JPS6238432B2 - - Google Patents
Info
- Publication number
- JPS6238432B2 JPS6238432B2 JP55068981A JP6898180A JPS6238432B2 JP S6238432 B2 JPS6238432 B2 JP S6238432B2 JP 55068981 A JP55068981 A JP 55068981A JP 6898180 A JP6898180 A JP 6898180A JP S6238432 B2 JPS6238432 B2 JP S6238432B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- transparent
- film layer
- film
- oxide
- 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.)
- Expired
Links
- 239000010408 film Substances 0.000 claims description 68
- 239000010409 thin film Substances 0.000 claims description 53
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 34
- 229910044991 metal oxide Inorganic materials 0.000 claims description 22
- 150000004706 metal oxides Chemical class 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052709 silver Inorganic materials 0.000 claims description 14
- 239000004332 silver Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 18
- 230000008020 evaporation Effects 0.000 description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 13
- 238000004544 sputter deposition Methods 0.000 description 13
- 238000007740 vapor deposition Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- 229910003437 indium oxide Inorganic materials 0.000 description 7
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 7
- 238000004804 winding Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 229910052738 indium Inorganic materials 0.000 description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 229910052691 Erbium Inorganic materials 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- -1 alumina Chemical class 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 238000010894 electron beam technology Methods 0.000 description 4
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 229910052735 hafnium Inorganic materials 0.000 description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 4
- 229920000620 organic polymer Polymers 0.000 description 4
- 229910052718 tin Inorganic materials 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- 229910052727 yttrium Inorganic materials 0.000 description 4
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000005192 partition Methods 0.000 description 3
- 229920002050 silicone resin Polymers 0.000 description 3
- 238000007738 vacuum evaporation Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 238000002310 reflectometry Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000132023 Bellis perennis Species 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000005633 Chrysanthemum balsamita Nutrition 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- BTYUGHWCEFRRRF-UHFFFAOYSA-N [As].[K] Chemical compound [As].[K] BTYUGHWCEFRRRF-UHFFFAOYSA-N 0.000 description 1
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- ZXGIFJXRQHZCGJ-UHFFFAOYSA-N erbium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Er+3].[Er+3] ZXGIFJXRQHZCGJ-UHFFFAOYSA-N 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 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
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000005368 silicate glass Substances 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
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
- Physical Vapour Deposition (AREA)
Description
本発明は、透明導電性積層体の製造方法に関す
る。更に詳細にはイート状基板上に金属薄膜層と
金属酸化物薄膜層とを積層して透明導電性を有す
る積層体を製造する方法に関する。
透明導電性積層体は、その導電性を利用した用
途、例えば液晶デイスプレイ用電極、電場発光体
用電極、光導電性感光体用電極、ブラウン管、各
種測定器の窓部分の透明静電遮蔽層、帯電防止
層、発熱体等の電気・電子分野の用途に広く利用
されており、それらの中で選択光透過性を有する
ものは、その赤外光反射能を利用して太陽エネル
ギー利用のためのコレクター用窓材や、建物の窓
材としても広く利用されている。
更にまた、情報化社会の進展と共に従来用いら
れてきたブラウン管に代つてエレクトロルミネツ
センスデイスプレイ、液晶デイスプレイ、プラズ
マデイスプレイ、強誘電体デイスプレイなどの固
体デイスプレイが開発されているが、かかる固体
デイスプレイには透明な電極が必要である。また
電気信号と光信号との相互作用又は相互変換を利
用した新しい電気光学素子や記録材料が今後の情
報処理技術の主役になろうとしているが、これら
の電気光学材料の構成の一部として透明性と導電
性を兼備した材料が要求されている。情報材料以
外にも自動車、飛行機などの交通機関の凍結防止
用窓ガラスとして透明導電性被膜を有する窓ガラ
スが要求されている。
一方、高分子成型物等の電気絶縁性物体におい
て、静電気の発生がしばしば重大な災害の原因と
なつている。これを防止する為に例えば金属やカ
ーボン等の導電体の粉末を高分子に混入して成型
することが試みられているが、着色、不透明化や
力学的特性の低下がさけられない。しかし高分子
等の電気絶縁性成型物の表面に透明導電性被膜を
設けることは帯電防止法として優れた方法であ
る。
選択光透過性被膜は、可視光域の光に対して透
明であるが、赤外光に対しては反射能を有してい
るので透明断熱膜としても有用である。従つて太
陽エネルギー集熱器（温水器）、太陽熱発電、グ
リーンハウス、建築物の窓部等に使用されうる。
特に近代建築物において壁面の大きな割合を占め
る窓からの太陽エネルギー利用及びエネルギー放
散を防げる透明断熱窓としての機能は今後益々重
要性を増す。亦、例えば野さい、かんきつ類の栽
培に用いられるグリーンハウス用フイルムとして
も重要性が大である。この様に、透明導電性被膜
および選択光透過膜はエレクトロニクス、太陽エ
ネルギー利用の観点から重要であり、均質で高性
能な膜が工業的に安価に且つ大量に供給されるこ
とが当該業界から望まれていた。
透明導電性被膜として従来から知られているも
のは
金、銀、銅、パラジウム等の金属薄膜
酸化インジウム、酸化スズ、ヨウ化銅等の化
合物半導体膜、および
金、銀、銅、パラジウム等の導電性金属膜を
ある波長領域にわたり選択的に透明にしたもの
が知られている。赤外光反射能の高い選択光透過
膜として、数千オングストロームの膜厚の酸化イ
ンジウム膜又は酸化錫膜および金属膜と透明誘電
体膜の積層膜等が知られている。しかしながら、
すぐれた性能の透明導電性膜又は選択光透過膜が
工業的に安価に製造されるに至つていないのが実
状である。
即ち、上記の金属薄膜は、金属が広い波長領
域にわたり反射能又は吸収能が高いために、可視
光透過率の高いものが得難い。可視光透過率を高
めると導電性又は赤外光反射能が著るしく低下す
る。導電性又は赤外光反射能を高めるために金属
薄膜の膜厚を高めると可視光透過率が著るしく低
下するので両方の性質に優れた透明導電性被膜又
は選択光透過性被膜は得難い。
上記の化合物半導体薄膜のうち酸化インジウ
ム薄膜層は、例えば真空蒸着法、スパツタリング
法等の真空中における薄膜形成法で形成される。
また従来より酸化スズ薄膜を形成させるため、塩
化スズ溶液の熱分解法が用いられているが、基板
温度を500℃程度に保つ必要があり熱的ヒズミの
問題で大面積基板の使用が困難である。更にこの
方法では高分子材料を基板として用いる場合耐熱
性の低い材料をその基板として使用できない等の
問題がある。酸化インジウム等の半導体で、すぐ
れた透明導電性又は選択透過性膜を得るために、
数千オングストローム程度の膜厚の酸化インジウ
ム等の半導体被膜が提案されているが、膜の生成
速度が著るしく遅くなるばかりでなく、貴重なイ
ンジウム等の資源を多く消費することになり、そ
の結果膜の製造コストが著るしく高くなる。更に
亦、この膜では赤外光反射能又は導電性の充分に
高いものが得られていない。
上記の透明導電性膜又は選択光透過性膜の代
表的な構成は、金属薄膜を透明高屈折率薄膜では
さんだ積層体であり、例えば真空蒸着、反応性蒸
着又はスパツタリングで形成させたBi2O3／Au／
Bi2O3，ZnS／Ag／ZnS又はTiO2／Ag／TiO2等の
サンドイツチ状構造の積層体が提案されている。
これらの中でも光学的特性からAgを金属層とし
たて用いるものが好ましく、銀薄膜を酸化チタン
などの金属酸化物で積層する方法に関して種々提
案されている。例えば米国特許第3962488号明細
書には金属チタンを酸素雰囲気中で反応させなが
ら、銀薄膜上に酸化チタン層を形成させる方法が
開示されており、又特開昭51−66841号公報には
酸化チタン（TiO2）をアルゴン雰囲気中でスパツ
タリングさせて銀薄膜上に酸化チタン層を形成さ
せる方法が記載されている。しかしながら前者の
方法にあつては金属チタンから出発して途中で酸
化して酸化チタンとするものであるために金属チ
タンの蒸発速度を高めることが出来ず、蒸着速度
を６Å／秒程度にしないとTiO2膜が得られな
い。亦、後者の方法にあつてはTiO2をターゲツ
トとするものではあるが、先ず、全圧７〜10×
10-3Torrのアルゴン酸素混合ガス（酸素10容量
％）中で15分間第１段目のプレスパツタリングを
し、次いで７〜10×10-3Torrのアルゴンガス雰
囲気中で15分間第２段目のプレスパツタリングを
し、更にその後、表面の調整された酸化チタンの
ターゲツトをアルゴンガス雰囲気中でスパツタリ
ングするという非常に複雑な手段を採るものであ
る。従つてスパツタリング速度が20〜30Å／分と
非常に遅いことともあいまつて、その生産速度は
極めて低いものである。
かかる状況に鑑み、本発明者らはベースフイル
ムを連続的に捲取りながら高速で透明導電性（選
択光透過性）フイルムを製造する方法について鋭
意研究した結果、金属酸化物を酸素を含む気体の
プラズマ中で加熱して蒸発せしめて20秒以内で透
明高屈折率薄膜層(C)を形成させることにより上記
の目的が達成されることを見出し本発明に到達し
た。
即ち本発明は、少くとも片面に銀を主成分とす
る金属薄膜層(B)が形成された透明なシート状基板
(A)の当該金属薄膜層(B)上に金属酸化物を主成分と
する透明高屈折率薄膜層Ｃを設けて透明導電性積
層体を製造する際に、金属酸化物を酸素を含む気
体のプラズマ中で加熱して蒸発せしめて20秒以内
で透明高屈折率薄膜層を形成させることを特徴と
する透明導電性積層体の製造方法である。
本発明において用いられる透明なシート状基板
(A)としては無機・有機或いは両者の複合した透明
シート状基板である。
無機質のシート状基板としては、例えばソーダ
ガラス、ホウ硅酸ガラス、硅酸ガラスなどのガラ
ス質；アルミナ、マグネシア、ジルコニア、シリ
カなどの金属酸化物；カリウム―ヒ素、インジウ
ム―リン等の化合物半導体；シリコン、ゲルマニ
ウム等の半導体による成型物が挙げられる。
亦、有機質のシート状基板としては、例えばポ
リエチレンテレフタレート樹脂、ポリエチレンナ
フタレート樹脂、ABS樹脂、ポリスチレン樹
脂、ポリアセタール樹脂、ポリエチレン樹脂、ポ
リプロピレン樹脂、ポリアミド樹脂、フツ素樹脂
等の熱可塑性樹脂；更には例えばばエポキシ樹
脂、ジアリルフタレート樹脂、ケイ素樹脂、不飽
和ポリエステル樹脂、フエノール系樹脂、尿素樹
脂などの熱硬化性樹脂；更にはポリビニルアルコ
ール、ポリアクリルニトリル、ポリウレタン、芳
香族ポリアミド、ポリイミド樹脂等の溶剤可溶型
樹脂等の成型物が挙げられる。これらは単独又は
混合して、或いは共重合物として、更には積層体
としても用いられる。
亦、無機・有機の複合体としては混合したもの
であることもできるし、積層されたものであるこ
ともできる。例えば、前記有機のシート状基板
に、更に有機又は無機のプライマー層を設けた
り、金属酸化物の薄膜層を設けることができる。
金属酸化物の薄膜層を設ける場合は当然本発明の
特徴である後述の製造条件に準拠することが有利
である。従つて本発明で用いられる透明なシート
状基板(A)としては、前記の有機高分子化合物のシ
ート上に、後記の透明高屈折率薄膜層(D)が設けら
れたものも包含する。
金属薄膜層(B)は銀を主成分としており、本発明
の目的とする効果を損なわない範囲で他の金属又
は、金属化合物が含まれていてもよい。例えば、
銅を0.1〜20重量％、好ましくは0.3〜10重量％銀
に添加すると、得られる積層体の耐候性が著じる
しく改良され、また、金を３〜30重量％添加させ
ると耐熱性が改良される。
この金属薄膜層(B)の厚さは50〜350Å、好まし
くは70〜200Åであり、薄すぎると導電性、赤外
線反射率および耐熱性が低くなりすぎ、また、厚
すぎると可視光の透過率が著じるしく低下し、実
用に供さない。
金属薄膜層(B)は真空蒸着またはスパツタリング
などで容易に形成させることができる。
金属薄膜層(B)を形成させる前に前記の如く基板
を予め透明な高屈折率薄膜層(D)で被覆しておくこ
とができる。層(D)の形成法には、特に限定はな
く、能率的な方法で形成するのがよいが、後述の
層(C)と同じでもよい。
層(D)の膜厚は50〜400Å、好ましくは100〜300
Åである。この膜厚の範囲であると得られる積層
体の可視光透過率、導電性、赤外線反射率および
耐熱性がすぐれている。
本発明方法において用いられる透明高屈折率薄
膜層(C)は、例えばチタン、ビスマス、インジウ
ム、錫、セリウム、タンタル、タングステン、モ
リブデン、エルビウム、ハフニウム、亜鉛、イツ
トリウム、ジルコニウムなどの酸化物を主成分と
するものであり、可視光に透明であり且つ可視光
における屈折率が高いものであり、屈折率が1.8
以上特に2.0以上が好ましい。
好ましい金属酸化物としては、チタン、亜鉛、
インジウム、錫、イツトリウム、エルビウム、ジ
ルコニウム、ハフニウムおよびセリウムの酸化物
が挙げられる。
上記透明高屈折率薄膜層(C)は金属酸化物を酸素
を含む気体のプラズマ中で加熱して蒸発せしめて
形成させることができる。
金属酸化物を真空中で加熱すると分解し、蒸着
を続けるとしだいに蒸着材料表面が還元され、還
元された金属酸化物層が金属薄膜層(B)上に形成さ
れる。
還元された金属酸化物層は、可視光に吸収があ
り、積層体の透過率と耐光性が低下する。
これを防ぐために、真空槽内に、酸素ガス又は
酸素ガスとアルゴン等の不活性ガスとの混合ガス
を導入して、真空槽内の真空度を適当な値に調整
した後高周波電力により酸素を含む気体のプラズ
マを発生させ、該プラズマ中で金属酸化物を蒸発
せしめる方法を検討した。かかる方法は、金属酸
化物層の透明性を向上させる方法としては好まし
いが、金属薄膜層(B)上に積層する場合には金属薄
膜層(B)が、酸素を含む気体のプラズマに曝される
ことにより劣化し、赤外線反射率および導電率が
低下する事がわかつた。
そこで、本発明者らは鋭意研究した結果、金属
酸化物層の形成速度を大きく、即ち形成時間を短
くすれば、金属薄膜層(B)が酸素を含む気体の高周
波プラズマに曝される時間が短かくなり、金属薄
膜層(B)の劣化なくなる事を見出した。金属酸化物
層の形成時間はできるだけ短くするのが良く、好
ましくは20秒以下、特に好ましくは10秒以下であ
る。
前記高周波プラズマは、例えば真空槽を十分に
排気し、酸素を好ましくは10モル％以上特に好ま
しくは50モル％以上含む気体を１〜10-4〜１×
10-3Torr導入し、基板と蒸発源との間の空間に
らせん状のアンテナを設け、これに13.56MHzの
高周波電力を100〜1000W加えることにより発生
させることができる。
酸素分圧が、１×10-5Torrより低い場合には
十分に透明な金属酸化物層を得ることができな
い。又、酸素分圧が、１×10-3Torrを超える場
合には、電子銃のフイラメント切れ等、蒸発源の
損傷が起こり易くなり好ましくない。
透明高屈折率薄膜層(C)の膜厚は50〜400Å、好
ましくは100〜300Åである。膜厚がこの範囲より
はずれると可視光透過率或いは耐熱性が著じるし
く低下する。かかる膜厚範囲の透明高屈折率薄膜
層(C)を20秒以内で形成するためには形成速度を20
Å／秒以上にしなければならないが、本発明の様
に、金属酸化物を酸素を含む気体のプラズマ中で
加熱して蒸発せしめることにより初めて実現する
ことができたのである。
蒸発源の金属酸化物を連続的に長時間蒸発させ
る場合、蒸着材料が減少して蒸発速度が低下する
ので連続的に一定量を供給してやるのが好まし
い。
本発明の積層体の上に本発明の目的とする効果
を損わない範囲で更に他の層を積層して、例えば
表面硬度、耐候性、接着性等の性質を改良するこ
とができる。このような層の形成に用いる材料と
しては、例えばポリメタクリル酸メチルなどのア
クリル系樹脂、エチルシリケートより得られる重
合体などのケイ素樹脂、ポリエステル樹脂、メラ
ミン樹脂、フツ素樹脂などの有機系高分子物質の
他に、酸化ケイ素、フツ化マグネシウム等の無機
物を挙げることができる。
とりわけ耐候性又は表面硬度を改良する場合に
はアクリル系樹脂、ケイ素樹脂など好ましく用い
られる。
本発明の一つの目的である透明導電性を有する
積層体は、可視光透過率が50％以上で且つ表面抵
抗が103Ω／□以下のものである。
本発明の方法は非常に生産性の高い方法であ
り、耐熱性の乏しい高分子フイルムを基板(A)とし
て用いることもでき、しかも連続的に積層する場
合フイルムを５〜100m／分の速度で巻取りなが
ら生産できる工業的にすぐれた方法である。
本発明は特許請求の範囲に記載された構成に加
え、以下の如き実施態様をも包含するものであ
る。
(2) 該金属薄膜層(B)が銅を0.1〜20wt％含有する
特許請求の範囲第１項（以下単に第１項と略称
する）記載の方法。
(3) 当該金属薄膜層(B)が金を３〜30wt％含有す
る第１項又は第２項記載の方法。
(4) 当該金属薄膜層(B)の厚さが50〜350Å、好ま
しくは70〜200Åである第１項記載の方法。
(5) 当該透明高屈折率薄膜層(C)がチタン、亜鉛、
インジウム、錫、イツトリウム、エルビウム、
ジルコニウム、ハフニウムおよびセリウムから
選ばれた１種以上の金属の酸化物からなる第１
項記載の方法。
(6) 当該透明高屈折率薄膜層(C)の厚さが50〜400
Åである第１項記載の方法法。
(7) 当該透明なシート状基板(A)が有機高分子から
なるものである第１項記載の方法。
(8) 当該透明なシート状基板(A)の厚さが10〜300
μｍである第７項記載の方法。
(9) 当該透明なシート状基板(A)が有機高分子から
なる透明シートとその上に設けられた透明高屈
折率薄膜層(D)とからなる積層体である第１項記
載の方法。
(10) 当該透明高屈折率薄膜層(D)がチタン、亜鉛、
インジウム、錫、イツトリウム、エルビウ
ム、、ジルコニウム、ハフニウムおよびセリウ
ムから選ばれた１種以上の金属の酸化物からな
る第９項記載の方法。
(11) 当該透明高屈折率薄膜層(D)の厚さが50〜400
Åである第９項記載の方法。
(12) 当該プラズマを全圧１×10-4〜１×
10-3Torr、酸素圧１×10-5〜１×10-3Torrの気
体の高周波放電により発生させる第１項記載の
方法。
以下、実施例により本発明を更に詳細に説明す
る。
実施例１〜３および比較例１
酸化チタン層の形成を以下のようにして行なつ
た。第１図に示した様なフイルム巻取式の真空蒸
着装置を用いる。
真空層１はフイルム巻取室２と蒸着室３とに仕
切り板４によつて仕切つてあり、それぞれ別の排
気口６，５から排気する。
仕切板４は、冷却ドラムには接触しておらずフ
イルムが自由に通過するに十分な程度の間隔を保
つて取付けられ、且つ、捲取室２と蒸着室３を異
つた真空度に保てる程度に調整されている。
フイルム１６は、送り出しロール７から、冷却
ドラム８を経由して、捲取ロール９に送られる。
捲取室２を10-4Torrに排気し、同時に蒸着室
３を５×10.6〜１×10-5Torrの排気し次に、ガス
導入口１０から、酸素ガスを導入し、蒸着室３の
真空度が１〜７×10-4Torrになる程度に酸化ガ
スの流量を調整する。
蒸発源１１と冷却ドラム８の空間に、ワイヤー
状の電極１２を設け、これに高周波電源１３より
電力を供給し、マツチングボツクス１４を調整す
ることにより、電極の周辺に放電が持続する。フ
イルムを送りながら蒸発源１１を電子銃１５など
で加熱することにより、フイルム面に高屈折率薄
膜層(C)が形成される。膜厚は蒸発速度とフイルム
の送り速度によつて決まる。
上記の如き装置により厚さ50μｍの透明なポリ
エステルフイルムの片面に酸化チタンを200Å蒸
着した。
蒸着は以下の条件で行つた。
酸素ガス分圧 ３×10-4Torr
高周波電力（13.56MHz） 300W
蒸発源 酸化チタン（TiO2）
電子ビーム出力 3KW
フイルム送り速度 12m／分
（以下得られたフイルムをフイルムＡと称す
る。）
フイルムＡの酸化チタン膜上に、銀を150Å、
３×10-6Torrの真空度で蒸着した。
（以下得られたフイルムをフイルムＢと称す
る。）
次に、フイルムＢの銀膜上に酸化チタンを300
Å蒸着した。蒸着条件は以下の通りである。
酸素分圧 ３×10-4Torr
高周波電力（13.56MHz） 300W
蒸発源 酸化チタン（TiO5）
但し、フイルム送り速度は、第１表に示した様
に0.9m／分〜8m／分まで変化させ、かつ、同じ
膜厚になる様に電子ビームの出力を調整した。得
られた、TiO2／Ag／TiO2構造の薄膜を形成した
フイルムの特性を第１表に合わせて示す。
The present invention relates to a method for manufacturing a transparent conductive laminate. More specifically, the present invention relates to a method of manufacturing a laminate having transparent conductivity by laminating a metal thin film layer and a metal oxide thin film layer on a sheet-like substrate. Transparent conductive laminates are used for applications that utilize their conductivity, such as electrodes for liquid crystal displays, electrodes for electroluminescent bodies, electrodes for photoconductive photoreceptors, cathode ray tubes, transparent electrostatic shielding layers for windows of various measuring instruments, It is widely used in electrical and electronic fields such as antistatic layers and heating elements, and among them, those with selective light transmission are used for solar energy utilization by utilizing their infrared light reflecting ability. It is also widely used as window material for collectors and buildings. Furthermore, with the advancement of the information society, solid-state displays such as electroluminescent displays, liquid crystal displays, plasma displays, and ferroelectric displays have been developed to replace the conventionally used cathode ray tubes. Transparent electrodes are required. In addition, new electro-optical elements and recording materials that utilize interaction or mutual conversion between electrical and optical signals are likely to become the mainstay of future information processing technology, but transparent There is a need for materials that have both properties and conductivity. In addition to information materials, window glasses with transparent conductive coatings are required as antifreeze window glasses for transportation such as automobiles and airplanes. On the other hand, generation of static electricity in electrically insulating objects such as polymer molded objects often causes serious disasters. In order to prevent this, attempts have been made to mold the polymer by mixing conductor powder such as metal or carbon into the polymer, but this inevitably results in coloring, opacity, and deterioration of mechanical properties. However, providing a transparent conductive coating on the surface of an electrically insulating molded product such as a polymer is an excellent antistatic method. The selective light transmitting film is transparent to light in the visible light range, but has the ability to reflect infrared light, so it is also useful as a transparent heat insulating film. Therefore, it can be used for solar energy collectors (water heaters), solar thermal power generation, greenhouses, windows of buildings, etc.
In particular, in modern buildings, windows occupy a large proportion of the wall surface, and their function as transparent heat-insulating windows that can prevent solar energy utilization and energy dissipation will become increasingly important in the future. In addition, it is also of great importance as a film for greenhouses used, for example, in the cultivation of wild daisies and citrus fruits. In this way, transparent conductive films and selective light transmission films are important from the viewpoint of electronics and solar energy utilization, and it is desired by the industry that homogeneous and high-performance films can be supplied industrially at low cost and in large quantities. It was rare. Conventionally known transparent conductive films include: thin metal films such as gold, silver, copper, and palladium, compound semiconductor films such as indium oxide, tin oxide, and copper iodide, and conductive films such as gold, silver, copper, and palladium. It is known that a transparent metal film is selectively made transparent over a certain wavelength range. As a selective light transmitting film with high infrared light reflecting ability, an indium oxide film or a tin oxide film with a thickness of several thousand angstroms, a laminated film of a metal film and a transparent dielectric film, etc. are known. however,
The reality is that transparent conductive films or selective light transmitting films with excellent performance have not yet been produced industrially and at low cost. That is, it is difficult to obtain the above-mentioned metal thin film with high visible light transmittance because the metal has high reflective ability or absorbing ability over a wide wavelength range. When visible light transmittance is increased, conductivity or infrared light reflection ability is significantly reduced. If the thickness of the metal thin film is increased in order to improve conductivity or infrared light reflection ability, the visible light transmittance will drop significantly, making it difficult to obtain a transparent conductive film or a selective light transmitting film that is excellent in both properties. Among the above compound semiconductor thin films, the indium oxide thin film layer is formed by a thin film forming method in vacuum, such as a vacuum evaporation method or a sputtering method.
Furthermore, thermal decomposition of a tin chloride solution has traditionally been used to form a tin oxide thin film, but the substrate temperature must be maintained at around 500°C, making it difficult to use large-area substrates due to thermal distortion. be. Further, in this method, when a polymeric material is used as a substrate, there is a problem that a material with low heat resistance cannot be used as the substrate. In order to obtain an excellent transparent conductive or permselective film using a semiconductor such as indium oxide,
Semiconductor films such as indium oxide with a film thickness of several thousand angstroms have been proposed, but not only would the film formation rate be significantly slow, but it would also consume a large amount of valuable resources such as indium. As a result, the manufacturing cost of the membrane increases significantly. Furthermore, this film does not have sufficiently high infrared reflectivity or conductivity. A typical structure of the above-mentioned transparent conductive film or selective light transmitting film is a laminate in which a metal thin film is sandwiched between transparent high refractive index thin films, such as Bi 2 O formed by vacuum evaporation, reactive evaporation, or sputtering. 3 ／Au／
Sandwich-like structured laminates of Bi 2 O 3 , ZnS/Ag/ZnS or TiO 2 /Ag/TiO 2 have been proposed.
Among these, those using Ag as a metal layer are preferred from the viewpoint of optical properties, and various methods have been proposed for laminating a silver thin film with a metal oxide such as titanium oxide. For example, U.S. Patent No. 3,962,488 discloses a method of forming a titanium oxide layer on a thin silver film while reacting titanium metal in an oxygen atmosphere, and A method is described in which titanium (TiO 2 ) is sputtered in an argon atmosphere to form a titanium oxide layer on a thin silver film. However, in the former method, since titanium metal is started and oxidized to titanium oxide during the process, the evaporation rate of titanium metal cannot be increased, and the evaporation rate must be set to about 6 Å/sec. TiO2 film cannot be obtained. In addition, although the latter method targets TiO 2 , first, the total pressure is 7 to 10×
First stage press sputtering for 15 minutes in an argon-oxygen mixed gas (oxygen 10% by volume) at 10 -3 Torr, followed by second stage press sputtering for 15 minutes in an argon gas atmosphere of 7 to 10 x 10 -3 Torr. This method employs a very complicated method of pre-sputtering the target, and then sputtering the surface-adjusted titanium oxide target in an argon gas atmosphere. Coupled with the very slow sputtering rate of 20 to 30 Å/min, the production rate is therefore extremely low. In view of this situation, the present inventors conducted intensive research on a method for manufacturing a transparent conductive (selective light transmitting) film at high speed while continuously winding a base film. The present invention was achieved by discovering that the above object can be achieved by forming a transparent high refractive index thin film layer (C) within 20 seconds by heating and evaporating it in plasma. That is, the present invention provides a transparent sheet-like substrate on which a metal thin film layer (B) mainly composed of silver is formed on at least one side.
When manufacturing a transparent conductive laminate by providing a transparent high refractive index thin film layer C containing a metal oxide as a main component on the metal thin film layer (B) of (A), the metal oxide is replaced with an oxygen-containing gas. This is a method for producing a transparent conductive laminate, which is characterized in that a transparent high refractive index thin film layer is formed within 20 seconds by heating and evaporating in plasma. Transparent sheet-like substrate used in the present invention
(A) is a transparent sheet-like substrate that is inorganic, organic, or a combination of both. Examples of inorganic sheet-like substrates include glass materials such as soda glass, borosilicate glass, and silicate glass; metal oxides such as alumina, magnesia, zirconia, and silica; compound semiconductors such as potassium-arsenic and indium-phosphorous; Examples include molded products made of semiconductors such as silicon and germanium. In addition, examples of the organic sheet-like substrate include thermoplastic resins such as polyethylene terephthalate resin, polyethylene naphthalate resin, ABS resin, polystyrene resin, polyacetal resin, polyethylene resin, polypropylene resin, polyamide resin, and fluororesin; For example, thermosetting resins such as epoxy resins, diallyl phthalate resins, silicone resins, unsaturated polyester resins, phenolic resins, and urea resins; and solvent-based resins such as polyvinyl alcohol, polyacrylonitrile, polyurethane, aromatic polyamides, and polyimide resins. Examples include molded products such as molten resin. These may be used alone or in combination, as a copolymer, or as a laminate. Furthermore, the inorganic/organic composite may be a mixture or a laminate. For example, the organic sheet-like substrate can be further provided with an organic or inorganic primer layer or a metal oxide thin film layer.
When providing a thin film layer of metal oxide, it is naturally advantageous to comply with the manufacturing conditions described below, which are the characteristics of the present invention. Therefore, the transparent sheet-like substrate (A) used in the present invention includes one in which a transparent high refractive index thin film layer (D) described below is provided on the sheet of the above-mentioned organic polymer compound. The metal thin film layer (B) mainly contains silver, and may contain other metals or metal compounds as long as the desired effects of the present invention are not impaired. for example,
Addition of 0.1 to 20% by weight of copper, preferably 0.3 to 10% by weight of silver, significantly improves the weather resistance of the resulting laminate, and addition of 3 to 30% by weight of gold improves heat resistance. Improved. The thickness of this metal thin film layer (B) is 50 to 350 Å, preferably 70 to 200 Å; if it is too thin, the conductivity, infrared reflectance and heat resistance will be too low, and if it is too thick, the visible light transmittance will be too low. is significantly reduced and cannot be put to practical use. The metal thin film layer (B) can be easily formed by vacuum evaporation or sputtering. Before forming the metal thin film layer (B), the substrate can be previously coated with a transparent high refractive index thin film layer (D) as described above. There is no particular limitation on the method of forming layer (D), and it is preferable to form it by an efficient method, but it may be the same as layer (C) described later. The thickness of layer (D) is 50 to 400 Å, preferably 100 to 300 Å.
It is Å. When the film thickness is within this range, the resulting laminate has excellent visible light transmittance, electrical conductivity, infrared reflectance, and heat resistance. The transparent high refractive index thin film layer (C) used in the method of the present invention is mainly composed of oxides such as titanium, bismuth, indium, tin, cerium, tantalum, tungsten, molybdenum, erbium, hafnium, zinc, yttrium, and zirconium. It is transparent to visible light and has a high refractive index in visible light, with a refractive index of 1.8.
The above value is particularly preferably 2.0 or more. Preferred metal oxides include titanium, zinc,
Mention may be made of oxides of indium, tin, yttrium, erbium, zirconium, hafnium and cerium. The transparent high refractive index thin film layer (C) can be formed by heating a metal oxide in an oxygen-containing gas plasma to evaporate it. When the metal oxide is heated in vacuum, it decomposes, and as the vapor deposition continues, the surface of the vapor deposition material is gradually reduced, and a reduced metal oxide layer is formed on the metal thin film layer (B). The reduced metal oxide layer absorbs visible light, reducing the transmittance and light resistance of the laminate. To prevent this, oxygen gas or a mixed gas of oxygen gas and an inert gas such as argon is introduced into the vacuum chamber, and after adjusting the degree of vacuum in the vacuum chamber to an appropriate value, oxygen is removed using high-frequency power. A method of generating a plasma containing a gas containing metal oxides and evaporating metal oxides in the plasma was investigated. Such a method is preferable as a method for improving the transparency of the metal oxide layer, but when laminated on the metal thin film layer (B), the metal thin film layer (B) is exposed to oxygen-containing gas plasma. It was found that the infrared reflectance and electrical conductivity deteriorated due to this. Therefore, as a result of intensive research, the inventors of the present invention found that if the formation rate of the metal oxide layer is increased, that is, the formation time is shortened, the time during which the metal thin film layer (B) is exposed to the high-frequency plasma of gas containing oxygen can be increased. It has been found that the metal thin film layer (B) does not deteriorate. The time for forming the metal oxide layer is preferably as short as possible, preferably 20 seconds or less, particularly preferably 10 seconds or less. The high-frequency plasma can be produced by, for example, sufficiently evacuating a vacuum chamber and adding a gas containing oxygen, preferably 10 mol% or more, particularly preferably 50 mol% or more, at 1 to 10 -4 to 1.times.
It can be generated by introducing 10 -3 Torr, installing a spiral antenna in the space between the substrate and the evaporation source, and applying 100 to 1000 W of 13.56 MHz high frequency power to this antenna. If the oxygen partial pressure is lower than 1×10 −5 Torr, a sufficiently transparent metal oxide layer cannot be obtained. Furthermore, if the oxygen partial pressure exceeds 1×10 -3 Torr, damage to the evaporation source, such as breakage of the filament of the electron gun, is likely to occur, which is undesirable. The thickness of the transparent high refractive index thin film layer (C) is 50 to 400 Å, preferably 100 to 300 Å. If the film thickness is outside this range, the visible light transmittance or heat resistance will be significantly reduced. In order to form a transparent high refractive index thin film layer (C) with such a film thickness within 20 seconds, the formation speed should be set to 20
Although it has to be at least Å/sec, this could only be achieved by heating the metal oxide in an oxygen-containing gas plasma to evaporate it, as in the present invention. When a metal oxide as an evaporation source is continuously evaporated for a long time, the amount of evaporation material decreases and the evaporation rate decreases, so it is preferable to continuously supply a constant amount. Other layers may be further laminated on the laminate of the present invention to the extent that the intended effects of the present invention are not impaired to improve properties such as surface hardness, weather resistance, and adhesion. Materials used to form such a layer include, for example, acrylic resins such as polymethyl methacrylate, silicone resins such as polymers obtained from ethyl silicate, organic polymers such as polyester resins, melamine resins, and fluorine resins. In addition to substances, inorganic substances such as silicon oxide and magnesium fluoride can be mentioned. In particular, when improving weather resistance or surface hardness, acrylic resins, silicone resins, etc. are preferably used. A laminate having transparent conductivity, which is one object of the present invention, has a visible light transmittance of 50% or more and a surface resistance of 10 3 Ω/□ or less. The method of the present invention is a highly productive method, and it is possible to use a polymer film with poor heat resistance as the substrate (A), and when laminating the film continuously, the film is laminated at a speed of 5 to 100 m/min. This is an industrially superior method that allows production while winding. In addition to the configurations described in the claims, the present invention also includes the following embodiments. (2) The method according to claim 1 (hereinafter simply referred to as paragraph 1), wherein the metal thin film layer (B) contains 0.1 to 20 wt% copper. (3) The method according to item 1 or 2, wherein the metal thin film layer (B) contains 3 to 30 wt% of gold. (4) The method according to item 1, wherein the metal thin film layer (B) has a thickness of 50 to 350 Å, preferably 70 to 200 Å. (5) The transparent high refractive index thin film layer (C) is made of titanium, zinc,
Indium, tin, yttrium, erbium,
A first comprising an oxide of one or more metals selected from zirconium, hafnium and cerium.
The method described in section. (6) The thickness of the transparent high refractive index thin film layer (C) is 50 to 400 mm.
The method according to item 1, which is . (7) The method according to item 1, wherein the transparent sheet-like substrate (A) is made of an organic polymer. (8) The thickness of the transparent sheet-like substrate (A) is 10 to 300 mm.
8. The method according to item 7, wherein the diameter is μm. (9) The method according to item 1, wherein the transparent sheet-like substrate (A) is a laminate consisting of a transparent sheet made of an organic polymer and a transparent high refractive index thin film layer (D) provided thereon. (10) The transparent high refractive index thin film layer (D) is made of titanium, zinc,
10. The method according to claim 9, comprising an oxide of one or more metals selected from indium, tin, yttrium, erbium, zirconium, hafnium, and cerium. (11) The thickness of the transparent high refractive index thin film layer (D) is 50 to 400 mm.
10. The method according to claim 9, wherein . (12) The total pressure of the plasma is 1×10 -4 ~1×
10 -3 Torr, oxygen pressure 1 x 10 -5 to 1 x 10 -3 Torr, the method according to item 1, which is generated by high frequency discharge of gas. Hereinafter, the present invention will be explained in more detail with reference to Examples. Examples 1 to 3 and Comparative Example 1 A titanium oxide layer was formed as follows. A film winding type vacuum evaporation apparatus as shown in FIG. 1 is used. The vacuum layer 1 is divided into a film winding chamber 2 and a vapor deposition chamber 3 by a partition plate 4, and the chambers are evacuated through separate exhaust ports 6 and 5, respectively. The partition plate 4 is not in contact with the cooling drum and is installed at a sufficient distance to allow the film to pass through freely, and is sufficient to maintain different degrees of vacuum between the winding chamber 2 and the vapor deposition chamber 3. has been adjusted. The film 16 is sent from the delivery roll 7 to the take-up roll 9 via the cooling drum 8. The winding chamber 2 is evacuated to 10 -4 Torr, and the vapor deposition chamber 3 is evacuated to 5 x 10.6 to 1 x 10 -5 Torr at the same time. Next, oxygen gas is introduced from the gas inlet 10, and the vapor deposition chamber 3 is evacuated to 1 x 10 -5 Torr. Adjust the flow rate of the oxidizing gas so that the degree of vacuum in step 3 is 1 to 7×10 -4 Torr. A wire-shaped electrode 12 is provided in the space between the evaporation source 11 and the cooling drum 8, and by supplying power to this from a high frequency power source 13 and adjusting a matching box 14, a discharge is sustained around the electrode. By heating the evaporation source 11 with an electron gun 15 or the like while feeding the film, a high refractive index thin film layer (C) is formed on the film surface. Film thickness is determined by evaporation rate and film feed rate. Titanium oxide was deposited to a thickness of 200 Å on one side of a 50 μm thick transparent polyester film using the apparatus described above. Vapor deposition was performed under the following conditions. Oxygen gas partial pressure 3×10 -4 Torr High frequency power (13.56MHz) 300W Evaporation source Titanium oxide (TiO 2 ) Electron beam output 3KW Film feed speed 12m/min (The obtained film is hereinafter referred to as film A.) Film A 150 Å of silver on the titanium oxide film of
Deposition was performed at a vacuum level of 3×10 −6 Torr. (Hereinafter, the obtained film will be referred to as film B.) Next, titanium oxide was coated on the silver film of film B at 300%
Å was deposited. The vapor deposition conditions are as follows. Oxygen partial pressure 3×10 -4 Torr High frequency power (13.56MHz) 300W Evaporation source Titanium oxide (TiO 5 ) However, the film feeding speed was varied from 0.9m/min to 8m/min as shown in Table 1. , and the output of the electron beam was adjusted so that the film thickness was the same. Table 1 shows the properties of the obtained film in which a thin film having a TiO 2 /Ag/TiO 2 structure was formed.
【表】
比較例 ２
実施例１で得たフイルムＢの銀膜上に酸化チタ
ンを高周波スパツタリング法で形成させた。スパ
ツタリングは以下の様にして行つた。
日本真空技術(株)製のプラナーマグネトロン方式
の低温スパツタリング装置を用いた。
フイルムＢの背面を水冷し、酸化チタン
（TiO2）ターゲツトを用いて10分間スパツタリン
グして酸化チタンを200Å形成させた。
スパツタリング条件は以下の通りである。
背圧 ３×10-6Torr
導入ガス Ar50％O250％
導入ガス圧 ５×10-3Torr
高周波電力 400W
得られたフイルムは、酸素を含むプラズマによ
つて銀膜が損傷しており、赤外線反射能および導
電性が著じるしく低下していた。
実施例４および比較例３
蒸発源として、酸化チタンを醸酸化インジウム
（In2O3）に置換え電子ビームの出力、高周波電
力、酸素分圧を調整する以外は同じにして、実施
例１を繰返した。
透明高屈折率薄膜層(D)として、ポリエステルフ
イルム上に、酸化インジウムを100Å蒸着した時
の電子ビームの出力は6KV―80mAであつた。
比較のため、透明高屈折率薄膜層(C)として酸化
イジウムを第２表に示した条件（酸素分圧、高周
波電力）で300Å蒸着した。
蒸着の安定性を調べるため、それぞれの条件で
６時間にわたつて蒸着した。
得られたフイルムの特性および、蒸着の安定性
を第２表にまとめて示した。[Table] Comparative Example 2 Titanium oxide was formed on the silver film of Film B obtained in Example 1 by high frequency sputtering. Sputtering was performed as follows. A planar magnetron type low temperature sputtering device manufactured by Japan Vacuum Technology Co., Ltd. was used. The back side of film B was cooled with water and sputtered using a titanium oxide (TiO 2 ) target for 10 minutes to form titanium oxide with a thickness of 200 Å. The sputtering conditions are as follows. Back pressure 3×10 -6 Torr Introduced gas Ar50%O 2 50% Introduced gas pressure 5×10 -3 Torr High frequency power 400W The obtained film has a silver film damaged by oxygen-containing plasma, and infrared rays Reflectivity and conductivity were significantly reduced. Example 4 and Comparative Example 3 Example 1 was repeated except for replacing titanium oxide with indium oxide (In 2 O 3 ) as the evaporation source and adjusting the electron beam output, high frequency power, and oxygen partial pressure. Ta. When indium oxide was evaporated to a thickness of 100 Å on a polyester film as a transparent high refractive index thin film layer (D), the electron beam output was 6 KV-80 mA. For comparison, 300 Å of idium oxide was deposited as a transparent high refractive index thin film layer (C) under the conditions (oxygen partial pressure, high frequency power) shown in Table 2. In order to examine the stability of vapor deposition, vapor deposition was carried out for 6 hours under each condition. The properties of the obtained film and the stability of vapor deposition are summarized in Table 2.
【表】【table】
【表】
実施例 ５〜14
蒸発源の酸化チタンを酸化錫（SnO2）、酸化セ
リウム（CeO2）、酸化タンタル（Ta2O5）、酸化
タングステン（WO3）、酸化亜鉛（ZnO）、酸化モ
リブデン（MoO3）、酸化エルビウム（Er2O3）、
酸化ジルコニウム（ZrO2）、酸化ハフニウム
（HfO2）および酸化イツトリウム（Y2O3）に置換
えて、実施例１を繰返した。この場合金属層は銀
90重量％、銅10重量％の合金をターゲツトにし、
直流スパツタリング法で形成させた。
形成した第１層〔透明高屈折率薄膜層(D)〕、第
２層〔金属薄膜層(B)〕、第３層〔透明高屈折率薄
膜層(C)〕の膜厚および得られた特性を第３表に示
す。[Table] Examples 5 to 14 Titanium oxide as an evaporation source was used as tin oxide (SnO 2 ), cerium oxide (CeO 2 ), tantalum oxide (Ta 2 O 5 ), tungsten oxide (WO 3 ), zinc oxide (ZnO), Molybdenum oxide (MoO 3 ), erbium oxide (Er 2 O 3 ),
Example 1 was repeated, substituting zirconium oxide (ZrO 2 ), hafnium oxide (HfO 2 ) and yttrium oxide (Y 2 O 3 ). In this case the metal layer is silver
Targeting an alloy of 90% by weight and 10% by weight of copper,
It was formed by direct current sputtering method. The film thicknesses of the formed first layer [transparent high refractive index thin film layer (D)], second layer [metal thin film layer (B)], and third layer [transparent high refractive index thin film layer (C)] and the obtained The characteristics are shown in Table 3.
【表】【table】
図面は本発明を実施する装置の一例を示す概念
図である。図中、各番号は以下のことを示す。
１：真空槽、２：フイルム巻取室、３：蒸着
室、４：仕切り板、５，６：排気口、７，９：ロ
ール、８：冷却ドラム、１０：ガス導入口、１
１：蒸発源、１２：電極、１３：高周波電源、１
４：マツチングボツクス、１５：電子銃、１６：
フイルム、１７：電子銃電源。
The drawing is a conceptual diagram showing an example of an apparatus for implementing the present invention. In the figure, each number indicates the following. 1: Vacuum chamber, 2: Film winding chamber, 3: Vapor deposition chamber, 4: Partition plate, 5, 6: Exhaust port, 7, 9: Roll, 8: Cooling drum, 10: Gas inlet, 1
1: Evaporation source, 12: Electrode, 13: High frequency power supply, 1
4: Matching box, 15: Electron gun, 16:
Film, 17: Electron gun power supply.
Claims (1)
片面に設けられた透明なシート状基板(A)の当該金
属薄膜層(B)上に金属酸化物を主成分とする透明高
屈折率薄膜層(C)を設けて透明導電性積層体を製造
する際に、当該透明高屈折率薄膜層(C)を、酸素を
含む気体のプラズマ中で金属酸化物を加熱して蒸
発せしめて20秒以内で当該透明高屈折率薄膜層(C)
を形成させることを特徴とする透明導電性積層体
の製造方法。1. A transparent sheet-like substrate (A) having a metal thin film layer (B) mainly composed of silver on at least one side, and a transparent high refractive index film mainly composed of a metal oxide on the metal thin film layer (B). When producing a transparent conductive laminate by providing a thin film layer (C), the transparent high refractive index thin film layer (C) is heated and evaporated by heating a metal oxide in an oxygen-containing gas plasma. The transparent high refractive index thin film layer (C) within seconds
A method for producing a transparent conductive laminate, the method comprising: forming a transparent conductive laminate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6898180A JPS56164850A (en) | 1980-05-26 | 1980-05-26 | Manufacture of transparent conductive laminate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6898180A JPS56164850A (en) | 1980-05-26 | 1980-05-26 | Manufacture of transparent conductive laminate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56164850A JPS56164850A (en) | 1981-12-18 |
| JPS6238432B2 true JPS6238432B2 (en) | 1987-08-18 |
Family
ID=13389344
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6898180A Granted JPS56164850A (en) | 1980-05-26 | 1980-05-26 | Manufacture of transparent conductive laminate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56164850A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6468403B1 (en) | 1993-07-28 | 2002-10-22 | Asahi Glass Company Ltd. | Methods for producing functional films |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58206008A (en) * | 1982-05-26 | 1983-12-01 | コニカ株式会社 | Method of forming transparent conductive laminate |
| US4565719A (en) * | 1982-10-08 | 1986-01-21 | Optical Coating Laboratory, Inc. | Energy control window film systems and methods for manufacturing the same |
| KR101968215B1 (en) * | 2015-03-16 | 2019-04-11 | 주식회사 엘지화학 | Conductive structure body and electronic device comprising the same |
-
1980
- 1980-05-26 JP JP6898180A patent/JPS56164850A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6468403B1 (en) | 1993-07-28 | 2002-10-22 | Asahi Glass Company Ltd. | Methods for producing functional films |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56164850A (en) | 1981-12-18 |
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