JP2016193512A - Metal substrate - Google Patents
Metal substrate Download PDFInfo
- Publication number
- JP2016193512A JP2016193512A JP2015073897A JP2015073897A JP2016193512A JP 2016193512 A JP2016193512 A JP 2016193512A JP 2015073897 A JP2015073897 A JP 2015073897A JP 2015073897 A JP2015073897 A JP 2015073897A JP 2016193512 A JP2016193512 A JP 2016193512A
- Authority
- JP
- Japan
- Prior art keywords
- metal substrate
- resin
- film
- organic
- metal
- 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.)
- Ceased
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 158
- 239000002184 metal Substances 0.000 title claims abstract description 158
- 239000000758 substrate Substances 0.000 title claims abstract description 153
- 239000010408 film Substances 0.000 claims abstract description 110
- 229920005989 resin Polymers 0.000 claims abstract description 102
- 239000011347 resin Substances 0.000 claims abstract description 102
- 239000010409 thin film Substances 0.000 claims abstract description 39
- 230000003746 surface roughness Effects 0.000 claims abstract description 24
- 239000000049 pigment Substances 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 19
- 229920001225 polyester resin Polymers 0.000 claims description 14
- 239000004645 polyester resin Substances 0.000 claims description 13
- 230000009477 glass transition Effects 0.000 claims description 3
- 238000000576 coating method Methods 0.000 abstract description 15
- 239000011248 coating agent Substances 0.000 abstract description 11
- 238000009413 insulation Methods 0.000 abstract description 11
- 239000010410 layer Substances 0.000 description 62
- 238000005498 polishing Methods 0.000 description 44
- 239000000203 mixture Substances 0.000 description 31
- 238000000034 method Methods 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- 239000003973 paint Substances 0.000 description 17
- 239000000126 substance Substances 0.000 description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 16
- 229920001187 thermosetting polymer Polymers 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- -1 aluminum phosphate salt compound Chemical class 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 239000001023 inorganic pigment Substances 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000001771 vacuum deposition Methods 0.000 description 5
- 229920000877 Melamine resin Polymers 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical class CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000012860 organic pigment Substances 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000004640 Melamine resin Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- 150000007519 polyprotic acids Polymers 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 206010027146 Melanoderma Diseases 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical class O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 150000003931 anilides Chemical class 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- VPUGDVKSAQVFFS-UHFFFAOYSA-N coronene Chemical compound C1=C(C2=C34)C=CC3=CC=C(C=C3)C4=C4C3=CC=C(C=C3)C4=C2C3=C1 VPUGDVKSAQVFFS-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
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- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- UWRZIZXBOLBCON-VOTSOKGWSA-N (e)-2-phenylethenamine Chemical class N\C=C\C1=CC=CC=C1 UWRZIZXBOLBCON-VOTSOKGWSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- KLCLIOISYBHYDZ-UHFFFAOYSA-N 1,4,4-triphenylbuta-1,3-dienylbenzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)=CC=C(C=1C=CC=CC=1)C1=CC=CC=C1 KLCLIOISYBHYDZ-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
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- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
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- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- WEELZNKFYGCZKL-UHFFFAOYSA-N 4-(4-phenylphenyl)-n,n-bis[4-(4-phenylphenyl)phenyl]aniline Chemical compound C1=CC=CC=C1C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC(=CC=2)C=2C=CC(=CC=2)C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)C=2C=CC=CC=2)C=C1 WEELZNKFYGCZKL-UHFFFAOYSA-N 0.000 description 1
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- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
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- 229910000799 K alloy Inorganic materials 0.000 description 1
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- XBDYBAVJXHJMNQ-UHFFFAOYSA-N Tetrahydroanthracene Natural products C1=CC=C2C=C(CCCC3)C3=CC2=C1 XBDYBAVJXHJMNQ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229910007567 Zn-Ni Inorganic materials 0.000 description 1
- 229910007614 Zn—Ni Inorganic materials 0.000 description 1
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- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
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- 150000001414 amino alcohols Chemical class 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
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- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
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- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical compound C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 description 1
- IZJDCINIYIMFGX-UHFFFAOYSA-N benzo[f][2]benzofuran-1,3-dione Chemical compound C1=CC=C2C=C3C(=O)OC(=O)C3=CC2=C1 IZJDCINIYIMFGX-UHFFFAOYSA-N 0.000 description 1
- WZJYKHNJTSNBHV-UHFFFAOYSA-N benzoquinoline Natural products C1=CN=C2C3=CC=CC=C3C=CC2=C1 WZJYKHNJTSNBHV-UHFFFAOYSA-N 0.000 description 1
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- 229910052796 boron Inorganic materials 0.000 description 1
- NNBFNNNWANBMTI-UHFFFAOYSA-M brilliant green Chemical compound OS([O-])(=O)=O.C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 NNBFNNNWANBMTI-UHFFFAOYSA-M 0.000 description 1
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- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
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- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical group [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 description 1
- XBZSBBLNHFMTEB-UHFFFAOYSA-N cyclohexane-1,3-dicarboxylic acid Chemical compound OC(=O)C1CCCC(C(O)=O)C1 XBZSBBLNHFMTEB-UHFFFAOYSA-N 0.000 description 1
- WZWSOGGTVQXXSN-UHFFFAOYSA-N cyclohexanone;toluene Chemical compound CC1=CC=CC=C1.O=C1CCCCC1 WZWSOGGTVQXXSN-UHFFFAOYSA-N 0.000 description 1
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- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
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- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011254 layer-forming composition Substances 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- PGYPOBZJRVSMDS-UHFFFAOYSA-N loperamide hydrochloride Chemical compound Cl.C=1C=CC=CC=1C(C=1C=CC=CC=1)(C(=O)N(C)C)CCN(CC1)CCC1(O)C1=CC=C(Cl)C=C1 PGYPOBZJRVSMDS-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- KHARCSTZAGNHOT-UHFFFAOYSA-N naphthalene-2,3-dicarboxylic acid Chemical compound C1=CC=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 KHARCSTZAGNHOT-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- 229910001000 nickel titanium Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- URLKBWYHVLBVBO-UHFFFAOYSA-N p-dimethylbenzene Natural products CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- YYMBJDOZVAITBP-UHFFFAOYSA-N rubrene Chemical compound C1=CC=CC=C1C(C1=C(C=2C=CC=CC=2)C2=CC=CC=C2C(C=2C=CC=CC=2)=C11)=C(C=CC=C2)C2=C1C1=CC=CC=C1 YYMBJDOZVAITBP-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000005394 sealing glass Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
- 229920005792 styrene-acrylic resin Polymers 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- IFLREYGFSNHWGE-UHFFFAOYSA-N tetracene Chemical compound C1=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C21 IFLREYGFSNHWGE-UHFFFAOYSA-N 0.000 description 1
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000001947 vapour-phase growth Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/842—Containers
- H10K50/8423—Metallic sealing arrangements
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/02—Details
- H05B33/04—Sealing arrangements, e.g. against humidity
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
- H10K30/80—Constructional details
- H10K30/81—Electrodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
-
- 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
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- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Optics & Photonics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Computer Hardware Design (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
- Photovoltaic Devices (AREA)
- Laminated Bodies (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
Abstract
Description
本発明は、サブストレート型薄膜太陽電池又はトップエミッション型有機ＥＬ素子に用いられる金属基板であって、太陽電池又は有機ＥＬ素子としたときに、絶縁性に優れ、かつ、ダークスポットが発生しない太陽電池又は有機ＥＬ素子となる金属基板に関するものである。 The present invention is a metal substrate used for a substrate type thin film solar cell or a top emission type organic EL element, and when used as a solar cell or an organic EL element, the solar cell is excellent in insulation and does not generate a dark spot. The present invention relates to a metal substrate to be a battery or an organic EL element.
アモルファスシリコンや、ＣｄＳ・ＣｕＩｎＳｅ2等の化合物半導体を用いた、いわゆる薄膜半導体太陽電池（以下、薄膜太陽電池という。）として、スーパーストレート型薄膜太陽電池とサブストレート型薄膜太陽電池の２種類の構造が知られている。 Or amorphous silicon, using a compound semiconductor such as CdS · CuInSe 2, so-called thin film semiconductor solar cell as a (hereinafter, referred to. Thin-film solar cells), 2 types of structures of a superstrate type thin film solar cell and a substrate type thin film solar cell It has been known.
スーパーストレート型薄膜太陽電池では、通常、基板、透明電極、光電変換層、裏面電極の順に積層された構造であり、基板側から光を入射させている。一方、サブストレート型薄膜太陽電池では、通常、基板、裏面電極、光電変換層、透明電極の順に積層された構造であり、透明電極側から光を入射させている。 In a super straight type thin film solar cell, it is the structure laminated | stacked in order of the board | substrate, the transparent electrode, the photoelectric converting layer, and the back electrode normally, and the light is entered from the board | substrate side. On the other hand, a substrate-type thin film solar cell usually has a structure in which a substrate, a back electrode, a photoelectric conversion layer, and a transparent electrode are laminated in this order, and light is incident from the transparent electrode side.
従来、薄膜太陽電池の基板として、透光性のガラスやプラスチック等が用いられてきた。しかし、ガラスは、割れやすい上に加工性に乏しく、重くてコストが高い等の問題があり、また、プラスチックは透湿性があるため、ガスバリア層を設ける必要があり、コストが割高になってしまうことに加え、熱を加えずに加工することは難しい。 Conventionally, translucent glass, plastic, or the like has been used as a substrate for a thin film solar cell. However, glass is easy to break and has problems such as poor workability, heavy and high cost, and plastic is moisture permeable, so it is necessary to provide a gas barrier layer, which increases the cost. In addition, it is difficult to process without applying heat.
ところで、サブストレート型薄膜太陽電池は透明電極側から光を入射させているため、サブストレート型薄膜太陽電池の基板には透光性が求められない。そのため、ガラスやプラスチックのような基板ではなく、金属板のような透光性を有さないが加工性に優れた基板を用いることができる。ただし、薄膜太陽電池として機能するためには、基板の表面が平滑であり、かつこの表面が絶縁性を有する必要があるが、金属板自身の表面は通常８００ｎｍ〜１μｍ程度以上の凹凸を有し、また導電性があるため、そのままでは基板として用いることができない。そこで、上記の条件を満たすように金属板上に平滑な樹脂皮膜を形成すれば、金属板を基板として用いることができるようになると考えられる。 By the way, since the substrate type thin film solar cell makes light incident from the transparent electrode side, the substrate of the substrate type thin film solar cell is not required to have translucency. Therefore, it is not possible to use a substrate such as glass or plastic but a substrate that does not have translucency such as a metal plate but has excellent workability. However, in order to function as a thin film solar cell, the surface of the substrate must be smooth and the surface needs to have insulating properties, but the surface of the metal plate itself usually has irregularities of about 800 nm to 1 μm or more. Moreover, since it is conductive, it cannot be used as it is as a substrate. Therefore, it is considered that if a smooth resin film is formed on the metal plate so as to satisfy the above conditions, the metal plate can be used as a substrate.
このような基板としては、例えば、特許文献１〜３には、表面粗さＲａを３０ｎｍ以下と非常に小さくした金属基板が記載されており、これらの特許文献に記載された金属基板の表面粗さＲａは、５０μｍ□又はそれより小さいエリアで測定して求めたものである。しかし、これらの金属基板では、３ｍｍ□における表面粗さＲａは８０〜８００ｎｍ程度となっている。 As such a substrate, for example, Patent Documents 1 to 3 describe metal substrates having a very small surface roughness Ra of 30 nm or less, and the surface roughness of the metal substrates described in these Patent Documents. The thickness Ra is obtained by measuring in an area of 50 μm □ or smaller. However, in these metal substrates, the surface roughness Ra at 3 mm □ is about 80 to 800 nm.
このように、５０μｍ□のような狭い領域では表面粗さＲａが非常に小さい金属基板であっても、３ｍｍ□における表面粗さＲａが大きいため、金属基板を用いて太陽電池又は有機ＥＬ素子を作製するにあたり、電極などの薄膜層を金属基板上に形成すると、金属基板における表面凹凸の凹部にピンホールが発生してしまう。ピンホール等の欠陥が存在すると、水分がピンホールから太陽電池や有機ＥＬ素子内に浸入し、ダークスポットと呼ばれる黒点非発光部が出現する。 Thus, even in a narrow region such as 50 μm □, even if the surface roughness Ra is very small, the surface roughness Ra at 3 mm □ is large, so that the solar cell or the organic EL element can be formed using the metal substrate. In manufacturing, if a thin film layer such as an electrode is formed on a metal substrate, a pinhole is generated in a concave portion of the surface unevenness of the metal substrate. When defects such as pinholes are present, moisture penetrates into the solar cells and organic EL elements from the pinholes, and black spot non-light emitting portions called dark spots appear.
また、３ｍｍ□における表面粗さＲａが大きいと、電極などの薄膜層を金属基板上に形成する際に、表面凹凸の凹部に薄膜層形成用組成物が集中してしまうことがあり、その場合には、金属基板上に薄膜層が形成されない箇所が発生し、短絡状態が生ずるおそれがある。加えて、金属基板表面にほこりやゴミ等の微小異物（通常、１０μｍより大きい）が付着している場合もあり、その場合にも、金属基板上に薄膜層が形成されない箇所が発生し、短絡状態が生ずるおそれがある。 In addition, if the surface roughness Ra at 3 mm □ is large, the thin film layer forming composition may concentrate on the concave portions of the surface irregularities when forming a thin film layer such as an electrode on the metal substrate. In some cases, a portion where the thin film layer is not formed on the metal substrate is generated, which may cause a short circuit. In addition, there may be cases where fine foreign matter such as dust or dust (usually larger than 10 μm) adheres to the surface of the metal substrate, and in this case, a portion where the thin film layer is not formed on the metal substrate occurs and short circuit occurs. Conditions may occur.
本発明は、サブストレート型薄膜太陽電池又はトップエミッション型有機ＥＬ素子に用いられる金属基板であって、太陽電池又は有機ＥＬ素子としたときに、絶縁性に優れ、かつ、ダークスポットが発生しない太陽電池又は有機ＥＬ素子となる金属基板の提供を課題として掲げた。 The present invention is a metal substrate used for a substrate type thin film solar cell or a top emission type organic EL element, and when used as a solar cell or an organic EL element, the solar cell is excellent in insulation and does not generate a dark spot. Providing a metal substrate to be a battery or an organic EL element was raised as an issue.
本発明者等は、金属板の少なくとも片面に、膜厚が３μｍ以上である所定の樹脂皮膜を積層した後に、積層した樹脂皮膜を研磨し、金属基板の３ｍｍ□における表面粗さＲａを十分に小さくした金属基板とすることによって、この金属基板が太陽電池又は有機ＥＬ素子に用いられたときに、絶縁性に優れ、かつ、ダークスポットが発生しない太陽電池又は有機ＥＬ素子となる金属基板を完成するに至った。 The inventors have laminated a predetermined resin film having a film thickness of 3 μm or more on at least one surface of the metal plate, and then polished the laminated resin film to sufficiently ensure the surface roughness Ra at 3 mm □ of the metal substrate. By making the metal substrate small, when this metal substrate is used in a solar cell or an organic EL element, a metal substrate that becomes a solar cell or an organic EL element that is excellent in insulation and does not generate dark spots is completed. It came to do.
すなわち、本発明のサブストレート型薄膜太陽電池又はトップエミッション型有機ＥＬ素子に用いられる金属基板は、金属板の少なくとも片面に、樹脂皮膜が積層された金属基板であって、上記樹脂皮膜の膜厚が３μｍ以上であり、上記金属基板の３ｍｍ□における表面粗さＲａが、１０ｎｍ以下であることを特徴とする。 That is, the metal substrate used for the substrate-type thin film solar cell or the top emission type organic EL element of the present invention is a metal substrate in which a resin film is laminated on at least one surface of a metal plate, and the film thickness of the resin film Is 3 μm or more, and the surface roughness Ra at 3 mm □ of the metal substrate is 10 nm or less.
上記樹脂皮膜を構成する樹脂のガラス転移温度が４０℃以上であることが好ましい。また、上記樹脂皮膜を構成する樹脂の数平均分子量が２０００以上１４０００以下であることが好ましい。上記樹脂皮膜は、ポリエステル樹脂を含むことが好ましい。 It is preferable that the glass transition temperature of resin which comprises the said resin film is 40 degreeC or more. Moreover, it is preferable that the number average molecular weight of resin which comprises the said resin film is 2000-14000. The resin film preferably contains a polyester resin.
上記金属基板の平均うねりＷａが５０ｎｍ以下であることが好ましい。 The average waviness Wa of the metal substrate is preferably 50 nm or less.
上記樹脂皮膜は、固体顔料の体積分率が１％以下であることが好ましい。 The resin film preferably has a solid pigment volume fraction of 1% or less.
本発明では、膜厚が３μｍ以上である樹脂皮膜が積層された金属基板の表面を研磨して金属基板表面（樹脂皮膜）を平滑にすることによって、太陽電池又は有機ＥＬ素子としたときに、絶縁性に優れ、かつ、ダークスポットが発生しない太陽電池又は有機ＥＬ素子となる金属基板を提供することができた。したがって、上記金属基板を用いることによって、低コストで、かつ高性能である薄膜太陽電池や有機ＥＬ素子を得ることが可能となった。 In the present invention, when the surface of the metal substrate on which the resin film having a film thickness of 3 μm or more is laminated to smooth the metal substrate surface (resin film), a solar cell or an organic EL element is obtained. The metal substrate used as the solar cell or organic EL element which was excellent in insulation and did not generate a dark spot could be provided. Therefore, by using the metal substrate, it has become possible to obtain a thin film solar cell and an organic EL element which are low in cost and high in performance.
本発明の金属基板は、サブストレート型薄膜太陽電池又はトップエミッション型有機ＥＬ素子に用いられるものであり、金属板の少なくとも片面に、少なくとも１層の樹脂皮膜が積層されている。具体的には、本発明の金属基板は、金属板の少なくとも片面に、１層以上の樹脂皮膜を積層した後に、金属基板の表面（樹脂皮膜）を研磨して表面を平滑化したものである。 The metal substrate of the present invention is used for a substrate type thin film solar cell or a top emission type organic EL element, and at least one resin film is laminated on at least one surface of a metal plate. Specifically, the metal substrate of the present invention is one in which one or more resin films are laminated on at least one surface of a metal plate, and then the surface (resin film) of the metal substrate is polished to smooth the surface. .
［３ｍｍ□における表面粗さＲａ］
サブストレート型薄膜太陽電池又はトップエミッション型有機ＥＬ素子を作製するときに金属基板上に積層される電極などの薄膜層は、数ｎｍ〜数十ｎｍ程度の厚さである。よって、絶縁性に優れ、かつ、ダークスポットが発生しない太陽電池又は有機ＥＬ素子とするためには、薄膜層を積層する前に金属板に積層された樹脂皮膜を研磨することによって、金属基板の３ｍｍ□におけるＲａをできるだけ小さくしておく必要がある。具体的には、金属基板の３ｍｍ□におけるＲａが１０ｎｍ以下であり、より好ましくは５ｎｍ以下であり、さらに好ましくは３ｎｍ以下である。金属基板表面にはうねりができており、うねりの山と谷との距離は３ｍｍ程度である。そのため、金属基板の３ｍｍ□におけるＲａが１０ｎｍ以下であることから、１０μｍ□程度の狭い範囲でＲａが小さいことに加えて、うねりの山谷のいずれの位置においてもＲａが小さくなっていることもわかる。
金属基板の３ｍｍ□におけるＲａが１０ｎｍを超えると、金属基板に電極などの薄膜層を積層して太陽電池又は有機ＥＬ素子とするときに、金属基板上に樹脂皮膜が形成されない箇所が発生したり、金属基板上に電極などの薄膜層を形成した際に、金属基板における表面凹凸の凹部にピンホールが発生したりするおそれがある。ピンホール等の欠陥が存在すると、水分がピンホールから太陽電池や有機ＥＬ素子内に浸入し、ダークスポットと呼ばれる黒点非発光部が出現してしまう。
また、金属基板の３ｍｍ□におけるＲａが１０ｎｍを超えると、電極などの薄膜層を金属基板上に形成する際に、表面凹凸の凹部に薄膜層形成用組成物が集中してしまうことがあり、その場合には、金属基板上に薄膜層が形成されない箇所が発生し、短絡状態が生ずるおそれがある。
金属基板の３ｍｍ□におけるＲａについては、後述の測定方法により測定することができる。
[Surface roughness Ra at 3 mm □]
A thin film layer such as an electrode laminated on a metal substrate when producing a substrate type thin film solar cell or a top emission type organic EL element has a thickness of about several nm to several tens of nm. Therefore, in order to obtain a solar cell or an organic EL element that is excellent in insulation and does not generate dark spots, by polishing the resin film laminated on the metal plate before laminating the thin film layer, It is necessary to make Ra at 3 mm □ as small as possible. Specifically, Ra at 3 mm □ of the metal substrate is 10 nm or less, more preferably 5 nm or less, and further preferably 3 nm or less. The metal substrate surface has undulations, and the distance between the undulation peaks and valleys is about 3 mm. Therefore, since Ra at 3 mm □ of the metal substrate is 10 nm or less, it can be seen that Ra is small in any position of the undulation valley in addition to small Ra in a narrow range of about 10 μm □. .
When Ra at 3 mm □ of the metal substrate exceeds 10 nm, when a thin film layer such as an electrode is laminated on the metal substrate to form a solar cell or an organic EL element, a portion where a resin film is not formed on the metal substrate may occur. When a thin film layer such as an electrode is formed on the metal substrate, there is a possibility that a pinhole is generated in the concave portion of the surface unevenness in the metal substrate. If there is a defect such as a pinhole, moisture enters the solar cell or the organic EL element from the pinhole, and a black spot non-light emitting portion called a dark spot appears.
In addition, when the Ra at 3 mm □ of the metal substrate exceeds 10 nm, the composition for forming a thin film layer may concentrate on the concave portions of the surface irregularities when forming a thin film layer such as an electrode on the metal substrate. In that case, the location where the thin film layer is not formed on the metal substrate occurs, and there is a possibility that a short circuit state occurs.
The Ra at 3 mm □ of the metal substrate can be measured by the measurement method described later.
［金属板］
本発明の金属基板に用いる金属板は、冷延鋼板、溶融純亜鉛めっき鋼板（ＧＩ）、または合金化溶融Ｚｎ−Ｆｅめっき鋼板（ＧＡ）、合金化溶融Ｚｎ−５％Ａｌめっき鋼板（ＧＦ）、電気純亜鉛めっき鋼板（ＥＧ）、電気Ｚｎ−Ｎｉめっき鋼板、アルミニウム板、チタン板、ガルバリウム鋼板等であり、ノンクロメートのものが好ましいが、クロメート処理あるいは無処理のものも使用可能である。金属板の厚みは特に限定されないが、０．３〜２．０ｍｍ程度のものを適宜使用することができる。
[Metal plate]
The metal plate used for the metal substrate of the present invention is a cold-rolled steel plate, a hot-dip galvanized steel plate (GI), an alloyed hot-dip Zn-Fe-plated steel plate (GA), an alloyed hot-dip Zn-5% Al-plated steel plate (GF). Electropure galvanized steel plate (EG), electroplated Zn—Ni plated steel plate, aluminum plate, titanium plate, galvalume steel plate and the like, preferably non-chromate, but chromate-treated or untreated can also be used. Although the thickness of a metal plate is not specifically limited, The thing of about 0.3-2.0 mm can be used suitably.
金属板には、リン酸系化成処理を施しておいてもよく、特に、特開２００５−２６４３１２号公報に示されたような、コロイダルシリカとリン酸アルミニウム塩化合物を含む酸性水溶液によって化成処理を施しておくことが好ましい。コロイダルシリカとリン酸アルミニウム塩化合物を含む酸性水性液を化成処理液として使用すると、酸性水性液によって亜鉛系めっき層の表面がエッチングされながら、亜鉛系めっき層の表面にリン酸アルミニウムの中でも難溶性（水またはアルカリ性水溶液に溶けにくい）のＡｌＰＯ4やＡｌ2（ＨＰＯ4）3主体の反応層が形成される。この反応層にシリカ微粒子が沈着して取り込まれることでリン酸アルミニウムとシリカ微粒子が複合一体化する。また、エッチングにより粗面化された亜鉛系めっき層との間で緻密な反応層が形成され、この反応層の上に形成される樹脂塗膜との結合も緻密で強固なものとなる。また、上記酸性水溶液にポリアクリル酸等の水溶性樹脂を含有させておくと、得られる反応層中のシリカ微粒子の沈着状態を一層強固なものとすることができる。 The metal plate may be subjected to a phosphoric acid-based chemical conversion treatment. In particular, the chemical conversion treatment is performed with an acidic aqueous solution containing colloidal silica and an aluminum phosphate salt compound as disclosed in JP-A-2005-264212. It is preferable to give it. When an acidic aqueous solution containing colloidal silica and an aluminum phosphate salt compound is used as the chemical conversion treatment solution, the surface of the zinc-based plating layer is etched by the acidic aqueous solution, and the surface of the zinc-based plating layer is hardly soluble among aluminum phosphates. A reaction layer mainly composed of AlPO 4 or Al 2 (HPO 4 ) 3 (which is hardly soluble in water or an alkaline aqueous solution) is formed. As the silica fine particles are deposited and taken into the reaction layer, the aluminum phosphate and the silica fine particles are combined and integrated. In addition, a dense reaction layer is formed with the zinc-based plating layer roughened by etching, and the bond with the resin coating formed on the reaction layer is also dense and strong. In addition, when the acidic aqueous solution contains a water-soluble resin such as polyacrylic acid, the deposited state of the silica fine particles in the obtained reaction layer can be further strengthened.
［樹脂皮膜］
本発明では、樹脂成分が含まれている皮膜形成用組成物を用いて、金属板に樹脂皮膜が積層されている。
[Resin film]
In this invention, the resin film is laminated | stacked on the metal plate using the composition for film formation containing the resin component.
樹脂成分は、特に限定されるものではないが、熱硬化性樹脂であることが好ましい。また、皮膜形成用組成物は、特に限定されるものではないが、熱硬化性樹脂と硬化剤とが配合されている皮膜形成用組成物が好ましい。 The resin component is not particularly limited, but is preferably a thermosetting resin. The film-forming composition is not particularly limited, but a film-forming composition in which a thermosetting resin and a curing agent are blended is preferable.
熱硬化性樹脂は、特に限定されるものではなく、例えば、フェノール樹脂、エポキシ樹脂、ユリア樹脂、メラミン樹脂、ジアリルフタレート樹脂等を挙げることができる。また、後述の硬化剤と共に用いることで、ポリエステル樹脂も一種の熱硬化性樹脂ということができる。熱硬化性樹脂は、一種類のみを用いてもよいし、二種類以上を混合して用いてもよいが、ポリエステル樹脂を用いるのが好ましい。すなわち、皮膜形成用組成物に、ポリエステル樹脂が含まれていることが好ましい。 A thermosetting resin is not specifically limited, For example, a phenol resin, an epoxy resin, a urea resin, a melamine resin, a diallyl phthalate resin etc. can be mentioned. Moreover, a polyester resin can also be called a kind of thermosetting resin by using with the below-mentioned hardener. Only one type of thermosetting resin may be used, or two or more types may be mixed and used, but a polyester resin is preferably used. That is, it is preferable that the film forming composition contains a polyester resin.
樹脂皮膜を複数層備えた金属基板においては、最表層（金属板から最も離れた樹脂皮膜）を形成する樹脂組成物に、熱硬化性樹脂が含まれていることが好ましく、ポリエステル樹脂が含まれていることがより好ましい。また、全ての層において、樹脂皮膜を形成する樹脂組成物に、熱硬化性樹脂が含まれていることが好ましく、ポリエステル樹脂が含まれていることがより好ましい。 In a metal substrate having a plurality of resin films, the resin composition that forms the outermost layer (the resin film furthest away from the metal plate) preferably contains a thermosetting resin, and contains a polyester resin. More preferably. Moreover, it is preferable that the thermosetting resin is contained in the resin composition which forms a resin film in all the layers, and it is more preferable that the polyester resin is contained.
ポリエステル樹脂は、二塩基酸等の多塩基酸と多価アルコール類との縮合反応によって得られるものである。 The polyester resin is obtained by a condensation reaction between a polybasic acid such as a dibasic acid and a polyhydric alcohol.
ポリエステル樹脂の原料として用いられる多塩基酸としては、例えば、マレイン酸、無水マレイン酸、フマル酸、イタコン酸、無水イタコン酸等のα，β−不飽和二塩基酸；フタル酸、無水フタル酸、ハロゲン化無水フタル酸、イソフタル酸、テレフタル酸、テトラヒドロフタル酸、テトラヒドロ無水フタル酸、ヘキサヒドロフタル酸、ヘキサヒドロイソフタル酸、ヘキサヒドロテレフタル酸、シクロペンタジエン−無水マレイン酸付加物、コハク酸、マロン酸、グルタル酸、アジピン酸、セバシン酸、１，１０−デカンジカルボン酸、２，６−ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸、２，３−ナフタレンジカルボン酸、２，３−ナフタレンジカルボン酸無水物、４，４’−ビフェニルジカルボン酸、および、これらのジアルキルエステル等の飽和二塩基酸等が挙げられるが、特に限定されるものではない。多塩基酸は、一種類のみを用いてもよいし、適宜、二種類以上を混合して用いてもよい。 Examples of the polybasic acid used as a raw material for the polyester resin include α, β-unsaturated dibasic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride; phthalic acid, phthalic anhydride, Halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, cyclopentadiene-maleic anhydride adduct, succinic acid, malonic acid , Glutaric acid, adipic acid, sebacic acid, 1,10-decanedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride , 4,4′-biphenyldicarboxylic acid, and their di Saturated dibasic acids such as alkyl esters are exemplified, but are not particularly limited. Only one type of polybasic acid may be used, or two or more types may be appropriately mixed and used.
ポリエステル樹脂の原料として用いられる多価アルコール類としては、例えばエチレングリコール、ジエチレングリコール、ポリエチレングリコール等のエチレングリコール類、プロピレングリコール、ジプロピレングリコール、ポリプロピレングリコール等のプロピレングリコール類、２−メチル−１，３−プロパンジオール、１，３−ブタンジオール、ビスフェノールＡとプロピレンオキシドまたはエチレンオキシドとの付加物、グリセリン、トリメチロールプロパン、１，３−プロパンジオール、１，２−シクロヘキサングリコール、１，３−シクロヘキサングリコール、１，４−シクロヘキサングリコール、パラキシレングリコール、ビシクロヘキシル−４，４’−ジオール、２，６−デカリングリコール、トリス（２−ヒドロキシエチル）イソシアヌレート等が挙げられるが、特に限定されるものではない。また、エタノールアミン等のアミノアルコール類を用いてもよい。これら多価アルコール類は、一種類のみを用いてもよいし、適宜、二種類以上を混合してもよい。また、必要によりエポキシ樹脂、ジイソシアナート、ジシクロペンタジエン等による変性を行ってもよい。 Examples of the polyhydric alcohol used as a raw material for the polyester resin include ethylene glycols such as ethylene glycol, diethylene glycol, and polyethylene glycol, propylene glycols such as propylene glycol, dipropylene glycol, and polypropylene glycol, and 2-methyl-1,3. -Propanediol, 1,3-butanediol, adduct of bisphenol A and propylene oxide or ethylene oxide, glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, para-xylene glycol, bicyclohexyl-4,4′-diol, 2,6-decalin glycol, tris (2-hydroxy Chill) isocyanurate, but not particularly limited. In addition, amino alcohols such as ethanolamine may be used. Only one kind of these polyhydric alcohols may be used, or two or more kinds may be appropriately mixed. If necessary, modification with epoxy resin, diisocyanate, dicyclopentadiene or the like may be performed.
樹脂皮膜を構成する樹脂のガラス転移温度（Ｔｇ）が４０℃以上であることが好ましく、４５℃以上であることがより好ましく、５０℃以上であることがさらに好ましい。Ｔｇが４０℃未満である場合、研磨時に発生する熱によって樹脂皮膜が軟化し、安定した研磨を行うことが困難となるため、研磨後の金属基板の３ｍｍ□におけるＲａが１０ｎｍを上回ってしまうおそれがある。なお、Ｔｇについては、示差走査型熱量計（ＤＳＣ）を用いて測定することができる。 The glass transition temperature (Tg) of the resin constituting the resin film is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, and further preferably 50 ° C. or higher. When Tg is less than 40 ° C., the resin film is softened by the heat generated during polishing, and it becomes difficult to perform stable polishing, so that the Ra at 3 mm □ of the metal substrate after polishing may exceed 10 nm. There is. In addition, about Tg, it can measure using a differential scanning calorimeter (DSC).
樹脂皮膜を複数層備えた金属基板においては、最表層を構成する樹脂のＴｇが４０℃以上であることが好ましく、４５℃以上であることがより好ましく、５０℃以上であることがさらに好ましい。また、全ての層において、樹脂皮膜を構成する樹脂のＴｇが上記温度以上であることがより好ましい。 In a metal substrate having a plurality of resin films, the Tg of the resin constituting the outermost layer is preferably 40 ° C. or higher, more preferably 45 ° C. or higher, and further preferably 50 ° C. or higher. Moreover, in all layers, it is more preferable that Tg of the resin constituting the resin film is equal to or higher than the above temperature.
樹脂皮膜を構成する樹脂の数平均分子量（Ｍｎ）が１４０００以下であることが好ましく、１２０００以下であることがより好ましく、１００００以下であることがさらに好ましい。Ｍｎが１４０００を超えると、金属基板の平均うねりＷａが５０ｎｍを超えたり、金属基板の３ｍｍ□におけるＲａが１０ｎｍを上回ってしまうおそれがある。平均うねりＷａについては後述する。Ｍｎは、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）を用いて測定することができる。樹脂皮膜を構成する樹脂の数平均分子量（Ｍｎ）は２０００以上であることが好ましく、３０００以上であることがより好ましい。 The number average molecular weight (Mn) of the resin constituting the resin film is preferably 14000 or less, more preferably 12000 or less, and even more preferably 10,000 or less. If Mn exceeds 14,000, the average waviness Wa of the metal substrate may exceed 50 nm, or Ra at 3 mm □ of the metal substrate may exceed 10 nm. The average swell Wa will be described later. Mn can be measured using gel permeation chromatography (GPC). The number average molecular weight (Mn) of the resin constituting the resin film is preferably 2000 or more, and more preferably 3000 or more.
樹脂皮膜を複数層備えた金属基板においては、最表層を構成する樹脂のＭｎが１４０００以下であることが好ましく、１２０００以下であることがより好ましく、１００００以下であることがさらに好ましい。また、樹脂皮膜を複数層備えた金属基板においては、最表層を構成する樹脂のＭｎが２０００以上であることが好ましく、３０００以上であることがより好ましい。また、全ての層において、樹脂皮膜を構成する樹脂のＭｎが上記分子量以上であることがより好ましく、上記分子量以下であることがより好ましい。 In a metal substrate provided with a plurality of resin films, the Mn of the resin constituting the outermost layer is preferably 14000 or less, more preferably 12000 or less, and even more preferably 10,000 or less. Further, in a metal substrate having a plurality of resin films, the Mn of the resin constituting the outermost layer is preferably 2000 or more, and more preferably 3000 or more. In all the layers, the Mn of the resin constituting the resin film is more preferably the molecular weight or more, and more preferably the molecular weight or less.
本発明における熱硬化性樹脂としては、種々の市販品を好適に用いることができ、特にポリエステル樹脂の市販品としては、例えば、バイロン（登録商標）２３ＣＳ、バイロン（登録商標）２９ＣＳ、バイロン（登録商標）２９ＸＳ、バイロン（登録商標）２０ＳＳ、バイロン（登録商標）２９ＳＳ（以上、東洋紡社製）等を挙げることができる。 Various commercially available products can be suitably used as the thermosetting resin in the present invention. Particularly, as commercially available polyester resins, for example, Byron (registered trademark) 23CS, Byron (registered trademark) 29CS, Byron (registered) (Trademark) 29XS, Byron (registered trademark) 20SS, Byron (registered trademark) 29SS (manufactured by Toyobo Co., Ltd.) and the like.
また、硬化剤としては、特に限定されるものではないが、熱硬化性樹脂との相溶性がよく、熱硬化性樹脂を架橋させることができ、更に、液安定性のよいものが好ましい。このような硬化剤としては、例えば、イソシアネート系では、ミリオネート（登録商標）Ｎ、コロネート（登録商標）Ｔ、コロネート（登録商標）ＨＬ、コロネート（登録商標）２０３０、スプラセック（登録商標）３３４０、ダルトセック１３５０、ダルトセック２１７０、ダルトセック２２８０（以上、日本ポリウレタン工業社製）等、メラミン系では、ニカラック（登録商標）ＭＳ−１１、ニカラック（登録商標）ＭＳ２１（以上、三和ケミカル社製）、スーパーベッカミン（登録商標）Ｌ−１０５−６０、スーパーベッカミン（登録商標）Ｊ−８２０−６０（以上、ＤＩＣ社製）、エポキシ系では、ハードナーＨＹ９５１、ハードナーＨＹ９５７（以上、ＢＡＳＦ社製）、スミキュアーＤＴＡ、スミキュアーＴＴＡ（以上、住友化学社製）等を挙げることができる。 In addition, the curing agent is not particularly limited, but a curing agent that has good compatibility with the thermosetting resin, can crosslink the thermosetting resin, and has good liquid stability is preferable. As such a curing agent, for example, in the isocyanate system, Millionate (registered trademark) N, Coronate (registered trademark) T, Coronate (registered trademark) HL, Coronate (registered trademark) 2030, Suprasec (registered trademark) 3340, Daltsec 1350, Daltosec 2170, Daltosec 2280 (Nippon Polyurethane Industry Co., Ltd.) and other melamine-based Nicarak (registered trademark) MS-11, Nicalac (registered trademark) MS21 (Sanwa Chemical Co., Ltd.), Super Becamine (Registered Trademark) L-105-60, Super Becamine (Registered Trademark) J-820-60 (above, manufactured by DIC Corporation), Epoxy, Hardener HY951, Hardener HY957 (above, manufactured by BASF Corporation), Sumicure DTA, Sumicure TTA (above, Sumitomo Chemical Etsu Chemical Co., Ltd.) and the like can be given.
また、皮膜形成用組成物には、熱硬化性樹脂が５０〜９０質量％含まれているのが好ましく、より好ましくは６０〜８０質量％である。そして、皮膜形成用組成物には、硬化剤が１０〜５０質量％含まれているのが好ましく、より好ましくは２０〜４０質量％である。なお、上記における熱硬化性樹脂及び硬化剤の質量％は、皮膜形成用組成物中の熱硬化性樹脂と硬化剤との合計質量に対する熱硬化性樹脂及び硬化剤の含有量の比率を指す。 Moreover, it is preferable that 50-90 mass% of thermosetting resins are contained in the composition for film formation, More preferably, it is 60-80 mass%. And it is preferable that 10-50 mass% of hardening | curing agents are contained in the composition for film formation, More preferably, it is 20-40 mass%. In addition, the mass% of the thermosetting resin and the curing agent in the above refers to the ratio of the content of the thermosetting resin and the curing agent to the total mass of the thermosetting resin and the curing agent in the film-forming composition.
樹脂皮膜を形成するに当たっては、金属板表面または既に積層された樹脂皮膜上に皮膜形成用組成物を塗布する塗布法により積層するのが好ましいため、皮膜形成用組成物は液状であることが望ましい。よって、皮膜形成用組成物は溶媒も含むことが推奨される。皮膜形成用組成物に用いる溶媒は、皮膜形成用組成物が含有すべき各成分を溶解または分散させ得るものであれば、特に制限はない。例えば、メタノール、エタノール、ｎ−プロパノール、イソプロパノール、ｎ−ブタノール、イソブタノール、エチレングリコール等のアルコール類；アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類；トルエン、ベンゼン、キシレン、ソルベッソ（登録商標）１００（エクソンモービル社製）、ソルベッソ（登録商標）１５０（エクソンモービル社製）等の芳香族炭化水素類；ヘキサン、ヘプタン、オクタン等の脂肪族炭化水素類；酢酸エチル、酢酸ブチル等のエステル類；等が挙げられる。皮膜形成用組成物は、こういった溶媒を用いて、固形分を調整することができ、皮膜形成用組成物中における溶媒の含有量は、好ましくは２０質量％以上、８０質量％以下であり、より好ましくは４０質量％以上、７０質量％以下である。固形分が２０質量％未満、すなわち有機溶媒が多すぎる場合、焼付け時に有機溶媒が大量に蒸発し、その結果、金属板表面近傍において気化した有機溶媒による対流が発生しやすくなり、樹脂皮膜表面の平滑性が損なわれるおそれがある。 In forming the resin film, it is preferable that the film forming composition is liquid because it is preferably laminated by a coating method in which the film forming composition is applied onto the surface of the metal plate or the already laminated resin film. . Therefore, it is recommended that the film-forming composition also contains a solvent. The solvent used in the film forming composition is not particularly limited as long as it can dissolve or disperse each component to be contained in the film forming composition. For example, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, ethylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; toluene, benzene, xylene, Solvesso (registered trademark) ) Aromatic hydrocarbons such as 100 (manufactured by ExxonMobil), Solvesso (registered trademark) 150 (manufactured by ExxonMobil); aliphatic hydrocarbons such as hexane, heptane and octane; esters such as ethyl acetate and butyl acetate And the like. The film-forming composition can adjust the solid content using such a solvent, and the content of the solvent in the film-forming composition is preferably 20% by mass or more and 80% by mass or less. More preferably, it is 40 mass% or more and 70 mass% or less. When the solid content is less than 20% by mass, that is, when the organic solvent is too much, a large amount of the organic solvent evaporates at the time of baking, and as a result, convection due to the organic solvent evaporated near the surface of the metal plate is likely to occur. Smoothness may be impaired.
なお、皮膜形成用組成物には、固体触媒などの固体状の物質を含まないことが好ましい。これら固体状の物質は、研磨剤に近い形状及び硬度であるため、平滑化されにくいのみならず、研磨によって、固体状の物質が除去された場合には固体状の物質が除去された形跡が残り、金属基板表面に凹状部分が形成されてしまい、樹脂皮膜中に固体状の物質が押し込められた場合には、金属基板表面に凸状部分が形成されてしまう。このような金属基板を用いて太陽電池又は有機ＥＬ素子を作製したときに、絶縁性に優れ、かつ、ダークスポットが発生しない太陽電池又は有機ＥＬ素子とすることが困難となる。 The film-forming composition preferably does not contain a solid substance such as a solid catalyst. Since these solid substances have a shape and hardness close to that of an abrasive, they are not only easily smoothed, but also when solid substances are removed by polishing, there is evidence that the solid substances have been removed. The remaining concave portion is formed on the surface of the metal substrate, and when a solid substance is pushed into the resin film, the convex portion is formed on the surface of the metal substrate. When a solar cell or an organic EL element is produced using such a metal substrate, it becomes difficult to obtain a solar cell or an organic EL element that is excellent in insulation and does not generate dark spots.
樹脂皮膜を複数層備えた金属基板においては、最表層を形成する樹脂皮膜形成用組成物には、固体状の物質を含まないことが好ましい。また、最表層以外の層を形成する皮膜形成用組成物においても、固体状の物質を含まないことがより好ましい。 In a metal substrate having a plurality of resin films, the resin film forming composition for forming the outermost layer preferably does not contain a solid substance. Moreover, it is more preferable that the film forming composition for forming a layer other than the outermost layer does not contain a solid substance.
［顔料］
金属基板の３ｍｍ□におけるＲａを１０ｎｍ以下とするためには、皮膜形成用組成物中の顔料が少量であるか、又は顔料を全く含まないことが好ましい。具体的には、皮膜形成用組成物中の固体顔料の体積分率が１％以下であることが好ましく、０．５％以下であることがより好ましく、０％（樹脂皮膜には固体顔料が含有されていない）であることがさらに好ましい。樹脂皮膜を複数層備えた金属基板では、全ての層を形成する皮膜形成用組成物において、固体顔料の体積分率が上記体積分率以下であることが好ましい。固体顔料の粒径は１０ｎｍよりも遙かに大きく、概ね１００ｎｍ以上であるため、皮膜形成用組成物中の固体顔料の体積分率が１％を超えると、金属基板の３ｍｍ□におけるＲａを１０ｎｍ以下とするのが困難になる。また、樹脂皮膜に固体状の物質である顔料が含有されていると、樹脂皮膜から顔料粒子が剥離してしまうおそれがあり、剥離した部分は凹部となってしまうことからも、皮膜形成用組成物中の顔料が少量であるか、又は顔料を全く含まないことが好ましい。
[Pigment]
In order to set the Ra at 3 mm □ of the metal substrate to 10 nm or less, it is preferable that the pigment in the film-forming composition is a small amount or contains no pigment. Specifically, the volume fraction of the solid pigment in the film-forming composition is preferably 1% or less, more preferably 0.5% or less, and 0% (a solid pigment is contained in the resin film). More preferably, it is not contained. In the metal substrate having a plurality of resin films, it is preferable that the volume fraction of the solid pigment is equal to or less than the volume fraction in the film-forming composition for forming all the layers. Since the particle size of the solid pigment is much larger than 10 nm and is approximately 100 nm or more, when the volume fraction of the solid pigment in the film forming composition exceeds 1%, the Ra at 3 mm □ of the metal substrate is 10 nm. It becomes difficult to: In addition, if the resin film contains a pigment that is a solid substance, the pigment particles may be peeled off from the resin film, and the peeled portion becomes a recess. It is preferred that the pigment in the product is small or contains no pigment.
皮膜形成用組成物中に顔料を少量含有させる場合、下記のそれぞれの色に着色するための顔料種類の例としては、白色：酸化チタン、炭酸カルシウム、酸化亜鉛、硫酸バリウム、リトポン、鉛白等の無機系顔料、黒色：アニリンブラック、ニグロシン等の有機系顔料、カーボンブラック、鉄黒等の無機系顔料、赤色：不溶性アゾ系（ナフトール系およびアニライド系）または溶性アゾ系等の有機系顔料や、べんがら、カドミウムレッド、鉛丹等の無機系顔料、黄色：不溶性アゾ系（ナフトール系およびアニライド系）、溶性アゾ系、キナクリドン系等の有機系顔料や、クロムエロー、カドミウムイエロー、ニッケルチタンイエロー、黄丹、ストロンチウムクロメート等の無機系顔料、緑色：有機フタロシアニン系顔料、青色：有機フタロシアニン系顔料、ジオキサジン系顔料、紺青、群青、コバルト青、エメラルドグリーン等の無機系顔料、橙色：ベンズイミダゾロン系、ピラゾロン系等の有機系顔料等が挙げられる。上記着色顔料のうち、同色でも化学構造の異なるもの、あるいは異なる色の着色顔料を２種類以上適当な配合比で混合することにより、灰色、茶色、紫色、赤紫色、青紫色、黄金色等所望の色に着色することができる。 When a small amount of pigment is contained in the film-forming composition, examples of pigment types for coloring the following colors are white: titanium oxide, calcium carbonate, zinc oxide, barium sulfate, lithopone, lead white, etc. Inorganic pigments such as black: organic pigments such as aniline black and nigrosine, inorganic pigments such as carbon black and iron black, red: organic pigments such as insoluble azo (naphthol and anilide) or soluble azo Inorganic pigments such as Bengala, Cadmium Red, and Red lead, Yellow: Organic pigments such as insoluble azo (naphthol and anilide), soluble azo, quinacridone, chrome yellow, cadmium yellow, nickel titanium yellow, yellow Inorganic pigments such as red and strontium chromate, green: organic phthalocyanine pigment, blue: organic phthalocyan Emissions-based pigments, dioxazine-based pigments, iron blue, ultramarine blue, cobalt blue, inorganic pigments such as emerald green, orange: benzimidazolone, organic pigments such pyrazolone and the like. Of the above-mentioned color pigments, those having the same color but different chemical structures, or by mixing two or more color pigments of different colors in an appropriate blending ratio, desired gray, brown, purple, red purple, blue purple, golden color, etc. Can be colored in different colors.
なお、顔料の偏析を抑制するために、皮膜形成用組成物には顔料分散剤を添加してもよい。好適な顔料分散剤は、水溶性アクリル樹脂、水溶性スチレンアクリル樹脂およびノニオン系界面活性剤よりなる群から選択される１種以上である。これらを用いた場合、着色塗膜には顔料分散剤が残存することになる。 In order to suppress the segregation of the pigment, a pigment dispersant may be added to the film forming composition. A suitable pigment dispersant is at least one selected from the group consisting of a water-soluble acrylic resin, a water-soluble styrene acrylic resin, and a nonionic surfactant. When these are used, the pigment dispersant remains in the colored coating film.
［樹脂皮膜の膜厚］
樹脂皮膜の膜厚は３μｍ以上であり、４μｍ以上であることが好ましい。膜厚３μｍ未満であると、金属基板の耐電圧が０．１ｋＶ未満となってしまい、耐電圧（絶縁耐性）を確保できないおそれがある。また、膜厚は６０μｍ以下であることが好ましく、５０μｍ以下であることがより好ましい。膜厚が６０μｍを超えると、樹脂皮膜が金属板から剥離するおそれが生じる。なお、樹脂皮膜を複数層積層する場合には、樹脂皮膜の膜厚は全部の層の合計膜厚のことである。また、複数層積層する場合には、好ましくは２層以上、４層以下の積層であり、より好ましくは２層のみの積層である。
[Thickness of resin film]
The film thickness of the resin film is 3 μm or more, and preferably 4 μm or more. If the film thickness is less than 3 μm, the withstand voltage of the metal substrate becomes less than 0.1 kV, and the withstand voltage (insulation resistance) may not be ensured. The film thickness is preferably 60 μm or less, and more preferably 50 μm or less. When the film thickness exceeds 60 μm, the resin film may be peeled off from the metal plate. In addition, when laminating | stacking several layers of resin films, the film thickness of a resin film is a total film thickness of all the layers. Moreover, when laminating | stacking two or more layers, Preferably it is lamination | stacking of 2 layers or more and 4 layers or less, More preferably, it is lamination | stacking of only 2 layers.
［樹脂皮膜の製造方法］
皮膜形成用組成物の塗布、乾燥方法は、特に制限されず、既知の方法を適宜採用することができる。本発明に係る金属基板を作製する際の皮膜形成用組成物の塗布方法としては、例えばバーコーター法、ロールコーター法、カーテンフローコーター法、スプレー法、スプレーリンガー法等によるプレコート法を挙げることができ、これらの中でも、コスト等の観点からバーコーター法、ロールコーター法、スプレーリンガー法が好ましい。また、上記以外の組成物の塗布方法として、静電塗装法、スピンコート法等によるポストコート法を用いることもできる。
[Production method of resin film]
The method for applying and drying the film-forming composition is not particularly limited, and known methods can be appropriately employed. Examples of the coating method of the film-forming composition for producing the metal substrate according to the present invention include a precoat method such as a bar coater method, a roll coater method, a curtain flow coater method, a spray method, and a spray ringer method. Among these, the bar coater method, the roll coater method, and the spray ringer method are preferable from the viewpoint of cost and the like. Further, as a method for applying a composition other than the above, a post coating method such as an electrostatic coating method or a spin coating method can also be used.
焼付け温度としては、特に限定されるものではなく、皮膜に用いる樹脂の硬化特性に応じて調整すれば良いが、例えば、プレコート法に用いるポリエステル系樹脂の場合には１９０℃以上２５０℃以下が好ましく、より好ましくは２００℃以上２４０℃以下である。焼付け温度を上記の範囲内にして、有機溶媒を激しく蒸発させないようにすることによって、金属板表面近傍において気化した有機溶媒による対流が発生しにくくなり、最表層の樹脂皮膜表面をより平滑にすることができる。また、乾燥温度としては、樹脂皮膜が熱により劣化しない程度であればよく、例えば、１９０〜２５０℃程度が好ましく、より好ましくは２００〜２４０℃程度である。なお、焼付け・乾燥温度は、到達板温（Ｐｅａｋ Ｍｅｔａｌ Ｔｅｍｐｅｒａｔｕｒｅ：ＰＭＴ）である。 The baking temperature is not particularly limited and may be adjusted according to the curing characteristics of the resin used for the film. For example, in the case of a polyester-based resin used for the precoat method, it is preferably 190 ° C. or higher and 250 ° C. or lower. More preferably, it is 200 degreeC or more and 240 degrees C or less. By setting the baking temperature within the above range and preventing the organic solvent from evaporating violently, convection due to the organic solvent evaporated near the surface of the metal plate is less likely to occur, and the surface of the outermost resin film becomes smoother. be able to. Moreover, as drying temperature, what is necessary is just a grade which a resin film does not deteriorate with heat, for example, about 190-250 degreeC is preferable, More preferably, it is about 200-240 degreeC. Note that the baking / drying temperature is a peak metal temperature (PMT).
［金属基板表面（樹脂皮膜）の研磨］
本発明の金属基板は、化学機械研磨（ＣＭＰ）を行うことによって、金属基板表面を平滑にしている。研磨方法は特に限定されておらず、研磨剤自体が有する表面化学作用や研磨液に含まれる化学成分の作用によって研磨される公知の研磨方法を用いればよい。研磨剤も特に限定されておらず、例えば、シリカ、アルミナ、セリア、チタニア、ジルコニア、ゲルマニア等を用いることができる。
[Polishing metal substrate surface (resin film)]
The metal substrate of the present invention smoothes the surface of the metal substrate by performing chemical mechanical polishing (CMP). The polishing method is not particularly limited, and a known polishing method for polishing by the surface chemical action of the polishing agent itself or the action of chemical components contained in the polishing liquid may be used. The abrasive is not particularly limited, and for example, silica, alumina, ceria, titania, zirconia, germania, or the like can be used.
［樹脂皮膜の被覆率］
金属基板上に樹脂皮膜が形成されない箇所が発生すると、金属基板に電極などの薄膜層を積層して太陽電池又は有機ＥＬ素子としたときに、薄膜層と金属板との間で短絡状態が生ずるおそれがある。そのため、研磨後の樹脂皮膜の被覆率は、９９％以上であることが好ましく、９９．９％以上であることがより好ましく、１００％であることが好ましい。
[Coating ratio of resin film]
When a portion where a resin film is not formed on a metal substrate occurs, a short circuit state occurs between the thin film layer and the metal plate when a thin film layer such as an electrode is laminated on the metal substrate to form a solar cell or an organic EL element. There is a fear. Therefore, the coverage of the resin film after polishing is preferably 99% or more, more preferably 99.9% or more, and preferably 100%.
［平均うねりＷａ］
金属基板の平均うねりＷａが５０ｎｍ以下であることが好ましく、４０ｎｍ以下であることがより好ましい。平均うねりＷａが５０ｎｍを超えると、金属基板の３ｍｍ□におけるＲａを１０ｎｍ以下とするのが困難になる。
また、金属基板の平均うねりＷａを小さくするためには、研磨前の金属基板の平均うねりＷａ’も出来るだけ小さいことが好ましい。具体的には、研磨前の金属基板の平均うねりＷａ’が１００ｎｍ以下であることが好ましく、７０ｎｍ以下であることがより好ましい。平均うねりＷａ’が１００ｎｍよりも大きいと、樹脂皮膜を研磨したとしても、平均うねりＷａが十分に小さくならないおそれがある。また、平均うねりＷａ’が１００ｎｍであると、樹脂皮膜の研磨量が少なくて済むため、低コストで金属基板が作製できる。
研磨後の金属基板の平均うねりＲａ、研磨前の金属基板の平均うねりＷａ’については、後述の測定方法により測定することができる。
[Average swell Wa]
The average waviness Wa of the metal substrate is preferably 50 nm or less, and more preferably 40 nm or less. When the average waviness Wa exceeds 50 nm, it becomes difficult to set the Ra at 3 mm □ of the metal substrate to 10 nm or less.
In order to reduce the average waviness Wa of the metal substrate, the average waviness Wa ′ of the metal substrate before polishing is preferably as small as possible. Specifically, the average waviness Wa ′ of the metal substrate before polishing is preferably 100 nm or less, and more preferably 70 nm or less. If the average waviness Wa ′ is greater than 100 nm, the average waviness Wa may not be sufficiently reduced even if the resin film is polished. Further, when the average waviness Wa ′ is 100 nm, the amount of polishing of the resin film can be reduced, so that a metal substrate can be produced at low cost.
The average waviness Ra of the metal substrate after polishing and the average waviness Wa ′ of the metal substrate before polishing can be measured by a measurement method described later.
［研磨前の表面粗さＲａ’］
本発明においては、研磨後の金属基板の表面が平滑であるためには、研磨前の状態で、金属基板の表面が平滑であることが好ましい。具体的には、研磨前の金属基板の３ｍｍ□におけるＲａ’が２００ｎｍ以下であることが好ましく、より好ましくは１５０ｎｍ以下である。研磨前の金属基板の３ｍｍ□におけるＲａ’が２００ｎｍを超えると、金属基板表面を研磨したにもかかわらず、研磨後の金属基板の３ｍｍ□におけるＲａが１０ｎｍを超えるおそれがある。研磨前の金属基板の３ｍｍ□におけるＲａ’については、研磨後の金属基板の３ｍｍ□におけるＲａと同様の測定方法により測定することができる。研磨前の表面粗さＲａ’の具体的な測定方法については、後述する。
[Surface roughness Ra ′ before polishing]
In the present invention, in order for the surface of the metal substrate after polishing to be smooth, it is preferable that the surface of the metal substrate is smooth before polishing. Specifically, Ra ′ at 3 mm □ of the metal substrate before polishing is preferably 200 nm or less, and more preferably 150 nm or less. If the Ra ′ at 3 mm □ of the metal substrate before polishing exceeds 200 nm, the Ra at 3 mm □ of the metal substrate after polishing may exceed 10 nm, even though the surface of the metal substrate is polished. Ra ′ at 3 mm □ of the metal substrate before polishing can be measured by the same measurement method as Ra at 3 mm □ of the metal substrate after polishing. A specific method for measuring the surface roughness Ra ′ before polishing will be described later.
［耐電圧］
耐電圧は後述の方法で測定でき、０．１ｋＶ以上が必要である。好ましくは０．３ｋＶ以上であり、さらに好ましくは１．０ｋＶ以上である。耐電圧が０．１ｋＶ未満であると、電極間のショートによる絶縁不良を招くおそれがある。
[Withstand voltage]
The withstand voltage can be measured by the method described later, and 0.1 kV or more is necessary. Preferably it is 0.3 kV or more, more preferably 1.0 kV or more. If the withstand voltage is less than 0.1 kV, there is a risk of causing an insulation failure due to a short circuit between the electrodes.
［サブストレート型薄膜太陽電池］
本発明に係る金属基板を備えたサブストレート型薄膜太陽電池について説明する。サブストレート型太陽電池は、本発明に係る金属基板を備えたものであれば、公知のいずれの構造でもよく、例えば、基本的には本発明に係る金属基板の樹脂皮膜上に、裏面電極、光電変換層、透明電極がこの順で積層された構造である。光電変換層は、透明電極を通過して到達した光を吸収して電流を発生させる層であり、裏面電極および透明電極は、いずれも光電変換層で発生した電流を取り出すためのものであり、いずれも導電性材料からなる。光入射側の透明電極は透光性を有する必要がある。裏面電極、光電変換層、透明電極については、公知のサブストレート型薄膜太陽電池と同様の材料を用いることができる。
[Substrate type thin film solar cell]
A substrate type thin film solar cell provided with a metal substrate according to the present invention will be described. The substrate type solar cell may have any known structure as long as it is provided with the metal substrate according to the present invention.For example, basically, on the resin film of the metal substrate according to the present invention, a back electrode, The photoelectric conversion layer and the transparent electrode are stacked in this order. The photoelectric conversion layer is a layer that absorbs light that has passed through the transparent electrode and generates a current, and the back electrode and the transparent electrode are both for taking out the current generated in the photoelectric conversion layer, Both are made of a conductive material. The transparent electrode on the light incident side needs to have translucency. About a back surface electrode, a photoelectric converting layer, and a transparent electrode, the material similar to a well-known substrate type thin film solar cell can be used.
裏面電極は、特に制限されるものではなく、例えば、Ｍｏ、Ｃｒ、Ｗ等の金属、およびこれらの金属を組み合わせたものを用いることができる。裏面電極は、単層構造でもよいし、２層構造等の積層構造でもよい。裏面電極の厚さは、特に制限されるものではないが、厚さが０．１μｍ以上であることが好ましく、０．４５〜１．０μｍであることがより好ましい。 The back electrode is not particularly limited, and for example, a metal such as Mo, Cr, W, or a combination of these metals can be used. The back electrode may have a single layer structure or a laminated structure such as a two-layer structure. The thickness of the back electrode is not particularly limited, but the thickness is preferably 0.1 μm or more, and more preferably 0.45 to 1.0 μm.
光電変換層の構成は、特に制限されるものではなく、例えば、少なくとも１種のカルコパイライト構造の化合物半導体である。また、光電変換層は、Ｉｂ族元素とＩＩＩｂ族元素とＶＩｂ族元素とからなる少なくとも１種の化合物半導体であってもよい。 The configuration of the photoelectric conversion layer is not particularly limited, and is, for example, at least one compound semiconductor having a chalcopyrite structure. The photoelectric conversion layer may be at least one compound semiconductor composed of a group Ib element, a group IIIb element, and a group VIb element.
さらに光吸収率が高く、高い光電変換効率が得られることから、光電変換層は、ＣｕおよびＡｇからなる群より選択された少なくとも１種のＩｂ族元素と、Ａｌ、ＧａおよびＩｎからなる群より選択された少なくとも１種のＩＩＩｂ族元素と、Ｓ、Ｓｅ、およびＴｅからなる群から選択された少なくとも１種のＶＩｂ族元素とからなる少なくとも１種の化合物半導体であることが好ましい。この化合物半導体としては、ＣｕＡｌＳ2、ＣｕＧａＳ2、ＣｕＩｎＳ2、ＣｕＡｌＳｅ2、ＣｕＧａＳｅ2、ＣｕＩｎＳｅ2（ＣＩＳ）、ＡｇＡｌＳ2、ＡｇＧａＳ2、ＡｇＩｎＳ2、ＡｇＡｌＳｅ2、ＡｇＧａＳｅ2、ＡｇＩｎＳｅ2、ＡｇＡｌＴｅ2、ＡｇＧａＴｅ2、ＡｇＩｎＴｅ2、Ｃｕ（Ｉｎ1-xＧａｘ）Ｓｅ2（ＣＩＧＳ）、Ｃｕ（Ｉｎ1-xＡｌx）Ｓｅ2、Ｃｕ（Ｉｎ1-xＧａx）（Ｓ、Ｓｅ）2、Ａｇ（Ｉｎ1-xＧａx）Ｓｅ2、およびＡｇ（Ｉｎ1-xＧａx）（Ｓ、Ｓｅ）2等が挙げられる。 Furthermore, since the light absorption rate is high and high photoelectric conversion efficiency is obtained, the photoelectric conversion layer is composed of at least one type Ib element selected from the group consisting of Cu and Ag, and a group consisting of Al, Ga, and In. It is preferably at least one compound semiconductor composed of at least one selected group IIIb element and at least one group VIb element selected from the group consisting of S, Se, and Te. As the compound semiconductor, CuAlS 2, CuGaS 2, CuInS 2, CuAlSe 2, CuGaSe 2, CuInSe 2 (CIS), AgAlS 2, AgGaS 2, AgInS 2, AgAlSe 2, AgGaSe 2, AgInSe 2, AgAlTe 2, AgGaTe 2 , AgInTe 2 , Cu (In 1-x Ga x ) Se 2 (CIGS), Cu (In 1-x Al x ) Se 2 , Cu (In 1-x Ga x ) (S, Se) 2 , Ag (In 1 -x Ga x) Se 2, and Ag (In 1-x Ga x ) (S, Se) 2 , and the like.
透明電極は、例えば、Ａｌ、Ｂ、Ｇａ、Ｓｂ等が添加されたＺｎＯ、ＩＴＯ（インジウム−錫酸化物）、またはＳｎＯ2およびこれらを組み合わせたものにより構成される。透明電極は、単層構造でもよいし、２層構造等の積層構造でもよい。また、透明電極の厚さは、特に制限されるものではないが、０．３〜１μｍが好ましい。 The transparent electrode is made of, for example, ZnO to which Al, B, Ga, Sb or the like is added, ITO (indium-tin oxide), SnO 2 or a combination thereof. The transparent electrode may have a single layer structure or a laminated structure such as a two-layer structure. The thickness of the transparent electrode is not particularly limited, but is preferably 0.3 to 1 μm.
サブストレート型薄膜太陽電池は公知の方法で作製することができ、例えば、以下の製造方法でサブストレート型薄膜太陽電池を作製することができる。まず、本発明に係る金属基板の上に、スパッタ法、真空蒸着法、熱ＣＶＤ法、湿式塗工法等の従来から知られている方法により裏面電極を形成する。次いで、裏面電極の上にスパッタ法、真空蒸着法、熱ＣＶＤ法、湿式塗工法等の従来から知られている方法により光電変換層を形成する。続いて、光電変換層の上にスパッタ法、真空蒸着法、熱ＣＶＤ法、湿式塗工法等の従来から知られている方法により透明電極を形成する。 A substrate type thin film solar cell can be produced by a known method. For example, a substrate type thin film solar cell can be produced by the following production method. First, a back electrode is formed on a metal substrate according to the present invention by a conventionally known method such as sputtering, vacuum deposition, thermal CVD, or wet coating. Next, a photoelectric conversion layer is formed on the back electrode by a conventionally known method such as sputtering, vacuum deposition, thermal CVD, or wet coating. Subsequently, a transparent electrode is formed on the photoelectric conversion layer by a conventionally known method such as a sputtering method, a vacuum deposition method, a thermal CVD method, or a wet coating method.
なお、透明電極の形成時に光電変換層を保護するために、光電変換層と透明電極との間にバッファ層を設けてもよい。また、透明電極の上に封止材を設けてもよい。 In addition, in order to protect a photoelectric converting layer at the time of formation of a transparent electrode, you may provide a buffer layer between a photoelectric converting layer and a transparent electrode. Moreover, you may provide a sealing material on a transparent electrode.
［トップエミッション型有機ＥＬ素子］
本発明に係る金属基板は、トップエミッション型有機ＥＬ素子にも適用可能である。このようなトップエミッション型有機ＥＬ素子は、本発明に係る金属基板を備えたものであれば、公知のいずれの構造でもよく、例えば、基本的には本発明に係る金属基板の樹脂皮膜上に、電極、有機層、透明導電膜がこの順に積層されたものである。電極、有機層、透明導電膜については、公知のトップエミッション型薄膜太陽電池と同様の材料を用いることができる。トップエミッション型有機ＥＬ素子では、光は透明導電性膜を透過して（基板を透過することなく）取り出されるため、基板として透明でない金属板を用いることができる。
[Top emission type organic EL element]
The metal substrate according to the present invention is also applicable to a top emission type organic EL element. Such a top emission type organic EL element may have any known structure as long as it is provided with the metal substrate according to the present invention. For example, the top emission type organic EL element is basically formed on the resin film of the metal substrate according to the present invention. The electrode, the organic layer, and the transparent conductive film are laminated in this order. About an electrode, an organic layer, and a transparent conductive film, the material similar to a well-known top emission type thin film solar cell can be used. In the top emission type organic EL element, since light is extracted through the transparent conductive film (without passing through the substrate), a non-transparent metal plate can be used as the substrate.
電極は、例えば、インジウム−錫酸化物（ＩＴＯ）、インジウム−亜鉛酸化物（ＩＺＯ）、錫酸化物、Ａｕ等の金属の極薄膜、導電性高分子、導電性の有機材料、ドーパント（ドナー又はアクセプタ）含有有機層、導電体と導電性有機材料（高分子含む）の混合物、又はこれらの積層体等が材料として用いられる。電極は、これら材料をスパッタ法やイオンプレーティング法等の気相成長法を用いて成膜することができる。 The electrode may be, for example, an indium-tin oxide (ITO), indium-zinc oxide (IZO), tin oxide, an ultrathin metal such as Au, a conductive polymer, a conductive organic material, a dopant (donor or An acceptor) -containing organic layer, a mixture of a conductor and a conductive organic material (including a polymer), or a laminate of these is used as the material. The electrodes can be formed using these materials by vapor phase growth methods such as sputtering and ion plating.
有機層の有機発光層は、例えば、アントラセン、ナフタレン、ピレン、テトラセン、コロネン、ペリレン、フタロペリレン、ナフタロペリレン、ジフェニルブタジエン、テトラフェニルブタジエン、クマリン、オキサジアゾール、ビスベンゾキサゾリン、ビススチリル、シクロペンタジエン、キノリン金属錯体、トリス（８−ヒドロキシキノリナート）アルミニウム錯体、トリス（４−メチル−８−キノリナート）アルミニウム錯体、トリス（５−フェニル−８−キノリナート）アルミニウム錯体、アミノキノリン金属錯体、ベンゾキノリン金属錯体、トリ−（ｐ−ターフェニル−４−イル）アミン、ピラン、キナクリドン、ルブレン、及びこれらの誘導体、あるいは、１−アリール−２，５−ジ（２−チエニル）ピロール誘導体、ジスチリルベンゼン誘導体、スチリルアリーレン誘導体、スチリルアミン誘導体、及びこれらの発光性化合物からなる基を分子の一部分に有する化合物あるいは高分子等が材料として用いられる。さらに、上記化合物に代表される蛍光色素由来の化合物のみならず、いわゆる燐光発光材料、例えば、Ｉｒ錯体、Ｏｓ錯体、Ｐｔ錯体、ユーロピウム錯体等の発光材料、若しくはそれらを分子内に有する化合物又は高分子も用いられる。有機層は、スパッタ法、真空蒸着法等の従来から知られている方法により形成することができる。なお、有機層は、有機発光層の他にも正孔注入層、正孔輸送層、電子輸送層、電子注入層等を含んでいてもよい。 The organic light-emitting layer is, for example, anthracene, naphthalene, pyrene, tetracene, coronene, perylene, phthaloperylene, naphthaloperylene, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, bisbenzoxazoline, bisstyryl, cyclopentadiene, quinoline Metal complex, tris (8-hydroxyquinolinato) aluminum complex, tris (4-methyl-8-quinolinato) aluminum complex, tris (5-phenyl-8-quinolinato) aluminum complex, aminoquinoline metal complex, benzoquinoline metal complex , Tri- (p-terphenyl-4-yl) amine, pyran, quinacridone, rubrene, and derivatives thereof, or 1-aryl-2,5-di (2-thienyl) pyrrole derivative, distili Benzene derivatives, styryl arylene derivatives, styrylamine derivatives, and compounds or polymers such having a group consisting of luminescent compounds in a part of the molecule is used as a material. In addition to compounds derived from fluorescent dyes typified by the above compounds, so-called phosphorescent materials, for example, luminescent materials such as Ir complexes, Os complexes, Pt complexes, and europium complexes, or compounds having these in the molecule or Molecules are also used. The organic layer can be formed by a conventionally known method such as sputtering or vacuum deposition. The organic layer may include a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, and the like in addition to the organic light emitting layer.
透明導電膜は、Ａｌや銀等の単体、又はＡｌや銀等と他の電極材料を組み合わせて積層構造に構成されたものが材料として用いられる。電極材料の組み合わせは、アルカリ金属とＡｌの積層体、アルカリ金属と銀の積層体、アルカリ金属のハロゲン化物とＡｌの積層体、アルカリ金属の酸化物とＡｌの積層体、アルカリ土類金属や希土類金属とＡｌの積層体、これらの金属種と他の金属の合金等が挙げられる。具体的には、例えば、ナトリウム、ナトリウム−カリウム合金、リチウム、マグネシウム等とＡｌの積層体、マグネシウム−銀混合物、マグネシウム−インジウム混合物、アルミニウム−リチウム合金、ＬｉＦとＡｌの混合物、ＡｌとＡｌ2Ｏ3の混合物等が挙げられる。透明導電膜は、スパッタ法、真空蒸着法等の従来から知られている方法により形成することができる。 As the transparent conductive film, a material composed of a single layer of Al, silver, or the like, or a layered structure obtained by combining Al, silver, or the like with another electrode material is used. Combinations of electrode materials include alkali metal and Al laminates, alkali metal and silver laminates, alkali metal halides and Al laminates, alkali metal oxides and Al laminates, alkaline earth metals and rare earths. A laminated body of metal and Al, alloys of these metal species and other metals, and the like can be given. Specifically, for example, sodium, sodium-potassium alloy, lithium, magnesium, etc. and Al laminate, magnesium-silver mixture, magnesium-indium mixture, aluminum-lithium alloy, mixture of LiF and Al, Al and Al 2 O And the like. The transparent conductive film can be formed by a conventionally known method such as sputtering or vacuum deposition.
以下に実施例を挙げて本発明をより具体的に説明するが、本発明は、下記実施例によって限定されるものではなく、前・後記の趣旨に適合しうる範囲で適宜変更して実施することも可能であり、それらはいずれも本発明の技術的範囲に包含される。また、実施例で用いた評価方法は、以下の通りである。なお、評価方法について、金属基板表面の研磨前後のいずれの供試材を用いたのかを特に記載していない場合は、金属基板表面を研磨した後の供試材を用いた。 The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples, and may be appropriately modified and implemented within a range that can meet the purpose described above and below. All of which are within the scope of the present invention. Moreover, the evaluation method used in the Example is as follows. In addition, about the evaluation method, when it was not described in particular which test material was used before and after the polishing of the metal substrate surface, the test material after polishing the metal substrate surface was used.
＜研磨前の金属基板の３ｍｍ□における表面粗さＲａ’＞
後述の作製方法で得られる供試材の研磨前の状態で表面粗さを測定した。具体的には、ＪＩＳ Ｂ ０６０１に規定される粗さの定義に基づき、原子間力顕微鏡（Ａｔｏｍｉｃ Ｆｏｒｃｅ Ｍｉｃｒｏｓｃｏｐｅ、ＡＦＭ）（セイコー電子工業製ＳＰＩ３８００Ｎ）を用いて、３ｍｍ×３ｍｍのエリアの四隅及び中央部の５箇所において、１０μｍ×１０μｍのエリア内の一方向の表面粗さＲａ１’及びそれに垂直な方向の表面粗さＲａ２’を測定し、Ｒａ１’とＲａ２’の平均値を１０μｍ×１０μｍのエリアの表面粗さとした。そして、上記５箇所の１０μｍ×１０μｍのエリアの表面粗さの平均値を研磨前の金属基板の３ｍｍ□における表面粗さＲａ’とした。
<Surface roughness Ra ′ at 3 mm □ of the metal substrate before polishing>
The surface roughness was measured in a state before polishing of the specimen obtained by the production method described later. Specifically, based on the definition of roughness defined in JIS B 0601, using an atomic force microscope (AFM) (SPI3800N manufactured by Seiko Denshi Kogyo), the four corners and the center of an area of 3 mm × 3 mm Measure the surface roughness Ra1 ′ in one direction and the surface roughness Ra2 ′ in the direction perpendicular to it in an area of 10 μm × 10 μm at five locations of the section, and determine the average value of Ra1 ′ and Ra2 ′ as an area of 10 μm × 10 μm Surface roughness. And the average value of the surface roughness of the five 10 μm × 10 μm areas was defined as the surface roughness Ra ′ at 3 mm □ of the metal substrate before polishing.
＜研磨後の金属基板の３ｍｍ□における表面粗さＲａ＞
後述の作製方法で得られる供試材を用いた以外は、研磨前の金属基板の３ｍｍ□における表面粗さＲａ’と同様の方法で表面粗さＲａを算出した。
<Surface roughness Ra of 3 mm □ of polished metal substrate>
The surface roughness Ra was calculated by the same method as the surface roughness Ra ′ at 3 mm □ of the metal substrate before polishing except that the test material obtained by the production method described later was used.
＜研磨前の金属基板の平均うねりＷａ’＞
後述の作製方法で得られる供試材の研磨前の状態で平均うねりＷａ’を測定した。具体的には、ＪＩＳ Ｂ ０６０１に規定される粗さの定義に基づき、表面粗さ・輪郭形状統合測定機（東京精密社製サーフコム（登録商標）１４００Ｄ）を用いて、２５．４ｍｍ×２５．４ｍｍのエリア内の一方向及びそれに垂直な方向の平均うねりを測定し、その平均値を平均うねりＷａ’とした。
<Average waviness Wa ′ of metal substrate before polishing>
The average waviness Wa ′ was measured in a state before polishing of the test material obtained by the production method described later. Specifically, based on the definition of roughness defined in JIS B 0601, using a surface roughness / contour shape integrated measuring machine (Surfcom (registered trademark) 1400D manufactured by Tokyo Seimitsu Co., Ltd.), 25.4 mm × 25. The average waviness in one direction in a 4 mm area and the direction perpendicular thereto was measured, and the average value was defined as the average waviness Wa ′.
＜研磨後の金属基板の平均うねりＷａ＞
後述の作製方法で得られる供試材を用いた以外は、研磨前の金属基板の３ｍｍ□における平均うねりＷａ’と同様の方法で平均うねりＷａを算出した。
<Average waviness Wa of metal substrate after polishing>
The average waviness Wa was calculated by the same method as the average waviness Wa ′ at 3 mm □ of the metal substrate before polishing, except that the test material obtained by the production method described later was used.
＜耐電圧（絶縁耐性）＞
後述の作製方法で寸法５０ｍｍ×５０ｍｍ×０．８ｍｍの供試材を作製した後、ＪＩＳ Ｃ ２１１０−１に準拠して、供試材の一方の面に外径２０ｍｍの球形電極を荷重５００ｇで接触させた状態で、絶縁破壊試験装置を用いて、２０〜４０秒程度で絶縁破壊が起こるような一定速度で厚み方向に直流電圧を印加し、絶縁破壊を生じたときの電圧を測定した。上記電圧測定を５回行い、その平均値を耐電圧とした。
<Withstand voltage (insulation resistance)>
After preparing a test material having dimensions of 50 mm × 50 mm × 0.8 mm by a manufacturing method described later, a spherical electrode having an outer diameter of 20 mm is applied to one surface of the test material with a load of 500 g in accordance with JIS C 2110-1. In the contacted state, using a dielectric breakdown test apparatus, a DC voltage was applied in the thickness direction at a constant speed such that dielectric breakdown occurred in about 20 to 40 seconds, and the voltage when dielectric breakdown occurred was measured. The voltage measurement was performed 5 times, and the average value was taken as the withstand voltage.
＜ダークスポットの有無＞
クリーンルーム内で下記要領にて有機ＥＬ素子を作製し、有機ＥＬ素子の発光状況を確認した。
（洗浄工程）
金属基板及び封止用ガラスキャップについて、超音波洗浄機を用いて、有機溶媒（ＥＬ規格品）で洗浄を行い、有機アルカリ水溶液（ＥＬ規格品）で洗浄を行い、その後、超純水で洗浄を行った。封止用ガラスキャップの詳細については後述する。次に、真空デシケーターを用いて、１５０℃で１５分間乾燥を行った。続いて、ＵＶオゾン洗浄機を用いて、ＵＶオゾン洗浄を行った。
（蒸着工程）
真空度：１〜２×１０-4Ｐａ、蒸着速度：１〜２Å／ｓで、金属基板上に、ＩＴＯ（膜厚１００ｎｍ）、ＰＥＤＯＴ（膜厚６０ｎｍ）、ＮＰＤ（膜厚８０ｎｍ）、Ａｌｑ（膜厚５０ｎｍ）、ＬｉＦ（膜厚０．８ｎｍ）、Ｍｇ：Ａｇ（膜厚１０ｎｍ）、ＩＺＯ（膜厚１００ｎｍ）の順に蒸着して積層し、有機ＥＬ素子を作製した。発光面積は約２×２ｍｍ２であった。
（作製工程）
Ｈ2Ｏ及びＯ2の濃度が１０ｐｐｍ未満であるグローブボックス内で、有機ＥＬ素子と有機ＥＬ素子を封止する封止用ガラスキャップとをシール剤（スリーボンド製ＵＶ硬化型エポキシ樹脂）を介して張り合わせた後に、グローブボックスの外に取り出してＵＶ照射を行った。その後、熱処理として、８０℃の恒温槽で３時間保温した。
（ダークスポットの有無の確認）
作製した有機ＥＬ素子を発光させ、顕微鏡で拡大観察することによりダークスポットを確認した。
<Presence of dark spots>
An organic EL element was produced in the following manner in a clean room, and the light emission state of the organic EL element was confirmed.
(Washing process)
The metal substrate and the glass cap for sealing are washed with an organic solvent (EL standard product) using an ultrasonic cleaner, washed with an organic alkaline aqueous solution (EL standard product), and then washed with ultrapure water. Went. Details of the glass cap for sealing will be described later. Next, drying was performed at 150 ° C. for 15 minutes using a vacuum desiccator. Subsequently, UV ozone cleaning was performed using a UV ozone cleaner.
(Deposition process)
Degree of vacuum: 1 to 2 × 10 −4 Pa, deposition rate: 1 to 2 Å / s, on a metal substrate, ITO (film thickness 100 nm), PEDOT (film thickness 60 nm), NPD (film thickness 80 nm), Alq ( A film thickness of 50 nm), LiF (film thickness of 0.8 nm), Mg: Ag (film thickness of 10 nm), and IZO (film thickness of 100 nm) were vapor-deposited and laminated in this order to produce an organic EL device. The light emission area was about 2 × 2 mm 2 .
(Production process)
In a glove box in which the concentration of H 2 O and O 2 is less than 10 ppm, the organic EL element and a sealing glass cap for sealing the organic EL element are passed through a sealing agent (three-bond UV curable epoxy resin). After pasting together, it was taken out of the glove box and irradiated with UV. Then, as heat processing, it heat-retained in the 80 degreeC thermostat for 3 hours.
(Check for dark spots)
The produced organic EL element was made to emit light, and a dark spot was confirmed by magnifying and observing with a microscope.
（塗料Ａの作製方法）
キシレン（沸点：１４０℃）とシクロヘキサノン（沸点：１５６℃）とを等量ずつ混合した溶媒に、ポリエステル樹脂（東洋紡社製バイロン（登録商標）２００（Ｔｇ：５３℃、Ｍｎ：３０００））を固形分換算で７５質量部、メラミン樹脂（ＤＩＣ社製スーパーベッカミン（登録商標）Ｊ−８２０−６０）を固形分換算で２５質量部加えて、塗料Ａを得た。ポリエステル樹脂とメラミン樹脂との合計の固形分が５８質量％となるようにキシレンとシクロヘキサノンとの混合溶媒の量を調整した。
(Preparation method of paint A)
Polyester resin (Byron (registered trademark) 200 manufactured by Toyobo Co., Ltd. (Tg: 53 ° C., Mn: 3000)) is solidified in a solvent in which xylene (boiling point: 140 ° C.) and cyclohexanone (boiling point: 156 ° C.) are mixed in equal amounts. 75 parts by mass, melamine resin (Super Becamine (registered trademark) J-820-60, manufactured by DIC) was added by 25 parts by mass in terms of solid content, and paint A was obtained. The amount of the mixed solvent of xylene and cyclohexanone was adjusted so that the total solid content of the polyester resin and the melamine resin was 58% by mass.
（塗料Ｂ〜Ｋの作製方法）
東洋紡社製バイロン（登録商標）２００を以下に記載のポリエステルに変更した点以外は、塗料Ａと同様にして塗料Ｂ〜Ｋを得た。ただし、塗料Ｉでは酸化チタン粒子（石原産業社製タイペーク（登録商標）ＣＲ−５０（平均粒子径０．２５μｍ））を樹脂及び架橋剤の合計１００質量部に対し、１００質量部添加した。
塗料Ｂ：東洋紡社製バイロン（登録商標）２２６（Ｔｇ：６５℃、Ｍｎ：８０００）
塗料Ｃ：東洋紡社製バイロン（登録商標）６６０（Ｔｇ：５５℃、Ｍｎ：８０００）
塗料Ｄ：東洋紡社製バイロン（登録商標）８８５（Ｔｇ：７９℃、Ｍｎ：８０００）
塗料Ｅ：東洋紡社製バイロン（登録商標）ＧＫ１３０（Ｔｇ：１５℃、Ｍｎ：７０００）
塗料Ｆ：東洋紡社製バイロン（登録商標）ＧＫ５９０（Ｔｇ：１５℃、Ｍｎ：７０００）
塗料Ｇ：東洋紡社製バイロン（登録商標）ＧＫ６８０（Ｔｇ：１０℃、Ｍｎ：６０００）
塗料Ｈ：東洋紡社製バイロン（登録商標）３００（Ｔｇ：７℃、Ｍｎ：２３０００）
塗料Ｉ：東洋紡社製バイロン（登録商標）２２０（Ｔｇ：５３℃、Ｍｎ：３０００）
塗料Ｊ：東洋紡社製バイロン（登録商標）１０３（Ｔｇ：４７℃、Ｍｎ：２３０００）
塗料Ｋ：東洋紡社製バイロン（登録商標）２００（Ｔｇ：６７℃、Ｍｎ：１７０００）
(Preparation method of paints B to K)
Coating materials B to K were obtained in the same manner as coating material A except that Byron (registered trademark) 200 manufactured by Toyobo Co., Ltd. was changed to the polyester described below. However, in the paint I, 100 parts by mass of titanium oxide particles (Ishihara Sangyo Typaque (registered trademark) CR-50 (average particle size 0.25 μm)) was added to 100 parts by mass of the resin and the crosslinking agent in total.
Paint B: Byron (registered trademark) 226 manufactured by Toyobo Co., Ltd. (Tg: 65 ° C., Mn: 8000)
Paint C: Byron (registered trademark) 660 manufactured by Toyobo Co., Ltd. (Tg: 55 ° C., Mn: 8000)
Paint D: Byon (registered trademark) 885 manufactured by Toyobo Co., Ltd. (Tg: 79 ° C., Mn: 8000)
Paint E: Byron (registered trademark) GK130 manufactured by Toyobo Co., Ltd. (Tg: 15 ° C., Mn: 7000)
Paint F: Toyobo Co., Ltd. Byron (registered trademark) GK590 (Tg: 15 ° C., Mn: 7000)
Paint G: Byron (registered trademark) GK680 manufactured by Toyobo Co., Ltd. (Tg: 10 ° C., Mn: 6000)
Paint H: Byron (registered trademark) 300 manufactured by Toyobo Co., Ltd. (Tg: 7 ° C., Mn: 23000)
Paint I: Byron (registered trademark) 220 manufactured by Toyobo Co., Ltd. (Tg: 53 ° C., Mn: 3000)
Paint J: Byron (registered trademark) 103 manufactured by Toyobo Co., Ltd. (Tg: 47 ° C., Mn: 23000)
Paint K: Byron (registered trademark) 200 manufactured by Toyobo Co., Ltd. (Tg: 67 ° C., Mn: 17000)
（実施例１）
金属板として、板厚０．８ｍｍ、金属板両面における各面当たりの亜鉛めっき付着量２０ｇ／ｍ2の電気亜鉛めっき金属板（ＥＧ）を用いた。この金属板の表面に、上記塗料Ａを膜厚が４μｍとなるようにバーコーターで塗布し、到達板温（Ｐｅａｋ Ｍｅｔａｌ Ｔｅｍｐｅｒａｔｕｒｅ：ＰＭＴ）が２２０℃となるように２分間焼付け・乾燥させ、後述の金属基板表面の研磨を行い、金属基板を得た。得られた金属基板の物性、評価結果を表１に示す。
Example 1
As the metal plate, an electrogalvanized metal plate (EG) having a plate thickness of 0.8 mm and a zinc plating adhesion amount of 20 g / m 2 on each side of the metal plate was used. The paint A is applied to the surface of the metal plate with a bar coater so as to have a film thickness of 4 μm, and is baked and dried for 2 minutes so that the ultimate plate temperature (PMT) is 220 ° C. The metal substrate surface was polished to obtain a metal substrate. Table 1 shows the physical properties and evaluation results of the obtained metal substrate.
（実施例２〜６、比較例１〜９）
金属板の表面に、上記塗料Ａ〜Ｋのいずれか一つを表１に記載の膜厚となるようにバーコーターで塗布した点以外は、実施例１と同様にして金属基板を得た。ただし、実施例５、６では、上記塗料Ａの塗布、焼付け、及び乾燥の工程を二度行い、２層の樹脂皮膜を積層した金属基板を得た。実施例５では、膜厚２μｍの樹脂皮膜を２層積層し、実施例６では、膜厚４μｍの樹脂皮膜を２層積層した。また、比較例９では、金属基板表面の研磨を行わなかった。得られた金属基板の物性、評価結果を表１に示す。
(Examples 2-6, Comparative Examples 1-9)
A metal substrate was obtained in the same manner as in Example 1 except that any one of the paints A to K was applied to the surface of the metal plate with a bar coater so as to have the film thickness shown in Table 1. However, in Examples 5 and 6, the coating, coating, and drying steps of the paint A were performed twice to obtain a metal substrate on which two resin films were laminated. In Example 5, two resin films having a film thickness of 2 μm were laminated, and in Example 6, two resin films having a film thickness of 4 μm were laminated. In Comparative Example 9, the metal substrate surface was not polished. Table 1 shows the physical properties and evaluation results of the obtained metal substrate.
（金属基板表面の研磨）
研磨装置の基板取り付け用の吸着パッドを貼り付けたホルダーに金属基板をセットし、樹脂皮膜を下にして研磨装置の定盤に取り付けた研磨パッド上にセットした。研磨剤として、粒径が約１００ｎｍのアルミナ粒子を用い、圧力６５ｇｆ／ｃｍ2、１周当たりの回転距離を１ｍ、基板と定盤との各回転速度５０ｒｐｍで１分間化学機械（ＣＭＰ）研磨を行った。いずれの実施例及び比較例においても、研磨後における樹脂皮膜の被覆率は１００％であった。
(Polishing the metal substrate surface)
A metal substrate was set in a holder to which a suction pad for mounting the substrate of the polishing apparatus was attached, and set on the polishing pad mounted on the surface plate of the polishing apparatus with the resin film facing down. As an abrasive, alumina particles having a particle diameter of about 100 nm are used, and a chemical mechanical (CMP) polishing is performed for 1 minute at a pressure of 65 gf / cm 2 , a rotation distance per rotation of 1 m, and a rotation speed of 50 rpm between the substrate and the surface plate. went. In any of the examples and comparative examples, the coverage of the resin film after polishing was 100%.
膜厚が３μｍ以上である樹脂皮膜が積層された金属基板の表面を研磨して表面を平滑にすることによって、この金属基板が太陽電池又は有機ＥＬ素子に用いられた場合に、絶縁性に優れ、かつ、ダークスポットが発生しない太陽電池又は有機ＥＬ素子とすることができる。 By polishing the surface of the metal substrate on which the resin film having a film thickness of 3 μm or more is laminated and smoothing the surface, the metal substrate is excellent in insulation when used for solar cells or organic EL elements. And it can be set as the solar cell or organic EL element which a dark spot does not generate | occur | produce.
Claims (6)
上記樹脂皮膜の膜厚が３μｍ以上であり、
上記金属基板の３ｍｍ□における表面粗さＲａが、１０ｎｍ以下である
ことを特徴とするサブストレート型薄膜太陽電池又はトップエミッション型有機ＥＬ素子に用いられる金属基板。 A metal substrate having a resin film laminated on at least one side of a metal plate,
The film thickness of the resin film is 3 μm or more,
The metal substrate used for a substrate-type thin film solar cell or a top emission type organic EL device, wherein the surface roughness Ra at 3 mm □ of the metal substrate is 10 nm or less.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015073897A JP2016193512A (en) | 2015-03-31 | 2015-03-31 | Metal substrate |
| PCT/JP2016/059423 WO2016158678A1 (en) | 2015-03-31 | 2016-03-24 | Metal substrate |
| CN201680017899.5A CN107409446A (en) | 2015-03-31 | 2016-03-24 | Metal substrate |
| KR1020177030963A KR20170131629A (en) | 2015-03-31 | 2016-03-24 | Metal substrate |
| TW105110345A TWI629801B (en) | 2015-03-31 | 2016-03-31 | Metal substrate for substrate type thin film solar cell or upper light emitting type organic EL element |
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| Application Number | Priority Date | Filing Date | Title |
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| JP2015073897A JP2016193512A (en) | 2015-03-31 | 2015-03-31 | Metal substrate |
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| JP2016193512A true JP2016193512A (en) | 2016-11-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| Country | Link |
|---|---|
| JP (1) | JP2016193512A (en) |
| KR (1) | KR20170131629A (en) |
| CN (1) | CN107409446A (en) |
| TW (1) | TWI629801B (en) |
| WO (1) | WO2016158678A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190133212A (en) * | 2017-03-30 | 2019-12-02 | 가부시키가이샤 고베 세이코쇼 | Insulation film laminated metal plate and metal substrate |
| JP2020038790A (en) * | 2018-09-04 | 2020-03-12 | 株式会社神戸製鋼所 | Organic electronic device and substrate for organic electronic device |
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| JP2010135300A (en) * | 2008-11-10 | 2010-06-17 | Kobe Steel Ltd | Reflecting anodic electrode for organic el display, and manufacturing method thereof |
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- 2016-03-24 CN CN201680017899.5A patent/CN107409446A/en active Pending
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- 2016-03-24 WO PCT/JP2016/059423 patent/WO2016158678A1/en active Application Filing
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| WO2004053819A1 (en) * | 2002-12-06 | 2004-06-24 | Citizen Watch Co., Ltd. | Liquid crystal display |
| JP2004191463A (en) * | 2002-12-09 | 2004-07-08 | Hitachi Metals Ltd | Substrate for display and method for manufacturing the same |
| JP2004303644A (en) * | 2003-03-31 | 2004-10-28 | Seiko Epson Corp | Manufacturing method for electrooptical device, and electrooptical device, as well as electronic apparatus |
| JP2010191466A (en) * | 2010-05-07 | 2010-09-02 | Dainippon Printing Co Ltd | Color filter substrate for organic electroluminescent element |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20190133212A (en) * | 2017-03-30 | 2019-12-02 | 가부시키가이샤 고베 세이코쇼 | Insulation film laminated metal plate and metal substrate |
| KR102338975B1 (en) | 2017-03-30 | 2021-12-13 | 가부시키가이샤 고베 세이코쇼 | Insulation coating laminated metal plate and metal substrate |
| JP2020038790A (en) * | 2018-09-04 | 2020-03-12 | 株式会社神戸製鋼所 | Organic electronic device and substrate for organic electronic device |
| WO2020049898A1 (en) * | 2018-09-04 | 2020-03-12 | 株式会社神戸製鋼所 | Organic electronic device and substrate for organic electronic device |
| JP7066578B2 (en) | 2018-09-04 | 2022-05-13 | 株式会社神戸製鋼所 | Organic electronic devices and substrates for organic electronic devices |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI629801B (en) | 2018-07-11 |
| TW201705503A (en) | 2017-02-01 |
| WO2016158678A1 (en) | 2016-10-06 |
| CN107409446A (en) | 2017-11-28 |
| KR20170131629A (en) | 2017-11-29 |
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