JP6491910B2 - Transparent conductive sheet and method for producing the same - Google Patents
Transparent conductive sheet and method for producing the same Download PDFInfo
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- JP6491910B2 JP6491910B2 JP2015048751A JP2015048751A JP6491910B2 JP 6491910 B2 JP6491910 B2 JP 6491910B2 JP 2015048751 A JP2015048751 A JP 2015048751A JP 2015048751 A JP2015048751 A JP 2015048751A JP 6491910 B2 JP6491910 B2 JP 6491910B2
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- transparent conductive
- conductive film
- conductive sheet
- transparent
- sheet according
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- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 239000011230 binding agent Substances 0.000 claims description 57
- 229920001940 conductive polymer Polymers 0.000 claims description 55
- 238000000576 coating method Methods 0.000 claims description 34
- 239000011248 coating agent Substances 0.000 claims description 32
- 239000000758 substrate Substances 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 26
- -1 polysiloxane Polymers 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 22
- 229910000077 silane Inorganic materials 0.000 claims description 19
- 239000003377 acid catalyst Substances 0.000 claims description 14
- 239000003586 protic polar solvent Substances 0.000 claims description 11
- 239000002798 polar solvent Substances 0.000 claims description 9
- 229920001296 polysiloxane Polymers 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 6
- 229920000123 polythiophene Polymers 0.000 claims description 5
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 4
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 2
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- 238000000034 method Methods 0.000 description 20
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
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- 239000003822 epoxy resin Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
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- 229920000647 polyepoxide Polymers 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 3
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- LULAYUGMBFYYEX-UHFFFAOYSA-N 3-chlorobenzoic acid Chemical class OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical class OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 101100284369 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) has-1 gene Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical class CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 238000007611 bar coating method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
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- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical class ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- BYOIQYHAYWYSCZ-UHFFFAOYSA-N prop-2-enoxysilane Chemical compound [SiH3]OCC=C BYOIQYHAYWYSCZ-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- UCSBCWBHZLSFGC-UHFFFAOYSA-N tributoxysilane Chemical compound CCCCO[SiH](OCCCC)OCCCC UCSBCWBHZLSFGC-UHFFFAOYSA-N 0.000 description 1
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- OZWKZRFXJPGDFM-UHFFFAOYSA-N tripropoxysilane Chemical compound CCCO[SiH](OCCC)OCCC OZWKZRFXJPGDFM-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- Paints Or Removers (AREA)
- Non-Insulated Conductors (AREA)
Description
本発明は、透明導電性シート及びその製造方法に関する。 The present invention relates to a transparent conductive sheet and a method for producing the same.
近年、チオフェン系やアニリン系の高分子は優れた安定性及び導電性を有することから、有機導電性材料としてその活用が期待されている。その活用の一つとして、液晶ディスプレイ、透明タッチパネル等の各種デバイスに用いられる透明電極の形成に、上記高分子にドーパントを付加した導電性高分子を溶媒に分散させたコーティング組成物が用いられている。しかし、上記導電性高分子をコーティング組成物として使用し、このコーティング組成物を用いて基材上に導電性膜を形成した場合、導電性膜の硬さや導電性膜の基材への密着性が十分ではない。特に、基材がガラス等の非吸液性材料から形成されている場合、基材の透明性を損なわずに、十分な硬さの導電性膜を形成することは難しい。このような問題に対して、例えば、特許文献１、特許文献２では、透明導電性膜の硬度や透明導電性膜の基材への密着性を向上できるバインダが提案されている。 In recent years, thiophene-based and aniline-based polymers have excellent stability and conductivity, and are expected to be used as organic conductive materials. As one of the applications, a coating composition in which a conductive polymer in which a dopant is added to the above polymer is dispersed in a solvent is used to form a transparent electrode used in various devices such as a liquid crystal display and a transparent touch panel. Yes. However, when the conductive polymer is used as a coating composition and a conductive film is formed on the substrate using the coating composition, the hardness of the conductive film and the adhesion of the conductive film to the substrate Is not enough. In particular, when the substrate is formed from a non-liquid-absorbing material such as glass, it is difficult to form a sufficiently hard conductive film without impairing the transparency of the substrate. For example, Patent Document 1 and Patent Document 2 propose a binder that can improve the hardness of the transparent conductive film and the adhesion of the transparent conductive film to the base material.
特許文献１では、バインダとしてポリビニルアルコール（ＰＶＡ）や有機ケイ素化合物（アルコキシシラン）等を用いることで、導電性膜の硬度、基材への密着性を改善できることが記載されている。特許文献２では、バインダとしてシランカップリング剤を用いることで、基材への密着性の高い導電性高分子膜を提供できることが記載されている。しかし、得られた導電性膜の電気特性、光学特性、物理特性及び耐湿熱性は十分ではなく、未だ改良の余地がある。 Patent Document 1 describes that the hardness of the conductive film and the adhesion to the substrate can be improved by using polyvinyl alcohol (PVA), an organic silicon compound (alkoxysilane), or the like as a binder. Patent Document 2 describes that a conductive polymer film having high adhesion to a substrate can be provided by using a silane coupling agent as a binder. However, the electrical properties, optical properties, physical properties and wet heat resistance of the obtained conductive film are not sufficient, and there is still room for improvement.
本発明は、上記問題を解消するためになされたものであり、電気特性、光学特性、物理特性及び耐湿熱性に優れた透明導電性膜を有する透明導電性シート及びその製造方法を提供する。 The present invention has been made to solve the above problems, and provides a transparent conductive sheet having a transparent conductive film excellent in electrical characteristics, optical characteristics, physical characteristics, and heat and moisture resistance, and a method for producing the same.
本発明の透明導電性シートは、透明基材と、前記透明基材の少なくとも一方の主面に形成された透明導電性膜とを含む透明導電性シートであって、前記透明導電性膜は、導電性高分子と、粒子状の無機系バインダとを含み、前記導電性高分子は、前記無機系バインダの粒子の間に配置され、前記無機系バインダは、ポリシロキサンを含むことを特徴とする。 The transparent conductive sheet of the present invention is a transparent conductive sheet comprising a transparent substrate and a transparent conductive film formed on at least one main surface of the transparent substrate, and the transparent conductive film is A conductive polymer and a particulate inorganic binder are included, the conductive polymer is disposed between particles of the inorganic binder, and the inorganic binder includes polysiloxane. .
また、本発明の透明導電性シートの製造方法は、導電性高分子と、シラン化合物と、溶媒と、酸触媒とを含む透明導電性膜形成用塗布液を作製する工程と、前記透明導電性膜形成用塗布液を透明基材の上に塗布して加熱することにより、前記透明基材の上に透明導電性膜を形成する工程とを含むことを特徴とする。 The method for producing a transparent conductive sheet of the present invention includes a step of preparing a coating liquid for forming a transparent conductive film containing a conductive polymer, a silane compound, a solvent, and an acid catalyst, and the transparent conductive film. Forming a transparent conductive film on the transparent base material by applying the film-forming coating solution on the transparent base material and heating it.
本発明によれば、電気特性、光学特性、物理特性及び耐湿熱性に優れた透明導電性膜を有する透明導電性シートを提供できる。 ADVANTAGE OF THE INVENTION According to this invention, the transparent conductive sheet which has a transparent conductive film excellent in an electrical property, an optical characteristic, a physical characteristic, and heat-and-moisture resistance can be provided.
（本発明の透明導電性シート）
本発明の透明導電性シートは、透明基材と、上記透明基材の少なくとも一方の主面に形成された透明導電性膜とを備え、上記透明導電性膜は、導電性高分子と、粒子状の無機系バインダとを含み、上記導電性高分子は、上記無機系バインダの粒子の間に配置され、上記無機系バインダは、ポリシロキサンを含むことを特徴とする。
(Transparent conductive sheet of the present invention)
The transparent conductive sheet of the present invention comprises a transparent substrate and a transparent conductive film formed on at least one main surface of the transparent substrate, and the transparent conductive film comprises a conductive polymer, particles The conductive polymer is disposed between particles of the inorganic binder, and the inorganic binder contains polysiloxane.
本発明の透明導電性シートの透明導電性膜は、導電性高分子が粒子状の無機系バインダの粒子の間に配置されているため、電気特性、光学特性、物理特性及び耐湿熱性に優れている。 The transparent conductive film of the transparent conductive sheet of the present invention is excellent in electrical characteristics, optical characteristics, physical characteristics, and heat-and-moisture resistance because the conductive polymer is disposed between the particles of the inorganic inorganic binder. Yes.
上記導電性高分子とは、Ｃｏｎｄｕｃｔｉｖｅ Ｐｏｌｙｍｅｒｓ（ＣＰｓ）と呼ばれる高分子であり、ドーパントによるドーピングによって、ポリラジカルカチオニック塩又はポリラジカルアニオニック塩が形成された状態で、それ自体が導電性を発揮し得る高分子をいう。 The conductive polymer is a polymer called Conductive Polymers (CPs), and it exhibits conductivity in a state where a polyradical cationic salt or a polyradical anionic salt is formed by doping with a dopant. Refers to a polymer that can.
本発明では、上記導電性高分子として、ポリチオフェン系化合物とドーパントとを含むものを用いる。本発明における導電性高分子としては、ポリチオフェン系化合物としてポリ（３，４−エチレンジオキシチオフェン）と、ドーパントとしてポリスチレンスルホン酸とを含む混合物（ＰＥＤＯＴ／ＰＳＳともいう。）を用いることができる。 In the present invention, the conductive polymer containing a polythiophene compound and a dopant is used. As the conductive polymer in the present invention, a mixture (also referred to as PEDOT / PSS) containing poly (3,4-ethylenedioxythiophene) as a polythiophene compound and polystyrene sulfonic acid as a dopant can be used.
上記無機系バインダとしては、透明性が高く、粒子状の無機系バインダを構成できるポリシロキサンを含むバインダを用いる。上記無機系バインダを粒子状に形成し、上記導電性高分子を上記無機系バインダの粒子の間に配置することにより、本発明の透明導電性シートの透明導電性膜の電気特性を向上できる。 As the inorganic binder, a binder containing polysiloxane that has high transparency and can form a particulate inorganic binder is used. By forming the inorganic binder in the form of particles and disposing the conductive polymer between the particles of the inorganic binder, the electrical characteristics of the transparent conductive film of the transparent conductive sheet of the present invention can be improved.
ここで上記透明導電性膜の電気特性が向上する理由について図１を用いて説明する。図１は、本発明の透明導電性シートの模式図である。図１において、本発明の透明導電性シート１０は、透明基材１１と、透明基材１１の上に形成された透明導電性膜１２とを備えている。また、透明導電膜１２は、粒子状の無機系バインダ１２ａと導電性高分子１２ｂから形成され、導電性高分子１２ｂが粒子状の無機系バインダ１２ａの粒子の間に配置されている。これにより、粒子状の無機系バインダ１２ａの粒子の間に配置された導電性高分子１２ｂにより、図１に示すように３次元的な導電パス１３を形成することができ、透明導電性シート１０の導電性を向上できると考えられる。 Here, the reason why the electrical characteristics of the transparent conductive film are improved will be described with reference to FIG. FIG. 1 is a schematic view of the transparent conductive sheet of the present invention. In FIG. 1, a transparent conductive sheet 10 of the present invention includes a transparent substrate 11 and a transparent conductive film 12 formed on the transparent substrate 11. The transparent conductive film 12 is formed of a particulate inorganic binder 12a and a conductive polymer 12b, and the conductive polymer 12b is disposed between the particles of the particulate inorganic binder 12a. As a result, the conductive polymer 12b disposed between the particles of the particulate inorganic binder 12a can form a three-dimensional conductive path 13 as shown in FIG. It is thought that the electrical conductivity of can be improved.
上記無機系バインダに含まれるポリシロキサンとしては、シラノール基を含むポリシロキサンを用いることができる。上記シラノール基を含むポリシロキサンの具体例としては、コルコート社製の“コルコートＰＸ”、“コルコートＮ−１０３Ｘ”（商品名）等が挙げられる。 As the polysiloxane contained in the inorganic binder, a polysiloxane containing a silanol group can be used. Specific examples of the polysiloxane containing a silanol group include “Colcoat PX” and “Colcoat N-103X” (trade name) manufactured by Colcoat.
また、上記無機系バインダとしては、アルコール溶媒を用いたシリケート加水分解液から形成することもできる。上記シリケート加水分解液の具体例としては、コルコート社製の“ＨＡＳ−１０”、“ＨＡＳ−６”、“ＨＡＳ−１”（商品名）等が挙げられる。 The inorganic binder can also be formed from a silicate hydrolyzate using an alcohol solvent. Specific examples of the silicate hydrolyzate include “HAS-10”, “HAS-6”, “HAS-1” (trade name) and the like manufactured by Colcoat.
また、上記無機系バインダの粒子の長軸径は、１０ｎｍ以上３００ｎｍ以下であることが好ましく、２０ｎｍ以上２００ｎｍ以下がより好ましい。上記無機系バインダの粒子の長軸径が上記範囲内にあれば、上記導電性高分子による導電パスを緻密に形成できるからである。 The major axis diameter of the inorganic binder particles is preferably 10 nm to 300 nm, and more preferably 20 nm to 200 nm. This is because if the long axis diameter of the inorganic binder particles is within the above range, a conductive path formed by the conductive polymer can be densely formed.
本発明において上記無機系バインダの粒子の長軸径は、上記透明導電性膜の断面を走査電子顕微鏡で観察して、少なくとも１００個のバインダ粒子の長軸径を求めて、それらの長軸径の算術平均値として求めるものとする。 In the present invention, the long axis diameter of the inorganic binder particles is determined by observing the cross section of the transparent conductive film with a scanning electron microscope to obtain the long axis diameters of at least 100 binder particles. It is calculated as the arithmetic average value of.
また、上記導電性高分子と上記無機系バインダとの体積比は、１：９９〜７０：３０とすることができる。上記導電性高分子と上記無機系バインダとの体積比が上記範囲内であれば、上記透明導電性膜の電気特性、光学特性、物理特性及び耐湿熱性を向上できる。特に、本発明の透明導電性シートを用いた透明電極の形成において、上記導電性高分子と上記無機系バインダとのより好ましい体積比は、５：９５〜３５：６５である。 The volume ratio of the conductive polymer to the inorganic binder can be 1:99 to 70:30. When the volume ratio between the conductive polymer and the inorganic binder is within the above range, the electrical characteristics, optical characteristics, physical characteristics, and wet heat resistance of the transparent conductive film can be improved. In particular, in the formation of a transparent electrode using the transparent conductive sheet of the present invention, a more preferable volume ratio of the conductive polymer and the inorganic binder is 5:95 to 35:65.
上記透明導電性膜は、有機系バインダを更に含んでいてもよい。上記透明導電性膜が有機系バインダを含むことにより、上記透明導電性膜と上記透明基材との密着性を向上できる。特に、上記透明基材としてプラスチックフィルム等のフレキシブル基材を用いる場合に、上記透明導電性膜が有機系バインダを含むことは、上記透明導電性膜と上記透明基材との密着性や追従性の観点で好ましい。 The transparent conductive film may further contain an organic binder. When the transparent conductive film contains an organic binder, adhesion between the transparent conductive film and the transparent substrate can be improved. In particular, when a flexible substrate such as a plastic film is used as the transparent substrate, the fact that the transparent conductive film contains an organic binder means that the adhesion and followability between the transparent conductive film and the transparent substrate are as follows. From the viewpoint of
上記有機系バインダとしては、例えば、アクリル樹脂、メラミン樹脂、ポリエステル樹脂、ポリアミド樹脂、ポリカーボネート樹脂、ポリウレタン樹脂、ポリスチレン樹脂、ポリ塩化ビニル樹脂、ポリ塩化ビニリデン樹脂、ポリ酢酸ビニル樹脂、ポリフッ化ビニリデン樹脂、ヒドロキシエチルセルロース、ポリビニルアルコール、ポリエチレングリコール（ＰＥＧ）、ポリエチレンオキサイド、ポリプロピレンオキサイド、多糖類、その他の光重合性樹脂等が挙げられる。また、上記有機系バインダの使用形態としては、溶媒溶解型又はエマルジョン型が使用できる。 Examples of the organic binder include acrylic resin, melamine resin, polyester resin, polyamide resin, polycarbonate resin, polyurethane resin, polystyrene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl acetate resin, polyvinylidene fluoride resin, Examples thereof include hydroxyethyl cellulose, polyvinyl alcohol, polyethylene glycol (PEG), polyethylene oxide, polypropylene oxide, polysaccharides, and other photopolymerizable resins. Moreover, as a usage form of the organic binder, a solvent dissolution type or an emulsion type can be used.
上記有機系バインダの含有量が多すぎると上記無機系バインダの効果が減少するため、上記有機系バインダの含有量は、上記無機系バインダと上記有機系バインダの合計体積量に対して、３０体積％以下とすることが好ましい。 If the content of the organic binder is too large, the effect of the inorganic binder is reduced. Therefore, the content of the organic binder is 30 volumes with respect to the total volume of the inorganic binder and the organic binder. % Or less is preferable.
上記透明導電性膜の表面抵抗値は、５０Ω／スクエア以上１０００Ω／スクエア以下であることが好ましい。表面抵抗値が小さいほど良好な電気特性を示す。 The surface resistance value of the transparent conductive film is preferably 50 Ω / square or more and 1000 Ω / square or less. The smaller the surface resistance, the better the electrical characteristics.
上記透明導電性膜の全光線透過率は、９０％以上であることが好ましく、より好ましくは９５％以上である。全光線透過率が高いほど良好な光学特性を示す。上記全光線透過率は、分光光度計、例えば、日本分光社製の“Ｖ−５７０”により測定可能である。 The total light transmittance of the transparent conductive film is preferably 90% or more, and more preferably 95% or more. The higher the total light transmittance, the better the optical properties. The total light transmittance can be measured with a spectrophotometer, for example, “V-570” manufactured by JASCO Corporation.
上記透明導電性膜の膜厚は、用途に応じて適宜設定されるものであるが、通常、０．０１〜１０μｍ程度である。膜厚が薄すぎても厚すぎても、均一な透明導電性膜を形成することが困難となる。上記導電性高分子の割合にもよるが、膜厚が薄いと、表面抵抗値が増加する傾向にあり、膜厚が厚すぎると、全光線透過率が低下する傾向にある。 Although the film thickness of the said transparent conductive film is suitably set according to a use, it is about 0.01-10 micrometers normally. If the film thickness is too thin or too thick, it becomes difficult to form a uniform transparent conductive film. Although depending on the proportion of the conductive polymer, the surface resistance tends to increase if the film thickness is thin, and the total light transmittance tends to decrease if the film thickness is too thick.
上記透明基材としては、例えば、プラスチック、ゴム、ガラス、セラミックス等の種々のものが使用できる。 As said transparent base material, various things, such as a plastics, rubber | gum, glass, ceramics, can be used, for example.
（本発明の透明導電性シートの製造方法）
本発明の透明導電性シートの製造方法は、導電性高分子と、シラン化合物と、溶媒と、酸触媒とを含む透明導電性膜形成用塗布液を作製する工程と、上記透明導電性膜形成用塗布液を透明基材の上に塗布して加熱することにより、上記透明基材の上に透明導電性膜を形成する工程とを備えることを特徴とする。
(Method for producing transparent conductive sheet of the present invention)
The method for producing a transparent conductive sheet of the present invention includes a step of preparing a coating liquid for forming a transparent conductive film containing a conductive polymer, a silane compound, a solvent, and an acid catalyst, and the formation of the transparent conductive film. Forming a transparent conductive film on the transparent substrate by applying the coating liquid on the transparent substrate and heating.
本発明の透明導電性シートの製造方法によれば、電気特性、光学特性、物理特性及び耐湿熱性に優れた透明導電性膜を備えた透明導電性シートを製造できる。 According to the method for producing a transparent conductive sheet of the present invention, it is possible to produce a transparent conductive sheet provided with a transparent conductive film excellent in electrical characteristics, optical characteristics, physical characteristics, and moisture and heat resistance.
＜透明導電性膜形成用塗布液＞
上記導電性高分子としては、前述のポリチオフェン系化合物としてポリ（３，４−エチレンジオキシチオフェン）と、ドーパントとしてポリスチレンスルホン酸とを含む混合物（ＰＥＤＯＴ／ＰＳＳ）を用いることができる。
<Coating liquid for forming transparent conductive film>
As the conductive polymer, a mixture (PEDOT / PSS) containing poly (3,4-ethylenedioxythiophene) as the polythiophene compound and polystyrene sulfonic acid as a dopant can be used.
上記透明導電性膜形成用塗布液における上記導電性高分子の含有量は、上記透明導電性膜形成用塗布液に含まれる全固形成分の質量に対して０．７質量％以上７０．０質量％以下であることが好ましい。上記導電性高分子の含有量が、上記透明導電性膜形成用塗布液に含まれる全固形成分の質量に対して０．７質量％を下回ると透明導電性膜の導電性が低下し、７０．０質量％を超えると透明導電性膜の物理特性や耐湿熱性が低下する傾向にある。 Content of the said conductive polymer in the said coating liquid for transparent conductive film formation is 0.7 to 70.0 mass% with respect to the mass of all the solid components contained in the said coating liquid for transparent conductive film formation. % Or less is preferable. When the content of the conductive polymer is less than 0.7% by mass with respect to the mass of all solid components contained in the coating liquid for forming a transparent conductive film, the conductivity of the transparent conductive film is reduced, and 70 If it exceeds 0.0 mass%, the physical properties and heat-and-moisture resistance of the transparent conductive film tend to decrease.
上記シラン化合物は、アルコキシシランであることが好ましい。また、上記アルコキシシランとしては、テトラアルコキシシラン、トリアルコキシシラン、ジアルコキシシラン及びアルコキシオリゴマーからなる群から選ばれる少なくとも１種の多官能アルコキシシランを含むものであることが好ましい。 The silane compound is preferably an alkoxysilane. The alkoxysilane preferably includes at least one polyfunctional alkoxysilane selected from the group consisting of tetraalkoxysilane, trialkoxysilane, dialkoxysilane and alkoxy oligomer.
上記テトラアルコキシシランの例としては、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトラｉｓｏ−プロポキシシラン、テトラｔ−ブトキシシラン等の炭素数１〜４のアルコキシ基でテトラ置換されたシランが挙げられる。具体例としては、信越化学社製の“ＫＢＥ−０４”（商品名）等が挙げられる。 Examples of the tetraalkoxysilane include silane tetrasubstituted with an alkoxy group having 1 to 4 carbon atoms, such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraiso-propoxysilane, and tetra-t-butoxysilane. It is done. Specific examples include “KBE-04” (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.
上記トリアルコキシシランの例としては、トリメトキシシラン、トリエトキシシラン、トリプロポキシシラン、トリブトキシシラン、トリｉｓｏ−プロポキシシラン、トリＬ−ブトキシシラン等の炭素数１〜４のアルコキシ基でトリ置換されたシランが挙げられる。 Examples of the trialkoxysilane include trimethoxysilane, triethoxysilane, tripropoxysilane, tributoxysilane, triiso-propoxysilane, tri-L-butoxysilane, etc. Silane.
上記ジアルコキシシランの例としては、ジメチルジメトキシシラン、ジフェニルジメトキシシラン、ジメチルジエトキシシラン、ジフェニルジエトキシシラン等が挙げられる。 Examples of the dialkoxysilane include dimethyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, diphenyldiethoxysilane, and the like.
上記アルコキシオリゴマーは、有機基とアルコキシシリル基を併せ持つ比較的低分子のレジンである。具体例としては、信越化学社製の“Ｘ−４０−２３０８”、“Ｘ−４０−９２２５”、“Ｘ−４０−９２２６”、“Ｘ−４０−９２３８”、“Ｘ−４０−９２４７”、“Ｘ−４０−９２５０”、“ＫＣ−８９Ｓ”、“ＫＲ−４０１Ｎ”、“ＫＲ−５００”、“ＫＲ−５１０”、“ＫＲ−９２１８”（商品名）、コルコート社製の“エチルシリケート４０”、“エチルシリケート４８”、“メチルシリケート５１”、“メチルシリケート５３Ａ”、“ＥＭＳ−４８５”、“ＳＳ１０１”（商品名）等が挙げられる。 The alkoxy oligomer is a relatively low-molecular resin having both an organic group and an alkoxysilyl group. Specific examples include “X-40-2308”, “X-40-9225”, “X-40-9226”, “X-40-9238”, “X-40-9247” manufactured by Shin-Etsu Chemical Co., Ltd. “X-40-9250”, “KC-89S”, “KR-401N”, “KR-500”, “KR-510”, “KR-9218” (trade name), “Ethyl silicate 40 manufactured by Colcoat Co., Ltd.” "," Ethyl silicate 48 "," methyl silicate 51 "," methyl silicate 53A "," EMS-485 "," SS101 "(trade name), and the like.
また、上記アルコキシシランとしては、ビニルメトキシシラン、ｐ−スチリルメトキシシラン、メチルトリメトキシシラン、ジメチルジメトキシシラン、フェニルトリメトキシシラン、メチルトリエトキシシラン、ジメチルジエトキシシラン、フェニルトリエトキシシラン、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、デシルトリメトキシシラン、トリフロロプロピルトリメトキシシラン等のアルコキシシランモノマーも用いることができる。 Examples of the alkoxysilane include vinylmethoxysilane, p-styrylmethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexyltrimethoxy. Alkoxysilane monomers such as silane, hexyltriethoxysilane, decyltrimethoxysilane, and trifluoropropyltrimethoxysilane can also be used.
上記アルコキシシランの具体例のうち、より高い硬度の透明導電性膜を形成するためには、テトラアルコキシランが好ましく、より安定した状態で再現性良く、良質の透明導電性膜を形成するためには、テトラアルコキシシラン及びトリアルコキシシランを併用することが好ましい。 Among the specific examples of the alkoxysilane, tetraalkoxylane is preferable for forming a transparent conductive film having a higher hardness. In order to form a high-quality transparent conductive film in a more stable state with good reproducibility. It is preferable to use tetraalkoxysilane and trialkoxysilane in combination.
上記アルコキシシランとして、テトラアルコキシシランとトリアルコキシシランとを併用する場合は、テトラアルコキシシランとトリアルコキシシランとのモル比は９：１〜５：５であることが好ましく、より好ましくは８：２〜６：４である。このモル比関係が好ましい理由は、透明導電性膜の硬度の低下を防止しつつ、経時変化によって透明導電性膜に亀裂が発生する危険性をより一層なくし、且つ透明基材との密着性をより高めることができるからである。上記テトラアルコキシシランは、高い膜硬度の発現に作用し、上記トリアルコキシシランは、透明導電性膜の亀裂発生防止、透明基材との密着性に作用すると考えられる。 When tetraalkoxysilane and trialkoxysilane are used in combination as the alkoxysilane, the molar ratio of tetraalkoxysilane to trialkoxysilane is preferably 9: 1 to 5: 5, more preferably 8: 2. ~ 6: 4. The reason why this molar ratio relationship is preferable is that while preventing a decrease in the hardness of the transparent conductive film, the risk of cracking in the transparent conductive film due to changes over time is further reduced, and adhesion to the transparent substrate is improved. It is because it can raise more. It is considered that the tetraalkoxysilane acts on the expression of high film hardness, and the trialkoxysilane acts on prevention of cracking of the transparent conductive film and adhesion to the transparent substrate.
上記アルコキシシランの含有量は、上記透明導電性膜形成用塗布液に含まれる全固形成分の質量に対して３０．０質量％以上９９．３質量％以下が好ましく、より好ましくは６５．０質量％以上９５．０質量％以下である。上記アルコキシシランの含有量が少なすぎると、十分な硬度を有する透明導電性膜が得られにくい傾向にあり、アルコキシシランの含有量が多すぎると、透明導電性膜が白濁化し、光学特性が悪化する傾向にある。 The content of the alkoxysilane is preferably 30.0% by mass or more and 99.3% by mass or less, more preferably 65.0% by mass with respect to the mass of all solid components contained in the coating liquid for forming a transparent conductive film. % Or more and 95.0% by mass or less. If the content of the alkoxysilane is too small, a transparent conductive film having sufficient hardness tends to be difficult to obtain. If the content of the alkoxysilane is too large, the transparent conductive film becomes cloudy and the optical properties deteriorate. Tend to.
上記アルコキシシランは、有機官能基を有するアルコキシシランを含み、その割合は、全アルコキシシラン中、８０モル％以下が好ましい。有機官能基を有するアクコキシシランを含むことで、後述する導電パターン形成工程において透明導電性膜のレジスト膜への密着性を良好なものとすることができる。即ち、後述の不活性化剤を用いる工程で、透明導電性膜とレジスト膜との間に不活性化剤が浸入するのを防ぎ、導電パターンを精度よく形成できる。但し、有機官能基を有するアクコキシシランの割合が大きくなりすぎると、透明導電性膜のレジスト膜への密着性が強くなり、その後のレジスト膜を剥離する工程で、レジスト膜の剥離が困難になるため、上記有機官能基を有するアルコキシシランの割合は、全アルコキシシラン中、８０モル％以下が好ましい。 The alkoxysilane contains an alkoxysilane having an organic functional group, and the proportion is preferably 80 mol% or less in the total alkoxysilane. By including an axoxysilane having an organic functional group, the adhesiveness of the transparent conductive film to the resist film can be improved in the conductive pattern forming step described later. That is, it is possible to prevent the inactivation agent from entering between the transparent conductive film and the resist film in the step of using the inactivation agent described later, and to form the conductive pattern with high accuracy. However, if the proportion of the alkoxysilane having an organic functional group becomes too large, the adhesion of the transparent conductive film to the resist film becomes strong, and it becomes difficult to remove the resist film in the subsequent process of peeling the resist film. The proportion of the alkoxysilane having an organic functional group is preferably 80 mol% or less in the total alkoxysilane.
上記有機官能基としては、有機物や無機物と反応しない安定且つ疏水性のある官能基を用いることができる。例えば、メチル基、エチル基、フェニル基、脂肪族系の長鎖アルキル基等が挙げられるが、導電性高分子との相溶性を考慮すると、メチル基及びエチル基がより好ましい。 As the organic functional group, a stable and hydrophobic functional group that does not react with an organic substance or an inorganic substance can be used. For example, a methyl group, an ethyl group, a phenyl group, an aliphatic long-chain alkyl group, and the like can be mentioned. In consideration of compatibility with a conductive polymer, a methyl group and an ethyl group are more preferable.
また、上記アルコキシシランは、その全てが有機官能基を有するアルコキシシランとした場合、十分な強度（硬度、耐溶剤性）の透明導電性膜が得られにくい傾向にあるため、有機官能基を有するアルコキシシランと、有機官能基を有さないアルコキシシランとを併用することが好ましい。上記有機官能基を有するアルコキシシランの割合は、全アルコキシシラン中、１モル％以上６０モル％以下が、より好ましい。 Moreover, when all the alkoxysilanes are alkoxysilanes having an organic functional group, a transparent conductive film having sufficient strength (hardness and solvent resistance) tends to be hardly obtained. It is preferable to use together an alkoxysilane and an alkoxysilane having no organic functional group. As for the ratio of the alkoxysilane which has the said organic functional group, 1 mol% or more and 60 mol% or less are more preferable in all the alkoxysilanes.
上記溶媒は、プロトン性極性溶媒と非プロトン性極性溶媒とを含むことが好ましい。プロトン性極性溶媒と非プロトン性極性溶媒とを併用することにより、比較的低い乾燥温度で透明性に優れた透明導電性膜を得ることができる。 The solvent preferably includes a protic polar solvent and an aprotic polar solvent. By using a protic polar solvent and an aprotic polar solvent in combination, a transparent conductive film excellent in transparency can be obtained at a relatively low drying temperature.
上記プロトン性極性溶媒としては、例えば、水、エチルアルコール、メチルアルコール、ｎ−プロピルアルコール、イソプロピルアルコール、ｎ−ブチルアルコール、イソブチルアルコール、エチレングリコール、プロピレングリコール、酢酸等が挙げられ、上記非プロトン性極性溶媒としては、ジメチルスルホキシド、Ｎ−メチルピロリドン、Ｎ−エチルピロリドン、Ｎ，Ｎ−ジメチルホルムアミド、アセトニトリル、アセトン、テトラヒドロフラン等が挙げられる。 Examples of the protic polar solvent include water, ethyl alcohol, methyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol, acetic acid, and the like. Examples of the polar solvent include dimethyl sulfoxide, N-methylpyrrolidone, N-ethylpyrrolidone, N, N-dimethylformamide, acetonitrile, acetone, tetrahydrofuran and the like.
上記非プロトン性極性溶媒の含有量は、上記溶媒の全質量に対して１．０質量％以上５０．０質量％以下であることが好ましい。上記非プロトン性極性溶媒の含有量が、上記溶媒の全質量に対して１．０質量％を下回ると透明導電性膜の光学特性が低下し、５０．０質量％を超えると透明導電性膜の耐湿熱性が低下する。 The content of the aprotic polar solvent is preferably 1.0% by mass or more and 50.0% by mass or less with respect to the total mass of the solvent. When the content of the aprotic polar solvent is less than 1.0% by mass with respect to the total mass of the solvent, the optical properties of the transparent conductive film are deteriorated, and when the content exceeds 50.0% by mass, the transparent conductive film is used. The heat-and-moisture resistance decreases.
上記溶媒の含有量は特に限定されないが、上記透明導電性膜形成用塗布液の全質量に対して、５０．０質量％以上９９．５質量％以下とすればよい。また、上記溶媒には、無極性溶媒を含んでいてもよい。 Although content of the said solvent is not specifically limited, What is necessary is just to be 50.0 mass% or more and 99.5 mass% or less with respect to the total mass of the said coating liquid for transparent conductive film formation. The solvent may contain a nonpolar solvent.
上記酸触媒としては、例えば、リン酸、塩酸、硫酸、酢酸等を用いることができる。また、水溶液中で酸性である導電性高分子も酸触媒として機能する。 Examples of the acid catalyst that can be used include phosphoric acid, hydrochloric acid, sulfuric acid, and acetic acid. A conductive polymer that is acidic in an aqueous solution also functions as an acid catalyst.
上記透明導電性膜形成用塗布液は、上記導電性高分子、上記シラン化合物、上記溶媒及び上記酸触媒を公知の手法により適宜混合することにより製造できる。例えば、上記各成分を、ボールミル、サンドミル、ピコミル、ペイントコンディショナー等のメディアを介在させた機械的処理により、又は超音波分散機、ホモジナイザー、ディスパー、ジェットミル等のメディアレス処理により、混合、分散することができる。 The coating liquid for forming a transparent conductive film can be produced by appropriately mixing the conductive polymer, the silane compound, the solvent, and the acid catalyst by a known method. For example, the above components are mixed and dispersed by a mechanical treatment with media such as a ball mill, sand mill, pico mill, paint conditioner, or by a media-less treatment such as an ultrasonic disperser, a homogenizer, a disper, or a jet mill. be able to.
また、上記各成分の添加順序も特に限定されず、例えば、導電性高分子と溶媒とからなる溶液に、シラン化合物と酸触媒とを加えてもよいし、導電性高分子と溶媒からなる溶液と、シラン化合物と酸触媒と溶媒とからなる溶液とを、別々に作製した後に、各溶液を混合してもよい。 The order of addition of the above components is not particularly limited, and for example, a silane compound and an acid catalyst may be added to a solution composed of a conductive polymer and a solvent, or a solution composed of a conductive polymer and a solvent. And a solution composed of a silane compound, an acid catalyst, and a solvent may be prepared separately, and then each solution may be mixed.
＜透明導電性膜の形成＞
上記透明導電性膜形成用塗布液を透明基材の上に塗布する方法としては、例えば、バーコート法、リバース法、グラビアコート法、マイクログラビアコート法、ダイコート法、ディッピング法、スピンコート法、スリットコート法、スプレーコート法等の公知の塗布方法を用いることができる。
<Formation of transparent conductive film>
Examples of the method for applying the transparent conductive film-forming coating solution on the transparent substrate include a bar coating method, a reverse method, a gravure coating method, a micro gravure coating method, a die coating method, a dipping method, a spin coating method, A known coating method such as a slit coating method or a spray coating method can be used.
上記塗布後の加熱は、上記透明導電性膜形成用塗布液の溶媒成分が蒸発する条件であればよく、１００〜１５０℃で５〜６０分間行うことが好ましい。溶媒が透明導電性膜に残っていると強度が劣る傾向にある。加熱方法としては、例えば、熱風乾燥法、加熱乾燥法、真空乾燥法、自然乾燥等により行うことができる。また、必要に応じて、塗膜にＵＶ光やＥＢ光を照射して塗膜を硬化させたりして、透明導電性膜を形成してもよい。 The heating after the application may be performed under the condition that the solvent component of the coating liquid for forming a transparent conductive film evaporates, and is preferably performed at 100 to 150 ° C. for 5 to 60 minutes. If the solvent remains in the transparent conductive film, the strength tends to be inferior. As the heating method, for example, a hot air drying method, a heating drying method, a vacuum drying method, natural drying, or the like can be used. Further, if necessary, the transparent conductive film may be formed by irradiating the coating film with UV light or EB light to cure the coating film.
次に、上記加熱により、上記アルコキシシラン（シラン化合物）は、脱水縮合反応によりポリシロキサンを含む粒子状の無機系バインダとなり、上記無機系バインダの粒子の間に上記導電性高分子が配置され、透明導電性膜の中に３次元的な導電パスが形成される。この３次元的な導電パスにより透明導電性膜の導電性（電気特性）が向上する。また、上記無機系バインダは、大きな硬度を有するため、透明導電性膜の硬度（物理特性）が向上する。 Next, by the heating, the alkoxysilane (silane compound) becomes a particulate inorganic binder containing polysiloxane by a dehydration condensation reaction, and the conductive polymer is disposed between the particles of the inorganic binder, A three-dimensional conductive path is formed in the transparent conductive film. This three-dimensional conductive path improves the conductivity (electrical characteristics) of the transparent conductive film. Moreover, since the said inorganic type binder has big hardness, the hardness (physical characteristic) of a transparent conductive film improves.
上記透明導電性膜形成用塗布液に、アルコキシシランと酸触媒とを含めることにより、アルコキシシランはそのアルコキシ基が酸性水中で加水分解してシラノール化反応が起こり、その後の脱水縮合反応により３次元構造を有する粒子状のポリシロキサンを含む無機系バインダを確実に形成できる。 By including an alkoxysilane and an acid catalyst in the coating liquid for forming a transparent conductive film, the alkoxysilane is hydrolyzed in acidic water to cause silanolation reaction, and then three-dimensionally by dehydration condensation reaction. An inorganic binder containing particulate polysiloxane having a structure can be reliably formed.
即ち、上記透明導電性膜形成用塗布液を作製する過程でシラノール化反応の時間制御を行うことにより、無機系バインダの粒子の長軸径を１０ｎｍ以上３００ｎｍ以下に調整することができる。上記調整方法の例を挙げると、最初に導電性高分子と溶媒とをディスパーで混合、攪拌しながら、アルコキシシラン（シラン化合物）、酸触媒の順で少量ずつ添加し、１０分ほど混合、攪拌する。その後、３０分から３００分ほど静置することにより、アルコキシシランのシラノール化を促進させることができ、長軸径が１０ｎｍ以上３００ｎｍ以下の無機系バインダ粒子を形成することができる。上記シラノール化反応の時間制御工程は、従来にはない新規な工程である。 That is, the long axis diameter of the inorganic binder particles can be adjusted to 10 nm or more and 300 nm or less by controlling the time of silanolation reaction in the process of producing the coating liquid for forming the transparent conductive film. As an example of the above adjustment method, first, while mixing and stirring the conductive polymer and solvent with a disper, add alkoxysilane (silane compound) and acid catalyst in small portions in this order, and mix and stir for about 10 minutes. To do. Thereafter, by allowing to stand for 30 to 300 minutes, silanolization of alkoxysilane can be promoted, and inorganic binder particles having a major axis diameter of 10 nm or more and 300 nm or less can be formed. The time control process of the silanolation reaction is a novel process that has not been conventionally performed.
＜導電パターンの形成工程＞
本発明の透明導電性シートの製造方法は、上記透明導電性膜上の導電パターンを形成する位置にレジスト膜を形成する工程と、導電性を失活させる不活性剤を用いて、上記レジスト膜をマスクとして、上記透明導電性膜の露出部の導電性を失活させる工程とを更に備えることができる。これにより、簡単且つ安価に高精度の導電パターンを透明基材の上に形成できる。
<Process for forming conductive pattern>
The method for producing a transparent conductive sheet of the present invention includes the steps of forming a resist film at a position where a conductive pattern is formed on the transparent conductive film, and an inert agent that deactivates the conductivity. And the step of deactivating the conductivity of the exposed portion of the transparent conductive film. Thereby, a highly accurate conductive pattern can be easily and inexpensively formed on a transparent substrate.
上記レジスト膜は、例えば、レジスト剤を上記透明導電性膜上にスクリーン印刷することにより形成できる。上記レジスト剤は特に限定されず、適宜選択できる。 The resist film can be formed, for example, by screen printing a resist agent on the transparent conductive film. The said resist agent is not specifically limited, It can select suitably.
上記不活性剤としては、上記導電性高分子を失活できるものであればよく、例えば、酸化性化合物、塩基性化合物が挙げられる。 The inactive agent is not particularly limited as long as it can deactivate the conductive polymer, and examples thereof include an oxidizing compound and a basic compound.
上記酸化性化合物としては、例えば、過酸化水素系化合物、過塩素酸系化合物、次亜塩素酸系化合物、過酢酸系化合物、メタクロロ安息香酸系化合物、亜硫酸系化合物等が挙げられる。 Examples of the oxidizing compound include hydrogen peroxide compounds, perchloric acid compounds, hypochlorous acid compounds, peracetic acid compounds, metachlorobenzoic acid compounds, sulfite compounds, and the like.
また、上記塩基性化合物としては、例えば、アンモニア、モノメチルアミン、ジメチルアミン、トリメチルアミン、モノエチルアミン、ジエチルアミン、トリエチルアミン、ピリジン、４−メチルピリジン、水酸化テトラメチルアンモニウム等が挙げられる。 Examples of the basic compound include ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, pyridine, 4-methylpyridine, and tetramethylammonium hydroxide.
以下、実施例を用いて本発明を詳細に述べる。但し、本発明は以下の実施例に限定されるものではない。特に指摘がない場合、下記において、「部」は「質量部」を意味する。 Hereinafter, the present invention will be described in detail using examples. However, the present invention is not limited to the following examples. Unless otherwise indicated, in the following, “part” means “part by mass”.
（実施例１）
＜透明導電性膜形成用塗布液の調製＞
先ず、以下の成分を添加、混合して透明導電性膜形成用塗布液を調製した。
（１）導電性高分子分散液（ヘレウス社製、商品名“クレビオスＰＨ１０００”、導電性高分子：ＰＥＤＯＴ−ＰＳＳ、固形分濃度：１．２質量％、溶媒：水）：１５．５８部
（２）シラン化合物：アルコキシシラン（信越化学工業社製、商品名“Ｘ−４０−２３０８”）：１．４５部
（３）酸触媒（リン酸）：０．０６部
（４）非プロトン性極性溶媒（ジメチルスルホキシド）：１２．５０部
（５）プロトン性極性溶媒（エチルアルコール）：７０．４１部
Example 1
<Preparation of coating liquid for forming transparent conductive film>
First, the following components were added and mixed to prepare a coating liquid for forming a transparent conductive film.
(1) Conductive polymer dispersion (manufactured by Heraeus, trade name “Clevios PH1000”, conductive polymer: PEDOT-PSS, solid content concentration: 1.2 mass%, solvent: water): 15.58 parts ( 2) Silane compound: Alkoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “X-40-2308”): 1.45 parts (3) Acid catalyst (phosphoric acid): 0.06 parts (4) Aprotic polarity Solvent (dimethyl sulfoxide): 12.50 parts (5) Protic polar solvent (ethyl alcohol): 70.41 parts
＜透明導電性シートの形成＞
次に、厚さ０．７ｍｍの１０ｃｍ角の無アルカリガラス（全光線透過率：９１．２％）を基板として用い、基板の一方の主面の全面に上記透明導電性膜形成用塗布液をスピンコーティング法により塗布し、その後１２０℃で１時間加熱した。これにより、一方の主面に透明導電膜性膜が形成された実施例１の透明導電性シートを作製した。上記透明導電性膜の膜厚は、２９０ｎｍであった。
<Formation of transparent conductive sheet>
Next, a 10 cm square non-alkali glass (total light transmittance: 91.2%) having a thickness of 0.7 mm is used as the substrate, and the coating liquid for forming the transparent conductive film is applied to the entire surface of one main surface of the substrate. It apply | coated by the spin coating method and it heated at 120 degreeC after that for 1 hour. This produced the transparent conductive sheet of Example 1 in which the transparent conductive film was formed on one main surface. The film thickness of the transparent conductive film was 290 nm.
＜透明導電性膜の断面構造の観察＞
作製した透明導電性シートの透明導電性膜の断面構造の観察を次にようにして行った。先ず、作製した透明導電性シートの透明導電性膜の上にエポキシ樹脂を塗布して包埋して、そのエポキシ樹脂面を機械研磨法にて整面した。その後、日本電子社製の断面試料作製装置“ＳＭ−０９０１０”（商品名）を用いてイオンポリッシングにより断面を作製し、フラットミリング処理して断面観察用試料を得た。その断面観察用試料を日立製作所製の電界放射形走査電子顕微鏡（ＦＥ−ＳＥＭ）を用いて、加速電圧：２．０ｋＶ、倍率：１０００００倍で観察して、二次・反射電子混成像を得た。その観察像を図２に示す。
<Observation of cross-sectional structure of transparent conductive film>
The cross-sectional structure of the transparent conductive film of the produced transparent conductive sheet was observed as follows. First, an epoxy resin was applied and embedded on the transparent conductive film of the produced transparent conductive sheet, and the epoxy resin surface was leveled by a mechanical polishing method. Thereafter, a cross-section was prepared by ion polishing using a cross-section sample preparation apparatus “SM-09010” (trade name) manufactured by JEOL Ltd., and flat milling was performed to obtain a cross-section observation sample. The sample for cross-sectional observation was observed with a field emission scanning electron microscope (FE-SEM) manufactured by Hitachi, Ltd. at an acceleration voltage of 2.0 kV and a magnification of 100,000, thereby obtaining a secondary / reflected electron hybrid image. It was. The observation image is shown in FIG.
図２から、透明導電性シート２０において、ガラス基板２１の上には、透明導電性膜２２が形成され、透明導電性膜２２の上には、エポキシ樹脂層２３が形成されていることが分かる。また、透明導電性膜２２は、粒子状のバインダ粒子２２ａと、バインダ粒子２２ａの間に配置された導電性高分子（ＰＥＤＯＴ−ＰＳＳ）２２ｂから形成されていることが確認できる。また、図２から、前述の方法で算出したバインダ粒子２２ａの長軸径は、１５０ｎｍであった。 As can be seen from FIG. 2, in the transparent conductive sheet 20, a transparent conductive film 22 is formed on the glass substrate 21, and an epoxy resin layer 23 is formed on the transparent conductive film 22. . Moreover, it can confirm that the transparent conductive film 22 is formed from the particulate binder particle | grains 22a and the conductive polymer (PEDOT-PSS) 22b arrange | positioned between the binder particle | grains 22a. Also, from FIG. 2, the major axis diameter of the binder particles 22a calculated by the above-described method was 150 nm.
（実施例２）
以下の成分を添加、混合して透明導電性膜形成用塗布液を調製し、その透明導電性膜形成用塗布液を用い、透明導電性膜の膜厚を１８０ｎｍとした以外は、実施例１と同様にして実施例２の透明導電性シートを作製した。
（１）導電性高分子分散液（ヘレウス社製、商品名“クレビオスＰＨ１０００”、導電性高分子：ＰＥＤＯＴ−ＰＳＳ、固形分濃度：１．２質量％、溶媒：水）：４６．６７部
（２）シラン化合物：メチルトリメトキシシラン（信越化学工業社製、商品名“ＫＢＭ−１３”）：０．１８部
（３）シラン化合物：テトラエトキシシラン（コルコート社製、商品名“エチルシリケート１８”）：１．０６部
（４）酸触媒（０．３５％塩酸）：０．５９部
（５）非プロトン性極性溶媒（ジメチルスルホキシド）：４．２０部
（６）プロトン性極性溶媒（ｎ−プロピルアルコール）：２６．１３部
（７）プロトン性極性溶媒（水）：２１．１７部
(Example 2)
Example 1 The following components were added and mixed to prepare a coating solution for forming a transparent conductive film, and the coating solution for forming a transparent conductive film was used. In the same manner, a transparent conductive sheet of Example 2 was produced.
(1) Conductive polymer dispersion (manufactured by Heraeus, trade name “Clevios PH1000”, conductive polymer: PEDOT-PSS, solid content concentration: 1.2 mass%, solvent: water): 46.67 parts ( 2) Silane compound: Methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-13”): 0.18 parts (3) Silane compound: Tetraethoxysilane (manufactured by Colcoat, trade name “ethyl silicate 18”) ): 1.06 parts (4) Acid catalyst (0.35% hydrochloric acid): 0.59 parts (5) Aprotic polar solvent (dimethyl sulfoxide): 4.20 parts (6) Protic polar solvent (n- Propyl alcohol): 26.13 parts (7) Protic polar solvent (water): 21.17 parts
また、作製した透明導電性シートの透明導電性膜の断面構造の観察を実施例１と同様にして行ったところ、図２と同様の観察像を得て、その観察像から前述の方法で算出したバインダ粒子の長軸径は、１００ｎｍであった。 Further, when the cross-sectional structure of the transparent conductive film of the produced transparent conductive sheet was observed in the same manner as in Example 1, an observation image similar to that in FIG. 2 was obtained and calculated from the observation image by the method described above. The major axis diameter of the binder particles was 100 nm.
（実施例３）
以下の成分を添加、混合して透明導電性膜形成用塗布液を調製し、その透明導電性膜形成用塗布液を用い、透明導電性膜の膜厚を１８０ｎｍとした以外は、実施例１と同様にして実施例３の透明導電性シートを作製した。
（１）導電性高分子分散液（ヘレウス社製、商品名“クレビオスＰＨ１０００”、導電性高分子：ＰＥＤＯＴ−ＰＳＳ、固形分濃度：１．２質量％、溶媒：水）：４６．４７部
（２）シラン化合物：メチルトリメトキシシラン（信越化学工業社製、商品名“ＫＢＭ−１３”）：０．１８部
（３）シラン化合物：テトラエトキシシラン（コルコート社製、商品名“エチルシリケート１８”）：１．００部
（４）有機系バインダ（ポリエチレングリコール、分子量：５００万）：０．０６部
（５）酸触媒（０．３５％塩酸）：０．５９部
（６）非プロトン性極性溶媒（ジメチルスルホキシド）：４．２０部
（７）プロトン性極性溶媒（ｎ−プロピルアルコール）：２６．１３部
（８）プロトン性極性溶媒（水）：２１．１７部
(Example 3)
Example 1 The following components were added and mixed to prepare a coating solution for forming a transparent conductive film, and the coating solution for forming a transparent conductive film was used. In the same manner, a transparent conductive sheet of Example 3 was produced.
(1) Conductive polymer dispersion (manufactured by Heraeus, trade name “Clevios PH1000”, conductive polymer: PEDOT-PSS, solid content concentration: 1.2 mass%, solvent: water): 46.47 parts ( 2) Silane compound: Methyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBM-13”): 0.18 parts (3) Silane compound: Tetraethoxysilane (manufactured by Colcoat, trade name “ethyl silicate 18”) ): 1.00 parts (4) Organic binder (polyethylene glycol, molecular weight: 5 million): 0.06 parts (5) Acid catalyst (0.35% hydrochloric acid): 0.59 parts (6) Aprotic polarity Solvent (dimethyl sulfoxide): 4.20 parts (7) Protic polar solvent (n-propyl alcohol): 26.13 parts (8) Protic polar solvent (water): 21.17 parts
また、作製した透明導電性シートの透明導電性膜の断面構造の観察を実施例１と同様にして行ったところ、図２と同様の観察像を得て、その観察像から前述の方法で算出したバインダ粒子の長軸径は、９０ｎｍであった。 Further, when the cross-sectional structure of the transparent conductive film of the produced transparent conductive sheet was observed in the same manner as in Example 1, an observation image similar to that in FIG. 2 was obtained and calculated from the observation image by the method described above. The major axis diameter of the binder particles was 90 nm.
（比較例１）
以下の成分を添加、混合して透明導電性膜形成用塗布液を調製し、その透明導電性膜形成用塗布液を用い、透明導電性膜の膜厚を３８９ｎｍとした以外は、実施例１と同様にして比較例１の透明導電性シートを作製した。
（１）導電性高分子分散液（ヘレウス社製、商品名“クレビオスＰＨ１０００”、導電性高分子：ＰＥＤＯＴ−ＰＳＳ、固形分濃度：１．２質量％、溶媒：水）：１５．５８部
（２）有機系バインダ（ポリエチレングリコール）：０．４４部
（３）非プロトン性極性溶媒（ジメチルスルホキシド）：１２．５０部
（４）プロトン性極性溶媒（エチルアルコール）：７１．４８部
(Comparative Example 1)
Example 1 The following components were added and mixed to prepare a coating liquid for forming a transparent conductive film, and the coating liquid for forming a transparent conductive film was used. The thickness of the transparent conductive film was changed to 389 nm. In the same manner, a transparent conductive sheet of Comparative Example 1 was produced.
(1) Conductive polymer dispersion (manufactured by Heraeus, trade name “Clevios PH1000”, conductive polymer: PEDOT-PSS, solid content concentration: 1.2 mass%, solvent: water): 15.58 parts ( 2) Organic binder (polyethylene glycol): 0.44 parts (3) Aprotic polar solvent (dimethyl sulfoxide): 12.50 parts (4) Protic polar solvent (ethyl alcohol): 71.48 parts
また、作製した透明導電性シートの透明導電性膜の断面構造の観察を実施例１と同様にして行ったところ、透明導電性膜の断面構造は均一な単層構造であることを確認し、粒子状のバインダ粒子は確認できなかった。 Moreover, when the cross-sectional structure of the transparent conductive film of the produced transparent conductive sheet was observed in the same manner as in Example 1, it was confirmed that the cross-sectional structure of the transparent conductive film was a uniform single layer structure, Particulate binder particles could not be confirmed.
（比較例２）
以下の成分を添加、混合して透明導電性膜形成用塗布液を調製し、その透明導電性膜形成用塗布液を用い、透明導電性膜の膜厚を３８９ｎｍとした以外は、実施例１と同様にして比較例２の透明導電性シートを作製した。
（１）導電性高分子分散液（ヘレウス社製、商品名“クレビオスＰＨ１０００”、導電性高分子：ＰＥＤＯＴ−ＰＳＳ、固形分濃度：１．２質量％、溶媒：水）：１５．５８部
（２）コロイダルシリカ（日産化学工業社製、商品名“スノーテックＯ"、粒子径：１５ｎｍ、固形分濃度：２０質量％、溶媒：水）：２．２０部
（３）非プロトン性極性溶媒（ジメチルスルホキシド）：１２．５０部
（４）プロトン性極性溶媒（エチルアルコール）：６９．７２部
(Comparative Example 2)
Example 1 The following components were added and mixed to prepare a coating liquid for forming a transparent conductive film, and the coating liquid for forming a transparent conductive film was used. The thickness of the transparent conductive film was changed to 389 nm. In the same manner, a transparent conductive sheet of Comparative Example 2 was produced.
(1) Conductive polymer dispersion (manufactured by Heraeus, trade name “Clevios PH1000”, conductive polymer: PEDOT-PSS, solid content concentration: 1.2 mass%, solvent: water): 15.58 parts ( 2) Colloidal silica (manufactured by Nissan Chemical Industries, trade name “Snowtech O”, particle size: 15 nm, solid content concentration: 20% by mass, solvent: water): 2.20 parts (3) aprotic polar solvent ( Dimethyl sulfoxide): 12.50 parts (4) Protic polar solvent (ethyl alcohol): 69.72 parts
また、作製した透明導電性シートの透明導電性膜の断面構造の観察を実施例１と同様にして行ったところ、透明導電性膜の断面構造は、コロイダルシリカ由来の粒子径１５ｎｍのシリカ粒子と導電性高分子とが混ざり合った均一な単層構造であることを確認した。 Moreover, when the cross-sectional structure of the transparent conductive film of the produced transparent conductive sheet was observed in the same manner as in Example 1, the cross-sectional structure of the transparent conductive film was found to be silica particles having a particle diameter of 15 nm derived from colloidal silica. It was confirmed that the structure was a uniform single layer mixed with conductive polymer.
次に、上記で得られた透明導電性シートについて、下記に示す各評価を行った。 Next, each evaluation shown below was performed about the transparent conductive sheet obtained above.
＜電気特性＞
透明導電性シートの電気特性は、下記のように透明導電性シートの透明導電性膜の表面抵抗値を測定することで評価した。
<Electrical characteristics>
The electrical characteristics of the transparent conductive sheet were evaluated by measuring the surface resistance value of the transparent conductive film of the transparent conductive sheet as follows.
透明導電性シートの透明導電性膜の表面抵抗値は、三菱化学アナリテック社製の抵抗率測定装置“Ｌｏｒｅｓｔａ−ＧＰ”（ＭＣＰ−Ｔ６１０型）とＬＳＰプローブを用いて測定した。 The surface resistance value of the transparent conductive film of the transparent conductive sheet was measured using a resistivity measuring apparatus “Loresta-GP” (MCP-T610 type) manufactured by Mitsubishi Chemical Analytech Co., Ltd. and an LSP probe.
上記測定の結果、表面抵抗値が５００Ω／スクエア以下の場合、電気特性は良好と判断し、表面抵抗値が５００Ω／スクエアより大きい場合、電気特性は不良と判断した。 As a result of the measurement, when the surface resistance value was 500 Ω / square or less, it was determined that the electrical characteristics were good, and when the surface resistance value was greater than 500 Ω / square, the electrical characteristics were determined to be poor.
＜光学特性＞
透明導電性シートの光学特性は、下記のように透明導電性シートの全光線透過率を測定することで評価した。
<Optical characteristics>
The optical characteristics of the transparent conductive sheet were evaluated by measuring the total light transmittance of the transparent conductive sheet as follows.
透明導電性シートの全光線透過率は、日本電色工業社製のヘイズメータ"ＮＤＨ２０００"を用いて測定した。 The total light transmittance of the transparent conductive sheet was measured using a haze meter “NDH2000” manufactured by Nippon Denshoku Industries Co., Ltd.
上記測定の結果、全光線透過率が９０％以上の場合、光学特性は良好と判断し、全光線透過率が９０％を下回った場合、光学特性は不良と判断した。 As a result of the measurement, when the total light transmittance was 90% or more, it was determined that the optical characteristics were good, and when the total light transmittance was less than 90%, the optical characteristics were determined to be poor.
＜物理特性＞
透明導電性シートの物理特性は、下記のように透明導電性シートの透明導電性膜の鉛筆硬度を測定することで評価した。
<Physical properties>
The physical properties of the transparent conductive sheet were evaluated by measuring the pencil hardness of the transparent conductive film of the transparent conductive sheet as follows.
透明導電性シートの透明導電性膜の鉛筆硬度は、日本工業規格（ＪＩＳ）Ｋ５４００に規定された鉛筆硬度の測定方法に基づき、新東科学社製の表面性試験機“ＨＥＩＤＯＮ−１４ＤＲ”を用いて測定した。 The pencil hardness of the transparent conductive film of the transparent conductive sheet is based on a pencil hardness measurement method defined in Japanese Industrial Standard (JIS) K5400, using a surface property tester “HEIDON-14DR” manufactured by Shinto Kagaku Co., Ltd. Measured.
＜耐湿熱性＞
透明導電性シートの耐湿熱性は、下記のように透明導電性シートの保存試験を行うことで評価した。
<Heat and heat resistance>
The moisture and heat resistance of the transparent conductive sheet was evaluated by conducting a storage test of the transparent conductive sheet as follows.
先ず、透明導電性シートの透明導電性膜の初期の表面抵抗値を前述の電気特性の評価と同様にして測定した。次に、透明導電性シートを恒温恒湿槽に入れて６５℃、相対湿度９０％で５００時間保存した。続いて、保存後の透明導電性シートの透明導電性膜の表面抵抗値を上記と同様にして測定した。最後に、下記式（１）により表面抵抗値の変化度を算出した。
表面抵抗値の変化度＝保存後の表面抵抗値／初期の表面抵抗値 （１）
First, the initial surface resistance value of the transparent conductive film of the transparent conductive sheet was measured in the same manner as in the evaluation of the electrical characteristics described above. Next, the transparent conductive sheet was placed in a constant temperature and humidity chamber and stored at 65 ° C. and a relative humidity of 90% for 500 hours. Subsequently, the surface resistance value of the transparent conductive film of the transparent conductive sheet after storage was measured in the same manner as described above. Finally, the degree of change in the surface resistance value was calculated by the following formula (1).
Change in surface resistance value = surface resistance value after storage / initial surface resistance value (1)
上記測定の結果、表面抵抗値の変化度が１．２以下の場合、耐湿熱性は良好と判断し、表面抵抗値の変化度が１．２を上回った場合、耐湿熱性は不良と判断した。 As a result of the above measurement, when the degree of change in the surface resistance value was 1.2 or less, it was judged that the moisture and heat resistance was good, and when the degree of change in the surface resistance value exceeded 1.2, the moisture and heat resistance was judged as poor.
上記評価の結果を表１に示す。 The results of the evaluation are shown in Table 1.
表１から、本発明の実施例１〜３の透明導電性シートは、電気特性、光学特性及び耐湿熱性の全てで良好との評価を得ることができ、更に物理特性である鉛筆硬度も全てＢ以上を得たことが分かる。 From Table 1, the transparent conductive sheets of Examples 1 to 3 of the present invention can be evaluated as being good in all of electric characteristics, optical characteristics, and heat-and-moisture resistance, and the pencil hardness, which is a physical characteristic, is all B. It turns out that the above was obtained.
一方、比較例１〜２では光学特性及び耐湿熱性が劣り、鉛筆硬度も２Ｂ以下となり物理特性も劣ることが分かる。 On the other hand, in Comparative Examples 1-2, it turns out that an optical characteristic and wet heat resistance are inferior, pencil hardness is also 2 B or less, and a physical characteristic is also inferior.
続いて、上記で得られた透明導電性シートについて、下記とおりパターニング適性の評価を行った。 Subsequently, the patterning suitability of the transparent conductive sheet obtained above was evaluated as follows.
＜レジスト膜の形成＞
先ず、透明導電性シートの透明導電性膜側の主面の中央部に５ｃｍ角の面積にスクリーン印刷法によりレジスト剤（ヘレウス社製、商品名“Ｃｌｖｉｏｕｓ ＳＥＴ Ｓ”）を印刷し、その後１００℃で５分間加熱した。これにより、透明導電性膜上にレジスト膜を形成した。
<Formation of resist film>
First, a resist agent (manufactured by Heraeus, trade name “Clvious SET S”) is printed on the central portion of the main surface of the transparent conductive sheet on the transparent conductive film side by a screen printing method, and then 100 ° C. For 5 minutes. Thereby, a resist film was formed on the transparent conductive film.
＜導電性の低下＞
次に、透明導電性膜上にレジスト膜が形成された透明導電性シートを、塩素系不活性剤（ヘレウス社製、商品名“Ｃｌｖｉｏｕｓ Ｅｔｃｈ”）を１０％水溶液に調製した溶液に２０分間浸漬した後、蒸留水で洗浄し、１００℃で５分間加熱した。これにより、透明導電性膜の露出部の導電性を低下させた。
<Decrease in conductivity>
Next, the transparent conductive sheet in which a resist film is formed on the transparent conductive film is immersed in a solution prepared by preparing a 10% aqueous solution of a chlorine-based inert agent (trade name “Clvious Etch” manufactured by Heraeus) for 20 minutes. Then, it was washed with distilled water and heated at 100 ° C. for 5 minutes. Thereby, the conductivity of the exposed portion of the transparent conductive film was lowered.
＜レジスト膜の剥離＞
次に、上記透明導電性シートをトルエンに３分間浸漬し、レジスト膜を剥離した後、蒸留水で洗浄し、１００℃で５分間乾燥した。
<Removal of resist film>
Next, the transparent conductive sheet was immersed in toluene for 3 minutes, the resist film was peeled off, washed with distilled water, and dried at 100 ° C. for 5 minutes.
次に、得られた透明導電性シートの電気特性を評価した。評価方法については以下に説明する。 Next, the electrical characteristics of the obtained transparent conductive sheet were evaluated. The evaluation method will be described below.
＜電気特性＞
先ず、透明導電性シートの導電パターン形成面において、導電パターンが形成されている導電部の表面抵抗値を、三菱化学アナリテック社製の抵抗率測定計“Ｌｏｒｅｓｔａ−ＧＰ”（ＭＣＰ−Ｔ６１０型）とＬＳＰプローブを用いて測定した。また、透明導電性シートの導電パターン形成面において、導電パターンが形成されていない非導電部の表面抵抗値を、三菱化学アナリテック社製の抵抗率測定計“Ｈｉｒｅｓｔａ−ＵＰ”（ＭＣＰ−ＨＴ４５０型）とＵＲＳプローブを用いて測定した。ここでは、導電部と非導電部の表面抵抗値の差が、１×１０6Ω／スクエア以上である場合は、良好な電気的コントラストが得られていると評価する。
<Electrical characteristics>
First, on the conductive pattern forming surface of the transparent conductive sheet, the surface resistance value of the conductive part on which the conductive pattern is formed is determined by a resistivity meter “Loresta-GP” (MCP-T610 type) manufactured by Mitsubishi Chemical Analytech. And LSP probe. In addition, on the conductive pattern forming surface of the transparent conductive sheet, the surface resistance value of the non-conductive portion where the conductive pattern is not formed is determined as a resistivity meter “Hiresta-UP” (MCP-HT450 type) manufactured by Mitsubishi Chemical Analytech. ) And a URS probe. Here, when the difference in surface resistance between the conductive portion and the non-conductive portion is 1 × 10 6 Ω / square or more, it is evaluated that a good electrical contrast is obtained.
その結果、実施例１〜３の透明導電性シートでは、良好な電気的コントラストが得られていたことが分かった。中でも、実施例２〜３では特に良好な電気的コントラストが得られており、導電部と非導電部の表面抵抗値の差は１×１０8Ω／スクエア以上であった。一方、比較例１〜２の透明導電性シートでは、良好な電気的コントラストが得られていないことが分かった。 As a result, it was found that good electrical contrast was obtained in the transparent conductive sheets of Examples 1 to 3. Especially, in Examples 2-3, particularly good electrical contrast was obtained, and the difference in surface resistance between the conductive part and the non-conductive part was 1 × 10 8 Ω / square or more. On the other hand, in the transparent conductive sheet of Comparative Examples 1-2, it turned out that favorable electrical contrast is not acquired.
１０、２０ 透明導電性シート
１１ 透明基材
２１ ガラス基板
１２、２２ 透明導電性膜
１２ａ、２２ａ バインダ粒子
１２ｂ、２２ｂ 導電性高分子
２３ エポキシ樹脂層
DESCRIPTION OF SYMBOLS 10, 20 Transparent conductive sheet 11 Transparent base material 21 Glass substrate 12, 22 Transparent conductive film 12a, 22a Binder particle 12b, 22b Conductive polymer 23 Epoxy resin layer
Claims (11)
前記透明導電性膜は、導電性高分子と、粒子状の無機系バインダとを含み、
前記導電性高分子は、前記無機系バインダの粒子の間に配置され、
前記無機系バインダは、ポリシロキサンを含むことを特徴とする透明導電性シート。 A transparent conductive sheet comprising a transparent substrate and a transparent conductive film formed on at least one main surface of the transparent substrate,
The transparent conductive film includes a conductive polymer and a particulate inorganic binder,
The conductive polymer is disposed between particles of the inorganic binder,
The transparent conductive sheet, wherein the inorganic binder contains polysiloxane.
導電性高分子と、シラン化合物と、溶媒と、酸触媒とを含む透明導電性膜形成用塗布液を作製する工程と、
前記透明導電性膜形成用塗布液を透明基材の上に塗布して加熱することにより、前記透明基材の上に透明導電性膜を形成する工程とを含み、
前記透明導電性膜形成用塗布液を作製する工程において、前記導電性高分子と前記溶媒とを混合、攪拌しながら、前記シラン化合物と前記酸触媒とをこの順で少量ずつ添加して１０分間混合、攪拌し、その後３０分〜３００分静置することを特徴とする透明導電性シートの製造方法。 It is a manufacturing method of the transparent conductive sheet according to any one of claims 1 to 7 ,
Producing a coating liquid for forming a transparent conductive film containing a conductive polymer, a silane compound, a solvent, and an acid catalyst;
By heating by coating the transparent conductive film-forming coating solution on a transparent substrate, seen including a step of forming a transparent conductive film on the transparent substrate,
In the step of preparing the coating liquid for forming the transparent conductive film, the silane compound and the acid catalyst are added little by little in this order for 10 minutes while mixing and stirring the conductive polymer and the solvent. A method for producing a transparent conductive sheet, which is mixed and stirred, and then allowed to stand for 30 minutes to 300 minutes .
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