WO2017163615A1 - 導電性組成物用バインダー樹脂、これを含む導電パターン形成用組成物及びポリウレタン - Google Patents

導電性組成物用バインダー樹脂、これを含む導電パターン形成用組成物及びポリウレタン Download PDF

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WO2017163615A1
WO2017163615A1 PCT/JP2017/003343 JP2017003343W WO2017163615A1 WO 2017163615 A1 WO2017163615 A1 WO 2017163615A1 JP 2017003343 W JP2017003343 W JP 2017003343W WO 2017163615 A1 WO2017163615 A1 WO 2017163615A1
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polyurethane
mass
metal
conductive
composition
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PCT/JP2017/003343
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English (en)
French (fr)
Japanese (ja)
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周平 米田
内田　博
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昭和電工株式会社
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Priority to KR1020187026815A priority Critical patent/KR102121758B1/ko
Priority to JP2018507093A priority patent/JP6994455B2/ja
Priority to CN201780019859.9A priority patent/CN109071938B/zh
Publication of WO2017163615A1 publication Critical patent/WO2017163615A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • 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
    • 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
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
    • 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
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • 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
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern

Definitions

  • the present invention relates to a binder resin for a conductive composition, a composition for forming a conductive pattern including the binder resin, and polyurethane.
  • a method of forming a wiring pattern by a lithography method using a combination of a copper foil and a photoresist is generally used, but this method has many processes, drainage, The burden of waste liquid treatment is large, and environmental improvement is desired.
  • a method of patterning a metal thin film produced by a heat deposition method or a sputtering method by a photolithography method is also known.
  • the heating vapor deposition method and the sputtering method are indispensable for a vacuum environment, and the price is very expensive. When applied to a wiring pattern, it is difficult to reduce the manufacturing cost.
  • Patent Document 1 discloses a step of discharging a conductive inorganic composition containing conductive inorganic metal particles on a substrate, and a conductive organic composition containing a conductive organometallic complex on the conductive inorganic composition.
  • a method for manufacturing a substrate is disclosed which includes a step of discharging the conductive inorganic composition and the conductive organic composition.
  • the method of using light energy or microwaves for heating can be said to be a very good method because it may heat only the ink portion.
  • the substrate may not be able to withstand the energy as in the case of firing in a heating furnace.
  • JP 2010-183082 A Special table 2008-522369 Pamphlet of WO2010 / 110969 Special table 2010-528428 Pamphlet of WO2013 / 077447 WO2015 / 064567 pamphlet
  • the conductive pattern formed on the substrate is more desirable as the electrical conductivity is higher (the volume resistivity is lower).
  • the lower the sintering energy for reaching the same electrical conductivity is, the lower the electrical conductivity for forming the conductive pattern is.
  • the composition can be said to have high performance. Therefore, it is desirable that the above-described conventional conductive composition also improve the conductivity with a lower sintering energy.
  • An object of the present invention is to provide a binder resin for a conductive composition capable of improving the conductivity of a conductive pattern with a low sintering energy, a composition for forming a conductive pattern and a polyurethane containing the binder resin.
  • an embodiment of the present invention is a binder resin for a conductive composition, wherein the binder resin is a carboxylate metal salt moiety represented by (COO) n M in a polymer skeleton. It includes a polyurethane having (M is a metal atom selected from metals belonging to Group 11 of the periodic table, and n is a valence of the metal atom M).
  • the polyurethane includes a urethane bond unit of (a1) a polyisocyanate compound and (a2) a dihydroxy compound having a carboxyl group as a structural unit.
  • the metal constituting the metal salt contains either silver or copper.
  • the (a2) carboxyl group-containing dihydroxy compound is preferably at least one of 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid.
  • the (a1) polyisocyanate compound is preferably an alicyclic polyisocyanate, and the alicyclic polyisocyanate is 3-isocyanate methyl-3,3,5-trimethylcyclohexane (IPDI, isophorone diisocyanate), Alternatively, bis- (4-isocyanatocyclohexyl) methane (hydrogenated MDI) is more preferable.
  • composition for conductive pattern formation Comprising: The said binder resin for conductive compositions (A), a conductive material (B), and the said binder resin for conductive compositions are included. And a solvent (C) that dissolves.
  • a conductive material (B) metal particles (B1), metal nanowires and / or metal nanotubes (B2) can be used.
  • the ratio of the metal particles (B1) to the entire conductive pattern forming composition is 20% by mass to 95% by mass, and the binder resin for the conductive composition is dissolved.
  • the content of the solvent (C) is 5 mass% to 80 mass%, and the binder resin for conductive composition (A) is 1 mass part to 15 mass parts with respect to 100 mass parts of the metal particles (B1). Is preferred.
  • the ratio of metal nanowires and / or metal nanotubes (B2) to the entire conductive pattern forming composition is 0.01% by mass to 10%.
  • the content of the solvent (C) for dissolving the binder resin for conductive composition is 90% by mass or more, and the binder resin for conductive composition (A) is a metal nanowire and / or metal nanotube (B2) 100.
  • the amount is preferably 10 to 400 parts by mass with respect to parts by mass.
  • the metal constituting the conductive material (B) preferably contains either silver or copper.
  • Another embodiment of the present invention is a polyurethane containing at least one of the structural units represented by the following formula (1).
  • the conductivity of the conductive pattern can be improved with a lower sintering energy than when a binder resin containing no metal atom is used in the polymer skeleton.
  • FIG. 3 is a graph showing the results of simultaneous differential thermal-thermogravimetric measurement of polyurethane silver salt (using silver nitrate) according to Example 1. It is a figure which shows the differential thermal-thermogravimetric simultaneous measurement result of the polyurethane silver salt (use silver oxide) concerning Example 2.
  • FIG. It is a figure which shows the measurement result of the infrared rays (IR) absorption spectrum of the polyurethane synthesize
  • FIG. It is a figure which shows the measurement result of IR absorption spectrum of the polyurethane silver salt concerning Example 1.
  • NMR nuclear magnetic resonance
  • FIG. 1 It is a figure which shows the measurement result of the NMR spectrum of the polyurethane silver salt concerning Example 1.
  • FIG. It is a figure which shows the differential thermal-thermogravimetric simultaneous measurement result of the polyurethane copper salt (use copper sulfate) concerning Example 3.
  • FIG. It is a figure which shows the measurement result of IR absorption spectrum of the polyurethane copper salt concerning Example 3.
  • FIG. It is a figure which shows the differential thermal-thermogravimetric simultaneous measurement result of the polyurethane silver salt (using silver nitrate) concerning Example 4.
  • FIG. 5 shows the differential thermal-thermogravimetric simultaneous measurement result of the polyurethane silver salt (use silver oxide) concerning Example 5.
  • FIG. It is a figure which shows the differential thermal-thermogravimetric simultaneous measurement result of the polyurethane silver salt (use silver nitrate) concerning Example 6.
  • FIG. It is a figure which shows the differential thermal-thermogravimetric simultaneous measurement result of the polyurethane silver salt (use silver nitrate) concerning Example 7.
  • FIG. It is a figure which shows the differential thermal-thermogravimetric simultaneous measurement result of the polyurethane silver salt (using silver nitrate) concerning Example 8.
  • FIG. It is a figure which shows the differential thermal-thermogravimetric simultaneous measurement result of the polyurethane silver salt (uses silver oxide) concerning Example 10.
  • FIG. It is a figure which shows the differential thermal-thermogravimetric simultaneous measurement result of the polyurethane silver salt (use silver oxide) concerning Example 11.
  • FIG. It is a figure which shows the differential thermal-thermogravimetric simultaneous measurement result of the polyurethane silver salt (uses silver oxide) concerning Example 12.
  • FIG. It is a figure which shows the differential thermal-thermogravimetric simultaneous measurement result of the polyurethane copper salt (using copper hydroxide) concerning Example 16.
  • the binder resin for a conductive composition according to the present embodiment is a metal atom selected from metals belonging to Group 11 of the periodic table, wherein the carboxylate metal salt moiety represented by (COO) n M in the polymer skeleton. , N includes a polyurethane having a valence of a metal atom M).
  • the polyurethane of this embodiment includes a urethane bond unit of at least a polyisocyanate compound and a dihydroxy compound having a carboxyl group in a structural unit.
  • a urethane bond unit between a polyisocyanate compound and a polyol other than a dihydroxy compound having a carboxyl group can be included. That is, it may be a polyurethane resin obtained by mixing (a1) a polyisocyanate compound and (a2) a dihydroxy compound having a carboxyl group with (a3) a polyol compound other than (a2) as required. .
  • (A1) Polyisocyanate Compound (a1) As the polyisocyanate compound, diisocyanate having two isocyanate groups per molecule is usually used.
  • the polyisocyanate compound include aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and araliphatic polyisocyanate.
  • a small amount of polyisocyanate having 3 or more isocyanate groups such as triphenylmethane triisocyanate can be used as long as the polyurethane containing carboxyl groups does not gel.
  • An alicyclic polyisocyanate is preferred in that it has less yellowing.
  • aliphatic polyisocyanate examples include 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene diisocyanate, 2 2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,2′-diethyl ether diisocyanate, dimer acid diisocyanate and the like.
  • Examples of the alicyclic polyisocyanate include 1,4-cyclohexane diisocyanate, 1,3-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) cyclohexane, 3-isocyanate methyl-3,3,5- Examples thereof include trimethylcyclohexane (IPDI, isophorone diisocyanate), bis- (4-isocyanatocyclohexyl) methane (hydrogenated MDI), hydrogenated (1,3- or 1,4-) xylylene diisocyanate, norbornane diisocyanate, and the like.
  • IPDI trimethylcyclohexane
  • isophorone diisocyanate isophorone diisocyanate
  • bis- (4-isocyanatocyclohexyl) methane hydrogenated (1,3- or 1,4-) xylylene diisocyanate
  • norbornane diisocyanate
  • aromatic polyisocyanate examples include 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, (1 , 2,1,3 or 1,4) -xylene diisocyanate, 3,3′-dimethyl-4,4′-diisocyanate biphenyl, 3,3′-dimethyl-4,4′-diisocyanate diphenylmethane, 1,5- Examples thereof include naphthylene diisocyanate, 4,4′-diphenyl ether diisocyanate, and tetrachlorophenylene diisocyanate.
  • Examples of the araliphatic polyisocyanate include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, ⁇ , ⁇ , ⁇ ′, ⁇ ′-tetramethylxylylene diisocyanate, and 3,3′-methylene ditolylene. -4,4'-diisocyanate and the like.
  • diisocyanates can be used singly or in combination of two or more.
  • IPDI 3-isocyanate methyl-3,3,5-trimethylcyclohexane
  • MDI bis- (4-isocyanatocyclohexyl) methane
  • (A2) Dihydroxy compound having a carboxyl group (a2)
  • the dihydroxy compound having a carboxyl group has a molecular weight of 200 or less having either a hydroxy group or two selected from a hydroxyalkyl group having 1 or 2 carbon atoms.
  • Carboxylic acid or aminocarboxylic acid is preferable in that the crosslinking point can be controlled. Specific examples include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, N, N-bishydroxyethylglycine, N, N-bishydroxyethylalanine, and the like. In view of solubility, 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid are particularly preferred.
  • These (a2) dihydroxy compounds having a carboxyl group can be used singly or in combination of two or more.
  • (A3) Polyol compound The number average of (a3) polyol compound (however, (a3) polyol compound does not include the above-mentioned (a2) dihydroxy compound having a carboxyl group) that can be used in combination as needed.
  • the molecular weight is usually 250 to 50,000, preferably 400 to 10,000, more preferably 500 to 5,000. This molecular weight is a value in terms of polystyrene measured by GPC under the conditions described later.
  • the number average molecular weight is 50,000 or less, the solubility in a solvent is high, and the viscosity becomes an appropriate viscosity even after dissolution, which is preferable in terms of easy use.
  • the polyol compound is, for example, a polycarbonate polyol, a polyether polyol, a polyester polyol, a polylactone polyol, a polybutadiene polyol, a hydroxylated polysilicon at both ends, and an oxygen atom only in the hydroxyl group and having 18 to 72 carbon atoms. It is a polyol compound.
  • the polycarbonate polyol can be obtained by reacting a diol having 3 to 18 carbon atoms with a carbonate or phosgene as a raw material, and is represented by the following structural formula (2), for example.
  • R 1 is a residue obtained by removing a hydroxyl group from the corresponding diol (HO—R 1 —OH), and n 1 is a positive integer, preferably 2 to 50.
  • n 1 is 50 or less, deterioration of solubility due to excessive increase in molecular weight can be suppressed.
  • the polycarbonate polyol represented by the formula (2) includes 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1 , 5-pentanediol, 1,8-octanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10 It can be produced by using decamethylene glycol or 1,2-tetradecanediol as a raw material.
  • the polycarbonate polyol may be a polycarbonate polyol having a plurality of types of alkylene groups in its skeleton (copolymerized polycarbonate polyol).
  • copolymerized polycarbonate polyol is often advantageous from the viewpoint of preventing crystallization of polyurethane having a carboxyl group.
  • the polyether polyol is obtained by dehydration condensation of a diol having 2 to 12 carbon atoms or ring-opening polymerization of an oxirane compound, oxetane compound or tetrahydrofuran compound having 2 to 12 carbon atoms. It is represented by the structural formula (3).
  • R 2 is a residue obtained by removing a hydroxyl group from the corresponding diol (HO—R 2 —OH), and n 2 is a positive integer, preferably 4 to 50.
  • the above diols having 2 to 12 carbon atoms can be used alone to form a homopolymer, or a combination of two or more can be used as a copolymer.
  • n 2 is 50 or less, deterioration of solubility due to excessive increase in molecular weight can be suppressed.
  • polyether polyol represented by the above formula (3) examples include polyethylene glycol, polypropylene glycol, poly-1,2-butylene glycol, polytetramethylene glycol (poly 1,4-butanediol), poly Examples include polyalkylene glycols such as -3-methyltetramethylene glycol and polyneopentyl glycol. Further, for the purpose of improving the compatibility of (polyether polyol) and the hydrophobicity of (polyether polyol), these copolymers such as 1,4-butanediol-neopentyl glycol can also be used.
  • the polyester polyol is obtained by dehydration condensation of a dicarboxylic acid and a diol or an ester exchange reaction between an esterified product of a lower alcohol of a dicarboxylic acid and a diol, and is represented by the following structural formula (4), for example. .
  • R 3 is a residue obtained by removing the hydroxyl group from the corresponding diol (HO—R 3 —OH), and R 4 represents two carboxyl groups from the corresponding dicarboxylic acid (HOCO—R 4 —COOH).
  • n 3 is a positive integer, preferably 2 to 50. When n 3 is 50 or less, deterioration of solubility due to excessive increase in molecular weight can be suppressed.
  • diol examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, , 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,3-cyclohexanedimethanol, 1,4- Cyclohexanedimethanol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decamethylene glycol or 1,2-tetradecanediol, 2,4-diethyl-1,5-pentanediol, Butylethylpropanediol, 1,3-cyclohexanedimethanol, 3-xylylene glycol
  • dicarboxylic acid examples include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, brassic acid, 1,4-cyclohexanedicarboxylic acid, hexa Hydrophthalic acid, methyltetrahydrophthalic acid, endomethylenetetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4- And naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid.
  • the polylactone polyol is obtained by a condensation reaction of a lactone ring-opening polymer and a diol, or a condensation reaction of a diol and a hydroxyalkanoic acid, and is represented, for example, by the following structural formula (5).
  • R 5 is a residue obtained by removing a hydroxyl group and a carboxyl group from the corresponding hydroxyalkanoic acid (HO—R 5 —COOH), and R 6 is a corresponding diol (HO—R 6 —OH). It is a residue excluding a hydroxyl group, and n 4 is a positive integer, preferably 2 to 50. When n 4 is 50 or less, deterioration in solubility due to excessive increase in molecular weight can be suppressed.
  • hydroxyalkanoic acid examples include 3-hydroxybutanoic acid, 4-hydroxypentanoic acid, and 5-hydroxyhexanoic acid.
  • the polybutadiene polyol is, for example, a diol obtained by polymerizing butadiene or isoprene by anionic polymerization and introducing hydroxyl groups at both ends by terminal treatment, and a diol obtained by hydrogen reduction of these double bonds.
  • polybutadiene polyol examples include hydroxylated polybutadiene mainly having 1,4-repeating units (for example, Poly bd R-45HT, Poly bd R-15HT (manufactured by Idemitsu Kosan Co., Ltd.)), hydroxylated hydrogenation Polybutadiene (for example, Polytail (registered trademark) H, Polytail (registered trademark) HA (manufactured by Mitsubishi Chemical Corporation)), hydroxylated polybutadiene having mainly 1,2-repeating units (for example, G-1000, G-2000, G-3000 (manufactured by Nippon Soda Co., Ltd.)), hydroxylated hydrogenated polybutadiene (for example, GI-1000, GI-2000, GI-3000 (manufactured by Nippon Soda Co., Ltd.)), hydroxylated polyisoprene (for example, Poly IP ( Idemitsu Kosan Co., Ltd.)), hydroxylated
  • R 7 is independently an aliphatic hydrocarbon divalent residue or an aromatic hydrocarbon divalent residue having 2 to 50 carbon atoms
  • n 5 is a positive integer, preferably 2 to 50 It is.
  • R 8 are each independently an aliphatic hydrocarbon group or an aromatic hydrocarbon group having 1 to 12 carbon atoms.
  • Examples of the commercial products of the both-end hydroxylated polysilicone include “X-22-160AS, KF6001, KF6002, KF-6003” manufactured by Shin-Etsu Chemical Co., Ltd., and the like.
  • Specific examples of the “polyol compound having an oxygen atom only in the hydroxyl group and having 18 to 72 carbon atoms” include a diol compound having a skeleton obtained by hydrogenating dimer acid.
  • SOVERMOL registered trademark
  • a diol having a molecular weight of 300 or less that does not have a repeating unit can be used as the (a3) polyol compound as long as the effects of the present invention are not impaired.
  • specific examples of such low molecular weight diols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, and 1,4-butane.
  • Diol 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decamethylene glycol, 1,2-tetradecanediol, 2,4-diethyl-1,5-pentanediol, butylethylpropanediol 1,3-cyclohexanedimethanol, 1,3-xylylene glycol, 1,4-xylylene Call, diethylene glycol, triethylene glycol, or dipropylene glycol.
  • the above-mentioned polyurethane having a carboxyl group can be synthesized only from the above components (a1), (a2) or (a1), (a2), (a3). And (a4) monohydroxy compound and / or (a5) monoisocyanate compound may be synthesized for the purpose of imparting properties or suppressing the influence of the isocyanate group or hydroxyl group residue at the end of the polyurethane. it can.
  • Monohydroxy compounds can be used singly or in combination of two or more.
  • 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, allyl alcohol, glycolic acid, and hydroxypivalic acid are preferable, and 2-hydroxyethyl (meth) ) Acrylate and 4-hydroxybutyl (meth) acrylate are more preferred.
  • (a4) monohydroxy compounds include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, t-butanol, amyl alcohol, hexyl alcohol, octyl alcohol and the like.
  • Monoisocyanate compound include (meth) acryloyloxyethyl isocyanate, 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate to diisocyanate compounds, Cyclohexanedimethanol mono (meth) acrylate, caprolactone or alkylene oxide adduct of each (meth) acrylate, glycerin di (meth) acrylate, trimethylol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta Radicals such as mono-adducts of (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, allyl alcohol, and allyloxyethanol It includes compounds having a carbon double bond - carbon.
  • examples of the monoisocyanate hydroxy compound used for the purpose of suppressing the influence of the terminal hydroxyl residue include phenyl isocyanate, hexyl isocyanate, and dodecyl isocyanate.
  • the above-mentioned polyurethane having a carboxyl group is obtained by using the above-mentioned (a1) polyisocyanate compound and (a2) carboxyl in the presence or absence of a known urethanization catalyst such as dibutyltin dilaurate using an appropriate organic solvent. It can be synthesized by reacting a dihydroxy compound having a group, (a3) a polyol compound, and (a4) a monohydroxy compound or (a5) a monoisocyanate compound as necessary. It is not necessary to consider the mixing of tin and the like.
  • the organic solvent is not particularly limited as long as it has low reactivity with the isocyanate compound, but when the polyurethane obtained after the reaction is used as a raw material for the conductive pattern forming composition (conductive ink) in a solution, A solvent having a boiling point of 110 ° C. or higher, preferably 150 ° C. or higher, more preferably 200 ° C. or higher is preferable. When the boiling point is 110 ° C. or higher, volatilization of the solvent during ink preparation can be suppressed.
  • solvents examples include toluene, xylene, ethylbenzene, nitrobenzene, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether monoacetate, propylene glycol monomethyl ether monoacetate, propylene glycol monoethyl ether monoacetate, diethylene Propylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, ethyl ethoxypropionate, n-butyl acetate, isoamyl acetate, ethyl lactate, cyclohexanone, N, N -Dimethylformamide, N, N-dimethylacetate Amide, N- methylpyrrolidone, .gamma.-butyrolactone, and di
  • the organic solvent with low solubility of the polyurethane to be produced is not preferable, and considering that polyurethane is used as the raw material of the ink in electronic material applications, among these, in particular, propylene glycol monomethyl ether monoacetate, propylene glycol monoacetate.
  • propylene glycol monomethyl ether monoacetate propylene glycol monoacetate.
  • Ethyl ether monoacetate, dipropylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, ⁇ -butyrolactone and the like are preferable.
  • the obtained polyurethane is used as a conductive ink raw material after solvent substitution, it is more preferable to use a solvent having a boiling point lower than 110 ° C. because the lower the boiling point, the easier the distillation under reduced pressure.
  • a solvent having a boiling point lower than 110 ° C. examples include cyclohexane, ethyl acetate, acetone, methyl ethyl ketone, chloroform, methylene chloride and the like. Even when a solvent having a boiling point of 110 ° C. or higher is used, there is no problem in carrying out the solvent replacement.
  • the order in which the raw materials are charged is not particularly limited.
  • (a2) a dihydroxy compound having a carboxyl group and (a3) a polyol compound are charged first and dissolved in a solvent, and more preferably 20 to 150 ° C. Is added dropwise with (a1) polyisocyanate compound at 50 to 120 ° C., and then reacted at 30 to 160 ° C., more preferably at 50 to 130 ° C.
  • the temperature at the time of dropping is 20 ° C. or higher
  • (a2) the dihydroxy compound having a carboxyl group is easily dissolved, and when it is 150 ° C. or lower, runaway due to rapid progress of the reaction at the time of dropping can be prevented.
  • the starting molar ratio of the raw material is adjusted according to the molecular weight and acid value of the target polyurethane resin, but when the (a4) monohydroxy compound is introduced into the polyurethane resin, the end of the polyurethane molecule becomes an isocyanate group.
  • these charged molar ratios are such that (a1) isocyanate group of polyisocyanate compound: ((a2) hydroxyl group of dihydroxy compound having carboxyl group + (a3) hydroxyl group of polyol compound) is 0.5 to 1. .5: 1, preferably 0.8 to 1.2: 1, more preferably 0.95 to 1.05. (A1) When the molar ratio of isocyanate groups of the polyisocyanate compound is 0.5 or more and 1.5 or less, it becomes easy to obtain a polyurethane having a large molecular weight.
  • the ratio of (a2) the hydroxyl group of the dihydroxy compound having a carboxyl group to ((a2) the hydroxyl group of the dihydroxy compound having a carboxyl group + (a3) the hydroxyl group of the polyol compound) is preferably 1: 0.05 to 1, preferably It is 1: 0.35 to 1, more preferably 1: 0.45 to 1. (A2) When the ratio of the hydroxyl group of the dihydroxy compound having a carboxyl group is 0.05 or more, an amount of a metal salt site necessary for improving the electrical conductivity can be introduced into the polyurethane.
  • the number of moles of the (a1) polyisocyanate compound is made larger than the number of moles of ((a2) dihydroxy compound having a carboxyl group + (a3) polyol compound), and (a4)
  • the monohydroxy compound is preferably used in an amount of 0.5 to 1.5 times mol, preferably 0.8 to 1.2 times mol, based on the excess number of moles of isocyanate groups.
  • the molar amount of the monohydroxy compound is 0.5 times the molar amount or more, the isocyanate group at the terminal of the polyurethane can be reduced, and when it is 1.5 times the molar amount or less, the unreacted monohydroxy compound Can be prevented from adversely affecting the subsequent processes.
  • the reaction between the (a2) dihydroxy compound having a carboxyl group and the (a3) polyol compound and the (a1) polyisocyanate compound is almost completed.
  • the (a4) monohydroxy compound is added to the reaction solution at 20 to 150 ° C., more preferably 70 ° C. Add dropwise at ⁇ 120 ° C and then hold at the same temperature to complete the reaction.
  • the dropping and the reaction temperature are 20 ° C. or higher, the reaction of the remaining isocyanate group and (a4) monohydroxy group proceeds rapidly, and when the temperature is 150 ° C. or lower, the reaction rapidly proceeds during the dropping. Can be prevented.
  • the number of moles of ((a2) dihydroxy compound having a carboxyl group + (a3) polyol compound) is made larger than the number of moles of (a1) polyisocyanate compound, and an excess of hydroxyl groups
  • the molar amount is 0.5 to 1.5 times the molar amount, preferably 0.8 to 1.2 times the molar amount.
  • the molar amount of the monoisocyanate compound is 0.5 times or more, it is possible to prevent the hydroxyl group from remaining at the terminal of the polyurethane, and when it is 1.5 times or less, the monoisocyanate compound. Can be prevented from adversely affecting the subsequent processes.
  • the reaction between the (a2) dihydroxy compound having a carboxyl group and the (a3) polyol compound and the (a1) polyisocyanate compound is almost completed.
  • the (a5) monoisocyanate compound is reacted in the reaction solution at 20 to 150 ° C., more preferably 50 to The reaction is completed by dropping at 120 ° C. and then holding at the same temperature.
  • the dropping and reaction temperature are 20 ° C. or higher, the reaction between the remaining hydroxyl group and the (a5) monoisocyanate compound proceeds rapidly, and when it is 150 ° C. or lower, the reaction proceeds rapidly during the dropping and runs away. Can be prevented.
  • the number average molecular weight of the polyurethane having a carboxyl group is preferably 1,000 to 100,000, and more preferably 3,000 to 50,000.
  • the molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (hereinafter referred to as GPC).
  • GPC gel permeation chromatography
  • the acid value of the polyurethane having a carboxyl group is preferably 5 to 160 mgKOH / g, more preferably 10 to 150 mgKOH / g.
  • an amount of the metal salt portion necessary for improving the conductivity can be introduced into the polyurethane.
  • the solubility to a solvent is favorable in it being 160 mgKOH / g or less, and there are many kinds of the solvent which can be used.
  • the acid value of resin is the value measured by the method described in the Example mentioned later.
  • the metal atom M forming a salt with all or part of the carboxyl groups of the polyurethane having a carboxyl group is a metal belonging to Group 11 of the periodic table.
  • the metal atom M silver and copper are preferable because of low volume resistivity.
  • the polyurethane metal salt may be synthesized by any method. For example, after neutralizing the carboxyl group in the said polyurethane with a base, it is made to react with the metal salt of inorganic acids, such as nitric acid, a sulfuric acid, and carbonic acid.
  • a basic oxide or hydroxide of a metal such as a carboxyl group and silver oxide, silver hydroxide, copper oxide, cuprous oxide, copper hydroxide or the like can be directly reacted.
  • the powder of the basic oxide or hydroxide may be added directly to the polyurethane solution, or the powder is dispersed in advance in a solvent. To the polyurethane solution.
  • the reaction temperature is 20 ° C to 150 ° C, more preferably 20 ° C to 120 ° C.
  • the reaction temperature is 20 ° C to 150 ° C, more preferably 20 ° C to 120 ° C.
  • the reaction proceeds rapidly, and even if the solid content concentration of the metal salt obtained as a solution is increased, the fluidity is increased, so that the reaction can be promoted. Therefore, the degree of freedom of the composition of the ink (conductive pattern forming composition) can be increased.
  • the ratio of being a metal salt is unclear because it is affected by the chemical structure, molecular weight, and acid value of the original polyurethane, but is preferably 5 to 100 mol%. 35 to 100 mol% is preferred.
  • the effect which improves electrical conductivity can be expressed as the ratio made into metal salt is 5 mol% or more.
  • the conductive pattern forming composition according to the embodiment includes the binder resin for conductive composition (A), the conductive material (B), and a solvent (C) for dissolving the binder resin for conductive composition. It is configured.
  • the conductive material (B) that can be used is not particularly limited as long as it has conductivity. It is preferable to use mainly at least one of metal particles (including metal nanoparticles), metal nanowires, and metal nanotubes.
  • a metal nanowire and / or a metal nanotube is a thin wire metal with a diameter of nanometer order size.
  • a metal nanowire is a wire shape, and a metal nanotube is a conductive material having a porous or non-porous tube shape. Material.
  • “wire” and “tube” are both linear, but the former is not hollow (hollow) along the long axis, and the latter is long along the long axis. Intended to be hollow (hollow).
  • the property may be flexible or rigid.
  • a metal nanowire or a metal nanotube may be used, or a mixture of both may be used.
  • the metal constituting the conductive material may be the same type of metal as the metal forming the metal salt in the binder resin for conductive compositions, or may be a different metal.
  • the metal species is appropriately selected according to the conductivity, corrosion resistance and other physical properties required for the conductive pattern forming composition (conductive ink). For example, silver, copper, nickel, gold, platinum, palladium, aluminum, etc. can be mentioned. In particular, it is preferable to use silver or copper because of its high conductivity.
  • the shape of the metal particles is not particularly limited, but the use of flat particles is preferable in that the area where the particles are in contact with each other is increased and resistance is easily reduced.
  • the shape of the flat metal particles was changed by observing 10 points by SEM at a magnification of 10,000 times to measure the thickness and width of the flat metal particles, and the thickness was obtained as the number average value thereof.
  • the thickness is preferably 5 nm to 2 ⁇ m, more preferably 20 nm to 1 ⁇ m.
  • an average particle diameter (approximate particle diameter in the case of spherical particles) of other shapes of metal particles including flat metal particles for example, those in the range of 0.01 to 100 ⁇ m can be used.
  • the thickness is preferably in the range of 0.02 to 50 ⁇ m, more preferably in the range of 0.04 to 10 ⁇ m.
  • the average particle diameter is a median diameter (D 50 ) measured by a laser diffraction method.
  • SALD-3100 manufactured by Shimadzu Corporation
  • LA-950V2 manufactured by Horiba Seisakusho
  • the average diameter of metal nanowires and metal nanotubes is preferably thinner from the viewpoint of conductivity, but thicker from the viewpoint of strength and ease of handling. Therefore, the average value of the wire diameter is preferably 500 nm or less, more preferably 200 nm or less, still more preferably 100 nm or less, and particularly preferably 80 nm or less from the viewpoint of conductivity. On the other hand, from the viewpoints of strength and ease of handling, the thickness is preferably 1 nm or more, more preferably 5 nm or more, and further preferably 10 nm or more.
  • the average length of the major axis of the metal nanowires and metal nanotubes is preferably longer from the viewpoint of conductivity, but it is necessary to limit the length to some extent in order to cope with the fine pattern. Therefore, the average value of the wire length is preferably 1 ⁇ m or more from the viewpoint of conductivity, more preferably 2 ⁇ m or more, and further preferably 5 ⁇ m or more. On the other hand, it is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, and even more preferably 30 ⁇ m or less from the viewpoint of handling fine patterns.
  • the average diameter thickness and the average long axis length satisfy the above ranges, and the average aspect ratio is preferably larger than 5, more preferably 10 or more, More preferably, it is more preferably 200 or more.
  • the aspect ratio is a value obtained by a / b when the average diameter of the metal nanowires and metal nanotubes is approximated as b and the average length of the major axis is approximated as a.
  • a and b can be arbitrarily measured using a scanning electron microscope and obtained as an average value.
  • metal oxides and carbon-based materials can be used.
  • the metal constituting the metal oxide particles may be the same type of metal as the metal forming the metal salt in the binder resin for conductive compositions, or may be a different metal.
  • the metal species is appropriately selected according to the electrical conductivity, corrosion resistance and other physical properties required for the conductive pattern forming composition.
  • the metal oxide include indium tin oxide (ITO), zinc oxide, tin dioxide, indium oxide and the like.
  • the carbon-based material include carbon black, graphite, and carbon nanotube.
  • the shape of the metal oxide particles is not particularly limited, but it is preferable to use flat particles like the metal particles. Moreover, about a preferable average particle diameter, it is equivalent to a metal particle.
  • the polyurethane which has a carboxyl group used for binder resin for conductive compositions can be melt
  • Specific examples include ethyl carbitol acetate, ethyl carbitol, butyl carbitol acetate, butyl carbitol, terpineol, dihydroterpineol, and isobornylcyclohexanol.
  • the ratio of the binder resin for conductive composition (A) in the composition for forming a conductive pattern, the ratio of the conductive material (B), and the ratio of the solvent (C) are obtained when the metal particles (B1) are used. This is different from the case of using metal nanowires and / or metal nanotubes (B2). In the case where the metal particles (B1) are electrically conductive, the metal particles (B1) are in contact with each other at points or planes, whereas when metal nanowires and / or metal nanotubes (B2) are used, the intersection (overlapping) portion.
  • the ratio of the metal composition (B1) to the entire composition is smaller than when the metal particle (B1) is used. Moreover, the ratio of the binder resin (A) and the ratio of the solvent (C) are relatively larger when the metal nanowires and / or metal nanotubes (B2) are used than when the metal particles (B1) are used.
  • the ratio of the binder resin (A) for the conductive composition is 1 to 15 parts by weight with respect to 100 parts by weight of the metal particles (B1) in the composition. Parts by mass, preferably 2 to 10 parts by mass, more preferably 2.5 to 5 parts by mass. When the ratio is 1 part by mass or more, the dispersibility of the conductive material is maintained, and the adhesion between the conductive pattern and the substrate is expressed. Moreover, when the ratio is 15 parts by mass or less, the deterioration of the conductivity due to the excessive increase of the polymer component contained in the finally formed conductive pattern can be suppressed.
  • the ratio of the metal particles (B1) to the whole composition is 20% by mass to 95% by mass, preferably 30% by mass to 92% by mass, and more preferably 45% by mass to 90% by mass.
  • the ratio of the metal particles is 20% by mass or more, the conductivity of the finally formed conductive pattern is obtained.
  • the ratio of the metal particles is 95% by mass or less, the viscosity of the conductive pattern forming composition becomes too high, and problems such as blurring do not occur when forming a conductive pattern by printing or coating.
  • the proportion of the solvent (C) is 5% by mass to 80% by mass, preferably 10% by mass to 70% by mass, and more preferably with respect to the entire composition. Is 15% by mass to 60% by mass. If it is 5 mass% or more, the said binder resin for conductive compositions (A) can fully be dissolved. Moreover, it can be set as the viscosity of the composition for conductive pattern formation which can carry out pattern printing as it is 80 mass% or less.
  • the ratio of the binder resin (A) for the conductive composition is the same as the metal nanowire and / or the metal nanotube (B2) 100 in the composition.
  • the amount is 10 parts by mass to 400 parts by mass, preferably 50 parts by mass to 300 parts by mass, and more preferably 100 parts by mass to 250 parts by mass with respect to parts by mass. If the ratio is 10 parts by mass or more, it can be expected that the resistance reduction effect derived from the metal salt site is exhibited. Moreover, when the ratio is 400 parts by mass or less, it is possible to suppress the deterioration of the conductivity due to the excessive increase of the polymer component contained in the finally formed conductive pattern.
  • the ratio of metal nanowires and / or metal nanotubes (B2) to the whole composition is 0.01 to 10% by mass, preferably 0.02 to 5% by mass, more preferably 0.05 to 2% by mass. .
  • the metal nanowires and / or metal nanotubes are 0.01% by mass or more, it is not necessary to print the transparent conductive layer thick in order to ensure desired conductivity, and printing becomes easy. Moreover, if it is 10 mass% or less, in order to ensure a desired optical characteristic, it becomes unnecessary to thinly print a transparent conductive film layer, and also in this case, printing becomes easy.
  • the ratio of the solvent (C) is 90% by mass or more, more preferably 98% by mass or more with respect to the entire composition.
  • the ratio is 90% by mass or more, it is possible to suppress deterioration of conductivity due to excessive increase of polymer components in the finally formed conductive pattern and deterioration of optical characteristics due to excessive increase of conductive components. .
  • the binder resin a carboxylate metal salt moiety represented by (COO) n M in the polymer skeleton (M is a metal atom selected from metals belonging to Group 11 of the periodic table, and n is a valence of the metal atom M).
  • the resin other than the polyurethane having the number can be used in combination as long as the effects of the present invention are not impaired.
  • the ratio of the said polyurethane with respect to all the binder resins is 50 mass% or more, It is more preferable that it is 70 mass% or more, It is further more preferable that it is 90 mass% or more.
  • binder resins that can be used in combination include poly-N-vinyl pyrrolidone, poly-N-vinylacetamide, poly-N-vinyl compounds such as poly-N-vinylcaprolactam, polyethylene glycol, polypropylene glycol, and polyTHF.
  • binder resins include poly-N-vinyl pyrrolidone, poly-N-vinylacetamide, poly-N-vinyl compounds such as poly-N-vinylcaprolactam, polyethylene glycol, polypropylene glycol, and polyTHF.
  • additives can be used in combination as necessary within a range not impairing the properties of the conductive pattern forming composition.
  • Additives that can be used in combination may contain additives such as surfactants, antioxidants, fillers, thixotropic agents, leveling agents, and UV absorbers.
  • a filler such as fumed silica can be used. These blending amounts (ratio to the whole composition) are preferably within 5% by mass.
  • the conductive pattern forming composition includes a conductive resin (A), a conductive material (B), and a solvent (C) that dissolves the conductive composition binder resin.
  • Additives that can be added as necessary are 100% by mass in total (ratio by mass), that is, binder resin for conductive composition (A) and conductive material (B ) And the solvent (C) for dissolving the binder resin for conductive composition, the total amount of the composition can be 100% by mass or less.
  • ratio by mass ratio by mass
  • the solvent (C) for dissolving the binder resin for conductive composition the total amount of the composition can be 100% by mass or less.
  • blend It can manufacture by mixing with a rotation revolution revolution stirrer, a homogenizer, a three roll, a high shear mixer, a propeller stirrer, a mix rotor, etc.
  • the conductivity of the conductive pattern can be improved with low sintering energy.
  • the conductive pattern is formed as a result of sintering the conductive material by printing the conductive pattern forming composition on a base material in a predetermined pattern and applying energy as necessary. Pattern.
  • This pattern is not necessarily a fine line, and a so-called solid shape such as a square having a certain area is also included in the pattern.
  • the substrate for applying and printing the conductive pattern forming composition of the present embodiment is not particularly limited as long as it is insulating. From the viewpoint of ease of application and printing, a plate shape, a sheet shape, and a film shape are preferable.
  • ceramics such as glass and alumina, polyester resins, cellulose resins, vinyl alcohol resins, vinyl chloride resins, cycloolefin resins, polycarbonate resins, acrylic resins, ABS resins, polyimide resins, and other thermoplastic resins, photocurable resins, A thermosetting resin etc. are mentioned.
  • glass having a functional group (hydroxyl group, carbonyl group, amino group, etc.) having an interaction (hydrogen bond, etc.) with urethane bond in the binder resin, polyester resin, cellulose resin, vinyl alcohol resin, acrylic resin, A polyimide resin or the like is preferable.
  • the conductive pattern printing method is not particularly limited as long as it is a known method. Spray coating, bar coating, roll coating, die coating, inkjet coating, screen coating, dip coating, letterpress printing method, intaglio printing method, gravure printing method Etc. can be used. Depending on the method of application and the conditions of the material, the substrate may be heated after wet coating to remove the applied material and the solvent used, or the process of washing away the solvent by washing, etc. .
  • the value of the weight average molecular weight is a value in terms of polystyrene measured by GPC, and the measurement conditions are as follows. ⁇ Measuring device Shodex GPC-101 ⁇ Column Shodex column LF-804 ⁇ Mobile phase Tetrahydrofuran (THF) ⁇ Flow rate 1.0mL / min ⁇ Measurement time 40min ⁇ Detector Shodex RI-71S ⁇ Temperature 40.0 °C Sample volume Sample loop 100 ⁇ L ⁇ Sample concentration Prepared to be about 1% by mass THF solution
  • the acid value of the resin was measured by the following method. About 1 g of a sample is precisely weighed with a precision balance in a 100 ml flask, and 30 ml of methanol is added to dissolve it. Furthermore, add 1 to 3 drops of phenolphthalein ethanol solution as an indicator and stir well until the sample is uniform. This is titrated with a 0.1N potassium hydroxide-ethanol solution, and the end point of neutralization is obtained when the indicator is slightly red for 30 seconds. The value obtained from the result using the following calculation formula is defined as the acid value of the resin.
  • TG-DTA Differential heat-thermogravimetry was performed under the following measurement conditions.
  • ⁇ Measurement device Differential thermothermal weight simultaneous measurement device TG / DTA6200 (SII Nanotechnology Inc.) ⁇ Temperature range 30 °C -500 °C ⁇ Temperature increase rate 10 °C / min ⁇ Atmosphere Nitrogen gas
  • DMBA dimethylolbutanoic acid
  • IPDI isophorone diisocyanate
  • the obtained polyurethane has a structural unit represented by the following formula (7).
  • n 6 represents a positive integer, is approximately 17 from the value of the weight-average molecular weight.
  • the measured value of the acid value of the solid content of the obtained polyurethane solution having a carboxyl group was 43 mgKOH / g, and the weight average molecular weight was 1.2 ⁇ 10 4 .
  • Example 1 Synthesis of polyurethane silver salt PU-1Ag 1 using silver nitrate
  • 2.03 g containing 0.73 mmol of carboxyl group
  • 20 ml of acetone manufactured by Wako Pure Chemical Industries, Ltd.
  • sodium hydroxide A solution prepared by dissolving 0.03 g (0.73 mmol) of Wako Pure Chemical Industries, Ltd. in 3 ml of water was added and stirred until uniform.
  • Fig. 1 shows the results of simultaneous differential thermal-thermogravimetric measurement (TG-DTA) of polyurethane silver salt.
  • the mass ratio of the residue after completion of the TG-DTA measurement was 9.9 mass%, which was a value close to 7.4 mass%, which is the theoretical value of the silver content calculated from the molecular formula.
  • Example 2 Synthesis of polyurethane silver salt PU-1Ag 2 using silver oxide
  • 6.04 g of the polyurethane solution having a carboxyl group obtained in Synthesis Example 1 (containing a carboxyl group corresponding to 2.2 mmol) was dissolved in 14.05 g of diethylene glycol monoethyl ether (manufactured by Junsei Chemical Co., Ltd.). .26 g of silver oxide (manufactured by Wako Pure Chemical Industries, Ltd.) (1.1 mmol, 2.2 mmol in terms of silver) was added. The mixture was stirred at room temperature for 10 hours under light shielding, and it was confirmed that silver oxide had disappeared and became a uniform solution.
  • a portion of the obtained silver salt solution (solid content concentration: 16% by mass) was dried under reduced pressure for 1 hour using a vacuum dryer while heating at 100 ° C.
  • TG-DTA measurement of the solid polyurethane silver salt obtained after drying was performed. The measurement results are shown in FIG.
  • the mass ratio of the residue after completion of the TG-DTA measurement was 8.1 mass%, which was a value close to 7.4 mass%, which is the theoretical value of the silver content calculated from the molecular formula. 1 and 2, it was confirmed that the same polyurethane silver salt obtained by the method using silver nitrate and the polyurethane silver salt obtained by the method using silver oxide were obtained.
  • the obtained silver salt of polyurethane has a structural unit represented by the following formula (8).
  • n 6 represents a positive integer, is approximately 17 from the value of the weight-average molecular weight.
  • Example 3 Synthesis of polyurethane copper salt PU-1Cu using copper sulfate
  • 2.02 g containing 0.73 mmol of carboxyl group
  • 20 ml of acetone manufactured by Wako Pure Chemical Industries, Ltd.
  • sodium hydroxide A solution prepared by dissolving 0.03 g (0.73 mmol) of Wako Pure Chemical Industries, Ltd. in 3 ml of water was added and stirred until uniform.
  • the TG-DTA measurement result of the obtained copper salt is shown in FIG.
  • the mass ratio of the residue after completion of the TG-DTA measurement was 2.3 mass%, which coincided with 2.3 mass%, which is the theoretical value of the copper content calculated from the molecular formula.
  • the obtained copper salt of polyurethane has a structural unit represented by the following formula (9). In the following formula, only the coordination structure around the copper atom is shown for simplification.
  • the dotted line in the formula represents a coordination bond.
  • Urethane bond units that are cross-linked by copper atoms may be contained in the same polyurethane skeleton, or may be contained in different polyurethane skeletons.
  • the divalent copper atom is a substitutionally active metal species, it is considered that the polyurethane chain cross-linked with the copper atom is exchanged over time.
  • a lanthanum type binuclear complex in which four carboxyl groups are coordinated to two copper atoms may be partially formed. In either case, the ratio of the carboxyl group and the copper atom is 2: 1. There is no change in the formation of salt.
  • the obtained polyurethane has a structural unit represented by the following formula (10).
  • n 7 is a positive integer and is approximately 9 from the value of the weight average molecular weight.
  • the actually measured value of the acid value of the solid content of the obtained polyurethane solution having a carboxyl group was 65 mgKOH / g, and the weight average molecular weight was 1.0 ⁇ 10 4 .
  • Example 4 Synthesis of polyurethane silver salt PU-2Ag 1 using silver nitrate
  • 2.53 g of the polyurethane solution having a carboxyl group obtained in Synthesis Example 2 (containing 1.1 mmol of carboxyl group) was dissolved in 20 ml of acetone (manufactured by Wako Pure Chemical Industries, Ltd.), and sodium hydroxide ( A solution prepared by dissolving 0.046 g (1.1 mmol) of Wako Pure Chemical Industries, Ltd. in 5 ml of water was added and stirred until uniform.
  • TG-DTA measurement results of polyurethane silver salt are shown in FIG.
  • the mass ratio of the residue after the TG-DTA measurement was 15.2% by mass, which was close to 11.0% by mass, which is the theoretical value of the silver content calculated from the molecular formula.
  • Example 5 Synthesis of polyurethane silver salt PU-2Ag 2 using silver oxide
  • 5.02 g (containing 2.2 mmol of carboxyl group) of the polyurethane solution having a carboxyl group obtained in Synthesis Example 2 was dissolved in 15.02 g of diethylene glycol monoethyl ether (manufactured by Junsei Chemical Co., Ltd.). .26 g of silver oxide (manufactured by Wako Pure Chemical Industries, Ltd.) (1.1 mmol, 2.2 mmol in terms of silver) was added. The mixture was stirred at room temperature for 15 hours under light shielding, and it was confirmed that the silver oxide disappeared and became a uniform solution.
  • a part of the obtained polyurethane silver salt solution (solid content concentration 11% by mass) was dried under reduced pressure for 1 hour using a vacuum dryer while heating at 100 ° C.
  • TG-DTA measurement of the solid silver salt obtained after drying was performed. The measurement results are shown in FIG.
  • the mass ratio of the residue after completion of the TG-DTA measurement was 10.9 mass%, which was close to 11.0 mass%, which is the theoretical value of the silver content calculated from the molecular formula. 9 and 10, it was confirmed that the same polyurethane silver salt obtained by the method using silver nitrate and the polyurethane silver salt obtained by the method using silver oxide were obtained.
  • the obtained silver salt of polyurethane has a structural unit represented by the following formula (11).
  • n 7 is a positive integer and is approximately 9 from the value of the weight average molecular weight.
  • the structural unit of the obtained polyurethane is represented by the following formula (12).
  • n 8 is a positive integer, is approximately 18 from the value of the weight-average molecular weight.
  • the obtained paste-like polyurethane group having a carboxyl group had an acid value of 150 mgKOH / g and a weight average molecular weight of 6.5 ⁇ 10 3 .
  • Example 6 Synthesis of polyurethane silver salt PU-3Ag 1 .
  • 1.74 g of the polyurethane composition having a paste-like carboxyl group obtained in Synthesis Example 3 (containing a carboxyl group corresponding to 2.6 mmol) was dissolved in 30 ml of methanol (manufactured by Wako Pure Chemical Industries, Ltd.)
  • the structural unit of the silver salt of the polyurethane is represented by the following formula (13).
  • n 8 is a positive integer, is approximately 18 from the value of the weight-average molecular weight.
  • the TG-DTA measurement result of the obtained polyurethane silver salt is shown in FIG.
  • the mass ratio of the residue after completion of the TG-DTA measurement was 20.5 mass%, which was close to the theoretical value of 22.6 mass% of the silver content calculated from the molecular formula.
  • the obtained polyurethane has a structural unit represented by the following formula (14).
  • Et represents an ethyl group
  • Bu represents an n-butyl group.
  • the obtained polyurethane solution having a carboxyl group had an acid value of 93 mgKOH / g and a weight average molecular weight of 9.0 ⁇ 10 3 .
  • Example 7 Synthesis of polyurethane silver salt PU-4Ag 1 ) 1.56 g of a polyurethane solution having a carboxyl group obtained in Synthesis Example 4 (containing a carboxyl group corresponding to 0.78 mmol) was dissolved in 10 ml of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.), and sodium hydroxide ( A solution prepared by dissolving 0.03 g (0.78 mmol) of Wako Pure Chemical Industries, Ltd. in 3 ml of water was added and stirred until uniform.
  • the precipitate was filtered with suction, and in order to completely remove the remaining solvent, it was dried under reduced pressure for 1 hour using a vacuum dryer while heating at 110 ° C. to obtain a silver salt of polyurethane (yield 0.41 g). .
  • the TG-DTA measurement result of the obtained silver salt is shown in FIG.
  • the mass ratio of the residue after completion of the TG-DTA measurement was 14.8% by mass, which coincided with 14.8% of the theoretical value of the silver content calculated from the molecular formula.
  • the obtained silver salt of polyurethane has a structural unit represented by the following formula (15).
  • Et represents an ethyl group
  • Bu represents an n-butyl group.
  • the obtained polyurethane has a structural unit represented by the following formula (16).
  • n 9 is a positive integer, is approximately 17 from the value of the weight-average molecular weight.
  • the actually measured value of the acid value of the solid content of the obtained polyurethane solution having a carboxyl group was 85 mgKOH / g, and the weight average molecular weight was 9.4 ⁇ 10 3 .
  • Example 8 Synthesis of polyurethane silver salt PU-5Ag 1 ) 2.00 g of a polyurethane solution having a carboxyl group obtained in Synthesis Example 5 (containing a carboxyl group equivalent to 1.3 mmol) was dissolved in 20 ml of acetone (manufactured by Wako Pure Chemical Industries, Ltd.), and sodium hydroxide ( A solution prepared by dissolving 0.05 g (1, 3 mmol) of Wako Pure Chemical Industries, Ltd. in 5 ml of water was added and stirred until uniform.
  • FIG. 13 shows the TG-DTA measurement result of the obtained polyurethane silver salt.
  • the mass ratio of the residue after completion of the TG-DTA measurement was 20.6 mass%, which was a value close to 14.7 mass% of the theoretical silver content calculated from the molecular formula.
  • the obtained silver salt of the polyurethane has a structural unit represented by the following formula (17).
  • n 9 is a positive integer, is approximately 17 from the value of the weight-average molecular weight.
  • the resulting polyurethane solution having a carboxyl group had an acid value of 62 mgKOH / g and a weight average molecular weight of 2.6 ⁇ 10 4 in the solid content.
  • the obtained polyurethane has a structural unit represented by the following formula (18).
  • n 10 is a positive integer, is about 3 from the value of the weight average molecular weight.
  • R 9 is an aliphatic hydrocarbon group having 5 or 6 carbon atoms.
  • Example 9 Synthesis of polyurethane silver salt PU-6Ag (8) in which silver atoms are bonded to 8% of carboxyl groups
  • 4.01 g of the polyurethane solution having a carboxyl group obtained in Synthesis Example 6 (containing a carboxyl group corresponding to 2.10 mmol) was dissolved in 5.96 g of diethylene glycol monoethyl ether (manufactured by Junsei Kagaku Co., Ltd.). 0.02 g of silver oxide (manufactured by Wako Pure Chemical Industries, Ltd., 0.16 mmol as Ag) was added. The mixture was stirred at room temperature for 6 hours under light shielding, and it was confirmed that the silver oxide disappeared and became a uniform solution.
  • a part of the obtained polyurethane silver salt solution (solid content concentration: 21% by mass) was dried under reduced pressure for 2 hours using a vacuum dryer while heating at 120 ° C.
  • TG-DTA measurement of the solid polyurethane silver salt obtained after drying was performed. The measurement results are shown in FIG.
  • the mass ratio of the residue after completion of the TG-DTA measurement was 2.0 mass%, which was close to 0.8 mass%, which is the theoretical value of the silver content calculated from the molecular formula.
  • Example 10 Synthesis of polyurethane silver salt PU-6Ag (63) in which silver atoms are bonded to 63% of carboxyl groups
  • 2.06 g of the polyurethane solution having a carboxyl group obtained in Synthesis Example 6 (containing a carboxyl group corresponding to 1.08 mmol) was dissolved in 7.99 g of diethylene glycol monoethyl ether (manufactured by Junsei Chemical Co., Ltd.).
  • 0.08 g of silver oxide manufactured by Wako Pure Chemical Industries, Ltd., 0.68 mmol as Ag was added. The mixture was stirred at room temperature for 6 hours under light shielding, and it was confirmed that the silver oxide disappeared and became a uniform solution.
  • a part of the obtained polyurethane silver salt solution (solid content concentration: 11% by mass) was dried under reduced pressure for 2 hours using a vacuum dryer while heating at 120 ° C.
  • TG-DTA measurement of the solid silver salt obtained after drying was performed. The measurement results are shown in FIG.
  • the mass ratio of the residue after completion of the TG-DTA measurement was 8.5 mass%, which was close to 6.4 mass%, which is the theoretical value of the silver content calculated from the molecular formula.
  • Example 11 Synthesis of polyurethane silver salt PU-6Ag (50) in which silver atoms are bonded to 50% of carboxyl groups
  • 8.00 g (containing a carboxyl group equivalent to 4.20 mmol) of the polyurethane solution having a carboxyl group obtained in Synthesis Example 6 was dissolved in 8.01 g of diethylene glycol monoethyl ether (manufactured by Junsei Chemical Co., Ltd.).
  • a part of the obtained polyurethane silver salt solution (solid content concentration: 23% by mass) was dried under reduced pressure for 2 hours using a vacuum dryer while heating at 120 ° C.
  • TG-DTA measurement of the solid silver salt obtained after drying was performed. The measurement results are shown in FIG.
  • the mass ratio of the residue after completion of the TG-DTA measurement was 5.5% by mass, which was close to 5.1% by mass, which is the theoretical value of the silver content calculated from the molecular formula.
  • Example 12 Synthesis of polyurethane silver salt PU-6Ag (100) in which silver atoms are bonded to 100% of carboxyl groups
  • a part of the obtained polyurethane silver salt solution (solid content concentration: 23% by mass) was dried under reduced pressure for 2 hours using a vacuum dryer while heating at 120 ° C.
  • TG-DTA measurement of the solid silver salt obtained after drying was performed. The measurement results are shown in FIG.
  • the mass ratio of the residue after completion of the TG-DTA measurement was 9.5 mass%, which was close to 10.2 mass%, which is the theoretical value of the silver content calculated from the molecular formula.
  • the resulting silver salt of polyurethane having silver atoms bonded to some or all of the carboxyl groups has a structural unit represented by the following formula (19).
  • n 10 is a positive integer, is about 3 from the value of the weight average molecular weight.
  • R 9 is an aliphatic hydrocarbon group having 5 or 6 carbon atoms.
  • the obtained polyurethane solution having a carboxyl group had an acid value of 59 mgKOH / g and a weight average molecular weight of 2.8 ⁇ 10 4 .
  • the obtained polyurethane has a structural unit represented by the following formula (20).
  • n 11 is a positive integer, is about 3 from the value of the weight average molecular weight.
  • R 10 is an aliphatic hydrocarbon group having 5 or 6 carbon atoms.
  • Example 13 (Synthesis of polyurethane silver salt PU-7Ag) 8.00 g of the polyurethane solution having a carboxyl group obtained in Synthesis Example 7 (containing a carboxyl group corresponding to 4.20 mmol) was dissolved in 7.99 g of diethylene glycol monoethyl ether (manufactured by Junsei Chemical Co., Ltd.). Subsequently, 0.49 g of silver oxide (manufactured by Wako Pure Chemical Industries, Ltd., 4.20 mmol as Ag) was dispersed in 4.00 g of diethylene glycol monoethyl ether (manufactured by Junsei Chemical Co., Ltd.). Added to the polyurethane solution. It stirred at 85 degreeC for 5 hours, and it confirmed that silver oxide disappeared and became a uniform solution.
  • a part of the obtained polyurethane silver salt solution (solid content concentration: 23% by mass) was dried under reduced pressure for 2 hours using a vacuum dryer while heating at 100 ° C.
  • TG-DTA measurement of the solid silver salt obtained after drying was performed. The measurement results are shown in FIG.
  • the mass ratio of the residue after completion of the TG-DTA measurement was 9.4 mass%, which was close to 10.3 mass%, which is the theoretical value of the silver content calculated from the molecular formula.
  • the obtained silver salt of polyurethane has a structural unit represented by the following formula (21).
  • n 11 is a positive integer, is about 3 from the value of the weight average molecular weight.
  • R 10 is an aliphatic hydrocarbon group having 5 or 6 carbon atoms.
  • Synthesis Example 8 ⁇ Silver salt of polyurethane containing polyethylene glycol 1000> (Synthesis of polyurethane PU-8) In a 500 mL four-necked separable flask equipped with a dropping funnel, a stirrer, a thermocouple for temperature measurement, and a Liebig condenser, 62.72 g of polyethylene glycol 1000 (weight average molecular weight 1000, manufactured by NOF Corporation) as a diol compound ( 62 mmol, 0.45 equivalents relative to diisocyanate), 11.41 g (77 mmol, 0.55 equivalents relative to diisocyanate) DMBA (manufactured by Huzhou Nagamori Chemical Co., Ltd.) as a dihydroxy compound having a carboxyl group, and as a solvent 105.05 g of ethyl carbitol acetate (manufactured by Daicel Corporation) was charged, and all raw materials were dissolved at 55 ° C.
  • the obtained polyurethane solution having a carboxyl group had an acid value of 42 mgKOH / g and a weight average molecular weight of 1.5 ⁇ 10 4 .
  • the obtained polyurethane has a structural unit represented by the following formula (22).
  • n 12 is a positive integer, is approximately 22 from the value of the weight-average molecular weight.
  • Example 14 Synthesis of polyurethane silver salt PU-8Ag (TP) using terpineol as reaction solvent
  • 2.01 g (containing 0.73 mmol of carboxyl group) of the polyurethane solution having a carboxyl group obtained in Synthesis Example 8 was dissolved in 8.00 g of terpineol C (manufactured by Nippon Terpene Chemical Co., Ltd.).
  • 08 g of silver oxide (manufactured by Wako Pure Chemical Industries, Ltd., 0.73 mmol as Ag) was added. The mixture was stirred at room temperature for 6 hours under light shielding, and it was confirmed that the silver oxide disappeared and became a uniform solution.
  • a part of the obtained polyurethane silver salt solution (solid content concentration: 11% by mass) was dried under reduced pressure for 2 hours using a vacuum dryer while heating at 100 ° C.
  • TG-DTA measurement of the solid silver salt obtained after drying was performed. The measurement results are shown in FIG.
  • the mass ratio of the residue after completion of the TG-DTA measurement was 7.7 mass%, which was close to 7.4 mass%, which is the theoretical value of the silver content calculated from the molecular formula.
  • the obtained silver salt of the polyurethane has a structural unit represented by the following formula (23).
  • n 12 is a positive integer, is approximately 22 from the value of the weight-average molecular weight.
  • Example 15 Synthesis of polyurethane silver salt PU-8Ag (ECA / EC) using ECA / EC as a reaction solvent
  • 0.08 g of silver oxide manufactured by Wako Pure Chemical Industries, Ltd., 0.73 mmol as Ag was added. The mixture was stirred at room temperature for 7 hours under light shielding, and it was confirmed that the silver oxide disappeared and became a uniform solution.
  • the obtained polyurethane silver salt solution was dried under reduced pressure while heating by the method shown in Example 14, and TG-DTA measurement of the solid silver salt obtained after drying was performed. Similar results were obtained.
  • Example 16 (Synthesis of polyurethane copper salt PU-8Cu using copper hydroxide) 4.02 g (containing a carboxyl group corresponding to 1.46 mmol) of the polyurethane solution having a carboxyl group obtained in Synthesis Example 8 was dissolved in 15.99 g of diethylene glycol monoethyl ether (manufactured by Junsei Kagaku Co., Ltd.). 0.07 g of copper hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) (0.73 mmol) was added. After heating to 120 ° C. in an oil bath, the mixture was stirred for 6 hours, and it was confirmed that copper hydroxide had disappeared and became a uniform solution.
  • diethylene glycol monoethyl ether manufactured by Junsei Kagaku Co., Ltd.
  • copper hydroxide manufactured by Wako Pure Chemical Industries, Ltd.
  • a part of the obtained polyurethane copper salt solution (solid content concentration 11% by mass) was dried under reduced pressure for 2 hours using a vacuum dryer while heating at 120 ° C.
  • TG-DTA measurement of the solid silver salt obtained after drying was performed. The measurement results are shown in FIG.
  • the mass ratio of the residue after completion of the TG-DTA measurement was 3.2 mass%, which was close to 2.3 mass%, which is the theoretical value of the copper content calculated from the molecular formula.
  • the obtained copper salt of the polyurethane has a crosslinked structure as shown in the above formula (9).
  • the obtained polyurethane solution having a carboxyl group had an acid value of 43 mgKOH / g and a weight average molecular weight of 2.0 ⁇ 10 4 in a solid content.
  • the obtained polyurethane has a structural unit represented by the following formula (24).
  • n 13 is a positive integer, is approximately 22 from the value of the weight-average molecular weight.
  • Example 17 Synthesis of polyurethane silver salt PU-9Ag (50) in which silver atoms are bonded to 50% of carboxyl groups
  • the obtained silver salt of polyurethane has a structural unit represented by the following formula (25).
  • n 13 is a positive integer, is approximately 22 from the value of the weight-average molecular weight.
  • the used solvent is Daicel Corporation's ethyl carbitol acetate (ECA) and Daicel Corporation's ethyl carbitol (EC).
  • ECA ethyl carbitol acetate
  • EC ethyl carbitol
  • EC ethyl carbitol
  • ⁇ Performance evaluation 1> (1) Volume resistivity After measuring the film thickness of the said conductive pattern with the micrometer, the surface resistance of the conductive pattern was measured with the resistivity meter Loresta GP (made by Mitsubishi Chemical Analytech Co., Ltd.) based on the 4-terminal method. The ESP mode was used for the measurement mode and the terminals used. The obtained film thickness was multiplied by the surface resistance to obtain the volume resistivity of the thin film. The results are shown in Table 1.
  • the polyurethane having a carboxyl group in which all or a part of the carboxyl group is a metal salt (silver salt or copper salt).
  • the Example Evaluation Examples 1 to 19 used have a lower volume resistivity than the Comparative Evaluation Examples 1 to 11 using a polyurethane having a carboxyl group which is not a metal salt.
  • a part of the carboxyl group is a metal salt, it is understood that the volume resistivity is further decreased as the ratio of the metal salt is increased.
  • the conductive paste using the polyurethane which has the carboxyl group in which all or one part of the carboxyl group concerning the Example became a metal salt is the conductive paste using the polyurethane which has the carboxyl group which is not a metal salt
  • the conductivity of the conductive pattern can be improved with lower sintering energy.
  • the amount of metal atoms in the metal (silver or copper) salt of polyurethane, which is a binder resin is larger than the metal atom comparative example, but the amount is 100 parts by mass of metal particles. Therefore, the influence on the change in conductivity is almost negligible.
  • the conductive paste using the polyurethane which has the carboxyl group in which all or a part of the carboxyl groups according to the examples are metal salts has two characteristics required for the conductive pattern, ie, volume resistivity and adhesion. It can be seen that both are well balanced.
  • a conductive paste was prepared in which the sum of the silver amount derived from the silver salt and the silver amount derived from the particles was made constant, and the performance was evaluated.
  • the conductive pattern formation and performance evaluation methods were the same as in the conductive pattern formation 1 and performance evaluation 1, and the results of baking at 120 ° C. and 170 ° C. were further added.
  • Examples 1 to 21 in which all or part of the carboxyl groups are silver salts are comparative evaluation examples that are not silver salts. It can be seen that the volume resistivity is lower than that of 1 to 18 without deteriorating the adhesion. In addition, as shown in Examples 1 to 9 and Comparative Evaluations 1 to 6, the volume resistivity is further decreased as the ratio of silver chloride of the carboxyl group is increased. It can be confirmed again that it originates from the part.
  • Examples 1 to 12 in which all or part of the carboxyl groups are silver salts are comparative evaluation examples that are not silver salts. It can be seen that the volume resistivity is lower than that of 1 to 12 without impairing the adhesion. As described above, even when silver particles other than AgC239 are used, the same results as in the performance evaluation can be obtained. Therefore, the effect of improving the conductivity is not limited to the case where specific particles are used. It was shown that a polyurethane silver salt of the present invention is applicable to a wide range.
  • ⁇ Conductive pattern formation 4 Composition for conductive pattern formation using silver nanoparticles> DF-AT-5100 manufactured by DOWA Electronics Co., Ltd. (spherical, the average value of the primary particle diameter is 40 nm) is used as the silver particles, and the rotation and revolution of each component and blending ratio (part by mass [g]) shown in Table 4 Mixing under normal temperature and normal pressure using mixer Awatori Nertaro (manufactured by Sinky Co., Ltd.) (spinning 600 rpm, revolution 1200 rpm for 3 minutes three times) to prepare 10 g of conductive paste (conductive pattern forming composition) did.
  • the solvent used is Daicel Corporation's ethyl carbitol acetate (ECA), Daicel Corporation's ethyl carbitol (EC), and Nippon Terpene Chemical Co., Ltd. Tersolve MTPH.
  • ECA ethyl carbitol acetate
  • EC ethyl carbitol
  • Nippon Terpene Chemical Co., Ltd. Tersolve MTPH Tersolve MTPH.
  • non-alkali glass product name Eagle XG, manufactured by Corning
  • ⁇ Performance evaluation 4> (1) Volume resistivity Since the film thickness of the conductive pattern was thinner than the measurable range of a micrometer, it was measured with a stylus type surface shape measuring device DEKTAK-6M (manufactured by Bruker Nano). The surface resistance of the conductive pattern was measured with a resistivity meter Loresta GP (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) based on the 4-terminal method, and the measurement mode and the terminals used were measured using the ESP mode. The obtained film thickness was multiplied by the surface resistance to obtain the volume resistivity of the thin film. The results are shown in Table 4.
  • the polyurethane silver salt of the present invention exhibits the effect of improving the conductivity not only when combined with micron-sized silver particles but also when combined with nano-sized silver particles.
  • composition for conductive pattern formation using silver nanowire Using silver nanowire as a conductive component, mixing at each component and mixing ratio (parts by mass [g]) shown in Table 5 under normal temperature and normal pressure using a rotating / revolving mixer Awatori Neritarou (Sinky Corp.) Then, 10 g of conductive paste (composition for forming a conductive pattern) was prepared (3 times for 3 minutes at 600 rpm for rotation and 1200 rpm for revolution).
  • Silver nanowires synthesized by the polyol method (average length 20 ⁇ m, average diameter 35 nm) were used, and terpineol C and tersolve MTPH (both manufactured by Nippon Terpene Chemical Co., Ltd.) were used as the solvent. Printing and baking are possible even when only polyurethane and polyurethane silver salt are used as the binder resin, but polyvinyl pyrrolidone K-90 (manufactured by BASF) was used in combination in order to keep the pattern shape after baking better.
  • the measuring device was a resistivity meter Loresta GP (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) based on the four-terminal method, and the measuring mode and terminals used were ESP mode. The results are shown in Table 5.

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KR102553367B1 (ko) * 2021-08-17 2023-07-10 ㈜ 엘프스 자가융착형 도전접속필름용 수지조성물, 이를 포함하는 자가융착형 도전접속필름 및 이의 제조방법

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WO2019203159A1 (ja) * 2018-04-19 2019-10-24 東洋インキＳｃホールディングス株式会社 成形フィルム用導電性組成物、成形フィルム、成形体およびその製造方法
JP2019189680A (ja) * 2018-04-19 2019-10-31 東洋インキＳｃホールディングス株式会社 成形フィルム用導電性組成物、成形フィルム、成形体およびその製造方法
US12064949B2 (en) 2018-04-19 2024-08-20 Artience Co., Ltd. Conductive composition for molded film, molded film, molded article, and method for production thereof
KR20220046583A (ko) 2019-08-09 2022-04-14 오사카 유키가가쿠고교 가부시키가이샤 신규 도전율 향상제

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KR102121758B1 (ko) 2020-06-11
TW201805323A (zh) 2018-02-16
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