A better conductive path can be obtained than when it is used.
  • the particle diameter of the silver fine particles can be measured by a dynamic light scattering method, a small angle X-ray scattering method, or a wide angle X-ray diffraction method.
  • the “average particle diameter” refers to a dispersion median diameter.
  • the dispersion median diameter is calculated by obtaining a dispersed particle diameter by using a dynamic light scattering method (Dynamic Light Scattering) with a particle diameter reference as a volume reference.
  • a DLS measuring device for example, a particle size distribution measuring device (model number: LB-550) manufactured by Horiba, Ltd. can be used.
  • the synthesized silver fine particle dispersion is diluted 100 times with terpineol, and the solvent refractive index is measured as 1.383.
  • the weight ratio of the silver fine particles to the whole nonvolatile content of the conductive paste is preferably 90% by weight or more.
  • the non-volatile content refers to components other than organic solvents, in addition to silver fine particles, organic components that cover silver fine particles described later, water-soluble polymers contained in conductive paste, polymer dispersants, thickeners, etc. Is included.
  • the weight ratio of the silver fine particles is 90% by weight or more, a conductive pattern having a high silver content can be formed. Since the silver fine particles are excellent in chemical stability, by using silver fine particles as the main, it is possible to form a conductive pattern that is difficult to be oxidized and whose volume resistance value is difficult to decrease.
  • a metal whose ionization column is more noble than hydrogen that is, gold, copper, platinum, palladium, etc. Particles may be added.
  • the conductive paste for gravure offset printing of the present invention contains metal particles other than silver, the content ratio of the silver fine particles to the total metal particles including the silver fine particles and the metal particles other than silver is 90% by weight or more. Preferably there is.
  • an organic component adheres to at least a part of the surface of the silver fine particles.
  • the surface of the silver fine particles is more preferably coated with an organic component.
  • the said organic component comprises an inorganic colloid particle substantially with the said silver fine particle as what is called a dispersing agent.
  • the organic component includes trace organic substances contained in the silver fine particles as impurities from the beginning, trace organic substances adhering to the silver fine particles mixed in the manufacturing process described later, residual reducing agent that could not be removed in the cleaning process, residual dispersant, etc. As described above, it is a concept that does not include organic substances or the like adhered to silver fine particles.
  • the “trace amount” specifically means less than 1% by weight in the inorganic colloidal particles.
  • the organic component is an organic substance capable of covering silver fine particles to prevent aggregation of silver fine particles and forming inorganic colloidal particles, and contains an amine and a carboxylic acid from the viewpoint of dispersibility and conductivity. Is preferred.
  • these organic components when these organic components are chemically or physically bonded to the silver fine particles, it may be considered that they are changed to anions and cations, and ions and complexes derived from these organic components are also Contained in the ingredients.
  • the amine may be linear or branched, and may have a side chain.
  • N- (3-methoxypropyl) propane-1,3-diamine, 1,2-ethanediamine, 2-methoxyethylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 1,4-butane Diamine diamine such as 1,5-pentanediamine, pentanolamine, aminoisobutanol, alkoxyamine or aminoalcohol, alkylamine such as propylamine, butylamine, pentylamine, hexylamine, hexylamine (linear alkylamine)
  • a cycloalkylamine such as cyclopentylamine and cyclohexylamine; a primary amine such as aniline and allylamine; a second amine such as dipropylamine, dibutylamine, piperidine, and hexamethyleneimine.
  • the amine may be a compound containing a functional group other than an amine such as a hydroxyl group, a carboxyl group, an alkoxy group, a carbonyl group, an ester group, or a mercapto group. Moreover, the said amine may be used independently and may use 2 or more types together.
  • the amine preferably has a boiling point at normal pressure of 300 ° C. or lower, and more preferably 250 ° C. or lower.
  • a carboxylic acid may be included in addition to the above amine.
  • the carboxyl group in one molecule of the carboxylic acid has a relatively high polarity and tends to cause an interaction due to a hydrogen bond, but a portion other than these functional groups has a relatively low polarity. Furthermore, the carboxyl group tends to exhibit acidic properties.
  • the compound which has at least 1 carboxyl group can be used widely, For example, formic acid, oxalic acid, acetic acid, hexanoic acid, acrylic acid, octylic acid, oleic acid etc. are mentioned.
  • a part of carboxyl groups of the carboxylic acid may form a salt with a metal ion.
  • 2 or more types of metal ions may be contained.
  • the carboxylic acid may be a compound containing a functional group other than a carboxyl group, such as an amino group, a hydroxyl group, an alkoxy group, a carbonyl group, an ester group, or a mercapto group.
  • the number of carboxyl groups is preferably equal to or greater than the number of functional groups other than carboxyl groups.
  • the said carboxylic acid may be used independently, respectively and may use 2 or more types together.
  • the carboxylic acid preferably has a boiling point at normal pressure of 300 ° C. or lower, and more preferably 250 ° C. or lower.
  • the amine and carboxylic acid form an amide group. Since the amide group also moderately adsorbs on the surface of the silver fine particles, the organic component may contain an amide group.
  • the content of the organic component in the inorganic colloid in the conductive paste for gravure offset printing of the present invention is preferably 0.5 to 50% by weight. If the organic component content is 0.5% by weight or more, the storage stability of the resulting conductive paste tends to be improved, and if it is 50% by weight or less, the conductivity of the conductive pattern tends to be good. . A more preferable content of the organic component is 1 to 30% by weight, and a more preferable content is 2 to 15% by weight.
  • the composition ratio (weight) of the amine and the carboxylic acid can be arbitrarily selected within the range of 1/99 to 99/1.
  • the composition ratio of the amine to the carboxylic acid is 20/80 to 98/2, and more preferably 30/70 to 97/3.
  • the conductive paste for gravure offset printing of the present invention contains an organic solvent as a dispersion medium for silver fine particles. Aggregation of silver fine particles can be suppressed by using an organic solvent as a dispersion medium. Moreover, since it generally has a high boiling point and is difficult to dry, it can be easily transferred to a blanket. In addition, since the surface tension is low, familiarity with silicone rubber generally used as a blanket is good. When water is used as the dispersion medium, silver fine particles may aggregate and clog the concave portions of the gravure plate. Further, water is not suitable as a dispersion medium for conductive paste used for gravure offset printing having a transfer process because of high surface tension, poor wettability to a blanket, low boiling point, and easy drying.
  • the organic solvent preferably contains a first organic solvent containing a hydroxyl group and having a boiling point of 200 ° C. or higher at normal pressure. Since the conductive paste for gravure offset printing of the present invention is suitably used for fine line printing with a line width of 10 ⁇ m or less, particularly 3 ⁇ m or less, it is preferable to use a solvent that is difficult to dry. When the boiling point of the first organic solvent at normal pressure is 200 ° C. or higher, the conductive paste can be prevented from being excessively dried on the gravure plate. In addition, when the first organic solvent contains a hydroxyl group, the dispersion of the silver fine particles becomes good, and the polarity of the organic solvent increases, so that the swelling of the blanket tends to be suppressed.
  • the first organic solvent examples include 2,4-diethyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, tripropylene glycol, It is preferable to use a diol solvent such as triethylene glycol, 1,2-hexanediol, 1.3 butylene glycol, 1,3-propanediol, dipropylene glycol, 2-butene-1,4-diol.
  • a diol solvent such as triethylene glycol, 1,2-hexanediol, 1.3 butylene glycol, 1,3-propanediol, dipropylene glycol, 2-butene-1,4-diol.
  • the content of the first organic solvent in the entire conductive paste is preferably 3 to 30% by weight.
  • a more preferred upper limit for the content of the first organic solvent is 25% by weight, and a more preferred upper limit is 20% by weight.
  • the organic solvent preferably contains 3.0 to 30% by weight of a second organic solvent having a blanket swelling rate of 2.0% or less.
  • the second organic solvent having a blanket swelling ratio of 2.0% or less is also referred to as a “low swelling organic solvent”.
  • the second organic solvent may also serve as the first organic solvent.
  • the blanket swelling ratio of the organic solvent is 2.0% or less, for example, it is possible to cope with the formation of a thin wire conductive pattern having a line width of 3 ⁇ m or less.
  • a more preferable blanket swelling ratio is 0.4% or less.
  • the content ratio of the second organic solvent to the entire conductive paste is 3.0% by weight or more, it is possible to impart appropriate coating properties (fluidity) to the conductive paste, For example, drying at the time of fine line printing with a line width of 3 ⁇ m or less can be suppressed.
  • the content By setting the content to 30% by weight or less, it is possible to prevent the spread during printing.
  • the more preferable upper limit of the content of the low swelling organic solvent is 25.0% by weight, and the more preferable upper limit is 20.0% by weight.
  • the outermost surface of a printing plate used for gravure offset printing is made of silicone rubber
  • the “blanket swelling ratio” in the present invention means a swelling ratio when silicone rubber is immersed in an organic solvent.
  • the blanket swelling rate is the same as the weight change rate of the blanket (silicone rubber) before and after the immersion when the blanket (silicone rubber) is immersed in an organic solvent.
  • a blanket (silicone rubber) is cut into a 1 cm square to obtain a test piece, and the test piece is immersed in an organic solvent under room temperature conditions (25 ° C. ⁇ 5 ° C.), taken out after 10 hours, and weight before and after immersion.
  • room temperature conditions 25 ° C. ⁇ 5 ° C.
  • the low-swelling organic solvent having a blanket swelling rate of 2.0% or less various solvents can be used as long as the effects of the present invention are not impaired.
  • the solvent which has a hydroxyl group as a functional group is preferable, for example, the polyhydric alcohol which has two or more hydroxyl groups, other monohydric alcohol solvents, etc. are mentioned.
  • a highly polar solvent such as a diol having a very low blanket swelling rate, drying of the fine line pattern on the blanket can be more effectively suppressed.
  • These solvents may be used alone or in combination of two or more.
  • Examples of the polyhydric alcohol having 2 to 3 hydroxyl groups include glycerin, 1,2,4-butanetriol, 1,2,6-hexanetriol, ethylene glycol, diethylene glycol, 1,2-butanediol, propylene Glycol, 2-methylpentane-2,4-diol and the like.
  • Examples of the monohydric alcohol include butyl triglycol, isobutyl diglycol, 2-butoxyethanol, 3-methoxy-3-methylbutanol, 2- (2-methoxyethoxy) ethanol, 2- (2-hexyloxyethoxy) ethanol Etc.
  • 2,4-diethyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, tripropylene Diol solvents such as glycol, triethylene glycol, 1,2-hexanediol, 1.3 butylene glycol, 1,3-propanediol, dipropylene glycol, and 2-butene-1,4-diol may be used.
  • the blanket swelling rate can be adjusted by adjusting the drying property.
  • a solvent having a high swelling ratio exceeding 2.0% may be mixed and used.
  • the number and combination of solvents to be mixed are not particularly limited.
  • Organic solvent with blanket swelling rate exceeding 2.0% examples include glycol ethers, glycol esters, terpene solvents, hydrocarbon solvents, alcohol solvents, and the like. These solvents may be used alone or in combination of two or more. If the concentration of the terpene solvent in the organic solvent is too high, the amount of solvent absorbed by the blanket increases, and drying tends to proceed on the blanket during transfer printing.Therefore, the diol solvent and the terpene solvent are balanced. It is preferable to mix.
  • organic solvent having a blanket swelling rate exceeding 2.0% include, for example, tripropylene glycol-n-butyl ether, butyl carbitol, diethylene glycol monomethyl ether, tripropylene glycol methyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol.
  • Examples include ether acetate.
  • the hydrocarbon solvent may contain an aliphatic hydrocarbon compound, may contain a cyclic hydrocarbon compound, or may contain an alicyclic hydrocarbon compound. .
  • aliphatic hydrocarbon compounds include saturated or unsaturated aliphatic compounds such as tetradecane, octadecane, heptamethylnonane, tetramethylpentadecane, hexane, heptane, octane, nonane, decane, tridecane, methylpentane, normal paraffin, and isoparaffin. There may be mentioned hydrocarbon compounds.
  • Examples of the cyclic hydrocarbon compound include toluene, xylene and the like.
  • Examples of the alicyclic hydrocarbon compound include limonene, dipentene, terpinene, terpinene (also referred to as terpinene), nesol, sinene, orange flavor, terpinolene, terpinolene (also referred to as terpinolene), ferrandrene, mentadiene, teleben, Examples thereof include dihydrocymene, moslen, isoterpinene, isoterpinene (also referred to as isoterpinene), clitomen, kautssin, cajeptene, oilimene, pinene, turpentine, menthane, pinane, terpene, and cyclohexane.
  • the alcohol solvent is a compound containing one or more hydroxyl groups in the molecular structure, and examples thereof include aliphatic alcohols, cyclic alcohols, and alicyclic alcohols. These alcohols may be used alone or in combination of two or more. Moreover, a part of hydroxyl group may be induced
  • aliphatic alcohol examples include heptanol, octanol (1-octanol, 2-octanol, 3-octanol, etc.), decanol (1-decanol, etc.), lauryl alcohol, tetradecyl alcohol, cetyl alcohol, 2-ethyl-1 -Saturated or unsaturated aliphatic alcohols having 6 to 30 carbon atoms such as hexanol, octadecyl alcohol, hexadecenol and oleyl alcohol.
  • Examples of the cyclic alcohol include cresol and eugenol.
  • alicyclic alcohol examples include cycloalkanols such as cyclohexanol, terpineol (including terpineol, ⁇ , ⁇ , ⁇ isomers, or any mixture thereof), and terpene alcohols such as dihydroterpineol (monoterpene alcohols). Etc.), dihydroterpineol, myrtenol, sobrerol, menthol, carveol, perillyl alcohol, pinocarveol, sobrerol, berbenol and the like.
  • the alicyclic alcohol may overlap with the terpene solvent.
  • the conductive paste for gravure offset printing of the present invention contains a water-soluble polymer.
  • a water-soluble polymer By containing a water-soluble polymer, the adsorption action to the blanket and adherend interface is enhanced, so that even if the conductive pattern has a line width of 3 ⁇ m or less, for example, without breaking, using the gravure offset printing method Can be formed.
  • water-soluble means one having a solubility of 1 g or more with respect to 1 L of water.
  • the water-soluble polymer is preferably a polymer that is soluble in both an organic solvent and water. Furthermore, the water-soluble polymer is required to have no adhesiveness to the substrate, transferability to the substrate, and difficulty in spreading the line on the blanket.
  • the adherend (base material) of the conductive paste is, for example, polyethylene terephthalate (PET), one having good adhesion to PET is preferable.
  • the water-soluble polymer preferably contains a polymerizable compound having a cyclic structure. Although solubility in organic solvents is limited, polyvinyl alcohol can also be used.
  • the cyclic structure is preferably ⁇ -lactam and preferably has a vinyl group. Especially, it is more preferable that the water-soluble polymer contains polyvinyl pyrrolidone.
  • Polyvinylpyrrolidone is a polymer represented by the following chemical formula (1).
  • n is a natural number.
  • Polyvinylpyrrolidone is highly soluble in highly polar polyhydric alcohols (especially diol solvents) and can be dissolved well in solvents such as esters and ketones. Can be dispersed. In particular, it dissolves well in a first organic solvent containing a hydroxyl group and having a boiling point of 200 ° C. or higher at normal pressure.
  • polyvinyl pyrrolidone is soluble in water, the adsorption action on the substrate interface can be remarkably enhanced. Furthermore, as a feature of gravure offset printing, a semi-solid / semi-liquid paste is transferred and printed on a blanket. Polyvinylpyrrolidone has a very high tack (adhesiveness) in a semi-solid / semi-liquid state. Therefore, it is very excellent in transferring from a blanket to a substrate. Therefore, the printability in thin line printing with a line width of, for example, 3 ⁇ m or less, which could not be printed with a conventional conductive paste, can be significantly improved.
  • the polyvinyl pyrrolidone preferably has an average molecular weight of 100,000 or less. When the average molecular weight is 100,000 or less, the viscosity of the conductive paste is not excessively increased, and transferability to a blanket or a substrate can be improved.
  • examples of such polyvinyl pyrrolidone include polyvinyl pyrrolidone K25 (average molecular weight: 25000), polyvinyl pyrrolidone K30 (average molecular weight: 40000) (both manufactured by Wako Pure Chemical Industries, Ltd.) and the like.
  • the average molecular weight is a weight average molecular weight and is measured by liquid chromatography.
  • LC-6AD pump For the measurement of the weight average molecular weight, LC-6AD pump, RID-10A RI detector, CLASS-LC10 Chromatopac data processor, and DGU-20A3 degasser manufactured by Shimadzu Corporation are used.
  • TSK-GEL G1000H, G2000H, and G2500H are used as columns, and the oven temperature is set to 40 ° C., and tetrahydrofuran (THF) is allowed to flow at a flow rate of 1.0 mL / min.
  • THF tetrahydrofuran
  • the content of the water-soluble polymer is preferably 3 to 8% by weight with respect to the entire conductive paste.
  • the content of the water-soluble polymer is less than 3% by weight, the adhesion to the adherend may be lowered.
  • the content of the water-soluble polymer exceeds 8% by weight, the volume resistance value of the conductive pattern formed by the conductive paste of the present invention may increase.
  • the upper limit with more preferable content of the said water-soluble polymer is 7 weight%.
  • conductive paste for gravure offset printing of the present invention in addition to the above components, functions such as appropriate viscosity, adhesion, drying property or printability according to the purpose of use within the range not impairing the effects of the present invention.
  • an optional component such as a polymer dispersant, an oligomer component, a surfactant, a thickener, or a surface tension adjuster may be added.
  • Such optional components are not particularly limited.
  • a commercially available polymer dispersant can be used as the polymer dispersant.
  • the commercially available polymer dispersing agent include Solsperse 11200, Solsperse 13940, Solsperse 16000, Solsperse 17000, Solsperse 18000, Solsperse 20000, Solsperse 24000, Solsperse 26000, Solsperse 27000, Solsperse 28000 (manufactured by Nippon Lubrizol) DISPERBYK-102, 110, 111, 170, 190.194N, 2015, 2090, 2096 (manufactured by Big Chemie Japan); EFKA-46, EFKA-47, EFKA-48, EFKA-49 (manufactured by EFKA Chemical); Polymer 100, Polymer 120, Polymer 150, Polymer 400, Polymer 401, Polymer 402, Polymer 403, Polymer 45 , Polymer 451, polymer 452, polymer 453 (manufactured by EFKA Chemical Co.); A
  • Solsperse 28000 examples include DA-375 and DA-1200. From the viewpoint of low temperature sinterability and dispersion stability, DISPER YK-102, Solsperse 11200, Solsperse 13940, Solsperse 16000, Solsperse 17000, Solsperse 18000, it is preferable to use Solsperse 28000 and the like.
  • the content of the polymer dispersant is preferably 0.1 to 15% by weight with respect to the entire conductive paste. If the content of the polymer dispersant is 0.1% by weight or more with respect to the entire conductive paste, the dispersion stability of the resulting conductive paste is improved, but if the content is too large, the dispersion stability is lowered. Will be. From such a viewpoint, the more preferable content of the polymer dispersant is 0.3 to 3% by weight, and the more preferable content is 0.5 to 2% by weight.
  • the thickener examples include clay minerals such as clay, bentonite or hectorite; emulsions such as polyester emulsion resins, acrylic emulsion resins, polyurethane emulsion resins or blocked isocyanates; methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, Examples thereof include cellulose derivatives such as hydroxypropylcellulose and hydroxypropylmethylcellulose; polysaccharides such as xanthan gum and guar gum, and these may be used alone or in combination of two or more.
  • clay minerals such as clay, bentonite or hectorite
  • emulsions such as polyester emulsion resins, acrylic emulsion resins, polyurethane emulsion resins or blocked isocyanates
  • methylcellulose, carboxymethylcellulose, hydroxyethylcellulose examples thereof include cellulose derivatives such as hydroxypropylcellulose and hydroxypropylmethylcellulose; polysaccharides such as xanthan gum and guar gum
  • a surfactant may be further added.
  • the coating surface becomes rough and the solid content tends to be uneven due to the difference in volatilization rate during drying.
  • the surfactant is not particularly limited, and an anionic surfactant, a cationic surfactant, a nonionic surfactant, and the like can be used. Specific examples include alkyl benzene sulfonate and quaternary ammonium salts. From the viewpoint of obtaining an effect with a small addition amount, a fluorine-based surfactant is more preferable.
  • the viscosity of the conductive paste is preferably 500 cP to 10,000 cP.
  • the viscosity can be measured with a cone plate viscometer (for example, a rheometer MCR301 manufactured by Anton Paar). The measurement is performed at a temperature of 25 ° C., and the viscosity at a cone rotation speed of 50 rpm can be adopted.
  • the viscosity can also be expressed as a shear viscosity, and the paste viscosity at a shear rate of 1 s ⁇ 1 is preferably 0.5 to 20 Pa ⁇ s. More preferably, the paste viscosity at a share rate of 1 s ⁇ 1 is 10 Pa ⁇ s or less, and the paste viscosity at a share rate of 100 s ⁇ 1 is 0.5 Pa ⁇ s or more.
  • Screen printing is also generally used for printing conductive patterns, but screen printing is stencil printing, so if the viscosity is low, paste will flow and it will be difficult to print according to the pattern.
  • a conductive paste having a higher viscosity than that for printing is used.
  • many conductive pastes used for screen printing have a viscosity range of about 50,000 to 100,000 cP. If a gravure plate for gravure offset printing is filled with a conductive paste for screen printing, the viscosity is too high and transfer to the blanket is difficult, and clogging occurs in the concave portion of the gravure plate.
  • the method for producing the conductive paste for gravure offset printing according to the present invention is not particularly limited. First, a silver fine particle dispersion is prepared, and the silver fine particle dispersion, the organic solvent, the water-soluble polymer, and, if necessary.
  • the conductive paste for gravure offset printing of the present invention can be obtained by mixing the above various components.
  • a first step of preparing a mixed solution of a silver compound that can be decomposed by reduction to produce silver and an amine, and reducing the silver compound in the mixed solution And a second step of generating silver fine particles in which the amine is attached to at least a part of the surface.
  • the first step it is preferable to add 2 mol or more of amine with respect to 1 mol of silver.
  • 2 mol or more of amine By making the addition amount of the amine 2 mol or more with respect to 1 mol of silver, an appropriate amount of the amine can be attached to the surface of the silver fine particles produced by reduction, and the silver fine particles are excellently dispersed in various dispersion media. And low-temperature sinterability can be imparted.
  • the composition of the liquid mixture in the first step and the reduction conditions (for example, the heating temperature and the heating time) in the second step are adjusted so that the particle diameter of the obtained silver fine particles is a nanometer size. It is preferable. This is because, by setting the particle diameter of the silver fine particles to a nanometer size, a melting point drop occurs and firing can be performed at a low temperature.
  • the particle diameter of the obtained silver fine particles is more preferably 1 to 200 nm. Micron-sized particles may be included as necessary.
  • the method for taking out the silver fine particles from the silver fine particle dispersion obtained in the second step is not particularly limited, and examples thereof include a method for washing the silver fine particle dispersion.
  • silver salts such as silver nitrate, silver sulfate, silver chloride, silver oxide, silver acetate, silver oxalate, silver formate, silver nitrite, silver chlorate, and silver sulfide. These are not particularly limited as long as they can be reduced, and may be dissolved in an appropriate solvent or may be used as dispersed in a solvent. These may be used alone or in combination. Of these, silver oxalate is preferred.
  • Silver oxalate is the simplest silver dicarboxylate, and the silver oxalate amine complex synthesized using silver oxalate is reduced at a low temperature in a short time. Is preferred. Furthermore, when silver oxalate is used, no by-product is generated during the synthesis, and only carbon dioxide derived from oxalate ions is generated outside the system.
  • Heating is preferred as a method for reducing the silver compound.
  • the heating method is not particularly limited.
  • a method of reducing the silver compound by the heating for example, a complex compound produced from a silver compound such as silver oxalate and an organic component such as amine is heated, and the oxalate ion contained in the complex compound or the like.
  • a method of aggregating atomic silver produced by decomposing a metal compound is mentioned. By the above method, silver fine particles coated with a protective film of an organic component such as amine can be produced.
  • the metal amine complex decomposition method for producing silver fine particles coated with amine by thermally decomposing a complex compound of silver compound in the presence of amine decomposition of silver amine complex which is a single kind of molecule is performed. Since atomic silver is generated by the reaction, it is possible to generate atomic silver uniformly in the reaction system, and the reaction is configured as compared to the case of generating silver atoms by reaction between multiple components. Inhomogeneity of the reaction due to fluctuations in the composition of the components is suppressed, which is particularly advantageous when a large amount of silver powder is produced on an industrial scale.
  • an amine molecule is coordinated to the silver atom to be generated, and the movement of the silver atom during aggregation is controlled by the action of the amine molecule coordinated to the silver atom. Inferred.
  • the metal amine complex decomposition method it is possible to produce metal particles that are very fine and have a narrow particle size distribution.
  • amine molecules form a relatively weak coordination bond on the surface of the silver fine particles to be produced, and these form a dense protective film on the surface of the silver fine particles, so that the storage stability is excellent. It becomes possible to produce organic coated silver fine particles having a clean surface.
  • the amine molecules forming the film can be easily desorbed by heating or the like, silver fine particles that can be sintered at a very low temperature can be produced.
  • the amine is mixed with the dispersant having an acid value constituting the coating of the coated silver fine particles. This facilitates the generation of a complex compound such as a complex compound, and makes it possible to produce the complex compound by mixing in a short time. Further, by mixing and using the amine, it is possible to produce coated silver fine particles having characteristics according to various uses.
  • the dispersion liquid containing silver fine particles coated with an amine or a protective dispersant having an acid value obtained as described above in addition to the silver fine particles, a metal salt counter ion, a dispersant, and a reducing agent residue Etc. exist, and the electrolyte concentration and organic substance concentration of the whole liquid tend to be high.
  • the liquid in such a state is likely to precipitate due to the coagulation of the metal particles due to high electrical conductivity. Or, even if it does not precipitate, if the counter ion of the metal salt, the excessive dispersant more than the amount necessary for dispersion, or the residue of the reducing agent remains, the conductivity may be deteriorated. Therefore, by washing the solution containing the silver fine particles to remove excess residues, the silver fine particles coated with the organic component can be reliably obtained.
  • a dispersion containing silver fine particles having at least a part of the surface coated with an organic component is allowed to stand for a certain period of time, and after removing the supernatant liquid, a solvent that precipitates silver fine particles (for example, water , Methanol, methanol / water mixed solvent, etc.), and a method of repeating the process several times by removing the supernatant liquid by standing again for a certain period of time.
  • a solvent that precipitates silver fine particles for example, water , Methanol, methanol / water mixed solvent, etc.
  • examples of other methods include a method of performing centrifugation instead of the above standing, a method of desalting with an ultrafiltration device, an ion exchange device, or the like.
  • the method for mixing the silver fine particle dispersion, the organic solvent, and the water-soluble polymer is not particularly limited, and can be performed by a conventionally known method using a stirrer or a stirrer.
  • An ultrasonic homogenizer with an appropriate output may be applied by stirring with a spatula or the like.
  • a fine conductive pattern can be formed by a gravure offset printing method using a gravure plate. That is, using the gravure offset printing method using a gravure plate, the gravure plate has a recess filled with a conductive paste for gravure offset printing on the printing surface, the width of the recess is 10 ⁇ m or less,
  • the conductive paste for gravure offset printing is also an embodiment of the present invention, and a method for forming a conductive pattern which is the conductive paste for gravure offset printing of the present invention.
  • FIG. 1 is a conceptual diagram schematically showing an example of a gravure offset printing method.
  • the gravure offset printing apparatus 100 includes a gravure plate 40 and a blanket 50.
  • the gravure offset printing apparatus 100 preferably further includes a pick-up roll 20 for applying the gravure offset printing conductive paste 10 to the gravure plate 40 and a blade 30 for removing excess conductive paste 10.
  • the gravure plate 40 has a recess 41 in which the printing surface is filled with the conductive paste 10 for gravure offset printing.
  • the width W of the recess 41 is 10 ⁇ m or less.
  • a conductive pattern having a line width of 10 ⁇ m or less can be formed.
  • the width W of the recess 41 is preferably 5 ⁇ m or less, and more preferably 3 ⁇ m or less.
  • the gravure offset printing conductive paste of the present invention a fine conductive pattern having a line width of 3 ⁇ m or less is formed without disconnection even when a gravure plate having a width W of 3 ⁇ m or less is used. be able to.
  • the gravure plate 40 may be plate-shaped or cylindrical.
  • the blanket 50 preferably has a silicone rubber layer.
  • the blanket 50 for example, Syl Blanc series manufactured by Kinyo Co., Ltd., # 700-STD manufactured by Fujikura Rubber Industrial Co., Ltd., or the like can be used.
  • the blanket 50 may be plate-shaped or cylindrical.
  • the substrate 60 is not particularly limited as long as it has at least one main surface on which the conductive paste 10 for gravure offset printing can be applied and baked by heating to mount the conductive pattern.
  • it is preferable that it is a base material excellent in heat resistance.
  • the conductive paste for gravure offset printing of the present invention can obtain a conductive pattern having sufficient conductivity even when heated and baked at a lower temperature than conventional conductive inks and conductive pastes. Therefore, it is possible to use a base material having a lower heat-resistant temperature than the conventional one in a temperature range higher than this low firing temperature.
  • Examples of the material constituting the substrate 60 include polyamide (PA), polyimide (PI), polyamideimide (PAI), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN). Examples include polyester, polycarbonate (PC), polyethersulfone (PES), vinyl resin, fluororesin, liquid crystal polymer, ceramics, glass, metal, and the like.
  • the substrate 60 may have various shapes such as a plate shape or a strip shape, and may be rigid or flexible. The thickness of the base material 60 can be appropriately selected. For the purpose of improving adhesion or adhesion, or other purposes, a base material on which a surface layer is formed or a base material that has been subjected to a surface treatment such as a hydrophilic treatment may be used.
  • the conductive pattern forming method includes a coating step of applying the gravure offset printing conductive paste 10 to the substrate 60, and baking the gravure offset printing conductive paste 10 applied to the substrate 60 to conduct the conductive pattern. It is preferable to have a firing step for forming the film.
  • FIG. 1 the arrows shown on the pickup roll 20, the gravure plate 40, and the blanket 50 indicate the respective rotation directions. Moreover, the arrow below the base material 60 indicates the moving direction of the base material 60.
  • the conductive paste 10 is applied to the gravure plate 40 by the pickup roll 20, and the excess conductive paste 10 is removed by the blade 30, whereby the conductive paste 10 is formed in the recess 41 provided on the printing surface of the gravure plate 40. Is filled ((a) of FIG. 1).
  • the conductive paste 10 filled in the concave portion 41 is transferred to the blanket 50 ((b) in FIG. 1).
  • the semi-solid / semi-liquid (wet or semi-dried) conductive paste 10 transferred to the blanket 50 is transferred to the substrate (adhered body) 60 ((c) of FIG. 1).
  • the substrate (adhered body) 60 ((c) of FIG. 1).
  • the conductive paste 10 When a thin line is printed using the conductive paste 10, a transfer defect is likely to occur during transfer from the gravure plate 40 to the blanket 50 and from the blanket 50 to the substrate 60. Since the conductive paste for offset printing contains a water-soluble polymer, the conductive paste 10 transferred onto the blanket 50 is difficult to spread, and has sufficient adhesion and transferability to the substrate 60. For example, even a conductive pattern having a line width of 10 ⁇ m or less, particularly a line width of 3 ⁇ m or less, can be formed without disconnection.
  • the viscosity of the conductive paste 10 may increase due to volatilization of the low boiling point solvent and absorption into the blanket 50 when left for a short time.
  • the organic solvent constituting the conductive paste 10 for gravure offset printing contains a hydroxyl group, the first organic solvent having a boiling point of 200 ° C. or higher at normal pressure, and / or the blanket swelling rate.
  • the second organic solvent When 2.0% or less of the second organic solvent is contained, absorption of the organic solvent into the blanket 50 is reduced, so that drying of the conductive paste 10 on the surface of the blanket 50 can be significantly suppressed. . Therefore, for example, a fine wire conductive pattern having a line width of 3 ⁇ m or less can be more suitably formed.
  • the firing temperature of the conductive paste in the firing step is preferably less than 140 ° C, and more preferably 120 ° C or less.
  • the method for performing the firing is not particularly limited, and for example, a conventionally known gear oven or the like can be used. Since the method for forming a conductive pattern of the present invention uses the conductive paste for gravure offset printing of the present invention, even when heated at a low temperature of less than 140 ° C. (preferably 120 ° C. or less), a conductive material that exhibits high conductivity. Sex patterns can be formed.
  • the lower limit of the firing temperature is not necessarily limited, and is a temperature at which a conductive pattern can be formed on a substrate, and the temperature at which the organic components and the like can be removed by evaporation or decomposition within a range not impairing the effects of the present invention.
  • the method for forming a conductive pattern of the present invention can be heat-treated at a low temperature of about 120 ° C., the conductive pattern can be formed even on a substrate that is relatively weak against heat. Further, the firing time is not particularly limited, and can be appropriately adjusted according to the firing temperature.
  • surface treatment of the substrate may be performed in order to further improve the adhesion between the substrate and the conductive pattern.
  • the surface treatment method include a method of performing dry treatment such as corona treatment, plasma treatment, UV treatment, and electron beam treatment, and a method of previously providing a primer layer and a conductive paste receiving layer on a substrate.
  • the film thickness of the conductive pattern after the firing step is, for example, 0.1 to 5 ⁇ m, preferably 0.1 to 1 ⁇ m. Since the method for forming a conductive pattern of the present invention uses the conductive paste for gravure offset printing of the present invention, a conductive pattern having sufficient conductivity can be obtained even when the film thickness is about 0.1 to 5 ⁇ m. It is done.
  • the film thickness t of the conductive pattern can be measured with a laser microscope (for example, a laser microscope VK-9510 manufactured by Keyence Corporation).
  • the film thickness t of the conductive pattern can be obtained using the following formula.
  • Formula: t m / (d ⁇ M ⁇ w)
  • m Weight of the conductive pattern (Measure the weight of the conductive pattern formed on the slide glass with an electronic balance)
  • d Conductive pattern density (g / cm 3 ) (10.5 g / cm 3 in the case of silver)
  • M Conductive pattern length (cm) (Measured length of conductive pattern formed on slide glass on a scale equivalent to JIS class 1)
  • w Conductive pattern width (cm) (Measured width of the conductive pattern formed on the slide glass on a scale equivalent to JIS class 1)
  • the volume resistance value of the conductive pattern obtained by the conductive pattern forming method of the present invention is preferably 110 ⁇ ⁇ cm or less, more preferably 100 ⁇ ⁇ cm or less, and 50 ⁇ ⁇ cm or less. Further preferred.
  • the volume resistance value can be measured, for example, by the following method. First, a conductive paste pattern with a width of 1 mm and a length of 1.5 cm is formed on a PET substrate, and sintered by baking at 120 ° C. for 30 minutes in a gear oven to form a coating (conductive pattern) To do. Thereafter, the resistance value R of the coating and the thickness t of the coating are measured.
  • the resistance value R of the film can be measured using, for example, “Digital Multimeter PM-3” manufactured by Sanwa Electric Instruments Co., Ltd.
  • the thickness t of the coating can be measured, for example, using a shape measurement laser microscope “VK-X100” manufactured by Keyence Corporation. From the obtained value, the volume resistance value can be converted based on the following formula (1).
  • (Volume resistance value ⁇ v) (resistance value R) ⁇ (film width w) ⁇ (film thickness t) / (distance L between terminals)
  • the manufacturing method of the conductive substrate which draws a conductive pattern on a base material using the formation method of the conductive pattern of the present invention is also one mode of the present invention.
  • the thing similar to the base material demonstrated with the formation method of the electroconductive pattern of this invention can be used.
  • the method for producing a conductive substrate of the present invention uses the method for forming a conductive pattern using the conductive paste for gravure offset printing of the present invention, for example, a thin wire having a line width of 10 ⁇ m or less, particularly a line width of 3 ⁇ m or less.
  • a conductive pattern can be formed. Therefore, a conductive substrate provided with a precise electronic circuit can be manufactured.
  • the conductive substrate include an electronic circuit substrate.
  • the conductive pattern is, for example, a wiring formed on an electronic circuit board.
  • the obtained mixed solution was transferred to an oil bath and heated and stirred at 120 ° C.
  • the reaction with the generation of carbon dioxide started immediately after the start of stirring, and then stirring was performed until the generation of carbon dioxide was completed, thereby obtaining a suspension in which silver fine particles were suspended in the amine mixture (No. 1). 2 steps).
  • the average particle diameter of the silver fine particles contained in the silver fine particle dispersion obtained in Synthesis Example 1 was 32 nm.
  • the average particle size is calculated by the dynamic light scattering method using a particle size distribution measuring device (model number: LB-550) manufactured by Horiba, Ltd. by diluting the obtained silver fine particle dispersion 100 times with a dispersion solvent. did. Turpineol was used as a dispersion solvent, and the solvent refractive index was measured as 1.383.
  • a water-soluble polymer mixed solution was prepared by dissolving 3.0 parts by weight of polyvinylpyrrolidone K30 as a water-soluble polymer in an organic solvent in which 3.0 parts by weight of Kyowadiol PD-9 and 14.0 parts by weight of terpineol were mixed. . If the above water-soluble polymer is difficult to dissolve, it may be heated as necessary.
  • Example 2 Example 1 except that the water-soluble polymer added is changed from 3.0 parts by weight of polyvinylpyrrolidone K30 to 3.0 parts by weight of polyvinylpyrrolidone K25 with respect to 80 parts by weight of the silver fine particle dispersion of Synthesis Example 1. Similarly, a conductive paste according to Example 2 was obtained.
  • Example 3 In Example 3, submicron-sized silver fine particles (submicron silver) (manufactured by Rare Metal Materials Laboratory, particle size distribution 0.2 to 1.0 ⁇ m) were used as silver fine particles. .
  • As the water-soluble polymer mixed solution 3.0 parts by weight of Kyowadiol PD-9 as an organic solvent and 13.0 parts by weight of terpineol, 3.0 parts by weight of polyvinylpyrrolidone K30 as a water-soluble polymer, A mixed solution in which 0.5 part by weight of CrystasenseMP was dissolved as a thickener and 0.5 part by weight of SOLPERSE41000 was dissolved as a polymer dispersant was used.
  • a conductive paste according to Example 3 was obtained in the same manner as Example 1 except that 20 parts by weight of the water-soluble polymer mixed solution was added to 80.0 parts by weight of the submicron-sized silver fine particles. It was.
  • Example 4 As silver fine particles, 60.0 parts by weight of the silver fine particle dispersion of Synthesis Example 1 and the submicron-sized silver fine particles used in Example 3 (manufactured by Rare Metals Laboratory, Inc., particle size distribution 0.2 to 1.0 ⁇ m) What mixed 20.0 weight part was used.
  • the conductivity according to Example 4 was the same as Example 1 except that 20.0 parts by weight of the water-soluble polymer mixed solution prepared in Example 3 was added to 80.0 parts by weight of the silver fine particles. A paste was obtained.
  • Example 5 In Example 5, instead of the organic solvent in which 3.0 parts by weight of Kyowadiol PD-9 and 14.0 parts by weight of terpineol were mixed, 3.0 weight parts of 2-ethyl-1,3-hexanediol isomer mixture was used. An organic solvent mixed with 14.0 parts by weight of terpineol was used. A conductive paste according to Example 5 was obtained in the same manner as in Example 1 except that 17.0 parts by weight of the mixed organic solvent was added to 80.0 parts by weight of the silver fine particle dispersion of Synthesis Example 1. It was.
  • Example 6 An organic solvent containing only 2-ethyl-1,3-hexanediol isomer mixture was used without mixing terpineol.
  • Example 1 was repeated except that 17.0 parts by weight of the 2-ethyl-1,3-hexanediol isomer mixture was added to 80.0 parts by weight of the silver fine particle dispersion of Synthesis Example 1.
  • a conductive paste according to Example 6 was obtained.
  • Example 7 The addition amount of the water-soluble polymer was changed from 3.0 parts by weight to 7.0 parts by weight, and an organic solvent mixed with 3.0 parts by weight of Kyowadiol PD-9 and 10.0 parts by weight of terpineol was used. A conductive paste according to Example 7 was obtained in the same manner as Example 1 except that.
  • Example 8> The addition amount of the water-soluble polymer was changed from 3.0 parts by weight to 8.0 parts by weight, and an organic solvent mixed with 3.0 parts by weight of Kyowadiol PD-9 and 9.0 parts by weight of terpineol was used.
  • a conductive paste according to Example 8 was obtained in the same manner as Example 1 except that.
  • Comparative Example 1 was carried out in the same manner as in Example 1 except that 3.0 parts by weight of non-water-soluble polyvinyl acetoacetal resin (manufactured by Sekisui Chemical Co., Ltd., ESREC KS-10) was added instead of polyvinyl pyrrolidone K30. Such a conductive paste was obtained.
  • Comparative Example 3 A conductive paste according to Comparative Example 3 was obtained in the same manner as Example 1 except that 3.0 parts by weight of polymethyl methacrylate that was not water-soluble was added instead of polyvinyl pyrrolidone K30.
  • Comparative example 4 A conductive paste according to Comparative Example 4 was obtained in the same manner as in Example 1 except that 3.0 parts by weight of a non-water-soluble vinyl chloride-vinyl acetate copolymer (Sorvain AL) was added instead of polyvinylpyrrolidone K30. It was.
  • a non-water-soluble vinyl chloride-vinyl acetate copolymer Sorvain AL
  • Comparative Example 5 A conductive paste according to Comparative Example 5 was obtained in the same manner as in Example 1 except that 3.0 parts by weight of a non-water-soluble vinyl chloride-vinyl acetate copolymer (Sorvain M5) was added instead of polyvinyl pyrrolidone K30. It was.
  • a non-water-soluble vinyl chloride-vinyl acetate copolymer (Sorvain M5) was added instead of polyvinyl pyrrolidone K30. It was.
  • Example 6 The same operation as in Example 1 was performed except that 3.0 parts by weight of non-water-soluble amorphous polyester resin (Byron 200) was added instead of polyvinylpyrrolidone K30, but Byron 200 was dissolved in the solvent. No conductive paste was obtained.
  • Byron 200 non-water-soluble amorphous polyester resin
  • the blanket was cut into 1 cm length and 1 cm width, and the weight was measured. Thereafter, the cut blanket was completely immersed in various organic solvents (20 g) and left for 10 hours. Immersion was performed under room temperature conditions (25 ° C. ⁇ 5 ° C.). After 10 hours, the blanket was taken out from each organic solvent, the adhered solvent was wiped off, the weight of the blanket after immersion was measured within 1 minute, and the weight increase rate before and after immersion was determined. The obtained numerical value was defined as the blanket swelling rate. Table 1 below shows the boiling point of each organic solvent and the measured blanket swelling rate.
  • Dilutable conductive paste was diluted 100 times with a dispersion medium (terpineol), and the dispersibility immediately after the dilution (initial) and the dispersibility after standing at room temperature for 1 week were evaluated visually.
  • the case where aggregation or silver mirror was not observed was evaluated as “ ⁇ ”
  • the case where aggregation / precipitation occurred was evaluated as “x”.
  • the concave portions of the first and second gravure plates are filled with the conductive pastes of the examples and comparative examples by a doctor blade, and then pressed and brought into contact with a rubber roller around which a silicone blanket is wound so that a desired pattern is formed on the blanket.
  • a silicone blanket was pressed and transferred to a sheet of PET film (thickness: 100 ⁇ m) and printed to produce printed patterns (printed wiring) having line widths of about 3 ⁇ m and 5 ⁇ m.
  • the silicone blanket Silblanc SP11-1 (rubber layer 0.6 mm, PET layer 0.25 mm) manufactured by Kinyo Co., Ltd. was used.
  • Adhesion test Adhesion was evaluated by the pull-off method. The evaluation was performed based on the state of rupture when Cellotape (registered trademark) was affixed to the printed wiring on the PET substrate used for the printability evaluation and peeled off. Specifically, the tape was strongly rubbed against five places of the printed wiring, and was peeled off in the vertical direction for evaluation. When the number of cellophane tapes that have been peeled off is 0 to 1, “ ⁇ ” is used for 2 to 3 sheets, “ ⁇ ” is used for 4 to 5 sheets, and “ ⁇ ” is used for 4 to 5 sheets. Even if it was a typical peeling, it was assumed that it was peeled and counted as one sheet.
  • Cellotape registered trademark
  • a pattern of the conductive paste having a width of 1 mm and a length of 1.5 cm is formed on the PET substrate.
  • Sintering was performed by firing at 120 ° C. for 30 minutes in a gear oven to form a coating (conductive pattern).
  • the resistance value R at both ends of the coating was measured.
  • the thickness t of the coating was measured using a shape measurement laser microscope “VK-X100” manufactured by Keyence Corporation. Then, based on the following formula (1), the volume resistance value was converted from the distance between the measurement terminals and the thickness t of the coating.
  • the conductive pastes of Examples 1 to 8 were all excellent in dispersibility and dilutability.
  • a conductive pattern with a width of 3 ⁇ m could be formed by gravure offset printing.
  • Examples 1, 2, and 5-8 using only nanometer-sized silver fine particles have higher printability
  • the results of Examples 3 and 4 show that not only nanometer-sized silver fine particles but also sub It has been found that a conductive pattern having a narrow line width can be printed by using micron-sized silver fine particles alone or by mixing nanometer-sized and submicron-sized silver fine particles.
  • Example 8 in which the addition amount of the water-soluble polymer was 8 parts by weight, fine line printing was possible although the volume resistance value was slightly increased.
  • the number of hydroxyl groups in the organic solvent is not a problem because it is possible to form a fine line only with a diol solvent without using a terpene solvent as the organic solvent. .

Abstract

La présente invention concerne une pâte conductrice pour impression offset par gravure, qui présente une conductivité suffisante et une bonne adhésion aux substrats, et qui permet l'impression de fines lignes. Cette pâte conductrice pour impression offset par gravure contient des particules d'argent, un solvant organique, et un polymère soluble dans l'eau. Les particules d'argent présentent une taille moyenne de particule de 1 µm ou moins. Le polymère soluble dans l'eau contient préférablement un composé polymérisable ayant une structure cyclique, et contient plus préférablement de la polyvinyl pyrrolidone.
PCT/JP2017/044157 2017-02-14 2017-12-08 Pâte conductrice pour impression offset par gravure, procédé de formation d'un motif conducteur, et procédé de fabrication d'un substrat conducteur WO2018150697A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021246858A1 (fr) * 2020-06-03 2021-12-09 Mimos Berhad Procédé de préparation de nanoparticules d'argent destinées à être utilisées comme encre
WO2023224555A3 (fr) * 2022-05-17 2024-01-04 National University Of Singapore Composition et matériau composite

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