JP2015069913A - Surface-treated ito conductive film and method for producing the same - Google Patents
Surface-treated ito conductive film and method for producing the same Download PDFInfo
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- JP2015069913A JP2015069913A JP2013205140A JP2013205140A JP2015069913A JP 2015069913 A JP2015069913 A JP 2015069913A JP 2013205140 A JP2013205140 A JP 2013205140A JP 2013205140 A JP2013205140 A JP 2013205140A JP 2015069913 A JP2015069913 A JP 2015069913A
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- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 28
- -1 silicate ester Chemical class 0.000 claims abstract description 20
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 18
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 16
- 125000003277 amino group Chemical group 0.000 claims abstract description 9
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 7
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract 5
- 239000012756 surface treatment agent Substances 0.000 claims description 36
- 238000004381 surface treatment Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 27
- 238000000576 coating method Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 16
- 239000011248 coating agent Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 238000003618 dip coating Methods 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 238000004528 spin coating Methods 0.000 claims description 6
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical group CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 6
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 claims description 5
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 claims description 5
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 claims description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 4
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical group CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000012808 vapor phase Substances 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims 1
- 238000010168 coupling process Methods 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 101
- 239000002245 particle Substances 0.000 description 40
- 239000000843 powder Substances 0.000 description 27
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 24
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 230000008859 change Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000010304 firing Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 8
- 230000002829 reductive effect Effects 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 206010021143 Hypoxia Diseases 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 150000002471 indium Chemical class 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 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 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000007611 bar coating method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005401 electroluminescence Methods 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
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
Description
本発明は、高温高湿下において電気抵抗値の上昇を抑制し得る表面処理されたＩＴＯ導電膜及びその製造方法に関するものである。本明細書において、ＩＴＯとはインジウム錫酸化物(Indium Tin Oxide)をいう。 The present invention relates to a surface-treated ITO conductive film capable of suppressing an increase in electrical resistance value under high temperature and high humidity, and a method for producing the same. In this specification, ITO refers to indium tin oxide.
ＬＣＤ(Liquid Crystal Display)やＰＤＰ(Plasma Display Panel)、有機ＥＬ(ElectroLuminescence)、タッチパネル等の表示装置には、透明電極が用いられている。この透明電極は、ＩＴＯ等からなる透明導電材料によって構成されることが多い。このような透明電極は、通常スパッタリング法などで膜状に形成される（例えば、特許文献１参照）。しかしながらスパッタリング装置は高価であり、かつ、成膜の効率が悪く、また、その膜はひび割れし易い等の問題がある。このひび割れの起こりにくい屈曲性に優れたＩＴＯ導電膜を形成する方法として、スパッタリング法に代わって、ＩＴＯ導電膜形成用塗料を基板に塗布する方法が提案されている。しかしながら、塗布方式で得られた透明電極は、高温高湿下におかれると、雰囲気中の酸素や水分に起因して電気抵抗値が上昇する傾向にあり、これが信頼性を低下させる一因となっていた。 Transparent electrodes are used in display devices such as LCD (Liquid Crystal Display), PDP (Plasma Display Panel), organic EL (ElectroLuminescence), and touch panels. This transparent electrode is often composed of a transparent conductive material made of ITO or the like. Such a transparent electrode is usually formed into a film by a sputtering method or the like (see, for example, Patent Document 1). However, the sputtering apparatus is expensive and has a problem that the film formation efficiency is low and the film is easily cracked. As a method of forming an ITO conductive film excellent in flexibility, which is less prone to cracking, a method of applying an ITO conductive film forming coating to a substrate instead of the sputtering method has been proposed. However, when the transparent electrode obtained by the coating method is placed under high temperature and high humidity, the electrical resistance value tends to increase due to oxygen and moisture in the atmosphere. It was.
この問題を解決するために、塗布方式によるＩＴＯ導電膜形成用塗料として、耐水性を有するＩＴＯ粉末のような導電粉の表面を表面処理剤で処理してなる表面処理導電粉と硬化性化合物を含む透明導電材料（例えば、特許文献２参照。）や、樹脂とＩＴＯ粉末のような透明導電粒子とシリカ材料とシランカップリング剤とを含有する透明導電材料（例えば、特許文献３参照）が提案されている。 In order to solve this problem, as a coating for forming an ITO conductive film by a coating method, a surface-treated conductive powder and a curable compound obtained by treating the surface of a conductive powder such as ITO powder having water resistance with a surface treatment agent Proposed transparent conductive material (for example, see Patent Document 2) and transparent conductive material containing transparent conductive particles such as resin, ITO powder, silica material, and silane coupling agent (for example, see Patent Document 3) Has been.
上記特許文献２及び３に示される透明導電材料により形成されたＩＴＯ導電膜の透明電極は、高温高湿下であっても水分の影響による電気抵抗値の上昇を十分に抑制することが可能である。しかしながら、近年では、透明電極の用途が一層多岐にわたっており、従来にも増して厳しい条件下であっても、高温高湿下における透明電極の電気抵抗値の上昇を抑制できるＩＴＯ導電膜が求められている。 The transparent electrode of the ITO conductive film formed of the transparent conductive material described in Patent Documents 2 and 3 can sufficiently suppress an increase in electrical resistance value due to the influence of moisture even under high temperature and high humidity. is there. However, in recent years, the use of transparent electrodes has become more diverse, and there has been a demand for an ITO conductive film that can suppress an increase in the electrical resistance value of a transparent electrode under high temperature and high humidity even under severer conditions than before. ing.
本発明の目的は、従来にも増して厳しい条件下であっても、高温高湿下における電気抵抗値の上昇を抑制可能な透明電極である表面処理されたＩＴＯ導電膜及びその製造方法を提供することにある。 An object of the present invention is to provide a surface-treated ITO conductive film which is a transparent electrode capable of suppressing an increase in electrical resistance value under high temperature and high humidity even under severer conditions than before, and a method for producing the same There is to do.
本発明の第１の観点は、炭素数が２以下であるアルコキシ基を４つ有する珪酸エステル又はこの珪酸エステルのオリゴマー体からなる表面処理剤により、或いは炭素数が２以下であるアルコキシ基を２つ以上有し、かつアミノ基若しくはメルカプト基を末端基に有するアルキル基、炭素数が６以上である長鎖のアルキル基、又は一部がフッ素で置換されたアルキル基のいずれか１種のアルキル基を１つ以上有するシランカップリング剤からなる表面処理剤により、表面処理されたＩＴＯ導電膜である。 According to a first aspect of the present invention, a surface treatment agent comprising a silicate ester having 4 alkoxy groups having 2 or less carbon atoms or an oligomer of the silicate ester, or 2 alkoxy groups having 2 or less carbon atoms. An alkyl group having at least one amino group or mercapto group as a terminal group, a long-chain alkyl group having 6 or more carbon atoms, or an alkyl group partially substituted with fluorine. It is an ITO conductive film surface-treated with a surface treatment agent comprising a silane coupling agent having one or more groups.
本発明の第２の観点は、第１の観点に基づく発明であって、更に珪酸エステルが、炭素数が１のアルキル基を有するテトラメトキシシラン、又は炭素数が２のアルキル基を有するテトラエトキシシランであることを特徴とする。 A second aspect of the present invention is the invention based on the first aspect, wherein the silicate ester further comprises tetramethoxysilane having an alkyl group having 1 carbon atom or tetraethoxy having an alkyl group having 2 carbon atoms. It is characterized by being silane.
本発明の第３の観点は、第１の観点に基づく発明であって、更にシランカップリング剤が、Ｎ−２−(アミノエチル)−３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリメトキシシラン、３−メルカプトプロピルメチルジメトキシシラン、３−メルカプトプロピルトリメトキシシラン、トリフルオロプロピルトリメトキシシラン、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン又はデシルトリメトキシシランであることを特徴とする。 A third aspect of the present invention is the invention based on the first aspect, wherein the silane coupling agent is N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxy. It is characterized by being silane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, trifluoropropyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane or decyltrimethoxysilane.
本発明の第４の観点は、第１ないし第３の観点のいずれかに基づく表面処理剤を溶剤に溶解した表面処理液の蒸気を容器に入れたＩＴＯ導電膜に気相暴露することによりＩＴＯ導電膜の表面を処理するＩＴＯ導電膜の製造方法である。 According to a fourth aspect of the present invention, there is provided an ITO film by exposing a vapor of a surface treatment solution obtained by dissolving a surface treatment agent according to any one of the first to third aspects in a solvent to an ITO conductive film placed in a container. It is a manufacturing method of the ITO electrically conductive film which processes the surface of an electrically conductive film.
本発明の第５の観点は、第１ないし第３の観点のいずれかに基づく表面処理剤をＩＴＯ導電膜の表面に塗布することによりＩＴＯ導電膜の表面を処理するＩＴＯ導電膜の製造方法である。 A fifth aspect of the present invention is a method for producing an ITO conductive film, wherein the surface of the ITO conductive film is treated by applying a surface treatment agent based on any of the first to third aspects to the surface of the ITO conductive film. is there.
本発明の第６の観点は、第５に基づく発明であって、塗布がスピンコート法又はディップコート法により行われるＩＴＯ導電膜の製造方法である。 A sixth aspect of the present invention is an invention based on the fifth aspect, which is a method for manufacturing an ITO conductive film in which coating is performed by a spin coating method or a dip coating method.
元来、ＩＴＯの主たる構成要素であるＩｎ２Ｏ３は、Bixbyite構造をなし、蛍石構造から規則的に酸素が抜けた構造と表現できる。この構造はドーパントであるＳｎの量が増えるなどすると、格子間に酸素を取り込みやすい構造になっている。このためＩＴＯ導電膜が高温高湿下におかれると、導電膜表面に吸着した水が導電膜を構成するＩＴＯ粉末表面のの酸素空孔や格子間に、−ＯＨとして結合し、キャリア電子をトラップすることから、ＩＴＯ導電膜の導電性を低下させる。 Originally, the main component of ITO, In2O3, has a Bixbyite structure, and can be expressed as a structure in which oxygen is regularly removed from the fluorite structure. This structure has a structure in which oxygen is easily taken in between lattices when the amount of Sn as a dopant is increased. For this reason, when the ITO conductive film is placed under high temperature and high humidity, the water adsorbed on the surface of the conductive film is bonded as —OH between oxygen vacancies and lattices on the surface of the ITO powder constituting the conductive film, and carrier electrons are Since it is trapped, the conductivity of the ITO conductive film is lowered.
本発明の第１の観点のＩＴＯ導電膜では、上述した特定の表面処理剤で処理されるため、表面処理剤が上記珪酸エステルの場合には、上記導電膜を構成するＩＴＯ粉末表面の酸素空孔や格子間に珪酸エステルが結合することで、また上記シランカップリング剤の場合には、上記導電膜を構成するＩＴＯ粉末表面の酸素空孔や格子間にアミノ基若しくはメルカプト基などが結合することで、それぞれ水に対する安定性が大幅に改善されると考えられる。また、通常のＩＴＯの表面には、既に粒子表面に−ＯＨが存在するため、ここに上記珪酸エステル又は上記シランカップリング剤が結合することによって、トラップされた電子が開放されることで、導電性が向上する効果も得られる。この結果、本発明の導電膜は、高温高湿下における電気抵抗値の上昇を抑制することができる。 Since the ITO conductive film according to the first aspect of the present invention is treated with the specific surface treatment agent described above, when the surface treatment agent is the silicate ester, oxygen vacancies on the surface of the ITO powder constituting the conductive film. In the case of the silane coupling agent, an amino group or a mercapto group is bonded between oxygen vacancies or lattices on the surface of the ITO powder constituting the conductive film in the case of the silane coupling agent. Therefore, it is considered that the stability to water is greatly improved. In addition, since —OH is already present on the surface of normal ITO on the surface of ITO, the trapped electrons are released by binding the silicate ester or the silane coupling agent to the conductive surface. The effect which improves property is also acquired. As a result, the conductive film of the present invention can suppress an increase in electrical resistance value under high temperature and high humidity.
本発明の第２の観点のＩＴＯ導電膜では、珪酸エステルとして、炭素数が１のアルキル基を有するテトラメトキシシラン、又は炭素数が２のアルキル基を有するテトラエトキシシランを選択することにより、炭素数が小さいため、反応性が高くなる。この結果、珪酸エステルがＩＴＯ表面に結合しやすい効果がある。 In the ITO conductive film according to the second aspect of the present invention, carbon is selected by selecting tetramethoxysilane having an alkyl group having 1 carbon atom or tetraethoxysilane having an alkyl group having 2 carbon atoms as a silicate ester. Since the number is small, the reactivity is high. As a result, there is an effect that the silicate ester is easily bonded to the ITO surface.
本発明の第３の観点のＩＴＯ導電膜では、シランカップリング剤として、Ｎ−２−(アミノエチル)−３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリメトキシシラン、３−メルカプトプロピルメチルジメトキシシラン、３−メルカプトプロピルトリメトキシシラン、トリフルオロプロピルトリメトキシシラン、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン又はデシルトリメトキシシランを選択することにより、末端基の持つ立体障害や極性のため、ＩＴＯ表面にＨ２Ｏの接近を阻害する効果がある。 In the ITO conductive film of the third aspect of the present invention, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxy are used as silane coupling agents. By selecting silane, 3-mercaptopropyltrimethoxysilane, trifluoropropyltrimethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, or decyltrimethoxysilane, the steric hindrance and polarity of the end group, the ITO surface Has the effect of inhibiting the approach of H2O.
次に本発明を実施するための形態を図面に基づいて説明する。 Next, an embodiment for carrying out the present invention will be described with reference to the drawings.
＜ＩＴＯ粉末＞
図１（ａ）及び（ｂ）に、本発明のＩＴＯ導電膜を形成するための材料であるＩＴＯ粉末の一例を示す。本発明のＩＴＯ導電膜はこのＩＴＯ粉末によらず、他の方法で製造されるＩＴＯ粉末により形成することができる。図１（ａ）及び（ｂ）に模式的に示されているように、このＩＴＯ粉末は、多結晶ＩＴＯ粒子１０からなる。多結晶ＩＴＯ粒子１０は、棒状中心核１１と複数の棒状体１２からなり、棒状中心核１１の長手方向に基本的に同じ向きに沿って棒状中心核１１を囲むようにして一体的に形成されている。更に図２の写真図に示すように、多結晶ＩＴＯ粒子は、複数の短い棒状体が小枝のように観察され、これらの短い棒状体が棒状中心核の周囲を囲みながら互いに隣接し合いながら同様の方向に並んで棒状中心核に固着していることが観察される。なお、図２に示すように複数の棒状体のそれぞれの径及び長さは必ずしも同一である必要はなく、その断面形状、表面形状も必ずしも同一である必要はない。
<ITO powder>
1A and 1B show an example of ITO powder which is a material for forming the ITO conductive film of the present invention. The ITO conductive film of the present invention can be formed of ITO powder produced by other methods without using this ITO powder. As schematically shown in FIGS. 1A and 1B, the ITO powder is made of polycrystalline ITO particles 10. The polycrystalline ITO particles 10 are composed of a rod-like central nucleus 11 and a plurality of rod-like bodies 12 and are integrally formed so as to surround the rod-like central nucleus 11 along the same direction in the longitudinal direction of the rod-like central nucleus 11. . Furthermore, as shown in the photographic diagram of FIG. 2, the polycrystalline ITO particles have a plurality of short rod-like bodies observed as twigs, and these short rod-like bodies surround each other around the rod-like central core and are adjacent to each other. It is observed that they are fixed to the rod-shaped central core in the direction of. In addition, as shown in FIG. 2, the diameter and length of each of the plurality of rod-shaped bodies are not necessarily the same, and the cross-sectional shape and the surface shape are not necessarily the same.
上記多結晶ＩＴＯ粒子１０の平均長さＬは、０．２〜５．０μｍ、好ましくは１．０〜５．０μｍの範囲にある。多結晶ＩＴＯ粒子１０の平均直径をＤとするとき、Ｌ／Ｄが２〜２０、好ましくは３〜１０の範囲にある。Ｌは０．２μｍ未満では、ＩＴＯ導電膜を形成する基板面に対して垂直に立ち易くなり、ラグビーボールのように倒れやすい効果が得られない。Ｌが５．０μｍを越えると、粒子同士のパッキングが悪くなる。またＬ／Ｄが２未満では異方性による導電性向上の効果が得られず、２０を越えると塗膜作製時に棒状粒子が破断し、短くなってしまうという不具合を生じる。 The average length L of the polycrystalline ITO particles 10 is in the range of 0.2 to 5.0 μm, preferably 1.0 to 5.0 μm. When the average diameter of the polycrystalline ITO particles 10 is D, L / D is in the range of 2 to 20, preferably 3 to 10. When L is less than 0.2 μm, it becomes easy to stand perpendicular to the substrate surface on which the ITO conductive film is formed, and the effect of being easily overturned like a rugby ball cannot be obtained. When L exceeds 5.0 μm, the packing between the particles is deteriorated. If L / D is less than 2, the effect of improving conductivity due to anisotropy cannot be obtained. If L / D is more than 20, the rod-like particles are broken and shortened when the coating film is produced.
上記多結晶ＩＴＯ粒子は、上記の形状を持つため、例えば塗布型ＩＴＯフィルムの製造時、樹脂フィルムに当該ＩＴＯ粉末を含む塗料を塗布したときや、塗布面を加圧したときに、塗布方向に沿って樹脂フィルム面に配向し易い。即ち、上記多結晶ＩＴＯ粒子は樹脂フィルム面に転がって横たわり易い。また、上記ＩＴＯ粒子は多結晶であるため、粒界で適度なずれが生じる結果、粒子間の空隙が充填され易くなり、多結晶ＩＴＯ粒子間が密になる。結果として、上記ＩＴＯ粒子を用いて透明電極である導電膜を形成したときに、より電気抵抗を下げ、これにより良好な導電性が得られる。またそればかりでなく、多結晶ＩＴＯ粒子間が充填される結果、透明基板やフィルム上に塗布したとき塗布層が緻密組織になり、これにより薄膜太陽電池の受光面やオプティカルデバイスの透明電極である導電膜の光透過率を良好とし、かつヘーズを低下させることができる。 Since the polycrystalline ITO particles have the above-mentioned shape, for example, when a coating-type ITO film is manufactured, when a paint containing the ITO powder is applied to a resin film, or when a coating surface is pressed, Along the resin film surface. That is, the polycrystalline ITO particles are easy to roll and lie on the resin film surface. In addition, since the ITO particles are polycrystalline, a moderate shift occurs at the grain boundary. As a result, voids between the particles are easily filled, and the polycrystalline ITO particles become dense. As a result, when a conductive film that is a transparent electrode is formed using the ITO particles, the electrical resistance is further lowered, and thereby good conductivity is obtained. Moreover, as a result of filling between the polycrystalline ITO particles, the coating layer becomes a dense structure when coated on a transparent substrate or film, thereby being a light-receiving surface of a thin film solar cell or a transparent electrode of an optical device. The light transmittance of the conductive film can be improved and haze can be reduced.
＜ＩＴＯ粉末の製造方法＞
先ず、第１の工程として、スズ塩とインジウム塩とを所定の割合で秤量混合し、当該混合物を純水に溶解してスズ塩とインジウム塩との混合溶液とし、当該混合溶液とアルカリとを反応させて、スズ含有水酸化インジウムの懸濁液を生成させる。混合の方法としては、スズ塩とインジウム塩との混合水溶液へ、アンモニア等のアルカリを添加して反応させる方法が好ましい。スズ塩とインジウム塩との混合水溶液へ、アルカリを添加すると、異方性粒子が生成し易い上に、アルカリ添加の際の温度、添加速度及び／又は粒子濃度を制御することによって、生成する水酸化物粒子の大きさや軸比を制御できる。
<Production method of ITO powder>
First, as a first step, a tin salt and an indium salt are weighed and mixed at a predetermined ratio, the mixture is dissolved in pure water to obtain a mixed solution of a tin salt and an indium salt, and the mixed solution and an alkali are mixed. React to produce a suspension of tin-containing indium hydroxide. As a mixing method, a method of adding an alkali such as ammonia to a mixed aqueous solution of a tin salt and an indium salt and reacting them is preferable. When an alkali is added to a mixed aqueous solution of a tin salt and an indium salt, anisotropic particles are likely to be generated, and the generated water is controlled by controlling the temperature, the addition rate and / or the particle concentration during the addition of the alkali. The size and axial ratio of the oxide particles can be controlled.
更に、この実施の形態では、所定周波数の超音波を混合中の上記反応液に照射する。この超音波の付与により、ＩＴＯ棒状中心核の周囲にこのＩＴＯ棒状中心核より短い複数のＩＴＯ棒状体が、ＩＴＯ棒状中心核の長手方向と同様の向きに沿いかつＩＴＯ棒状中心核を囲むように一体的に形成された多結晶ＩＴＯ粒子からなるＩＴＯ粉末を製造することができる。超音波の周波数は２０〜１００００ｋＨｚとする。周波数が、２０ｋＨｚ未満では超音波の攪拌効果が弱く、一方、１００００ｋＨｚを越えると超音波の出力が落ちて、十分な効果が得られない。周波数は更に２０〜１０００ｋＨｚとすることが好ましい。 Further, in this embodiment, the reaction liquid being mixed is irradiated with ultrasonic waves having a predetermined frequency. By applying this ultrasonic wave, a plurality of ITO rods shorter than the ITO rod-shaped central core are arranged around the ITO rod-shaped central core along the same direction as the longitudinal direction of the ITO rod-shaped central core and surround the ITO rod-shaped central core. An ITO powder composed of integrally formed polycrystalline ITO particles can be produced. The frequency of the ultrasonic wave is 20 to 10000 kHz. If the frequency is less than 20 kHz, the ultrasonic stirring effect is weak. On the other hand, if it exceeds 10,000 kHz, the output of the ultrasonic wave is lowered and a sufficient effect cannot be obtained. The frequency is preferably 20 to 1000 kHz.
超音波を上記の懸濁液に付与する所定時間は、周波数や中和液の容量等によって適宜調整する必要がある。例えば、超音波の周波数が１００ｋＨｚのときで、反応液の容量が１Ｌのときには超音波を照射しながら、アルカリを滴下する時間は、２０〜６００分が好ましい。超音波の付与時間は短すぎると、超音波照射の効果が十分に得られない不具合があり、長すぎると、粒子が長くなりすぎる不具合がある。超音波が反応液に均一に付与されるように、反応液の液面は超音波照射装置の液面（照射装置から反応器へ超音波を伝える媒体）と同一になるようにする。この超音波の付与によって、異方性ＩＴＯ粒子の単体同士の凝集を防ぐと同時に、ＩＴＯ棒状中心核の周囲に中心核より短い複数のＩＴＯ棒状体が、ＩＴＯ棒状中心核の長手方向と同様の向きに沿いかつＩＴＯ棒状中心核を囲むように固着された多結晶ＩＴＯ粒子を得ることができる。 The predetermined time for applying the ultrasonic wave to the above suspension needs to be appropriately adjusted depending on the frequency, the volume of the neutralizing solution, and the like. For example, when the frequency of the ultrasonic wave is 100 kHz and the volume of the reaction solution is 1 L, the time for dropping the alkali while irradiating the ultrasonic wave is preferably 20 to 600 minutes. If the application time of the ultrasonic wave is too short, there is a problem that the effect of ultrasonic irradiation cannot be sufficiently obtained, and if it is too long, there is a problem that the particles become too long. The liquid level of the reaction liquid is set to be the same as the liquid level of the ultrasonic irradiation apparatus (medium for transmitting ultrasonic waves from the irradiation apparatus to the reactor) so that the ultrasonic waves are uniformly applied to the reaction liquid. By applying this ultrasonic wave, agglomeration of single pieces of anisotropic ITO particles is prevented, and at the same time, a plurality of ITO rods shorter than the central core around the ITO rod central core are the same as the longitudinal direction of the ITO rod central core. Polycrystalline ITO particles fixed along the direction and surrounding the ITO rod-like central core can be obtained.
ここで、スズ及びインジウムの塩としては、塩酸塩、硫酸塩、又は硝酸塩などがあるが、一般的には塩酸塩が好ましい。また、アルカリとしては、アンモニア、苛性ソーダ、苛性カリ、又はそれらの炭酸塩が用いられるが、スズ含有水酸化インジウムのスラリー生成後における不純物を削減する観点からアンモニアを用いることが好ましい。 Here, as a salt of tin and indium, there are hydrochloride, sulfate, nitrate, etc., but hydrochloride is generally preferable. As the alkali, ammonia, caustic soda, caustic potash, or a carbonate thereof is used, but ammonia is preferably used from the viewpoint of reducing impurities after the slurry formation of tin-containing indium hydroxide.
生成したスズ含有水酸化インジウムのスラリーを固液分離により採集し、純水により不純物を洗浄することで、純度を高めたスズ含有水酸化インジウムのケーキが得られる。得られたケーキを、室温以上、望ましくは８０℃以上の温度で乾燥することにより、スズ含有水酸化インジウムの乾燥粉が得られる。 The produced tin-containing indium hydroxide slurry is collected by solid-liquid separation, and impurities are washed with pure water to obtain a tin-containing indium hydroxide cake having an increased purity. The obtained cake is dried at a temperature of room temperature or higher, preferably 80 ° C. or higher, whereby a dry powder of tin-containing indium hydroxide is obtained.
スズ含有水酸化インジウム中において、スズは水酸化インジウムのインジウムと置換している場合もあるが、酸化スズ及び／又は水酸化スズとして水酸化インジウムと共沈している場合もあり、酸化スズ及び／又は水酸化スズとして水酸化インジウムと非晶質の混合体となっている場合もある。 In tin-containing indium hydroxide, tin may be substituted for indium in indium hydroxide, but may be co-precipitated with indium hydroxide as tin oxide and / or tin hydroxide. In some cases, the mixture is in the form of indium hydroxide and amorphous as tin hydroxide.
上述したように、スズ含有水酸化インジウムの粒子径は、水酸化物を得る工程で決定される。具体的には、反応温度を４０〜９０℃の範囲に、反応時間（全中和にかかる時間）を２０〜６００分の範囲に、最終粒子濃度を０．０１〜３ｍｏｌ／リットルの範囲にそれぞれ制御することで所望の粒径を有するスズ含有水酸化インジウムを得ることができる。 As described above, the particle size of the tin-containing indium hydroxide is determined in the step of obtaining a hydroxide. Specifically, the reaction temperature is in the range of 40 to 90 ° C., the reaction time (time required for total neutralization) is in the range of 20 to 600 minutes, and the final particle concentration is in the range of 0.01 to 3 mol / liter. By controlling, tin-containing indium hydroxide having a desired particle size can be obtained.
ここで、例えば多結晶ＩＴＯ粒子の平均長さＬが０．２μｍ、平均直径Ｄが１μｍであるスズ含有水酸化インジウムの針状粒子を合成する場合には、反応温度を６０℃、反応時間（全中和にかかる時間）を７５分、最終粒子濃度を０．５ｍｏｌ／リットルとすれば良い。一方、スズ含有水酸化インジウムの針状粒子より平均長さの小さな粒子を製造する場合は、反応温度を低く設定するか、反応速度を短くするか又は粒子濃度を高くすればよい。なお、最終的に生成される多結晶ＩＴＯ粒子のサイズは、当該スズ含有水酸化物のサイズによりほぼ決定される。即ち、当該スズ含有水酸化物はＩＴＯ粒子へ変化する際、平均長さＬ及び平均直径Ｄ共に７０〜８０％程度収縮する。 Here, for example, when synthesizing needle-like particles of tin-containing indium hydroxide having an average length L of polycrystalline ITO particles of 0.2 μm and an average diameter D of 1 μm, the reaction temperature is 60 ° C., the reaction time ( The time required for total neutralization) may be 75 minutes, and the final particle concentration may be 0.5 mol / liter. On the other hand, when producing particles having an average length smaller than the needle-like particles of tin-containing indium hydroxide, the reaction temperature may be set low, the reaction rate may be shortened, or the particle concentration may be increased. Note that the size of the finally produced polycrystalline ITO particles is substantially determined by the size of the tin-containing hydroxide. That is, when the tin-containing hydroxide changes to ITO particles, both the average length L and the average diameter D shrink about 70 to 80%.
次に、第２の工程である、得られたスズ含有水酸化インジウムを焼成する工程について説明する。この焼成工程の目的は、スズ含有水酸化インジウムから、酸化物であるＩＴＯを生成させること及び得られるＩＴＯの結晶に酸素欠損を与えることである。従って、この焼成工程はＩＴＯの結晶に酸素欠損を与えるために不活性ガスと還元性ガスとを混合した弱還元雰囲気下で行われる。通常、弱還元雰囲気として、窒素やヘリウム、アルゴン等の不活性ガスに、水素や一酸化炭素、アンモニアガス、アルコールを混合した混合ガスが用いられる。混合ガスにおける各ガスの混合比率はＩＴＯの結晶に付与しようとする酸素欠損量により適宜決定される。但し混合ガスの還元力が強すぎると、スズ含有水酸化インジウムはＩｎＯ、金属Ｉｎ等になってしまう。また、水素や一酸化炭素等の混合比率は、混合ガスが大気中で爆発限界を越えない程度の濃度にすることが望ましい。 Next, the step of firing the obtained tin-containing indium hydroxide, which is the second step, will be described. The purpose of this firing step is to generate ITO as an oxide from tin-containing indium hydroxide and to give oxygen deficiency to the resulting ITO crystals. Therefore, this firing step is performed in a weak reducing atmosphere in which an inert gas and a reducing gas are mixed to give oxygen deficiency to the ITO crystal. Usually, as a weak reducing atmosphere, a mixed gas in which hydrogen, carbon monoxide, ammonia gas, or alcohol is mixed with an inert gas such as nitrogen, helium, or argon is used. The mixing ratio of each gas in the mixed gas is appropriately determined depending on the amount of oxygen deficiency to be imparted to the ITO crystal. However, if the reducing power of the mixed gas is too strong, the tin-containing indium hydroxide becomes InO, metal In, or the like. In addition, the mixing ratio of hydrogen, carbon monoxide, or the like is desirably set to such a concentration that the mixed gas does not exceed the explosion limit in the atmosphere.
焼成工程では、初めに焼成が行われ、続いて還元処理が行われる。焼成は、スズ含有水酸化インジウムを脱水して酸化インジウムにする。焼成温度は３００〜１０００℃である。３００℃以上で完全な酸化物を得ることができ、１０００℃以下でＩＴＯ粒子間同士の激しい焼結を回避できる。好ましい焼成温度は３５０〜８００℃以下である。焼成時間は０．１時間以上であればよいが、脱水反応が終了すれば、それ以上は不要である。雰囲気は大気とする。 In the firing step, firing is performed first, followed by reduction treatment. In the baking, the tin-containing indium hydroxide is dehydrated into indium oxide. The firing temperature is 300 to 1000 ° C. A complete oxide can be obtained at 300 ° C. or higher, and intense sintering between ITO particles can be avoided at 1000 ° C. or lower. A preferable firing temperature is 350 to 800 ° C. or less. The firing time may be 0.1 hours or longer, but is not necessary once the dehydration reaction is completed. The atmosphere is air.
焼成後の還元処理は、好ましくは２００〜５００℃未満の温度で上述した還元雰囲気下で行われる。２００℃以上あれば酸素欠損を付与でき、５００℃未満であれば、適当な還元力が得られるので絶縁性のＩｎＯが生成されない。還元処理時間は０．５〜５時間である。０．５時間未満では酸素欠損の形成が不十分であり、５時間を越えても優位な変化が見られない。以上の工程を経て、多結晶ＩＴＯ粒子からなるＩＴＯ粉末を得ることができる。このように不活性ガスにアルコールを混合した混合ガスで焼成したＩＴＯ粉末では、粉末表面にＯＨ基が多いことから、後述する表面処理剤である珪酸エステル又はシランカップリング剤がこのＯＨ基と結合しやすいため、珪酸エステル又はシランカップリング剤による表面処理の効果がより高く、高温高湿下におけるＩＴＯ導電膜の電気抵抗値の上昇をより一層抑制することができる。 The reduction treatment after firing is preferably performed at a temperature of 200 to 500 ° C. in the reducing atmosphere described above. If it is 200 degreeC or more, an oxygen deficiency can be provided, and if it is less than 500 degreeC, since an appropriate reduction power is obtained, insulating InO is not produced | generated. The reduction treatment time is 0.5 to 5 hours. If it is less than 0.5 hours, oxygen deficiency is not sufficiently formed, and no significant change is observed even if it exceeds 5 hours. Through the above steps, an ITO powder composed of polycrystalline ITO particles can be obtained. Since ITO powder baked with a mixed gas in which alcohol is mixed with an inert gas in this manner has many OH groups on the powder surface, a silicate ester or silane coupling agent, which will be described later, binds to the OH group. Therefore, the effect of surface treatment with a silicate ester or a silane coupling agent is higher, and an increase in the electrical resistance value of the ITO conductive film under high temperature and high humidity can be further suppressed.
＜ＩＴＯ導電膜形成用塗料の製造方法＞
上記ＩＴＯ粉末を、分散媒のアルコール系溶液１００質量％に対して１〜７０質量％の割合となるように混合し、ミキサーで攪拌することにより、ＩＴＯ導電膜形成用塗料を調製する。ＩＴＯ粉末の分散媒としては、エタノール、２−ブタノール、１−プロパノール等のアルコール系溶液が例示される。ＩＴＯ粉末はこのアルコール系溶液１００質量％に対して１〜７０質量％の範囲で添加混合する。１質量％未満では導電膜に十分な厚さの膜を形成するのが困難となり、７０質量％を越えると分散液の粘度が高く、塗布が困難となる。また必要に応じて上記ＩＴＯ導電膜形成用塗料をホモジェナイザーやビーズミル粉砕機等に入れて、この塗料中のＩＴＯ粉末を粉砕処理する。更に必要に応じて、抵抗を悪化させない範囲で、シリカゾルゲルやアクリル樹脂等のバインダを上記ＩＴＯ導電膜形成用塗料に添加することができる。
<Method for producing ITO conductive film forming paint>
The ITO powder is mixed so as to have a ratio of 1 to 70% by mass with respect to 100% by mass of the alcohol-based solution of the dispersion medium, and stirred with a mixer to prepare an ITO conductive film forming coating material. Examples of the ITO powder dispersion medium include alcohol-based solutions such as ethanol, 2-butanol, and 1-propanol. The ITO powder is added and mixed in the range of 1 to 70% by mass with respect to 100% by mass of the alcoholic solution. If the amount is less than 1% by mass, it is difficult to form a film having a sufficient thickness on the conductive film, and if it exceeds 70% by mass, the viscosity of the dispersion liquid is high and application becomes difficult. If necessary, the ITO conductive film forming coating material is put in a homogenizer, a bead mill pulverizer or the like, and the ITO powder in the coating material is pulverized. Furthermore, if necessary, a binder such as silica sol gel or acrylic resin can be added to the ITO conductive film forming paint within a range not deteriorating the resistance.
＜表面処理するまでのＩＴＯ導電膜の製造方法＞
表面処理するまでのＩＴＯ導電膜は、例えば次のようにして製造される。予めＩＴＯ導電膜を形成するための基材を作製しておく。この基材は、片面にポリウレタンが塗布されたポリエチレンテレフタレート（ＰＥＴ）等のフィルムであって、このフィルムのうちポリウレタンが塗布されていない面をガラス基板上に両面粘着テープ等を用いて貼付けて作製される。先ず、ＩＴＯ導電膜形成用塗料を、ガラス基板上に固定された基材上にバーコート法、ダイコート法、ドクターブレード法等により塗布した後に、乾燥させる。次にＩＴＯ導電膜形成用塗料が塗布された基材をガラス基板から剥離し、基材のうちＩＴＯ導電膜形成用塗料の塗布面にＰＥＴ等の別のフィルムを重ね合せ、この状態でロールプレス機にてロール圧力１００〜２０００ｋｇ／ｃｍ、送り出し速度１０〜５０ｃｍ／分の条件で圧力を加えた後に、別のフィルムを剥離する。これによりフィルム上にＩＴＯ導電膜が形成される。
<Method for producing ITO conductive film until surface treatment>
The ITO conductive film until the surface treatment is produced, for example, as follows. A base material for forming the ITO conductive film is prepared in advance. This base material is a film such as polyethylene terephthalate (PET) coated with polyurethane on one side, and the surface on which the polyurethane is not coated is stuck on a glass substrate using a double-sided adhesive tape or the like. Is done. First, an ITO conductive film forming coating material is applied to a base material fixed on a glass substrate by a bar coating method, a die coating method, a doctor blade method, or the like, and then dried. Next, the base material coated with the ITO conductive film forming paint is peeled off from the glass substrate, and another film such as PET is superimposed on the surface of the base material where the ITO conductive film forming paint is applied. After applying a pressure with a machine under conditions of a roll pressure of 100 to 2000 kg / cm and a delivery speed of 10 to 50 cm / min, another film is peeled off. Thereby, an ITO conductive film is formed on the film.
＜ＩＴＯ導電膜の表面処理剤＞
上記ＩＴＯ導電膜は表面処理剤により表面処理される。ここで、表面処理剤は、炭素数が２以下であるアルコキシ基を４つ有する珪酸エステル又はこの珪酸エステルのオリゴマー体からなる表面処理剤により、或いは炭素数が２以下であるアルコキシ基を２つ以上有し、かつアミノ基（-Ｒ-ＮＨ２、-Ｒ-ＮＨＲ、-Ｒ-ＮＲ1Ｒ2）若しくはメルカプト基（-Ｒ-ＳＨ）を末端基に有するアルキル基、炭素数が６以上である長鎖のアルキル基、又は一部がフッ素で置換されたアルキル基のいずれか１種のアルキル基を１つ以上有するシランカップリング剤からなる。ここでＲ、Ｒ1、Ｒ2はそれぞれアルキル基である。
<Surface treatment agent for ITO conductive film>
The ITO conductive film is surface-treated with a surface treatment agent. Here, the surface treatment agent is a silicate ester having four alkoxy groups having 2 or less carbon atoms or a surface treatment agent comprising an oligomer of this silicate ester, or two alkoxy groups having 2 or less carbon atoms. An alkyl group having an amino group (—R—NH 2, —R—NHR, —R—NR 1 R 2 ) or a mercapto group (—R—SH) as a terminal group, and having 6 or more carbon atoms It consists of a silane coupling agent having one or more alkyl groups of any one of long-chain alkyl groups or alkyl groups partially substituted with fluorine. Here, R, R 1 and R 2 are each an alkyl group.
炭素数が２以下であるアルコキシ基を４つ有する珪酸エステルとしては、テトラメトキシシラン（炭素数１）、又はテトラエトキシシラン（炭素数２）が例示され、上記珪酸エステルのオリゴマーとしては、テトラメトキシシラン（炭素数１）の３〜５量体、又はテトラエトキシシラン（炭素数２）の３〜５量体が例示される。 Examples of the silicic acid ester having four alkoxy groups having 2 or less carbon atoms include tetramethoxysilane (carbon number 1) or tetraethoxysilane (carbon number 2). Examples are silane (carbon number 1) 3-5 mer or tetraethoxysilane (carbon number 2) 3-5 mer.
また炭素数が２以下であるアルコキシ基を２つ以上有し、かつアミノ基若しくはメルカプト基を末端基に有するアルキル基を１つ以上有するシランカップリング剤としては、Ｎ−２−(アミノエチル)−３−アミノプロピルトリメトキシシラン、３−アミノプロピルトリメトキシシラン、３−メルカプトプロピルメチルジメトキシシラン、又は３−メルカプトプロピルトリメトキシシランが例示される。 Further, as a silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more alkyl groups having an amino group or a mercapto group as a terminal group, N-2- (aminoethyl) Examples are -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, or 3-mercaptopropyltrimethoxysilane.
また炭素数が２以下であるアルコキシ基を２つ以上有し、かつ炭素数が６以上の長鎖のアルキル基を１つ以上有するシランカップリング剤としては、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン又はデシルトリメトキシシランが例示される。 Examples of the silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more long-chain alkyl groups having 6 or more carbon atoms include hexyltrimethoxysilane and hexyltriethoxysilane. Or decyltrimethoxysilane is illustrated.
更に炭素数が２以下であるアルコキシ基を２つ以上有し、かつ一部にフッ素で置換されたアルキル基を１つ以上有するシランカップリング剤としては、トリフルオロプロピルトリメトキシシランが例示される。なお、本発明の珪酸エステルは、粒子表面に結合した後、ＳｉＯ２としてネットワークを組みやすい、複数のエステル結合を持つものが好ましい。 Further, trifluoropropyltrimethoxysilane is exemplified as the silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more alkyl groups partially substituted with fluorine. . The silicate ester of the present invention is preferably one having a plurality of ester bonds that can easily form a network as SiO 2 after being bonded to the particle surface.
＜ＩＴＯ導電膜の表面処理方法（表面処理を含むＩＴＯ導電膜の製造方法）＞
（１）表面処理剤の気相暴露法
先ず、表面処理剤の濃度が１０〜１００質量％となるようにこの表面処理剤を溶剤に溶解して表面処理液を作製する。この溶剤には、アルコール、ケトン、水又はこれらを含む混合溶媒を用いることができる。次いで、この表面処理液中で２０〜１５０℃に予熱した窒素ガスをバブリングすることにより、窒素ガスに表面処理剤を含ませる。内容積５Ｌのガラス製の容器に、上記の方法で作製したＩＴＯフィルムを入れ、表面処理剤の蒸気を含ませたガスを、０．１〜５Ｌ／分で１〜１８０分間流通させることにより、ＩＴＯフィルムの表面処理を行う。表面処理剤の濃度、ガス流量、流通時間、ガス温度がそれぞれ上記下限値未満では十分な表面処理効果が得られず、上記上限値を超えると、表面処理効果が得られないと同時に、表面処理液がＩＴＯ膜表面に結露し易く、好ましくない。
<Surface Treatment Method for ITO Conductive Film (Method for Producing ITO Conductive Film Including Surface Treatment)>
(1) Gas-phase exposure method of surface treatment agent First, this surface treatment agent is dissolved in a solvent so that the concentration of the surface treatment agent is 10 to 100% by mass to prepare a surface treatment solution. As this solvent, alcohol, ketone, water, or a mixed solvent containing these can be used. Next, the surface treatment agent is included in the nitrogen gas by bubbling nitrogen gas preheated to 20 to 150 ° C. in the surface treatment liquid. By putting the ITO film produced by the above method into a glass container with an internal volume of 5 L, and circulating the gas containing the surface treatment agent vapor at 0.1 to 5 L / min for 1 to 180 minutes, Surface treatment of ITO film is performed. If the concentration of the surface treatment agent, the gas flow rate, the circulation time, and the gas temperature are less than the above lower limit values, sufficient surface treatment effect cannot be obtained. The liquid tends to condense on the ITO film surface, which is not preferable.
（２）表面処理剤の塗布法
塗布法の代表例として、スピンコート法及びディップコート法を説明する。スピンコート法では、先ず、表面処理剤の濃度が０．１〜１０質量％となるようにこの表面処理剤を溶剤に溶解して表面処理液を作製する。この溶剤には、アルコール、ケトン、水又はこれらを含む混合溶媒を用いることができる。次いで、上記の方法で作製したＩＴＯフィルムに水平に配置して回転させ、その表面に上記表面処理液を滴下することにより、ＩＴＯフィルムの表面処理を行う。表面処理剤の濃度が上記下限値未満では表面処理効果が十分に得られず、上記上限値を超えると過剰な表面処理液がフィルム上に残留することで、ＩＴＯ膜にムラが生じてしまうため、好ましくない。スピコートの回転速度は好ましくは１００〜５０００ｒｐｍであるが、膜にムラが生じない範囲であれば、この範囲に限定されない。
(2) Coating method of surface treatment agent A spin coating method and a dip coating method will be described as representative examples of the coating method. In the spin coating method, first, a surface treatment solution is prepared by dissolving the surface treatment agent in a solvent so that the concentration of the surface treatment agent is 0.1 to 10% by mass. As this solvent, alcohol, ketone, water, or a mixed solvent containing these can be used. Next, the ITO film prepared by the above method is horizontally disposed and rotated, and the surface treatment liquid is dropped onto the surface of the ITO film to perform surface treatment of the ITO film. If the concentration of the surface treatment agent is less than the lower limit value, the surface treatment effect cannot be sufficiently obtained, and if the concentration exceeds the upper limit value, an excessive surface treatment liquid remains on the film, resulting in unevenness in the ITO film. Is not preferable. The rotation speed of the spin coat is preferably 100 to 5000 rpm, but is not limited to this range as long as the film does not cause unevenness.
次にディップコート法を説明する。先ず、表面処理剤の濃度が０．０１〜１０質量％となるようにこの表面処理剤を溶剤に溶解して表面処理液を作製する。この溶剤には、アルコール、ケトン、水又はこれらを含む混合溶媒を用いることができる。次いで、この表面処理液中に、上記の方法で作製したＩＴＯフィルムを０．１〜６０分間浸漬（ディッピング）した後、乾燥させることにより、ＩＴＯフィルムの表面処理を行う。表面処理剤の濃度が上記下限値未満では表面処理効果が十分に得られず、上記上限値を超えると過剰な表面処理液がフィルム上に残留し、これによりＩＴＯ膜に処理ムラが生じてしまうため、好ましくない。乾燥には特に制限はないが、残液によりムラが生じやすいことから、エアガン等で残液を吹き飛ばすことが好ましい。なお、塗布法は、スピンコート法、ディップコート法に限らず、他のコーティング法も本発明に用いることができる。 Next, the dip coating method will be described. First, the surface treatment liquid is prepared by dissolving the surface treatment agent in a solvent so that the concentration of the surface treatment agent is 0.01 to 10% by mass. As this solvent, alcohol, ketone, water, or a mixed solvent containing these can be used. Next, the ITO film produced by the above method is immersed (dipped) in this surface treatment solution for 0.1 to 60 minutes, and then dried to perform surface treatment of the ITO film. When the concentration of the surface treatment agent is less than the above lower limit value, the surface treatment effect cannot be sufficiently obtained, and when the concentration exceeds the above upper limit value, an excessive surface treatment liquid remains on the film, thereby causing uneven treatment on the ITO film. Therefore, it is not preferable. Although there is no restriction | limiting in particular in drying, Since nonuniformity arises easily with a residual liquid, it is preferable to blow off a residual liquid with an air gun etc. The coating method is not limited to the spin coating method and the dip coating method, and other coating methods can be used in the present invention.
＜ＩＴＯ導電膜の評価方法＞
上記のように表面処理された透明導電膜について、以下のようにして表面抵抗の評価を行った。即ち、上記のように表面処理された透明導電膜の予め定められた測定点につき、三菱油化製ＬｏｒｅｓｔａＡＰ ＭＣＰ−Ｔ４００により測定し、その測定値を初期電気抵抗値とした。その後、８５℃、相対湿度８５％ＲＨに制御された恒温恒湿槽内に、２０００時間保管した後に、初期抵抗測定時に定めた測定点において再度電気抵抗の値を測定し、これを加湿後電気抵抗値とした。そして、下記式に基づいて変化率を算出した。
変化率 ＝ [加湿後電気抵抗値／ 初期電気抵抗値]
<Evaluation method of ITO conductive film>
About the transparent conductive film surface-treated as mentioned above, surface resistance was evaluated as follows. That is, a predetermined measurement point of the transparent conductive film surface-treated as described above was measured by LorestaAP MCP-T400 manufactured by Mitsubishi Yuka Co., Ltd., and the measured value was used as an initial electric resistance value. Then, after storing for 2000 hours in a constant temperature and humidity chamber controlled at 85 ° C. and a relative humidity of 85% RH, the value of electrical resistance is measured again at the measurement point determined at the time of initial resistance measurement. Resistance value was used. And the rate of change was computed based on the following formula.
Rate of change = [electric resistance value after humidification / initial electric resistance value]
次に本発明の実施例を比較例とともに詳しく説明する。 Next, examples of the present invention will be described in detail together with comparative examples.
＜実施例１〜１２、比較例１〜６＞
前述した方法で、多結晶ＩＴＯ粒子の平均長さＬが０．２μｍ、平均直径Ｄが１μｍであるスズ含有水酸化インジウムの針状粒子を作製した。この針状粒子の作製に際し、前述した超音波の周波数は３４ｋＨｚであり、その付与時間は６０分であり、スズ及びインジウムの塩は塩酸塩であり、アルカリはアンモニアである。得られたケーキを１１０℃で乾燥した。焼成は窒素の不活性ガス雰囲気で、６００℃、３時間行った。焼成後の還元処理は、水素を３％添加した窒素ガス雰囲気で、３００℃、２時間行った。
<Examples 1-12, Comparative Examples 1-6>
By the method described above, needle-like particles of tin-containing indium hydroxide having an average length L of 0.2 μm and an average diameter D of 1 μm were prepared. In producing the acicular particles, the frequency of the ultrasonic wave described above is 34 kHz, the application time is 60 minutes, the salt of tin and indium is hydrochloride, and the alkali is ammonia. The resulting cake was dried at 110 ° C. Firing was performed at 600 ° C. for 3 hours in an inert gas atmosphere of nitrogen. The reduction treatment after firing was performed at 300 ° C. for 2 hours in a nitrogen gas atmosphere to which 3% of hydrogen was added.
こうして得られたＩＴＯ粉末を、分散媒に対して２５質量％の割合となるように添加混合し、超音波ホモジェナイザーで３０分間攪拌して分散させることにより、ＩＴＯ導電膜形成用塗料を調製した。このＩＴＯ導電膜形成用塗料を、前述した透明導電膜の製造方法に従って、ＰＥＴフィルム上に、バーコート法で成膜し、この膜にロール圧力７００ｋｇ／ｃｍ、送り出し速度３０ｃｍ／分で圧力を加えることで、ＰＥＴフィルム上に形成されたＩＴＯ導電膜を得た。 The ITO powder thus obtained is added and mixed so that the ratio is 25% by mass with respect to the dispersion medium, and is stirred and dispersed with an ultrasonic homogenizer for 30 minutes to prepare a coating for forming an ITO conductive film. did. This ITO conductive film forming coating is formed on a PET film by a bar coating method in accordance with the method for producing a transparent conductive film described above, and pressure is applied to this film at a roll pressure of 700 kg / cm and a delivery speed of 30 cm / min. Thus, an ITO conductive film formed on the PET film was obtained.
このようにして得られたＩＴＯ導電膜を５ｃｍ×５ｃｍの大きさに切り出して、表１に示す表面処理剤を用いて、前述した処理法で表面処理した。このとき、気相暴露法による表面処理は、ガラス製の容器に上記の方法で作製したＩＴＯフィルムを入れ、表面処理剤の蒸気を含ませたガスを、０．５Ｌ／分で６０分間流通させることにより行った。このガスは、８０℃の予熱した窒素ガスを、表面処理液中でバブリングすることにより、表面処理剤を含ませた。スピンコート法による表面処理は、表面処理剤の濃度が1質量％となるようにエタノールで希釈した表面処理液を、上記の方法で作製した５ｃｍ角のＩＴＯフィルムに５００μｌ滴下し、５００ｒｐｍで６０秒間回転させることにより行った。ディップコート法（浸漬法）による表面処理は、表面処理剤の濃度が1質量％となるようにエタノールで希釈した表面処理液に、上記の方法で作製した５ｃｍ角のＩＴＯフィルムを１分間浸漬した後に、エアガンで残液を吹き飛ばし、室温で乾燥させた。 The ITO conductive film thus obtained was cut into a size of 5 cm × 5 cm and surface-treated with the above-described treatment method using the surface treatment agent shown in Table 1. At this time, in the surface treatment by the vapor phase exposure method, the ITO film produced by the above method is put in a glass container, and the gas containing the vapor of the surface treatment agent is circulated at 0.5 L / min for 60 minutes. Was done. This gas contained a surface treatment agent by bubbling preheated nitrogen gas at 80 ° C. in the surface treatment liquid. In the surface treatment by the spin coating method, 500 μl of a surface treatment solution diluted with ethanol so that the concentration of the surface treatment agent is 1% by mass is dropped on the 5 cm square ITO film prepared by the above method, and then at 500 rpm for 60 seconds. This was done by rotating. In the surface treatment by the dip coating method (immersion method), the 5 cm square ITO film prepared by the above method was immersed for 1 minute in a surface treatment solution diluted with ethanol so that the concentration of the surface treatment agent was 1% by mass. Later, the remaining liquid was blown off with an air gun and dried at room temperature.
＜比較試験１及び評価＞
実施例１〜１２及び比較例１〜６の表面処理されたＩＴＯ導電膜を前述した評価方法に基づいて、各膜毎に初期電気抵抗値と加湿後電気抵抗値を測定した。そのうえで、加湿後電気抵抗値を初期電気抵抗値で除して変化率を求めた。その結果を表１に示す。
<Comparative test 1 and evaluation>
Based on the evaluation method described above for the surface-treated ITO conductive films of Examples 1 to 12 and Comparative Examples 1 to 6, the initial electric resistance value and the electric resistance value after humidification were measured for each film. Then, the rate of change was determined by dividing the electrical resistance value after humidification by the initial electrical resistance value. The results are shown in Table 1.
表１から明らかなように、表面処理なしのＩＴＯ導電膜の比較例１では、加湿後電気抵抗値が１４９５７Ω／□と大きくなり、初期電気抵抗値から加湿後電気抵抗値への変化率が５０．６倍と大きくなった。これに対し、テトラメトキシシラン、テトラメトキシシランの３〜５量体、テトラエトキシシラン及びテトラエトキシシランの３〜５量体で表面処理したＩＴＯ導電膜の実施例１〜４では、加湿後電気抵抗値が１９１０〜３１６３Ω／□と小さくなり、初期電気抵抗値から加湿後電気抵抗値への変化率が６．１〜９．７倍と小さくなった。これにより炭素数が２以下であるアルコキシ基を４つ有する珪酸エステルからなる表面処理剤により、又はこれらの珪酸エステルのオリゴマー体からなる表面処理剤により、表面処理されたＩＴＯ導電膜は、加湿後電気抵抗値が比較的低く、かつ高温高湿下であっても、電気抵抗値の上昇を十分に抑制できることが判った。 As is clear from Table 1, in Comparative Example 1 of the ITO conductive film without surface treatment, the electric resistance value after humidification was as large as 14957 Ω / □, and the rate of change from the initial electric resistance value to the electric resistance value after humidification was 50. .6 times larger. On the other hand, in Examples 1-4 of the ITO conductive film surface-treated with tetramethoxysilane, tetramethoxysilane 3-5 mer, tetraethoxysilane and tetraethoxysilane 3-5 mer, electric resistance after humidification The value decreased to 1910-3163 Ω / □, and the rate of change from the initial electrical resistance value to the electrical resistance value after humidification decreased to 6.1 to 9.7 times. As a result, the ITO conductive film surface-treated with a surface treatment agent comprising a silicate ester having four alkoxy groups having 2 or less carbon atoms or a surface treatment agent comprising an oligomer of these silicate esters is obtained after humidification. It has been found that the increase in the electric resistance value can be sufficiently suppressed even when the electric resistance value is relatively low and the temperature and humidity are high.
また、表１から明らかなように、アミノ基を末端基ではなく中央に有するヘキサメチルジシラザンで表面処理したＩＴＯ導電膜の比較例４では、加湿後電気抵抗値が２１３１３Ω／□と大きくなり、初期電気抵抗値から加湿後電気抵抗値への変化率が４９．２倍と大きくなった。これに対し、アミノ基を末端基に有するＮ−２−(アミノエチル)−３−アミノプロピルトリメトキシシラン、及び３−アミノプロピルトリメトキシシランで表面処理したＩＴＯ導電膜の実施例５及び６では、加湿後電気抵抗値が８２３Ω／□及び６０２Ω／□と小さくなり、初期電気抵抗値から加湿後電気抵抗値への変化率が２．６倍及び２．１倍と小さくなった。またメルカプト基を末端基に有する３−メルカプトプロピルメチルジメトキシシラン、及び３−メルカプトプロピルトリメトキシシランで表面処理したＩＴＯ導電膜の実施例７及び８では、加湿後電気抵抗値が７３９Ω／□及び６２４Ω／□と小さくなり、初期電気抵抗値から加湿後電気抵抗値への変化率が２．３倍及び１．８倍と小さくなった。これにより炭素数が２以下であるアルコキシ基を２つ以上有し、かつアミノ基若しくはメルカプト基を末端基に有するアルキル基を１つ以上有するシランカップリング剤からなる表面処理剤により、表面処理されたＩＴＯ導電膜は、加湿後電気抵抗値が比較的低く、かつ高温高湿下であっても、電気抵抗値の上昇を十分に抑制できることが判った。 Further, as apparent from Table 1, in Comparative Example 4 of the ITO conductive film surface-treated with hexamethyldisilazane having an amino group at the center instead of a terminal group, the electric resistance value after humidification was increased to 21313 Ω / □, The rate of change from the initial electrical resistance value to the electrical resistance value after humidification was as large as 49.2 times. On the other hand, in Examples 5 and 6 of the ITO conductive film surface-treated with N-2- (aminoethyl) -3-aminopropyltrimethoxysilane having an amino group as a terminal group and 3-aminopropyltrimethoxysilane, The electric resistance values after humidification were reduced to 823 Ω / □ and 602 Ω / □, and the rate of change from the initial electric resistance value to the electric resistance value after humidification was reduced to 2.6 times and 2.1 times. Further, in Examples 7 and 8 of the ITO conductive film surface-treated with 3-mercaptopropylmethyldimethoxysilane having a mercapto group as a terminal group and 3-mercaptopropyltrimethoxysilane, the electric resistance values after humidification were 739Ω / □ and 624Ω. / □, and the rate of change from the initial electrical resistance value to the electrical resistance value after humidification was reduced to 2.3 times and 1.8 times. Thus, the surface treatment is performed by the surface treatment agent comprising a silane coupling agent having at least two alkoxy groups having 2 or less carbon atoms and at least one alkyl group having an amino group or a mercapto group as a terminal group. It has been found that the ITO conductive film has a relatively low electrical resistance value after humidification and can sufficiently suppress an increase in the electrical resistance value even under high temperature and high humidity.
また、表１から明らかなように、炭素数が６以上である長鎖のアルキル基を有しないビニルトリメトキシシラン、ｐ−スチリルメトキシシラン、フェニルトリメトキシシラン、及びジメチルジメトキシシランで表面処理したＩＴＯ導電膜の比較例２、３、５及び６では、加湿後電気抵抗値が１１０１４〜１４２０４Ω／□と大きくなり、初期電気抵抗値から加湿後電気抵抗値への変化率が２９．８〜４２．０倍と大きくなった。これに対し、炭素数が６以上である長鎖のアルキル基を有するヘキシルトリメトキシシラン、デシルトリメトキシシラン及びヘキシルトリエトキシシランで表面処理したＩＴＯ導電膜の実施例１０、１１及び１２では、加湿後電気抵抗値が１０２５〜１４７３Ω／□と小さくなり、初期電気抵抗値から加湿後電気抵抗値への変化率が３．１〜４．５倍と小さくなった。これにより炭素数が２以下であるアルコキシ基を２つ以上有し、かつ炭素数が６以上である長鎖のアルキル基を１つ以上有するシランカップリング剤からなる表面処理剤により、表面処理されたＩＴＯ導電膜は、加湿後電気抵抗値が比較的低く、かつ高温高湿下であっても、電気抵抗値の上昇を十分に抑制できることが判った。 Further, as is apparent from Table 1, ITO surface-treated with vinyltrimethoxysilane, p-styrylmethoxysilane, phenyltrimethoxysilane, and dimethyldimethoxysilane having no long-chain alkyl group having 6 or more carbon atoms. In Comparative Examples 2, 3, 5, and 6 of the conductive film, the electric resistance value after humidification was increased to 11014 to 14204 Ω / □, and the rate of change from the initial electric resistance value to the electric resistance value after humidification was 29.8 to 42.42. Increased to 0 times. On the other hand, in Examples 10, 11 and 12 of the ITO conductive film surface-treated with hexyltrimethoxysilane, decyltrimethoxysilane and hexyltriethoxysilane having a long-chain alkyl group having 6 or more carbon atoms, humidification was performed. The post-electric resistance value was reduced to 1025 to 1473 Ω / □, and the rate of change from the initial electric resistance value to the post-humidified electric resistance value was reduced to 3.1 to 4.5 times. Thus, the surface treatment is performed by the surface treatment agent comprising a silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more long-chain alkyl groups having 6 or more carbon atoms. It has been found that the ITO conductive film has a relatively low electrical resistance value after humidification and can sufficiently suppress an increase in the electrical resistance value even under high temperature and high humidity.
更に、表１から明らかなように、一部がフッ素で置換されたアルキル基を有するトリフルオロプロピルトリメトキシシランで表面処理したＩＴＯ粉末を用いてＩＴＯ導電膜を形成した実施例９では、加湿後電気抵抗値が９６４Ω／□と小さくなり、初期電気抵抗値から加湿後電気抵抗値への変化率が３．５倍と小さくなった。これにより炭素数が２以下であるアルコキシ基を２つ以上有し、かつ一部がフッ素で置換されたアルキル基を１つ以上有するシランカップリング剤からなる表面処理剤により、表面処理されたＩＴＯ導電膜は、加湿後電気抵抗値が比較的低く、かつ高温高湿下であっても、電気抵抗値の上昇を十分に抑制できることが判った。 Furthermore, as apparent from Table 1, in Example 9 in which the ITO conductive film was formed using ITO powder surface-treated with trifluoropropyltrimethoxysilane having an alkyl group partially substituted with fluorine, The electrical resistance value was reduced to 964Ω / □, and the rate of change from the initial electrical resistance value to the electrical resistance value after humidification was reduced to 3.5 times. As a result, ITO surface-treated with a surface treatment agent comprising a silane coupling agent having two or more alkoxy groups having 2 or less carbon atoms and one or more alkyl groups partially substituted with fluorine. It has been found that the conductive film has a relatively low electrical resistance value after humidification and can sufficiently suppress an increase in the electrical resistance value even under high temperature and high humidity.
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| EP3998370A1 (en) | 2015-03-30 | 2022-05-18 | Tosoh Corporation | Gallium nitride-based film and method for manufacturing same |
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| Publication number | Publication date |
|---|---|
| WO2015046561A1 (en) | 2015-04-02 |
| TW201529481A (en) | 2015-08-01 |
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