JP2011063478A - Phosphorus-containing antimony pentoxide microparticle, coating liquid for forming transparent conductive film containing the microparticle, and base material with transparent conductive film - Google Patents
Phosphorus-containing antimony pentoxide microparticle, coating liquid for forming transparent conductive film containing the microparticle, and base material with transparent conductive film Download PDFInfo
- Publication number
- JP2011063478A JP2011063478A JP2009215538A JP2009215538A JP2011063478A JP 2011063478 A JP2011063478 A JP 2011063478A JP 2009215538 A JP2009215538 A JP 2009215538A JP 2009215538 A JP2009215538 A JP 2009215538A JP 2011063478 A JP2011063478 A JP 2011063478A
- Authority
- JP
- Japan
- Prior art keywords
- phosphorus
- antimony pentoxide
- transparent conductive
- conductive film
- fine particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 title claims abstract description 316
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 116
- 239000011574 phosphorus Substances 0.000 title claims abstract description 116
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000007788 liquid Substances 0.000 title claims abstract description 29
- 239000011859 microparticle Substances 0.000 title claims abstract description 14
- 238000000576 coating method Methods 0.000 title claims description 55
- 239000011248 coating agent Substances 0.000 title claims description 54
- 239000000463 material Substances 0.000 title claims description 16
- 239000006185 dispersion Substances 0.000 claims abstract description 42
- 239000002245 particle Substances 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims abstract description 8
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- -1 phosphorus compound Chemical class 0.000 claims abstract description 7
- 239000010419 fine particle Substances 0.000 claims description 150
- 239000000758 substrate Substances 0.000 claims description 55
- 239000007787 solid Substances 0.000 claims description 44
- 239000011159 matrix material Substances 0.000 claims description 12
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002612 dispersion medium Substances 0.000 claims description 5
- 238000004040 coloring Methods 0.000 abstract description 18
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 130
- 229920005989 resin Polymers 0.000 description 41
- 239000011347 resin Substances 0.000 description 41
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical class COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 33
- 239000000243 solution Substances 0.000 description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 21
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 16
- 239000011324 bead Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- 239000002585 base Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 238000002834 transmittance Methods 0.000 description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 10
- 239000003999 initiator Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 8
- 229910000410 antimony oxide Inorganic materials 0.000 description 7
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 229920001187 thermosetting polymer Polymers 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 229910052787 antimony Inorganic materials 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000002242 deionisation method Methods 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 5
- 229910001887 tin oxide Inorganic materials 0.000 description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910003437 indium oxide Inorganic materials 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920002284 Cellulose triacetate Polymers 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- HCGFUIQPSOCUHI-UHFFFAOYSA-N 2-propan-2-yloxyethanol Chemical compound CC(C)OCCO HCGFUIQPSOCUHI-UHFFFAOYSA-N 0.000 description 2
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- XDJWZONZDVNKDU-UHFFFAOYSA-N 1314-24-5 Chemical compound O=POP=O XDJWZONZDVNKDU-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 description 1
- PSLRXNFNXYNXEK-UHFFFAOYSA-N 2-triethoxysilylethyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCOC(=O)C=C PSLRXNFNXYNXEK-UHFFFAOYSA-N 0.000 description 1
- BUJVPKZRXOTBGA-UHFFFAOYSA-N 2-trimethoxysilylethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCOC(=O)C=C BUJVPKZRXOTBGA-UHFFFAOYSA-N 0.000 description 1
- HJIMAFKWSKZMBK-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F HJIMAFKWSKZMBK-UHFFFAOYSA-N 0.000 description 1
- LZKBJDFRBKBJLP-UHFFFAOYSA-N 3-[diethoxy(3-methylbutan-2-yloxy)silyl]propylurea Chemical compound CC(C)C(C)O[Si](OCC)(OCC)CCCNC(N)=O LZKBJDFRBKBJLP-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- KVSARZIUYVGMGF-UHFFFAOYSA-N C(C=C)(=O)OCOOO[SiH3] Chemical compound C(C=C)(=O)OCOOO[SiH3] KVSARZIUYVGMGF-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- BPCRGIAAAKYTMD-UHFFFAOYSA-N bis(1,1,1,2,3,3,3-heptafluoropropan-2-yloxy)-[1,1,1,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-icosafluoro-2-(trifluoromethyl)decan-2-yl]oxy-(1,1,2,2,2-pentafluoroethyl)silane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(C(F)(F)F)(C(F)(F)F)O[Si](OC(F)(C(F)(F)F)C(F)(F)F)(OC(F)(C(F)(F)F)C(F)(F)F)C(F)(F)C(F)(F)F BPCRGIAAAKYTMD-UHFFFAOYSA-N 0.000 description 1
- XGZGKDQVCBHSGI-UHFFFAOYSA-N butyl(triethoxy)silane Chemical compound CCCC[Si](OCC)(OCC)OCC XGZGKDQVCBHSGI-UHFFFAOYSA-N 0.000 description 1
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 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
- AJOVZBDITZPKCO-UHFFFAOYSA-N diethoxy-octan-2-yloxy-(7,7,7-triethoxyheptylsilyl)silane Chemical compound C(CCCCC)C(C)O[Si](OCC)(OCC)[SiH2]CCCCCCC(OCC)(OCC)OCC AJOVZBDITZPKCO-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-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
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- DIJRHOZMLZRNLM-UHFFFAOYSA-N dimethoxy-methyl-(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](C)(OC)CCC(F)(F)F DIJRHOZMLZRNLM-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 1
- 229960003493 octyltriethoxysilane Drugs 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-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
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- MLXDKRSDUJLNAB-UHFFFAOYSA-N triethoxy(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F MLXDKRSDUJLNAB-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
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-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
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- QNKXRZAXBKSFQC-UHFFFAOYSA-N trimethoxy-[3-[2-(oxiran-2-ylmethoxy)ethoxy]propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCCOCC1CO1 QNKXRZAXBKSFQC-UHFFFAOYSA-N 0.000 description 1
- JPPHEZSCZWYTOP-UHFFFAOYSA-N trimethoxysilylmethyl prop-2-enoate Chemical compound CO[Si](OC)(OC)COC(=O)C=C JPPHEZSCZWYTOP-UHFFFAOYSA-N 0.000 description 1
- AAPLIUHOKVUFCC-UHFFFAOYSA-N trimethylsilanol Chemical compound C[Si](C)(C)O AAPLIUHOKVUFCC-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Paints Or Removers (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
Abstract
Description
本発明は、導電性を向上させた五酸化アンチモン微粒子および該微粒子を含む透明導電性被膜形成用塗布液ならびに透明導電性被膜付基材に関する。 The present invention relates to antimony pentoxide fine particles having improved conductivity, a coating liquid for forming a transparent conductive film containing the fine particles, and a substrate with a transparent conductive film.
従来より、ガラス、プラスチックシート、プラスチックレンズ等の基材表面の耐擦傷性を向上させるため、基材表面にハードコート機能を有する透明被膜を形成することが知られており、このような透明被膜として有機樹脂膜あるいは無機膜をガラスやプラスチック等の表面に形成することが行われている。さらに、有機樹脂膜あるいは無機膜中に樹脂粒子あるいはシリカ等の無機粒子を配合してさらに耐擦傷性を向上させることが行われている。また、このようなハードコート膜付の樹脂基材を表示装置前面板等に貼り付けて使用される場合がある。 Conventionally, it has been known that a transparent film having a hard coat function is formed on the surface of the base material in order to improve the scratch resistance of the surface of the base material such as glass, plastic sheet, and plastic lens. For example, an organic resin film or an inorganic film is formed on the surface of glass or plastic. Furthermore, it is practiced to further improve the scratch resistance by blending resin particles or inorganic particles such as silica in an organic resin film or an inorganic film. Further, there are cases where such a resin base material with a hard coat film is used by being attached to a display device front plate or the like.
また、表示装置等に使用する場合、ハードコート性に加えてゴミ、埃などの静電付着を防止するために導電性を有する透明被膜を形成することも行われている。
このような導電性を付与するために導電性酸化物粒子を配合することが知られている。
Further, when used in a display device or the like, in addition to hard coat properties, a conductive transparent film is also formed in order to prevent electrostatic adhesion such as dust and dirt.
In order to impart such conductivity, it is known to incorporate conductive oxide particles.
導電性酸化物粒子としては、酸化錫、Ｓｂ、ＦまたはＰドープ酸化錫、酸化インジウム、ＳｎまたはＦドープ酸化インジウム、五酸化アンチモン、低次酸化チタン等が知られている。（特許文献１：特開２００２−７９６１６号公報）
また、本願出願人は、パイロクロア構造を有する五酸化アンチモン微粒子を含む透明帯電防止膜付基材（特許文献２：特開２００１−７２９２９号公報）、五酸化アンチモン微粒子を含むハードコート膜付基材（特許文献３：特開２００４−５０８１０号公報）が記載されている。
As the conductive oxide particles, tin oxide, Sb, F or P-doped tin oxide, indium oxide, Sn or F-doped indium oxide, antimony pentoxide, low-order titanium oxide, and the like are known. (Patent Document 1: JP 2002-79616 A)
The applicant of the present application also provides a substrate with a transparent antistatic film containing antimony pentoxide fine particles having a pyrochlore structure (Patent Document 2: JP-A-2001-72929), and a substrate with a hard coat film containing antimony pentoxide fine particles. (Patent Document 3: Japanese Patent Application Laid-Open No. 2004-50810) is described.
酸化錫、酸化インジウムについては、上記したようにドーピング剤をドープすることによって導電性が向上することが従来から知られていた。しかしながら、五酸化アンチモン微粒子にリンをドープすることは、本願出願人の出願による特許文献４（特開２００５−１３９０２６号公報）以外には全く開示されていない。なお、特許文献４には、鎖状酸化アンチモン微粒子にスズ、リン等のドーピング剤が含まれていると、さらに体積抵抗値の低い鎖状酸化アンチモン微粒子が得られることが開示されている。 Regarding tin oxide and indium oxide, it has been conventionally known that conductivity is improved by doping a doping agent as described above. However, doping antimony pentoxide fine particles with phosphorus is not disclosed at all except for Patent Document 4 (Japanese Patent Laid-Open No. 2005-139026) filed by the present applicant. Patent Document 4 discloses that, when the chain antimony oxide fine particles contain a doping agent such as tin and phosphorus, the chain antimony oxide fine particles having a lower volume resistance can be obtained.
しかしながら、従来の導電性酸化物粒子を用いたハードコート膜、透明帯電防止膜では、単に五酸化アンチモン微粒子を用いた場合、透明性には優れるものの導電性が低く帯電防止性能が不充分であった。また、Ｐドープ酸化錫を用いた場合は、五酸化アンチモン微粒子を用いた場合に比較して帯電防止性能は向上するものの透明性が不充分となり、Ｓｂドープ酸化錫を用いると帯電防止性能はさらに向上するものの透明性が低下し、着色する場合があった。さらに、Ｓｎドープ酸化インジウム（ＩＴＯ）を用いると帯電防止性能はさらに向上するものの透明性、着色性に問題があった。 However, in the conventional hard coat film and transparent antistatic film using conductive oxide particles, when simply using antimony pentoxide fine particles, the transparency is excellent, but the conductivity is low and the antistatic performance is insufficient. It was. Further, when P-doped tin oxide is used, the antistatic performance is improved as compared with the case of using antimony pentoxide fine particles, but the transparency becomes insufficient. When Sb-doped tin oxide is used, the antistatic performance is further improved. Although improved, the transparency was lowered and sometimes colored. Further, when Sn-doped indium oxide (ITO) is used, the antistatic performance is further improved, but there is a problem in transparency and colorability.
また、特許文献４には、確かに鎖状酸化アンチモン微粒子にスズ、リン等のドーピング剤が含まれていると、さらに体積抵抗値の低い鎖状酸化アンチモン微粒子が得られることを開示している。しかしながら、実際にドープされた酸化アンチモンを評価した例はなく、その製造方法も全く開示がない。さらに、本発明者らのその後の検討により五酸化アンチモン微粒子にリンをドーピングすると体積抵抗値は若干低下するものの、黄色に変色するという新たな問題も見つかった。 Further, Patent Document 4 discloses that a chain antimony oxide fine particle having a lower volume resistance can be obtained if the chain antimony oxide fine particle contains a doping agent such as tin or phosphorus. . However, there is no example of evaluating actually doped antimony oxide, and the manufacturing method thereof is not disclosed at all. Furthermore, a new problem has been found that when the antimony pentoxide fine particles are doped with phosphorus, the volume resistance value is slightly lowered, but the color is changed to yellow when the present inventors have conducted further studies.
なお、特開２００１−７２９２９号公報によれば、導電性五酸化アンチモン微粒子はパイロクロア構造を有し、プロトン導電性による導電性を有しているが、着色あるいは変色のない五酸化アンチモン微粒子およびそのための有効な製造方法は、本願出願当時、全く知られていなかった。 According to Japanese Patent Laid-Open No. 2001-72929, the conductive antimony pentoxide fine particles have a pyrochlore structure and have conductivity due to proton conductivity, but are not colored or discolored, and therefore No effective manufacturing method was known at the time of filing this application.
本発明者らは、このような問題点に鑑み鋭意検討した結果、リンをドープするのではなく、五酸化アンチモン微粒子に所定量のリンを担持させると導電性が大きく向上することを見出して本発明を完成するに至った。 As a result of intensive studies in view of such problems, the present inventors have found that the conductivity is greatly improved when a predetermined amount of phosphorus is supported on fine particles of antimony pentoxide rather than doping phosphorus. The invention has been completed.
なお、ドーピングでは、リンが五酸化アンチモン結晶内に取り込まれている。これに対し、本発明では、リンが五酸化アンチチモン結晶内に取り込まれず、リン化合物が五酸化アンチモン微粒子表面または細孔内に担持されているものである。このような形態でリンを五酸化アンチモン微粒子に含有させるという技術的発想は従来されておらず、ドープでなはく、リン化合物を担持させ、五酸化アンチモン微粒子自体は知られていなかった。 In doping, phosphorus is taken into the antimony pentoxide crystal. In contrast, in the present invention, phosphorus is not taken into the antimony pentoxide crystal, and the phosphorus compound is supported on the surface or pores of the antimony pentoxide fine particles. The technical idea of incorporating phosphorous into the antimony pentoxide fine particles in such a form has not been heretofore known, and the antimony pentoxide fine particles themselves have not been known by supporting a phosphorus compound, not a dope.
[1]リン酸化物を、Ｐ2Ｏ5として０．１〜１５重量％の範囲で含有してなるリン含有五酸化アンチモン微粒子。
[2]平均粒子径が５〜５０ｎｍの範囲にある[1]のリン含有五酸化アンチモン微粒子。
[3]リン酸化物が、五酸化アンチモン微粒子に担持されてなる[1]または[2]のリン含有五酸化アンチモン微粒子。
[4]前記リン含有五酸化アンチモン微粒子が、鎖状に連結し、平均連結数が２〜３０個の範囲にある[1]〜[4]のリン含有五酸化アンチモン微粒子。
[5]体積抵抗値が１〜１０3Ω・ｃｍの範囲にある[4]のリン含有五酸化アンチモン微粒子。
[6]五酸化アンチモン微粒子分散液に、リン化合物を添加したのち、８０〜２５０℃で０．５〜１２時間、乾燥加熱処理して得られたものであることを特徴とする請求項１〜５のいずれかに記載のリン含有五酸化アンチモン微粒子。
[7]前記[1]〜[6]のリン含有五酸化アンチモン微粒子とマトリックス形成成分と分散媒とを含むことを特徴とする透明導電性被膜形成用塗布液。
[8]前記リン含有五酸化アンチモン微粒子の濃度が固形分として０．５〜５７重量％の範囲にあり、マトリックス形成成分の濃度が固形分として０．５〜５７重量％の範囲にあり、全固形分濃度が１〜６０重量％の範囲にある[7]の透明導電性被膜形成用塗布液。
[9]基材と、基材上に形成された透明導電性被膜とからなり、該透明導電性被膜が[1]〜[8]のリン含有五酸化アンチモン微粒子とマトリックス成分を含み、透明導電性被膜中のリン含有五酸化アンチモン微粒子の含有量が５〜９５重量％の範囲にあることを特徴とする透明導電性被膜付基材。
[10]前記透明導電性被膜の膜厚が０．１〜２０μｍの範囲にある[9]の透明導電性被膜付基材。
[1] Phosphorus-containing antimony pentoxide fine particles containing phosphorus oxide in the range of 0.1 to 15% by weight as P 2 O 5 .
[2] Phosphorus-containing antimony pentoxide fine particles according to [1] having an average particle diameter in the range of 5 to 50 nm.
[3] The phosphorus-containing antimony pentoxide fine particles according to [1] or [2], wherein the phosphorous oxide is supported on the antimony pentoxide fine particles.
[4] The phosphorus-containing antimony pentoxide fine particles according to [1] to [4], wherein the phosphorus-containing antimony pentoxide fine particles are linked in a chain and have an average number of linkages of 2 to 30.
[5] Phosphorus-containing antimony pentoxide fine particles according to [4] having a volume resistance of 1 to 10 3 Ω · cm.
[6] The antimony pentoxide fine particle dispersion is obtained by adding a phosphorus compound, followed by drying and heat treatment at 80 to 250 ° C. for 0.5 to 12 hours. 5. The phosphorus-containing antimony pentoxide fine particles according to any one of 5 above.
[7] A coating liquid for forming a transparent conductive film, comprising the phosphorus-containing antimony pentoxide fine particles of [1] to [6], a matrix-forming component, and a dispersion medium.
[8] The concentration of the phosphorus-containing antimony pentoxide fine particles is in the range of 0.5 to 57% by weight as the solid content, and the concentration of the matrix forming component is in the range of 0.5 to 57% by weight as the solid content. The coating liquid for forming a transparent conductive film according to [7], wherein the solid content concentration is in the range of 1 to 60% by weight.
[9] A transparent conductive film comprising a base material and a transparent conductive film formed on the base material, wherein the transparent conductive film contains the phosphorous-containing antimony pentoxide fine particles and matrix components of [1] to [8] A substrate with a transparent conductive film, wherein the content of the phosphorus-containing antimony pentoxide fine particles in the conductive film is in the range of 5 to 95% by weight.
[10] The substrate with a transparent conductive film according to [9], wherein the film thickness of the transparent conductive film is in the range of 0.1 to 20 μm.
本発明によれば、リン（五酸化リン）を含有させることにより導電性を向上させたリン含有五酸化アンチモン微粒子が得られる。このような五酸化アンチモン微粒子は導電性が高く、また着色あるいは変色も抑制されている。また、該微粒子を含む透明性被膜形成用塗布液を用いることで、帯電防止性能、透明性等に優れるとともに膜強度、耐擦傷性、基材との密着性等にも優れた透明導電性被膜が形成可能となる。 According to the present invention, phosphorus-containing antimony pentoxide fine particles having improved conductivity by containing phosphorus (phosphorus pentoxide) can be obtained. Such antimony pentoxide fine particles have high conductivity, and coloring or discoloration is also suppressed. In addition, by using a coating liquid for forming a transparent film containing the fine particles, a transparent conductive film having excellent antistatic performance, transparency and the like, as well as film strength, scratch resistance, adhesion to a substrate, etc. Can be formed.
[リン含有五酸化アンチモン微粒子]
本発明に係るリン含有五酸化アンチモン微粒子は、リンを、Ｐ2Ｏ5として０．１〜１５重量％の範囲で含有してなる。
[Phosphorus-containing antimony pentoxide fine particles]
The phosphorus-containing antimony pentoxide fine particles according to the present invention contain phosphorus in the range of 0.1 to 15% by weight as P 2 O 5 .
リンは、酸化物状態で、五酸化アンチモン微粒子に含有されるが、五酸化二リン(Ｐ2Ｏ5)であっても、二酸化リンや三酸化二リンであってもよく、リン酸、亜リン酸、過リン酸、ホスホン酸などのオキソ酸またはその塩（たとえば、Na、K、Mg、アンモニウム（4級も含む）、ホスホニウム（4級も含む））であってもよい。本発明では、リン酸化物は、ドーピングのように五酸化アンチモン結晶内に取り込まれているのではなく、微粒子表面または細孔に担持されている。 Phosphorus is in an oxide state and is contained in the antimony pentoxide fine particles, but it may be diphosphorus pentoxide (P 2 O 5 ), phosphorous dioxide or diphosphorus trioxide. It may be an oxo acid such as phosphoric acid, superphosphoric acid, phosphonic acid or a salt thereof (for example, Na, K, Mg, ammonium (including quaternary), phosphonium (including quaternary)). In the present invention, the phosphorous oxide is not incorporated in the antimony pentoxide crystal as in doping, but is supported on the surface of fine particles or pores.
ドーピングとの違いは、単に含有している場合、Ｘ線回折で、ピーク高が若干低下する以外、ピーク位置は変わらず、一方、ドーピングが起きるためか、ピーク高は低下し、同時に、水分の低下、導電性の低下、着色をともなう。 The difference from doping is that if it is simply contained, the peak position is not changed by X-ray diffraction except that the peak height is slightly reduced. On the other hand, because the doping occurs, the peak height decreases, and at the same time, It is accompanied by a decrease, a decrease in conductivity, and coloring.
前記範囲で、リンが含まれていると、導電性を高くすることができ、また、ドーピングのように五酸化アンチモン結晶内に取り込まれているのではないため、着色も抑制できる。 When phosphorus is contained within the above range, the conductivity can be increased, and since it is not incorporated into the antimony pentoxide crystal as in doping, coloring can also be suppressed.
リン含有量が少ない場合、体積抵抗値の低下が不充分で、得られる透明被膜の導電性の向上が不充分となる場合がある。上記上限を超えてリン酸化物を含有させることは困難であり、できたとしてもさらに体積抵抗値が低下することもない。 When the phosphorus content is small, the volume resistance value is not sufficiently lowered, and the resulting transparent film may not be sufficiently improved in conductivity. It is difficult to contain the phosphorus oxide beyond the upper limit, and even if it can be done, the volume resistance value will not be further lowered.
リン含有五酸化アンチモン微粒子のさらに好ましいリン酸化物の含有量はＰ2Ｏ5として０．５〜１２重量％の範囲である。
本発明のリン含有五酸化アンチモン微粒子の平均粒子径が５〜５０ｎｍ、さらには１０〜４０ｎｍの範囲にあることが好ましい。
The more preferable content of phosphorus oxide in the phosphorus-containing antimony pentoxide fine particles is in the range of 0.5 to 12% by weight as P 2 O 5 .
The average particle diameter of the phosphorus-containing antimony pentoxide fine particles of the present invention is preferably in the range of 5 to 50 nm, more preferably 10 to 40 nm.
リン含有五酸化アンチモン微粒子の平均粒子径が小さいと、結晶性が不充分なためか、充分な低体積抵抗値、導電性が得られない場合がある。また、粒子が凝集する傾向があり、導電性透明被膜に用いた場合、充分な導電性が得られない場合がある。 If the average particle diameter of the phosphorus-containing antimony pentoxide fine particles is small, sufficient crystallinity may be insufficient, and sufficient low volume resistance and conductivity may not be obtained. Moreover, there exists a tendency for particle | grains to aggregate, and when it uses for an electroconductive transparent film, sufficient electroconductivity may not be acquired.
リン含有五酸化アンチモン微粒子の平均粒子径が大きすぎると、導電性が不充分となる場合があり、さらに可視光の散乱が大きくなり、導電性透明被膜の透明性が不充分となる場合がある。 If the average particle size of the phosphorus-containing antimony pentoxide fine particles is too large, the conductivity may be insufficient, the visible light scattering may be increased, and the transparency of the conductive transparent film may be insufficient. .
本発明ではリン含有五酸化アンチモン微粒子の平均粒子径は微粒子の透過型電子顕微鏡写真（ＴＥＭ）を撮影し、１００個の粒子について粒子径を測定し、その平均値として測定することができる。 In the present invention, the average particle diameter of the phosphorus-containing antimony pentoxide fine particles can be measured by taking a transmission electron micrograph (TEM) of the fine particles, measuring the particle diameter of 100 particles, and measuring the average value.
かかるリン含有五酸化アンチモン微粒子の体積抵抗値が１０〜１０5Ω・ｃｍ、さらには１０〜５ｘ１０4Ω・ｃｍの範囲にあることが好ましい。上記リン含有量であれば前記範囲の体積抵抗値となる。なおリン含有量を上記範囲で多くしても、前記範囲より体積抵抗値が低いものは得ることが困難である。また、リン含有量が少ないと、体積抵抗値が大きすぎると、従来の五酸化アンチモン微粒子の体積抵抗値と大きく変わらず、導電性を向上させる効果、帯電防止性能を向上させる効果が充分得られない場合がある。 The phosphorus-containing antimony pentoxide fine particles preferably have a volume resistance of 10 to 10 5 Ω · cm, more preferably 10 to 5 × 10 4 Ω · cm. If it is the said phosphorus content, it will become the volume resistance value of the said range. Even if the phosphorus content is increased in the above range, it is difficult to obtain a material having a volume resistance lower than the above range. In addition, when the phosphorus content is low, if the volume resistance value is too large, the volume resistance value of the conventional antimony pentoxide fine particles is not greatly changed, and the effect of improving the conductivity and the effect of improving the antistatic performance are sufficiently obtained. There may not be.
本発明での体積抵抗値（Ω・ｃｍ）は、セラミックス性セル（内部に円柱状のくりぬき（断面積：０．５ｃｍ2）を有する）を用い、まず、架台電極上にセルを置き、内部に試料粉体を充填し、円柱状突起を有する上部電極の突起を挿入し、油圧機にて上下電極を加圧し、１００ｋｇ／ｃｍ（９．８０ＭＰａ）加圧時の抵抗値（Ω）と試料の高さ（ｃｍ）を測定し、抵抗値（Ω）に断面積を乗じ、これを高さで除することによって求めることができる。 The volume resistance value (Ω · cm) in the present invention is determined by using a ceramic cell (with a cylindrical hollow (cross-sectional area: 0.5 cm 2 ) inside). The sample powder is filled in, the protrusion of the upper electrode having a cylindrical protrusion is inserted, the upper and lower electrodes are pressurized with a hydraulic machine, and the resistance value (Ω) and the sample when 100 kg / cm (9.80 MPa) is applied are measured. Can be obtained by measuring the height (cm), multiplying the resistance value (Ω) by the cross-sectional area, and dividing this by the height.
本発明では、2個以上の前記リン含有五酸化アンチモン微粒子が鎖状に連結してもよい。その平均連結数は２〜３０個、好ましくは５〜３０の範囲にあることが好ましい。また、連結することで、粒界抵抗による導電性の損失がなくなるため、体積抵抗は、連結していないものに比べ、小さくできる。具体的には、連結数にもよるが、体積抵抗値が１〜１０3Ω・ｃｍ、さらには１〜５ｘ１０2Ω・ｃｍの範囲にあるものを望ましい。 In the present invention, two or more phosphorus-containing antimony pentoxide fine particles may be linked in a chain. The average number of connections is 2 to 30, preferably 5 to 30. Further, since the conductive loss due to the grain boundary resistance is eliminated by the connection, the volume resistance can be made smaller than that of the unconnected one. Specifically, although depending on the number of connections, the volume resistance is preferably 1 to 10 3 Ω · cm, more preferably 1 to 5 × 10 2 Ω · cm.
本発明にかかるリン含有五酸化アンチモン微粒子の製造方法は、前記した範囲の五酸化燐を含有し、体積抵抗値を有するリン含有五酸化アンチモン微粒子が得られれば特に制限はないが、まず、本願出願人の出願（特開平２−１８０７１７号公報、特開２００７−１７６７１０号公報）に開示した方法に準じて、五酸化アンチモン微粒子を製造することができる。 The method for producing phosphorus-containing antimony pentoxide fine particles according to the present invention is not particularly limited as long as the phosphorus-containing antimony pentoxide fine particles containing the above-mentioned range of phosphorus pentoxide and having a volume resistance value are obtained. Antimony pentoxide fine particles can be produced according to the method disclosed in the applicant's application (Japanese Patent Laid-Open Nos. 2-180717 and 2007-176710).
具体的に、特開平２−１８０７１７号公報に開示した方法では、三酸化アンチモン、アルカリ物質および過酸化水素水を反応させてアンチモンゾルを製造するが、三酸化アンチモンとアルカリ物質と過酸化水素水のモル比を１：２．０〜２．５：０．８〜１．５とし、三酸化アンチモンとアルカリ物質を含む系に過酸化水素を三酸化アンチモン１ｍｏｌｅ当たり０．２ｍｏｌｅ／ｈｒの速度で添加する。 Specifically, in the method disclosed in Japanese Patent Application Laid-Open No. 2-180717, antimony trioxide, an alkali substance and hydrogen peroxide solution are reacted to produce an antimony sol. The molar ratio of 1: 2.0 to 2.5: 0.8 to 1.5, and hydrogen peroxide is added to the system containing antimony trioxide and an alkaline substance at a rate of 0.2 mole / hr per mole of antimony trioxide. Added.
また、特開２００７−１７６７１０号公報に開示した方法では、酸化アンチモンとアルカリ物質を反応させた後、過酸化水素と反応させ、ついで、イオン交換樹脂で脱イオン処理した後、熟成してアンチモンゾルを製造する方法において、所定量の斜方晶形三酸化アンチモンを含む三酸化アンチモンを用い、三酸化アンチモンとアルカリ物質と過酸化水素水のモル比を１：２．０〜２．５：０．８〜３．５とし、５０〜２００℃で熟成する。
このようにして得られた五酸化アンチモン微粒子の平均粒子径は５〜５０ｎｍ、さらには１０〜４０ｎｍの範囲にあることが好ましい。
Further, in the method disclosed in Japanese Patent Application Laid-Open No. 2007-176710, antimony oxide and an alkaline substance are reacted, then reacted with hydrogen peroxide, then deionized with an ion exchange resin, and aged to be antimony sol. In the method for producing the antimony, an antimony trioxide containing a predetermined amount of orthorhombic antimony trioxide is used, and the molar ratio of the antimony trioxide, the alkaline substance, and the hydrogen peroxide solution is 1: 2.0 to 2.5: 0. 8 to 3.5 and ripen at 50 to 200 ° C.
The average particle diameter of the antimony pentoxide fine particles thus obtained is preferably 5 to 50 nm, more preferably 10 to 40 nm.
ついで、得られた五酸化アンチモン微粒子分散液に、リン酸化物となる原料を添加する。本発明では、添加量の制御や取り扱い性などから、リン化合物としては、リン酸またはその塩（アンモニウムなど）を使用することが望ましく、特にリン酸が望ましい。 Next, a raw material to be phosphorous oxide is added to the obtained antimony pentoxide fine particle dispersion. In the present invention, it is desirable to use phosphoric acid or a salt thereof (such as ammonium) as the phosphorus compound, and phosphoric acid is particularly desirable from the viewpoint of control of the addition amount and handleability.
このときの、五酸化アンチモン微粒子分散液の濃度は特に制限はないが概ね１〜３０重量％の範囲にあることが好ましい。
五酸化アンチモン微粒子分散液の濃度が低ければ、生産性が低下し、経済性が不利になり、多すぎても、強く凝集した五酸化アンチモン微粒子となる場合がある。また、分散液の温度は特に制限はないが、通常常温で行う。
The concentration of the antimony pentoxide fine particle dispersion at this time is not particularly limited but is preferably in the range of 1 to 30% by weight.
If the concentration of the antimony pentoxide fine particle dispersion is low, the productivity is lowered, the economy is disadvantageous, and if it is too much, the antimony pentoxide fine particles may be strongly aggregated. The temperature of the dispersion is not particularly limited, but it is usually carried out at room temperature.
リン酸の添加量は、得られるリン含有五酸化アンチモン微粒子中のリン酸化物の含有量がＰ2Ｏ5として前記範囲となるように添加する。
リン酸の添加速度は、一時に添加しても良いが、連続的にあるいは断続的にすることが好ましく、製造装置、製造規模等によって異なるが、例えば、含有量基準で１重量％を概ね０．５分〜３０分の速度で添加し、それに応じて添加速度を調整することが好ましい。
The addition amount of phosphoric acid is added so that the phosphorus oxide content in the obtained phosphorus-containing antimony pentoxide fine particles falls within the above range as P 2 O 5 .
The addition rate of phosphoric acid may be added at a time, but is preferably continuous or intermittent, and varies depending on the production equipment, production scale, etc. It is preferable to add at a rate of 5 to 30 minutes and adjust the addition rate accordingly.
リン酸を添加した後、必要に応じて撹拌を継続してもよい。
得られた分散液を、濾過し、分離し、乾燥または加熱処理し、必要に応じて塊砕してリン含有五酸化アンチモン微粒子を得ることができる。
After adding phosphoric acid, stirring may be continued as necessary.
The obtained dispersion can be filtered, separated, dried or heat-treated, and crushed as necessary to obtain phosphorus-containing antimony pentoxide fine particles.
乾燥、加熱処理方法は特に制限はなく、従来公知の方法で乾燥、加熱処理することができる。
加熱乾燥条件は、リン含有五酸化アンチモン微粒子中の付着水を除去でき、後述するｎの値、あるいは水分含有量の範囲となればよく、８０〜２５０℃で０．５〜１２時間であり、好ましくは９０〜１５０℃、１〜６時間である。加熱処理温度が高温になりすぎると、リンが五酸化アンチモン微粒子の結晶にドーピングされるためか、得られるリン含有五酸化アンチモン微粒子が黄色に変色する傾向があり、場合によっては体積抵抗値が低くならず、透明導電性被膜に用いるには不向きである。
There are no particular limitations on the drying and heat treatment methods, and drying and heat treatment can be performed by a conventionally known method.
The heating and drying conditions can remove the adhering water in the phosphorus-containing antimony pentoxide fine particles, and may be a value of n or a water content in the range described later, and is 0.5 to 12 hours at 80 to 250 ° C., Preferably they are 90-150 degreeC and 1 to 6 hours. If the heat treatment temperature becomes too high, phosphorus is doped into the crystals of antimony pentoxide fine particles, or the resulting phosphorus-containing antimony pentoxide fine particles tend to turn yellow, and in some cases the volume resistance value is low. In other words, it is not suitable for use in a transparent conductive film.
なお、連結した鎖状のリン含有五酸化アンチモン微粒子は、本願出願人の出願による特開２００５−１３９０２６号公報に開示した鎖状五酸化アンチモン微粒子を用いて、同様にリン酸化物原料を含有させることによって製造することができる。 The linked chain-containing phosphorus-containing antimony pentoxide fine particles are similarly incorporated with the phosphorous oxide raw material using the chain-shaped antimony pentoxide fine particles disclosed in JP-A-2005-139026 filed by the applicant of the present application. Can be manufactured.
本発明のリン含有五酸化アンチモン微粒子は下記式(1)によって表すことができる。
Ｓｂ2Ｏ5・ｘＰ2Ｏ5・ｎＨ2Ｏ・・・・・（１）
（ｘは、Ｓｂ2Ｏ5を１モルとしたときのＰ2Ｏ5のモル数であり、ｎはリン含有五酸化アンチモン微粒子が含有するＯＨ基に由来する水分子のモル数である。）
なお、本発明に用いる五酸化アンチモン微粒子はパイロクロア構造（アンチモン原子を中心にして６個の酸素原子およびＯＨ基により８面体が形成され、これら８面体の頂点共有によって形成された骨格構造）を有し、チャンネル（骨格構造の隙間）を形成している。このチャンネルがＯＨ基のプロトン移動の通路となり、導電性を発現する。このような五酸化アンチモン微粒子の結晶構造は、パイロクロア構造を有し、Ｘ線回折により、主に（１１１）、（３１１）、（２２２）および（４００）面のピークによって同定される。なお、本発明のようにリンを含むもものでは、新たなピークは出現せず、ピーク高さも大きく変化しないが、高温で加熱処理させてドーピングすると各ピーク高が大きく低下する。
The phosphorus-containing antimony pentoxide fine particles of the present invention can be represented by the following formula (1).
Sb 2 O 5 xP 2 O 5 nH 2 O (1)
(X is the number of moles of P 2 O 5 when Sb 2 O 5 is 1 mole, and n is the number of moles of water molecules derived from OH groups contained in the phosphorus-containing antimony pentoxide fine particles.)
The antimony pentoxide fine particles used in the present invention have a pyrochlore structure (a skeletal structure in which an octahedron is formed by six oxygen atoms and OH groups centered on an antimony atom, and is formed by sharing the vertices of these octahedrons). In addition, a channel (a gap in the skeleton structure) is formed. This channel serves as a path for proton transfer of the OH group and develops conductivity. The crystal structure of such antimony pentoxide fine particles has a pyrochlore structure, and is identified mainly by peaks on the (111), (311), (222) and (400) planes by X-ray diffraction. In the case of containing phosphorus as in the present invention, a new peak does not appear and the peak height does not change greatly. However, when doping is performed by heating at a high temperature, each peak height is greatly reduced.
上記において、ｘは、リンを五酸化二リンに換算したときの含有量に相当し、上記割合から0.0023〜0.3418、好ましくは、0.0114〜0.2735であり、これは、リン含有五酸化アンチモン微粒子中のＰ2Ｏ5としての含有量が０．１〜１５重量％、さらには0.5〜12重量％となる範囲である。また、ｎは０．１〜３、さらには０．５〜３の範囲にあることが好ましい。これを水分含有量に換算すると概ね０．５〜１４重量％、好ましくは１〜１４重量％の範囲となる。
ｎによって、導電性が変化し、ｎが少ないと導電性は低くなり、多すぎると、一部が水酸化物となったりして、安定性が低下することがある。
In the above, x corresponds to the content when phosphorus is converted to diphosphorus pentoxide, and is 0.0023 to 0.3418, preferably 0.0114 to 0.2735 from the above ratio, and this is in the phosphorus-containing antimony pentoxide fine particles. The content of P 2 O 5 is in the range of 0.1 to 15% by weight, further 0.5 to 12% by weight. Further, n is preferably in the range of 0.1 to 3, more preferably 0.5 to 3. When this is converted into the moisture content, it is generally in the range of 0.5 to 14% by weight, preferably 1 to 14% by weight.
Depending on n, the conductivity changes, and if n is small, the conductivity is low, and if it is too large, a part thereof may become a hydroxide and the stability may be lowered.
[透明導電性被膜形成用塗布液]
本発明に係る透明導電性被膜形成用塗布液は、前記リン含有五酸化アンチモン微粒子とマトリックス形成成分と分散媒とからなり、リン含有五酸化アンチモン微粒子中のリンの含有量がＰ2Ｏ5として０．１〜１５重量％の範囲にあることを特徴としている。
[Coating liquid for forming transparent conductive film]
The coating liquid for forming a transparent conductive film according to the present invention comprises the phosphorus-containing antimony pentoxide fine particles, a matrix-forming component, and a dispersion medium, and the phosphorus content in the phosphorus-containing antimony pentoxide fine particles is P 2 O 5. It is characterized by being in the range of 0.1 to 15% by weight.
リン含有五酸化アンチモン微粒子
本発明に用いるリン含有五酸化アンチモン微粒子としては前記したリン含有五酸化アンチモン微粒子(鎖状粒子も含む)を用いる。
Phosphorus-containing antimony pentoxide fine particles As the phosphorus-containing antimony pentoxide fine particles used in the present invention, the above-mentioned phosphorus-containing antimony pentoxide fine particles (including chain particles) are used.
リン含有五酸化アンチモン微粒子は、透明導電性被膜に用いるには従来公知の方法で、シランカップリング剤で処理したり、樹脂で被覆して、マトリックス形成成分への分散性を向上させて用いることが好ましい。 Phosphorus-containing antimony pentoxide fine particles should be used in a transparent conductive film by a conventionally known method, treated with a silane coupling agent or coated with a resin to improve dispersibility in matrix forming components. Is preferred.
マトリックス形成成分
マトリックス形成成分としては、シリコーン系（ゾルゲル系）マトリックス形成成分または有機樹脂マトリックス形成成分が用いられる。
Matrix-forming component As the matrix-forming component, a silicone (sol-gel) matrix-forming component or an organic resin matrix-forming component is used.
シリコーン系マトリックス形成成分としては、下記式(1)で表される有機ケイ素化合物の加水分解物が用いられる。
Ｒn-ＳiＸ4-n （１）
（但し、式中、Ｒは炭素数１〜１０の非置換または置換炭化水素基であって、互いに同一であっても異なっていてもよい。Ｘ：炭素数１〜４のアルコキシ基、水酸基、ハロゲン、水素、ｎ：０〜３の正数）
As the silicone-based matrix-forming component, a hydrolyzate of an organosilicon compound represented by the following formula (1) is used.
R n -SiX 4-n (1 )
(In the formula, R is an unsubstituted or substituted hydrocarbon group having 1 to 10 carbon atoms, and may be the same or different from each other. X: an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, (Halogen, hydrogen, n: positive number from 0 to 3)
具体的には、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、テトラブトキシシラン、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、ジフェニルジメトキシシラン、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、ジフェニルジエトキシシラン、イソブチルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス（βメトキシエトキシ）シラン、3,3,3−トリフルオロプロピルトリメトキシシラン、メチル-3,3,3−トリフルオロプロピルジメトキシシラン、β−（3,4-エポキシシクロヘキシル）エチルトリメトキシシラン、
γ-グリシドキシメチルトリメトキシシラン、γ-グリシドキシメチルトリエキシシラン、γ-グリシドキシエチルトリメトキシシラン、γ-グリシドキシエチルトリエトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリメトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、γ-グリシドキシプロピルトリエトキシシラン、γ−（β−グリシドキシエトキシ）プロピルトリメトキシシラン、γ-（メタ）アクリロオキシメチルトリメトキシシラン、γ-（メタ）アクリロオキシメチルトリエキシシラン、γ-（メタ）アクリロオキシエチルトリメトキシシラン、γ-（メタ）アクリロオキシエチルトリエトキシシラン、γ-（メタ）アクリロオキシプロピルトリメトキシシラン、γ-（メタ）アクリロオキシプロピルトリメトキシシラン、γ-（メタ）アクリロオキシプロピルトリエトキシシラン、γ-（メタ）アクリロオキシプロピルトリエトキシシラン、ブチルトリメトキシシラン、イソブチルトリエトキシシラン、ヘキシルトリエトキシシラオクチルトリエトキシシラン、デシルトリエトキシシラン、ブチルトリエトキシシラン、イソブチルトリエトキシシラン、ヘキシルトリエトキシシラン、オクチルトリエトキシシラン、デシルトリエトキシシラン、3-ウレイドイソプロピルプロピルトリエトキシシラン、パーフルオロオクチルエチルトリメトキシシラン、パーフルオロオクチルエチルトリエトキシシラン、パーフルオロオクチルエチルトリイソプロポキシシラン、トリフルオロプロピルトリメトキシシラン、Ｎ−β（アミノエチル）γ-アミノプロピルメチルジメトキシシラン、Ｎ−β（アミノエチル）γ-アミノプロピルトリメトキシシラン、Ｎ-フェニル-γ-アミノプロピルトリメトキシシラン、γ-メルカプトプロピルトリメトキシシラン、トリメチルシラノール、メチルトリクロロシラン等が挙げられる。
Specifically, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyl Triethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (βmethoxyethoxy) silane, 3,3,3-trifluoropropyltrimethoxysilane, methyl-3,3 , 3-trifluoropropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane,
γ-glycidoxymethyltrimethoxysilane, γ-glycidoxymethyltriethoxysilane, γ-glycidoxyethyltrimethoxysilane, γ-glycidoxyethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β-glycidoxyethoxy) propyltrimethoxysilane, γ- (meth) Acryloxymethyltrimethoxysilane, γ- (meth) acrylooxymethyltrioxysilane, γ- (meth) acrylooxyethyltrimethoxysilane, γ- (meth) acrylooxyethyltriethoxysilane, γ- ( (Meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyl Trimethoxysilane, γ- (meth) acrylooxypropyltriethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, butyltrimethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilaoctyltriethoxysilane, decyl Triethoxysilane, butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 3-ureidoisopropylpropyltriethoxysilane, perfluorooctylethyltrimethoxysilane, perfluorooctylethyl Triethoxysilane, perfluorooctylethyltriisopropoxysilane, trifluoropropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyl Examples include methyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, trimethylsilanol, and methyltrichlorosilane.
本発明では有機樹脂マトリックス形成成分が好適に用いられ、有機樹脂マトリックス形成成分として、具体的には塗料用樹脂として公知の熱硬化性樹脂、熱可塑性樹脂等のいずれも採用することができる。たとえば、従来から用いられているポリエステル樹脂、ポリカーボネート樹脂、ポリアミド樹脂、ポリフェニレンオキサイド樹脂、熱可塑性アクリル樹脂、塩化ビニル樹脂、フッ素樹脂、酢酸ビニル樹脂、シリコーンゴムなどの熱可塑性樹脂、ウレタン樹脂、メラミン樹脂、ケイ素樹脂、ブチラール樹脂、反応性シリコーン樹脂、フェノール樹脂、エポキシ樹脂、不飽和ポリエステル樹脂、熱硬化性アクリル樹脂などの熱硬化性樹脂などが挙げられる。さらにはこれら樹脂の２種以上の共重合体や変性体であってもよい。 In the present invention, an organic resin matrix-forming component is preferably used, and as the organic resin matrix-forming component, specifically, any of thermosetting resins, thermoplastic resins, and the like known as coating resins can be employed. For example, conventionally used polyester resins, polycarbonate resins, polyamide resins, polyphenylene oxide resins, thermoplastic acrylic resins, vinyl chloride resins, fluororesins, vinyl acetate resins, silicone rubber and other thermoplastic resins, urethane resins, melamine resins And thermosetting resins such as silicon resin, butyral resin, reactive silicone resin, phenol resin, epoxy resin, unsaturated polyester resin, and thermosetting acrylic resin. Further, it may be a copolymer or modified body of two or more of these resins.
これらの樹脂は、エマルジョン樹脂、水溶性樹脂、親水性樹脂であってもよい。さらに、熱硬化型、紫外線硬化型、電子線硬化型のものであってもよく、熱硬化性樹脂の場合、硬化触媒が含まれていてもよい。 These resins may be emulsion resins, water-soluble resins, and hydrophilic resins. Furthermore, a thermosetting type, an ultraviolet curable type, an electron beam curable type may be used, and in the case of a thermosetting resin, a curing catalyst may be included.
分散媒
本発明に用いる分散媒としては前記マトリックス形成成分、必要に応じて用いる硬化触媒を溶解あるいは分散できるとともに前記したリン含有五酸化アンチモン微粒子を均一に分散することができれば特に制限はなく、従来公知の溶媒を用いることができる。具体的には、メタノール、エタノール、プロパノール、2-プロパノール（ＩＰＡ）、ブタノール、ジアセトンアルコール、フルフリルアルコール、テトラヒドロフルフリルアルコール、エチレングリコール、ヘキシレングリコール、イソプロピルグリコールなどのアルコール類；酢酸メチルエステル、酢酸エチルエステル、酢酸ブチルなどのエステル類；ジエチルエーテル、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールイソプルピルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテルなどのエーテル類；アセトン、メチルエチルケトン、メチルイソブチルケトン、ブチルメチルケトン、シクロヘキサノン、メチルシクロヘキサノン、ジプロピルケトン、メチルペンチルケトン、ジイソブチルケトン、イソホロン、アセチルアセトン、アセト酢酸エステルなどのケトン類、トルエン、キシレン等が挙げられる。これらは単独で使用してもよく、また２種以上混合して使用することもできる。
Dispersion medium The dispersion medium used in the present invention is not particularly limited as long as it can dissolve or disperse the matrix-forming component and, if necessary, the curing catalyst used and can uniformly disperse the above-mentioned phosphorus-containing antimony pentoxide fine particles. A known solvent can be used. Specifically, alcohols such as methanol, ethanol, propanol, 2-propanol (IPA), butanol, diacetone alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, hexylene glycol, isopropyl glycol; methyl acetate , Esters such as ethyl acetate, butyl acetate; diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol isopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl Ethers such as ether and propylene glycol monoethyl ether; Acetone, methyl ethyl ketone, methyl isobutyl ketone, butyl methyl ketone, cyclohexanone, methyl cyclohexanone, dipropyl ketone, methyl pentyl ketone, diisobutyl ketone, isophorone, acetylacetone, ketones such as acetoacetate, toluene, xylene and the like. These may be used alone or in combination of two or more.
透明導電性被膜形成用塗布液の濃度は、特に制限されないが、塗工性、経済性などの観点から、全固形分として１〜６０重量％、さらには２〜４０重量％の範囲にあることが好ましい。 The concentration of the coating liquid for forming a transparent conductive film is not particularly limited, but from the viewpoint of coating property, economy, etc., it should be in the range of 1 to 60% by weight, further 2 to 40% by weight as the total solid content. Is preferred.
透明導電性被膜形成用塗布液の全固形分濃度が少なすぎると、１回の塗布で厚膜の透明導電性被膜を得ることが困難な場合があり、繰り返し塗布、乾燥を繰り返すと、膜の強度が低下したり、経済性が低下する問題がある。 If the total solid concentration of the coating liquid for forming the transparent conductive film is too small, it may be difficult to obtain a thick transparent conductive film by one application. There is a problem that the strength is lowered or the economy is lowered.
透明導電性被膜形成用塗布液の全固形分濃度が多すぎると、塗布液の粘度が高くなり、塗布性が低下したり、得られる透明導電性被膜のヘーズが高くなったり、耐擦傷性が不充分となる場合がある。 If the total solid concentration of the coating liquid for forming the transparent conductive film is too high, the viscosity of the coating liquid becomes high, the coating property decreases, the haze of the resulting transparent conductive film increases, and the scratch resistance is high. It may be insufficient.
透明導電性被膜形成用塗布液中のリン含有五酸化アンチモン微粒子の濃度は固形分として０．５〜５７重量％、さらには０．１〜４５重量％の範囲にあることが好ましい。透明導電性被膜形成用塗布液中のリン含有五酸化アンチモン微粒子の濃度が少ないと、導電性が不充分となり、得られる透明導電性被膜付基材の帯電防止性能が不充分となる場合があり、また、耐擦傷性、基材との密着性が不充分となる場合がある。また濃度が多すぎてもマトリックス成分が少なくなるために透明導電性被膜の耐擦傷性、基材との密着性が不充分となる場合がある。 The concentration of the phosphorus-containing antimony pentoxide fine particles in the coating liquid for forming a transparent conductive film is preferably in the range of 0.5 to 57% by weight, more preferably 0.1 to 45% by weight as the solid content. If the concentration of phosphorus-containing antimony pentoxide fine particles in the coating solution for forming a transparent conductive film is low, the conductivity may be insufficient and the resulting antistatic performance of the substrate with the transparent conductive film may be insufficient. In addition, the scratch resistance and the adhesion to the substrate may be insufficient. Further, even if the concentration is too high, the matrix component is reduced, so that the scratch resistance of the transparent conductive film and the adhesion to the substrate may be insufficient.
透明導電性被膜形成用塗布液中のマトリックス形成成分の濃度は固形分として０．５〜５７重量％、さらには０．１〜４５重量％の範囲にあることが好ましい。
透明導電性被膜形成用塗布液中のマトリックス形成成分の濃度が少ないと、マトリックス成分が少なくなるために透明導電性被膜の耐擦傷性、基材との密着性が不充分となる場合がある。また濃度が高すぎると、リン含有五酸化アンチモン微粒子が少なくなるために導電性が不充分となり、得られる透明導電性被膜付基材の帯電防止性能が不充分となる場合があり、また、耐擦傷性、基材との密着性が不充分となる場合がある。
The concentration of the matrix-forming component in the coating solution for forming a transparent conductive film is preferably in the range of 0.5 to 57% by weight, more preferably 0.1 to 45% by weight as the solid content.
If the concentration of the matrix-forming component in the coating liquid for forming the transparent conductive film is small, the matrix component is decreased, so that the scratch resistance of the transparent conductive film and the adhesion to the substrate may be insufficient. On the other hand, if the concentration is too high, the amount of phosphorus-containing antimony pentoxide fine particles is reduced, resulting in insufficient conductivity, and the resulting antistatic performance of the substrate with a transparent conductive film may be insufficient. In some cases, scratch resistance and adhesion to the substrate may be insufficient.
なお、リン含有五酸化アンチモン微粒子と、マトリックス形成成分との重量比は、5：95〜95：5、好ましくは10：90〜90：10の範囲にあることが望ましい。
このような塗布液をディップ法、スプレー法、スピナー法、ロールコート法等の周知の方法で前記した基材に塗布し、乾燥し、加熱処理、紫外線照射等によって硬化させることによって透明導電性被膜を形成することができる。
The weight ratio between the phosphorus-containing antimony pentoxide fine particles and the matrix-forming component is desirably in the range of 5:95 to 95: 5, preferably 10:90 to 90:10.
A transparent conductive film is formed by applying such a coating solution to a substrate as described above by a known method such as a dipping method, a spray method, a spinner method, a roll coating method, drying, and curing by heat treatment, ultraviolet irradiation, or the like. Can be formed.
[透明導電性被膜付基材]
本発明に係る透明導電性被膜付基材は、基材と、基材上に形成された透明導電性被膜とからなり、該透明導電性被膜が前記リン含有五酸化アンチモン微粒子とマトリックス成分を含み、透明導電性被膜中のリン含有五酸化アンチモン微粒子の含有量が５〜９５重量％の範囲にあることが好ましい。
[Base material with transparent conductive film]
A substrate with a transparent conductive film according to the present invention comprises a substrate and a transparent conductive film formed on the substrate, and the transparent conductive film contains the phosphorus-containing antimony pentoxide fine particles and a matrix component. The content of the phosphorus-containing antimony pentoxide fine particles in the transparent conductive film is preferably in the range of 5 to 95% by weight.
基材
本発明に用いる基材としては、従来公知のガラス、ポリカーボネート、アクリル樹脂、ＰＥＴ、ＴＡＣ等のプラスチックシート、プラスチックフィルム等、プラスチックパネル等を用いることができる。
なかでもトリアセチルセルロース（ＴＡＣ）基材、ＰＥＴ等ポリオレフィン系樹脂基材、ポリビニルアルコール系樹脂基材、ポリエーテルスルフォン系樹脂機材等が好適に用いられる。
The base material used for the substrate present invention may be used conventionally known glass, polycarbonate, acrylic resin, PET, plastic sheet, such as TAC, plastic film, a plastic panel or the like.
Of these, a triacetyl cellulose (TAC) base material, a polyolefin resin base material such as PET, a polyvinyl alcohol resin base material, a polyether sulfone base resin material, and the like are preferably used.
リン含有五酸化アンチモン微粒子
本発明に用いるリン含有五酸化アンチモン微粒子としては前記した通りである。
Phosphorus-containing antimony pentoxide fine particles The phosphorus-containing antimony pentoxide fine particles used in the present invention are as described above.
マトリックス成分
マトリックス成分としては、前記シリコーン系（ゾルゲル系）マトリックス形成成分の硬化物または前記有機樹脂マトリックス形成成分の硬化物が用いられる。なお熱可塑性樹脂の場合、マトリックス形成成分とマトリックス成分は同じであり、熱硬化性樹脂の場合、重合ないし反応した硬化物である。
As the matrix component, a cured product of the silicone-based (sol-gel) matrix-forming component or a cured product of the organic resin matrix-forming component is used. In the case of a thermoplastic resin, the matrix forming component and the matrix component are the same, and in the case of a thermosetting resin, it is a cured product obtained by polymerization or reaction.
本発明では有機樹脂マトリックス形成成分の硬化物が好適である。
透明導電性被膜中のリン含有五酸化アンチモン微粒子の含有量は、固形分として５〜９５重量％、さらには１０〜９０重量％の範囲にあることが好ましい。
In the present invention, a cured product of the organic resin matrix-forming component is suitable.
The content of the phosphorus-containing antimony pentoxide fine particles in the transparent conductive film is preferably in the range of 5 to 95% by weight, more preferably 10 to 90% by weight as the solid content.
透明導電性被膜中のリン含有五酸化アンチモン微粒子の含有量が少ないと、導電性が不充分となり、得られる透明導電性被膜付基材の帯電防止性能が不充分となる場合があり、また、耐擦傷性、基材との密着性が不充分となる場合がある。 If the content of the phosphorus-containing antimony pentoxide fine particles in the transparent conductive film is small, the conductivity may be insufficient, and the resulting antistatic performance of the substrate with the transparent conductive film may be insufficient, In some cases, the scratch resistance and the adhesion to the substrate may be insufficient.
透明導電性被膜中のリン含有五酸化アンチモン微粒子の含有量が多すぎると、マトリックス成分が少なくなるために透明導電性被膜の耐擦傷性、基材との密着性が不充分となる場合がある。 If the content of the phosphorus-containing antimony pentoxide fine particles in the transparent conductive film is too large, the matrix component may decrease, and the scratch resistance of the transparent conductive film and the adhesion to the substrate may be insufficient. .
本発明の透明導電性被膜の膜厚は、０．１〜２０μｍ、さらには０．２〜１５μｍの範囲にあることが好ましい。この範囲にあれば、高い帯電防止性能・耐擦傷性を発揮できる。 The film thickness of the transparent conductive film of the present invention is preferably in the range of 0.1 to 20 μm, more preferably 0.2 to 15 μm. Within this range, high antistatic performance and scratch resistance can be exhibited.
透明導電性被膜が薄いと、帯電防止性能が不充分となる場合があり、また、透明導電性被膜表面に加わる応力を充分吸収することがでないために、耐擦傷性が不充分となる。透明導電性被膜が厚すぎても、膜の厚さが均一になるように塗布したり、均一に乾燥することが困難となり、さらに収縮が大きくなるので基材の種類によってはカーリング（透明導電性被膜付基材が湾曲）が生じることがある。また、膜厚が厚すぎて透明性が不充分となることがある。 If the transparent conductive film is thin, the antistatic performance may be insufficient, and the stress applied to the surface of the transparent conductive film may not be sufficiently absorbed, resulting in insufficient scratch resistance. Even if the transparent conductive film is too thick, it becomes difficult to apply the film so that the film thickness is uniform or to dry uniformly, and further shrinkage increases, so depending on the type of substrate, curling (transparent conductive The coated substrate may be curved). Also, the film thickness may be too thick and the transparency may be insufficient.
[実施例]
以下、実施例により本発明をさらに具体的に説明するが、本発明はこれらの実施例により限定されるものではない。
[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples.
[実施例1]
リン含有五酸化アンチモン微粒子(1)分散液の調製
純水８００ｇに苛性カリ（旭硝子(株)製：純度８５％）２５ｇを溶解した溶液中に三酸化アンチモン（日本精鉱(株)：ＰＡＴＯＸ-Ｍ、純度９８．５％）５０ｇを懸濁した。この懸濁液を９５℃に加熱し、次いで、過酸化水素水（林純薬(株)製：特級、濃度３５重量％）１５ｇを純水５０ｇで希釈した水溶液を９時間で添加し、三酸化アンチモンを溶解し、その後、１１時間熟成した。ついで、冷却後、得られた溶液から８００ｇをとり、この溶液を純水４８００ｇで希釈した後、陽イオン交換樹脂（三菱化学(株)製：ｐｋ−２１６）でｐＨが２．８になるまで脱イオン処理を行った。脱イオン処理して得られた溶液を温度７０℃で１０時間熟成した後、限外膜で濃縮して固形分濃度１４重量％の五酸化アンチモン微粒子(1)分散液を調製した。この五酸化アンチモン微粒子(1)分散液のｐＨは４．０、五酸化アンチモン微粒子(1)の平均粒子径は２０ｎｍであった。
[Example 1]
Preparation of Phosphorus-Containing Antimony Pentoxide Fine Particles (1) Dispersion Antimony trioxide (Nippon Seiko Co., Ltd .: PATOX-M) in a solution of 25 g of caustic potash (Asahi Glass Co., Ltd .: 85% purity) dissolved in 800 g of pure water , Purity 98.5%) 50 g was suspended. This suspension was heated to 95 ° C., and then an aqueous solution obtained by diluting 15 g of hydrogen peroxide solution (produced by Hayashi Junyaku Co., Ltd .: special grade, concentration 35% by weight) with 50 g of pure water was added in 9 hours. Antimony oxide was dissolved and then aged for 11 hours. Then, after cooling, 800 g is taken from the obtained solution, and after diluting this solution with 4800 g of pure water, the pH is 2.8 with a cation exchange resin (Mitsubishi Chemical Corporation: pk-216). Deionization treatment was performed. The solution obtained by deionization was aged at a temperature of 70 ° C. for 10 hours, and then concentrated on an ultra-thin film to prepare a dispersion of antimony pentoxide fine particles (1) having a solid concentration of 14% by weight. The pH of the antimony pentoxide fine particles (1) dispersion was 4.0, and the average particle size of the antimony pentoxide fine particles (1) was 20 nm.
ついで、固形分濃度１４重量％の五酸化アンチモン微粒子(1)分散液２１００ｇにリン酸水溶液（関東化学（株）製：濃度８５重量％）を、常温で７分かけて２５ｇ添加し、１３分攪拌した。その後、バットへ取り出し９０℃で１８時間乾燥した。乾燥粉末をメノウで解砕し、さらに１１０℃で１２時間乾燥してリン含有五酸化アンチモン微粒子(1)を得た。リン含有五酸化アンチモン微粒子(1)のリンの含有量はＰ2Ｏ5として５重量％、水分含有量１１重量％、平均粒子径は２０ｎｍ、体積抵抗値は５００Ω・ｃｍであった。 Next, 25 g of phosphoric acid aqueous solution (manufactured by Kanto Chemical Co., Inc .: concentration 85 wt%) was added to 2100 g of the antimony pentoxide fine particles (1) dispersion having a solid content concentration of 14 wt% at room temperature over 7 minutes, and 13 minutes. Stir. Thereafter, it was taken out into a vat and dried at 90 ° C. for 18 hours. The dried powder was crushed with agate and further dried at 110 ° C. for 12 hours to obtain phosphorus-containing antimony pentoxide fine particles (1). The phosphorus content of the phosphorus-containing antimony pentoxide fine particles (1) was 5% by weight as P 2 O 5 , the water content was 11% by weight, the average particle size was 20 nm, and the volume resistance value was 500 Ω · cm.
次に、リン含有五酸化アンチモン微粒子(1)粉末１２０ｇを、有機溶媒としてプロピレングリコールモノメチルエーテル(ＰＧＭＥ)２２４ｇ、分散剤（第一工業製薬(株)製：プライサーフＡ-２１７Ｅ）１２ｇ、ガラスビーズ６２８ｇを入れたビーズミルに充填し、分散処理をして固形分濃度３０重量％のリン含有五酸化アンチモン微粒子(1)分散液を調製した。 Next, 120 g of phosphorus-containing antimony pentoxide fine particles (1) powder, 224 g of propylene glycol monomethyl ether (PGME) as an organic solvent, 12 g of a dispersant (Daiichi Kogyo Seiyaku Co., Ltd .: Prisurf A-217E), glass beads A bead mill containing 628 g was filled and subjected to a dispersion treatment to prepare a phosphorus-containing antimony pentoxide fine particle (1) dispersion having a solid content concentration of 30% by weight.
透明導電性被膜形成用塗布液(1)の調製
リン含有五酸化アンチモン微粒子(1)分散液１０ｇに紫外線硬化樹脂（DIC(株)製:ユニデック１７−８２４−９、固形分濃度７９重量％）８．９ｇと光重合開始剤（ビーエーエスエフジャパン(株)製:ルシリンＴＰＯ、ＰＧＭＥに固形分濃度１０重量％に溶解）４．２ｇおよびＰＧＭＥ１０．２ｇとを充分に混合して透明導電性被膜形成用塗布液(1)を調製した。
Preparation of coating liquid (1) for forming transparent conductive film Ultraviolet curable resin (manufactured by DIC Corporation: Unidec 17-824-9, solid content concentration 79% by weight) to 10 g of dispersion-containing antimony pentoxide fine particles (1) dispersion 8.9 g and a photopolymerization initiator (manufactured by BSF Japan Ltd .: Lucyrin TPO, dissolved in PGME at a solid content concentration of 10% by weight) 4.2 g and 10.2 g of PGME were mixed thoroughly to form a transparent conductive film. A coating solution (1) was prepared.
透明導電性被膜付基材(1)の製造
透明導電性被膜形成用塗布液(1)を易接着層付ＰＥＴフィルム(東洋紡績（株）製：コスモシャインＡ４３００)にバーコーター法（♯１２）で塗布し、８０℃で１分間乾燥した後、高圧水銀灯（６００ｍＪ／ｃｍ2）を照射して硬化させ、透明導電性被膜付基材(1)を調製した。このときの透明導電性被膜の厚さは３μｍであった。
Production of substrate with transparent conductive film (1) Coating liquid for forming transparent conductive film (1) is applied to PET film with easy-adhesion layer (Toyobo Co., Ltd .: Cosmo Shine A4300) by bar coater method (# 12) After coating at 80 ° C. for 1 minute, it was cured by irradiation with a high-pressure mercury lamp (600 mJ / cm 2 ) to prepare a substrate (1) with a transparent conductive film. The thickness of the transparent conductive film at this time was 3 μm.
この透明導電性被膜付基材(1)の全光線透過率、ヘーズ、着色、表面抵抗、密着性、鉛筆硬度、耐擦傷性を表１に示す。全光線透過率およびヘーズは、ヘーズメーター（日本電色工業（株）製）により、表面抵抗は表面抵抗計（三菱化学(株)製:ＬＯＲＥＳＴＡ）で測定し、結果を表1に示した。なお、ヘーズは基材のヘーズ（0.8％）込みの値である。
また、着色、鉛筆硬度、密着性及び耐擦傷性を下記の方法で評価し、結果を表に示した。
Table 1 shows the total light transmittance, haze, coloring, surface resistance, adhesion, pencil hardness, and scratch resistance of the substrate with transparent conductive film (1). The total light transmittance and haze were measured with a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd.), and the surface resistance was measured with a surface resistance meter (manufactured by Mitsubishi Chemical Co., Ltd .: LORESTA). The results are shown in Table 1. The haze is a value including the haze (0.8%) of the base material.
The coloring, pencil hardness, adhesion and scratch resistance were evaluated by the following methods, and the results are shown in the table.
着色観察
透明導電性被膜の着色状況を目視観察し、以下の基準で評価した。
Coloring observation The colored state of the transparent conductive film was visually observed and evaluated according to the following criteria.
全く透明で、着色は認められなかった ： ○
透明性は高いが僅かに着色が認められた ： △
透明性は比較的高いが明らかに着色が認められた ： ×
It was completely transparent and coloring was not recognized: ○
High transparency but slight coloration:
Transparency is relatively high, but clear coloring was observed: ×
鉛筆硬度
鉛筆硬度は、ＪＩＳ Ｋ ５４００に準じて、鉛筆硬度試験器で測定した。即ち、透明導電性被膜表面に対して４５度の角度に鉛筆をセットし、所定の加重を負荷して一定速度で引っ張り、傷の有無を観察した。
Pencil hardness Pencil hardness was measured with a pencil hardness tester in accordance with JIS K 5400. That is, a pencil was set at an angle of 45 degrees with respect to the surface of the transparent conductive coating, and a predetermined load was applied and pulled at a constant speed to observe the presence or absence of scratches.
耐擦傷性の測定
＃００００スチールウールを用い、荷重250ｇ／ｃｍ2で２０回摺動し、膜の表面を目視観察し、以下の基準で評価し、結果を表に示した。
Measurement of Scratch Resistance Using # 0000 steel wool, sliding 20 times at a load of 250 g / cm 2 , visually observing the surface of the film and evaluating according to the following criteria, the results are shown in the table.
評価基準：
筋条の傷が認められない ：◎
筋条に傷が僅かに認められる ：○
筋条に傷が多数認められる ：△
面が全体的に削られている ：×
Evaluation criteria:
No streak injury is found: ◎
Slightly scratched streak: ○
Many scratches are found in the streak: △
The surface has been cut entirely: ×
密着性
透明導電性被膜付基材（1)の表面にナイフで縦横１ｍｍの間隔で１１本の平行な傷を付け１００個の升目を作り、これにセロファンテープを接着し、次いで、セロファンテープを剥離したときに被膜が剥離せず残存している升目の数を、以下の３段階に分類することによって密着性を評価した。結果を表１に示す。
残存升目の数９０個以上 ：◎
残存升目の数８５〜８９個：○
残存升目の数８４個以下 ：△
Adhesive transparent conductive film-coated substrate (1) surface is made of 11 parallel scratches with a knife at intervals of 1 mm in length and width to make 100 squares, cellophane tape is adhered to this, and then cellophane tape is attached. Adhesion was evaluated by classifying the number of cells remaining without peeling off when the film was peeled into the following three stages. The results are shown in Table 1.
Number of remaining squares more than 90: ◎
Number of remaining squares: 85 to 89: ○
Number of remaining squares: 84 or less: △
[実施例２]
透明導電性被膜形成用塗布液(2)の調製
リン含有五酸化アンチモン微粒子(1)分散液１６．７ｇに紫外線硬化樹脂（DIC(株)製:ユニデック１７−８２４−９、固形分濃度７９重量％）６．３ｇと光重合開始剤(ビーエーエスエフジャパン(株)製:ルシリンＴＰＯ、ＰＧＭＥで固形分濃度１０％に溶解)３．８ｇおよびＰＧＭＥ６．５ｇとを充分に混合して透明導電性被膜形成用塗布液（2）を調製した。
[Example 2]
Preparation of coating liquid for forming transparent conductive film (2) Phosphorus-containing antimony pentoxide fine particles (1) 16.7 g of dispersion liquid and UV curable resin (DIC Corporation: Unidec 17-824-9, solid content concentration 79 wt. %) 6.3 g and photopolymerization initiator (manufactured by BSF Japan Ltd .: Lucyrin TPO, dissolved in solid content concentration of 10% with PGME) 3.8 g and 6.5 g of PGME were mixed well and the transparent conductive film A forming coating solution (2) was prepared.
透明導電性被膜付基材(2)の製造
実施例１において、透明導電性被膜形成用塗布液(2)を用いた以外は同様にして透明導電性被膜付基材(2)を調製した。このときの透明導電性被膜の厚さは３μｍであった。
この透明導電性被膜付基材(2)の全光線透過率、ヘーズ、着色、表面抵抗、密着性、鉛筆硬度、耐擦傷性を表１に示す。
Production of transparent conductive film-coated substrate (2) A transparent conductive film-coated substrate (2) was prepared in the same manner as in Example 1 except that the transparent conductive film-forming coating solution (2) was used. The thickness of the transparent conductive film at this time was 3 μm.
Table 1 shows the total light transmittance, haze, coloring, surface resistance, adhesion, pencil hardness, and scratch resistance of this substrate (2) with a transparent conductive film.
[実施例３]
透明導電性被膜形成用塗布液(3)の調製
リン含有五酸化アンチモン微粒子(1)分散液２３．３ｇに紫外線硬化樹脂（DIC(株)製:ユニデック１７−８２４−９、固形分濃度７９重量％）３．８ｇと光重合開始剤(ビーエーエスエフジャパン(株)製:ルシリンＴＰＯ、ＰＧＭＥで固形分濃度１０％に溶解)２．３ｇおよびＰＧＭＥ３．９ｇとを充分に混合して透明導電性被膜形成用塗布液(3)を調製した。
[Example 3]
Preparation of coating liquid for forming transparent conductive film (3) Phosphorus-containing antimony pentoxide fine particles (1) Dispersed in 23.3 g of ultraviolet curable resin (DIC Corporation: Unidec 17-824-9, solid content concentration 79 wt. %) 3.8 g and a photopolymerization initiator (manufactured by BASF Japan KK: Lucyrin TPO, dissolved in solid content concentration of 10% with PGME) 2.3 g and 3.9 g of PGME were sufficiently mixed to form a transparent conductive film A forming coating solution (3) was prepared.
透明導電性被膜付基材(3)の製造
実施例１において、透明導電性被膜形成用塗布液(3)を用いた以外は同様にして透明導電性被膜付基材(3)を調製した。このときの透明導電性被膜の厚さは３μｍであった。
この透明導電性被膜付基材(3)の全光線透過率、ヘーズ、着色、表面抵抗、密着性、鉛筆硬度、耐擦傷性を表１に示す。
Production of transparent conductive film-coated substrate (3) In Example 1, a transparent conductive film-coated substrate (3) was prepared in the same manner except that the transparent conductive film-forming coating solution (3) was used. The thickness of the transparent conductive film at this time was 3 μm.
Table 1 shows the total light transmittance, haze, coloring, surface resistance, adhesion, pencil hardness, and scratch resistance of this substrate (3) with a transparent conductive film.
[実施例４]
リン含有五酸化アンチモン微粒子(2)分散液の調製
実施例１において、リン酸水溶液（関東化学（株）製：濃度８５重量％）を、常温で７分かけて５ｇを添加した以外は同様にして、リン修飾五酸化アンチモン微粒子分散液(2)を得た。
[Example 4]
Preparation of Phosphorus-Containing Antimony Pentoxide Fine Particles (2) Dispersion In Example 1, except that 5 g of phosphoric acid aqueous solution (manufactured by Kanto Chemical Co., Inc .: concentration 85% by weight) was added at room temperature over 7 minutes. Thus, a phosphorus-modified antimony pentoxide fine particle dispersion (2) was obtained.
透明導電性被膜形成用塗布液(4)の調製
リン含有五酸化アンチモン微粒子(2)分散液１６．７ｇに紫外線硬化樹脂（DIC(株)製:ユニデック１７−８２４−９、固形分濃度７９重量％）６．３ｇと光重合開始剤(ビーエーエスエフジャパン(株)製:ルシリンＴＰＯ、ＰＧＭＥで固形分濃度１０％に溶解)３．８ｇおよびＰＧＭＥ６．５ｇとを充分に混合して透明導電性被膜形成用塗布液(4)を調製した。
Preparation of coating liquid for forming transparent conductive film (4) 16.7 g of phosphorus-containing antimony pentoxide fine particle (2) dispersion was added to an ultraviolet curable resin (DIC Corporation: Unidec 17-824-9, solid content concentration 79 wt. %) 6.3 g and photopolymerization initiator (manufactured by BSF Japan Ltd .: Lucyrin TPO, dissolved in solid content concentration of 10% with PGME) 3.8 g and 6.5 g of PGME were mixed well and the transparent conductive film A forming coating solution (4) was prepared.
透明導電性被膜付基材(4)の製造
実施例１において、透明導電性被膜形成用塗布液(4)を用いた以外は同様にして透明導電性被膜付基材(4)を調製した。このときの透明導電性被膜の厚さは３μｍであった。
この透明導電性被膜付基材(4)の全光線透過率、ヘーズ、着色、表面抵抗、密着性、鉛筆硬度、耐擦傷性を表１に示す。
Production of transparent conductive film-coated substrate (4) In Example 1, a transparent conductive film-coated substrate (4) was prepared in the same manner except that the transparent conductive film-forming coating solution (4) was used. The thickness of the transparent conductive film at this time was 3 μm.
Table 1 shows the total light transmittance, haze, coloring, surface resistance, adhesion, pencil hardness, and scratch resistance of this substrate (4) with a transparent conductive film.
[実施例５]
リン含有五酸化アンチモン微粒子(3)分散液の調製
実施例１において、リン酸水溶液（関東化学（株）製：濃度８５重量％）を、常温で７分かけて５０ｇを添加した以外は同様にして、リン修飾五酸化アンチモン微粒子分散液(3)を得た。
[Example 5]
Preparation of Phosphorus-Containing Antimony Pentoxide Fine Particles (3) Dispersion In Example 1, except that 50 g of phosphoric acid aqueous solution (manufactured by Kanto Chemical Co., Inc .: concentration 85% by weight) was added at room temperature over 7 minutes. Thus, a phosphorus-modified antimony pentoxide fine particle dispersion (3) was obtained.
透明導電性被膜形成用塗布液(5)の調製
リン含有五酸化アンチモン微粒子(3)分散液１６．７ｇに紫外線硬化樹脂（DIC(株)製:ユニデック１７−８２４−９、固形分濃度７９重量％）６．３ｇと光重合開始剤(ビーエーエスエフジャパン(株)製:ルシリンＴＰＯ、ＰＧＭＥで固形分濃度１０％に溶解)３．８ｇおよびＰＧＭＥ６．５ｇとを充分に混合して透明導電性被膜形成用塗布液(5)を調製した。
Preparation of coating liquid for forming transparent conductive film (5) 16.7 g of phosphorus-containing antimony pentoxide fine particle (3) dispersion was added to UV curable resin (DIC Corporation: Unidec 17-824-9, solid content concentration 79 wt. %) 6.3 g and photopolymerization initiator (manufactured by BSF Japan Ltd .: Lucyrin TPO, dissolved in solid content concentration of 10% with PGME) 3.8 g and 6.5 g of PGME were mixed well and the transparent conductive film A forming coating solution (5) was prepared.
透明導電性被膜付基材(5)の製造
実施例１において、透明導電性被膜形成用塗布液(5)を用いた以外は同様にして透明導電性被膜付基材(5)を調製した。このときの透明導電性被膜の厚さは３μｍであった。
この透明導電性被膜付基材(5)の全光線透過率、ヘーズ、着色、表面抵抗、密着性、鉛筆硬度、耐擦傷性を表１に示す。
Production of transparent conductive film-coated substrate (5) In Example 1, a transparent conductive film-coated substrate (5) was prepared in the same manner except that the transparent conductive film-forming coating solution (5) was used. The thickness of the transparent conductive film at this time was 3 μm.
Table 1 shows the total light transmittance, haze, coloring, surface resistance, adhesion, pencil hardness, and scratch resistance of this substrate (5) with a transparent conductive film.
[実施例６]
リン含有五酸化アンチモン微粒子(4)分散液の調製
実施例１と同様にしてリン含有五酸化アンチモン微粒子(1)を調製した。
[Example 6]
Preparation of phosphorus-containing antimony pentoxide fine particles (4) dispersion Phosphorous-containing antimony pentoxide fine particles (1) were prepared in the same manner as in Example 1.
次に、リン含有五酸化アンチモン微粒子(1)粉末１２０ｇを、有機溶媒としてプロピレングリコールモノメチルエーテル(ＰＧＭＥ)２２４ｇ、被覆用樹脂として２−メタクリロイロキシエチルアシッドホスフェート（共栄社化学（株）製：ライトアクリレートＰ−２Ｍ）１２ｇ、石英ビーズ６２８ｇを入れたビーズミルに充填し、メカノケミカル処理して樹脂で被覆し、ついで、ビーズを分離して固形分濃度３０重量％の樹脂で被覆したリン含有五酸化アンチモン微粒子(4)分散液を調製した。樹脂被覆リン含有五酸化アンチモン微粒子(4)の平均粒子径は２２ｎｍであった。 Next, 120 g of phosphorus-containing antimony pentoxide fine particles (1) powder, 224 g of propylene glycol monomethyl ether (PGME) as an organic solvent, and 2-methacryloyloxyethyl acid phosphate as a coating resin (manufactured by Kyoeisha Chemical Co., Ltd .: Light acrylate) P-2M) Filled into a bead mill containing 12 g of quartz beads and 628 g of quartz beads, coated with a resin after mechanochemical treatment, and then separated into beads and coated with a resin having a solid content of 30% by weight. A fine particle (4) dispersion was prepared. The average particle size of the resin-coated phosphorus-containing antimony pentoxide fine particles (4) was 22 nm.
透明導電性被膜形成用塗布液(6)の調製
樹脂で被覆したリン含有五酸化アンチモン微粒子(4)分散液１６．７ｇに紫外線硬化樹脂（DIC(株)製:ユニデック１７−８２４−９、固形分濃度７９重量％）６．３ｇと光重合開始剤(ビーエーエスエフジャパン(株)製:ルシリンＴＰＯ、ＰＧＭＥで固形分濃度１０％に溶解)３．８ｇおよびＰＧＭＥ６．５ｇとを充分に混合して透明導電性被膜形成用塗布液(6)を調製した。
Preparation of coating liquid for forming transparent conductive film (6) Phosphorus-containing antimony pentoxide fine particles (4) coated with a resin 16.7 g of an ultraviolet curable resin (manufactured by DIC Corporation: Unidec 17-824-9, solid 6.3 g of a photopolymerization initiator (manufactured by BASF Japan KK: Lucyrin TPO, dissolved in a solid content of 10% with PGME) 3.8 g and 6.5 g of PGME were mixed thoroughly. A coating liquid (6) for forming a transparent conductive film was prepared.
透明導電性被膜付基材(6)の製造
実施例１において、透明導電性被膜形成用塗布液(6)を用いた以外は同様にして透明導電性被膜付基材(6)を調製した。このときの透明導電性被膜の厚さは３μｍであった。
この透明導電性被膜付基材(6)の全光線透過率、ヘーズ、着色、表面抵抗、密着性、鉛筆硬度、耐擦傷性を表１に示す。
Production of transparent conductive film-coated substrate (6) In Example 1, a transparent conductive film-coated substrate (6) was prepared in the same manner except that the transparent conductive film-forming coating solution (6) was used. The thickness of the transparent conductive film at this time was 3 μm.
Table 1 shows the total light transmittance, haze, coloring, surface resistance, adhesion, pencil hardness, and scratch resistance of this substrate (6) with a transparent conductive film.
[実施例７]
リン含有五酸化アンチモン微粒子(5)分散液の調製
純水１８００ｇに苛性カリ（旭硝子(株)製：純度８５％）５７ｇを溶解した溶液中に三酸化アンチモン（日本精鉱(株)：ＰＡＴＯＸ-Ｍ、純度９８．５％）１１１ｇを懸濁した。この懸濁液を９５℃に加熱し、次いで、過酸化水素水（林純薬(株)製：特級、濃度３５重量％）３２．８ｇを純水１１１ｇで希釈した水溶液を９時間で添加し、三酸化アンチモンを溶解し、その後、１１時間熟成した。ついで、冷却後、得られた溶液から１０００ｇを採り、この溶液を純水６０００ｇで希釈した後、陽イオン交換樹脂槽（三菱化学(株)製：ｐｋ−２１６）に通して脱イオン処理を行った。このときのｐＨは２．１、伝導度は２．４ｍＳ／ｃｍであった。
[Example 7]
Preparation of Phosphorus-Containing Antimony Pentoxide Fine Particles (5) Dispersion Antimony trioxide (Nippon Seiko Co., Ltd .: PATOX-M) in a solution of 57 g of caustic potash (Asahi Glass Co., Ltd .: purity 85%) dissolved in 1800 g of pure water , Purity 98.5%) 111 g was suspended. This suspension was heated to 95 ° C., and then an aqueous solution obtained by diluting 32.8 g of hydrogen peroxide solution (produced by Hayashi Junyaku Co., Ltd .: special grade, concentration 35% by weight) with 111 g of pure water was added in 9 hours. Antimony trioxide was dissolved and then aged for 11 hours. Next, after cooling, 1000 g was taken from the obtained solution, and this solution was diluted with 6000 g of pure water, and then passed through a cation exchange resin tank (Mitsubishi Chemical Co., Ltd .: pk-216) for deionization treatment. It was. At this time, the pH was 2.1 and the conductivity was 2.4 mS / cm.
ついで、陰イオン交換樹脂槽（三菱化学（株）製：ＳＡ−２０Ａ）に通してｐＨが２．５、伝導度が１．０ｍＳ／ｃｍになるまで脱イオン処理を行った。
脱イオン処理して得られた溶液を温度７０℃で１０時間熟成した後、限外膜で濃縮して固形分濃度１４重量％の鎖状の五酸化アンチモン微粒子(5)分散液を調製した。この五酸化アンチモン微粒子(1)分散液のｐＨは３．０、伝導度が０．１ｍＳ／ｃｍであった。
Subsequently, it was passed through an anion exchange resin tank (manufactured by Mitsubishi Chemical Co., Ltd .: SA-20A), and deionization treatment was performed until the pH was 2.5 and the conductivity was 1.0 mS / cm.
The solution obtained by deionization was aged at a temperature of 70 ° C. for 10 hours, and then concentrated with an ultra-membrane to prepare a dispersion of chain antimony pentoxide fine particles (5) having a solid concentration of 14% by weight. The antimony pentoxide fine particle (1) dispersion had a pH of 3.0 and a conductivity of 0.1 mS / cm.
鎖状五酸化アンチモン微粒子(5)の平均粒子径は１５ｎｍ、連結数は５であった。
ついで、固形分濃度１４重量％の鎖状五酸化アンチモン微粒子(5)分散液２１００ｇにリン酸水溶液（関東化学（株）製：濃度８５重量％）を、常温で７分かけて２５ｇ添加し、１３分攪拌した。その後、バットへ取り出し９０℃で１８時間乾燥した。乾燥粉末をメノウで解砕し、さらに１１０℃で１２時間乾燥して鎖状リン含有五酸化アンチモン微粒子(5)を得た。鎖状リン含有五酸化アンチモン微粒子(5)のリンの含有量はＰ2Ｏ5として５重量％、体積抵抗値は１０Ω・ｃｍであった。
The average particle diameter of the chain antimony pentoxide fine particles (5) was 15 nm, and the number of connections was 5.
Next, 25 g of phosphoric acid aqueous solution (manufactured by Kanto Chemical Co., Ltd .: concentration 85 wt%) was added to 2100 g of the chain antimony pentoxide fine particles (5) dispersion having a solid content concentration of 14 wt% at room temperature over 7 minutes, Stir for 13 minutes. Thereafter, it was taken out into a vat and dried at 90 ° C. for 18 hours. The dried powder was crushed with agate and further dried at 110 ° C. for 12 hours to obtain chain phosphorus-containing antimony pentoxide fine particles (5). The phosphorus content of the chain phosphorus-containing antimony pentoxide fine particles (5) was 5% by weight as P 2 O 5 , and the volume resistance value was 10 Ω · cm.
次に、鎖状リン含有五酸化アンチモン微粒子(5)粉末１２０ｇを、有機溶媒としてプロピレングリコールモノメチルエーテル(ＰＧＭＥ)２２４ｇ、分散剤（第一工業製薬(株)製：プライサーフＡ-２１７Ｅ）１２ｇ、ガラスビーズ６２８ｇを入れたビーズミルに充填し、分散処理をして固形分濃度３０重量％の鎖状リン含有五酸化アンチモン微粒子(5)分散液を調製した。 Next, 120 g of chain phosphorus-containing antimony pentoxide fine particles (5) powder, 224 g of propylene glycol monomethyl ether (PGME) as an organic solvent, 12 g of a dispersant (Daiichi Kogyo Seiyaku Co., Ltd .: Prisurf A-217E), A bead mill containing 628 g of glass beads was filled and dispersed to prepare a dispersion of chain phosphorus-containing antimony pentoxide fine particles (5) having a solid concentration of 30% by weight.
透明導電性被膜形成用塗布液(7)の調製
鎖状リン含有五酸化アンチモン微粒子(5)分散液１６．７ｇに紫外線硬化樹脂（DIC(株)製:ユニデック１７−８２４−９、固形分濃度７９重量％）６．３ｇと光重合開始剤(ビーエーエスエフジャパン(株)製:ルシリンＴＰＯ、ＰＧＭＥで固形分濃度１０％に溶解)３．８ｇおよびＰＧＭＥ６．５ｇとを充分に混合して透明導電性被膜形成用塗布液(7)を調製した。
Preparation of coating liquid for forming transparent conductive film (7) 16.7 g of chain phosphorus-containing antimony pentoxide fine particles (5) dispersion and UV curable resin (DIC Corporation: Unidec 17-824-9, solid content concentration) 79 wt%) 6.3 g and a photopolymerization initiator (manufactured by BASF Japan KK: Lucyrin TPO, dissolved in solid content concentration of 10% with PGME) 3.8 g and 6.5 g of PGME were mixed well to be transparent conductive A coating solution (7) for forming a conductive film was prepared.
透明導電性被膜付基材(7)の製造
実施例１において、透明導電性被膜形成用塗布液(7)を用いた以外は同様にして透明導電性被膜付基材(7)を調製した。このときの透明導電性被膜の厚さは３μｍであった。
この透明導電性被膜付基材(7)の全光線透過率、ヘーズ、着色、表面抵抗、密着性、鉛筆硬度、耐擦傷性を表１に示す。
Production of transparent conductive film-coated substrate (7) A transparent conductive film-coated substrate (7) was prepared in the same manner as in Example 1 except that the transparent conductive film-forming coating solution (7) was used. The thickness of the transparent conductive film at this time was 3 μm.
Table 1 shows the total light transmittance, haze, coloring, surface resistance, adhesion, pencil hardness, and scratch resistance of this substrate (7) with a transparent conductive film.
[比較例1]
五酸化アンチモン微粒子(R1)分散液の調製
実施例１と同様にして固形分濃度１４重量％の五酸化アンチモン微粒子(1)分散液を調製した。
[Comparative Example 1]
Preparation of antimony pentoxide microparticles (R1) dispersion An antimony pentoxide microparticles (1) dispersion having a solid concentration of 14% by weight was prepared in the same manner as in Example 1.
ついで、バットへ取り出し９０℃で１８時間乾燥した。乾燥粉末をメノウで解砕し、さらに１１０℃で１２時間乾燥して五酸化アンチモン微粒子(R1)を得た。五酸化アンチモン微粒子(R1)の平均粒子径は２０ｎｍ、体積抵抗値は１０００Ω・ｃｍであった。 Then, it was taken out into a vat and dried at 90 ° C. for 18 hours. The dried powder was crushed with agate and further dried at 110 ° C. for 12 hours to obtain antimony pentoxide fine particles (R1). Antimony pentoxide fine particles (R1) had an average particle diameter of 20 nm and a volume resistance of 1000 Ω · cm.
次に、五酸化アンチモン微粒子(R1)粉末１２０ｇを、有機溶媒としてプロピレングリコールモノメチルエーテル(ＰＧＭＥ)２２４ｇ、分散剤（第一工業製薬(株)製：プライサーフＡ-２１７Ｅ）１２ｇ、ガラスビーズ６２８ｇを入れたビーズミルに充填し、分散処理をして固形分濃度３０重量％の五酸化アンチモン微粒子(R1)分散液を調製した。 Next, 120 g of antimony pentoxide fine particles (R1) powder, 224 g of propylene glycol monomethyl ether (PGME) as an organic solvent, 12 g of a dispersant (Daiichi Kogyo Seiyaku Co., Ltd .: Prisurf A-217E), and 628 g of glass beads The bead mill was charged and dispersed to prepare a dispersion of antimony pentoxide fine particles (R1) having a solid concentration of 30% by weight.
透明導電性被膜形成用塗布液(R1)の調製
五酸化アンチモン微粒子(R1)分散液１６．７ｇに紫外線硬化樹脂（DIC(株)製:ユニデック１７−８２４−９、固形分濃度７９重量％）６．３ｇと光重合開始剤(ビーエーエスエフジャパン(株)製:ルシリンＴＰＯ、ＰＧＭＥで固形分濃度１０％に溶解)３．８ｇおよびＰＧＭＥ６．５ｇとを充分に混合して透明導電性被膜形成用塗布液(R1)を調製した。
Preparation of coating liquid (R1) for forming transparent conductive film Ultraviolet curable resin (DIC Corporation: Unidec 17-824-9, solid content concentration 79% by weight) to 16.7 g of antimony pentoxide fine particle (R1) dispersion 6.3 g and photopolymerization initiator (manufactured by BSF Japan Ltd .: Lucyrin TPO, dissolved in solid content concentration of 10% with PGME) 3.8 g and 6.5 g of PGME are mixed well to form a transparent conductive film A coating solution (R1) was prepared.
透明導電性被膜付基材(R1)の製造
実施例１において、透明導電性被膜形成用塗布液(R1)を用いた以外は同様にして透明導電性被膜付基材(R1)を調製した。このときの透明導電性被膜の厚さは３μｍであった。
この透明導電性被膜付基材(R1)の全光線透過率、ヘーズ、着色、表面抵抗、密着性、鉛筆硬度、耐擦傷性を表１に示す。
Production of transparent conductive film-coated substrate (R1) In Example 1, a transparent conductive film-coated substrate (R1) was prepared in the same manner except that the transparent conductive film-forming coating solution (R1) was used. The thickness of the transparent conductive film at this time was 3 μm.
Table 1 shows the total light transmittance, haze, coloring, surface resistance, adhesion, pencil hardness, and scratch resistance of this substrate with transparent conductive film (R1).
[比較例２]
五酸化アンチモン微粒子(R2)分散液の調製
実施例７と同様にして固形分濃度１４重量％の鎖状の五酸化アンチモン微粒子(5)分散液を調製した。
[Comparative Example 2]
Preparation of antimony pentoxide fine particle (R2) dispersion A chain antimony pentoxide fine particle (5) dispersion having a solid content of 14% by weight was prepared in the same manner as in Example 7.
ついで、バットへ取り出し９０℃で１８時間乾燥した。乾燥粉末をメノウで解砕し、さらに１１０℃で１２時間乾燥して鎖状五酸化アンチモン微粒子(R2)を得た。鎖状五酸化アンチモン微粒子(R2)の平均粒子径は１５ｎｍ、連結数は５であった。また、体積抵抗値は５０Ω・ｃｍであった。 Then, it was taken out into a vat and dried at 90 ° C. for 18 hours. The dried powder was crushed with agate and further dried at 110 ° C. for 12 hours to obtain chain antimony pentoxide fine particles (R2). The average particle diameter of the chain antimony pentoxide fine particles (R2) was 15 nm, and the number of connections was 5. Further, the volume resistance value was 50 Ω · cm.
次に、鎖状五酸化アンチモン微粒子(R2)粉末１２０ｇを、有機溶媒としてプロピレングリコールモノメチルエーテル(ＰＧＭＥ)２２４ｇ、分散剤（第一工業製薬(株)製：プライサーフＡ-２１７Ｅ）１２ｇ、ガラスビーズ６２８ｇを入れたビーズミルに充填し、分散処理をして固形分濃度３０重量％の鎖状五酸化アンチモン微粒子(R2)分散液を調製した。 Next, 120 g of chain antimony pentoxide fine particles (R2) powder, 224 g of propylene glycol monomethyl ether (PGME) as an organic solvent, 12 g of a dispersant (Daiichi Kogyo Seiyaku Co., Ltd .: Prisurf A-217E), glass beads A bead mill containing 628 g was filled and dispersed to prepare a dispersion of chain antimony pentoxide fine particles (R2) having a solid concentration of 30% by weight.
透明導電性被膜形成用塗布液(R2)の調製
鎖状五酸化アンチモン微粒子(R2)分散液１６．７ｇに紫外線硬化樹脂（DIC(株)製:ユニデック１７−８２４−９、固形分濃度７９重量％）６．３ｇと光重合開始剤(ビーエーエスエフジャパン(株)製:ルシリンＴＰＯ、ＰＧＭＥで固形分濃度１０％に溶解)３．８ｇおよびＰＧＭＥ６．５ｇとを充分に混合して透明導電性被膜形成用塗布液(R2)を調製した。
Preparation of coating solution (R2) for forming transparent conductive film Ultraviolet curable resin (made by DIC Corporation: Unidec 17-824-9, solid content concentration 79 weight) to 16.7 g of chain antimony pentoxide fine particle (R2) dispersion %) 6.3 g and photopolymerization initiator (manufactured by BSF Japan Ltd .: Lucyrin TPO, dissolved in solid content concentration of 10% with PGME) 3.8 g and 6.5 g of PGME were mixed well and the transparent conductive film A forming coating solution (R2) was prepared.
透明導電性被膜付基材(R2)の製造
実施例１において、透明導電性被膜形成用塗布液(R2)を用いた以外は同様にして透明導電性被膜付基材(R2)を調製した。このときの透明導電性被膜の厚さは３μｍであった。
この透明導電性被膜付基材(R2)の全光線透過率、ヘーズ、着色、表面抵抗、密着性、鉛筆硬度、耐擦傷性を表１に示す。
Production of transparent conductive film-coated substrate (R2) A transparent conductive film-coated substrate (R2) was prepared in the same manner as in Example 1 except that the transparent conductive film-forming coating solution (R2) was used. The thickness of the transparent conductive film at this time was 3 μm.
Table 1 shows the total light transmittance, haze, coloring, surface resistance, adhesion, pencil hardness, and scratch resistance of this substrate with transparent conductive film (R2).
[参考例]
リン含有五酸化アンチモン微粒子(R3)分散液の調製
実施例１と同様にしてリン含有五酸化アンチモン微粒子(1)粉末を調製し、ついで、４５０℃で２時間加熱処理してリン含有五酸化アンチモン微粒子(R3)を得た。この時、粉末は白色から黄赤色に変化した。したがって、リン酸化物がドープされたことを示した。
[Reference example]
Preparation of Phosphorus-Containing Antimony Pentoxide Fine Particles (R3) Dispersion Liquid Phosphorus-containing antimony pentoxide fine particles (1) powder was prepared in the same manner as in Example 1, followed by heat treatment at 450 ° C. for 2 hours to produce phosphorus-containing antimony pentoxide. Fine particles (R3) were obtained. At this time, the powder changed from white to yellow-red. Therefore, it was shown that the phosphorus oxide was doped.
リン含有五酸化アンチモン微粒子(R3)のリンの含有量はＰ2Ｏ5として５重量％、平均粒子径は２０ｎｍ、体積抵抗値は６００Ω・ｃｍであった。
次に、リン含有五酸化アンチモン微粒子(R3)粉末１２０ｇを、有機溶媒としてプロピレングリコールモノメチルエーテル(ＰＧＭＥ)２２４ｇ、分散剤（第一工業製薬(株)製：プライサーフＡ-２１７Ｅ）１２ｇ、ガラスビーズ６２８ｇを入れたビーズミルに充填し、分散処理をして固形分濃度３０重量％のリン含有五酸化アンチモン微粒子(R3)分散液を調製した。
The phosphorus content of the phosphorus-containing antimony pentoxide fine particles (R3) was 5% by weight as P 2 O 5 , the average particle diameter was 20 nm, and the volume resistance value was 600 Ω · cm.
Next, 120 g of phosphorus-containing antimony pentoxide fine particles (R3) powder, 224 g of propylene glycol monomethyl ether (PGME) as an organic solvent, 12 g of a dispersant (Daiichi Kogyo Seiyaku Co., Ltd .: Prisurf A-217E), glass beads A bead mill containing 628 g was filled and dispersed to prepare a phosphorus-containing antimony pentoxide fine particle (R3) dispersion having a solid concentration of 30% by weight.
透明導電性被膜形成用塗布液(R3)の調製
リン含有五酸化アンチモン微粒子(R3)分散液１６．７ｇに紫外線硬化樹脂（DIC(株)製:ユニデック１７−８２４−９、固形分濃度７９重量％）６．３ｇと光重合開始剤(ビーエーエスエフジャパン(株)製:ルシリンＴＰＯ、ＰＧＭＥで固形分濃度１０％に溶解)３．８ｇ及びＰＧＭＥ６．５ｇとを充分に混合して透明導電性被膜形成用塗布液(R3)を調製した。
Preparation of coating liquid (R3) for forming transparent conductive film To 16.7 g of phosphorus-containing antimony pentoxide fine particle (R3) dispersion, UV curable resin (DIC Corporation: Unidec 17-824-9, solid content concentration: 79 wt. %) 6.3 g and a photopolymerization initiator (manufactured by BSF Japan Ltd .: Lucyrin TPO, dissolved in solid content concentration of 10% with PGME) 3.8 g and 6.5 g of PGME were mixed well and a transparent conductive film A forming coating solution (R3) was prepared.
透明導電性被膜付基材(R3)の製造
実施例１において、透明導電性被膜形成用塗布液(R3)を用いた以外は同様にして透明導電性被膜付基材(R3)を調製した。このときの透明導電性被膜の厚さは３μｍであった。
Production of transparent conductive film-coated substrate (R3) In Example 1, a transparent conductive film-coated substrate (R3) was prepared in the same manner except that the transparent conductive film-forming coating solution (R3) was used. The thickness of the transparent conductive film at this time was 3 μm.
この透明導電性被膜付基材(R3)の全光線透過率、ヘーズ、着色、表面抵抗、密着性、鉛筆硬度、耐擦傷性を表１に示す。
実施例２、４、５と比較例１、および実施例７と比較例２とを対比すれば、五酸化リンの含有量が多くなるほど、五酸化アンチモン微粒子の導電性が高く、表面抵抗値は低くなることがわかる。また、鎖状粒子とすることで、鎖状とすることで、導電性を向上することができ、さらに鉛筆硬度を高くすることができる。
Table 1 shows the total light transmittance, haze, coloring, surface resistance, adhesion, pencil hardness, and scratch resistance of this transparent conductive film-coated substrate (R3).
When Examples 2, 4, and 5 are compared with Comparative Example 1 and Example 7 and Comparative Example 2 are compared, the greater the content of phosphorus pentoxide, the higher the conductivity of antimony pentoxide fine particles, and the surface resistance value is It turns out that it becomes low. Moreover, by setting it as chain | strand-shaped particle | grains, by making it chain | strand shape, electroconductivity can be improved and also pencil hardness can be made high.
なお、リンがドープされた参考例では、大きく着色していることがわかった。 It was found that the reference example doped with phosphorus was highly colored.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009215538A JP5534758B2 (en) | 2009-09-17 | 2009-09-17 | Phosphorus-containing antimony pentoxide fine particles, a transparent conductive film-forming coating solution containing the fine particles, and a substrate with a transparent conductive film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009215538A JP5534758B2 (en) | 2009-09-17 | 2009-09-17 | Phosphorus-containing antimony pentoxide fine particles, a transparent conductive film-forming coating solution containing the fine particles, and a substrate with a transparent conductive film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2011063478A true JP2011063478A (en) | 2011-03-31 |
| JP5534758B2 JP5534758B2 (en) | 2014-07-02 |
Family
ID=43950119
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009215538A Active JP5534758B2 (en) | 2009-09-17 | 2009-09-17 | Phosphorus-containing antimony pentoxide fine particles, a transparent conductive film-forming coating solution containing the fine particles, and a substrate with a transparent conductive film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5534758B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013149644A (en) * | 2012-01-17 | 2013-08-01 | Mitsubishi Materials Corp | Transparent conductive film composition for solar cell and transparent conductive film |
| KR20140037759A (en) * | 2012-09-19 | 2014-03-27 | 니끼 쇼꾸바이 카세이 가부시키가이샤 | Coating solution for preparing transparent film and substrate with transparent film |
| WO2014142121A1 (en) * | 2013-03-14 | 2014-09-18 | 日立マクセル株式会社 | Transparent conductive coating composition, transparent conductive film, and in-plane switching liquid crystal display panel with built-in touch panel function |
| KR101877810B1 (en) * | 2010-07-20 | 2018-07-12 | 니끼 쇼꾸바이 카세이 가부시키가이샤 | Coating solution for forming transparent film and substrate coated by transparent film |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6041536A (en) * | 1983-08-16 | 1985-03-05 | Nissan Chem Ind Ltd | Preparation of antimony pentoxide sol |
| JPS61227918A (en) * | 1985-04-03 | 1986-10-11 | Nissan Chem Ind Ltd | Production of antimony pentoxide sol |
| JPS61266308A (en) * | 1985-05-22 | 1986-11-26 | Nippon Seiko Kk | Production of fine powdery sb2o3-sb2o5 composite oxide |
| JPH02107523A (en) * | 1988-10-13 | 1990-04-19 | Nissan Chem Ind Ltd | Antimony pentoxide sol having large particle size and production thereof |
| JPH05208823A (en) * | 1991-09-30 | 1993-08-20 | Nyacol Prod Inc | Colloidal antimony pentaoxide powder and its production |
| JP2004307325A (en) * | 2003-03-27 | 2004-11-04 | Nissan Chem Ind Ltd | Antimony pentaoxide sol and preparation method therefor |
| JP2005139026A (en) * | 2003-11-06 | 2005-06-02 | Catalysts & Chem Ind Co Ltd | Chain-like antimony oxide fine particles, method for producing dispersion including the fine particles, and application of the dispersion |
-
2009
- 2009-09-17 JP JP2009215538A patent/JP5534758B2/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6041536A (en) * | 1983-08-16 | 1985-03-05 | Nissan Chem Ind Ltd | Preparation of antimony pentoxide sol |
| JPS61227918A (en) * | 1985-04-03 | 1986-10-11 | Nissan Chem Ind Ltd | Production of antimony pentoxide sol |
| JPS61266308A (en) * | 1985-05-22 | 1986-11-26 | Nippon Seiko Kk | Production of fine powdery sb2o3-sb2o5 composite oxide |
| JPH02107523A (en) * | 1988-10-13 | 1990-04-19 | Nissan Chem Ind Ltd | Antimony pentoxide sol having large particle size and production thereof |
| JPH05208823A (en) * | 1991-09-30 | 1993-08-20 | Nyacol Prod Inc | Colloidal antimony pentaoxide powder and its production |
| JP2004307325A (en) * | 2003-03-27 | 2004-11-04 | Nissan Chem Ind Ltd | Antimony pentaoxide sol and preparation method therefor |
| JP2005139026A (en) * | 2003-11-06 | 2005-06-02 | Catalysts & Chem Ind Co Ltd | Chain-like antimony oxide fine particles, method for producing dispersion including the fine particles, and application of the dispersion |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101877810B1 (en) * | 2010-07-20 | 2018-07-12 | 니끼 쇼꾸바이 카세이 가부시키가이샤 | Coating solution for forming transparent film and substrate coated by transparent film |
| JP2013149644A (en) * | 2012-01-17 | 2013-08-01 | Mitsubishi Materials Corp | Transparent conductive film composition for solar cell and transparent conductive film |
| KR20140037759A (en) * | 2012-09-19 | 2014-03-27 | 니끼 쇼꾸바이 카세이 가부시키가이샤 | Coating solution for preparing transparent film and substrate with transparent film |
| JP2014058652A (en) * | 2012-09-19 | 2014-04-03 | Jgc Catalysts & Chemicals Ltd | Transparent film-forming coating liquid and substrate with transparent film |
| KR102052942B1 (en) * | 2012-09-19 | 2019-12-06 | 니끼 쇼꾸바이 카세이 가부시키가이샤 | Coating solution for preparing transparent film and substrate with transparent film |
| WO2014142121A1 (en) * | 2013-03-14 | 2014-09-18 | 日立マクセル株式会社 | Transparent conductive coating composition, transparent conductive film, and in-plane switching liquid crystal display panel with built-in touch panel function |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5534758B2 (en) | 2014-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5700458B2 (en) | Silica-based fine particles, coating material for coating formation and substrate with coating | |
| KR101877810B1 (en) | Coating solution for forming transparent film and substrate coated by transparent film | |
| JP6016548B2 (en) | Coating liquid for forming transparent film and substrate with transparent film | |
| JP5757673B2 (en) | Substrate with transparent film and paint for forming transparent film | |
| JP5142617B2 (en) | Surface treatment method for metal oxide particles, dispersion containing the surface treated metal oxide particles, coating liquid for forming a transparent film, and substrate with transparent film | |
| JP4592274B2 (en) | Antimony oxide-coated silica fine particles, method for producing the fine particles, and coated substrate containing the fine particles | |
| JP5546239B2 (en) | Base material with hard coat film and coating liquid for forming hard coat film | |
| JP7360294B2 (en) | Particles containing silica and having a cavity inside an outer shell, a method for producing the same, a coating liquid containing the particles, and a substrate with a transparent coating containing the particles | |
| JP5148846B2 (en) | Paint for forming transparent film and substrate with transparent film | |
| JP2018123043A (en) | Method for producing silica-based particle dispersion, silica-based particle dispersion, coating liquid for forming transparent coating film, and substrate with transparent coating film | |
| JP5534758B2 (en) | Phosphorus-containing antimony pentoxide fine particles, a transparent conductive film-forming coating solution containing the fine particles, and a substrate with a transparent conductive film | |
| JP5754884B2 (en) | Phosphoric acid (excluding phosphoric acid salt) -treated metal oxide fine particles and production method thereof, coating solution for forming a transparent film containing the phosphoric acid (excluding phosphoric acid salt) -treated metal oxide fine particles, and transparent Substrate with coating | |
| JP2011137097A (en) | Coating liquid for transparent film formation, substrate with transparent film, and method for producing hydrophobic metal oxide particle | |
| KR101163539B1 (en) | Chain inorganic oxide fine particle groups, process for preparing dispersion of the fine particle groups, and uses of the fine particle groups | |
| JP5554904B2 (en) | Paint for forming transparent film and substrate with transparent film | |
| JP5642535B2 (en) | Novel silica-based hollow fine particles, base material with transparent film, and paint for forming transparent film | |
| JP5680372B2 (en) | Substrate with transparent film and coating liquid for forming transparent film | |
| JP5026172B2 (en) | Base material with hard coat film and coating liquid for forming hard coat film | |
| JP2011093754A (en) | Antimony pentoxide based complex oxide fine particle, coating liquid for forming transparency coating film containing the fine particle, and base material with transparency coating film | |
| TW202235374A (en) | Dispersion liquid of chain particles and method for producing same, coating material for forming coating film, and method for producing substrate with film | |
| JP2009059506A (en) | Substrate with transparent conductive film, and coating liquid for transparent conductive film formation | |
| JP5089312B2 (en) | Base material with hard coat film and coating liquid for forming hard coat film | |
| JP5766251B2 (en) | Method for producing a coating for forming a transparent film | |
| JP5503241B2 (en) | Base material with hard coat film and coating liquid for forming hard coat film | |
| JP5686942B2 (en) | Hard coat film-forming coating material and substrate with hard coat film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120807 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130912 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130924 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140415 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140422 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5534758 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |