JP4968410B2 - Conductive paste, conductive film, touch panel, and method of manufacturing conductive thin film - Google Patents
Conductive paste, conductive film, touch panel, and method of manufacturing conductive thin film Download PDFInfo
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- JP4968410B2 JP4968410B2 JP2011503684A JP2011503684A JP4968410B2 JP 4968410 B2 JP4968410 B2 JP 4968410B2 JP 2011503684 A JP2011503684 A JP 2011503684A JP 2011503684 A JP2011503684 A JP 2011503684A JP 4968410 B2 JP4968410 B2 JP 4968410B2
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- component
- resin
- conductive paste
- thin film
- parts
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- 239000010408 film Substances 0.000 title claims description 50
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- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
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- PSGAAPLEWMOORI-PEINSRQWSA-N medroxyprogesterone acetate Chemical compound C([C@@]12C)CC(=O)C=C1[C@@H](C)C[C@@H]1[C@@H]2CC[C@]2(C)[C@@](OC(C)=O)(C(C)=O)CC[C@H]21 PSGAAPLEWMOORI-PEINSRQWSA-N 0.000 description 1
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- SOOARYARZPXNAL-UHFFFAOYSA-N methyl-thiophenol Natural products CSC1=CC=CC=C1O SOOARYARZPXNAL-UHFFFAOYSA-N 0.000 description 1
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 description 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- TVWWSIKTCILRBF-UHFFFAOYSA-N molybdenum trisulfide Chemical class S=[Mo](=S)=S TVWWSIKTCILRBF-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
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- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
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- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
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- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
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- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920005792 styrene-acrylic resin Polymers 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 150000003509 tertiary alcohols Chemical class 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- NUBZKXFFIDEZKG-UHFFFAOYSA-K trisodium;5-sulfonatobenzene-1,3-dicarboxylate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=CC(C([O-])=O)=CC(S([O-])(=O)=O)=C1 NUBZKXFFIDEZKG-UHFFFAOYSA-K 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003739 xylenols Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
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- 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
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
- C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
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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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
- C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
- C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
- C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
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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
- C08G18/70—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
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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
- C08G18/70—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
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K3/04—Carbon
-
- 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
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- C08K3/02—Elements
- C08K3/08—Metals
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2203/00—Indexing scheme relating to G06F3/00 - G06F3/048
- G06F2203/041—Indexing scheme relating to G06F3/041 - G06F3/045
- G06F2203/04103—Manufacturing, i.e. details related to manufacturing processes specially suited for touch sensitive devices
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Theoretical Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Human Computer Interaction (AREA)
- General Physics & Mathematics (AREA)
- Wood Science & Technology (AREA)
- Conductive Materials (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Non-Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Position Input By Displaying (AREA)
Description
本発明は、導電性ペーストおよびその利用に関するものであり、さらに詳しくはバインダー樹脂としてポリウレタン樹脂を含有する導電性ペースト、該導電性ペーストを用いてなる導電性薄膜及びその製造方法、該導電性薄膜が透明導電性層上に積層した導電性積層体、並びにその導電性積層体を用いたタッチパネルに関する。 The present invention relates to a conductive paste and use thereof, and more specifically, a conductive paste containing a polyurethane resin as a binder resin, a conductive thin film using the conductive paste, a manufacturing method thereof, and the conductive thin film The present invention relates to a conductive laminate laminated on a transparent conductive layer, and a touch panel using the conductive laminate.
指や専用のペン等で画面に触れることにより操作を行う透明タッチパネルはATM、カーナビゲーションシステム、ゲーム機、駅の切符自動販売機、複写機、博物館の解説端末、及びコンビニの情報端末等、幅広い用途に用いられている。 A wide range of transparent touch panels that operate by touching the screen with a finger or a dedicated pen, such as ATMs, car navigation systems, game machines, station ticket vending machines, photocopiers, museum commentary terminals, and convenience store information terminals Used for applications.
透明タッチパネルは、透明な二枚の導電性薄膜を重ね合わせてスイッチを形成するように構成されている。一般的にこの種の透明タッチパネルの透明導電性薄膜は、蒸着法やスパッタ法により、透明電極材料となる酸化インジウム・スズ膜(以下ITO膜と略記する場合がある)をポリエステルフィルム、ガラス等の基材に付着させ、そのITO膜をエッチングすることによりパターニングして形成されている。 The transparent touch panel is configured to form a switch by superposing two transparent conductive thin films. In general, the transparent conductive thin film of this type of transparent touch panel is made of indium tin oxide film (hereinafter may be abbreviated as ITO film), which becomes a transparent electrode material, by vapor deposition or sputtering. It is formed by patterning by adhering to a substrate and etching the ITO film.
タッチパネルには種々の方式があり、抵抗膜方式と静電容量方式が代表的である。 There are various types of touch panels, and a resistive film type and a capacitance type are typical.
抵抗膜方式は、圧力を感知して触った位置を特定するというシンプルな仕組みで、製造が簡単で低コストで生産できるのが特徴であり、細かな位置検出がしやすく、ペンによる文字入力にも対応できる。一方、デメリットとしては、液晶の上に導電膜フィルムを貼る構造のため、画面の透過率が低くなり、鮮明な画面を実現しにくい点が挙げられる。 The resistive film method is a simple mechanism that detects the pressure and identifies the touched position. It is easy to manufacture and can be produced at low cost. Can also respond. On the other hand, as a demerit, since the conductive film is pasted on the liquid crystal, the transmittance of the screen is lowered and it is difficult to realize a clear screen.
静電容量方式は、指や専用のペンでパネルに触れることで起こる放電現象等を感知して位置を特定する方式で、多点感知できることが特徴である。 The electrostatic capacity method is a method that identifies a position by sensing a discharge phenomenon or the like caused by touching the panel with a finger or a dedicated pen, and is characterized by multipoint sensing.
タッチパネルはペンや指先等で入力しようとすると、その固定電極側の透明導電性薄膜と可動電極(フィルム電極)側の透明導電性薄膜との透明導電性薄膜同士が接触又は接近するようになっているが、近年、ゲーム機等に見られるペン入力形態の多様化に伴い、入力時の荷重、特にペン入力による荷重で透明導電性薄膜にクラック、剥離等の破壊が生じることが問題となっている。そのためペン摺動耐久性を向上させることが必須となってきており、透明導電性薄膜の強度を向上させる試みが近年活発に行われている。 When an attempt is made to input with a pen or a fingertip on the touch panel, the transparent conductive thin film on the fixed electrode side and the transparent conductive thin film on the movable electrode (film electrode) side come into contact or approach each other. However, in recent years, with the diversification of pen input forms found in game machines and the like, there is a problem that cracks, peeling, etc. occur in the transparent conductive thin film due to the load at the time of input, particularly the load due to pen input. Yes. Therefore, it is essential to improve pen sliding durability, and attempts to improve the strength of the transparent conductive thin film have been actively made in recent years.
透明導電性薄膜の強度を上げるための試みとして、例えば、薄膜を構成する酸化物を結晶化することが有効であると考えられている。透明導電性薄膜を結晶化させるためには、非結晶性の透明導電性薄膜をプラスチックフィルム基材上に成膜した後、得られた積層フィルムを透明導電性薄膜の結晶化温度以上に加熱するという手法がある(例えば、特許文献1)。 As an attempt to increase the strength of the transparent conductive thin film, for example, it is considered effective to crystallize an oxide constituting the thin film. In order to crystallize a transparent conductive thin film, after forming an amorphous transparent conductive thin film on a plastic film substrate, the obtained laminated film is heated to a temperature equal to or higher than the crystallization temperature of the transparent conductive thin film. (For example, Patent Document 1).
その他には特許文献2に示されるように比表面積値、平均粒径を規定した酸化インジウム粉末、及び酸化スズ粉末を混合・粉砕させ、酸化スズの含有量を規定した上で加圧成形することにより成形体を得て結晶性ITO薄膜を得る方法等、各社耐久性向上のため、結晶化率の向上を目指している。 In addition, as shown in Patent Document 2, indium oxide powder with a specific surface area value and average particle size, and tin oxide powder are mixed and pulverized, and the content of tin oxide is specified, followed by pressure molding The aim is to improve the crystallization rate in order to improve the durability of each company, such as a method for obtaining a crystalline ITO thin film by obtaining a molded body by the above method.
一方で前記のように透明導電性薄膜を構成する酸化物の結晶化に伴い、透明導電性薄膜上に形成される導電性塗膜の密着性を確保することが難しくなってきている。接続電極である導電性塗膜形成は一般的に、銀等の導電性粉末を含む導電性ペーストのスクリーン印刷塗布によって実施されるが、透明導電性薄膜を構成する酸化物が結晶性の場合、結晶化により透明導電性薄膜の表面構造の秩序が保たれているため、表面活性も低く、凹凸によるアンカー効果が低下する傾向にある。さらに構造の秩序が保たれているため、導電性ペースト中に存在する溶剤の下地層への浸透効果が非晶性透明導電性薄膜よりも弱まる傾向にある。これらの理由により、乾燥後の密着性を確保するのが困難である。 On the other hand, with the crystallization of the oxide constituting the transparent conductive thin film as described above, it has become difficult to ensure the adhesion of the conductive coating film formed on the transparent conductive thin film. The conductive coating forming the connection electrode is generally performed by screen printing application of a conductive paste containing a conductive powder such as silver, but when the oxide constituting the transparent conductive thin film is crystalline, Since the order of the surface structure of the transparent conductive thin film is maintained by crystallization, the surface activity is low and the anchor effect due to the unevenness tends to be reduced. Furthermore, since the structural order is maintained, the permeation effect of the solvent present in the conductive paste into the underlayer tends to be weaker than that of the amorphous transparent conductive thin film. For these reasons, it is difficult to ensure adhesion after drying.
以上のことから、特に結晶性透明導電性薄膜に対しての密着性が良好で、導電性を確保した低温加工可能な導電性ペーストが現在強く求められているが、現状はそのような導電性ペーストの開発は十分ではない。 In light of the above, there is a strong demand for conductive pastes that can be processed at low temperatures and that have good adhesion to crystalline transparent conductive thin films and ensure conductivity. Paste development is not enough.
従来のタッチパネル用の導電性ペーストとしては、従来のメンブレンスイッチや感圧センサ等の電極用途として用いられる導電性ペーストをタッチパネル用途に転用して用いる場合が多い。例えば、特許文献3で示される導電性ペーストにおいては、ガラス転移温度が80℃以上のポリエステル樹脂を用いているが、このようなポリエステル樹脂においてはタッチパネル用途として用いた場合、密着性という観点では、透明導電性薄膜を構成する酸化物と相互作用できる部位がなく、密着性の観点から不適である。同様に特許文献4にはポリエステル樹脂やポリウレタン樹脂をバインダー樹脂とする導電性ペーストが開示されているが、結晶性透明導電性薄膜に対する密着性は必ずしも十分ではない。言い換えるならば透明導電性薄膜を構成する酸化物との密着性を向上させるための樹脂や添加剤の設計思想が盛り込まれておらず、酸化物の種類によって密着性にバラツキが生じ、特に結晶性透明導電性薄膜に対する密着性については極めて乏しいといわざるを得ない。 As a conductive paste for a conventional touch panel, a conductive paste used for electrode applications such as a conventional membrane switch and a pressure sensor is often used by being diverted to a touch panel application. For example, in the conductive paste shown in Patent Document 3, a polyester resin having a glass transition temperature of 80 ° C. or higher is used, but in such a polyester resin, when used as a touch panel application, in terms of adhesion, There is no site capable of interacting with the oxide constituting the transparent conductive thin film, which is unsuitable from the viewpoint of adhesion. Similarly, Patent Document 4 discloses a conductive paste using a polyester resin or a polyurethane resin as a binder resin, but adhesion to a crystalline transparent conductive thin film is not always sufficient. In other words, the design philosophy of resins and additives for improving the adhesion with the oxide constituting the transparent conductive thin film is not incorporated, and the adhesion varies depending on the type of oxide, especially the crystallinity. It must be said that the adhesion to the transparent conductive thin film is extremely poor.
また、特許文献5には、ガラス転移温度50℃以上の有機樹脂、特にポリエステル樹脂を構成成分とする導電性ペーストが開示されている。特許文献5の実施例および比較例において使用されているポリエステル樹脂は、ガラス転移温度のみによって特定されていて具体性に欠け、その効果を検証することが困難であるが、本発明者らの検討によれば、結晶性透明導電性薄膜に対する密着性は必ずしも十分ではない。また、特許文献4の場合と同様、透明導電性薄膜を構成する酸化物との密着性を向上させるための樹脂や添加剤の設計思想が盛り込まれておらず、酸化物の種類によって密着性にバラツキが生じ、特に結晶性透明導電性薄膜に対する密着性については極めて乏しいといわざるを得ない。 Patent Document 5 discloses a conductive paste containing an organic resin having a glass transition temperature of 50 ° C. or higher, particularly a polyester resin as a constituent component. The polyester resin used in the examples and comparative examples of Patent Document 5 is specified only by the glass transition temperature, lacks concreteness, and it is difficult to verify the effect. According to the above, the adhesion to the crystalline transparent conductive thin film is not always sufficient. In addition, as in Patent Document 4, the design concept of a resin or additive for improving the adhesion with the oxide constituting the transparent conductive thin film is not incorporated, and the adhesion depends on the type of oxide. There is variation, and it must be said that the adhesion to the crystalline transparent conductive thin film is extremely poor.
一方、特許文献6で用いられているような熱硬化タイプの導電性ペーストにおいては樹脂として透明導電性薄膜を構成する酸化物と相互作用できる部位がないということに加え、熱硬化タイプであるため、150℃以上の加工温度が必要であり、下地層の熱変形を引き起こす懸念及び生産性の低下という問題点がある。 On the other hand, in the thermosetting type conductive paste used in Patent Document 6, in addition to the fact that there is no part that can interact with the oxide constituting the transparent conductive thin film as a resin, it is a thermosetting type. Further, a processing temperature of 150 ° C. or higher is necessary, and there is a problem of causing thermal deformation of the underlayer and a problem of lowering productivity.
他方、特許文献3においてはタッチパネル用銀ペーストとしてシランカップリング剤を配合することによってITOとの密着性を確保しようとした試みがなされている。しかしながら、シランカップリング剤は低分子であるため、可塑剤的な働きにより導電性や表面硬度に影響を与えるばかりか、長期信頼性の面でも好ましくない。また、シランカップリング剤は少量の添加剤的に使用されているものであるため塗膜内のばらつきが生じやすく、塗膜の長期間の保管によりブリードアウトする可能性が懸念される。 On the other hand, Patent Document 3 attempts to secure adhesion with ITO by blending a silane coupling agent as a silver paste for a touch panel. However, since the silane coupling agent has a low molecular weight, it not only has an influence on conductivity and surface hardness due to its plasticizer function, but is not preferable in terms of long-term reliability. In addition, since the silane coupling agent is used as a small amount of additive, variations in the coating film are likely to occur, and there is a concern that bleeding may occur due to long-term storage of the coating film.
本発明は、透明導電性層等を有する基材に対して、密着性を顕著に向上させ、高信頼性及び高導電性を付与できる導電性薄膜を形成させるための導電性ペーストを提供することを目的とする。 The present invention provides a conductive paste for forming a conductive thin film capable of remarkably improving adhesion and imparting high reliability and high conductivity to a substrate having a transparent conductive layer and the like. With the goal.
このような問題を解決するために、鋭意検討した結果、導電性ペースト中に特定の数平均分子量、酸価、及びガラス転移温度を有するポリウレタン樹脂をバインダー樹脂として含有することが、導電性薄膜を形成する導電性ペーストとして有用であるという知見を得た。本発明は、斯かる知見に基づき完成されたものである。 In order to solve such problems, as a result of intensive studies, it was found that the conductive paste contained a polyurethane resin having a specific number average molecular weight, an acid value, and a glass transition temperature as a binder resin. The knowledge that it is useful as a conductive paste to be formed was obtained. The present invention has been completed based on such findings.
項1:(A)成分:酸価が50〜500eq/ton、ガラス転移温度が60〜150℃である、ポリウレタン樹脂からなるバインダー樹脂、
(B)成分:金属粉末、及び
(C)成分:有機溶媒
を含有する導電性ペースト。Item 1: Component (A): a binder resin made of a polyurethane resin having an acid value of 50 to 500 eq / ton and a glass transition temperature of 60 to 150 ° C.
(B) component: Metal powder, and (C) component: Conductive paste containing an organic solvent.
項2:(A)成分が、
(A1)数平均分子量1,000〜10,000及びガラス転移温度30〜80℃の非晶性ポリオール、
(A2)数平均分子量1,000未満であって、1分子に2個以上のイソシアネートと反応し得る官能基を有する化合物、並びに
(A3)ポリイソシアネートを
重付加反応することによって得られる構造を有するポリウレタン樹脂からなるバインダー樹脂である、項1に記載の導電性ペースト。Item 2: Component (A) is
(A1) an amorphous polyol having a number average molecular weight of 1,000 to 10,000 and a glass transition temperature of 30 to 80 ° C.,
(A2) A compound having a number average molecular weight of less than 1,000 and having a functional group capable of reacting with two or more isocyanates per molecule, and (A3) a structure obtained by polyaddition reaction of polyisocyanate. Item 2. The conductive paste according to Item 1, which is a binder resin made of a polyurethane resin.
項3:(A)成分が、
(A1)数平均分子量1,000〜10,000及びガラス転移温度30〜80℃の非晶性ポリオール、
(A2)数平均分子量1,000未満であって、1分子に2個以上のイソシアネートと反応し得る官能基を有する化合物、
(A3)ポリイソシアネート、並びに
(A4)数平均分子量1,000〜10,000及びガラス転移温度30℃未満の非晶性ポリオール、を
重付加反応することによって得られる構造を有するポリウレタン樹脂からなるバインダー樹脂である、項1又は2に記載の導電性ペースト。Item 3: Component (A) is
(A1) an amorphous polyol having a number average molecular weight of 1,000 to 10,000 and a glass transition temperature of 30 to 80 ° C.,
(A2) a compound having a number average molecular weight of less than 1,000 and having a functional group capable of reacting with two or more isocyanates in one molecule;
(A3) Polyisocyanate, and (A4) A binder comprising a polyurethane resin having a structure obtained by polyaddition reaction of an amorphous polyol having a number average molecular weight of 1,000 to 10,000 and a glass transition temperature of less than 30 ° C. Item 3. The conductive paste according to Item 1 or 2, which is a resin.
項4:前記非晶性ポリオール(A1)が、非晶性ポリエステルポリオールであって、非晶性ポリエステルポリオールは全ポリカルボン酸及び全ポリオール成分をそれぞれ100モル%としたとき、全ポリカルボン酸成分の内、芳香族ジカルボン酸が60モル%以上であり、全ポリオール成分の内、主鎖の炭素数が4以下であるグリコールが60モル%以上であることを特徴とする項2又は3に記載の導電性ペースト。 Item 4: The amorphous polyol (A1) is an amorphous polyester polyol, and the amorphous polyester polyol has a total polycarboxylic acid component when the total polycarboxylic acid and the total polyol component are each 100 mol%. Item 2 or 3, wherein the aromatic dicarboxylic acid is 60 mol% or more, and among all the polyol components, glycol having a main chain having 4 or less carbon atoms is 60 mol% or more. Conductive paste.
項5:化合物(A2)におけるイソシアネートと反応し得る官能基が、水酸基又はアミノ基である項2〜4のいずれかに記載の導電性ペースト。 Item 5: The conductive paste according to any one of Items 2 to 4, wherein the functional group capable of reacting with isocyanate in the compound (A2) is a hydroxyl group or an amino group.
項6:化合物(A2)が、さらにカルボキシル基を含有する化合物である項2〜5のいずれかに記載の導電性ペースト。 Item 6: The conductive paste according to any one of Items 2 to 5, wherein the compound (A2) is a compound further containing a carboxyl group.
項7:(B)成分が、さらに金属粉末以外の導電性粉末を含有する項1〜6のいずれかに記載の導電性ペースト。 Item 7: The conductive paste according to any one of Items 1 to 6, wherein the component (B) further contains conductive powder other than metal powder.
項8:(B)成分の含有量が、バインダー樹脂(A)100質量部に対して、400〜1,900質量部である項1〜7のいずれかに記載の導電性ペースト。 Item 8: The conductive paste according to any one of Items 1 to 7, wherein the content of the component (B) is 400 to 1,900 parts by mass with respect to 100 parts by mass of the binder resin (A).
項9:(C)成分の含有量が、バインダー樹脂(A)100質量部に対して、150〜500質量部である項1〜8のいずれかに記載の導電性ペースト。 Item 9: The conductive paste according to any one of Items 1 to 8, wherein the content of the component (C) is 150 to 500 parts by mass with respect to 100 parts by mass of the binder resin (A).
項10:項1〜9のいずれかに記載の導電性ペーストを用いてなる導電性薄膜。 Item 10: A conductive thin film using the conductive paste according to any one of Items 1 to 9.
項11:項10に記載の導電性薄膜を透明導電性層上に積層した導電性積層体。 Item 11: A conductive laminate in which the conductive thin film according to Item 10 is laminated on a transparent conductive layer.
項12:透明導電性層が酸化インジウム・スズを主成分としてなるITO膜である項11に記載の導電性積層体。 Item 12: The conductive laminate according to Item 11, wherein the transparent conductive layer is an ITO film containing indium tin oxide as a main component.
項13:項11又は12に記載の導電性積層体を用いたタッチパネル。 Item 13: A touch panel using the conductive laminate according to Item 11 or 12.
項14:項1〜9のいずれかに記載の導電性ペーストを基材上に塗布又は印刷する工程、及び
80〜150℃で加熱する工程を含む導電性薄膜の製造方法。Item 14: A method for producing a conductive thin film, comprising a step of applying or printing the conductive paste according to any one of Items 1 to 9 on a substrate, and a step of heating at 80 to 150 ° C.
本発明の導電性ペーストは、含有するバインダー樹脂が高いガラス転移温度を有するため、薄膜を形成した際に、高温環境下においても良好な膜を維持することができ、高い信頼性を有する。また、バインダー樹脂において特定の酸価を有するため、基材上で薄膜を形成する際、基材上に存在する吸着水等の付着物による剥離が少なく、他材との密着性を著しく向上させることができる。 Since the binder resin contained in the conductive paste of the present invention has a high glass transition temperature, a good film can be maintained even in a high temperature environment when a thin film is formed, and the conductive paste has high reliability. In addition, since the binder resin has a specific acid value, when forming a thin film on the substrate, there is little peeling due to adhering water or other adhering water present on the substrate, and the adhesion to other materials is remarkably improved. be able to.
そのため、特に良好な密着性と高い信頼性、導電性の要求されるタッチパネル等の用途に適している。 Therefore, it is suitable for applications such as touch panels that require particularly good adhesion, high reliability, and conductivity.
以下、本発明の導電性ペーストの各成分について、詳細に説明する。 Hereinafter, each component of the electrically conductive paste of this invention is demonstrated in detail.
(A)成分
ポリウレタン樹脂であるバインダー樹脂(A)は、ウレタン結合を有することが必須となる。 The binder resin (A), which is the component (A) component polyurethane resin, must have a urethane bond.
ウレタン結合を有することで、導電性ペーストの塗布又は印刷後の硬化において、分子間の水素結合に起因する高い凝集力により塗膜内部の金属粉末等の導電性粉末相互の距離が接近することにより高導電性を発現することができる。また、低温乾燥において、たとえ溶剤が残存している場合においてもバインダー樹脂の高い凝集力により高導電性と基材への高密着性を発現することができる。ウレタン結合は、少なくとも非晶性ポリオールとポリイソシアネートとの反応によって形成され、さらに、数平均分子量1,000未満であって、1分子に2個以上のイソシアネートと反応し得る官能基を有する化合物と、ポリイソシアネートとの反応によって形成されるものが含まれていることが好ましい実施態様である。 By having a urethane bond, when the conductive paste is applied or cured after printing, the distance between the conductive powders such as metal powder inside the coating film approaches due to the high cohesive force resulting from intermolecular hydrogen bonding. High conductivity can be expressed. Further, in low-temperature drying, even when the solvent remains, high conductivity and high adhesion to the substrate can be expressed by the high cohesive force of the binder resin. The urethane bond is formed by the reaction of at least an amorphous polyol and a polyisocyanate, and further has a number average molecular weight of less than 1,000 and a compound having a functional group capable of reacting with two or more isocyanates per molecule. It is a preferred embodiment that those formed by reaction with polyisocyanate are included.
バインダー樹脂の数平均分子量は、バインダー樹脂の耐久性の観点から10,000以上であり、好ましくは20,000以上である。数平均分子量が10,000未満であると長期耐久性に問題が出る他、ペースト粘度が低下し、印刷性が低下することがある。また、バインダー樹脂の数平均分子量は、ペースト粘度(スクリーン印刷適性)、溶解性の観点より100,000以下が好ましい。 The number average molecular weight of the binder resin is 10,000 or more, preferably 20,000 or more, from the viewpoint of durability of the binder resin. If the number average molecular weight is less than 10,000, there will be a problem in long-term durability, the paste viscosity may be lowered, and the printability may be lowered. The number average molecular weight of the binder resin is preferably 100,000 or less from the viewpoint of paste viscosity (screen printing suitability) and solubility.
バインダー樹脂は、ガラス転移温度が60℃以上であり、70℃以上が好ましい。ガラス転移温度が60℃より低いと、硬化剤を配合しない場合に、高温時に樹脂が軟化するため、ペーストとしての信頼性が低下するおそれがある。また、表面硬度の低下を誘発し、また、タック性により製造工程及び/又は使用の際に接触相手側への樹脂、配合物の移行が生じ、信頼性が低下するおそれがある。また、バインダー樹脂のガラス転移温度は、密着性、溶解性、ペースト粘度、及び印刷性等を考慮すると150℃以下が好ましく、120℃以下がより好ましく、100℃以下が更に好ましい。バインダー樹脂のガラス転移温度は非晶性ポリオールA1、A4、1分子に2個以上のイソシアネートと反応し得る官能基を有する化合物A2、ポリイソシアネートA3の組成比及びA1,A2,A3,A4の化学構造を選択することによって調整することができる。本発明の請求項範囲内のガラス転移温度を発現させるためには、A1のガラス転移温度が40℃以上であることが好ましく、ポリイソシアネートとして少なくとも1種は脂環族骨格及び/又は芳香族骨格を有していることが好ましく、その組成比が質量比でA1>A3>A2であることが好ましく、またA1>A4であることが好ましい。 The binder resin has a glass transition temperature of 60 ° C. or higher, and preferably 70 ° C. or higher. When the glass transition temperature is lower than 60 ° C., when the curing agent is not blended, the resin softens at a high temperature, which may reduce the reliability as a paste. In addition, a decrease in surface hardness is induced, and due to tackiness, there is a possibility that the resin and the compound are transferred to the contact partner side during the production process and / or use, and the reliability may be lowered. The glass transition temperature of the binder resin is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 100 ° C. or lower in consideration of adhesion, solubility, paste viscosity, printability, and the like. The glass transition temperature of the binder resin is amorphous polyols A1, A4, the compound A2 having functional groups capable of reacting with two or more isocyanates per molecule, the composition ratio of polyisocyanate A3, and the chemistry of A1, A2, A3, A4. It can be adjusted by selecting the structure. In order to develop the glass transition temperature within the scope of the claims of the present invention, the glass transition temperature of A1 is preferably 40 ° C. or higher, and at least one polyisocyanate is an alicyclic skeleton and / or an aromatic skeleton. The composition ratio is preferably A1> A3> A2 by mass ratio, and preferably A1> A4.
バインダー樹脂は、特定の範囲の酸価を有する。酸価を付与することで、透明導電性層中に存在する吸着水との化学的相互作用により密着性を著しく向上させることができる。 The binder resin has an acid value in a specific range. By imparting an acid value, adhesion can be remarkably improved by chemical interaction with adsorbed water present in the transparent conductive layer.
バインダー樹脂の酸価は、50〜500eq/tonであり、100〜350eq/tonが好ましい。酸価が50eq/tonより低いと、得られる導電性薄膜と透明導電性層との密着性向上効果が小さくなる傾向がある。一方、酸価が500eq/tonを超えると吸水性が高くなる上、触媒作用によりバインダー樹脂の加水分解を促進する可能性があり、導電性薄膜を形成したときの電極としての信頼性の低下につながる傾向がある。 The acid value of the binder resin is 50 to 500 eq / ton, preferably 100 to 350 eq / ton. When the acid value is lower than 50 eq / ton, the effect of improving the adhesion between the obtained conductive thin film and the transparent conductive layer tends to be small. On the other hand, when the acid value exceeds 500 eq / ton, the water absorption increases, and the hydrolysis of the binder resin may be promoted by a catalytic action, which reduces the reliability as an electrode when a conductive thin film is formed. There is a tendency to connect.
バインダー樹脂に酸価を導入する方法としては、バインダー樹脂であるポリウレタン樹脂を製造する工程における、ポリオールとポリイソシアネートの鎖延長工程において、ジメチロールブタン酸、ジメチロールプロピオン酸等のカルボキシル基を含有する1分子に2個以上の官能基を含有する化合物を共重合することや、無水トリメリット酸、ベンゾフェノンテトラカルボン酸、トリメチロール無水酸等の多価カルボン酸無水物で分子中や分子末端に酸価を導入する方法等が挙げられる。本発明の酸価を導入する方法としては前記のいずれを用いてもよい。 As a method of introducing an acid value into the binder resin, a carboxyl group such as dimethylolbutanoic acid or dimethylolpropionic acid is contained in a chain extending step of polyol and polyisocyanate in a step of producing a polyurethane resin as a binder resin. Copolymerization of compounds containing two or more functional groups in one molecule, or polyvalent carboxylic acid anhydrides such as trimellitic anhydride, benzophenone tetracarboxylic acid, trimethylol anhydride, etc. And a method of introducing a valence. Any of the above methods may be used as the method for introducing the acid value of the present invention.
バインダー樹脂(A)は、少なくとも(A1)分子量1,000〜10,000、好ましくは、1,500〜7,000であり、ガラス転移温度30℃〜80℃、好ましくは45〜70℃の非晶性ポリオールと、(A2)数平均分子量1,000未満、好ましくは60〜400であって、1分子に2個以上のイソシアネートと反応し得る官能基を有する化合物と、(A3)ポリイソシアネートの重付加反応によって製造された、ポリエステルウレタン樹脂であることが好ましい。また、バインダー樹脂(A)は、少なくとも(A1)分子量1,000〜10,000、好ましくは1,500〜7,000であり、ガラス転移温度30℃〜80℃、好ましくは45〜70℃の非晶性ポリオールと、(A2)数平均分子量1,000未満、好ましくは60〜400であって、1分子に2個以上のイソシアネートと反応し得る官能基を有する化合物と、(A3)ポリイソシアネートと、(A4)分子量1,000〜10,000、好ましくは、1,500〜7,000であり、ガラス転移温度30℃未満の非晶性ポリオール、の重付加反応によって製造された、ポリエステルウレタン樹脂であることも好ましい。非晶性ポリオールとしてはポリエーテルポリオール、ポリエステルポリオール等が挙げられるが、分子設計の自由度からポリエステルポリオールが好ましい。ポリエステルポリオールは、ジカルボン酸とポリオールの縮合により得られるものが好ましい。なお、ジカルボン酸は、炭素数1〜12のアルコールでエステル化されたジカルボン酸エステルであってもよい。 The binder resin (A) is at least (A1) having a molecular weight of 1,000 to 10,000, preferably 1,500 to 7,000, and a glass transition temperature of 30 to 80 ° C., preferably 45 to 70 ° C. A crystalline polyol, (A2) a number average molecular weight of less than 1,000, preferably 60-400, a compound having a functional group capable of reacting with two or more isocyanates per molecule, and (A3) a polyisocyanate A polyester urethane resin produced by a polyaddition reaction is preferred. The binder resin (A) has at least (A1) a molecular weight of 1,000 to 10,000, preferably 1,500 to 7,000, and a glass transition temperature of 30 to 80 ° C, preferably 45 to 70 ° C. An amorphous polyol, (A2) a number average molecular weight of less than 1,000, preferably 60 to 400, a compound having a functional group capable of reacting with two or more isocyanates per molecule, and (A3) polyisocyanate And (A4) a polyester urethane produced by a polyaddition reaction of an amorphous polyol having a molecular weight of 1,000 to 10,000, preferably 1,500 to 7,000 and a glass transition temperature of less than 30 ° C. A resin is also preferable. Examples of amorphous polyols include polyether polyols and polyester polyols, and polyester polyols are preferred because of the degree of freedom in molecular design. The polyester polyol is preferably obtained by condensation of dicarboxylic acid and polyol. The dicarboxylic acid may be a dicarboxylic acid ester esterified with an alcohol having 1 to 12 carbon atoms.
前記ポリエステルポリオールの製造において使用されるジカルボン酸としては、テレフタル酸、イソフタル酸、オルソフタル酸、2,6−ナフタレンジカルボン酸等の芳香族ジカルボン酸;コハク酸、グルタル酸、アジピン酸、セバシン酸、ドデカンジカルボン酸、アゼライン酸等の脂肪族ジカルボン酸;ダイマー酸等の炭素数12〜28の二塩基酸;1,4−シクロヘキサンジカルボン酸、1,3−シクロヘキサンジカルボン酸、1,2−シクロヘキサンジカルボン酸、4−メチルヘキサヒドロ無水フタル酸、3−メチルヘキサヒドロ無水フタル酸、2−メチルヘキサヒドロ無水フタル酸、ジカルボキシ水素添加ビスフェノールA、ジカルボキシ水素添加ビスフェノールS、ダイマー酸、水素添加ダイマー酸、水素添加ナフタレンジカルボン酸、トリシクロデカンジカルボン酸等の脂環族ジカルボン酸又は脂環族ジカルボン酸無水物;ヒドロキシ安息香酸、乳酸等のヒドロキシカルボン酸が挙げられる。また、発明の効果を損なわない範囲で、無水トリメリット酸、無水ピロメリット酸等の多価のカルボン酸、フマール酸等の不飽和ジカルボン酸、さらに、5−スルホイソフタル酸ナトリウム塩等のスルホン酸金属塩基含有ジカルボン酸を共重合してもよい。 Examples of the dicarboxylic acid used in the production of the polyester polyol include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, and 2,6-naphthalenedicarboxylic acid; succinic acid, glutaric acid, adipic acid, sebacic acid, and dodecane. Aliphatic dicarboxylic acids such as dicarboxylic acid and azelaic acid; dibasic acids having 12 to 28 carbon atoms such as dimer acid; 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 2-methylhexahydrophthalic anhydride, dicarboxy hydrogenated bisphenol A, dicarboxy hydrogenated bisphenol S, dimer acid, hydrogenated dimer acid, hydrogen Additive naphthalene carbo Acid, alicyclic dicarboxylic acid or an alicyclic dicarboxylic acid anhydride such as tricyclodecane acid; hydroxybenzoic acid, hydroxycarboxylic acids such as lactic acid. In addition, polycarboxylic acids such as trimellitic anhydride and pyromellitic anhydride, unsaturated dicarboxylic acids such as fumaric acid, and sulfonic acids such as 5-sulfoisophthalic acid sodium salt, as long as the effects of the invention are not impaired. A metal base-containing dicarboxylic acid may be copolymerized.
非晶性ポリオール(A1)はポリエステルポリオールであることが好ましく、強度や耐熱性、耐湿性、及び耐熱衝撃性等の耐久性等の観点から、ポリエステルポリオールを構成する全酸成分のうち芳香族ジカルボン酸が60モル%以上共重合されていることが好ましく、より好ましくは80モル%以上、さらに好ましくは90モル%以上、特に好ましくは98モル%以上である。全酸成分が芳香族ジカルボン酸からなることは好ましい実施態様である。芳香族ジカルボン酸成分が60モル%より少ないと本発明のポリウレタン樹脂(A)のガラス転移温度が60℃より低くなるおそれがあり、耐湿熱性、耐久性が低下するおそれがある。一方、非晶性ポリオール(A4)はポリエステルポリオールであることが好ましく、ポリエステルポリオールを構成する全酸成分の内、芳香族ジカルボン酸が30モル%以上であることが好ましく、50モル%以上であることが好ましく、70モル%以上であることがさらに好ましい。 The amorphous polyol (A1) is preferably a polyester polyol, and from the viewpoints of durability such as strength, heat resistance, moisture resistance, and thermal shock resistance, aromatic dicarboxylic acid among all acid components constituting the polyester polyol. The acid is preferably copolymerized in an amount of 60 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and particularly preferably 98 mol% or more. It is a preferred embodiment that the total acid component consists of an aromatic dicarboxylic acid. When the amount of the aromatic dicarboxylic acid component is less than 60 mol%, the glass transition temperature of the polyurethane resin (A) of the present invention may be lower than 60 ° C., and the heat and moisture resistance and durability may be lowered. On the other hand, the amorphous polyol (A4) is preferably a polyester polyol. Of all the acid components constituting the polyester polyol, the aromatic dicarboxylic acid is preferably 30 mol% or more, and 50 mol% or more. It is preferably 70 mol% or more.
前記ポリエステルポリオールの製造において使用されるジオールとしては、エチレングリコール、プロピレングリコール、1,3−プロパンジオール、1,4−ブタンジオール、1,5−ペンタンジオール、ネオペンチルグリコール、1,6−ヘキサンジオール、3−メチル−1,5−ペンタンジオール、2−メチル−1,5−ペンタンジオール、2−メチル−1、3−プロパンジオール、2,2−ジエチル−1,3−プロパンジオール、2−ブチル−2−エチル−1,3−プロパンジオール、1,9−ノナンジオール、1,10−デカンジオール等の脂肪族ジオール、1,4−シクロヘキサンジメタノール、1,3−シクロヘキサンジメタノール、1,2−シクロヘキサンジメタノール、ダイマージオール等の脂環族ジオールが挙げられる。また、発明の効果を損なわない範囲でトリメチロールエタン、トリメチロールプロパン、グリセリン、ペンタエリスリトール、ポリグリセリン等の多価ポリオールを併用してもよい。 Examples of the diol used in the production of the polyester polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol. 3-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-butyl Aliphatic diols such as 2-ethyl-1,3-propanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2 -Alicyclic diols such as cyclohexanedimethanol and dimer diolMoreover, you may use multivalent polyols, such as a trimethylol ethane, a trimethylol propane, glycerol, a pentaerythritol, a polyglycerol, in the range which does not impair the effect of invention.
非晶性ポリオール(A1)はポリエステルポリオールであることが好ましく、強度や耐熱性、耐湿性、及び耐熱衝撃性等の耐久性等の観点から、ポリエステルポリオールを構成する全ポリオール成分の内、主鎖の炭素数が4以下であるグリコールが60モル%以上であることが好ましく、80モル%以上であることがより好ましく、95モル%以上であることがさらに好ましい。全ポリオール成分の内、主鎖の炭素数が4以下であるグリコールが60モル%より少なくなると本発明のポリウレタン樹脂Aのガラス転移温度が60℃より低くなるおそれがあり、耐湿熱性、耐久性が低下するおそれがある。一方、非晶性ポリオール(A4)はポリエステルポリオールであることが好ましく、ポリエステルポリオールを構成する全ポリオール成分の内、主鎖の炭素数が4以下であるグリコールが80モル%以下であることが好ましく、70モル%以下であることが好ましく、60モル%以下であることがさらに好ましい。 The amorphous polyol (A1) is preferably a polyester polyol. From the viewpoint of durability such as strength, heat resistance, moisture resistance, and thermal shock resistance, the main chain of all polyol components constituting the polyester polyol The glycol having 4 or less carbon atoms is preferably 60 mol% or more, more preferably 80 mol% or more, and further preferably 95 mol% or more. Among all the polyol components, when the glycol having 4 or less carbon atoms in the main chain is less than 60 mol%, the glass transition temperature of the polyurethane resin A of the present invention may be lower than 60 ° C., and the heat and moisture resistance and durability are improved. May decrease. On the other hand, the amorphous polyol (A4) is preferably a polyester polyol, and among all polyol components constituting the polyester polyol, the glycol having a main chain having 4 or less carbon atoms is preferably 80 mol% or less. 70 mol% or less, more preferably 60 mol% or less.
本発明で用いるバインダー樹脂(A)は、少なくとも前記非晶性ポリオール(A1)と、数平均分子量1,000未満であって、1分子に2個以上のイソシアネートと反応し得る官能基を有する化合物(A2)と、以下に示すポリイソシアネート(A3)の重付加反応よって製造することができる。また、バインダー樹脂(A)は、少なくとも前記非晶性ポリオール(A1)、(A4)と、数平均分子量1,000未満であって、1分子に2個以上のイソシアネートと反応し得る官能基を有する化合物(A2)と、以下に示すポリイソシアネート(A3)の重付加反応よって製造することができる。化合物(A2)におけるイソシアネートと反応し得る官能基としては、水酸基及びアミノ基が好ましく、化合物(A2)としてはいずれか一方を有するものでも双方を有するものであっても良い。具体的な(A2)成分としては、先に酸価導入手法としての使用を述べたジメチロールブタン酸、ジメチロールプロピオン酸のような、カルボキシル基を含有する化合物の他、1,2−プロピレングリコール、1,2−ブチレングリコール、1,3−ブチレングリコール、2,3−ブチレングリコール、2,2−ジメチル−1,3−プロパンジオール、3−メチル−1,5−ペンタンジオール、2,2,4−トリメチル−1,3−ペンタンジオール、2−エチル−1,3−ヘキサンジオール、2,2−ジメチル−3−ヒドロキシプロピル−2’,2’−ジメチル−3−ヒドロキシプロパネート、2−ノルマルブチル−2−エチル−1,3−プロパンジオール、3−エチル−1,5−ペンタンジオール、3−プロピル−1,5−ペンタンジオール、2,2−ジエチル−1,3−プロパンジオール、3−オクチル−1,5−ペンタンジオール、3−フェニル−1,5−ペンタンジオール、2,5−ジメチル−3−ナトリウムスルホ−2,5−ヘキサンジオール、ダイマージオール(PRIPOL-2033(ユニケマ・インターナショナル社製))等の1分子中に2個の水酸基を有する化合物、トリメチロールエタン、トリメチロールプロパン、グリセリン、ペンタエリスリトール、ポリグリセリン等の多価アルコール、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等の1分子に1個以上の水酸基とアミノ基を有するアミノアルコール、エチレンジアミン、1,6−ヘキサンジアミン、1,8−オクタンジアミン、1,9−ノナンジアミン、1,10-デカンジアミン、1,11-ウンデカンジアミン、1,12-ドデカンジアミンなどの脂肪族ジアミンやメタキシレンジアミン、4,4’-ジアミノジフェニルメタン、3,4’−ジアミノジフェニルエーテル、4,4’−ジアミノジフェニルエーテル等の1分子中に2個のアミノ基を有する芳香族ジアミン等が挙げられる。上記の数平均分子量1,000未満であって、1分子に2個以上のイソシアネートと反応し得る官能基を有する化合物は単独で用いてもよいし複数を併用しても何ら問題はない。 The binder resin (A) used in the present invention is a compound having at least the amorphous polyol (A1), a number average molecular weight of less than 1,000, and a functional group capable of reacting with two or more isocyanates per molecule. It can be produced by a polyaddition reaction between (A2) and the polyisocyanate (A3) shown below. The binder resin (A) has at least the amorphous polyols (A1) and (A4) and a functional group having a number average molecular weight of less than 1,000 and capable of reacting with two or more isocyanates per molecule. It can be produced by a polyaddition reaction of the compound (A2) having a polyisocyanate (A3) shown below. The functional group capable of reacting with isocyanate in the compound (A2) is preferably a hydroxyl group or an amino group, and the compound (A2) may have either one or both. Specific examples of the component (A2) include compounds containing a carboxyl group, such as dimethylolbutanoic acid and dimethylolpropionic acid, which have been used as an acid value introduction method, and 1,2-propylene glycol. 1,2-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2, 4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,2-dimethyl-3-hydroxypropyl-2 ′, 2′-dimethyl-3-hydroxypropanate, 2-normal Butyl-2-ethyl-1,3-propanediol, 3-ethyl-1,5-pentanediol, 3-propyl-1,5-pentanediol, 2 2,2-diethyl-1,3-propanediol, 3-octyl-1,5-pentanediol, 3-phenyl-1,5-pentanediol, 2,5-dimethyl-3-sodium sulfo-2,5-hexane Diols, dimer diols (PRIPOL-2033 (manufactured by Unikema International)), etc., compounds having two hydroxyl groups in one molecule, polyhydric alcohols such as trimethylolethane, trimethylolpropane, glycerin, pentaerythritol, polyglycerin Amino alcohol having at least one hydroxyl group and amino group in one molecule such as monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecane 2 in one molecule such as amine, aliphatic diamine such as 1,12-dodecanediamine, metaxylenediamine, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, etc. An aromatic diamine having an amino group is exemplified. The compound having a number average molecular weight of less than 1,000 and having a functional group capable of reacting with two or more isocyanates per molecule may be used alone or in combination with a plurality of compounds without any problem.
バインダー樹脂(A)を構成するポリイソシアネート(A3)としては、2,4−トリレンジイソシアネート、2,6−トリレンジイソシアネート、p−フェニレンジイソシアネート、4,4’−ジフェニルメタンジイソシアネート、m−フェニレンジイソシアネート、3,3’−ジメトキシ−4,4’−ビフェニレンジイソシアネート、2,6−ナフタレンジイソシアネート、3,3’−ジメチル−4,4’−ビフェニレンジイソシアネート、4,4’−ジフェニレンジイソシアネート、4,4’−ジイソシアネートジフェニルエーテル、1,5−ナフタレンジイソシアネート、m−キシレンジイソシアネート、イソホロンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、トルエンジイソシアネート等が挙げられる。 As the polyisocyanate (A3) constituting the binder resin (A), 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, m-phenylene diisocyanate, 3,3′-dimethoxy-4,4′-biphenylene diisocyanate, 2,6-naphthalene diisocyanate, 3,3′-dimethyl-4,4′-biphenylene diisocyanate, 4,4′-diphenylene diisocyanate, 4,4 ′ -Diisocyanate diphenyl ether, 1,5-naphthalene diisocyanate, m-xylene diisocyanate, isophorone diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, etc. It is below.
前記ポリイソシアネート(A3)と非晶性ポリオール(A1)及び数平均分子量1,000未満であって、1分子に2個以上のイソシアネートと反応し得る官能基を有する化合物(A2)を反応させることによって、バインダー樹脂(A)にウレタン結合を導入することができる。また、前記ポリイソシアネート(A3)と非晶性ポリオール(A1)、(A4)及び数平均分子量1,000未満であって、1分子に2個以上のイソシアネートと反応し得る官能基を有する化合物(A2)を反応させることによって、バインダー樹脂(A)にウレタン結合を導入することができる。 Reacting the polyisocyanate (A3) with an amorphous polyol (A1) and a compound (A2) having a number average molecular weight of less than 1,000 and having a functional group capable of reacting with two or more isocyanates per molecule. The urethane bond can be introduced into the binder resin (A). The polyisocyanate (A3), the amorphous polyols (A1) and (A4), and a compound having a number average molecular weight of less than 1,000 and having a functional group capable of reacting with two or more isocyanates per molecule ( A urethane bond can be introduced into the binder resin (A) by reacting A2).
バインダー樹脂(A)は、溶剤中にて重合することができるが、その溶剤は沸点80℃以上であることが好ましい。沸点が80℃以上の溶剤であれば揮発性が低いので、金属粉末及び所望の金属粉末以外の導電性粉末やその他配合物を配合した後に三本ロール等で分散させる際に、溶剤置換をする必要が無く、高率的に作業を行うことができ、コスト的観点からもメリットが生じる。一方、バインダー樹脂(A)を無溶剤で重合した後に、沸点80℃以上の溶剤に溶解しても何ら問題はない。 The binder resin (A) can be polymerized in a solvent, and the solvent preferably has a boiling point of 80 ° C. or higher. If the solvent has a boiling point of 80 ° C. or higher, the volatility is low. Therefore, when a conductive powder other than the metal powder and the desired metal powder or other compound is blended, the solvent is replaced when dispersed with a three roll or the like. There is no need, the work can be performed at a high rate, and there is a merit from the viewpoint of cost. On the other hand, there is no problem if the binder resin (A) is polymerized without solvent and then dissolved in a solvent having a boiling point of 80 ° C. or higher.
前記沸点80℃以上の溶剤としては、トルエン、キシレン、テトラメチルベンゼン、ソルベッソ100、ソルベッソ150、ソルベッソ200、テトラリン等の芳香族炭化水素系;デカリン等の脂肪族炭化水素系;ターピオネール等のアルコール系;メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系;エチレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールモノエチルエーテル、ジプロピレングリコールジエチルエーテル、ジオキサン、ジエチルエーテル、テトラヒドロフラン等のエーテル系;セロソルブアセテート、エチルセロソルブ、ブチルセロソルブ等のセロソルブ系;カルビトール、ブチルカルビトール等のカルビトール類の各種溶剤を使用することができる。重合においては前記溶剤を2種以上混合しても何ら問題はない。 Examples of the solvent having a boiling point of 80 ° C. or more include aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, Solvesso 100, Solvesso 150, Solvesso 200, and tetralin; aliphatic hydrocarbons such as decalin; alcohols such as terpionol. Type; ketone type such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ether type such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, dipropylene glycol diethyl ether, dioxane, diethyl ether, tetrahydrofuran; cellosolve acetate, ethyl cellosolve, butyl cellosolve Use of various solvents such as carbitols such as carbitol and butyl carbitol Kill. In the polymerization, there is no problem even if two or more of the above solvents are mixed.
バインダー樹脂(A)を製造する際の各モノマーの配合の際に、前記溶剤の他、三本ロール時の揮発の影響を抑制できる限りにおいては、80℃より沸点の低い溶剤を添加することは何ら問題がない。また使用前に沸点80℃未満の溶剤を添加することにも制限を設けない。 When blending each monomer when producing the binder resin (A), as long as the influence of volatilization at the time of three rolls can be suppressed, it is possible to add a solvent having a boiling point lower than 80 ° C. There is no problem. Further, there is no restriction on adding a solvent having a boiling point of less than 80 ° C. before use.
バインダー樹脂には、本発明の効果を損なわない程度にウレタン結合を有するポリウレタン樹脂と反応し得る硬化剤を配合してもよい。硬化剤を配合することにより、硬化温度が高くなる可能性があるが、塗膜物性の向上による信頼性の向上が期待できる。本発明のバインダー樹脂に反応し得る硬化剤は、種類は限定しないが接着性、耐屈曲性、硬化性等からイソシアネート化合物が特に好ましい。さらに、これらのイソシアネート化合物はイソシアネート基をブロック化したものを使用することが貯蔵安定性から好ましい。イソシアネート化合物以外の硬化剤としては、メチル化メラミン、ブチル化メラミン、ベンゾグアナミン、尿素樹脂等のアミノ樹脂、酸無水物、イミダゾール類、エポキシ樹脂、フェノール樹脂等の公知の化合物が挙げられる。 You may mix | blend the hardening | curing agent which can react with the polyurethane resin which has a urethane bond to such an extent that the effect of this invention is not impaired to binder resin. By blending a curing agent, the curing temperature may be increased, but an improvement in reliability due to an improvement in physical properties of the coating film can be expected. The curing agent capable of reacting with the binder resin of the present invention is not particularly limited, but an isocyanate compound is particularly preferred from the viewpoint of adhesiveness, flex resistance, curability and the like. Furthermore, it is preferable from the storage stability that these isocyanate compounds use what blocked the isocyanate group. Examples of curing agents other than isocyanate compounds include known compounds such as amino resins such as methylated melamine, butylated melamine, benzoguanamine, and urea resin, acid anhydrides, imidazoles, epoxy resins, and phenol resins.
イソシアネート化合物としては、芳香族又は脂肪族のジイソシアネート、3価以上のポリイソシアネート等があり、低分子化合物、高分子化合物のいずれでもよい。例えば、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート等の脂肪族ジイソシアネート、トルエンジイソシアネート、ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、等の芳香族ジイソシアネート、水素化ジフェニルメタンジイソシアネート、水素化キシリレンジイソシアネート、ダイマー酸ジイソシアネート、イソホロンジイソシアネート等の脂環族ジイソシアネート、あるいはこれらのイソシアネート化合物の3量体、及びこれらのイソシアネート化合物の過剰量と例えばエチレングリコール、プロピレングリコール、トリメチロールプロパン、グリセリン、ソルビトール、エチレンジアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等の低分子活性水素化合物又は各種ポリエステルポリオール類、ポリエーテルポリオール類、ポリアミド類の高分子活性水素化合物等と反応させて得られる末端イソシアネート基含有化合物が挙げられる。 Examples of the isocyanate compound include aromatic or aliphatic diisocyanates, trivalent or higher polyisocyanates, and any of low molecular compounds and high molecular compounds may be used. For example, aliphatic diisocyanates such as tetramethylene diisocyanate and hexamethylene diisocyanate, aromatic diisocyanates such as toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, etc. Alicyclic diisocyanates, or trimers of these isocyanate compounds, and excess amounts of these isocyanate compounds such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine Low molecular active hydrogen compounds such as Polyester polyols, polyether polyols, terminal isocyanate group-containing compounds obtained by reacting a polymeric active hydrogen compound such as polyamides and the like.
イソシアネート基のブロック化剤としては、例えばフェノール、チオフェノール、メチルチオフェノール、エチルチオフェノール、クレゾール、キシレノール、レゾルシノール、ニトロフェノール、クロロフェノール等のフェノール類;アセトキシム、メチルエチルケトオキシム、シクロヘキサノンオキシム等のオキシム類;メタノール、エタノール、プロパノール、ブタノール等のアルコール類;エチレンクロルヒドリン、1,3−ジクロロ−2−プロパノール等のハロゲン置換アルコール類;t−ブタノール、t−ペンタノール等の第三級アルコール類;ε−カプロラクタム、δ−バレロラクタム、γ−ブチロラクタム、β−プロピロラクタム等のラクタム類が挙げられ、その他にも芳香族アミン類、イミド類、アセチルアセトン、アセト酢酸エステル、マロン酸エチルエステル等の活性メチレン化合物、メルカプタン類、イミン類、イミダゾール類、尿素類、ジアリール化合物類、重亜硫酸ソーダ等も挙げられる。このうち、硬化性よりオキシム類、イミダゾール類、アミン類が特に好ましい。 Examples of the isocyanate group blocking agent include phenols such as phenol, thiophenol, methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol, and chlorophenol; oximes such as acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime; Alcohols such as methanol, ethanol, propanol and butanol; halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol; tertiary alcohols such as t-butanol and t-pentanol; -Lactams such as caprolactam, δ-valerolactam, γ-butyrolactam, β-propylolactam and the like, and other aromatic amines, imides, acetylacetone, acetoacetate Esters, active methylene compounds such as malonic acid ethyl ester, mercaptans, imines, imidazoles, ureas, diaryl compounds, sodium bisulfite, etc. can be mentioned. Of these, oximes, imidazoles, and amines are particularly preferable from the viewpoint of curability.
これらの硬化剤には、その種類に応じて選択された公知の触媒あるいは促進剤を併用することもできる。 These curing agents can be used in combination with a known catalyst or accelerator selected according to the type.
硬化剤の配合量としては、本発明の効果を損なわない程度に配合されるものであり、特に制限されるものではないが、バインダー樹脂100質量部に対して、0.5〜50質量部が好ましく、1〜30質量部がより好ましく、2〜20質量部がさらに好ましい。 As a compounding quantity of a hardening | curing agent, it mix | blends to such an extent that the effect of this invention is not impaired, Although it does not restrict | limit in particular, 0.5-50 mass parts with respect to 100 mass parts of binder resin. Preferably, 1-30 mass parts is more preferable, and 2-20 mass parts is further more preferable.
バインダー樹脂(A)を導電性ペーストに含有することにより、導電性薄膜を形成させるために低温乾燥(例えば135℃以下)を施しても、積層される透明電極層に対して極めて優れた密着性を有し、高導電性を発現することができる。 By including the binder resin (A) in the conductive paste, extremely excellent adhesion to the laminated transparent electrode layer even when subjected to low-temperature drying (eg, 135 ° C. or lower) to form a conductive thin film And exhibit high conductivity.
本発明の導電性ペーストは、バインダー樹脂(A)に加え、その他の樹脂として、前記で特定したポリウレタン樹脂以外のウレタン系樹脂、ポリエステル樹脂、エポキシ樹脂、フェノール樹脂、アクリル樹脂、スチレン−アクリル樹脂、スチレン−ブタジエン共重合体、ポリスチレン、ポリアミド樹脂、ポリカーボネート樹脂、塩化ビニル−酢酸ビニル共重合樹脂、エチレン−酢酸ビニル共重合樹脂等を併用することにも何ら制限は設けない。但し、バインダー樹脂(A)の特徴を損なわない程度にバインダー樹脂(A)に対して30重量%以下含有されることが好ましい。前記の樹脂を併用する際、その種類に制限はないが、基材への密着性、耐屈曲性及び溶剤溶解性、相溶性の観点から、ポリエステル樹脂、バインダー樹脂(A)以外のウレタン系樹脂が好ましい。 In addition to the binder resin (A), the conductive paste of the present invention includes, as other resins, urethane resins other than the polyurethane resins specified above, polyester resins, epoxy resins, phenol resins, acrylic resins, styrene-acrylic resins, There is no limitation on using a styrene-butadiene copolymer, polystyrene, polyamide resin, polycarbonate resin, vinyl chloride-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin, or the like. However, it is preferably contained in an amount of 30% by weight or less based on the binder resin (A) so as not to impair the characteristics of the binder resin (A). When the above resins are used in combination, the type is not limited, but from the viewpoints of adhesion to a substrate, flex resistance, solvent solubility, and compatibility, urethane resins other than polyester resins and binder resins (A) Is preferred.
(B)成分
本発明に使用する金属粉末(B)としては、銀粉、金粉、白金粉、パラジウム粉等の貴金属粉、銅粉、ニッケル粉、アルミ粉、真鍮粉等の卑金属粉、銀等の貴金属でめっき、又は合金化した卑金属粉等が挙げられる。これらの金属粉末は、単独で用いてもよく、また、併用してもよい。これらの中で、銀粉単独又は銀粉を主体とするものが好ましい。 (B) Component As the metal powder (B) used in the present invention, noble metal powder such as silver powder, gold powder, platinum powder and palladium powder, base metal powder such as copper powder, nickel powder, aluminum powder and brass powder, silver, etc. Examples thereof include a base metal powder plated or alloyed with a noble metal. These metal powders may be used alone or in combination. Among these, silver powder alone or those mainly composed of silver powder are preferable.
金属粉末の形状としては、公知のフレーク状(リン片状)、球状、樹枝状(デンドライト状)、特開平9−306240号公報に記載されている球状の1次粒子が3次元状に凝集した形状等が挙げられるが、これらの中で、フレーク状銀粉、前述した球状の1次粒子が3次元状に凝集した形状の銀粉が導電性の面で特に好ましい。 As the shape of the metal powder, known flaky shapes (flaky shapes), spherical shapes, dendritic shapes (dendritic shapes), and spherical primary particles described in JP-A-9-306240 are aggregated three-dimensionally. Among these, flaky silver powder and silver powder having a shape in which the above-described spherical primary particles are aggregated three-dimensionally are particularly preferable in terms of conductivity.
また、前記の金属粉末以外に、さらに金属粉末以外の導電性粉末を含有してもよい。金属粉末以外の導電性粉末の含有量としては、高い導電性を得るという点から、金属粉末100質量部に対して、11質量部以下が好ましく、9質量部以下がより好ましい。金属粉末以外の導電性粉末の含有量の下限としては、特に限定されないが、金属粉末100質量部に対して、0.5質量部以上が好ましく、1質量部以上がより好ましい。金属粉末以外の導電性粉末としては、公知の無機物を添加してもよく、例えば、カーボンブラック、グラファイト粉等の炭素系のフィラー;炭化ケイ素、炭化ホウ素、炭化チタン、炭化ジルコニウム、炭化ハフニウム、炭化バナジウム、炭化タンタル、炭化ニオブ、炭化タングステン、炭化クロム、炭化モリブテン、炭化カルシウム、ダイヤモンドカーボンラクタム等の各種炭化物;窒化ホウ素、窒化チタン、窒化ジルコニウム等の各種窒化物、ホウ化ジルコニウム等の各種ホウ化物;酸化チタン(チタニア)、酸化カルシウム、酸化マグネシウム、酸化亜鉛、酸化銅、酸化アルミニウム、シリカ、コロイダルシリカ等の各種酸化物;チタン酸カルシウム、チタン酸マグネシウム、チタン酸ストロンチウム等の各種チタン酸化合物;二硫化モリブデン等の硫化物;フッ化マグネシウム、フッ化炭素等の各種フッ化物;ステアリン酸アルミニウム、ステアリン酸カルシウム、ステアリン酸亜鉛、ステアリン酸マグネシウム等の各種金属石鹸;その他、滑石、ベントナイト、タルク、炭酸カルシウム、ベントナイト、カオリン、ガラス繊維、雲母等を用いることができる。上記のような無機物を添加することによって、耐熱性や耐久性を向上させることが可能となる場合がある。 Moreover, you may contain electroconductive powder other than metal powder other than the said metal powder. As content of electroconductive powder other than metal powder, 11 mass parts or less are preferable with respect to 100 mass parts of metal powder, and 9 mass parts or less are more preferable from the point of obtaining high electroconductivity. Although it does not specifically limit as a minimum of content of electroconductive powder other than metal powder, 0.5 mass part or more is preferable with respect to 100 mass parts of metal powder, and 1 mass part or more is more preferable. As the conductive powder other than the metal powder, known inorganic substances may be added. For example, carbon-based fillers such as carbon black and graphite powder; silicon carbide, boron carbide, titanium carbide, zirconium carbide, hafnium carbide, carbonized Various carbides such as vanadium, tantalum carbide, niobium carbide, tungsten carbide, chromium carbide, molybdenum carbide, calcium carbide and diamond carbon lactam; various nitrides such as boron nitride, titanium nitride and zirconium nitride; various borides such as zirconium boride Various oxides such as titanium oxide (titania), calcium oxide, magnesium oxide, zinc oxide, copper oxide, aluminum oxide, silica, colloidal silica; various titanate compounds such as calcium titanate, magnesium titanate, strontium titanate; Molybdenum disulfide Sulfides such as Buden; Various fluorides such as magnesium fluoride and carbon fluoride; Various metal soaps such as aluminum stearate, calcium stearate, zinc stearate, magnesium stearate; Other talc, bentonite, talc, calcium carbonate, Bentonite, kaolin, glass fiber, mica and the like can be used. By adding the above inorganic substances, it may be possible to improve heat resistance and durability.
また、導電性、耐湿性等の環境特性、コスト面より、カーボンブラック、グラファイト粉が好ましい。カーボンブラック、グラファイト粉を含む場合の、カーボンブラック及び/又はグラファイト粉の含有量としては、金属粉末100質量部に対して、25質量部以下、さらに好ましくは11質量部以下で配合することが好ましい。 Carbon black and graphite powder are preferred from the viewpoints of environmental characteristics such as conductivity and moisture resistance, and cost. When carbon black and graphite powder are contained, the content of carbon black and / or graphite powder is preferably 25 parts by mass or less, more preferably 11 parts by mass or less, with respect to 100 parts by mass of metal powder. .
また、チキソ性付与剤、消泡剤、難燃剤、粘着付与剤、加水分解防止剤、レベリング剤、可塑剤、酸化防止剤、紫外線吸収剤、難燃剤、顔料、染料を用いることができる。さらには樹脂分解抑制剤としてカルボジイミド、エポキシ等を適宜使用することもできる。これらは単独もしくは併用で用いることができる。 Further, thixotropic agents, antifoaming agents, flame retardants, tackifiers, hydrolysis inhibitors, leveling agents, plasticizers, antioxidants, ultraviolet absorbers, flame retardants, pigments and dyes can be used. Furthermore, carbodiimide, epoxy, or the like can be appropriately used as a resin degradation inhibitor. These can be used alone or in combination.
(B)成分の含有量は、形成された導電性薄膜の導電性が良好であるという観点から、バインダー樹脂(A)100質量部に対して、400質量部以上が好ましく、560質量部以上がより好ましく、700質量部以上がさらに好ましい。また、(B)成分の含有量は、透明導電性層との密着性において良好であるという観点から、バインダー樹脂(A)100質量部に対して、1,900質量部以下が好ましく、1,230質量部以下がより好ましく、750質量部以下がさらに好ましい。 The content of the component (B) is preferably 400 parts by mass or more, preferably 560 parts by mass or more with respect to 100 parts by mass of the binder resin (A), from the viewpoint that the conductivity of the formed conductive thin film is good. More preferred is 700 parts by mass or more. In addition, the content of the component (B) is preferably 1,900 parts by mass or less with respect to 100 parts by mass of the binder resin (A) from the viewpoint of good adhesion with the transparent conductive layer, 230 mass parts or less are more preferable, and 750 mass parts or less are still more preferable.
(C)成分
(C)成分である有機溶媒としては、(A)成分であるバインダー樹脂が可溶であり、かつ、(B)成分である導電性粉末を良好に分散させることができるものが好ましい。具体例としては、エチルジグリコールアセテート(ECA)、ブチルグリコールアセテート(BCA)、シクロヘキサノン、メチルエチルケトン、トルエン、イソホロン、γ-ブチロラクトン、ベンジルアルコール、エクソン化学製のソルベッソ100,150,200、プロピレングリコールモノメチルエーテルアセテート、ターピオネール等が挙げられるが、これらの中で、溶解性、スクリーン印刷性において良好であるという観点から、エチルジグリコールアセテート(ECA)、ブチルグリコールアセテート(BCA)又はその混合溶媒が好ましい。 (C) Component (C) The organic solvent that is the component (C) is one in which the binder resin (A) is soluble and the conductive powder (B) can be dispersed well. preferable. Specific examples include ethyl diglycol acetate (ECA), butyl glycol acetate (BCA), cyclohexanone, methyl ethyl ketone, toluene, isophorone, γ-butyrolactone, benzyl alcohol, Solvesso 100, 150, 200 manufactured by Exxon Chemical, propylene glycol monomethyl ether Acetate, terpionol, and the like can be mentioned. Among these, ethyldiglycol acetate (ECA), butyl glycol acetate (BCA), or a mixed solvent thereof is preferable from the viewpoint of good solubility and screen printability.
(C)成分の含有量は、スクリーン印刷において印刷後のかすれや版詰まりを抑制する点において良好であるという観点から、バインダー樹脂(A)100質量部に対して、150質量部以上が好ましく、200質量部以上がより好ましく、240質量部以上がさらに好ましい。また、(C)成分の含有量は、スクリーン印刷におけるにじみの抑制、膜厚の均一性を保つ点において良好であるという観点から、バインダー樹脂(A)100質量部に対して、500質量部以下が好ましく、400質量部以下がより好ましく、300質量部以下がさらに好ましい。 The content of the component (C) is preferably 150 parts by mass or more with respect to 100 parts by mass of the binder resin (A) from the viewpoint that it is favorable in terms of suppressing blurring after printing and plate clogging in screen printing. 200 mass parts or more are more preferable, and 240 mass parts or more are still more preferable. In addition, the content of the component (C) is 500 parts by mass or less with respect to 100 parts by mass of the binder resin (A), from the viewpoint of suppressing bleeding in screen printing and maintaining film thickness uniformity. Is preferably 400 parts by mass or less, and more preferably 300 parts by mass or less.
本発明の導電性ペーストは、タッチパネル用として好適に用いられるが、タッチパネル以外にも、電磁波シールド用途、電子部品の回路形成用途、端子やリード線の導電性接着剤等の用途にも使用することが可能である。 The conductive paste of the present invention is suitably used for touch panels. However, in addition to touch panels, it is also used for applications such as electromagnetic shielding applications, circuit formation of electronic components, and conductive adhesives for terminals and lead wires. Is possible.
本発明の導電性ペーストは、F値が60〜95%であることが好ましく、より好ましくは75〜95%である。F値とはペースト中に含まれる全固形分100質量部に対するフィラー質量部を示す数値であり、F値=(フィラー質量部/固形分質量部)×100で表される。ここで言うフィラー質量部とは導電性粉末(B)の質量部、固形分質量部とは溶剤以外の成分の質量部であり、導電性粉末(B)、バインダー樹脂、その他の硬化剤や添加剤を全て含む。F値が60%未満であると良好な導電性が得られず、95%をこえると密着性及び/又は硬度が低下する傾向にある。印刷性の低下も避けられない。 The conductive paste of the present invention preferably has an F value of 60 to 95%, more preferably 75 to 95%. The F value is a numerical value indicating the filler mass part with respect to 100 mass parts of the total solid content contained in the paste, and is represented by F value = (filler mass part / solid mass part) × 100. Filler parts by weight here are parts by weight of the conductive powder (B), solid parts by weight are parts by weight of components other than the solvent, conductive powder (B), binder resin, other curing agents and additions Contains all agents. When the F value is less than 60%, good conductivity cannot be obtained, and when it exceeds 95%, the adhesion and / or hardness tends to be lowered. A decrease in printability is inevitable.
また本発明は、前記の導電性ペーストを用いてなる導電性薄膜及びその製造方法にも関する。 The present invention also relates to a conductive thin film using the conductive paste and a method for producing the same.
導電性薄膜は、基材上に、導電性ペーストを塗布又は印刷し、そののち、加熱することによって塗布又は印刷した導電性ペーストを硬化することにより得られる。塗布方法としては、アプリケーター、バーコーターによる塗布や、スピンコート法、ディップコート法等の方法が挙げられる。また、印刷により導電性薄膜を形成する場合の印刷方法としては、スクリーン印刷法、グラビア印刷、フレキソ印刷、オフセット印刷等の方法が挙げられる。 The conductive thin film is obtained by applying or printing a conductive paste on a substrate and then curing the applied or printed conductive paste by heating. Examples of the application method include application using an applicator and a bar coater, spin coating, and dip coating. Examples of the printing method for forming the conductive thin film by printing include screen printing, gravure printing, flexographic printing, and offset printing.
塗布又は印刷した導電性ペーストを硬化する際の加熱温度としては、乾燥後の導電性薄膜の導電性や密着性、表面硬度において良好であるという観点から、80℃以上が好ましく、100℃以上がより好ましく、110℃以上がさらに好ましい。また、加熱温度としては、下地の透明導電性層の耐熱性、及び生産工程における省エネルギーにおいて良好であるという観点から、150℃以下が好ましく、135℃以下がより好ましく、130℃以下がさらに好ましい。 The heating temperature for curing the applied or printed conductive paste is preferably 80 ° C. or higher, and preferably 100 ° C. or higher, from the viewpoint of good conductivity, adhesion, and surface hardness of the conductive thin film after drying. More preferably, 110 degreeC or more is further more preferable. In addition, the heating temperature is preferably 150 ° C. or lower, more preferably 135 ° C. or lower, and further preferably 130 ° C. or lower, from the viewpoint of good heat resistance of the underlying transparent conductive layer and energy saving in the production process.
導電性薄膜の厚さは、用いられる用途によって異なるが、乾燥後の導電性薄膜の導電性において良好であるという観点から、5μm以上が好ましく、7μm以上がより好ましく、9μm以上がさらに好ましい。また、導電性薄膜の厚さは、スクリーン印刷性において良好である点、ペースト中の銀含有量低減によるコストメリットの観点から、30μm以下が好ましく、25μm以下がより好ましく、20μm以下がさらに好ましい。 Although the thickness of the conductive thin film varies depending on the application used, it is preferably 5 μm or more, more preferably 7 μm or more, and even more preferably 9 μm or more from the viewpoint of good conductivity of the conductive thin film after drying. The thickness of the conductive thin film is preferably 30 μm or less, more preferably 25 μm or less, and even more preferably 20 μm or less from the viewpoint of good screen printability and cost merit due to reduction of the silver content in the paste.
また、導電性ペーストが塗布される基材としては、例えば、ポリカーボネート、アクリル、ポリイミド、ポリエステル等が挙げられ、タッチパネルの用途に用いられる場合には、基材と導電性膜との間に、透明導電性層を設け、導電性薄膜が透明導電性層上に積層した導電性積層体とすることが好ましい。透明導電性層としては、酸化インジウム・スズを主成分としてなるITO膜であることが好ましく、従来の結晶性ITO膜を用いた際に生じる導電性薄膜との密着性についても極めて優れた密着性を有するため、ITO膜の表面形状が、平坦なものや凹凸のあるもの等、どのような表面形状のものであっても適用することが可能となる。 In addition, examples of the substrate to which the conductive paste is applied include polycarbonate, acrylic, polyimide, polyester, and the like. When used for touch panel applications, a transparent material is used between the substrate and the conductive film. It is preferable to provide a conductive laminate in which a conductive layer is provided and a conductive thin film is laminated on the transparent conductive layer. The transparent conductive layer is preferably an ITO film containing indium tin oxide as a main component, and has excellent adhesion with respect to the conductive thin film produced when a conventional crystalline ITO film is used. Therefore, the present invention can be applied to any surface shape such as a flat surface or an uneven surface.
さらに本発明は、前記導電性積層体を用いたタッチパネルにも関する。タッチパネルとしては、抵抗膜方式と静電容量方式のものが挙げられるが、いずれのタッチパネルであっても適用が可能である。 Furthermore, this invention relates also to the touchscreen using the said electroconductive laminated body. Examples of the touch panel include a resistance film type and a capacitance type, but any touch panel can be applied.
タッチパネルの製造方法としては、特に限定されるものではないが、例えば、ITO膜等の透明導電性層を積層した基材上に、硬化後、導電性を与える回路を形成するように、導電性ペーストを塗布又は印刷し、加熱により塗布又は印刷した導電性ペーストを硬化させ、導電性積層体を形成させ、得られる導電性積層体を別の導電性積層体と貼り合わせることにより製造することができる。 The touch panel manufacturing method is not particularly limited. For example, a conductive film is formed on a base material on which a transparent conductive layer such as an ITO film is laminated. It can be manufactured by applying or printing a paste, curing the conductive paste applied or printed by heating, forming a conductive laminate, and bonding the resulting conductive laminate to another conductive laminate. it can.
以下に実施例及び比較例を示して、本発明をさらに具体的に説明する。なお、本発明は、以下の実施形態に限定されるものではない。また、特に断らない限り例中の「部」は「質量部」を示し、固形分濃度とは溶剤を完全に揮発させた後の不揮発分のことを示す。 The present invention will be described more specifically with reference to the following examples and comparative examples. In addition, this invention is not limited to the following embodiment. Further, unless otherwise specified, “part” in the examples indicates “part by mass”, and the solid content concentration indicates a non-volatile content after the solvent is completely volatilized.
後述する製造例において製造されたポリエステル樹脂(P)及びポリウレタン樹脂(U)の物性評価(1.数平均分子量、2.ガラス転移温度(Tg)、3.酸価及び4.樹脂組成)の測定方法を以下に示す。 Measurement of physical properties (1. number average molecular weight, 2. glass transition temperature (Tg), 3. acid value and 4. resin composition) of polyester resin (P) and polyurethane resin (U) produced in the production examples described later. The method is shown below.
また、製造例において製造されたポリエステル樹脂(P)及びポリウレタン樹脂(U)を用いて調製した導電性ペーストの10.貯蔵安定性、及び導電性ペーストを用いて形成したテストピースについての物性評価(5.密着性、6.比抵抗、7.鉛筆硬度、8.環境試験及び9.耐ブロッキング性)の測定方法を以下に示す。 Moreover, 10. 10 of the electrically conductive paste prepared using the polyester resin (P) and polyurethane resin (U) which were manufactured in the manufacture example. Measurement methods for storage stability and physical property evaluation (5. adhesion, 6. specific resistance, 7. pencil hardness, 8. environmental test, and 9. anti-blocking property) of test pieces formed using conductive paste It is shown below.
1.数平均分子量
試料樹脂を、樹脂濃度が0.5重量%程度となるようにテトラヒドロフランに溶解または希釈し、孔径0.5μmのポリ四フッ化エチレン製メンブランフィルターで濾過し、GPC測定試料とした。テトラヒドロフランを移動相とし、島津製作所社製のゲル浸透クロマトグラフ(GPC)Prominenceを用い、示差屈折計(RI計)を検出器として、カラム温度30℃、流量1ml/分にて樹脂試料のGPC測定を行なった。数平均分子量既知の単分散ポリスチレンのGPC測定結果を用いて試料樹脂のポリスチレン換算数平均分子量を求め、それを本願における試料樹脂の数平均分子量とした。ただしカラムは昭和電工(株)製のshodex KF−802、804L、806Lを用いた。1. Number average molecular weight The sample resin was dissolved or diluted in tetrahydrofuran so that the resin concentration was about 0.5% by weight, and filtered through a polytetrafluoroethylene membrane filter having a pore size of 0.5 μm to obtain a GPC measurement sample. GPC measurement of a resin sample using tetrahydrofuran as a mobile phase, a gel permeation chromatograph (GPC) Prominence manufactured by Shimadzu Corporation, and a differential refractometer (RI meter) as a detector at a column temperature of 30 ° C. and a flow rate of 1 ml / min. Was done. Using the GPC measurement result of monodisperse polystyrene having a known number average molecular weight, the polystyrene-reduced number average molecular weight of the sample resin was determined and used as the number average molecular weight of the sample resin in the present application. However, shodex KF-802, 804L, and 806L manufactured by Showa Denko KK were used as the column.
2.ガラス転移温度(Tg)
試料樹脂5mgをアルミニウム製サンプルパンに入れて密封し、セイコーインスツルメンツ(株)製の示差走査熱量分析計(DSC)DSC−220を用いて、200℃まで、昇温速度20℃/分にて測定し、ガラス転移温度以下のベースラインの延長線と遷移部における最大傾斜を示す接線との交点の温度で求めた。2. Glass transition temperature (Tg)
5 mg of sample resin is put in an aluminum sample pan, sealed, and measured using a differential scanning calorimeter (DSC) DSC-220 manufactured by Seiko Instruments Inc. up to 200 ° C. at a temperature rising rate of 20 ° C./min. And the temperature at the intersection of the base line extension below the glass transition temperature and the tangent indicating the maximum slope at the transition.
3.酸価
試料樹脂0.2gを精秤し20mlのクロロホルムに溶解した。ついで、0.01Nの水酸化カリウム(エタノール溶液)で滴定して求めた。指示薬には、フェノールフタレイン溶液を用いた。酸価の単位はeq/ton、すなわち試料1トン当たりの当量とした。3. Acid value 0.2 g of sample resin was precisely weighed and dissolved in 20 ml of chloroform. Subsequently, it titrated with 0.01N potassium hydroxide (ethanol solution). A phenolphthalein solution was used as an indicator. The unit of the acid value was eq / ton, that is, the equivalent per ton of the sample.
4.樹脂組成
クロロホルム−dに試料樹脂を溶解し、VARIAN製400MHz-NMR装置を用い、1H−NMRにより樹脂組成比を求めた。4). Resin Composition A sample resin was dissolved in chloroform-d, and a resin composition ratio was determined by 1 H-NMR using a VARIAN 400 MHz-NMR apparatus.
5.密着性
作製した導電性ペーストを厚み100μmのアニール処理をしたPETフィルム又は結晶性ITO膜にスクリーン印刷法により25×200mmのパターンを印刷し、150℃で30分乾燥、硬化したものをテストピースとした。乾燥膜厚は20〜30μmになるように調整した。このテストピースを用いてJIS K−5600−5−6:1991に従って、セロテープ(登録商標)(ニチバン(株)製)を用い、剥離試験により評価した。但し、格子パターンの各方向のカット数は11個、カット間隔は1mmとした。100/100は剥離がなく密着性が良好であることを示し、0/100は全て剥離してしまい、密着性が劣ることを表す。5. Adhesiveness A 25 x 200 mm pattern was printed on a PET film or crystalline ITO film that had been annealed to a thickness of 100 μm by screen printing, and dried and cured at 150 ° C. for 30 minutes. did. The dry film thickness was adjusted to 20 to 30 μm. Using this test piece, according to JIS K-5600-5-6: 1991, it was evaluated by a peel test using Cellotape (registered trademark) (manufactured by Nichiban Co., Ltd.). However, the number of cuts in each direction of the lattice pattern was 11, and the cut interval was 1 mm. 100/100 indicates that there is no peeling and good adhesion, and 0/100 indicates that all are peeled off, resulting in poor adhesion.
6.比抵抗
5.と同様に作製したテストピースを25×450mm幅に切り取り、シート抵抗と膜厚を測定し、比抵抗を算出した。なお、膜厚はゲージスタンドST-022(小野測器社製)を用い、PETフィルムの厚みをゼロ点として硬化塗膜の厚みを5点測定し、その平均値を用いた。シート抵抗はMILLIOHMMETER4338B(HEWLETT PACKARD社製)を用いて25×450mm幅のテストピースを4枚測定し、その平均値を用いた。6). Specific resistance The test piece produced in the same manner as above was cut to a width of 25 × 450 mm, the sheet resistance and the film thickness were measured, and the specific resistance was calculated. The film thickness was measured using a gauge stand ST-022 (manufactured by Ono Sokki Co., Ltd.), and the thickness of the cured coating film was measured at five points with the thickness of the PET film as the zero point, and the average value was used. For the sheet resistance, four test pieces having a width of 25 × 450 mm were measured using MILLIOHMMETER4338B (manufactured by HEWLETT PACKARD), and the average value thereof was used.
7.鉛筆硬度
5.密着性試験で作製したテストピースを厚さ2mmのSUS304板上に置き、JIS K 5600−5−4:1999に従って測定し、剥離の有無で判断した。7). 4. Pencil hardness The test piece produced in the adhesion test was placed on a 2 mm thick SUS304 plate, measured according to JIS K 5600-5-4: 1999, and judged by the presence or absence of peeling.
8.環境試験:
5.密着性試験でITO膜上に作製したテストピースを、80℃で300時間加熱する耐熱試験及び85℃、85%RH(相対湿度)で300時間加熱する耐湿熱試験を行い、加熱終了後24時間常温で放置した後、抵抗値を測定した。
環境試験の良否は、前記耐熱試験及び耐湿熱試験の実施前後における導電性塗膜の密着性及び鉛筆硬度の評価にて行った。8). Environmental testing:
5. A test piece produced on the ITO film in the adhesion test is subjected to a heat resistance test in which heating is performed at 80 ° C. for 300 hours and a heat resistance test in which heating is performed at 85 ° C. and 85% RH (relative humidity) for 300 hours. After leaving at room temperature, the resistance value was measured.
The quality of the environmental test was evaluated by evaluating the adhesion of the conductive coating film and the pencil hardness before and after the heat resistance test and the moist heat resistance test.
9.耐ブロッキング性:
5.密着性試験のようにITO膜上に作製した塗膜を2枚、塗膜面を接するように重ね合わせ、導電性塗膜部分に500gの荷重を印加して、80℃で72時間放置した。ついで荷重を取り除き常温で1時間放置した後に以下の基準で外観により良否を判定した。
○:塗膜双方への転写がなく、元の塗膜状態を保持している。
×:双方への転写が見られ、ハガレが生じている。9. Blocking resistance:
5. Two coating films prepared on the ITO film as in the adhesion test were overlapped so that the coating film surface was in contact, and a load of 500 g was applied to the conductive coating film part and left at 80 ° C. for 72 hours. Next, after removing the load and leaving it to stand at room temperature for 1 hour, the quality was judged by the appearance according to the following criteria.
○: There is no transfer to both coating films, and the original coating film state is maintained.
X: Transfer on both sides is observed, and peeling occurs.
10.貯蔵安定性
導電性ペーストをポリ容器に入れ、密栓したものを40℃で1ヶ月貯蔵した。貯蔵後に粘度及び4と同様に作製したテストピースを用い、比抵抗、鉛筆硬度、密着性を測定した。
○:著しい粘度変化はなく、初期の比抵抗、鉛筆硬度、密着性を維持している。
×:かなりの粘度上昇が認められ、比抵抗、鉛筆硬度、密着性の低下が認められる。10. Storage stability The conductive paste was put in a plastic container and the sealed one was stored at 40 ° C. for 1 month. The specific resistance, pencil hardness, and adhesion were measured using a test piece prepared in the same manner as the viscosity and 4 after storage.
◯: There is no significant change in viscosity, and the initial specific resistance, pencil hardness, and adhesion are maintained.
X: A considerable increase in viscosity is observed, and a decrease in specific resistance, pencil hardness, and adhesion is observed.
樹脂の製造例
ポリエステルポリオール(P)の合成
ポリエステルポリオール(P-1)
攪拌機、コンデンサー、及び温度計を具備した反応容器にテレフタル酸ジメチル700部、イソフタル酸ジメチル700部、エチレングリコール671部、ネオペンチルグリコール526部、テトラブチルチタネート0.48部を仕込み、180℃、3時間エスエル交換を行なった。次に、1mmHg以下まで徐々に減圧し、240℃、1.5時間重合した。得られた共重合ポリエステルP-1の組成は、テレフタル酸/イソフタル酸//エチレングリコール/ネオペンチルグリコール=50/50//50/50(モル比)で、数平均分子量2,000、酸価2eq/ton、Tg=58℃であった。結果を表1に示す。Example of resin production Polyester polyol (P) Synthetic polyester polyol (P-1)
A reaction vessel equipped with a stirrer, a condenser, and a thermometer was charged with 700 parts of dimethyl terephthalate, 700 parts of dimethyl isophthalate, 671 parts of ethylene glycol, 526 parts of neopentyl glycol, and 0.48 part of tetrabutyl titanate. The time was changed. Next, the pressure was gradually reduced to 1 mmHg or less, and polymerization was carried out at 240 ° C. for 1.5 hours. The composition of the obtained copolymer polyester P-1 is terephthalic acid / isophthalic acid // ethylene glycol / neopentyl glycol = 50/50 // 50/50 (molar ratio), number average molecular weight 2,000, acid value It was 2 eq / ton, Tg = 58 ° C. The results are shown in Table 1.
ポリエステルポリオール(P-2)〜(P-5)、及び(P-7)
ポリエステルポリオール(P-1)において、表1に示す酸成分及びグリコール成分を用い、表1のモル比となるように、モノマーを代えた以外は、ポリエステルポリオール(P-1)の合成方法と同様の方法にて合成した。ポリエステルポリオール(P-1)〜(P-5)、及び(P-7)の組成並びに樹脂物性を表1に示す。Polyester polyol (P-2) to (P-5) and (P-7)
The polyester polyol (P-1) is the same as the method for synthesizing the polyester polyol (P-1) except that the acid component and glycol component shown in Table 1 were used and the monomers were changed so as to achieve the molar ratio shown in Table 1. It was synthesized by the method. Table 1 shows the compositions and resin properties of polyester polyols (P-1) to (P-5) and (P-7).
ポリエステル樹脂(P-6)の合成
攪拌機、コンデンサー、及び温度計を具備した反応容器にテレフタル酸700部、イソフタル酸700部、無水トリメリット酸16.9部、エチレングリコール983部、2−メチル−1、3−プロパンジオール154部、窒素雰囲気2気圧加圧下、160℃から230℃まで3時間かけてエステル化反応を行った。放圧後、テトラブチルチタネート0.92部を仕込み、次いで系内を徐々に減圧していき、20分かけて5mmHgまで減圧し、さらに0.3mmHg以下の真空下、260℃にて40分間重縮合反応を行った。窒素気流下、220℃まで冷却し、無水トリメリット酸を50.6部投入し、30分間反応を行いポリエステル樹脂を得た。得られた共重合ポリエステル(P-6)の組成はテレフタル酸/イソフタル酸/トリメリット酸//エチレングリコール/2−メチル−1,3−プロパンジオール=48/48/4//85/15(モル比)で、数平均分子量20,000、酸価250eq/ton、ガラス転移温度62℃であった。Synthesis of polyester resin (P-6) In a reaction vessel equipped with a stirrer, a condenser, and a thermometer, 700 parts of terephthalic acid, 700 parts of isophthalic acid, 16.9 parts of trimellitic anhydride, 983 parts of ethylene glycol, 2-methyl- The esterification reaction was carried out from 160 ° C. to 230 ° C. over 3 hours under 154 parts of 1,3-propanediol and 2 atmospheres of nitrogen atmosphere. After releasing the pressure, 0.92 part of tetrabutyl titanate was added, and then the pressure inside the system was gradually reduced to 5 mmHg over 20 minutes, and then the pressure was reduced to 260 ° C. for 40 minutes under a vacuum of 0.3 mmHg or less. A condensation reaction was performed. Under a nitrogen stream, the mixture was cooled to 220 ° C., 50.6 parts of trimellitic anhydride was added, and reacted for 30 minutes to obtain a polyester resin. The composition of the obtained copolyester (P-6) was terephthalic acid / isophthalic acid / trimellitic acid // ethylene glycol / 2-methyl-1,3-propanediol = 48/48/4 // 85/15 ( The number average molecular weight was 20,000, the acid value was 250 eq / ton, and the glass transition temperature was 62 ° C.
結果を表1に示す。 The results are shown in Table 1.
ポリウレタン樹脂の合成
ポリウレタン樹脂(U-1)の合成
攪拌機、コンデンサー、温度計を具備した反応容器に合成例のポリエステルポリオール(P-1)を1000部、ネオペンチルグリコール(NPG)を80部、ジメチロールブタン酸(DMBA)を90部投入した後、エチルジグリコールアセテート815部、ブチルグリコールアセテート272部を仕込み、85℃において溶解した。その後、4,4’−ジフェニルメタンジイソシアネート(MDI)を460部加え、85℃、2時間反応を行った後、触媒としてジブチルチンジラウレートを0.5部添加し、85℃でさらに4時間反応させた。ついで、エチルカルビトールアセテート1455部、ブチルセロソルブアセテート485部で溶液を希釈し、ポリウレタン樹脂(U-1)を得た。得られたポリウレタン樹脂溶液の固形分濃度は35(質量%)であった。このようにして得た樹脂溶液をポリプロピレンフィルム上に滴下し、ステンレス鋼製のアプリケーターを用いて延展し、樹脂溶液の薄膜を得た。これを120℃に調整した熱風乾燥機内に3時間静置して溶媒を揮散させ、次いでポリプロピレンフィルムから樹脂薄膜を剥がし、フィルム状の乾燥樹脂薄膜を得た。乾燥樹脂薄膜の厚みは約30μmであった。左記乾燥樹脂薄膜をポリウレタン樹脂(U-1)の試料樹脂として、各種樹脂物性の評価を行ったところ、数平均分子量は55,000、酸価は380eq/ton、Tgは70℃であった。ポリウレタン樹脂(U-1)を製造する際に用いた各成分及び樹脂物性を表2に示す。Synthesis of polyurethane resin Synthesis of polyurethane resin (U-1) In a reaction vessel equipped with a stirrer, condenser and thermometer, 1000 parts of polyester polyol (P-1) of synthesis example, 80 parts of neopentyl glycol (NPG), di After 90 parts of methylol butanoic acid (DMBA) was added, 815 parts of ethyl diglycol acetate and 272 parts of butyl glycol acetate were charged and dissolved at 85 ° C. Thereafter, 460 parts of 4,4′-diphenylmethane diisocyanate (MDI) was added and reacted at 85 ° C. for 2 hours, and then 0.5 part of dibutyltin dilaurate was added as a catalyst and reacted at 85 ° C. for another 4 hours. . Subsequently, the solution was diluted with 1455 parts of ethyl carbitol acetate and 485 parts of butyl cellosolve acetate to obtain a polyurethane resin (U-1). The solid content concentration of the obtained polyurethane resin solution was 35 (mass%). The resin solution thus obtained was dropped on a polypropylene film and spread using a stainless steel applicator to obtain a resin solution thin film. This was left to stand in a hot air dryer adjusted to 120 ° C. for 3 hours to volatilize the solvent, and then the resin thin film was peeled off from the polypropylene film to obtain a film-like dry resin thin film. The thickness of the dry resin thin film was about 30 μm. When the dry resin thin film shown on the left was used as a sample resin for polyurethane resin (U-1) and various resin properties were evaluated, the number average molecular weight was 55,000, the acid value was 380 eq / ton, and Tg was 70 ° C. Table 2 shows the components and resin properties used when producing the polyurethane resin (U-1).
ポリウレタン樹脂(U-2)〜(U-6)の合成
ポリウレタン樹脂(U-2)〜(U-6)の合成は、ポリエステルポリオール、イソシアネートと反応する基を有する化合物及びポリイソシアネートを表2に示すものに代えた以外は、ポリウレタン樹脂(U-1)の合成方法と同様の方法にて合成した。ポリウレタン樹脂(U-2)〜(U-6)を製造する際に用いた各成分及び樹脂物性を表2に示す。なお、ポリウレタン樹脂溶液(U-2)〜(U-6)の固形分濃度は、35±1(質量%)の範囲であった。Synthesis of polyurethane resins (U-2) to (U-6) The synthesis of polyurethane resins (U-2) to (U-6) is as follows. Polyester polyol, compound having a group that reacts with isocyanate, and polyisocyanate are shown in Table 2. The synthesis was carried out in the same manner as the synthesis method of the polyurethane resin (U-1) except that the ones shown were replaced. Table 2 shows each component and resin physical properties used in producing the polyurethane resins (U-2) to (U-6). The solid content concentrations of the polyurethane resin solutions (U-2) to (U-6) were in the range of 35 ± 1 (% by mass).
表2に記載される略称は、以下のとおりである。
DMBA:ジメチロールブタン酸
DMPA:ジメチロールプロピオン酸
NPG:ネオペンチルグリコール
DMH:2−ブチル−2−エチル−1,3−プロパンジオール
MDI:4,4’−ジフェニルメタンジイイソシアネート
IPDI:イソホロンジイソシアネート Abbreviations described in Table 2 are as follows.
DMBA: dimethylol butanoic acid DMPA: dimethylol propionic acid NPG: neopentyl glycol DMH: 2-butyl-2-ethyl-1,3-propanediol MDI: 4,4′-diphenylmethane diisocyanate IPDI: isophorone diisocyanate
ポリウレタン樹脂(U-7)の合成
攪拌機、コンデンサー及び温度計を具備した反応容器中に合成例のポリエステルポリオール(P-1)を1,000部、ポリエステルポリオール(P-5)を1,500部、1,6−ヘキサンジオール(1,6HD)50部、ネオペンチルグリコール(NPG)150部、ジメチロールブタン酸(DMBA)30部を投入した後、溶剤としてエチルジグリコールアセテート1730部、ブチルグリコールアセテート577部を仕込み、85℃で溶解した。次いで、4,4’−ジフェニルメタンジイイソシアネート(MDI)810部を加え、2時間反応を行った後、ジブチルチンジラウレートを0.8部添加し、さらに85℃で4時間反応させた。その後、エチルカルビトールアセテート3089部、ブチルセロソルブアセテート1030部を加えて希釈し、ポリウレタン樹脂(U-7)を得た。得られたポリウレタン樹脂溶液の固形分濃度は35質量%であった。数平均分子量は40,000、酸価60eq/ton、Tg:−12℃であった。ポリウレタン樹脂(U-7)を製造する際に用いた各成分及び樹脂物性を表3に示す。Synthesis of polyurethane resin (U-7) 1,000 parts of polyester polyol (P-1) of synthesis example and 1,500 parts of polyester polyol (P-5) in a reaction vessel equipped with a stirrer, condenser and thermometer , 50 parts of 1,6-hexanediol (1,6HD), 150 parts of neopentyl glycol (NPG), 30 parts of dimethylol butanoic acid (DMBA), 1730 parts of ethyl diglycol acetate as a solvent, butyl glycol acetate 577 parts were charged and dissolved at 85 ° C. Next, after adding 810 parts of 4,4′-diphenylmethane diisocyanate (MDI) and reacting for 2 hours, 0.8 part of dibutyltin dilaurate was added and further reacted at 85 ° C. for 4 hours. Thereafter, 3089 parts of ethyl carbitol acetate and 1030 parts of butyl cellosolve acetate were added and diluted to obtain a polyurethane resin (U-7). The solid content concentration of the obtained polyurethane resin solution was 35% by mass. The number average molecular weight was 40,000, the acid value was 60 eq / ton, and Tg was −12 ° C. Table 3 shows each component and resin physical properties used in producing the polyurethane resin (U-7).
ポリウレタン樹脂(U-8)〜(U-11)の合成
ポリウレタン樹脂(U-8)〜(U-11)の合成は、ポリエステルポリオール、イソシアネートと反応する基を有する化合物及びポリイソシアネートを表3に示すものに代えた以外は、ポリウレタン樹脂(U-7)の合成方法と同様の方法にて合成した。ポリウレタン樹脂(U-8)〜(U-11)を製造する際に用いた各成分及び樹脂物性を表3に示す。なお、前記ポリウレタン樹脂溶液(U-8)〜(U-11)の固形分濃度は35±1(質量%)の範囲であった。Synthesis of polyurethane resins (U-8) to (U-11) The synthesis of polyurethane resins (U-8) to (U-11) is shown in Table 3 for polyester polyols, compounds having groups that react with isocyanates, and polyisocyanates. The synthesis was performed in the same manner as the synthesis method of the polyurethane resin (U-7), except for the ones shown. Table 3 shows the components and resin physical properties used in producing the polyurethane resins (U-8) to (U-11). The solid content concentration of the polyurethane resin solutions (U-8) to (U-11) was in the range of 35 ± 1 (mass%).
表3中における略称は、表2と同様のものであり、1,6HDは、1,6−ヘキサンジオールを意味する。 Abbreviations in Table 3 are the same as those in Table 2, and 1,6HD means 1,6-hexanediol.
ポリウレタン樹脂(U-12)の合成
冷却管を具備した四口セパラブルフラスコに、ポリエステル樹脂(P-7)100部、酢酸ジエチレングリコールモノエチルエーテル112部、ジブチルチンジラウレート0.1部を仕込み80℃で溶解した。ついで、ジフェニルメタン−4,4’−ジイソシアネート(MDI)12.4部を仕込み、窒素気流下80℃で残存イソシアネートが無くなるまで重合した。反応完了後、酢酸ジエチレングリコールモノエチルエーテルで希釈し、固形分が25%になるように調整した。得られたポリウレタン樹脂のガラス転移点温度は58℃、還元粘度は1.8dl/g、数平均分子量58,000、酸価は10eq/ton、ワニスの粘度は320dPa・sであった。Synthesis of polyurethane resin (U-12) A four-necked separable flask equipped with a cooling tube was charged with 100 parts of polyester resin (P-7), 112 parts of diethylene glycol monoethyl ether acetate and 0.1 part of dibutyltin dilaurate at 80 ° C. And dissolved. Next, 12.4 parts of diphenylmethane-4,4′-diisocyanate (MDI) was charged and polymerized under a nitrogen stream at 80 ° C. until there was no residual isocyanate. After completion of the reaction, the reaction mixture was diluted with diethylene glycol monoethyl ether acetate to adjust the solid content to 25%. The obtained polyurethane resin had a glass transition temperature of 58 ° C., a reduced viscosity of 1.8 dl / g, a number average molecular weight of 58,000, an acid value of 10 eq / ton, and a varnish viscosity of 320 dPa · s.
実施例1
固形分濃度35質量%のポリウレタン樹脂溶液(U-1)を2,858部(固形部換算1,000部)、フェロ・ジャパン(株)製のフレーク状銀粉SF70Aを6,540部、カーボンブラックとしてライオン(株)製のECP600JDを76部、(株)中越黒鉛工業所製のグラファイトBFを76部、レベリング剤として共栄社化学(株)製のMKコンクを58部、分散剤としてビックケミー・ジャパン(株)製のDisperbyk2155を16部、溶剤としてエチルジグリコールアセテート(ECA)を640部、ブチルカルビトールアセテート(BCA)を210部配合し、チルド三本ロール混練り機で3回通して分散した。表4に全溶液中の各成分の量を示す。得られた銀ペーストをアニール処理をしたPETフィルムを基材とし、5.密着性試験において規定した方法で印刷した後、120℃×30分で乾燥した。得られた塗膜物性は、比抵抗は4.9×10-5Ω・cm、密着性100/100、鉛筆硬度Hで良好であった。結果を表4に示す。Example 1
2,858 parts (1,000 parts in terms of solid part) of polyurethane resin solution (U-1) having a solid content concentration of 35% by mass, 6,540 parts of flaky silver powder SF70A manufactured by Ferro Japan Co., Ltd., carbon black As a leveling agent, 76 parts of ECP600JD manufactured by Lion Co., Ltd., 76 parts of graphite BF manufactured by Chuetsu Graphite Industries Co., Ltd., 58 parts of MK Conk manufactured by Kyoeisha Chemical Co., Ltd. as leveling agents, and Big Chemie Japan ( 16 parts of Disperbyk 2155 manufactured by Co., Ltd., 640 parts of ethyl diglycol acetate (ECA) and 210 parts of butyl carbitol acetate (BCA) as a solvent were blended and dispersed by passing three times with a chilled three-roll kneader. Table 4 shows the amount of each component in the total solution. 4. PET film obtained by annealing the obtained silver paste as a base material; After printing by the method prescribed in the adhesion test, it was dried at 120 ° C. for 30 minutes. As for the obtained coating film properties, the specific resistance was good at 4.9 × 10 −5 Ω · cm, adhesion 100/100, and pencil hardness H. The results are shown in Table 4.
一方で、基材として結晶性ITOフィルムKA500(尾池工業(株)製)を用い、5.密着性試験において記述した方法で印刷、乾燥し評価した。また環境試験を実施した。評価結果を表4に示す。 On the other hand, a crystalline ITO film KA500 (manufactured by Oike Industry Co., Ltd.) is used as a base material. It was printed, dried and evaluated by the method described in the adhesion test. Environmental tests were also conducted. The evaluation results are shown in Table 4.
実施例2〜7
表4に示す成分及び配合により実施例1と同様に銀ペーストを作製し、アニール処理をしたPETフィルムを基材として塗膜を作製した。塗膜物性を表4に示す。Examples 2-7
A silver paste was prepared in the same manner as in Example 1 with the components and blends shown in Table 4, and a coating film was prepared using an annealed PET film as a base material. Table 4 shows the physical properties of the coating film.
また、実施例1と同様に結晶性ITOフィルムKA500(尾池工業(株)製)を用い、5.密着性試験において記述した方法で印刷、乾燥し評価した。また環境試験を実施した。評価結果を表4に示す。 Further, as in Example 1, a crystalline ITO film KA500 (manufactured by Oike Industry Co., Ltd.) was used. It was printed, dried and evaluated by the method described in the adhesion test. Environmental tests were also conducted. The evaluation results are shown in Table 4.
いずれの実施例もオーブン120℃×30分という低温短時間な条件で良好な塗膜物性を得た。またITOへの密着性、環境試験後の密着性、耐ブロッキング性等も良好であった。 In all the examples, good film properties were obtained under conditions of a low temperature and a short time of 120 ° C. for 30 minutes in an oven. Moreover, the adhesion to ITO, the adhesion after the environmental test, and the blocking resistance were also good.
なお、表4に示す、導電粉末、添加剤及び溶剤は以下のものを用いた。
銀粉1:フェロ・ジャパン(株)製のSF70A
銀粉2:福田金属箔粉工業(株)製のAgC-2011
カーボンブラック:ライオン(株)製のケッチェンECP600JD
グラファイト粉:(株)中越黒鉛工業所製のグラファイトBF
硬化剤:旭化成ケミカルズ(株)製のMF-K60X
硬化触媒:共同薬品(株)製のKS1260
レベリング剤:共栄社化学(株)のMKコンク
分散剤1:ビックケミー・ジャパン(株)社製のDieperbyk2155
分散剤2:ビックケミー・ジャパン(株) 社製のDieperbyk180
ECA:ダイセル化学工業(株)製のエチルジグリコールアセテート
BCA:ダイセル化学工業(株)製のブチルグリコールアセテートIn addition, the following were used for the conductive powder, additive, and solvent shown in Table 4.
Silver powder 1: SF70A manufactured by Ferro Japan
Silver powder 2: AgC-2011 manufactured by Fukuda Metal Foil Powder Industry Co., Ltd.
Carbon black: Ketjen ECP600JD made by Lion Corporation
Graphite powder: Graphite BF manufactured by Chuetsu Graphite Co., Ltd.
Curing agent: MF-K60X manufactured by Asahi Kasei Chemicals Corporation
Curing catalyst: KS1260 manufactured by Kyodo Pharmaceutical Co., Ltd.
Leveling agent: MK Conch, Kyoeisha Chemical Co., Ltd. Dispersant 1: Dieperbyk2155, manufactured by Big Chemie Japan Co., Ltd.
Dispersant 2: Dieperbyk180 manufactured by Big Chemie Japan Co., Ltd.
ECA: Ethyl diglycol acetate manufactured by Daicel Chemical Industries, Ltd.
BCA: Butyl glycol acetate manufactured by Daicel Chemical Industries, Ltd.
比較例1
ポリエステル樹脂(P-6)を固形分濃度35質量%(エチルジグリコールアセテート:ブチルグリコールアセテート=75:25(質量比)に調整した溶液を2,858部(固形部換算1,000部)、フェロ・ジャパン(株)製のフレーク状銀粉SF70Aを6540部、カーボンブラックとしてライオン(株)製のケッチェンECP600JDを76部、(株)中越黒鉛工業所製のグラファイトBFを76部、レベリング剤として共栄社化学(株)製のMKコンクを58部、分散剤1としてビックケミー・ジャパン(株)製のDiesperbyk2155を16部、溶剤としてエチルジグリコールアセテートを640部、ブチルカルビトールアセテートを210部配合し、チルド三本ロール混練り機で3回通して分散した。表5に全溶液中の各成分の量を示す。得られた銀ペーストをアニール処理をしたPETフィルムに5.密着性試験において記述した方法で印刷した後、120℃×30分で乾燥した。得られた塗膜物性は、比抵抗は9.2×10-5Ω・cm、密着性100/100、鉛筆硬度HBで良好であった。結果を表5に示す。Comparative Example 1
2,858 parts (1,000 parts in terms of solid part) of a solution prepared by adjusting the polyester resin (P-6) to a solid content concentration of 35% by mass (ethyl diglycol acetate: butyl glycol acetate = 75: 25 (mass ratio)), 6540 parts of flaky silver powder SF70A manufactured by Ferro Japan Co., Ltd., 76 parts of Ketjen ECP600JD manufactured by Lion Co., Ltd. as carbon black, 76 parts of graphite BF manufactured by Chuetsu Graphite Industries Co., Ltd., Kyoeisha as a leveling agent Compounding 58 parts of MK Conch manufactured by Chemical Co., Ltd., 16 parts of Diesperbyk 2155 manufactured by Big Chemie Japan Co. as Dispersant 1, 640 parts of ethyl diglycol acetate and 210 parts of butyl carbitol acetate as solvent, Dispersed by passing three times with a three-roll kneader. The obtained silver paste was printed on the annealed PET film by the method described in 5. Adhesion test, and then dried at 120 ° C. for 30 minutes. The specific resistance was good at 9.2 × 10 −5 Ω · cm, adhesion 100/100, and pencil hardness HB, and the results are shown in Table 5.
一方で、基材として結晶性ITOフィルムKA500(尾池工業社製)を用い、5.密着性試験において記述した方法で印刷、乾燥し評価した。また環境試験を実施した。結果を表5に示す。 On the other hand, a crystalline ITO film KA500 (manufactured by Oike Kogyo Co., Ltd.) is used as a substrate. It was printed, dried and evaluated by the method described in the adhesion test. Environmental tests were also conducted. The results are shown in Table 5.
比較例2〜7
表5に示す成分及び配合により実施例1と同様に銀ペーストを作製し、アニール処理をしたPETフィルムを基材として塗膜を作製した。塗膜物性を表5に示す。Comparative Examples 2-7
A silver paste was prepared in the same manner as in Example 1 using the components and blends shown in Table 5, and a coating film was prepared using an annealed PET film as a base material. Table 5 shows the physical properties of the coating film.
なお、比較例6に関しては、高粘度で印刷が困難であったため、以降の評価を中止した。 In addition, since the comparative example 6 had high viscosity and printing was difficult, subsequent evaluation was stopped.
比較例6を除いては、比較例1と同様に結晶性ITOフィルムKA500(尾池工業社製)を用い、5.密着性試験において記述した方法で印刷、乾燥し評価した。また環境試験を実施した。評価結果を表5に示す。 4. A crystalline ITO film KA500 (manufactured by Oike Kogyo Co., Ltd.) was used as in Comparative Example 1 except for Comparative Example 6. It was printed, dried and evaluated by the method described in the adhesion test. Environmental tests were also conducted. The evaluation results are shown in Table 5.
いずれの比較例もオーブン120℃×30分という低温短時間な条件でITO基材への密着性をはじめとした塗膜物性は不良であった。また環境試験後のITO密着性、耐ブロッキング性等も不良であった。 In any of the comparative examples, the physical properties of the coating film including adhesion to the ITO base material were poor under conditions of a low temperature and a short time of 120 ° C. for 30 minutes in an oven. Moreover, the ITO adhesion and the blocking resistance after the environmental test were also poor.
評価結果を表5に示す。なお、表5に示す、導電粉末、添加剤及び溶剤は、表4のものと同じである。 The evaluation results are shown in Table 5. In addition, the conductive powder, additive, and solvent shown in Table 5 are the same as those in Table 4.
Claims (14)
(B)成分:金属粉末、及び
(C)成分:有機溶媒
を含有する導電性ペースト。Component (A): acid value 50~500eq / ton, the glass transition temperature of 60 to 150 ° C., the binder resin comprising a poly ester urethane resin,
(B) component: Metal powder, and (C) component: Conductive paste containing an organic solvent.
(A1)数平均分子量1,000〜10,000及びガラス転移温度30〜80℃の非晶性ポリオール、
(A2)数平均分子量1,000未満であって、1分子に2個以上のイソシアネートと反応し得る官能基を有する化合物、並びに
(A3)ポリイソシアネートを
重付加反応することによって得られる構造を有するポリウレタン樹脂からなるバインダー樹脂である、請求項1に記載の導電性ペースト。(A) component is
(A1) an amorphous polyol having a number average molecular weight of 1,000 to 10,000 and a glass transition temperature of 30 to 80 ° C.,
(A2) A compound having a number average molecular weight of less than 1,000 and having a functional group capable of reacting with two or more isocyanates per molecule, and (A3) a structure obtained by polyaddition reaction of polyisocyanate. The conductive paste according to claim 1, which is a binder resin made of a polyurethane resin.
(A1)数平均分子量1,000〜10,000及びガラス転移温度30〜80℃の非晶性ポリオール、
(A2)数平均分子量1,000未満であって、1分子に2個以上のイソシアネートと反応し得る官能基を有する化合物、
(A3)ポリイソシアネート、並びに
(A4)数平均分子量1,000〜10,000及びガラス転移温度30℃未満の非晶性ポリオール、を
重付加反応することによって得られる構造を有するポリウレタン樹脂からなるバインダー樹脂である、請求項1又は2に記載の導電性ペースト。(A) component is
(A1) an amorphous polyol having a number average molecular weight of 1,000 to 10,000 and a glass transition temperature of 30 to 80 ° C.,
(A2) a compound having a number average molecular weight of less than 1,000 and having a functional group capable of reacting with two or more isocyanates in one molecule;
(A3) Polyisocyanate, and (A4) A binder comprising a polyurethane resin having a structure obtained by polyaddition reaction of an amorphous polyol having a number average molecular weight of 1,000 to 10,000 and a glass transition temperature of less than 30 ° C. The conductive paste according to claim 1 or 2, which is a resin.
80〜150℃で加熱する工程を含む導電性薄膜の製造方法。The manufacturing method of an electroconductive thin film including the process of apply | coating or printing the electrically conductive paste in any one of Claims 1-9 on a base material, and the process of heating at 80-150 degreeC.
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Also Published As
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TW201122064A (en) | 2011-07-01 |
TWI486413B (en) | 2015-06-01 |
KR20120052408A (en) | 2012-05-23 |
CN102576581A (en) | 2012-07-11 |
JPWO2011046076A1 (en) | 2013-03-07 |
WO2011046076A1 (en) | 2011-04-21 |
CN102576581B (en) | 2015-07-22 |
KR101223408B1 (en) | 2013-01-16 |
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