JPH01243068A - Photosensitive body and its production - Google Patents
Photosensitive body and its productionInfo
- Publication number
- JPH01243068A JPH01243068A JP7146488A JP7146488A JPH01243068A JP H01243068 A JPH01243068 A JP H01243068A JP 7146488 A JP7146488 A JP 7146488A JP 7146488 A JP7146488 A JP 7146488A JP H01243068 A JPH01243068 A JP H01243068A
- Authority
- JP
- Japan
- Prior art keywords
- protective layer
- surface protective
- layer
- photoreceptor
- fluorine atoms
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 239000011241 protective layer Substances 0.000 claims abstract description 148
- 239000010410 layer Substances 0.000 claims abstract description 115
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 51
- 229920005989 resin Polymers 0.000 claims abstract description 33
- 239000011347 resin Substances 0.000 claims abstract description 33
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 18
- 238000010030 laminating Methods 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 108091008695 photoreceptors Proteins 0.000 claims description 72
- 238000000034 method Methods 0.000 claims description 35
- 239000000758 substrate Substances 0.000 claims description 33
- 238000000576 coating method Methods 0.000 claims description 20
- 150000002736 metal compounds Chemical class 0.000 claims description 20
- 125000004429 atom Chemical group 0.000 claims description 9
- 238000007740 vapor deposition Methods 0.000 claims description 8
- 238000007788 roughening Methods 0.000 claims description 5
- 229920000620 organic polymer Polymers 0.000 claims description 3
- 230000001771 impaired effect Effects 0.000 abstract description 2
- -1 C r2O3 Inorganic materials 0.000 description 31
- 239000007789 gas Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 21
- 230000000694 effects Effects 0.000 description 17
- 229910052731 fluorine Inorganic materials 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- 239000011737 fluorine Substances 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 150000002222 fluorine compounds Chemical class 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 230000006870 function Effects 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 230000000737 periodic effect Effects 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 206010034972 Photosensitivity reaction Diseases 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 230000036211 photosensitivity Effects 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- FAMPSKZZVDUYOS-UHFFFAOYSA-N 2,6,6,9-tetramethylcycloundeca-1,4,8-triene Chemical compound CC1=CCC(C)(C)C=CCC(C)=CCC1 FAMPSKZZVDUYOS-UHFFFAOYSA-N 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 3
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-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
- 229920000877 Melamine resin Polymers 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 150000001787 chalcogens Chemical group 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229910052976 metal sulfide Inorganic materials 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- IBXNCJKFFQIKKY-UHFFFAOYSA-N 1-pentyne Chemical compound CCCC#C IBXNCJKFFQIKKY-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- WGLLSSPDPJPLOR-UHFFFAOYSA-N 2,3-dimethylbut-2-ene Chemical group CC(C)=C(C)C WGLLSSPDPJPLOR-UHFFFAOYSA-N 0.000 description 2
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 2
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N 2-Methylheptane Chemical compound CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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
- 239000005062 Polybutadiene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 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
- 150000001501 aryl fluorides Chemical class 0.000 description 2
- CJPQIRJHIZUAQP-MRXNPFEDSA-N benalaxyl-M Chemical compound CC=1C=CC=C(C)C=1N([C@H](C)C(=O)OC)C(=O)CC1=CC=CC=C1 CJPQIRJHIZUAQP-MRXNPFEDSA-N 0.000 description 2
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical compound CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- SQNZJJAZBFDUTD-UHFFFAOYSA-N durene Chemical compound CC1=CC(C)=C(C)C=C1C SQNZJJAZBFDUTD-UHFFFAOYSA-N 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 description 2
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910001512 metal fluoride Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- NMRPBPVERJPACX-UHFFFAOYSA-N octan-3-ol Chemical compound CCCCCC(O)CC NMRPBPVERJPACX-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- NPNUFJAVOOONJE-ZIAGYGMSSA-N β-(E)-Caryophyllene Chemical compound C1CC(C)=CCCC(=C)[C@H]2CC(C)(C)[C@@H]21 NPNUFJAVOOONJE-ZIAGYGMSSA-N 0.000 description 2
- AFVDZBIIBXWASR-AATRIKPKSA-N (E)-1,3,5-hexatriene Chemical compound C=C\C=C\C=C AFVDZBIIBXWASR-AATRIKPKSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 description 1
- ZVJOQYFQSQJDDX-UHFFFAOYSA-N 1,1,2,3,3,4,4,4-octafluorobut-1-ene Chemical compound FC(F)=C(F)C(F)(F)C(F)(F)F ZVJOQYFQSQJDDX-UHFFFAOYSA-N 0.000 description 1
- PBWHQPOHADDEFU-UHFFFAOYSA-N 1,1,2,3,3,4,4,5,5,5-decafluoropent-1-ene Chemical compound FC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F PBWHQPOHADDEFU-UHFFFAOYSA-N 0.000 description 1
- RMHCWMIZBMGHKV-UHFFFAOYSA-N 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluorohex-1-ene Chemical compound FC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RMHCWMIZBMGHKV-UHFFFAOYSA-N 0.000 description 1
- CDAVUOSPHHTNBU-UHFFFAOYSA-N 1,1,2,3,3,4,4,5,5,6,6,7,7,7-tetradecafluorohept-1-ene Chemical compound FC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CDAVUOSPHHTNBU-UHFFFAOYSA-N 0.000 description 1
- YCBPKOZNGFQMPB-UHFFFAOYSA-N 1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,8-hexadecafluorooct-1-ene Chemical compound FC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YCBPKOZNGFQMPB-UHFFFAOYSA-N 0.000 description 1
- UAFOIVDGAVVKTE-UHFFFAOYSA-N 1,1,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-octadecafluoronon-1-ene Chemical compound FC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F UAFOIVDGAVVKTE-UHFFFAOYSA-N 0.000 description 1
- JDCMOHAFGDQQJX-UHFFFAOYSA-N 1,2,3,4,5,6,7,8-octafluoronaphthalene Chemical compound FC1=C(F)C(F)=C(F)C2=C(F)C(F)=C(F)C(F)=C21 JDCMOHAFGDQQJX-UHFFFAOYSA-N 0.000 description 1
- USPWUOFNOTUBAD-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(trifluoromethyl)benzene Chemical compound FC1=C(F)C(F)=C(C(F)(F)F)C(F)=C1F USPWUOFNOTUBAD-UHFFFAOYSA-N 0.000 description 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- CGHIBGNXEGJPQZ-UHFFFAOYSA-N 1-hexyne Chemical compound CCCCC#C CGHIBGNXEGJPQZ-UHFFFAOYSA-N 0.000 description 1
- XBGUIVFBMBVUEG-UHFFFAOYSA-N 1-methyl-4-(1,5-dimethyl-4-hexenylidene)-1-cyclohexene Chemical compound CC(C)=CCCC(C)=C1CCC(C)=CC1 XBGUIVFBMBVUEG-UHFFFAOYSA-N 0.000 description 1
- ONVABDHFQKWOSV-UHFFFAOYSA-N 16-Phyllocladene Natural products C1CC(C2)C(=C)CC32CCC2C(C)(C)CCCC2(C)C31 ONVABDHFQKWOSV-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical compound CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- FPZWZCWUIYYYBU-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl acetate Chemical compound CCOCCOCCOC(C)=O FPZWZCWUIYYYBU-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- WFSMVVDJSNMRAR-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]ethanol Chemical compound CCOCCOCCOCCO WFSMVVDJSNMRAR-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- TZYRSLHNPKPEFV-UHFFFAOYSA-N 2-ethyl-1-butanol Chemical compound CCC(CC)CO TZYRSLHNPKPEFV-UHFFFAOYSA-N 0.000 description 1
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 1
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 1
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 description 1
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 1
- AEXMKKGTQYQZCS-UHFFFAOYSA-N 3,3-dimethylpentane Chemical compound CCC(C)(C)CC AEXMKKGTQYQZCS-UHFFFAOYSA-N 0.000 description 1
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 1
- KUKRLSJNTMLPPK-UHFFFAOYSA-N 4,7,7-trimethylbicyclo[2.2.1]hept-2-ene Chemical group C1CC2(C)C=CC1C2(C)C KUKRLSJNTMLPPK-UHFFFAOYSA-N 0.000 description 1
- YFBGSHHKHHCVDI-UHFFFAOYSA-N 4-ethoxybutan-2-one Chemical compound CCOCCC(C)=O YFBGSHHKHHCVDI-UHFFFAOYSA-N 0.000 description 1
- LVSQXDHWDCMMRJ-UHFFFAOYSA-N 4-hydroxybutan-2-one Chemical compound CC(=O)CCO LVSQXDHWDCMMRJ-UHFFFAOYSA-N 0.000 description 1
- NVEQFIOZRFFVFW-UHFFFAOYSA-N 9-epi-beta-caryophyllene oxide Natural products C=C1CCC2OC2(C)CCC2C(C)(C)CC21 NVEQFIOZRFFVFW-UHFFFAOYSA-N 0.000 description 1
- GLVKGYRREXOCIB-UHFFFAOYSA-N Bornylene Natural products CC1CCC(C(C)(C)C)C=C1 GLVKGYRREXOCIB-UHFFFAOYSA-N 0.000 description 1
- VMYXUZSZMNBRCN-AWEZNQCLSA-N Curcumene Natural products CC(C)=CCC[C@H](C)C1=CC=C(C)C=C1 VMYXUZSZMNBRCN-AWEZNQCLSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- DQUHDYWUEKWRLN-UHFFFAOYSA-N Isophyllocladen Natural products C1CC2C3(C)CCCC(C)(C)C3CCC22C=C(C)C1C2 DQUHDYWUEKWRLN-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N Lactic Acid Natural products CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- CBSRFDQDBGGSEA-UHFFFAOYSA-N Selinene Natural products CC(=C1CCC2(C)CCCC(=C)C2(C)C1)C CBSRFDQDBGGSEA-UHFFFAOYSA-N 0.000 description 1
- JWQKMEKSFPNAIB-UHFFFAOYSA-N Silvestrene Natural products CC(=C)C1CCC=C(C)C1 JWQKMEKSFPNAIB-UHFFFAOYSA-N 0.000 description 1
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- WWMMWLRYCXLQNM-UHFFFAOYSA-N [O-2].O.[Zn+2].[SeH2] Chemical compound [O-2].O.[Zn+2].[SeH2] WWMMWLRYCXLQNM-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- YHBUQBJHSRGZNF-HNNXBMFYSA-N alpha-bisabolene Natural products CC(C)=CCC=C(C)[C@@H]1CCC(C)=CC1 YHBUQBJHSRGZNF-HNNXBMFYSA-N 0.000 description 1
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- XILYOLONIFWGMT-UHFFFAOYSA-N benzene;dihydrochloride Chemical compound Cl.Cl.C1=CC=CC=C1 XILYOLONIFWGMT-UHFFFAOYSA-N 0.000 description 1
- ULKGULQGPBMIJU-UHFFFAOYSA-N benzene;hydron;bromide Chemical compound Br.C1=CC=CC=C1 ULKGULQGPBMIJU-UHFFFAOYSA-N 0.000 description 1
- NPNUFJAVOOONJE-UHFFFAOYSA-N beta-cariophyllene Natural products C1CC(C)=CCCC(=C)C2CC(C)(C)C21 NPNUFJAVOOONJE-UHFFFAOYSA-N 0.000 description 1
- 229930003493 bisabolene Natural products 0.000 description 1
- MZJUGRUTVANEDW-UHFFFAOYSA-N bromine fluoride Chemical compound BrF MZJUGRUTVANEDW-UHFFFAOYSA-N 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 150000004648 butanoic acid derivatives Chemical class 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229930006737 car-3-ene Natural products 0.000 description 1
- BQOFWKZOCNGFEC-UHFFFAOYSA-N carene Chemical compound C1C(C)=CCC2C(C)(C)C12 BQOFWKZOCNGFEC-UHFFFAOYSA-N 0.000 description 1
- 229930007796 carene Natural products 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- NPNUFJAVOOONJE-UONOGXRCSA-N caryophyllene Natural products C1CC(C)=CCCC(=C)[C@@H]2CC(C)(C)[C@@H]21 NPNUFJAVOOONJE-UONOGXRCSA-N 0.000 description 1
- 229940117948 caryophyllene Drugs 0.000 description 1
- IRAQOCYXUMOFCW-CXTNEJHOSA-N cedrene Chemical compound C1[C@]23[C@H](C)CC[C@H]3C(C)(C)[C@H]1C(C)=CC2 IRAQOCYXUMOFCW-CXTNEJHOSA-N 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- 238000012217 deletion Methods 0.000 description 1
- 230000037430 deletion Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- IRAQOCYXUMOFCW-UHFFFAOYSA-N di-epi-alpha-cedrene Natural products C1C23C(C)CCC3C(C)(C)C1C(C)=CC2 IRAQOCYXUMOFCW-UHFFFAOYSA-N 0.000 description 1
- PWEVMPIIOJUPRI-UHFFFAOYSA-N dimethyltin Chemical compound C[Sn]C PWEVMPIIOJUPRI-UHFFFAOYSA-N 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- LMBMDLOSPKIWAP-UHFFFAOYSA-N embutramide Chemical compound OCCCC(=O)NCC(CC)(CC)C1=CC=CC(OC)=C1 LMBMDLOSPKIWAP-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 229940117360 ethyl pyruvate Drugs 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- OMRRUNXAWXNVFW-UHFFFAOYSA-N fluoridochlorine Chemical compound ClF OMRRUNXAWXNVFW-UHFFFAOYSA-N 0.000 description 1
- GNTRBBGWVVMYJH-UHFFFAOYSA-M fluoro(dimethyl)alumane Chemical compound [F-].C[Al+]C GNTRBBGWVVMYJH-UHFFFAOYSA-M 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- BXWQUXUDAGDUOS-UHFFFAOYSA-N gamma-humulene Natural products CC1=CCCC(C)(C)C=CC(=C)CCC1 BXWQUXUDAGDUOS-UHFFFAOYSA-N 0.000 description 1
- 229940052308 general anesthetics halogenated hydrocarbons Drugs 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- YVXHZKKCZYLQOP-UHFFFAOYSA-N hept-1-yne Chemical compound CCCCCC#C YVXHZKKCZYLQOP-UHFFFAOYSA-N 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- YUWFEBAXEOLKSG-UHFFFAOYSA-N hexamethylbenzene Chemical compound CC1=C(C)C(C)=C(C)C(C)=C1C YUWFEBAXEOLKSG-UHFFFAOYSA-N 0.000 description 1
- QBNFBHXQESNSNP-UHFFFAOYSA-N humulene Natural products CC1=CC=CC(C)(C)CC=C(/C)CCC1 QBNFBHXQESNSNP-UHFFFAOYSA-N 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- PDJAZCSYYQODQF-UHFFFAOYSA-N iodine monofluoride Chemical compound IF PDJAZCSYYQODQF-UHFFFAOYSA-N 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- UEBCFKSPKUURKQ-UHFFFAOYSA-L methylaluminum(2+);difluoride Chemical compound [F-].[F-].[Al+2]C UEBCFKSPKUURKQ-UHFFFAOYSA-L 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 150000007823 ocimene derivatives Chemical class 0.000 description 1
- QYSGYZVSCZSLHT-UHFFFAOYSA-N octafluoropropane Chemical compound FC(F)(F)C(F)(F)C(F)(F)F QYSGYZVSCZSLHT-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- BEZDDPMMPIDMGJ-UHFFFAOYSA-N pentamethylbenzene Chemical compound CC1=CC(C)=C(C)C(C)=C1C BEZDDPMMPIDMGJ-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 229960004624 perflexane Drugs 0.000 description 1
- KAVGMUDTWQVPDF-UHFFFAOYSA-N perflubutane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)F KAVGMUDTWQVPDF-UHFFFAOYSA-N 0.000 description 1
- 229950003332 perflubutane Drugs 0.000 description 1
- ZJIJAJXFLBMLCK-UHFFFAOYSA-N perfluorohexane Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZJIJAJXFLBMLCK-UHFFFAOYSA-N 0.000 description 1
- 229960004065 perflutren Drugs 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- ONVABDHFQKWOSV-NDLGOLERSA-N phyllocladene Chemical compound C1C[C@@H](C2)C(=C)C[C@]32CC[C@@H]2C(C)(C)CCC[C@@]2(C)[C@@H]31 ONVABDHFQKWOSV-NDLGOLERSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- KIWATKANDHUUOB-UHFFFAOYSA-N propan-2-yl 2-hydroxypropanoate Chemical compound CC(C)OC(=O)C(C)O KIWATKANDHUUOB-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- KKOXKGNSUHTUBV-UHFFFAOYSA-N racemic zingiberene Natural products CC(C)=CCCC(C)C1CC=C(C)C=C1 KKOXKGNSUHTUBV-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 229960005265 selenium sulfide Drugs 0.000 description 1
- VPQBJIRQUUEAFC-UHFFFAOYSA-N selinene Natural products C1CC=C(C)C2CC(C(C)C)CCC21C VPQBJIRQUUEAFC-UHFFFAOYSA-N 0.000 description 1
- 150000003598 selinene derivatives Chemical class 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- ZGGXZRVTYVVPBU-UHFFFAOYSA-N styrene;hydrofluoride Chemical class F.C=CC1=CC=CC=C1 ZGGXZRVTYVVPBU-UHFFFAOYSA-N 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- XJPBRODHZKDRCB-UHFFFAOYSA-N trans-alpha-ocimene Natural products CC(=C)CCC=C(C)C=C XJPBRODHZKDRCB-UHFFFAOYSA-N 0.000 description 1
- 229960002415 trichloroethylene Drugs 0.000 description 1
- RRBYUSWBLVXTQN-VZCHMASFSA-N tricyclene Natural products C([C@@H]12)C3C[C@H]1C2(C)C3(C)C RRBYUSWBLVXTQN-VZCHMASFSA-N 0.000 description 1
- RRBYUSWBLVXTQN-UHFFFAOYSA-N tricyclene Chemical compound C12CC3CC2C1(C)C3(C)C RRBYUSWBLVXTQN-UHFFFAOYSA-N 0.000 description 1
- ULIAPOFMBCCSPE-UHFFFAOYSA-N tridecan-7-one Chemical compound CCCCCCC(=O)CCCCCC ULIAPOFMBCCSPE-UHFFFAOYSA-N 0.000 description 1
- MLSXQSHQPJCECC-UHFFFAOYSA-K trifluoro(methyl)stannane Chemical compound [F-].[F-].[F-].[Sn+3]C MLSXQSHQPJCECC-UHFFFAOYSA-K 0.000 description 1
- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 description 1
- YYPUUFWMUHDIRL-UHFFFAOYSA-M trimethylstannanylium;fluoride Chemical compound C[Sn](C)(C)F YYPUUFWMUHDIRL-UHFFFAOYSA-M 0.000 description 1
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- KKOXKGNSUHTUBV-LSDHHAIUSA-N zingiberene Chemical compound CC(C)=CCC[C@H](C)[C@H]1CC=C(C)C=C1 KKOXKGNSUHTUBV-LSDHHAIUSA-N 0.000 description 1
- 229930001895 zingiberene Natural products 0.000 description 1
- VMYXUZSZMNBRCN-UHFFFAOYSA-N α-curcumene Chemical compound CC(C)=CCCC(C)C1=CC=C(C)C=C1 VMYXUZSZMNBRCN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/14—Inert intermediate or cover layers for charge-receiving layers
- G03G5/147—Cover layers
- G03G5/14704—Cover layers comprising inorganic material
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Photoreceptors In Electrophotography (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は導電性基板上に有機系感光層と表面保護層とを
順次積層して構成される感光体及びその製造方法に関す
る。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a photoreceptor constructed by sequentially laminating an organic photosensitive layer and a surface protective layer on a conductive substrate, and a method for manufacturing the same.
従来の技術
従来、可視光に感度を有する電子写真用感光体は複写機
、プリンター等に広く使用されている。2. Description of the Related Art Conventionally, electrophotographic photoreceptors sensitive to visible light have been widely used in copying machines, printers, and the like.
このような電子写真用感光体としては、セレン酸化亜鉛
、硫化カドミウム等の無機光導電物質を主成分とする感
光層を設けた無機感光体が広く使用されている。しかし
ながら、これらの無機感光体は、複写機等の電子写真感
光体として要求される暗抵抗、明抵抗などの光感度特性
に優れるものの、熱安定性、耐湿性、耐久性等の特性に
おいて必ずしも満足できるものではない。例えばセレン
は熱や手で触ったときの指紋の汚れ等により結晶化する
ため、電子写真感光体としての上記の特性が劣化し易い
。また硫化カドミウムを用いた電子写真感光体は耐湿性
、耐久性に劣り、又酸化亜鉛を用いた電子写真感光体は
耐久性に問題がある。又、セレン、硫化カドミウムの電
子写真感光体は製造上、取扱いの制約が大きいという欠
点もある。As such electrophotographic photoreceptors, inorganic photoreceptors provided with a photosensitive layer containing an inorganic photoconductive substance such as selenium zinc oxide or cadmium sulfide as a main component are widely used. However, although these inorganic photoreceptors have excellent photosensitivity characteristics such as dark resistance and bright resistance required for electrophotographic photoreceptors such as copying machines, they do not necessarily satisfy characteristics such as thermal stability, moisture resistance, and durability. It's not possible. For example, since selenium crystallizes due to heat or fingerprint stains when touched, the above-mentioned characteristics as an electrophotographic photoreceptor are likely to deteriorate. Further, electrophotographic photoreceptors using cadmium sulfide have poor moisture resistance and durability, and electrophotographic photoreceptors using zinc oxide have problems in durability. Furthermore, electrophotographic photoreceptors made of selenium or cadmium sulfide have the disadvantage that there are significant restrictions in their handling during manufacture.
このような無機光導電性物質の問題点を改善するために
、種々の有機の光導電性物質を電子写真感光体の感光層
に使用することが試みられ、近年活発に研究、開発が行
われている。In order to improve these problems with inorganic photoconductive materials, attempts have been made to use various organic photoconductive materials in the photosensitive layer of electrophotographic photoreceptors, and active research and development has been carried out in recent years. ing.
このような有機光導電性物質としては、ポリビニルカル
バゾールなどをあげることができる。しかし、このよう
な感光体も、感度及び耐湿性、耐久性において十分では
ない。そのため、感光層を二層に分けて、キャリア発生
層とキャリア輸送層を別々に構成し、それぞれにキャリ
ア発生物質、キャリア輸送物質を含有させた機能分離型
の電子写真感光体が開発された。これはキャリア発生機
能と、キャリア輸送機能を異なる物質に閏別に分担させ
ることができるため、各機能を発揮する物質を広い範囲
のものから選択することができるので、任意の特性を有
する電子写真感光体を比較的容易に得られ、したがって
感度が高く、耐湿性、耐久性の大きい有機感光体が得ら
れることが期待されている。Examples of such organic photoconductive substances include polyvinylcarbazole. However, such photoreceptors are also insufficient in sensitivity, moisture resistance, and durability. Therefore, a functionally separated electrophotographic photoreceptor has been developed in which the photosensitive layer is divided into two layers, a carrier generation layer and a carrier transport layer are separately configured, and each contains a carrier generation substance and a carrier transport substance. This is because the carrier generation function and the carrier transport function can be divided into different substances, and the substances that perform each function can be selected from a wide range of materials. Therefore, it is expected that an organic photoreceptor with high sensitivity, moisture resistance, and durability can be obtained.
一般に実用に供している有機感光体はその表面が柔らか
く、（ＪＩＳ −Ｋ −５４００規格の鉛筆で５Ｂ〜Ｂ
程度）、そのため感光層は複写機等内で、種々の接触部
材（クリーナーブレード、親像剤、転写紙等）との摩擦
により常時削りとられるため、感光層膜厚がすぐに薄く
なり、帯電電位の低下を招き、長期に渡って使用するこ
とができないという問題点があった。Generally, the organic photoreceptor used in practical use has a soft surface (5B to B with a JIS-K-5400 standard pencil).
For this reason, the photosensitive layer is constantly scraped off by friction with various contact members (cleaner blade, image parent, transfer paper, etc.) in copying machines, etc., so the thickness of the photosensitive layer quickly becomes thinner and the charging There was a problem in that it caused a drop in potential and could not be used for a long period of time.
この有機感光体の耐久性の不足という問題点の解決のた
め、種々の表面保護層を設けることが提案されており、
例えば同じ有機系のものでも硬度の高いものを塗布によ
って積層させる方法、真空蒸着等の手段によって無機層
を積層させる方法、さらには熱履歴を与えることにより
表面硬化可能な材料を積層させる方法などが提案されて
いるが、公知の有機系感光層材料においては、耐熱性に
乏しい化合物が殆どであり、保護膜形成時に高温加熱状
態を経る事ができない。このため、例えば、熱硬化性樹
脂を塗布し、加熱硬化すれば、３Ｈ乃至６Ｈ程度の硬膜
が得られるが、加熱処理により感光層が変性し、好適な
感度が得られなくなる。従って、有機系感光層材料の種
類によっても異なるが、保護膜形成温度は常温が最も好
ましく、僅かに加熱するにしても、その最高温度は高々
１００℃までに抑える必要がある。In order to solve the problem of lack of durability of organic photoreceptors, it has been proposed to provide various surface protective layers.
For example, there are methods of laminating organic materials with high hardness by coating, methods of laminating inorganic layers by means such as vacuum evaporation, and methods of laminating materials that can harden the surface by applying heat history. Although this has been proposed, most of the known organic photosensitive layer materials include compounds with poor heat resistance and cannot be subjected to high-temperature heating during the formation of a protective film. For this reason, for example, if a thermosetting resin is applied and cured by heating, a hard film of about 3H to 6H can be obtained, but the heat treatment modifies the photosensitive layer and makes it impossible to obtain suitable sensitivity. Therefore, although it varies depending on the type of organic photosensitive layer material, the temperature for forming the protective film is most preferably room temperature, and even if it is slightly heated, the maximum temperature must be kept to at most 100°C.
さらにこれらの方法はいずれも削れに対する保護層とし
ての機能、つまり耐久性は十分であるものの、保護層と
有機感光層との接着性の乏しさ等に起因する耐湿性の悪
さという問題点には不十分であった。Furthermore, although all of these methods function as a protective layer against scratching, that is, have sufficient durability, they do not address the problem of poor moisture resistance due to poor adhesion between the protective layer and the organic photosensitive layer. It was insufficient.
上記のような事情から、耐湿性と耐久性の双方に優れた
保護層（例として特開昭６２−１５６６６４などを例示
できる。）をもつ有機感光体が望まれており、本発明者
らの研究によれば、アモルファスカーボンの保護層中に
フン素原子を含有させたところ、耐湿性ど耐久性にすぐ
れた有機感光体が得られることが確かめられた。さらに
上記保護層中のフッ素原子濃度を高めてゆく程、より耐
湿性に優れた感光体が得られることが見出された。Due to the above-mentioned circumstances, an organic photoreceptor with a protective layer having excellent moisture resistance and durability (for example, JP-A-62-156664 can be cited) is desired, and the inventors of the present invention have proposed According to research, it has been confirmed that by incorporating fluorine atoms into the protective layer of amorphous carbon, an organic photoreceptor with excellent moisture resistance and durability can be obtained. Furthermore, it has been found that as the fluorine atom concentration in the protective layer is increased, a photoreceptor with better moisture resistance can be obtained.
しかしながら上記のようなフッ素を含有する表面保護層
を有する有機感光体を実際に複写機等で使用したところ
、複写初期に保護層表面に多数存在するフッ素原子の電
気陰性度の大きさに起因すると思われる画像カブリが発
生することが認められた。即ち、本発明者らの推察によ
れば、所謂電子写真プロセスのうち、現像プロセス時に
フッ素原子を含有する表面保護層を有する感光体の非画
像部と現像剤が接触する場合、この表面保護層中の７ノ
素原子が非常に電気陰性度が大きいために、接触した現
像剤はその材質の如何にかかわらず全て感光体に対して
静電気系列的に正に帯電させられ、表面保護層中のフッ
素原子と静電気的に吸引し合い、その結果、感光体の非
画像部にも現像剤が保持され、画像カブリが発生するも
のである。However, when an organic photoreceptor with a fluorine-containing surface protective layer as described above was actually used in a copying machine, it was found that this was due to the high electronegativity of the fluorine atoms present in large numbers on the surface of the protective layer at the initial stage of copying. It was observed that some image fogging occurred. That is, according to the inventors' speculation, in the so-called electrophotographic process, when a developer comes into contact with a non-image area of a photoreceptor having a surface protective layer containing fluorine atoms during the development process, this surface protective layer Because the seven atoms in the photoreceptor have extremely high electronegativity, all the developer that comes into contact with the photoreceptor is electrostatically positively charged, regardless of its material, and the surface protective layer is electrostatically positively charged. The developer is electrostatically attracted to the fluorine atoms, and as a result, the developer is retained even in non-image areas of the photoreceptor, causing image fogging.
これらのメカニズムは必ずしも明白ではないが、現像剤
と表面保護層との接触摩擦帯電や、接触電位差により静
電力的に吸引させられ、−指付着後は、ファンデルワー
ルス力が付加するので、そのまま転写部まで運ばれ、転
写紙に転写してしまい、前述のカプリを引き起こすと思
われる。さらに本発明らは、上記の様な画像カブリが２
成分の接触、非接触現像方法にかかわらず、又１成分の
接触、非接触現像方法にかかわらず、現像剤と感光体が
物理的に接触する場合には必ず発生することを確認して
いる。（ただし、キャリア材は磁力、電場等で現像スリ
ーブに強く吸引している為、表面保護層には付着せず、
摩擦帯電電荷を付与することにのみ寄与していると考え
られる。）
本発明は、これらの新たな知見を用いることにより、有
機系感光層に好適な表面保護層を設け、耐久性、耐湿性
に優れ、かつ初期画像カブリを発生しない有機系の感光
体とその製造方法を提供するものである。Although these mechanisms are not necessarily clear, the developer is electrostatically attracted to the surface protective layer due to contact friction charging and contact potential difference. It is thought that the image is carried to the transfer unit and transferred to the transfer paper, causing the aforementioned capri. Furthermore, the present inventors have discovered that the above-mentioned image fog can be reduced by 2.
It has been confirmed that this phenomenon always occurs when the developer and the photoreceptor come into physical contact, regardless of the contact or non-contact development method of the components, or the contact or non-contact development method of one component. (However, since the carrier material is strongly attracted to the developing sleeve by magnetic force, electric field, etc., it does not adhere to the surface protective layer.
It is thought that it only contributes to imparting a triboelectric charge. ) By using these new findings, the present invention provides an organic photoreceptor that provides a suitable surface protection layer for the organic photosensitive layer, has excellent durability and moisture resistance, and does not cause initial image fog, and its organic photoreceptor. A manufacturing method is provided.
本発明は導電性基板上に有機系感光層と表面保護層とを
設けた・感光体において、
有機系感光層本来の高感度な静電特性、光感度特性を損
わないという課題、
複写機等における実使用においても、傷を受けたり、摩
耗したりしないだけの高硬度を有し、耐刷性を向上させ
るという課題、
特に高温高湿時における耐湿性を向上させるとともに、
画像カブリを防止するという課題、などを解決しようと
するものであり、さらに、酸、アルカリなどの耐溶剤性
等の外部要因に対する耐性を向上させるという課題、
第１の表面保護層と第２の表面保護層との接着性を向上
させるという課題、
などを解決しようとするものである。The present invention solves the problem of not impairing the highly sensitive electrostatic properties and photosensitivity characteristics inherent to the organic photosensitive layer in a photoconductor in which an organic photosensitive layer and a surface protective layer are provided on a conductive substrate, and a copying machine. The problem was to improve printing durability by having high hardness that would not be scratched or abraded even in actual use, especially in high temperature and high humidity conditions.
The first surface protection layer and the second surface protection layer are This aims to solve the following problems: improving the adhesion with the surface protective layer.
本発明は、上記課題を解決するために、導電性基板上に
有機系感光層、フッ素原子を含むアモルファスカーボン
を主体とする第１の表面保護層、及び、フッ素原子を含
まない第２の表面保護１層を順次積層する感光体を用い
るものであり、さらに、
第２の表面保護層を透光性低抵抗無機金属化合物により
形成する感光体を用いるものであり、第２の表面保護層
と接する第１の表面保護層の面を粗面処理する感光体を
用いるものであり、第１の表面保護層中に層方向に不均
一にフッ素原子を含ませる感光体を用いるものである。In order to solve the above problems, the present invention provides an organic photosensitive layer on a conductive substrate, a first surface protective layer mainly made of amorphous carbon containing fluorine atoms, and a second surface layer not containing fluorine atoms. This method uses a photoreceptor in which one protective layer is sequentially laminated, and a photoreceptor in which a second surface protection layer is formed of a light-transmitting, low-resistance inorganic metal compound. A photoreceptor is used in which the surface of the first surface protection layer in contact with the surface is roughened, and a photoreceptor is used in which the first surface protection layer contains fluorine atoms nonuniformly in the layer direction.
さらに、第１の表面保護層をグロー放電法により形成し
た後、Ａｒボンバード等の所謂ボンバード処理により粗
面処理する工程を有する感光体の製造方法を用いるもの
である。Furthermore, a method for manufacturing a photoreceptor is used which includes a step of forming the first surface protective layer by a glow discharge method and then roughening the surface by so-called bombardment treatment such as Ar bombardment.
本発明においては、第１の表面保護層と第２の表面保護
層の構成は、それぞれに求められる要求から決定されな
くてはならない。In the present invention, the configurations of the first surface protective layer and the second surface protective layer must be determined based on the respective requirements.
まず、第１の表面保護層は、高感度であり、様々な静電
的性質を付加することが容易な有機系感光層を有する感
光体において、所謂画像流れ等に代表される耐湿性の悪
さを向上させるために少なくともフッ素原子を含有する
ことが必須の要件である。First, the first surface protective layer is highly sensitive and has poor moisture resistance, as typified by so-called image deletion, in a photoreceptor having an organic photosensitive layer to which it is easy to add various electrostatic properties. It is essential to contain at least a fluorine atom in order to improve the
本発明において、第１の表面保護層中に、フッ素原子が
含まれない場合には、例えば、オージェ分析でフッ素原
子が検出されないような場合には、有機系感光層との電
気的不整合性から、主に高温高湿の環境下においては不
整合面での電荷の横流れ等を誘発し、所謂画像流れが発
生し、さらには残留電位の上昇、或は複数枚複写時に前
の画像が次の画像にポジまだはネガ像として現れる所謂
メモリー現象の発生などを引き起こす。また、有機系感
光層との接着性に乏しくなり、複写機内での実使用時に
おける機械的な力、或は、温湿度の変化により表面保護
層の剥離が発生しやすくなる。In the present invention, if the first surface protective layer does not contain fluorine atoms, for example, if fluorine atoms are not detected by Auger analysis, electrical incompatibility with the organic photosensitive layer may occur. Therefore, mainly in high temperature and high humidity environments, it induces cross-flow of charges on mismatched surfaces, causing so-called image drift, and furthermore, an increase in residual potential, or when copying multiple sheets, the previous image may overlap with the next image. This causes the so-called memory phenomenon in which positive images appear as negative images. Furthermore, the adhesiveness with the organic photosensitive layer becomes poor, and the surface protective layer tends to peel off due to mechanical force or changes in temperature and humidity during actual use in a copying machine.
前述の電気的不整合性は、この接着性の乏しさに起因す
るものとも考えられる。The electrical inconsistency described above is also considered to be due to this poor adhesion.
さらに、本発明の第１の表面保護層はアモルファスカー
ボンを主体とし、所望により周期第■族原子、酸素原子
及び、又は窒素原子２周期表第■族原子及び、又は周期
表第Ｖ族原子、カルコゲン原子の中から選ばれた１つ又
はそれ以上を添加させてもよい。周期表第■族原子を添
加することにより感光体全体としての光疲労防止効果を
、酸素原子及び、又は窒素原子を添加することによりよ
り光感度特性の経時変化の安定効果を、周期表第■族及
び、又は周期表第■族原子を添加することにより帯電能
の向上効果を、カルコゲン原子を添加することによりフ
ィルミング防止効果を得ることが可能である。Furthermore, the first surface protective layer of the present invention is mainly composed of amorphous carbon, and optionally includes periodic group (I) atoms, oxygen atoms and/or nitrogen atoms, group (IV) atoms of the periodic table, and/or group V atoms of the periodic table. One or more chalcogen atoms selected from chalcogen atoms may be added. By adding atoms of group Ⅰ of the periodic table, the photoreceptor as a whole has an anti-photofatigue effect, and by adding oxygen atoms and/or nitrogen atoms, it has the effect of stabilizing changes in photosensitivity characteristics over time. It is possible to obtain the effect of improving charging ability by adding atoms of Group 1 and/or Group Ⅰ of the periodic table, and to obtain the effect of preventing filming by adding chalcogen atoms.
また、本発明において第１の表面保護層をグロー放電法
により形成する場合、第１の表面保護層中に化学的修飾
物質として含有させるフッ素原子の量は、主に、プラズ
マ反応を行う反応室への少なくともフッ素原子を含む化
合物ガスの導入量を増減する事により制御する事が可能
である。フン素化合物ガスの導入量を増大させれば、本
発明によるアモルファスカーボン膜中へのフッ素原子の
添加量を高くず色ことが可能であり、逆にフッ素化合物
の導入量を減少させれば、本発明によるアモルファスカ
ーボン膜中へのフッ素原子の添加量を低くすることが可
能である。Further, in the present invention, when the first surface protective layer is formed by a glow discharge method, the amount of fluorine atoms to be contained as a chemical modifier in the first surface protective layer is mainly determined by This can be controlled by increasing or decreasing the amount of compound gas containing at least a fluorine atom introduced. By increasing the amount of fluorine compound gas introduced, it is possible to reduce the amount of fluorine atoms added to the amorphous carbon film according to the present invention without increasing the amount; conversely, by decreasing the amount of fluorine compound introduced, According to the present invention, it is possible to reduce the amount of fluorine atoms added to the amorphous carbon film.
そして、実際に複写機等内で本発明の感光体を使用した
場合、・特に高温高湿環境下において満足できる耐湿性
を得るためには、第１の表面保護層中には少なくとも５
ａｔｍ％以上のフッ素原子濃度が必要であり、また、感
光体全体としての耐湿性向上という観点からは出来る限
りフッ素原子濃度は高い方が望ましいが、その上限は製
造面からの要求から必然的に決定される。When the photoreceptor of the present invention is actually used in a copying machine, etc., in order to obtain satisfactory moisture resistance, especially in a high temperature and high humidity environment, the first surface protective layer must contain at least 5
A fluorine atom concentration of atm% or higher is required, and from the perspective of improving the moisture resistance of the photoreceptor as a whole, it is desirable that the fluorine atom concentration be as high as possible, but the upper limit is necessarily determined by manufacturing requirements. It is determined.
さらに、本発明において、第１の表面保護層の膜厚も本
発明の目的を効果的に達成するだめの重要な要素として
あげられる。Furthermore, in the present invention, the thickness of the first surface protective layer is also an important factor for effectively achieving the object of the present invention.
即ち、第１の表面保護層の膜厚は概ね０．０１ 乃至
・１．０μｍが好ましく、より好ましくは０．１乃至０
．４μｍであればよい。第１の表面保護層の膜厚が０．
０１μｍより薄い場合は、表面保護層全体の表面硬度が
下地である有機系感光層の低硬度の影響を受けやすくな
り、好ましい耐久性が確保されず、４．０μｍより厚い
場合には、表面保護層全体として必ずしも十分な可視光
透過率が確保できるとは限らず有機系感光層が本来持つ
高感度性能を損なってしまう。That is, the thickness of the first surface protective layer is preferably approximately 0.01 to 1.0 μm, more preferably 0.1 to 0.0 μm.
．． It is sufficient if it is 4 μm. The thickness of the first surface protective layer is 0.
If it is thinner than 0.01 μm, the surface hardness of the entire surface protection layer will be easily affected by the low hardness of the underlying organic photosensitive layer, and desirable durability will not be ensured. If it is thicker than 4.0 μm, the surface It is not always possible to ensure sufficient visible light transmittance for the entire layer, which impairs the high sensitivity performance inherent to the organic photosensitive layer.
次に、第２の表面保護層はフッ素原子を含有する表面保
護層を有する感光体において、フッ素原子の電気陰性度
の大きさに起因すると考えられる画像カブリの防止とい
う要求から、少なくともフン素原子を含まない物質によ
り構成されることが必須の要件である。Next, in a photoreceptor having a surface protective layer containing fluorine atoms, the second surface protective layer contains at least fluorine atoms in order to prevent image fogging, which is considered to be caused by the large electronegativity of fluorine atoms. It is an essential requirement that it be composed of substances that do not contain.
具体的には第２の表面保護層を透光性無機金属化合物、
透光性低抵抗無機金属化合物、透光性樹脂、などにより
形成することにより本発明の目的・効果を達成すること
ができる。Specifically, the second surface protective layer is made of a translucent inorganic metal compound,
The objects and effects of the present invention can be achieved by forming it from a light-transmitting low-resistance inorganic metal compound, a light-transmitting resin, or the like.
まず、第２の表面保護層を透光性無機金属化合物で形成
する場合、該表面保護層を上記第１の表面保護層上に金
属酸化物、金属硫化物、及び金属窒化物よりなる群から
選ばれた１種又はそれ以上の化合物からなる透光性無機
金属化合物蒸着膜として得ることができる。上記した金
属酸化物としては、Ａｌ ２０３ 、ＳｉＯ１ＳｉＯｚ
、 ＣａＯ、ＣｅＯ２、Ｃｅ２Ｏ３、Ｂｉ２Ｏ３、Ｃ
ｒ２Ｏ３、Ｇｄ２Ｏ３、ＳｎＯ２、Ｐｒ６Ｏ１１，５ｂ
２０４、ＬａｚＯ：＋ 、 ＴａｚＯ３、Ｔｈ０ｚ、及
びＺｎ０ｚ等、そして金属硫化物としては、ＺｎＳ 、
ＣｄＳ、及びｐｂｓ等さらに金属窒化物としてはＡＩ
Ｎ 、 Ｔｉ ３Ｎ４ 、ＢＮ 、 ＰＮ 、及びＳｉ
Ｎ等があげられる。First, when the second surface protective layer is formed of a translucent inorganic metal compound, the surface protective layer is formed on the first surface protective layer from the group consisting of metal oxides, metal sulfides, and metal nitrides. It can be obtained as a transparent inorganic metal compound vapor-deposited film made of one or more selected compounds. Examples of the metal oxides mentioned above include Al 203 , SiO1SiOz
, CaO, CeO2, Ce2O3, Bi2O3, C
r2O3, Gd2O3, SnO2, Pr6O11,5b
204, LazO:+, TazO3, Th0z, Zn0z, etc., and metal sulfides include ZnS,
CdS, pbs, etc. Furthermore, as metal nitrides, AI
N, Ti3N4, BN, PN, and Si
Examples include N.
これらの無機金属化合物は第４図に示されるような公知
の蒸着装置により第１の表面保護層上に少くとも可視波
長領域を透過させる透光性蒸着膜として形成することが
できる。These inorganic metal compounds can be formed as a transparent vapor deposited film that transmits at least visible wavelength region on the first surface protective layer using a known vapor deposition apparatus as shown in FIG.
そして、このようにして得られた透光性無機金属化合物
蒸着膜の膜厚は第１の表面保護層中に含まれるフッ素原
子の影響、表面保護層全体としての光透過性、強度など
から各原料無機金属化合物ごとに最適化されなくてはな
らないが、概ね２０乃至２０００λが好ましい。The thickness of the transparent inorganic metal compound vapor-deposited film thus obtained varies depending on the influence of fluorine atoms contained in the first surface protective layer, the light transmittance of the surface protective layer as a whole, the strength, etc. Although it must be optimized for each raw material inorganic metal compound, it is preferably approximately 20 to 2000λ.
膜厚が２０λ以下ならば、第１の表面保護層に含まれる
フッ素原子の影響が無視できずに、所謂画像カブリを生
じ、光透過性、強度などの点からも好ましくなく、まだ
、膜厚が２０００人を越える場合には、必ずしも十分な
透過光を得られるとは限らず、有機系感光層が本来持つ
高感度性能を損なってしまう。If the film thickness is less than 20λ, the influence of fluorine atoms contained in the first surface protective layer cannot be ignored, resulting in so-called image fog, which is unfavorable from the viewpoint of light transmittance and strength. If the number exceeds 2,000 people, it is not necessarily possible to obtain sufficient transmitted light, and the high sensitivity performance inherent to the organic photosensitive layer is impaired.
上記したように、第２の表面保護層を透光性無機金属化
合物で形成した本発明の感光体を、実際に複写機等にお
いて使用した場合、静電特性、耐久性、耐湿性及び画像
カプリの点で十分満足できる結果を得ることが確認され
たが、本発明者らは第２の表面保護層を概ね１×１０〜
９×１０ Ω・副体積抵抗の透光性低抵抗無機金属化合
物で形成すると、感光体の耐溶剤性や、水分の付着等の
外部要因に対し、その耐性が向上することが確認された
。As described above, when the photoreceptor of the present invention in which the second surface protective layer is formed of a light-transmitting inorganic metal compound is actually used in a copying machine, etc., the electrostatic properties, durability, moisture resistance, and image capacitance are improved. Although it was confirmed that sufficiently satisfactory results were obtained in terms of
It was confirmed that when the photoreceptor is formed from a light-transmitting, low-resistance inorganic metal compound with a sub-volume resistance of 9×10 Ω, the photoreceptor's resistance to solvents and external factors such as moisture adhesion is improved.
上記した体積抵抗値の透光性低抵抗無機金属化合物層が
外部要因に対し、より耐性が向上する理由を以下に述べ
る。The reason why the light-transmitting, low-resistance inorganic metal compound layer having the above-mentioned volume resistivity value is more resistant to external factors will be described below.
第２の表面保護層が十分に薄く、また層の面方向の電気
抵抗が層厚方向に対して十分大きく、表面電荷が面方向
にリークせず、画像形成に必要な抵抗値を持ち、かつ帯
電器から発生した電荷が第２の表面保護層表面に載り、
このとき形成される高電界により電荷が第２の表面保護
層を通過し、第１の表面保護層との界面近傍にすばやく
移動できるだけの抵抗値であり、かつ、第１の表面保護
層に比へ１Ｏ−ｚｌｏ 抵抗値が小きいならば、第１
の表面保護層と第２の表面保護層の界面が静電気的なエ
ネルギー障壁となり、帯電器で発生させられた電荷は常
に第２の表面保護層中に保持されるので、この状態で露
光により潜像形成を行った場合、有機感光層中で発生し
たキャリアと上記した第２の表面保護層中に保持された
電荷が結合し、静電気的にキャンセルされることに潜像
形成が行われたことから、第２の表面保護層中の電荷は
全く外部の要因による影響を受けないものであると考え
られる。従って例えば酸、アルカリ等の溶媒等に対する
耐性も向上し、また、感光体表面に付着する水分などに
対する耐性も向上し、結果、耐湿性等もさらに向上する
ものと考えられる。The second surface protective layer is sufficiently thin, the electrical resistance in the in-plane direction of the layer is sufficiently large relative to the layer thickness direction, the surface charge does not leak in the in-plane direction, and the resistance value necessary for image formation is obtained. Charges generated from the charger are placed on the surface of the second surface protective layer,
The resistance value is high enough to allow charges to pass through the second surface protection layer due to the high electric field formed at this time and move quickly to the vicinity of the interface with the first surface protection layer. to 1O−zlo If the resistance value is small, the first
The interface between the surface protective layer and the second surface protective layer acts as an electrostatic energy barrier, and the charges generated by the charger are always retained in the second surface protective layer. When image formation is performed, latent image formation occurs when carriers generated in the organic photosensitive layer and charges held in the above-mentioned second surface protective layer combine and are electrostatically canceled. Therefore, it is considered that the charge in the second surface protective layer is completely unaffected by external factors. Therefore, resistance to solvents such as acids and alkalis is improved, and resistance to moisture adhering to the surface of the photoreceptor is also improved, resulting in further improvement in moisture resistance.
そして、上記したような現象を得る具体的な第２の表面
保護層の抵抗値は、本発明の感光体においては、以上の
ような理由から、
概ねｌＸ１０〜９×１００・（７）の体積抵抗値となっ
ていると考えられる。またその膜厚は２０乃至２０００
人ならば上記した効果が得られた。In the photoreceptor of the present invention, the specific resistance value of the second surface protective layer that achieves the above-described phenomenon is approximately 1×10 to 9×100·(7) in volume for the reasons described above. It is thought that it is a resistance value. Also, the film thickness is 20 to 2000
In humans, the above effects were obtained.
これらの透光性低抵抗無機金属化合物層は、前記しだ透
光性無機金属化合物として使用できる金属酸化物、金属
硫化物、及び金属窒化物群に５ｎ０２、Ｉｎ２Ｏ３、Ｚ
ｎＯ等とをあらかじめ混合して蒸着膜として得るか、又
は公知の２元蒸着法により蒸着膜として得ることにより
、抵抗値を上記した範囲に調整することが可能である。These light-transmitting low-resistance inorganic metal compound layers are made of metal oxides, metal sulfides, and metal nitrides that can be used as the light-transmitting inorganic metal compounds, such as 5n02, In2O3, and Z.
The resistance value can be adjusted within the above range by pre-mixing with nO or the like to obtain a vapor deposited film, or by obtaining a vapor deposited film by a known binary vapor deposition method.
さらに、本発明の感光体は第２の表面保護層を透光性樹
脂で形成することによっても実現が可能である。Furthermore, the photoreceptor of the present invention can also be realized by forming the second surface protective layer from a light-transmitting resin.
本発明に使用する上記透光性樹脂は、例えば熱可塑性樹
脂、熱硬化性樹脂、光硬化性樹脂等を挙げることができ
、より詳しくは、例えばポリエステル樹脂、ポリアミド
樹脂、ポリブタジェン、アクリル樹脂、エチレン−酢酸
ビニル共重合体、イオン交換オレフィン共重合体（アイ
オノマー）、スチレン −ブタンエンブロノク共重合体
、ポリカーボネート、塩化ビニル−酢酸ビニル共重合体
、セルロースエステル、ポリイミド等の熱可塑性樹脂：
エポキシ樹脂、ウレタン樹脂、シリコーン樹脂、フェノ
ール樹脂、メラミン樹脂、キシレン樹脂、アルキッド樹
脂、熱硬化性アクリル樹脂等の熱硬化性樹脂；ポリ−Ｎ
−ビニルカルバゾール、ポリビニルピレン、ポリビニル
アントラセン等の光導電性樹脂等を挙げることができ、
好ましい樹脂はシリコーン樹脂、アクリル樹脂、メラミ
ン樹脂、ポリカーボネート樹脂、ポリブタジェン、エポ
キシ樹脂等である。Examples of the light-transmitting resin used in the present invention include thermoplastic resins, thermosetting resins, photocurable resins, etc. More specifically, examples include polyester resins, polyamide resins, polybutadiene, acrylic resins, and ethylene resins. - Thermoplastic resins such as vinyl acetate copolymer, ion-exchanged olefin copolymer (ionomer), styrene-butane-embronok copolymer, polycarbonate, vinyl chloride-vinyl acetate copolymer, cellulose ester, polyimide, etc.:
Thermosetting resins such as epoxy resins, urethane resins, silicone resins, phenolic resins, melamine resins, xylene resins, alkyd resins, thermosetting acrylic resins; Poly-N
- photoconductive resins such as vinylcarbazole, polyvinylpyrene, polyvinylanthracene, etc.;
Preferred resins include silicone resin, acrylic resin, melamine resin, polycarbonate resin, polybutadiene, and epoxy resin.
これらの樹脂は、体積抵抗が１×１０ Ω・α以上ある
ことが望ましい。It is desirable that these resins have a volume resistivity of 1×10 Ω·α or more.
上記した本発明の透光性樹脂層は、上記した樹脂群のう
ち１種又はそれ以上を適当な溶媒中に溶解させた溶液を
第１の表面保護層の表面に乾燥後の膜厚が概ね０．０１
〜５μｍ、好ましくは０．０５〜２μｍとなるように塗
布乾燥することにより形成される。樹脂層の膜厚が０．
０１μｍより薄いと必ずしも十分な帯電が行われず、５
μｍより厚いと残留電位の上昇が無視できなくなり、さ
らに透光性の低下による感度低下も問題となる。The light-transmitting resin layer of the present invention described above is prepared by applying a solution prepared by dissolving one or more of the resin groups described above in an appropriate solvent to the surface of the first surface protective layer so that the film thickness after drying is approximately 0.01
It is formed by coating and drying to a thickness of ~5 μm, preferably 0.05 to 2 μm. The thickness of the resin layer is 0.
If it is thinner than 0.01 μm, sufficient charging will not necessarily occur;
If it is thicker than μm, an increase in residual potential cannot be ignored, and furthermore, a decrease in sensitivity due to a decrease in transparency becomes a problem.
塗布方法としては公知のスプレー法、デイ７・ピング法
、バーコーター塗布法等を適用することができる。これ
らの塗布方法以外に、真空蒸着やスソバソタ法で樹脂層
を設けることも可能である。As a coating method, a known spray method, day ping method, bar coater coating method, etc. can be applied. In addition to these coating methods, it is also possible to provide the resin layer by vacuum evaporation or a sloppy method.
樹脂層を形成するだめの塗布用溶液に使用可能な溶剤は
、選択した樹脂に合わせて適宜選定すればよいが、乾燥
しやすいものが好ましく、係る溶剤としては例えばガソ
リン、石油、ベンジン、ミネラルスピリット、石油ナツ
タ、Ｖ ０Ｍ 、 ＆ Ｐ 、ナツタ、デカリン、テト
ラリン、Ｐ−シメンあるいはヘキサン等の脂肪族炭化水
素類、ベンゼン、トルエン、キシレン等の芳香族炭化水
素、トリクロルエチレン、パークロルエチレン、クロロ
ホルム、四塩化炭素、三塩化エチレン、−塩化ベンゼン
、−臭化ベンゼン、二塩化ベンゼン等のハロゲン化炭化
水素類、アミルアルコール、エチルアルコール、イノプ
ロピルアルコール、２−エチルブチルアルコール、２−
エチルヘキシルアルコール、シクロヘキサノール、メチ
ルアルコール、メチルアミルアルコール、ベンジルアル
コール、メチルアルコール等のアルコール類、アセトン
、アセトニルアセトン、ジ・イソブチルケトン、ジエチ
ルケトン、ジプロピルケトン、メチルアミルケトン、メ
チルブチルケトン、メチルシクロヘキサノン、メチルジ
プロピルケトン、メチルエチルケトン、メチル正ヘキシ
ルケトン、メチルイソブチルケトン、メチルプロピルケ
トン、メシチルオキノド等のケトン類、酢酸エステル類
、酪酸エステル類、プロピオン酸エステル類、ギ酸エス
テル類等のエステル類、乳酸フチノペ乳酸イソプロピル
、乳酸−ｒ−ｆル、オキンプロビオン酸エチル、マレイ
ン酸ジエチル等のアルコールエステル類、アセト酢酸エ
チル、ピルビン酸エチル、イソプロピルエーテル、エチ
ルエーテル、ジェチルヵービトーノペジエチルセロソル
ブ、ブチルエーテル等のエーテル類、アセトニルメタノ
ール、ジアセトンアルコール、ジヒドロキジルアセトン
、ビルビルアルコール等のケトンアルコール類、イソプ
ロピルセロソルブ、カービトール、グリシドール、セロ
ソルブ、り＋Ｊコールエーテル、ペンジルセロソルフ、
プチルカービトール、ブチルセロソルブ、メチルカービ
トール、メチルセロンルプ、トリエチレングリコールモ
ノエチルエーテル等のエーテルアルコール頌、アセター
ルエチルニーテール、アセトニルメタノールエチルエー
テル、メチルエトオキ／エチルエーテル等のケトンエー
テル類、酢酸プチルカーピトール、酢酸ブチルセロソル
ブ、酢酸カービトール、酢酸セロソルブ、酢酸３−メト
キシブチ／ｌｚ酢酸メチルカービトール、酢酸メチルセ
ロソルブ等のエステルエーテル類等またはそれらの混合
溶剤が挙げられ、特に酢酸エチル、酢酸ブチル、ヘキサ
ン、トルエン、メチルイソブチルケトン、酢酸セロソル
ブ、あるいはそれらの混合溶剤が好ましい。The solvent that can be used in the coating solution for forming the resin layer may be selected as appropriate depending on the resin selected, but it is preferable to use a solvent that dries easily. Examples of such solvents include gasoline, petroleum, benzine, and mineral spirits. , Petroleum Natsuta, V0M, &P, Natsuta, decalin, tetralin, aliphatic hydrocarbons such as P-cymene or hexane, aromatic hydrocarbons such as benzene, toluene, xylene, trichlorethylene, perchloroethylene, chloroform, Halogenated hydrocarbons such as carbon tetrachloride, ethylene trichloride, benzene chloride, benzene bromide, benzene dichloride, amyl alcohol, ethyl alcohol, inopropyl alcohol, 2-ethylbutyl alcohol, 2-
Alcohols such as ethylhexyl alcohol, cyclohexanol, methyl alcohol, methyl amyl alcohol, benzyl alcohol, methyl alcohol, acetone, acetonylacetone, di-isobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone, methyl butyl ketone, methyl Ketones such as cyclohexanone, methyl dipropyl ketone, methyl ethyl ketone, methyl normal hexyl ketone, methyl isobutyl ketone, methyl propyl ketone, mesityloquinod, esters such as acetate esters, butyrate esters, propionate esters, formate esters, lactic acid Alcohol esters such as isopropyl lactate, r-f lactate, ethyl oquinprobionate, diethyl maleate, ethyl acetoacetate, ethyl pyruvate, isopropyl ether, ethyl ether, diethyl carbitonopediethyl cellosolve, butyl ether, etc. ethers, acetonyl methanol, diacetone alcohol, dihydroxyylacetone, ketone alcohols such as bilbyl alcohol, isopropyl cellosolve, carbitol, glycidol, cellosolve, ly+J col ether, pendyl cellosolve,
Ether alcohols such as butyl carbitol, butyl cellosolve, methyl carbitol, methyl selonol, triethylene glycol monoethyl ether, ketone ethers such as acetal ethyl niter, acetonyl methanol ethyl ether, methyl ethoxylate/ethyl ether, butyl acetate Examples include ester ethers such as pitol, butyl cellosolve acetate, carbitol acetate, cellosolve acetate, 3-methoxybutylacetate/lz methyl carbitol acetate, methyl cellosolve acetate, and mixed solvents thereof, particularly ethyl acetate, butyl acetate, hexane, Toluene, methyl isobutyl ketone, cellosolve acetate, or a mixed solvent thereof is preferred.
樹脂層を形成するための塗布用溶液に使用する樹脂の量
は、該塗布溶液に対して０．４〜２０．０重量％、好ま
しくは０．９〜６．０重量％、より好ましくは１．０〜
５．０重量％である。０．４重量％より少なくなると、
所望の膜厚を得るために、塗布乾燥の工程を数多く繰り
返す必要が生じる。また、２０重量％より多くなると溶
液の粘度が高くなりすぎて、塗布むらが発生したり、膜
厚の制御が困難になる等の問題が生じる。The amount of resin used in the coating solution for forming the resin layer is 0.4 to 20.0% by weight, preferably 0.9 to 6.0% by weight, more preferably 1% by weight based on the coating solution. .0～
It is 5.0% by weight. When it is less than 0.4% by weight,
In order to obtain the desired film thickness, it becomes necessary to repeat the coating and drying process many times. Moreover, if the amount exceeds 20% by weight, the viscosity of the solution becomes too high, causing problems such as uneven coating and difficulty in controlling the film thickness.
本発明において、第１の表面保護層、第２の表面保護層
の接着性も本発明の目的を効果的に達成するための要素
としてあげることができる。In the present invention, the adhesiveness of the first surface protective layer and the second surface protective layer can also be cited as a factor for effectively achieving the object of the present invention.
本発明の第１の表面保護層をグロー放電法により、少な
くともフン素原子を含有するプラズマ有機重合膜として
形成した場合、該第１の表面保護層表面上に、そのまま
第２の表面保護層を蒸着膜又は同じくグロー放電法によ
り形成した場合、主に、第１の表面保護層を形成する物
質の物性と第２の表面保護層とのそれとの相違に起因し
、時に第２の表面保護層を蒸着膜として形成した場合に
は、複写機内での実使用時における機械的な力、或は、
温湿度の変化により必ずしも両者の接着性の良さが確保
されるとは限らない。When the first surface protective layer of the present invention is formed as a plasma organic polymer film containing at least fluorine atoms by a glow discharge method, the second surface protective layer is directly formed on the surface of the first surface protective layer. When a vapor-deposited film or a glow discharge method is used to form a film, the difference between the physical properties of the substance forming the first surface protective layer and that of the second surface protective layer is sometimes caused. When formed as a vapor deposited film, mechanical force during actual use in a copying machine or
Good adhesion between the two may not necessarily be ensured due to changes in temperature and humidity.
そのため、第１の表面保護層の表面を粗面処理すること
により第２の表面保護層との接着性を確保することが可
能である。Therefore, by roughening the surface of the first surface protection layer, it is possible to ensure adhesion with the second surface protection layer.
具体的には、第２図及び第３図に示すグロー放電分解装
置を用いて得られた第１の表面保護層の表面上をＡｒな
どの不活性ガスにより所謂ボンバード処理することによ
り粗面処理を行うことができる。このように処理された
第１の表面保護層上に公知の蒸着法により蒸着膜を形成
すると、処理しない場合より接着性が向上させることが
可能であり、表面上に樹脂層を設ける場合にも、接着性
が向上させることができる。Specifically, the surface of the first surface protective layer obtained using the glow discharge decomposition apparatus shown in FIGS. 2 and 3 is roughened by performing so-called bombardment treatment with an inert gas such as Ar. It can be performed. If a vapor deposited film is formed on the first surface protective layer treated in this way by a known vapor deposition method, it is possible to improve the adhesion compared to the case without treatment, and also when a resin layer is provided on the surface. , adhesion can be improved.
尚、本発明の感光体においては、第１の表面保護層をフ
ッ素原子を含むアモルファスカーボンを主体として形成
し、第２の表面保護層は少なくともフッ素原子を含まな
い物質により形成することを特徴とするが、第１の表面
保護層に含ませるフッ素原子の含有量を層方向に不均一
にすることにより、より効果的に本発明の目的と達成す
るととができる。The photoreceptor of the present invention is characterized in that the first surface protective layer is formed mainly of amorphous carbon containing fluorine atoms, and the second surface protective layer is formed of a substance that does not contain at least fluorine atoms. However, the object of the present invention can be more effectively achieved by making the content of fluorine atoms contained in the first surface protective layer non-uniform in the layer direction.
即ち、本発明において、第１の表面保護層のフッ素原子
含有濃度を感光層側で高く、第２の表面保護層との界面
側が低くして、層方向に不均一な濃度とすることにより
、フッ素原子の電気陰性度に起因すると思われる画像カ
プリをより効果的に防止することが可能であり、同時に
、感光層側には十分なフッ素量を確保し、電気的な整合
性を十分に確保することにより、耐湿性を確保すること
が可能である。That is, in the present invention, the fluorine atom content concentration of the first surface protective layer is made high on the photosensitive layer side and low on the interface side with the second surface protective layer, so that the concentration is non-uniform in the layer direction. It is possible to more effectively prevent image capri, which is thought to be caused by the electronegativity of fluorine atoms, and at the same time, ensure a sufficient amount of fluorine on the photosensitive layer side to ensure sufficient electrical consistency. By doing so, it is possible to ensure moisture resistance.
本発明の第１の表面保護層、即ちフッ素原子を含むアモ
ルファスカーボン膜をグロー放電法により、有機プラズ
マ重合膜として得る場合、原料ガスとして炭化水素ガス
及びフッ素化合物を用いることができ、キャリアーガス
には、一般に使用される水素ガス或はアルゴンガス等が
用いられる。When the first surface protective layer of the present invention, that is, an amorphous carbon film containing fluorine atoms, is obtained as an organic plasma polymerized film by a glow discharge method, a hydrocarbon gas and a fluorine compound can be used as the raw material gas, and a carrier gas can be used. For example, commonly used hydrogen gas or argon gas is used.
該炭化水素ガスの相状態は常温常圧において必ずしも気
相で有る必要は無く、加熱或は減圧等により溶融、蒸発
、昇華等を経て気化し得るものであれば、液相でも固相
でも使用可能である。該炭化水素としては、例えば、飽
和炭化水素、不飽和炭化水素、脂環式炭化水素、芳香族
炭化水素、等・が用いられる。The phase state of the hydrocarbon gas does not necessarily have to be a gas phase at room temperature and normal pressure; it can be either a liquid phase or a solid phase as long as it can be vaporized through melting, evaporation, sublimation, etc. by heating or reduced pressure. It is possible. Examples of the hydrocarbons used include saturated hydrocarbons, unsaturated hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and the like.
使用可能な炭化水素には種類が多いが、飽和炭化水素と
しては、例えば、メタン、エタン、プロパン、ブタン、
ペンタン、ヘキサン、ヘプタン、オクタン、イソブタン
、イソペンタン、ネオペンタン、イソヘキサン、ネオヘ
キサン、ジメチルブタン、メチルヘキサン、エチルペン
タン、ジメチルペンタン、トリブタン、メチルへブタン
、ジメチルヘキサン、トリメチルペンタン、イソナノン
、等が用いられる。不飽和炭化水素としては、例えば、
エチレン、プロピレン、インブチレン、ブテン、ペンテ
ン、メチルブテン、ヘキセン、テトラメチルエチレン、
ヘプテン、オクテン１アレン、メチルアレン、フタジエ
ン、ペンタジェン、ヘキサジエン、シクロペンタジェン
、オシメン、アロシメン、ミルセン、ヘキサトリエン、
アセチレン、ジアセチレン、メチルアセチレン、ブチン
、ペンチン、ヘキシン、ヘプチン、オクチン等が用いら
れる。脂環式炭化水素としては、例、（ば、シクロプロ
パン、シクロブタン、シクロペンタン、シクロヘキサン
、シクロへブタン、シクロオクタン、／クロプロペン、
シクロブテン、シクロペンテン、シクロヘキセン、シク
ロヘプテン、シクロオクテン、リモネン、′テルビルン
、フエランドレン、シルベストレン、ツエン、カレン、
ヒネン、ボルニレン、カンフエン、フェンチェン、シク
ロブタンチエン、トリシクレン、ビサボレン、ジンギベ
レン、クルクメン、フムレン、カジネンセスベニヘン、
セリネン、カリオフィレン、サンタレン、セドレン、カ
ンホレン、フィロクラデン、ポドカルプレン、ミレン等
が用いられる。芳香族炭化水素としては、例えば、ベン
ゼン、トルエン、キシレン、ヘミメリテン、ランイドク
メン、メシチレン、フレニテン、インジュレン、ジュレ
ン、ペンタメチルベンゼン、ヘキサメチルベンゼン、エ
チルベンゼン、フロビルベンゼン、クメン、スチレン、
ピフェニル、テルフェニル、ジフェニルメタン、トリフ
ェニルメタン、ジベンジル、スチルベン、インデン、ナ
フタリン、テトラリン、アントラセン、フェナントレン
等が用いらレル。There are many types of hydrocarbons that can be used, but examples of saturated hydrocarbons include methane, ethane, propane, butane,
Pentane, hexane, heptane, octane, isobutane, isopentane, neopentane, isohexane, neohexane, dimethylbutane, methylhexane, ethylpentane, dimethylpentane, tributane, methylhebutane, dimethylhexane, trimethylpentane, isonanone, etc. are used. Examples of unsaturated hydrocarbons include:
Ethylene, propylene, imbutylene, butene, pentene, methylbutene, hexene, tetramethylethylene,
Heptene, octene-1-alene, methylalene, phtadiene, pentadiene, hexadiene, cyclopentadiene, ocimene, allocimene, myrcene, hexatriene,
Acetylene, diacetylene, methylacetylene, butyne, pentyne, hexyne, heptyne, octyne, etc. are used. Examples of alicyclic hydrocarbons include (eg, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cyclohebutane, cyclooctane, /chloropropene,
Cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, limonene, 'tervirun, phelandrene, silvestrene, tsene, carene,
Hinene, bornylene, kanghuen, fenchen, cyclobutanethien, tricyclene, bisabolene, zingiberene, curcumene, humulene, casinenses benihen,
Selinene, caryophyllene, santarene, cedrene, campholene, phyllocladene, podocarprene, mylene, etc. are used. Examples of aromatic hydrocarbons include benzene, toluene, xylene, hemimelithene, ranidocumene, mesitylene, frenitene, indulene, durene, pentamethylbenzene, hexamethylbenzene, ethylbenzene, flobylbenzene, cumene, styrene,
Piphenyl, terphenyl, diphenylmethane, triphenylmethane, dibenzyl, stilbene, indene, naphthalene, tetralin, anthracene, phenanthrene, etc. are used.
さらに、使用可能なフッ素化合物もまた、常温常圧にお
いて必ずしも気相である必要はなく、加熱或は減圧等に
より溶融、蒸発、昇華等を経て気化し得るものであれば
、液相でも固相でも使用可、能である。フッ素化合物と
しては、フッ素、フッ化水素、フッ化塩素、フッ化臭素
、フッ化沃素等の無機化合物、及びフッ化アルカン、フ
ン化アルチル金属、フッ化アリール、フッ化スチレン、
フッ化アルカン、フッ素置換オルガノミラン等の有機化
合物を用いることができる。Furthermore, the fluorine compounds that can be used do not necessarily have to be in a gas phase at normal temperature and pressure, but can be in either a liquid phase or a solid phase as long as they can be vaporized through melting, evaporation, sublimation, etc. by heating or reduced pressure. However, it is possible to use it. Examples of fluorine compounds include inorganic compounds such as fluorine, hydrogen fluoride, chlorine fluoride, bromine fluoride, and iodine fluoride, as well as alkanes fluorides, alkyl metal fluorides, aryl fluorides, styrene fluorides,
Organic compounds such as fluorinated alkanes and fluorinated organomilans can be used.
フッ化アルカンとしては、例えば、四フフ化メタン、六
フッ化エタン、パーフルオロプロパン、パーフルオロブ
タン、パーフルオロヘキサン等作用いられる。Examples of the fluorinated alkane include tetrafluorinated methane, hexafluorinated ethane, perfluoropropane, perfluorobutane, and perfluorohexane.
フッ化アルキル金属としては、例えば、フッ化ジメチル
アルミニウム、ニフッ化メチルアルミニウム、フッ化ト
リメチルスズ、ニフフ化ジメチルスズ、三フッ化メチル
スズ等や、上記化合物を全フッ素置換した化合物が用い
られる。As the alkyl metal fluoride, for example, dimethylaluminum fluoride, methylaluminum difluoride, trimethyltin fluoride, dimethyltin nifluoride, methyltin trifluoride, and compounds obtained by substituting the above compounds with all fluorine are used.
フン化アリールとしては、例えば、パーフルオロベンゼ
ン、パーフルオロトルエン、パーフルオロナフタリン、
等が用いられる。Examples of the aryl fluoride include perfluorobenzene, perfluorotoluene, perfluoronaphthalene,
etc. are used.
フッ化スチレンとしては、例えば、フルオロスチレン等
が用いられる。As the fluorinated styrene, for example, fluorostyrene or the like is used.
フッ化アルケンとしては、例えば、四フフ化エチレン、
パーフルオロプロペン、パーフルオロブテン、パーフル
オロペンテン、パーフルオロヘキセン、パーフルオロヘ
プテン、パーフルオロオクテン、パーフルオロノネン等
が用いラレル。Examples of fluorinated alkenes include tetrafluorinated ethylene,
Perfluoropropene, perfluorobutene, perfluoropentene, perfluorohexene, perfluoroheptene, perfluorooctene, perfluorononene, etc. are used as larel.
フッ素置換オルガノミランとしては、例えば、テトラフ
ルオロメチルミラン、フルオロフェニルトリクロロメチ
ルミラン、等が用いられる。As the fluorine-substituted organomilan, for example, tetrafluoromethylmilane, fluorophenyltrichloromethylmilane, etc. are used.
第１図は、導電性基板（１）上に有機系感光層（２）及
び第１の表面保護層（３）、第２の表面保護層（４）を
この順に順次積層した、本発明による感光体の構成を示
したものである。尚、上記感光層は、電荷発生と電荷輸
送を兼ねる一層でもよく、両機能を分離した２層でも良
い。FIG. 1 shows a method according to the present invention in which an organic photosensitive layer (2), a first surface protective layer (3), and a second surface protective layer (4) are laminated in this order on a conductive substrate (1). This figure shows the structure of the photoreceptor. Note that the photosensitive layer may be a single layer that serves both charge generation and charge transport, or may be a two-layer layer that performs both functions separately.
第２図は本発明に係わる感光体の第１の表面保護層、即
ち、アモルファスカーボン膜を形成するだめの製造装置
を示し、図中（２０１）〜（２０６）は常温において気
相状態にある原料及びキャリアガスを密封した第１乃至
第６タンクで、各々のタンクは第１乃至第６調節弁（２
０７）〜（２１２）と第１乃至第６流量制御器（２１３
）〜（２１８）に接続されている。図中（２１９）〜（
２２１）は常温において液相または固相状態にある原料
を封入した第１乃至第３容器で、各々の容器は気化のた
め、第１乃至第３温調器（２２２）〜（２２４）により
与熱可能であり、さらに各々の容器は第７乃至第９調節
弁（２２５）〜（２２７）と第７乃至第９流量制御器（
２２８）〜（２３０）に接続されている。これらのガス
は混合器（２３１）で混合された後、主管（２３２）を
介して反応室（２３３）に送り込まれる。FIG. 2 shows a manufacturing apparatus for forming the first surface protective layer of a photoreceptor, that is, an amorphous carbon film according to the present invention, and in the figure (201) to (206) are in a gas phase at room temperature. The first to sixth tanks seal the raw material and carrier gas, and each tank has the first to sixth control valves (2
07) to (212) and the first to sixth flow rate controllers (213)
) to (218). In the figure (219) to (
221) are first to third containers filled with raw materials that are in a liquid or solid state at room temperature, and each container is heated by the first to third temperature regulators (222) to (224) for vaporization. Further, each container has seventh to ninth control valves (225) to (227) and seventh to ninth flow rate controllers (225) to (227).
228) to (230). These gases are mixed in a mixer (231) and then sent into the reaction chamber (233) via the main pipe (232).
途中の配管は、常温において液相または固相状態にあっ
た原料化合物が気化したガスが、途中で凝結しないよう
に、適宜配置された配管加熱器（２３４）により、与熱
可能とされている。反応室内には接他電極（２３５）と
電力印加電極（２３６）が対向して設置され、各々の電
極は電極加熱器（２３７）により与熱可能とされている
。電力印加電極（２３６）には、高周波電力用整合器（
２３８）を介して高周波電源（２３９）、低周波電力用
整合器（２４０）を介して低周波電源（２４１）、ロー
パスフィルタ（２４２）を介して直流電源（２４３）が
接続されており、接続選択スイッチ（２４４，）により
周波数の異なる電力が印加可能とされている。反応室（
２３３）内の圧力は圧力制御弁（２４５）により調整可
能であり、反応室（２３３）内の減圧は、排気系選択弁
（２４６）を介して、拡散ポンプ（２４７）、油回転ポ
ンプ（２４８）、’或は、冷却除外装置（２４９）、メ
カニカルブースターポンプ（２５０）、油回転ポンプ（
２４８）により行なわれる。排ガスについては、さらに
適当な除外装置（２５３）により安全無害化した後、大
気中に排気される。これら排気系配管に就いても、常温
において液相または固相状態にあった原料化合物が気化
したガスが、途中で凝結しない様に、適宜配置された配
管加熱器（２３４）により、与熱可能とされている。反
応室（２３３）も同様の理由から反応室加熱器（２５１
）により与熱可能とされ、内部に配された電極上には、
予め有機系感光層が導電性基体上に形成された基板（２
５２）が、設置される。第２図において基板（２５２）
は接地電極（２３・５）に固定して配されているが、電
力印加電極（２３６）に固定して配されても良く、さら
に双方に配されても良い。The pipes along the way can be heated by appropriately placed pipe heaters (234) so that the gas, which is the vaporized raw material compound that is in a liquid or solid state at room temperature, does not condense on the way. . A reciprocal electrode (235) and a power application electrode (236) are installed facing each other in the reaction chamber, and each electrode can be heated by an electrode heater (237). The power application electrode (236) is equipped with a matching box for high frequency power (
238), a low frequency power source (241) through a low frequency power matching box (240), and a DC power source (243) through a low pass filter (242). Power with different frequencies can be applied by a selection switch (244,). reaction chamber (
The pressure inside the reaction chamber (233) can be adjusted by the pressure control valve (245), and the pressure inside the reaction chamber (233) can be reduced by the diffusion pump (247) and the oil rotary pump (248) through the exhaust system selection valve (246). ),' or cooling exclusion device (249), mechanical booster pump (250), oil rotary pump (
248). The exhaust gas is further rendered safe and harmless by an appropriate exclusion device (253) and then exhausted into the atmosphere. These exhaust system pipes can also be heated by appropriately placed pipe heaters (234) so that the gas, which is the vaporized raw material compound that is in a liquid or solid state at room temperature, does not condense on the way. It is said that The reaction chamber (233) is also equipped with a reaction chamber heater (251) for the same reason.
), and on the electrodes arranged inside,
A substrate (2) on which an organic photosensitive layer is previously formed on a conductive substrate.
52) is installed. In FIG. 2, the substrate (252)
are fixedly arranged on the ground electrode (23, 5), but may be fixedly arranged on the power application electrode (236), or may be arranged on both.
第３図は本発明に係わる感光体の第１の表面保護層、即
ち、アモルファスカーボン膜を形成するだめの製造装置
の別の一形態を示し、反応室（３３３）内部の形態以外
は、第２図に示した本発明に係わる製造装置と同様であ
る。即ち、第２図における２００番台の図中番号を、第
３図においては３００番台に置き換えて解すればよい。FIG. 3 shows another embodiment of the manufacturing apparatus for forming the first surface protective layer of the photoreceptor, that is, the amorphous carbon film according to the present invention. This is similar to the manufacturing apparatus according to the present invention shown in FIG. That is, the numbers in the 200s in FIG. 2 may be replaced with numbers in the 300s in FIG. 3.
第３図において、反応室（３３３）内部には、第２図に
おける接地電極（２３５）を兼ねた、予め有機系感光層
が導電性基体上に形成された円筒形の基板（、３５２）
が設置され、両側には電極加熱器（３３７）が配されて
いる。基板（３５２）周囲には同じく円筒形状をした電
力印加電極（３３６）が配され、外側には電極加熱器（
３３７）が配されている。有機系感光層が形成されてい
る基板（３５２）は、外部より駆動モータ（３５４）を
用いて自転可能となっている。In FIG. 3, inside the reaction chamber (333) is a cylindrical substrate (352) on which an organic photosensitive layer is previously formed on a conductive substrate, which also serves as the ground electrode (235) in FIG.
is installed, and electrode heaters (337) are arranged on both sides. A similarly cylindrical power application electrode (336) is arranged around the substrate (352), and an electrode heater (336) is arranged on the outside.
337) are arranged. The substrate (352) on which the organic photosensitive layer is formed is rotatable using an external drive motor (354).
反応室は、拡散ポンプにより予め１ｏ 乃至１ｏ−６
Ｔｏｒｒ程度にまで減圧し、真空度の確認と装置内部に
吸着したガスの脱着を行なう。同時に電極加熱器により
、電極並びに電極に固定して配された基板を、必要に応
じ、所定の温度まで昇温する。The reaction chamber is preliminarily heated from 1o to 1o-6 by a diffusion pump.
The pressure is reduced to approximately Torr, the degree of vacuum is confirmed, and the gas adsorbed inside the device is desorbed. At the same time, the electrode and the substrate fixedly disposed on the electrode are heated to a predetermined temperature using an electrode heater, if necessary.
この時、有機系感光層の熱変成を防止するために、基板
温度は１００℃以下（常温乃至１００ ℃）に温度設定
される。次いで、第１乃至第６タンク及び第１乃至第３
容器から適宜炭化水素並びにフッ素化合物よりなる原料
ガスを第１乃至第９流量制御器を用いて定流量化しなが
ら反応室内に導入し、圧力調節弁により反応室内を一定
の減圧状態に保つ。At this time, the substrate temperature is set to 100° C. or less (room temperature to 100° C.) in order to prevent thermal denaturation of the organic photosensitive layer. Next, the first to sixth tanks and the first to third tanks
A raw material gas consisting of hydrocarbons and fluorine compounds is introduced from the container into the reaction chamber at a constant flow rate using the first to ninth flow rate controllers, and the inside of the reaction chamber is maintained at a constant reduced pressure using the pressure control valve.
ガス流量が安定した後、接続選択スイッチにより、例え
ば高周波電源を選択し、電力印加電極に高周波電力を投
入する。両電極間には放電が開始され、時間と共に基板
上に固相の膜が形成される。反応時間により膜厚を制御
し、所定の膜厚に達したところで放電を停止し、アモル
ファスカーボン膜ヲ本発明による感光体の表面保護層と
して得る。このアモルファスカーボン膜は、本発明によ
り生成したフッ素原子を含有するプラズマ有機重合膜で
ある。以上の過程により、本発明による表面保護層を有
する感光体を得る。After the gas flow rate is stabilized, a connection selection switch is used to select, for example, a high frequency power source, and high frequency power is applied to the power application electrode. A discharge is started between the two electrodes, and a solid phase film is formed on the substrate over time. The film thickness is controlled by the reaction time, and when a predetermined film thickness is reached, the discharge is stopped to obtain an amorphous carbon film as a surface protective layer of the photoreceptor according to the present invention. This amorphous carbon film is a plasma organic polymer film containing fluorine atoms produced according to the present invention. Through the above process, a photoreceptor having a surface protective layer according to the present invention is obtained.
第４図は、本発明に係わる感光体の第２の表面保護層を
形成するための製造装置を示す。FIG. 4 shows a manufacturing apparatus for forming the second surface protective layer of a photoreceptor according to the present invention.
図中（４０１）は真空槽を示し、内部には基板保持部材
（４０２）により保持された基板（４０３）が設置され
ている。基板（４０３）と対向して蒸発源材料を載置し
た第１ボー） （４０４）及び第２ポート（４０５）が
配置されている。各ポートはそれぞれ第１電極（４０６
）及び第２電極（４０７）に接続され、電力印加により
加熱可能とされている。第１ポートは所謂ボート昇温に
よる抵抗加熱蒸着法を用いるが、第２ポートは抵抗加熱
蒸着法に加え電子ビーム加熱蒸着法を併用できるように
、その下部に電子銃（４１３）を備えている。In the figure, (401) indicates a vacuum chamber, and a substrate (403) held by a substrate holding member (402) is installed inside. A first port (404) on which an evaporation source material is placed and a second port (405) are arranged facing the substrate (403). Each port has a first electrode (406
) and a second electrode (407), and can be heated by applying electric power. The first port uses a so-called resistance heating evaporation method using boat heating, but the second port is equipped with an electron gun (413) at the bottom so that it can use an electron beam heating evaporation method in addition to the resistance heating evaporation method. .
そして、第１ボート（＝１０４ ）と第２ポート（４０
５）と基板との間には開閉可能な第１遮蔽板（４０８）
及び第２遮蔽板（４０９）が設けられ、真空槽（４０１
）内は排気ポンプ（４１１）により減圧可能である。Then, the first boat (=104) and the second port (40
5) and a first shielding plate (408) that can be opened and closed between the board and the board.
and a second shielding plate (409), and a vacuum chamber (401).
) can be depressurized by an exhaust pump (411).
（以 下 余 白 ）以下、本発明
の詳細な説明するだめに実施例及び比較例をあげて説明
してゆく。(The following is a blank space.) Hereinafter, in order to provide a detailed explanation of the present invention, examples and comparative examples will be given and explained.
下記構造式〔Ｉ〕；
〔Ｉ〕
で示されるジスアゾ化合物２重冊部、ポリエステル樹脂
（東洋紡社製Ｖ−５００）１重量部、メチルエチルケト
ン１００重量部をボールミルで、２４時間分散した。こ
の分散液を直径８０×長さ３３０間の円筒状アルミニウ
ム基板上にディッピングにより乾燥後の膜厚が３０００
Ａとなるように塗布し、電荷発生層を形成した。Two volumes of a disazo compound represented by the following structural formula [I]; [I], 1 part by weight of polyester resin (V-500 manufactured by Toyobo Co., Ltd.), and 100 parts by weight of methyl ethyl ketone were dispersed in a ball mill for 24 hours. This dispersion was dipped onto a cylindrical aluminum substrate with a diameter of 80 mm and a length of 330 mm, resulting in a film thickness of 3000 mm after drying.
A was applied to form a charge generation layer.
次いで、この電荷発生層の上に、下記構造式〔■〕（以
下 余 白 ）
に示されるヒドラゾン化合物１０重量部、ポリカーボネ
ート樹脂（帝人化成社製に−１３００）１０重量部をテ
トラヒドロフラン８０重量部に溶解させた塗布液を乾燥
後の膜厚が２０μｍとなるように塗布、乾燥して電荷輸
送層を形成し、有機系感光層Ａを得た。Next, 10 parts by weight of a hydrazone compound represented by the following structural formula [■] (hereinafter referred to as "margin") and 10 parts by weight of polycarbonate resin (manufactured by Teijin Kasei Co., Ltd. -1300) were added onto this charge generation layer, and 80 parts by weight of tetrahydrofuran. An organic photosensitive layer A was obtained by coating and drying a coating solution in which a coating solution was dissolved in 100% to give a film thickness of 20 μm after drying to form a charge transport layer.
下記構造式（Ｉｌｌ〕
（ＩＩＩ）
で示されるジスアゾ化合物２重量部、ポリエステル樹脂
（東洋紡社製Ｖ−５００）１重量部、メチルエチルケト
ン１００重量部をボールミルで、２４時間分散した。こ
の分散液を直径８０×長さ３３０咽の円筒状アルミニウ
ム基板上にディッピングにより乾燥後の膜厚が２５００
λとなるように塗布し、電荷発生層を形成した。2 parts by weight of a disazo compound represented by the following structural formula (Ill) (III), 1 part by weight of polyester resin (V-500 manufactured by Toyobo Co., Ltd.), and 100 parts by weight of methyl ethyl ketone were dispersed in a ball mill for 24 hours. The film thickness after drying is 2500mm by dipping on a cylindrical aluminum substrate measuring 80mm x 330mm long.
A charge generation layer was formed by coating the film so as to give a charge generation layer of λ.
次いで、この電荷発生層の上に、下記構造式〔■〕（Ｉ
Ｖ）
で示されるスチリル化合物１０重量部、ポリアクリレー
ト樹脂（ユニチカ社製Ｕ−４０００）１０重量部をテト
ラヒドロフラン８５重量部に溶解させた塗布液を乾燥後
の膜厚が２０μｍとなるように塗布、乾燥して電荷輸送
層を形成し、有機系感光層Ｂを得た。Next, on this charge generation layer, the following structural formula [■] (I
V) A coating solution prepared by dissolving 10 parts by weight of the styryl compound shown by formula 1 and 10 parts by weight of polyacrylate resin (U-4000 manufactured by Unitika Co., Ltd.) in 85 parts by weight of tetrahydrofuran is applied so that the film thickness after drying is 20 μm, The organic photosensitive layer B was obtained by drying to form a charge transport layer.
下記構造式〔■〕；
で示されるジスアゾ化合物２重量部、ポリエステル樹脂
（東洋紡社製Ｖ−５００）１重量部、メチルエチルケ）
、７１００重量部をボールミルで、２４時間分散した
。この分散液を直径８０×長さ３３０闇の円筒状アルミ
ニウム基板上にディッピングにより乾燥後の膜厚が３０
００人となるように塗布し、電荷発生層を形成した。2 parts by weight of a disazo compound represented by the following structural formula [■], 1 part by weight of polyester resin (V-500 manufactured by Toyobo Co., Ltd., methyl ethyl chloride)
, 7100 parts by weight were dispersed in a ball mill for 24 hours. This dispersion was dipped onto a dark cylindrical aluminum substrate with a diameter of 80 mm and a length of 330 mm, so that the film thickness after drying was 30 mm.
00 to form a charge generation layer.
次いで、この電荷発生層の上に、下記構造式〔■〕〔■
〕
で示されるスチリル化合物１０重量部、メチルツタクリ
レート樹脂（三菱レーヨン社製ＢＲ−８５）１０重量部
をテトラヒドロフラン８０重量部に溶解させた塗布液を
乾燥後の膜厚が２０μｍとなるように塗布、乾燥して電
荷輸送層を形成し、有機系感光層Ｃを得だ。Next, on this charge generation layer, the following structural formula [■] [■
] A coating solution prepared by dissolving 10 parts by weight of the styryl compound represented by the formula and 10 parts by weight of methyl ivy acrylate resin (BR-85 manufactured by Mitsubishi Rayon Co., Ltd.) in 80 parts by weight of tetrahydrofuran was prepared so that the film thickness after drying was 20 μm. A charge transport layer was formed by coating and drying to obtain an organic photosensitive layer C.
第１の表面保護層（ａ）の作製
第３図に示すグロー放電分解装置において、まず反応室
（３３３）の内部を１０ Ｔｏｒｒ程度の高真空にし
た後、第１及び第２調節弁（３０７）及び（３０８）を
解放し、第１タンク（３０１）よりパーフルオロプロピ
レン、第２タンク（３０２）よ１１）Ｉ−１２ガスを出
力圧ゲージ２ ｋ’ｌ／ｄの下でマスフローコントロー
ラ（３１３’）及び（３１４）内へ流入させた。Preparation of the first surface protective layer (a) In the glow discharge decomposition apparatus shown in FIG. ) and (308), and the perfluoropropylene from the first tank (301) and the I-12 gas from the second tank (302) are transferred to the mass flow controller (313) under the output pressure gauge 2 k'l/d. ) and (314).
そして各マスフローコントローラの目盛を調節してパー
フルオロプロピレンの流量を６０ ｓｃｃｍ％ＩＩ２を
１２０ＳＣＣｍとなるように設定して反応室（３３３）
内へ流入した。それぞれの流量が安定した後に、反応室
（３３３）の内圧がＱ、５Ｔｏｒｒとなるように調節し
た。一方、導電性円筒型基板（３３５）上に有機系感光
層Ａを設けた基板を用いて、５０℃に予め加熱しておき
、各ガス流量が安定した状態で低周波電源（３４１）を
投入し、円筒型電極板（３３６）に１００ ｗａｔｔｓ
の電力（周波数２００ ＫＨ２）を印加して約３分間プ
ラズマ重合を行い、導電性円筒型基板（３３５）上の有
機系感光層Ａ上に厚さ約０．１９μｍの第１の表面保護
層（ａ）を形成した。Then, by adjusting the scale of each mass flow controller, the flow rate of perfluoropropylene was set to 60 sccm% II2 to 120 SCCm, and the flow rate was adjusted to the reaction chamber (333).
It flowed inside. After each flow rate became stable, the internal pressure of the reaction chamber (333) was adjusted to Q, 5 Torr. On the other hand, a conductive cylindrical substrate (335) with an organic photosensitive layer A is preheated to 50°C, and the low frequency power source (341) is turned on when each gas flow rate is stable. 100 watts on the cylindrical electrode plate (336)
A power (frequency: 200 KH2) was applied to perform plasma polymerization for about 3 minutes, and a first surface protective layer (about 0.19 μm thick) was formed on the organic photosensitive layer A on the conductive cylindrical substrate (335). a) was formed.
パーフルオロプロピレンの流量を８Ｑ ｓｃｃｍにした
他は、第１の表面保護層（ａ）の作製と同様にして導電
性円筒型基板（３３５）上の有機系感光層Ｂを設けた基
板上に厚さ約０．３００μｍの第１の表面保護層（ｂ）
を作製した。A thick layer was formed on the conductive cylindrical substrate (335) on which the organic photosensitive layer B was formed in the same manner as in the preparation of the first surface protective layer (a), except that the flow rate of perfluoropropylene was changed to 8Q sccm. First surface protective layer (b) with a thickness of about 0.300 μm
was created.
第１の表面保護層（Ｃ）の作製
第３図に示すグロー放電分解装置において、まず反応室
（３３３）の内部を１０ Ｔｏｒｒ程度の高真空にし
だ後、第一、第二及び第三調節弁（３０７）。Preparation of the first surface protective layer (C) In the glow discharge decomposition apparatus shown in FIG. Valve (307).
（３０８）及び（３０９）及びを解放し、第一タンク（
３０１）！リバーフルオロプロピレン、第二タンク（３
０２）より８２ガス、第三タンク（３０３）よりプロピ
レンを出力圧ゲージ２ Ｋ？／ｄの下でマスフローコン
トローラ（３１３）、（３１４）及び（３１５）内へ流
入させた。そして各マスフロコントローラーの目盛りを
調節してパーフルオロプロピレンの流量を６０ ｓｅｃ
ｍ、 Ｈ２を１２０ ｓｅｃｍ、プロピＬ／７をＯｓｃ
ｃｍとなるように設定して反応室内へ流入した。それぞ
れの流量が安定した後に、反応室（３３３）の内圧が、
Ｑ、５Ｔｏｒｒとなるように調節した。一方、導電性円
筒型基板（３３５）上に有機系感光層Ｃを設けた基板を
用いて３０℃に予め加熱しておき、各ガス流量が安定し
、内圧が安定した状態で低周波電源を投入し、円筒型電
極板（３３６）に３００ｗａｔｔｓの電力（周波数２０
０ Ｋ）ＩＺ ）を印加して約１７０秒間プラズマ重合
を行ない、この時点でマスフローコントローラ（３１３
）及び（３１５）を調節して、パーフルオロプロピレン
の流量ヲＯｓｃｃｍ、プロピレンを６０ｓｅｃｍとなる
ように設定し、（このＫＮの変更は、マスフローコント
ローラー自体の応答速度、マスフローコントローラーか
ら反応室までの配管の内容量などが、緩衝効果をもたら
すため、反応室内では、表１のように緩慢な流量変化と
成る。）約１０秒間のプラズマ重合を行ない、合計約３
分間のプラズマ重合を行ない、導電性円筒型基板（３３
５）上の有機系感光層Ｃ上に厚さ約０．２６μｍの第１
の表面保護層（Ｃ）を形成した。Release (308) and (309) and the first tank (
301)! River fluoropropylene, second tank (3
Output pressure gauge 2 K?82 gas from 02) and propylene from the third tank (303). /d into mass flow controllers (313), (314) and (315). Then, adjust the scale of each mass flow controller to adjust the flow rate of perfluoropropylene to 60 sec.
m, H2 120 sec, propylene L/7 Osc
cm, and flowed into the reaction chamber. After each flow rate becomes stable, the internal pressure of the reaction chamber (333) becomes
Q: Adjusted to 5 Torr. On the other hand, a conductive cylindrical substrate (335) with an organic photosensitive layer C provided thereon is preheated to 30°C, and the low frequency power source is turned on after each gas flow rate is stabilized and the internal pressure is stabilized. 300 watts of power (frequency 20
0 K)IZ) was applied for about 170 seconds, and at this point the mass flow controller (313
) and (315) to set the flow rate of perfluoropropylene to Osccm and propylene to 60 seconds. (Because the content of the liquid causes a buffering effect, the flow rate changes slowly in the reaction chamber as shown in Table 1.) Plasma polymerization is performed for about 10 seconds, and a total of about 3
Plasma polymerization was performed for 30 minutes, and a conductive cylindrical substrate (33
5) On the upper organic photosensitive layer C, a first layer having a thickness of about 0.26 μm is applied.
A surface protective layer (C) was formed.
（以 下 余 白）
このようにして得られた第１の表面保護層（ｃ）内のフ
ッ素原子濃度は層方向に不均一であり、感光層側で高濃
度であることが、オージェ分析、ＣＩＩＮ分析等により
確認された。(Margins below) The fluorine atom concentration in the first surface protective layer (c) obtained in this way is non-uniform in the layer direction, and the concentration is higher on the photosensitive layer side, as shown by Auger analysis and Confirmed by CIIN analysis etc.
表 １
０ １７０ ｔ
ｓ。Table 1 0 170 t
s.
第１の表面保護層（ｄ）の作製
第３図に示すグロー放電分解装置において、まず反応室
（３３３）の内部をｌ□ Ｔｏｒｒ程度の高真空にし
た後、第−及び第二調節弁（３０７）及び（３０８）を
解放し、第一タンク（３０１）よりパーフルオロプロピ
レン、第二タンク（３０２）よりＨ２ガスを出力圧ケー
ジ２Ｋｐ／ａｆの下でマスフローコントロー５ （３１
３）および（３１４）内へ流入させた。そして各マスフ
ロコントローラーの目盛りを調節してパーフルオロプロ
ピレンの流量を５Ｑ ＳＣＣｍ１を１２０ ｓ ｃ ｃ
ｍとなるように設定して反応室内へ流入した。それぞれ
の流量が安定した後に、反応室（３３３）の内圧が、Ｑ
、５Ｔｏｒｒとなるように調節した。一方、導電性円筒
型基板（３３５）上に有機系感光層Ａを設けた基板を用
いて６０℃に予め加熱しておき、各ガス流量が安定し、
内圧が安定した状態で低周波電源を投入し、円筒型電極
板（３３５）に２ＱＱｗａ ｔ ｔ ｓの電力（周波数
２００１Ｇ（ｚ ）を印加して約１５０秒間のプラズマ
重合を行ない、導電性円筒型基板（３３５）上の有機系
感光層Ａ上に厚さ約０．２３μｍの第１の表面保護層を
設けた。この第１の表面保護層の表面を粗面処理するた
め更に反応室（３３３）の内部を１０ Ｔｏｒｒ程度
の高真空にした後、第二調節弁（３０８）を解放［７、
第二タンク（３０２）よりＡｒガスを出力圧ゲージ２Ｋ
Ｆ／ａ（の下でマスフローコントローラ（３１４）内へ
流入させた。そしてマスフロコントローラーの目盛りを
調節してＡｒを２００ｓｅｃｍとなるように設定して反
応室内へ流入した。流量が安定した後に、反応室（３３
３）の内圧が、１．ＯＴｏ ｒ ｒとなるように調節し
た。ガス流量が安定し、内圧が安定した状態で低周波電
源を投入し、円筒型電極板（３３６）に１００ ｗａｔ
ｔｓの電力（周波数ｌＱＱ ＫＨｚ ）を印加して約３
０秒間の放電を行ない、即ち、所謂ボンバード処理を行
ない、導電性円筒型基板（３３５）上の有機系感光層Ａ
上の第１の表面保護層（ｄ）を形成した。Preparation of the first surface protective layer (d) In the glow discharge decomposition apparatus shown in FIG. 307) and (308), and perfluoropropylene from the first tank (301) and H2 gas from the second tank (302) under an output pressure cage of 2 Kp/af and a mass flow controller 5 (31
3) and (314). Then, adjust the scale of each mass flow controller to set the perfluoropropylene flow rate to 5Q SCCm1 to 120 s c c
m, and flowed into the reaction chamber. After each flow rate becomes stable, the internal pressure of the reaction chamber (333) becomes Q
, 5 Torr. On the other hand, a conductive cylindrical substrate (335) on which an organic photosensitive layer A is provided is heated in advance to 60°C, and the flow rate of each gas is stabilized.
When the internal pressure is stable, a low frequency power source is turned on, and a power of 2QQwatts (frequency 2001G(z)) is applied to the cylindrical electrode plate (335) to perform plasma polymerization for about 150 seconds. A first surface protective layer having a thickness of approximately 0.23 μm was provided on the organic photosensitive layer A on the substrate (335).A reaction chamber (333) was further provided to roughen the surface of this first surface protective layer. ) After creating a high vacuum of about 10 Torr inside the second control valve (308), open the second control valve (308) [7,
Output pressure gauge 2K for Ar gas from the second tank (302)
Ar was flowed into the mass flow controller (314) under F/a (under F/a). Then, the scale of the mass flow controller was adjusted to set Ar to 200 seconds and flowed into the reaction chamber. After the flow rate was stabilized, Reaction chamber (33
3) The internal pressure of 1. It was adjusted so that it became OTo r r. When the gas flow rate is stable and the internal pressure is stable, turn on the low frequency power and apply 100 watts to the cylindrical electrode plate (336).
Approximately 3 ts of power (frequency lQQ KHz) is applied.
The organic photosensitive layer A on the conductive cylindrical substrate (335) is discharged for 0 seconds, that is, the so-called bombardment process is performed.
An upper first surface protective layer (d) was formed.
以後、第１の表面保護層（ａ）〜（ｄ）という場合には
、特に断わらない限り、導電性円筒型基板（３３５）及
び、第１の表面保護層（ａ）〜（ｄ）の作製中に述べた
それぞれの有機系感光層Ａ、Ｃを含むものとする。Hereinafter, when referring to the first surface protective layers (a) to (d), unless otherwise specified, it refers to the production of the conductive cylindrical substrate (335) and the first surface protective layers (a) to (d). The organic photosensitive layers A and C mentioned above are included.
実施例１〜４
第４図に示す真空蒸着装置を用い、第１の表面保護層（
−）〜（ｄ）上に、表２−１のとおりの化合物を用い第
２の表面保護層、即ち、透光性無機金属化合物の蒸着膜
を形成し、本発明の感光体である実施例１〜４を得た。Examples 1 to 4 The first surface protective layer (
-) to (d) A second surface protective layer, that is, a vapor deposited film of a translucent inorganic metal compound is formed using the compounds shown in Table 2-1, and the photoreceptor of the present invention is an example. 1 to 4 were obtained.
尚、蒸着方法は、第１のボー） （４０４）を用いた抵
抗加熱蒸着法を用いた。The vapor deposition method used was a resistance heating vapor deposition method using the first bow (404).
得られた第２の表面保護層の膜厚、及び、第２の表面保
護層を蒸着する前に、オージェ分析で測定した第１の表
面保護層中のフン素原子濃度、他をあわせて第２・−１
に示す。The thickness of the second surface protective layer obtained, the fluorine atom concentration in the first surface protective layer measured by Auger analysis, and other factors were calculated before depositing the second surface protective layer. 2・-1
Shown below.
表２−１
＊１．＊２ ；オージェ分析によれば、表面近傍のフッ
素量しか測定できないが、＊１．＊２の場合も本発明の
効果を得るのに十分なフッ素量（４０〜７Ｑ ３１ｍ％
）が含まれていることが、本発明者らの研究により確認
されている。Table 2-1 *1. *2; According to Auger analysis, only the amount of fluorine near the surface can be measured, but *1. *In the case of 2, the amount of fluorine sufficient to obtain the effects of the present invention (40 to 7Q 31m%
) has been confirmed through research by the present inventors.
実施例５〜８
第４図に示す真空蒸着装置を用い、第１の表面保護層（
ａ）〜（ｄ）上に表２−２のとおりの化合物を用い、第
２の表面保護層、即ち、透光性低抵抗無機金属化合物の
蒸着膜を形成し、本発明の感光体である実施例５〜８を
得た。尚、蒸着は表２−２に示す２つの化合物をそれぞ
れ第１のボー）（４０４）第２のボー） （４０５）に
載置、加熱を行う２元蒸着法の公知手法により行った。Examples 5 to 8 The first surface protective layer (
A second surface protective layer, that is, a vapor deposited film of a light-transmitting, low-resistance inorganic metal compound, is formed on a) to (d) using the compounds shown in Table 2-2 to form the photoreceptor of the present invention. Examples 5 to 8 were obtained. Incidentally, the vapor deposition was performed by a known method of binary vapor deposition in which the two compounds shown in Table 2-2 were placed on a first bow (404) and a second bow (405) and heated.
得られた第２の表面保護層の膜厚、及び、第２の表面保
護層を蒸着する前にオージェ分析により測定した、第１
の表面保護層中のフッ素原子濃度、 −他をあわせて
表２−２に示す。The thickness of the obtained second surface protective layer and the thickness of the first surface protective layer measured by Auger analysis before depositing the second surface protective layer.
The fluorine atom concentration in the surface protective layer of - and others are shown in Table 2-2.
（以 下 余 白 ）表２−２
＊１．＊２ ：前記
実施例９〜１２
第１の表面保護層（ａ）〜（ｄ）上に、以下の樹脂層■
〜■を形成し、本発明の感光体である実施例９〜１２を
得た。(Margin below) Table 2-2 *1. *2: Examples 9 to 12 The following resin layer ■ was applied on the first surface protective layers (a) to (d).
-■ were formed to obtain Examples 9 to 12, which are photoreceptors of the present invention.
樹脂層■
ポリカーボネイト（奇人化成社製に−１３００）１重量
部をＴＨＦ１０重量部に溶解させ、第１の表面保護層上
に塗布し、約８０℃で１．２時間乾燥させ、樹脂層■を
形成する。Resin layer ■ 1 part by weight of polycarbonate (manufactured by Kijin Kasei Co., Ltd. -1300) was dissolved in 10 parts by weight of THF, coated on the first surface protective layer, and dried at about 80°C for 1.2 hours to form the resin layer ■. Form.
樹脂層■
アクリルメラミン熱硬化樹脂（犬日本インキ製Ａ４０５
とスーーパーベツカミンＪ８２０の混合部）５０重量部
を有機溶媒（キシレン７重量部とブタノール３重量部の
混合物）５００重量部の混合液を第１の表面保護層上に
塗布し、約１００℃で１．５時間乾燥させ、樹脂層■を
形成する。Resin layer ■ Acrylic melamine thermosetting resin (A405 manufactured by Inu Nippon Ink)
A mixture of 50 parts by weight of 50 parts by weight of an organic solvent (a mixture of 7 parts by weight of xylene and 3 parts by weight of butanol) of 7 parts by weight of Dry for 1.5 hours to form a resin layer (2).
樹脂層■
エポキシ樹脂（エピクロン１０５０大日本インキ製）３
．５重ｉ％、トルエン９６．５重量％からなる塗布溶液
を第１の表面保護層上にスプレー塗布し、約９５℃で１
時間乾燥させ、樹脂層■を形成する、
樹脂層■
メチルエチルケト７７６．１重量％、アイソパーＨ（エ
ッソ化学社製）２０重量％との混合溶媒中に、アクリル
ポリオール（アクリディックＡ３０８：大日本インキ製
）２．０重量％、イソシアネート化合物（パーノックＤ
Ｎ９５０：大日本イソノアネート社製）１９重量％とを
混合し、１時間攪拌した塗布液により第１の表面保護層
上にデイピング塗布法によって樹脂層■を形成する。Resin layer ■ Epoxy resin (Epicron 1050 manufactured by Dainippon Ink) 3
．． A coating solution consisting of 5% by weight and 96.5% by weight of toluene was spray-coated onto the first surface protective layer and heated at about 95°C.
Resin layer ■ Acrylic polyol (Acridic A308: Dainippon Ink Co., Ltd.) was added to a mixed solvent of 776.1% by weight of methyl ethyl keto and 20% by weight of Isopar H (manufactured by Esso Chemical Co., Ltd.). ) 2.0% by weight, isocyanate compound (Parnock D
N950 (manufactured by Dainippon Isonoanate Co., Ltd.) in an amount of 19% by weight and stirred for 1 hour to form a resin layer (2) on the first surface protective layer by dipping coating.
得られた第２の表面保護層の膜厚、及び、第２の表面保
護層を塗布する前にオージェ分析により測定した第１・
の表面保護層のフッ素原子濃度、他をあわせて表２−３
に示す。The film thickness of the obtained second surface protective layer and the first layer measured by Auger analysis before applying the second surface protective layer.
Table 2-3 including the fluorine atom concentration of the surface protective layer and others
Shown below.
、表２−３
比較例１゜
第２の表面保護層をテフロン（Ｃ；２Ｆ４）ｎにより形
成した他は、実施例１．と同様にして比較例１．の感光
体を得た。, Table 2-3 Comparative Example 1゜ Example 1 except that the second surface protective layer was formed of Teflon (C; 2F4)n. Comparative example 1. A photoreceptor was obtained.
テフロンは第４図に示す真空蒸薗装置において第２のポ
ート（４０５）上にテフロンを載置し、電子銃（４１３
）との併用による電子ビーム蒸着方法によって蒸着膜と
した。Teflon is placed on the second port (405) in the vacuum steamer shown in FIG.
) was used in combination with electron beam evaporation to form a vapor deposited film.
比較例２゜
第２の表面保護層を形成しない他は、実施例１゜と同様
にして比較例２．の感光体を得た。Comparative Example 2 Comparative Example 2. Comparative Example 2. A photoreceptor was obtained.
比較例３、
前記した第１の表面保護層（３）の作製において、パー
フルオロプロピレンをプロピレンとした他は第１の表面
保護層＜＞の作製と同様にして、第１の表面保護層（ａ
）′を作製し、導電性円筒型基板（３３５）上に有機系
感光層Ａを形成し、その上に厚さ約０２０μｍの第１の
表面保護層（ａ）′を形成し、第２の表面保護層は設け
ず、比較例３．の感光体を得た。Comparative Example 3 In the production of the first surface protection layer (3) described above, the first surface protection layer ( a
)', an organic photosensitive layer A is formed on a conductive cylindrical substrate (335), a first surface protective layer (a)' with a thickness of about 020 μm is formed thereon, and a second Comparative example 3. No surface protective layer was provided. A photoreceptor was obtained.
比較例４゜
前記した有機系感光層Ａの作製において、その後筒１及
び第２の表面保護層を設けない感光体を比較例４．とす
る。Comparative Example 4 In the production of the organic photosensitive layer A described above, a photoreceptor without the cylinder 1 and the second surface protective layer was prepared in Comparative Example 4. shall be.
実施例１〜１２、及び比較例１〜４で得られた感光体を
常用のカールソンプロセスの中でコロナ放電を用いて一
６００ｖに初期帯電（Ｖｏ）Ｌ半減光量Ｅ１／２及び残
留電位Ｖｒを測定した。The photoconductors obtained in Examples 1 to 12 and Comparative Examples 1 to 4 were subjected to an initial charging (Vo)L half-decrement amount E1/2 and residual potential Vr to -600V using corona discharge in a commonly used Carlson process. It was measured.
又、Ｊ Ｉ Ｓ−に−５４００規格による鉛筆硬度を測
定し、実際の複写機（ミノルタカメラ社製ＥＰ４７０Ｚ
）に搭載してＡ４複写紙１０万枚の耐刷試験を行い、膜
厚減少を観察した。さらに高温高湿環境下（温度３５℃
、湿度８５％）での画像流れを観察し、常温常湿及び高
温高湿環境下での初期画像カブリを観察した。In addition, the pencil hardness was measured according to the JIS-5400 standard, and the hardness of an actual copying machine (EP470Z manufactured by Minolta Camera Co., Ltd.
), and a printing durability test was conducted on 100,000 sheets of A4 copy paper, and a decrease in film thickness was observed. Furthermore, under a high temperature and high humidity environment (temperature 35℃)
, 85% humidity), and initial image fogging was observed under normal temperature and normal humidity and high temperature and high humidity environments.
以上の結果をあわせて表３に示す。The above results are shown in Table 3.
（以 下 余 白 ）
表 ３
比較例１及び２からは、第２の表面保護層を７ノ素原子
を含まない層とすることによる効果が、比較例３からは
、表面保護層中にフッ素原子が含有されることによる効
果が、比較例４からは表面保護層アモルファスカーボン
を主体とする膜で形成することによる効果が理解された
。(Margin below) Table 3 Comparative Examples 1 and 2 show that the effect of making the second surface protective layer a layer that does not contain 7 atoms, and Comparative Example 3 shows that the effect of using fluorine in the surface protective layer It was understood from Comparative Example 4 that the effect due to the inclusion of atoms is the effect due to the surface protective layer formed of a film mainly composed of amorphous carbon.
発明の効果
以上の様に、本発明の感光体によれば、有機系感光層上
にフン素原子を含むアモルファスカーボンを主体とする
第１の表面保護層、及び、フッ素原子を含まない第２の
表面保護層を順次積層することにより、
有機系感光層本来の高感度な静電特性、光感度特性を損
わないという効果、
複写機等における実使用においても、傷を受けたり、摩
耗したりしないだけの高硬度を有し耐刷性に優れるとい
う効果、
第１の表面保護層がフッ素原子を含むことにより、耐湿
性に優れるという効果、
第２の表面保護層がフッ素原子を含ｔないことにより、
画像カブリを防止するという効果、などを得る。さらに
、
第２の表面保護層を透光性低抵抗無機金属化合物により
形成することにより、耐溶剤性等の外部要因に対する耐
性を向上させるという効果、第２の表面保護層と接する
第１の表面保護層の面を粗面処理することにより、第１
の表面保護層と第２の表面保護層との接着性を向上させ
るという効果、
第１の表面保護層中に層方向に不均一にフッ素原子を含
ませることにより、より効果的に画像カブリを防止する
という効果、
などを得る。さらに、第１の表面保護層と第２の表面保
護層との接着性の向上は、
第１の表面保護層をグロー放電法により形成した後、Ａ
ｒボンバード等のボンバード処理により粗面処理を行う
工程を有する、本発明の感光体の製造方法によって、効
果的に達成される。Effects of the Invention As described above, according to the photoreceptor of the present invention, a first surface protective layer mainly made of amorphous carbon containing fluorine atoms is provided on the organic photosensitive layer, and a second surface protection layer containing no fluorine atoms is provided on the organic photosensitive layer. By sequentially laminating the surface protective layers, the organic photosensitive layer has the effect of not impairing its inherent high-sensitivity electrostatic properties and photosensitivity properties, and also prevents scratches and abrasion during actual use in copying machines, etc. The first surface protective layer contains fluorine atoms and has excellent moisture resistance.The second surface protective layer contains fluorine atoms and has excellent printing durability. By not having
The effect of preventing image fogging, etc. can be obtained. Furthermore, by forming the second surface protective layer from a light-transmitting low-resistance inorganic metal compound, the first surface in contact with the second surface protective layer has the effect of improving resistance to external factors such as solvent resistance. By roughening the surface of the protective layer, the first
The effect of improving the adhesion between the surface protective layer and the second surface protective layer, and by including fluorine atoms unevenly in the layer direction in the first surface protective layer, image fogging can be more effectively prevented. Obtain the effect of preventing, etc. Furthermore, the adhesion between the first surface protective layer and the second surface protective layer can be improved by forming the first surface protective layer by a glow discharge method.
This can be effectively achieved by the photoreceptor manufacturing method of the present invention, which includes a step of roughening the surface by a bombardment process such as r-bombardment.
第１図は本発明の感光体の構成を示す図面、第２図乃至
第４図は本発明に係る感光体の製造装置を示す図面であ
る。
出願人 ミノルタカメラ株式会社FIG. 1 is a drawing showing the structure of a photoreceptor according to the present invention, and FIGS. 2 to 4 are drawings showing an apparatus for manufacturing a photoreceptor according to the present invention. Applicant Minolta Camera Co., Ltd.
Claims (1)
び第２の表面保護層を順次積層することにより構成され
る感光体において 上記第１の表面保護層はフッ素原子を含むアモルファス
カーボンを主体としてなり、 上記第２の表面保護層はフッ素原子を含まない透光性無
機金属化合物により形成されることを特徴とする感光体
。 ２、透光性無機金属化合物が透光性低抵抗無機金属化合
物である請求項１記載の感光体。３、透光性低抵抗無機
金属化合物の体積抵抗値が１×１０＾９〜９×１０＾１
＾０Ω・ｃｍである請求項２記載の感光体。 ４、導電性基板上に有機系感光層、第１の表面保護層、
及び第２の表面保護層を順次積層することにより構成さ
れる感光体において、 上記第１の表面保護層はフッ素原子を含むアモルファス
カーボンを主体としてなり、 上記第２の表面保護層はフッ素原子を含まない透光性樹
脂により形成されることを特徴とする感光体。 ５、第２の表面保護層と接する第１の表面保護層の面が
、粗面処理された面である請求項１又は請求項４記載の
感光体。 ６、第１の表面保護層に含まれるフッ素原子が層方向に
不均一である請求項１又は請求項４記載の感光体。 ７、導電性基板上に有機系感光層を形成する工程と、該
感光層上に第１の表面保護層と第２の表面保護層を順次
形成する感光体の製造方法において、 第１の表面保護層をグロー放電法により、少なくともフ
ッ素原子を含有するプラズマ有機重合膜として形成する
工程と、 該第１の表面保護層表面を不活性元素原子により粗面処
理する工程と、 第２の表面保護層を蒸着法により、フッ素原子を含有し
ない無機金属蒸着膜として形成する工程とを 有することを特徴とする感光体の製造方法。 ８、第２の表面保護層を塗布法により、透光性樹脂膜と
して形成する請求項７記載の感光体の製造方法。[Scope of Claims] 1. In a photoreceptor constructed by sequentially laminating an organic photosensitive layer, a first surface protective layer, and a second surface protective layer on a conductive substrate, the first surface protective layer A photoreceptor comprising mainly amorphous carbon containing fluorine atoms, and wherein the second surface protective layer is formed of a translucent inorganic metal compound containing no fluorine atoms. 2. The photoreceptor according to claim 1, wherein the light-transmitting inorganic metal compound is a light-transmitting low-resistance inorganic metal compound. 3. The volume resistivity of the translucent low-resistance inorganic metal compound is 1 x 10^9 to 9 x 10^1
The photoreceptor according to claim 2, which has a resistance of ^0 Ω·cm. 4. An organic photosensitive layer and a first surface protective layer on the conductive substrate,
and a photoreceptor constructed by sequentially laminating second surface protective layers, wherein the first surface protective layer is mainly made of amorphous carbon containing fluorine atoms, and the second surface protective layer is mainly composed of amorphous carbon containing fluorine atoms. A photoreceptor characterized in that it is formed from a transparent resin that does not contain any light. 5. The photoreceptor according to claim 1 or 4, wherein the surface of the first surface protective layer that is in contact with the second surface protective layer is a roughened surface. 6. The photoreceptor according to claim 1 or 4, wherein the fluorine atoms contained in the first surface protective layer are non-uniform in the layer direction. 7. In a method for manufacturing a photoreceptor, the method includes forming an organic photosensitive layer on a conductive substrate, and sequentially forming a first surface protective layer and a second surface protective layer on the photosensitive layer, the first surface a step of forming a protective layer as a plasma organic polymer film containing at least fluorine atoms by a glow discharge method; a step of roughening the surface of the first surface protective layer with atoms of an inert element; and a second surface protection step. 1. A method for producing a photoreceptor, comprising the step of forming a layer as an inorganic metal vapor-deposited film containing no fluorine atoms by a vapor deposition method. 8. The method for manufacturing a photoreceptor according to claim 7, wherein the second surface protective layer is formed as a transparent resin film by a coating method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7146488A JPH01243068A (en) | 1988-03-24 | 1988-03-24 | Photosensitive body and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7146488A JPH01243068A (en) | 1988-03-24 | 1988-03-24 | Photosensitive body and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01243068A true JPH01243068A (en) | 1989-09-27 |
Family
ID=13461339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7146488A Pending JPH01243068A (en) | 1988-03-24 | 1988-03-24 | Photosensitive body and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01243068A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008076520A (en) * | 2006-09-19 | 2008-04-03 | Fuji Xerox Co Ltd | Electrophotographic photoreceptor, and process cartridge and image forming apparatus using the same |
| JP2008076877A (en) * | 2006-09-22 | 2008-04-03 | Fuji Xerox Co Ltd | Electrophotographic photoreceptor, image forming apparatus and process cartridge |
| JP2008076876A (en) * | 2006-09-22 | 2008-04-03 | Fuji Xerox Co Ltd | Electrophotographic photoreceptor, and process cartridge and image forming apparatus using the same |
| JP2008268410A (en) * | 2007-04-18 | 2008-11-06 | Fuji Xerox Co Ltd | Electrophotographic photoreceptor, process cartridge and image forming apparatus |
-
1988
- 1988-03-24 JP JP7146488A patent/JPH01243068A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008076520A (en) * | 2006-09-19 | 2008-04-03 | Fuji Xerox Co Ltd | Electrophotographic photoreceptor, and process cartridge and image forming apparatus using the same |
| JP2008076877A (en) * | 2006-09-22 | 2008-04-03 | Fuji Xerox Co Ltd | Electrophotographic photoreceptor, image forming apparatus and process cartridge |
| JP2008076876A (en) * | 2006-09-22 | 2008-04-03 | Fuji Xerox Co Ltd | Electrophotographic photoreceptor, and process cartridge and image forming apparatus using the same |
| JP2008268410A (en) * | 2007-04-18 | 2008-11-06 | Fuji Xerox Co Ltd | Electrophotographic photoreceptor, process cartridge and image forming apparatus |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4439509A (en) | Process for preparing overcoated electrophotographic imaging members | |
| JPH01227161A (en) | Photosensitive body and production thereof | |
| US4939056A (en) | Photosensitive member | |
| JPH01243068A (en) | Photosensitive body and its production | |
| US5125644A (en) | Separating device for sheet-like member including separating pawl coated with amorphous carbon layer | |
| US4797338A (en) | Photosensitive member comprising charge generating layer and charge transporting layer | |
| US4851313A (en) | Photosensitive member comprising charge generating layer and charge transporting layer and process for preparing same | |
| JP2590971B2 (en) | Photoconductor | |
| JP2780305B2 (en) | Photoconductor | |
| JPS6397963A (en) | Photosensitive body and its manufacture | |
| US4876168A (en) | Photosensitive member comprising charge generating layer and charge transporting layer comprising amorphous carbon containing chalogen or transition metal | |
| JPH02108063A (en) | Photosensitive body | |
| JPS6397964A (en) | Photosensitive body and its manufacture | |
| JPH01225959A (en) | Photosensitive body | |
| JP2556024B2 (en) | Photoreceptor and manufacturing method thereof | |
| JPS6315255A (en) | Photosensitive body | |
| JP2636261B2 (en) | Photoconductor | |
| JPS63220168A (en) | Photosensitive body and its production | |
| JPS6315257A (en) | Photosensitive body | |
| JP3574779B2 (en) | Photoconductor and image forming apparatus | |
| JPH025069A (en) | Photosensitive body | |
| JPH01219755A (en) | Photosensitve body and production thereof | |
| EP0261652A2 (en) | Photosensitive member comprising charge generating layer and charge transporting layer | |
| JPH01138563A (en) | Photosensitive body | |
| JPH023071A (en) | Process for treating photosensitive body |