JP2004111152A - Transparent conductive film - Google Patents
Transparent conductive film Download PDFInfo
- Publication number
- JP2004111152A JP2004111152A JP2002270383A JP2002270383A JP2004111152A JP 2004111152 A JP2004111152 A JP 2004111152A JP 2002270383 A JP2002270383 A JP 2002270383A JP 2002270383 A JP2002270383 A JP 2002270383A JP 2004111152 A JP2004111152 A JP 2004111152A
- Authority
- JP
- Japan
- Prior art keywords
- transparent conductive
- conductive film
- aliphatic
- polyimide
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010408 film Substances 0.000 claims abstract description 47
- 229920001721 polyimide Polymers 0.000 claims abstract description 43
- 239000004642 Polyimide Substances 0.000 claims abstract description 30
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 239000010409 thin film Substances 0.000 claims abstract description 14
- 230000004888 barrier function Effects 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 5
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000009477 glass transition Effects 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 239000004020 conductor Substances 0.000 claims description 3
- 238000010030 laminating Methods 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 abstract description 9
- 238000004544 sputter deposition Methods 0.000 abstract description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 abstract description 6
- 150000004984 aromatic diamines Chemical class 0.000 abstract description 6
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 6
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 abstract description 5
- 229910003437 indium oxide Inorganic materials 0.000 abstract description 4
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 4
- 150000004706 metal oxides Chemical class 0.000 abstract description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001887 tin oxide Inorganic materials 0.000 abstract description 4
- 239000000470 constituent Substances 0.000 abstract description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 abstract description 3
- 239000011787 zinc oxide Substances 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 2
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000151 deposition Methods 0.000 abstract 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 abstract 1
- -1 Polyethylene terephthalate Polymers 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 150000004985 diamines Chemical class 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- LJMPOXUWPWEILS-UHFFFAOYSA-N 3a,4,4a,7a,8,8a-hexahydrofuro[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1C2C(=O)OC(=O)C2CC2C(=O)OC(=O)C21 LJMPOXUWPWEILS-UHFFFAOYSA-N 0.000 description 7
- 229920005575 poly(amic acid) Polymers 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000009719 polyimide resin Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- KRPRVQWGKLEFKN-UHFFFAOYSA-N 3-(3-aminopropoxy)propan-1-amine Chemical compound NCCCOCCCN KRPRVQWGKLEFKN-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZPAKUZKMGJJMAA-UHFFFAOYSA-N Cyclohexane-1,2,4,5-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)CC1C(O)=O ZPAKUZKMGJJMAA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000007733 ion plating Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- FHBXQJDYHHJCIF-UHFFFAOYSA-N (2,3-diaminophenyl)-phenylmethanone Chemical compound NC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1N FHBXQJDYHHJCIF-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- VQZRLBWPEHFGCD-UHFFFAOYSA-N 3-chloro-4-methylphenol Chemical compound CC1=CC=C(O)C=C1Cl VQZRLBWPEHFGCD-UHFFFAOYSA-N 0.000 description 1
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- ZYEDGEXYGKWJPB-UHFFFAOYSA-N 4-[2-(4-aminophenyl)propan-2-yl]aniline Chemical compound C=1C=C(N)C=CC=1C(C)(C)C1=CC=C(N)C=C1 ZYEDGEXYGKWJPB-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- YGYCECQIOXZODZ-UHFFFAOYSA-N 4415-87-6 Chemical compound O=C1OC(=O)C2C1C1C(=O)OC(=O)C12 YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 1
- 229920002799 BoPET Polymers 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XZAHJRZBUWYCBM-UHFFFAOYSA-N [1-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1(CN)CCCCC1 XZAHJRZBUWYCBM-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- OXIKYYJDTWKERT-UHFFFAOYSA-N [4-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCC(CN)CC1 OXIKYYJDTWKERT-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- XMSVKICKONKVNM-UHFFFAOYSA-N bicyclo[2.2.1]heptane-3,4-diamine Chemical compound C1CC2(N)C(N)CC1C2 XMSVKICKONKVNM-UHFFFAOYSA-N 0.000 description 1
- BKDVBBSUAGJUBA-UHFFFAOYSA-N bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid Chemical compound C1=CC2C(C(O)=O)C(C(=O)O)C1C(C(O)=O)C2C(O)=O BKDVBBSUAGJUBA-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- PQRHREUWMOAJOW-UHFFFAOYSA-N ctk1a6096 Chemical class N[SiH](N)[SiH3] PQRHREUWMOAJOW-UHFFFAOYSA-N 0.000 description 1
- RZIPTXDCNDIINL-UHFFFAOYSA-N cyclohexane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCCC1(C(O)=O)C(O)=O RZIPTXDCNDIINL-UHFFFAOYSA-N 0.000 description 1
- AVKNGPAMCBSNSO-UHFFFAOYSA-N cyclohexylmethanamine Chemical compound NCC1CCCCC1 AVKNGPAMCBSNSO-UHFFFAOYSA-N 0.000 description 1
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 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
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- KQSABULTKYLFEV-UHFFFAOYSA-N naphthalene-1,5-diamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1N KQSABULTKYLFEV-UHFFFAOYSA-N 0.000 description 1
- GOGZBMRXLADNEV-UHFFFAOYSA-N naphthalene-2,6-diamine Chemical compound C1=C(N)C=CC2=CC(N)=CC=C21 GOGZBMRXLADNEV-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 239000012808 vapor phase Substances 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
- H10K77/10—Substrates, e.g. flexible substrates
- H10K77/111—Flexible substrates
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/805—Electrodes
- H10K59/8051—Anodes
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/87—Passivation; Containers; Encapsulations
- H10K59/873—Encapsulations
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Liquid Crystal (AREA)
- Electroluminescent Light Sources (AREA)
- Laminated Bodies (AREA)
- Non-Insulated Conductors (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は透明性および耐熱性が良好なポリイミドを用いた透明導電性フィルムに関するものであり、液晶表示素子、有機ＥＬ表示素子の透明基板やタッチパネルの透明電極などの電子・光デバイスに利用される。
【０００２】
【従来の技術】
透明な高分子フィルム上に酸化スズ、酸化インジウム、インジウム−スズ複合酸化物、酸化亜鉛などの透明な導電性薄膜を形成した透明導電性フィルムは、液晶表示素子、有機ＥＬ表示素子やタッチパネルの透明電極などの電子・光デバイスに広く利用されている。
【０００３】
基材になる透明な高分子フィルムとしては、ポリエチレンテレフタレートやポリカーボネート等が使用されている（例えば、特許文献１参照。）が、これらのフィルムは耐熱性が不充分で、透明導電性薄膜を製膜するプロセスの温度を低く保つ必要があり、そのために透明導電膜の結晶化度が低く、表面抵抗値が高くなるという欠点がある。また、耐熱性の高いプラスチック基板の構成材料として、ポリアリレート樹脂やポリエーテルスルホン樹脂等も一部使用されている（例えば、特許文献２参照。）が、透明導電性薄膜を２００℃以上の高温で製膜する場合や透明導電性フィルム上にさらに薄膜トランジスタ（ＴＦＴ）形成を行う場合には、このレベルの耐熱性でも不充分である。
【０００４】
【特許文献１】特開平０６−２５１６３１号公報（第２−３頁）
【特許文献２】特開平０６−０４４８２６号公報（第２−３頁）
【０００５】
一方、耐熱性や寸法安定性に優れる樹脂としてポリイミド樹脂が知られている。芳香族テトラカルボン酸二無水物と芳香族ジアミン類との重縮合反応により得られる全芳香族ポリイミド樹脂は４００℃以上の高温で使用可能、、熱膨張係数が小さく、寸法安定性が良い等の優れた特性を有し、高温化で使用するフィルム、電線被覆、接着剤、塗料等の原料として、航空宇宙産業、電子産業を中心に様々な分野で利用されている。しかし、この様な全芳香族ポリイミド樹脂は、淡黄色から赤褐色に着色している為に、透明導電性フィルムの基材には不向きである。
【０００６】
【発明が解決しようとする課題】
本発明の課題は、上述の従来用いられてきた透明導電性フィルムの有する問題点を解決し、透明性、耐熱性に優れ、表面抵抗値が低い透明導電性フィルムを提供することにある。
【０００７】
【課題を解決するための手段】
本発明者らは上記の課題を解決するため鋭意検討し、本発明に到達した。 すなわち本発明は、下記の一般式Ｉで示される繰り返し単位を有する脂肪族ポリイミドからなる基板上に透明導電性薄膜が積層された透明導電性フィルムに関する。
【０００８】
【化２】
２〜３９の２価の脂肪族基または芳香族基である）
【０００９】
さらにまた本発明は、一般式Ｉで示される繰り返し単位を有する脂肪族ポリイミドからなる基板上に少なくとも１層の酸化ケイ素および／または窒化ケイ素からなるガスバリア層と透明導電性薄膜とが積層された透明導電性フィルムに関する。
【００１０】
【発明の実施の形態】
本発明に用いられる一般式Ｉの脂肪族ポリイミドは、４価の脂肪族テトラカルボン酸と２価のジアミンとを構成成分とするポリイミドであり、脂肪族テトラカルボン酸またはその誘導体とジアミンまたはその誘導体とを反応させることにより得られる。脂肪族テトラカルボン酸またはその誘導体としては、脂肪族テトラカルボン酸、脂肪族テトラカルボン酸エステル類、脂肪族テトラカルボン酸二無水物などが挙げられるが、好ましいのは脂肪族テトラカルボン酸二無水物である。ジアミンおよびその誘導体としては、ジアミン、ジイソシアネート、ジアミノジシラン類などが上げられるが、好ましいのはジアミンである。
【００１１】
本発明の脂肪族ポリイミドの合成に用いられる脂肪族テトラカルボン酸二無水物としては、１，２，３，４−シクロブタンテトラカルボン酸二無水物、１，２，４，５−シクロペンタンテトラカルボン酸二無水物、１，２，４，５−シクロヘキサンテトラカルボン酸二無水物、ビシクロ［２，２，２］オクト−７−エン−２，３，５，６−テトラカルボン酸二無水物などが例示されるが、特に好ましいのは１，２，４，５−シクロヘキサンテトラカルボン酸二無水物である。
【００１２】
一般に、脂肪族ジアミンを構成成分とするポリイミドは、中間生成物であるポリアミド酸とジアミンが強固な錯体を形成するために高分子化しにくいので、錯体の溶解性が比較的高い溶剤−例えばクレゾール−を用いるなどの工夫が必要になる。しかし、１，２，４，５−シクロへキサンテトラカルボン酸二無水物と脂肪族ジアミンを構成成分とするポリイミドでは、ポリアミド酸とジアミンの錯体は比較的弱い結合で結ばれているので、高分子量化容易で、フレキシブルなフィルムが得られ易い。
【００１３】
本発明の脂肪族ポリイミドの合成に用いられるジアミンは、脂肪族ジアミンであっても芳香族ジアミンであってもよく、それらの混合物でもよいが、特に好ましいのは脂肪族ジアミンである。脂肪族ジアミンに芳香族ジアミンを併用する場合、脂肪族ジアミンに対する芳香族ジアミンの重量比率が大きくなるほど全光線透過率は小さくなるので、混合重量比率は３：１以下が好ましい。
【００１４】
本発明の脂肪族ポリイミドの合成に用いられる脂肪族ジアミンとしては、例えば、エチレンジアミン、ヘキサメチレンジアミン、ポリエチレングリコールビス（３−アミノプロピル）エーテル、ポリプロピレングリコールビス（３−アミノプロピル）エーテル、１，３−ビス（アミノメチル）シクロヘキサン、１，４−ビス（アミノメチル）シクロヘキサン、メタキシリレンジアミン、パラキシリレンジアミン、イソフォロンジアミン、ノルボルナンジアミン、シロキサンジアミン類などが挙げられる。
【００１５】
さらに、本発明の脂肪族ポリイミドの合成に用いられる芳香族ジアミンとしては、例えば、４，４’−ジアミノジフェニルエーテル、４，４’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルスルホン、２，２−ビス（４−アミノフェニル）プロパン、メタフェニレンジアミン、パラフェニレンジアミン、ジアミノベンゾフェノン、２，６−ジアミノナフタレン、１，５−ジアミノナフタレンなどが挙げられる。
【００１６】
本発明に用いられるポリイミド樹脂を製造するに当たっては、例えば、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルスルホキシド、ヘキサメチルホスホルアミド、テトラメチレンスルホン、Ｐ−クロルフェノール、ｍ−クレゾール、２−クロル−４−ヒドロキシトルエンなどの溶剤が用いられる。
【００１７】
本発明に用いられるポリイミドフィルムは、ジアミンの溶液に酸二無水物を添加、あるいは酸二無水物の溶液にジアミンを添加し、好ましくは８０℃以下、特に室温付近ないしそれ以下の温度に保ってポリアミド酸溶液を得た後、その溶液をガラス板、金属板などの基板上に塗布し、２００℃〜３５０℃に加熱して脱水反応を行うことにより製造される。また、下記の（１）から（３）の方法でポリイミド溶液を直接調整した後、その溶液をガラス板、金属板などの基板上に塗布し、２００℃〜３５０℃に加熱して溶剤を蒸発させることにより製造される。
【００１８】
（１）反応中間体のポリアミド酸溶液にトルエンあるいはキシレンなどの共沸脱水溶剤を添加して、生成水を共沸により系外へ除きつつ脱水反応を行い、ポリイミド溶液を得る。
（２）反応中間体のポリアミド酸溶液に無水酢酸などの脱水剤を用いてイミド化させた後、メタノールなどのポリイミドの溶解性が乏しい溶剤を添加して、ポリイミドを沈殿させ、ろ過・洗浄・乾燥により固体として分離し、Ｎ，Ｎ−ジメチルアセトアミドなどの溶剤に溶解させたポリイミド溶液を得る。イミドカに際しては、触媒としてトリエチルアミン、ピリジンあるいはβ―ピコリンなどの３級アミンを併用することが出来る。
（３）クレゾールなどの高沸点溶剤を用いてポリアミド酸溶液を調整し、そのまま１５０℃以上に保ってポリイミド化させた後、メタノールなどのポリイミドの溶解性が乏しい溶剤を添加して、ポリイミドを沈殿させ、ろ過・洗浄・乾燥により固体として分離し、Ｎ，Ｎ−ジメチルアセトアミドなどの溶剤に溶解させたポリイミド溶液を得る。
【００１９】
透明性フィルムを有機ＥＬ素子や液晶表示素子などのディスプレーの基板に用いる場合、低屈折率が求められる。屈折率が大きいと反射率が大きくなり、表示能力が著しく低下する。本発明に用いられるポリイミドフィルムは、脂肪族の酸二無水物を用いることにより、屈折率＜１．６１が達成され、ディスプレーのプラスチック基板として好適に使用される。
【００２０】
本発明における透明導電性薄膜層としては、公知の金属酸化物膜等が適用できる。例えば、不純物としてスズ、テルル、カドミウム、モリブテン、タングステン、フッ素、亜鉛、ゲルマニウム等を添加した酸化インジウム、酸化カドミウム及び酸化スズ、不純物としてアルミニウムを添加した酸化亜鉛、酸化チタン等の金属酸化物膜が挙げられる。中でも酸化スズを２〜１５重量％含有した酸化インジウム（ＩＴＯ）の薄膜が、透明性、導電性が優れており、好ましく用いられる。上記透明導電性薄膜層の膜厚は目的の表面抵抗に応じて設定されるが、５ｎｍ〜１０ｎｍが好ましい。
【００２１】
これらの透明導電性薄膜層をポリイミドフィルム上に直接またはバリア層を介して積層する場合、スパッタ法、真空蒸着法、イオンプレーティング法、プラズマＣＶＤ法等の気相中より材料を堆積させて膜形成する気相堆積法が適用される。透明導電性薄膜層の比抵抗を１ｍΩ・ｃｍ以下にするためには、製膜時の基材温度を２５０℃から３５０℃とする必要があるために、ポリイミド基材のガラス転移温度は２５０℃以上が好ましい。
【００２２】
本発明の透明導電性フィルムを有機ＥＬ素子や液晶表示素子用の電極基板として用いる場合は、ポリイミドフィルム上に少なくとも一層のガスバリヤー層を積層することが好ましい。ガスバリヤー層としては、珪素、アルミニウム、マグネシウムおよび亜鉛からなる群から選ばれる１種または２種以上の金属を主成分とする金属酸化物または金属窒化物を挙げることができる。これらは、ガスバリヤー性に優れている材料として知られているものである。これら酸化物の層は例えばスパッタ法、真空蒸着法、イオンプレーティング法、プラズマＣＶＤ法等の気相中より材料を堆積させて膜形成する気相堆積法により作製することができる。なお、ガスバリヤー層および透明導電性薄膜層等を形成する際に、亀裂や剥離の発生を防ぐためには、ポリイミド基材のガラス転移温度よりも低い温度における線膨張係数が、４５ｐｐｍ／℃以下であることが好ましい。
【００２３】
【実施例】
以下、実施例により本発明を具体的に説明する。但し、本発明はこれらの実施例により何ら制限されるものではない。
【００２４】
参考例
１，２，４，５−シクロヘキサンテトラカルボン酸二無水物の合成
内容積５リットルのハステロイ製（ＨＣ２２）オートクレーブにピロメリット酸５５２ｇ、活性炭にＲｈを担持させた触媒（エヌ・イーケムキャット（株）製）２００ｇ、水１６５６ｇを仕込み、攪拌をしながら反応器内を窒素ガスで置換した。次に水素ガスで反応器内を置換し、反応器の水素圧を５．０ＭＰａとして６０℃まで昇温した。水素圧を５．０ＭＰａに保ちながら２時間反応させた。反応器内の水素ガスを窒素ガスで置換し、反応液をオートクレーブより抜き出し、この反応液を熱時濾過して触媒を分離した。濾過液をロータリーエバポレーターで減圧下に水を飛ばして濃縮し、結晶を析出させた。析出した結晶を室温で固液分離し、乾燥して１，２，４，５−シクロヘキサンテトラカルボン酸４８１ｇ（収率８５．０％）を得た。
【００２５】
続いて、得られた１，２，４，５−シクロヘキサンテトラカルボン酸４５０ｇと無水酢酸４０００ｇとを、５リットルのガラス製セパラブルフラスコ（ジムロート冷却管付）にを仕込み、攪拌をしながら反応器内を窒素ガスで置換した。窒素ガス雰囲気下に溶媒の還流温度まで昇温し、１０分間溶媒を還流させた。攪拌しながら室温まで冷却し、結晶を析出させた。析出した結晶を固液分離し、乾燥して一次結晶を得た。更に分離母液をロータリーエバポレーターで減圧下に濃縮し、結晶を析出させた。この結晶を固液分離し、乾燥して二次結晶を得た。一次結晶、二次結晶を合わせて１，２，４，５−シクロヘキサンテトラカルボン酸二無水物３７５ｇが得られた（無水化の収率９６．６％）。
【００２６】
実施例１
温度計、撹拌器、窒素導入環、側管付き滴下ロート、分縮器付き冷却管を備えた５００ｍＬ５つ口フラスコに、参考例で合成した１，２，４，５−シクロヘキサンテトラカルボン酸二無水物１１．２ｇ（０．０５モル）と溶剤としてＮ−メチル−２−ピロリドン３７．７ｇを仕込んで溶解させ、氷水バスを用いて５℃に冷却した。同温度に保ちながら、４、４‘−ジアミノジフェニルエーテル１０．０ｇ（０．０５モル）を４０．０ｇのＮ−メチル−２−ピロリドンに溶解させた溶液を滴下ロートより３０分かけて滴下し、滴下終了後氷水バスを外して室温下２時間撹拌した。次に共沸脱水溶剤としてキシレン３０．０ｇを添加して１７０℃に昇温し、留出液を留去させながら、４時間かけて２００℃まで昇温て反応終了とし、内温が６０℃になるまで空冷して反応液を取り出した。この溶液の重量は８７．９ｇ、また留出液総重量は３７．７ｇであった。得られた溶液をガラス板に塗布し、５０℃のホットプレート上で１時間乾燥後、ガラス板から剥がして自立膜を得、ステンレス製の固定治具に固定して熱風乾燥器中２００℃で１時間乾燥させ、薄茶色のフレキシブルな膜厚１００μｍのフィルムを得た。このフィルムのＩＲスペクトルを図１に示す。ν（Ｃ＝Ｏ）１７７２、１７００（ｃｍ−１）よりイミドの生成が確認された。さらにこのフィルム０．５ｇを濃硫酸１０ｍｌに溶解させて３０℃の温度条件で測定した固有粘度ηは、０．５８、ＤＳＣで測定したガラス転移温度は３１５℃であった。
【００２７】
得られれたポリイミドフィルム上に、スパッタ法にて厚さ５００ｎｍの酸化ケイ素層を、さらにその上に１００ｎｍの酸化インジウム・スズ（ＩＴＯ，Ｉｎ：Ｓｎ＝９：１）を積層して、透明導電性フィルムを得た。
【００２８】
実施例２
実施例１と同じ５００ｍｌの５つ口のフラスコに、参考例で合成した１，２，４，５−シクロヘキサンテトラカルボン酸二無水物（１１．２ｇ（０．０５モル）と１，４−ビス（アミノメチル）シクロヘキサン７．１ｇ（０．０５モル）および溶剤としてｍ−クレゾールを６０ｇ仕込んで溶解させて１００℃に昇温した。同温度で４時間撹拌した後、さらに約２００℃に昇温して、還流下４時間反応を行い、反応終了とした。反応液を室温まで冷却した後、１０００ｍｌのメタノールに注ぎ入れてポリマーを沈殿させ、ろ過、メタノール洗浄を行った後、１００℃の乾燥機中２４時間乾燥させ、白色粉末９．５８ｇ（収率９６．８％）を得た。この粉末のＩＲスペクトルを図２に示す。ν（Ｃ＝Ｏ）１７６８、１６９５（ｃｍ−１）よりイミドの生成が確認された。さらにこの粉末０．５ｇを濃硫酸１０ｍｌに溶解させて３０℃の温度条件で測定した固有粘度ηは、０．４４、ＤＳＣで測定したガラス転移温度は２５６℃であり、ジメチルホルムアミドあるいはＮ−メチル−２−ピロリドンに可溶であることが確認された。
【００２９】
得られたポリイミド粉末５ｇを２５ｇのＮ−メチル−２−ピロリドンに溶解させた溶液をガラス板に塗布し、８０℃のホットプレート上で１時間乾燥後、ガラス板から剥がして自立膜を得、ステンレス製の固定治具に固定して熱風乾燥器中２００℃で１時間乾燥させ、無色透明でフレキシブルな膜厚１００μｍのフィルムを得た。得られたポリイミドフィルム上に、スパッタ法にて厚さ５００ｎｍの酸化ケイ素層を、さらにその上に１００ｎｍの酸化インジウム・スズ（ＩＴＯ，Ｉｎ：Ｓｎ＝９：１）を積層して、透明導電性フィルムを得た。
【００３０】
比較例１
実施例１と同じ５００ｍｌの５つ口のフラスコに、４、４‘−ジアミノジフェニルエーテル１０．０ｇ（０．０５モル）と溶剤としてジメチルアセトアミド３７．７ｇを仕込んで溶解させ、窒素気流下室温にてピロメリット酸二無水物１０．９ｇ（０．０５モル）を固体のまま約１時間かけて添加し、添加終了後室温下３時間撹拌し、ポリアミド酸溶液を得た。得られた溶液をガラス板に塗布し、５０℃のホットプレート上で１時間乾燥後、ガラス板から剥がして自立膜を得、ステンレス製の固定治具に固定して熱風乾燥機中、１００℃で３時間、２００℃で３時間、２５０℃で２時間、３００℃で１時間、さらに４００℃で１時間の乾燥を行い、褐色でフレキシブルな膜厚１００μｍのフィルムを得た。得られたポリイミドフィルム上に、スパッタ法にて１００ｎｍの酸化インジウム・スズ（ＩＴＯ，Ｉｎ：Ｓｎ＝９：１）を積層して、透明導電性フィルムを得た。
【００３１】
比較例２
１００μｍのＰＥＴフィルム（東レ（株）：ルミラー＃１００）上に、スパッタ法にて１００ｎｍの酸化インジウム・スズ（ＩＴＯ，Ｉｎ：Ｓｎ＝９：１）を積層して、透明導電性フィルムを得た。
【００３２】
実施例および比較例で得られたポリイミドフィルムおよび透明導電性フィルムの評価は以下のように行った。
＜ガラス転移温度＞島津製作所製示差走査熱量計装置（ＤＳＣ−５０）を用い、昇温速度１０℃／ｍｉｎの条件でＤＳＣ測定を行い、ガラス転移温度を求めた。
＜屈折率＞（株）アタゴ製屈折率測定装置（ＤＲ−Ｍ２）を用い、５８９ｎｍの干渉フィルターをセットして、２３℃で屈折率を測定した。
＜線膨張係数＞セイコー電子工業（株）製熱機械的分析装置（ＴＭＡ１００）を用いて、昇温速度１０℃／ｍｉｎの条件で測定を行い、１００℃〜２００℃の平均値を求めた。
＜全光線透過率＞ＪＩＳ Ｋ７１０５に準拠し、全光線透過率をヘイズメーター（日本電色（株）製、Ｚ−Σ８０）を用いて測定した。
＜表面抵抗率＞ＪＩＳ Ｋ７１９４に準拠し、４端子法で表面抵抗率を測定した。測定機は三菱油化（株）製、Ｌｏｔｅｓｔ ＡＭＣＰ−Ｔ４００を使用した。
＜酸素透過率＞ＪＩＳ Ｋ７１２６に準拠し、酸素透過率測定装置（モダンコントロール社製、ＯＸ−ＴＲＡＮ１０／５０Ａ）を用いてフィルムの酸素透過率を２３℃、相対湿度６０％の条件下で測定した。
＜水蒸気透過率＞ＪＩＳ Ｚ０２０８に準拠し、フィルムの水蒸気透過率を４０℃、相対湿度９０％の条件下で水蒸気透過率を測定した。
【００３３】
【表１】
ＣＴＤＡ：シクロヘキサンテトラカルボン酸二無水物
ＰＭＤＡ：ピロメリット酸二無水物
ＯＤＡ：オキシジアニリン
ＢＡＣ：ビス（アミノメチル）シクロヘキサン
【００３５】
【発明の効果】
本発明により得られる透明導電性フィルムは、透明性および耐熱性が良好で、表面抵抗が低く、液晶表示素子、有機ＥＬ表示素子の透明基板やタッチパネルの透明電極などの電子・光デバイスに利用される。
【図面の簡単な説明】
【図１】実施例１で得られたポリイミドフィルムの赤外吸収スペクトル
【図２】実施例２で得られたポリイミド粉末の赤外吸収スペクトル[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a transparent conductive film using polyimide having good transparency and heat resistance, and is used for electronic and optical devices such as liquid crystal display elements, transparent substrates of organic EL display elements, and transparent electrodes of touch panels. .
[0002]
[Prior art]
A transparent conductive film in which a transparent conductive thin film such as tin oxide, indium oxide, indium-tin composite oxide, and zinc oxide is formed on a transparent polymer film is a liquid crystal display element, an organic EL display element, and a touch panel. Widely used in electronic and optical devices such as electrodes.
[0003]
Polyethylene terephthalate, polycarbonate, or the like is used as a transparent polymer film as a base material (see, for example, Patent Document 1), but these films are insufficient in heat resistance, and a transparent conductive thin film is produced. It is necessary to keep the temperature of the film forming process low, and there are disadvantages that the crystallinity of the transparent conductive film is low and the surface resistance value is high. In addition, polyarylate resin, polyethersulfone resin, and the like are partially used as a constituent material of a plastic substrate having high heat resistance (see, for example, Patent Document 2). This level of heat resistance is inadequate when the film is formed by the above method or when a thin film transistor (TFT) is further formed on the transparent conductive film.
[0004]
[Patent Document 1] Japanese Patent Application Laid-Open No. 06-251631 (page 2-3)
[Patent Document 2] Japanese Patent Application Laid-Open No. 06-044826 (page 2-3)
[0005]
On the other hand, a polyimide resin is known as a resin excellent in heat resistance and dimensional stability. The wholly aromatic polyimide resin obtained by polycondensation reaction of aromatic tetracarboxylic dianhydride and aromatic diamines can be used at a high temperature of 400 ° C. or higher, has a low thermal expansion coefficient, good dimensional stability, etc. It has excellent characteristics and is used in various fields, mainly in the aerospace industry and the electronics industry, as raw materials for films, wire coatings, adhesives, paints, etc. used at high temperatures. However, such a wholly aromatic polyimide resin is colored from light yellow to reddish brown, and thus is not suitable for a substrate of a transparent conductive film.
[0006]
[Problems to be solved by the invention]
The subject of this invention is providing the transparent conductive film which is excellent in transparency and heat resistance, and has a low surface resistance value, solving the problem which the above-mentioned transparent conductive film used conventionally.
[0007]
[Means for Solving the Problems]
The inventors of the present invention have intensively studied to solve the above problems, and have reached the present invention. That is, the present invention relates to a transparent conductive film in which a transparent conductive thin film is laminated on a substrate made of an aliphatic polyimide having a repeating unit represented by the following general formula I.
[0008]
[Chemical formula 2]
[0009]
Furthermore, the present invention provides a transparent laminate in which at least one gas barrier layer made of silicon oxide and / or silicon nitride and a transparent conductive thin film are laminated on a substrate made of an aliphatic polyimide having a repeating unit represented by the general formula I. The present invention relates to a conductive film.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
The aliphatic polyimide of the general formula I used in the present invention is a polyimide composed of a tetravalent aliphatic tetracarboxylic acid and a divalent diamine, and includes an aliphatic tetracarboxylic acid or a derivative thereof and a diamine or a derivative thereof. It is obtained by reacting. Aliphatic tetracarboxylic acids or derivatives thereof include aliphatic tetracarboxylic acids, aliphatic tetracarboxylic acid esters, aliphatic tetracarboxylic dianhydrides, etc., preferably aliphatic tetracarboxylic dianhydrides. It is. Examples of diamines and derivatives thereof include diamines, diisocyanates, and diaminodisilanes, with diamines being preferred.
[0011]
Examples of the aliphatic tetracarboxylic dianhydride used for the synthesis of the aliphatic polyimide of the present invention include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,2,4,5-cyclopentanetetracarboxylic. Acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, bicyclo [2,2,2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, etc. Are particularly preferred, but 1,2,4,5-cyclohexanetetracarboxylic dianhydride is particularly preferred.
[0012]
Generally, a polyimide having an aliphatic diamine as a constituent component is difficult to be polymerized because a polyamic acid, which is an intermediate product, and a diamine form a strong complex, so that a solvent having a relatively high solubility of the complex, such as cresol, is used. It is necessary to devise such as using. However, in polyimides composed of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and aliphatic diamine, the complex of polyamic acid and diamine is bound by a relatively weak bond. It is easy to obtain a molecular weight and a flexible film is easily obtained.
[0013]
The diamine used for the synthesis of the aliphatic polyimide of the present invention may be an aliphatic diamine or an aromatic diamine, or a mixture thereof, but an aliphatic diamine is particularly preferable. When the aromatic diamine is used in combination with the aliphatic diamine, the total light transmittance decreases as the weight ratio of the aromatic diamine to the aliphatic diamine increases, so that the mixing weight ratio is preferably 3: 1 or less.
[0014]
Examples of the aliphatic diamine used in the synthesis of the aliphatic polyimide of the present invention include ethylene diamine, hexamethylene diamine, polyethylene glycol bis (3-aminopropyl) ether, polypropylene glycol bis (3-aminopropyl) ether, 1,3. -Bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, metaxylylenediamine, paraxylylenediamine, isophorone diamine, norbornane diamine, siloxane diamines and the like.
[0015]
Furthermore, examples of the aromatic diamine used for the synthesis of the aliphatic polyimide of the present invention include 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, and 2,2- Bis (4-aminophenyl) propane, metaphenylenediamine, paraphenylenediamine, diaminobenzophenone, 2,6-diaminonaphthalene, 1,5-diaminonaphthalene and the like can be mentioned.
[0016]
In producing the polyimide resin used in the present invention, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, hexamethylphosphoramide, tetramethylene sulfone, Solvents such as P-chlorophenol, m-cresol, and 2-chloro-4-hydroxytoluene are used.
[0017]
The polyimide film used in the present invention is prepared by adding acid dianhydride to a diamine solution, or adding diamine to an acid dianhydride solution, preferably at a temperature of 80 ° C. or less, particularly near room temperature or lower. After the polyamic acid solution is obtained, the solution is applied on a substrate such as a glass plate or a metal plate and heated to 200 ° C. to 350 ° C. to perform a dehydration reaction. In addition, after directly adjusting the polyimide solution by the following methods (1) to (3), the solution is applied onto a substrate such as a glass plate or a metal plate, and heated to 200 ° C. to 350 ° C. to evaporate the solvent. Manufactured.
[0018]
(1) An azeotropic dehydration solvent such as toluene or xylene is added to the polyamic acid solution of the reaction intermediate, and a dehydration reaction is performed while removing generated water out of the system by azeotropy to obtain a polyimide solution.
(2) After imidizing the polyamic acid solution of the reaction intermediate with a dehydrating agent such as acetic anhydride, a solvent having poor solubility of polyimide such as methanol is added to precipitate the polyimide, followed by filtration, washing, A polyimide solution which is separated as a solid by drying and dissolved in a solvent such as N, N-dimethylacetamide is obtained. In the case of imidoca, a tertiary amine such as triethylamine, pyridine or β-picoline can be used in combination as a catalyst.
(3) Prepare a polyamic acid solution using a high-boiling solvent such as cresol, and keep it at 150 ° C. or higher to make a polyimide, and then add a solvent having poor polyimide solubility such as methanol to precipitate the polyimide. Then, it is separated as a solid by filtration, washing and drying to obtain a polyimide solution dissolved in a solvent such as N, N-dimethylacetamide.
[0019]
When a transparent film is used for a display substrate such as an organic EL element or a liquid crystal display element, a low refractive index is required. When the refractive index is large, the reflectance is increased and the display capability is remarkably deteriorated. The polyimide film used in the present invention achieves a refractive index <1.61 by using an aliphatic acid dianhydride, and is suitably used as a plastic substrate for display.
[0020]
As the transparent conductive thin film layer in the present invention, a known metal oxide film or the like can be applied. For example, metal oxide films such as indium oxide, cadmium oxide and tin oxide to which tin, tellurium, cadmium, molybdenum, tungsten, fluorine, zinc, germanium and the like are added as impurities, zinc oxide and titanium oxide to which aluminum is added as impurities, Can be mentioned. Among them, an indium oxide (ITO) thin film containing 2 to 15% by weight of tin oxide is excellent in transparency and conductivity, and is preferably used. Although the film thickness of the said transparent conductive thin film layer is set according to the target surface resistance, 5-10 nm is preferable.
[0021]
When laminating these transparent conductive thin film layers directly on a polyimide film or through a barrier layer, the material is deposited from the gas phase such as sputtering, vacuum deposition, ion plating, plasma CVD, etc. The vapor deposition method to be formed is applied. In order to reduce the specific resistance of the transparent conductive thin film layer to 1 mΩ · cm or less, it is necessary to set the substrate temperature during film formation to 250 ° C. to 350 ° C. Therefore, the glass transition temperature of the polyimide substrate is 250 ° C. The above is preferable.
[0022]
When the transparent conductive film of the present invention is used as an electrode substrate for an organic EL device or a liquid crystal display device, it is preferable to laminate at least one gas barrier layer on the polyimide film. Examples of the gas barrier layer include metal oxides or metal nitrides mainly composed of one or more metals selected from the group consisting of silicon, aluminum, magnesium, and zinc. These are known as materials having excellent gas barrier properties. These oxide layers can be manufactured by vapor deposition such as sputtering, vacuum deposition, ion plating, plasma CVD, or the like, in which a material is deposited in a vapor phase to form a film. In order to prevent the occurrence of cracks and peeling when forming a gas barrier layer, a transparent conductive thin film layer, etc., the linear expansion coefficient at a temperature lower than the glass transition temperature of the polyimide substrate is 45 ppm / ° C. or less. Preferably there is.
[0023]
【Example】
Hereinafter, the present invention will be described specifically by way of examples. However, this invention is not restrict | limited at all by these Examples.
[0024]
Reference Example 1,2,4,5-Cyclohexanetetracarboxylic dianhydride synthesis A catalyst (N-Echemcat) in which 552 g of pyromellitic acid and Rh are supported on activated carbon in a 5-liter Hastelloy (HC22) autoclave having an internal volume of 5 liters 200 g and 1656 g of water were charged, and the inside of the reactor was replaced with nitrogen gas while stirring. Next, the inside of the reactor was replaced with hydrogen gas, and the temperature of the reactor was increased to 60 ° C. with a hydrogen pressure of 5.0 MPa. The reaction was carried out for 2 hours while maintaining the hydrogen pressure at 5.0 MPa. The hydrogen gas in the reactor was replaced with nitrogen gas, the reaction solution was extracted from the autoclave, and the reaction solution was filtered while hot to separate the catalyst. The filtrate was concentrated by removing water with a rotary evaporator under reduced pressure to precipitate crystals. The precipitated crystals were separated into solid and liquid at room temperature and dried to obtain 481, g (yield: 85.0%) of 1,2,4,5-cyclohexanetetracarboxylic acid.
[0025]
Subsequently, 450 g of the obtained 1,2,4,5-cyclohexanetetracarboxylic acid and 4000 g of acetic anhydride were charged into a 5 liter glass separable flask (with Dimroth condenser), and the reactor was stirred. The inside was replaced with nitrogen gas. The temperature was raised to the reflux temperature of the solvent under a nitrogen gas atmosphere, and the solvent was refluxed for 10 minutes. While stirring, the mixture was cooled to room temperature to precipitate crystals. The precipitated crystals were separated into solid and liquid and dried to obtain primary crystals. Further, the separated mother liquor was concentrated under reduced pressure using a rotary evaporator to precipitate crystals. The crystals were separated into solid and liquid and dried to obtain secondary crystals. The primary crystal and the secondary crystal were combined to obtain 375 g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (anhydrous yield of 96.6%).
[0026]
Example 1
1,2,4,5-Cyclohexanetetracarboxylic dianhydride synthesized in Reference Example in a 500 mL five-necked flask equipped with a thermometer, stirrer, nitrogen introduction ring, dropping funnel with side tube and condenser tube with a condenser 11.2 g (0.05 mol) of the product and 37.7 g of N-methyl-2-pyrrolidone as a solvent were charged and dissolved, and cooled to 5 ° C. using an ice water bath. While maintaining the same temperature, a solution prepared by dissolving 10.0 g (0.05 mol) of 4,4′-diaminodiphenyl ether in 40.0 g of N-methyl-2-pyrrolidone was dropped from the dropping funnel over 30 minutes, After completion of dropping, the ice water bath was removed and the mixture was stirred at room temperature for 2 hours. Next, 30.0 g of xylene was added as an azeotropic dehydration solvent, the temperature was raised to 170 ° C., and the reaction was completed by raising the temperature to 200 ° C. over 4 hours while distilling off the distillate. The reaction solution was taken out by air cooling until. The weight of this solution was 87.9 g, and the total weight of the distillate was 37.7 g. The obtained solution was applied to a glass plate, dried on a hot plate at 50 ° C. for 1 hour, then peeled off from the glass plate to obtain a self-supporting film, fixed on a stainless steel fixing jig, and heated in a hot air dryer at 200 ° C. It was dried for 1 hour to obtain a light brown flexible film having a thickness of 100 μm. The IR spectrum of this film is shown in FIG. The production | generation of imide was confirmed from (nu) (C = O) 1772, 1700 (cm < -1 >). Furthermore, 0.5 g of this film was dissolved in 10 ml of concentrated sulfuric acid, the intrinsic viscosity η measured under the temperature condition of 30 ° C. was 0.58, and the glass transition temperature measured by DSC was 315 ° C.
[0027]
On the obtained polyimide film, a silicon oxide layer having a thickness of 500 nm is laminated by sputtering, and further 100 nm of indium tin oxide (ITO, In: Sn = 9: 1) is laminated thereon to obtain a transparent conductive material. A film was obtained.
[0028]
Example 2
Into the same 500 ml five-necked flask as in Example 1, 1,2,4,5-cyclohexanetetracarboxylic dianhydride (11.2 g (0.05 mol) and 1,4-bis) synthesized in Reference Example were added. 7.1 g (0.05 mol) of (aminomethyl) cyclohexane and 60 g of m-cresol as a solvent were added and dissolved, and the temperature was raised to 100 ° C. After stirring at the same temperature for 4 hours, the temperature was further raised to about 200 ° C. After the reaction was completed for 4 hours under reflux, the reaction was completed, and the reaction solution was cooled to room temperature, poured into 1000 ml of methanol to precipitate a polymer, filtered, washed with methanol, and dried at 100 ° C. After drying in the machine for 24 hours, 9.58 g (yield 96.8%) of a white powder was obtained, and the IR spectrum of this powder is shown in Fig. 2. From ν (C = O) 1768 and 1695 (cm -1 ). Imi Furthermore, 0.5 g of this powder was dissolved in 10 ml of concentrated sulfuric acid and the intrinsic viscosity η measured at 30 ° C. was 0.44, and the glass transition temperature measured by DSC was 256 ° C. It was confirmed that it was soluble in dimethylformamide or N-methyl-2-pyrrolidone.
[0029]
A solution obtained by dissolving 5 g of the obtained polyimide powder in 25 g of N-methyl-2-pyrrolidone was applied to a glass plate, dried on an 80 ° C. hot plate for 1 hour, and then peeled off from the glass plate to obtain a self-supporting film. The film was fixed on a stainless steel fixing jig and dried at 200 ° C. for 1 hour in a hot air dryer to obtain a colorless, transparent and flexible film with a thickness of 100 μm. On the obtained polyimide film, a silicon oxide layer having a thickness of 500 nm is laminated by sputtering, and further 100 nm of indium tin oxide (ITO, In: Sn = 9: 1) is laminated thereon to obtain a transparent conductive material. A film was obtained.
[0030]
Comparative Example 1
In the same 500 ml five-necked flask as in Example 1, 10.0 g (0.05 mol) of 4,4′-diaminodiphenyl ether and 37.7 g of dimethylacetamide as a solvent were dissolved and dissolved at room temperature under a nitrogen stream. 10.9 g (0.05 mol) of pyromellitic dianhydride was added as a solid over about 1 hour, and after completion of the addition, the mixture was stirred at room temperature for 3 hours to obtain a polyamic acid solution. The obtained solution was applied to a glass plate, dried on a hot plate at 50 ° C. for 1 hour, then peeled off from the glass plate to obtain a self-supporting film, fixed on a stainless steel fixing jig, and heated in a hot air dryer at 100 ° C. For 3 hours, 200 ° C. for 3 hours, 250 ° C. for 2 hours, 300 ° C. for 1 hour, and further 400 ° C. for 1 hour to obtain a brown and flexible film having a thickness of 100 μm. On the obtained polyimide film, 100 nm of indium tin oxide (ITO, In: Sn = 9: 1) was laminated by sputtering to obtain a transparent conductive film.
[0031]
Comparative Example 2
On a 100 μm PET film (Toray Industries, Inc .: Lumirror # 100), 100 nm indium tin oxide (ITO, In: Sn = 9: 1) was laminated by sputtering to obtain a transparent conductive film. .
[0032]
The polyimide films and transparent conductive films obtained in Examples and Comparative Examples were evaluated as follows.
<Glass Transition Temperature> Using a differential scanning calorimeter device (DSC-50) manufactured by Shimadzu Corporation, DSC measurement was performed under a temperature rising rate of 10 ° C./min to obtain a glass transition temperature.
<Refractive Index> Using Atago Co., Ltd. refractive index measuring device (DR-M2), an interference filter of 589 nm was set, and the refractive index was measured at 23 ° C.
<Linear expansion coefficient> Using a thermomechanical analyzer (TMA100) manufactured by Seiko Electronic Industry Co., Ltd., measurement was performed under the condition of a temperature rising rate of 10 ° C / min, and an average value of 100 ° C to 200 ° C was obtained.
<Total light transmittance> Based on JIS K7105, the total light transmittance was measured using a haze meter (Nippon Denshoku Co., Ltd. product, Z-Σ80).
<Surface resistivity> The surface resistivity was measured by a four-terminal method in accordance with JIS K7194. The measuring machine used was Lotest AMCP-T400 manufactured by Mitsubishi Yuka Co., Ltd.
<Oxygen permeability> Based on JIS K7126, the oxygen permeability of the film was measured under the conditions of 23 ° C. and 60% relative humidity using an oxygen permeability measuring device (Modern Control, OX-TRAN10 / 50A). .
<Water vapor transmission rate> Based on JIS Z0208, the water vapor transmission rate of the film was measured under the conditions of 40 ° C. and relative humidity of 90%.
[0033]
[Table 1]
CTDA: cyclohexanetetracarboxylic dianhydride PMDA: pyromellitic dianhydride ODA: oxydianiline BAC: bis (aminomethyl) cyclohexane
【The invention's effect】
The transparent conductive film obtained by the present invention has good transparency and heat resistance, low surface resistance, and is used in electronic and optical devices such as liquid crystal display elements, transparent substrates of organic EL display elements and transparent electrodes of touch panels. The
[Brief description of the drawings]
1 is an infrared absorption spectrum of the polyimide film obtained in Example 1. FIG. 2 is an infrared absorption spectrum of the polyimide powder obtained in Example 2.
Claims (7)
２〜３９の２価の脂肪族基または芳香族基である）A transparent conductive film in which a transparent conductive thin film is laminated on a substrate made of an aliphatic polyimide having a repeating unit represented by the following general formula I.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002270383A JP4247448B2 (en) | 2002-09-17 | 2002-09-17 | Transparent conductive film |
| US10/284,370 US6962756B2 (en) | 2001-11-02 | 2002-10-31 | Transparent electrically-conductive film and its use |
| CNB021483000A CN1285080C (en) | 2001-11-02 | 2002-11-01 | Transparent conducting film and its use |
| TW91132409A TWI282560B (en) | 2001-11-02 | 2002-11-01 | Transparent electrically-conductive film and its use |
| KR1020020067475A KR100952588B1 (en) | 2001-11-02 | 2002-11-01 | Transparent electrically-conductive film and its use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002270383A JP4247448B2 (en) | 2002-09-17 | 2002-09-17 | Transparent conductive film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004111152A true JP2004111152A (en) | 2004-04-08 |
| JP4247448B2 JP4247448B2 (en) | 2009-04-02 |
Family
ID=32268033
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002270383A Expired - Lifetime JP4247448B2 (en) | 2001-11-02 | 2002-09-17 | Transparent conductive film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4247448B2 (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005085541A (en) * | 2003-09-05 | 2005-03-31 | Jsr Corp | Manufacturing method of transparent conductive layered product and touch panel |
| JP2005338394A (en) * | 2004-05-26 | 2005-12-08 | Mitsubishi Gas Chem Co Inc | Color filter substrate |
| JP2006083209A (en) * | 2004-09-14 | 2006-03-30 | Fuji Photo Film Co Ltd | Optical film and image display device |
| WO2006112286A1 (en) * | 2005-04-14 | 2006-10-26 | Mitsubishi Gas Chemical Company, Inc. | Process for producing polyimide film |
| KR100717375B1 (en) | 2005-07-04 | 2007-05-10 | 부산대학교 산학협력단 | Fully Aliphatic Polyimide with Enhanced Flexibility and Optical Transparency |
| WO2013021942A1 (en) | 2011-08-08 | 2013-02-14 | Ｊｘ日鉱日石エネルギー株式会社 | Transparent film, transparent conductive laminate, and touch panel, solar cell and display device, using same |
| JP5224011B2 (en) * | 2011-04-15 | 2013-07-03 | 東洋紡株式会社 | LAMINATE, MANUFACTURING METHOD THEREOF, AND DEVICE STRUCTURE MANUFACTURING METHOD USING THE SAME |
| WO2013114685A1 (en) * | 2012-02-01 | 2013-08-08 | 東洋紡株式会社 | Laminate, method for producing same, and method for producing device structure using same |
| US9456495B2 (en) | 2012-09-26 | 2016-09-27 | Jx Nippon Oil & Energy Corporation | Norbornane-2-spiro-α-cycloalkanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloalkanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic acid and ester thereof, method for producing norbornane-2-spiro-α-cycloalkanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride, polyimide obtained by using the same, and method for producing polyimide |
| JP2016186936A (en) * | 2016-05-30 | 2016-10-27 | 新日鉄住金化学株式会社 | Method for producing transparent conductive film |
| JP2017073348A (en) * | 2015-10-09 | 2017-04-13 | 新日鉄住金マテリアルズ株式会社 | Metal laminate substrate for organic el element and manufacturing method for the same |
| KR20200098641A (en) | 2017-12-20 | 2020-08-20 | 스미또모 가가꾸 가부시키가이샤 | Transparent film substrate for touch sensor panel and touch sensor panel using the same |
| KR20210146921A (en) | 2019-03-27 | 2021-12-06 | 가부시키가이샤 오사카소다 | Polyamic acid composition, polyimide composition, and polyimide molded article |
| WO2023199718A1 (en) * | 2022-04-15 | 2023-10-19 | 三菱瓦斯化学株式会社 | Copolyimide |
-
2002
- 2002-09-17 JP JP2002270383A patent/JP4247448B2/en not_active Expired - Lifetime
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005085541A (en) * | 2003-09-05 | 2005-03-31 | Jsr Corp | Manufacturing method of transparent conductive layered product and touch panel |
| JP2005338394A (en) * | 2004-05-26 | 2005-12-08 | Mitsubishi Gas Chem Co Inc | Color filter substrate |
| JP4525903B2 (en) * | 2004-05-26 | 2010-08-18 | 三菱瓦斯化学株式会社 | Color filter substrate |
| JP2006083209A (en) * | 2004-09-14 | 2006-03-30 | Fuji Photo Film Co Ltd | Optical film and image display device |
| JP4490217B2 (en) * | 2004-09-14 | 2010-06-23 | 富士フイルム株式会社 | Optical film and image display device |
| WO2006112286A1 (en) * | 2005-04-14 | 2006-10-26 | Mitsubishi Gas Chemical Company, Inc. | Process for producing polyimide film |
| JPWO2006112286A1 (en) * | 2005-04-14 | 2008-12-11 | 三菱瓦斯化学株式会社 | Method for producing polyimide film |
| US7871554B2 (en) | 2005-04-14 | 2011-01-18 | Mitsubishi Gas Chemical Company, Inc. | Process for producing polyimide film |
| JP4826583B2 (en) * | 2005-04-14 | 2011-11-30 | 三菱瓦斯化学株式会社 | Method for producing polyimide film |
| KR100717375B1 (en) | 2005-07-04 | 2007-05-10 | 부산대학교 산학협력단 | Fully Aliphatic Polyimide with Enhanced Flexibility and Optical Transparency |
| JP5224011B2 (en) * | 2011-04-15 | 2013-07-03 | 東洋紡株式会社 | LAMINATE, MANUFACTURING METHOD THEREOF, AND DEVICE STRUCTURE MANUFACTURING METHOD USING THE SAME |
| WO2013021942A1 (en) | 2011-08-08 | 2013-02-14 | Ｊｘ日鉱日石エネルギー株式会社 | Transparent film, transparent conductive laminate, and touch panel, solar cell and display device, using same |
| US9768328B2 (en) | 2011-08-08 | 2017-09-19 | Jx Nippon Oil & Energy Corporation | Transparent film, transparent electro-conductive laminate, and touch panel, solar cell, and display device using the same |
| WO2013114685A1 (en) * | 2012-02-01 | 2013-08-08 | 東洋紡株式会社 | Laminate, method for producing same, and method for producing device structure using same |
| US9456495B2 (en) | 2012-09-26 | 2016-09-27 | Jx Nippon Oil & Energy Corporation | Norbornane-2-spiro-α-cycloalkanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride, norbornane-2-spiro-α-cycloalkanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic acid and ester thereof, method for producing norbornane-2-spiro-α-cycloalkanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride, polyimide obtained by using the same, and method for producing polyimide |
| JP2017073348A (en) * | 2015-10-09 | 2017-04-13 | 新日鉄住金マテリアルズ株式会社 | Metal laminate substrate for organic el element and manufacturing method for the same |
| JP2016186936A (en) * | 2016-05-30 | 2016-10-27 | 新日鉄住金化学株式会社 | Method for producing transparent conductive film |
| KR20200098641A (en) | 2017-12-20 | 2020-08-20 | 스미또모 가가꾸 가부시키가이샤 | Transparent film substrate for touch sensor panel and touch sensor panel using the same |
| KR20210146921A (en) | 2019-03-27 | 2021-12-06 | 가부시키가이샤 오사카소다 | Polyamic acid composition, polyimide composition, and polyimide molded article |
| WO2023199718A1 (en) * | 2022-04-15 | 2023-10-19 | 三菱瓦斯化学株式会社 | Copolyimide |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4247448B2 (en) | 2009-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6962756B2 (en) | Transparent electrically-conductive film and its use | |
| JP6721070B2 (en) | Polyimide precursor composition, method for producing polyimide, polyimide, polyimide film, and substrate | |
| KR101238967B1 (en) | Process for producing polyimide film | |
| JP2003141936A (en) | Transparent conductive film | |
| US9073297B2 (en) | Method for manufacturing transparent, heat-resistant gas-barrier film | |
| JP4247448B2 (en) | Transparent conductive film | |
| WO2016063993A1 (en) | Polyimide film, polyimide precursor, and polyimide | |
| WO2015053312A1 (en) | Polyimide precursor, polyimide, polyimide film, varnish, and substrate | |
| WO2016063988A1 (en) | Polyimide precursor, polyimide, and polyimide film | |
| JP2003168800A (en) | Thin film transistor substrate | |
| WO2006022207A1 (en) | Metal-clad white laminate | |
| CN111363354A (en) | Polyimide colorless transparent film, preparation method thereof and optical PI film | |
| JP2009286854A (en) | Polyesterimide precursor and polyesterimide | |
| JP2008101187A (en) | Polyesterimide and method for producing the same | |
| KR20060049446A (en) | Color filter substrate | |
| JP5124921B2 (en) | Metal-clad white laminate | |
| JP6687442B2 (en) | Utilization of polyamic acid, polyimide, polyamic acid solution, and polyimide | |
| JP2009286853A (en) | Polyesterimide precursor and polyesterimide | |
| JP2007314443A (en) | Ester group-containing tetracarboxylic acid compound, polyesterimide precursror, polyesterimide, and method for producing them | |
| CN113348200A (en) | Method for producing polyimide resin powder | |
| WO2022071443A1 (en) | Polyamidimide copolymer and film which uses same | |
| WO2024122599A1 (en) | Multilayer body | |
| JP2021178881A (en) | Polyamide acid, polyamide acid solution, polyimide, polyimide film, laminate and flexible device, and method for producing polyimide film | |
| KR20230092934A (en) | Polyamic acid, polyamic acid solution, polyimide, polyimide film, laminate, electronic device, and method for producing polyimide film | |
| CN115216005A (en) | Polyamic acid, polyimide, assembly containing polyamic acid and polyimide and forming method of assembly |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20050901 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20070604 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080625 |
|
| A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20080801 |
|
| A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20080806 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20080807 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080918 |
|
| TRDD | Decision of grant or rejection written | ||
| A072 | Dismissal of procedure [no reply to invitation to correct request for examination] |
Free format text: JAPANESE INTERMEDIATE CODE: A073 Effective date: 20081202 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20081210 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20081223 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120123 Year of fee payment: 3 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 4247448 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120123 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120123 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130123 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140123 Year of fee payment: 5 |
|
| EXPY | Cancellation because of completion of term |