JPH0690538B2 - Electrophotographic photoreceptor - Google Patents
Electrophotographic photoreceptorInfo
- Publication number
- JPH0690538B2 JPH0690538B2 JP27441489A JP27441489A JPH0690538B2 JP H0690538 B2 JPH0690538 B2 JP H0690538B2 JP 27441489 A JP27441489 A JP 27441489A JP 27441489 A JP27441489 A JP 27441489A JP H0690538 B2 JPH0690538 B2 JP H0690538B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- resin
- parts
- layer
- etherified melamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 108091008695 photoreceptors Proteins 0.000 title claims description 22
- 239000010410 layer Substances 0.000 claims description 68
- 239000011248 coating agent Substances 0.000 claims description 45
- 238000000576 coating method Methods 0.000 claims description 45
- 239000011241 protective layer Substances 0.000 claims description 43
- 229920002050 silicone resin Polymers 0.000 claims description 40
- 229920001187 thermosetting polymer Polymers 0.000 claims description 34
- 239000007787 solid Substances 0.000 claims description 32
- 229920000877 Melamine resin Polymers 0.000 claims description 30
- -1 methyl-butyl Chemical group 0.000 claims description 26
- 229920005992 thermoplastic resin Polymers 0.000 claims description 20
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 16
- 239000011118 polyvinyl acetate Substances 0.000 claims description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 14
- 229920000058 polyacrylate Polymers 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229920005989 resin Polymers 0.000 description 41
- 239000011347 resin Substances 0.000 description 41
- 239000000243 solution Substances 0.000 description 41
- 239000000463 material Substances 0.000 description 39
- 239000002245 particle Substances 0.000 description 35
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 33
- 239000007788 liquid Substances 0.000 description 31
- 239000006104 solid solution Substances 0.000 description 24
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 21
- 229910001887 tin oxide Inorganic materials 0.000 description 21
- JMHCCAYJTTWMCX-QWPJCUCISA-M sodium;(2s)-2-amino-3-[4-(4-hydroxy-3,5-diiodophenoxy)-3,5-diiodophenyl]propanoate;pentahydrate Chemical compound O.O.O.O.O.[Na+].IC1=CC(C[C@H](N)C([O-])=O)=CC(I)=C1OC1=CC(I)=C(O)C(I)=C1 JMHCCAYJTTWMCX-QWPJCUCISA-M 0.000 description 19
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- 239000011230 binding agent Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 229910000410 antimony oxide Inorganic materials 0.000 description 10
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 10
- 239000010408 film Substances 0.000 description 10
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 10
- 229910052814 silicon oxide Inorganic materials 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 206010034972 Photosensitivity reaction Diseases 0.000 description 9
- 239000000084 colloidal system Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 230000036211 photosensitivity Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 8
- 235000019256 formaldehyde Nutrition 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 8
- 239000002356 single layer Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910052787 antimony Inorganic materials 0.000 description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 239000010419 fine particle Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000002612 dispersion medium Substances 0.000 description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 229910000077 silane Inorganic materials 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000007974 melamines Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000000057 synthetic resin Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910008051 Si-OH Inorganic materials 0.000 description 3
- 229910006358 Si—OH Inorganic materials 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 2
- YGBCLRRWZQSURU-UHFFFAOYSA-N 4-[(diphenylhydrazinylidene)methyl]-n,n-diethylaniline Chemical compound C1=CC(N(CC)CC)=CC=C1C=NN(C=1C=CC=CC=1)C1=CC=CC=C1 YGBCLRRWZQSURU-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 229920000297 Rayon Polymers 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- YGCOKJWKWLYHTG-UHFFFAOYSA-N [[4,6-bis[bis(hydroxymethyl)amino]-1,3,5-triazin-2-yl]-(hydroxymethyl)amino]methanol Chemical compound OCN(CO)C1=NC(N(CO)CO)=NC(N(CO)CO)=N1 YGCOKJWKWLYHTG-UHFFFAOYSA-N 0.000 description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 229910003437 indium oxide Inorganic materials 0.000 description 2
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
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- 239000002184 metal Substances 0.000 description 2
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- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
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- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
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- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-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
- IYZMXHQDXZKNCY-UHFFFAOYSA-N 1-n,1-n-diphenyl-4-n,4-n-bis[4-(n-phenylanilino)phenyl]benzene-1,4-diamine Chemical compound C1=CC=CC=C1N(C=1C=CC(=CC=1)N(C=1C=CC(=CC=1)N(C=1C=CC=CC=1)C=1C=CC=CC=1)C=1C=CC(=CC=1)N(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 IYZMXHQDXZKNCY-UHFFFAOYSA-N 0.000 description 1
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- JFJWVJAVVIQZRT-UHFFFAOYSA-N 2-phenyl-1,3-dihydropyrazole Chemical class C1C=CNN1C1=CC=CC=C1 JFJWVJAVVIQZRT-UHFFFAOYSA-N 0.000 description 1
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- CLQYLLIGYDFCGY-UHFFFAOYSA-N 4-(2-anthracen-9-ylethenyl)-n,n-diethylaniline Chemical compound C1=CC(N(CC)CC)=CC=C1C=CC1=C(C=CC=C2)C2=CC2=CC=CC=C12 CLQYLLIGYDFCGY-UHFFFAOYSA-N 0.000 description 1
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- XYPMAZCBFKBIFK-UHFFFAOYSA-N 9,10-dinitroanthracene Chemical compound C1=CC=C2C([N+](=O)[O-])=C(C=CC=C3)C3=C([N+]([O-])=O)C2=C1 XYPMAZCBFKBIFK-UHFFFAOYSA-N 0.000 description 1
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- 206010070834 Sensitisation Diseases 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
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- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- CECABOMBVQNBEC-UHFFFAOYSA-K aluminium iodide Chemical compound I[Al](I)I CECABOMBVQNBEC-UHFFFAOYSA-K 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 150000008376 fluorenones Chemical class 0.000 description 1
- IVJISJACKSSFGE-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine Chemical compound O=C.NC1=NC(N)=NC(N)=N1 IVJISJACKSSFGE-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Chemical class N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical compound C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- XHNQXIBDPQINOF-UHFFFAOYSA-N n-(9h-carbazol-1-yl)fluoren-9-imine Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NC1=CC=CC2=C1NC1=CC=CC=C12 XHNQXIBDPQINOF-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 150000004866 oxadiazoles Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000002080 perylenyl group Chemical class C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 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
- 229920002382 photo conductive polymer Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- 150000003219 pyrazolines Chemical class 0.000 description 1
- RQGPLDBZHMVWCH-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole Chemical class C1=NC2=CC=NC2=C1 RQGPLDBZHMVWCH-UHFFFAOYSA-N 0.000 description 1
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical class C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Landscapes
- Photoreceptors In Electrophotography (AREA)
Description
【発明の詳細な説明】 〈産業上の利用分野〉 この発明は電子写真感光体に関し、より詳細には、表面
保護層を有する電子写真感光体に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Field of Industrial Application> The present invention relates to an electrophotographic photoreceptor, and more particularly to an electrophotographic photoreceptor having a surface protective layer.
〈従来の技術〉 いわゆるカールソンプロセスを利用した、複写機等の画
像形成装置においては、導電性を有する基材上に感光層
を形成した電子写真感光体が用いられている。<Prior Art> In an image forming apparatus such as a copying machine utilizing a so-called Carlson process, an electrophotographic photoreceptor having a photosensitive layer formed on a conductive base material is used.
電子写真感光体は、画像形成プロセス時に電気的、光学
的、機械的な衝撃を繰返し受けるので、これら衝撃に対
する耐久性を向上させる等の目的で、感光層の上に、結
着樹脂からなる表面保護層を積層することが行われてい
る。The electrophotographic photosensitive member is repeatedly subjected to electrical, optical and mechanical shocks during the image forming process. Therefore, for the purpose of improving durability against these shocks, a surface made of a binder resin is formed on the photosensitive layer. Laminating a protective layer is performed.
結着樹脂としては、表面保護層の硬度を向上させるた
め、熱硬化性シリコーン樹脂が主として用いられる。し
かし、上記熱硬化性シリコーン樹脂単独では、摺動摩擦
に対して脆く、損傷を受けやすい等の問題がある。As the binder resin, a thermosetting silicone resin is mainly used in order to improve the hardness of the surface protective layer. However, the thermosetting silicone resin alone has problems that it is brittle against sliding friction and is easily damaged.
そこで、表面保護層の結着樹脂として熱硬化性シリコー
ン樹脂と、ポリ酢酸ビニル等の熱可塑性樹脂とを併用し
た電子写真感光体（特開昭63-18354号公報参照）や、熱
硬化性シリコーン樹脂とブチルエーテル化メラミン・ホ
ルムアルデヒド樹脂とを併用した電子写真感光体が提案
されている（特開昭63-2071号公報参照）。Therefore, an electrophotographic photosensitive member (see JP-A-63-18354) using a thermosetting silicone resin as a binder resin for the surface protective layer and a thermoplastic resin such as polyvinyl acetate, or a thermosetting silicone An electrophotographic photoreceptor using a resin and a butyl etherified melamine / formaldehyde resin in combination has been proposed (see JP-A-63-2071).
〈発明が解決しようとする課題〉 しかしながら、前者の併用系においては、感光体の感度
が十分でなく、また、熱硬化性シリコーン樹脂単独の場
合に比べて表面硬度が低く、却って損傷を受けやすい
等、表面保護層の物性の面で問題がある他、特に熱硬化
性シリコーン樹脂にポリ酢酸ビニルを併用した系では、
表面保護層を形成するための塗布液が安定性に欠け、ポ
ットライフを過ぎると膜の白化が生じるという問題もあ
った。<Problems to be Solved by the Invention> However, in the former combination system, the sensitivity of the photoconductor is not sufficient, and the surface hardness is low as compared with the case of using the thermosetting silicone resin alone, and it is rather easily damaged. Etc., there is a problem in terms of the physical properties of the surface protective layer, and especially in a system in which polyvinyl acetate is used in combination with a thermosetting silicone resin,
There is also a problem that the coating solution for forming the surface protective layer lacks stability, and whitening of the film occurs after the pot life.
一方、後者の併用系では、系を構成する樹脂が、何れも
硬化によって硬度の高い３次元構造を形成する熱硬化性
樹脂であるため、形成された表面保護層は表面硬度が高
いものとなるが、層中におけるシリコーンサイトとメラ
ミンサイトとの間の相溶性が十分でないため、両サイト
間に、構造的なトラップとなる空隙を多数生じて、帯電
特性が悪化したり、繰返し露光を行うと電位の安定性が
低下したりする等、電子写真感光体の感光特性に悪影響
を及ぼす虞があった。On the other hand, in the latter combined system, since the resin constituting the system is a thermosetting resin that forms a three-dimensional structure having high hardness by curing, the formed surface protective layer has high surface hardness. However, since the compatibility between the silicone site and the melamine site in the layer is not sufficient, a large number of voids that serve as structural traps are generated between the two sites, which deteriorates the charging characteristics and causes repeated exposure. There is a possibility that the photosensitive characteristics of the electrophotographic photosensitive member may be adversely affected, for example, the stability of the potential may be reduced.
本発明者らの検討によれば、上記ブチルエーテル化メラ
ミン・ホルムアルデヒド樹脂に代えて、メチルエーテル
化メラミン・ホルムアルデヒド樹脂またはメチル−ブチ
ル混合エーテル化メラミン・ホルムアルデヒド樹脂（以
下、上記２つをまとめて「特定エーテル化メラミン・ホ
ルムアルデヒド樹脂」という）を使用した併用系では、
上記特定エーテル化メラミン・ホルムアルデヒド樹脂
が、従来のブチルエーテル化メラミン・ホルムアルデヒ
ド樹脂に比べて架橋性が高く、硬化時に、熱硬化性シリ
コーン樹脂のSi-OH基と共有結合することはないが、上
記Si-OH基との間に十分に大きい分子相互作用を生じる
ため、層中におけるシリコーンサイトとメラミンサイト
との相溶性が向上し、構造的トラップの少ない緻密な膜
を形成し得ることが判明した。しかし、上記併用系で
は、メラミンの芳香族π電子によって層の導電性を向上
させるために、熱硬化性シリコーン樹脂の非揮発性固形
分100重量部に対して、メチルエーテル化メラミン・ホ
ルムアルデヒド樹脂の場合には15重量部、メチル−ブチ
ル混合エーテル化メラミン・ホルムアルデヒド樹脂の場
合には30重量部を超えて配合した場合には、熱硬化性シ
リコーン樹脂に対する相互作用が強すぎて、表面保護層
に内部応力が生じ、クラック等が発生するという問題が
あった。According to the study by the present inventors, instead of the butyl etherified melamine / formaldehyde resin, a methyl etherified melamine / formaldehyde resin or a methyl-butyl mixed etherified melamine / formaldehyde resin (hereinafter, the above two are collectively referred to as “specification”). In the combined system using "etherified melamine formaldehyde resin",
The specific etherified melamine / formaldehyde resin has a higher cross-linking property than the conventional butyl etherified melamine / formaldehyde resin, and does not covalently bond with the Si-OH group of the thermosetting silicone resin at the time of curing. It has been found that since a sufficiently large molecular interaction is generated with the -OH group, the compatibility between the silicone site and the melamine site in the layer is improved, and a dense film with few structural traps can be formed. However, in the above combined system, in order to improve the conductivity of the layer by the aromatic π-electrons of melamine, in order to improve the non-volatile solid content of the thermosetting silicone resin 100 parts by weight of the methyl etherified melamine formaldehyde resin In the case of 15 parts by weight, and in the case of a methyl-butyl mixed etherified melamine-formaldehyde resin, when blended in an amount of more than 30 parts by weight, the interaction with the thermosetting silicone resin is too strong and the surface protective layer is There is a problem that internal stress occurs and cracks and the like occur.
この発明は、以上の事情に鑑みてなされたものであっ
て、電子写真感光体の感光特性、物性等に悪影響を与え
ることなく、且つ熱硬化性シリコーン樹脂単独の場合に
比べて摺動摩擦に対する脆さ等が改善されており、しか
も、より導電性に優れた表面保護層を有する電子写真感
光体を提供することを目的としている。The present invention has been made in view of the above circumstances, and is fragile to sliding friction without adversely affecting the photosensitivity and physical properties of the electrophotographic photoreceptor and compared to the case of using a thermosetting silicone resin alone. It is an object of the present invention to provide an electrophotographic photoreceptor having a surface protective layer which has improved surface roughness and has improved conductivity.
〈課題を解決するための手段および作用〉 上記課題を解決するための、この発明の電子写真感光体
は、熱硬化性シリコーン樹脂と、この熱硬化性シリコー
ン樹脂の非揮発性固形分100重量部に対して５〜50重量
部の特定エーテル化メラミン・ホルムアルデヒド樹脂
と、上記熱硬化性シリコーン樹脂の非揮発性固形分およ
び特定エーテル化メラミン・ホルムアルデヒド樹脂の合
計量に対して１〜11重量％の熱可塑性樹脂と、導電性付
与剤とを含有する塗布液を感光層上に塗布し、硬化させ
てなる表面保護層を有することを特徴としている。<Means and Actions for Solving the Problems> In order to solve the above problems, the electrophotographic photoreceptor of the present invention comprises a thermosetting silicone resin and a nonvolatile solid content of 100 parts by weight of the thermosetting silicone resin. 5 to 50 parts by weight of the specific etherified melamine-formaldehyde resin, 1 to 11% by weight based on the total amount of the nonvolatile solid content of the thermosetting silicone resin and the specific etherified melamine-formaldehyde resin. It is characterized in that it has a surface protective layer formed by applying a coating solution containing a thermoplastic resin and a conductivity-imparting agent onto the photosensitive layer and curing it.
上記構成からなる、この発明の電子写真感光体において
は、塗布液中に含有される特定エーテル化メラミン・ホ
ルムアルデヒド樹脂が、従来のブチルエーテル化メラミ
ン・ホルムアルデヒド樹脂に比べて架橋性が高く、硬化
時に、熱硬化性シリコーン樹脂のSi-OH基と共有結合す
ることはないが、上記Si-OH基との間に十分に大きい分
子相互作用を生じるため、層中におけるシリコーンサイ
トとメラミンサイトとの相溶性が向上し、構造的トラッ
プの少ない緻密な膜が形成される。また、塗布液中に含
有される熱可塑性樹脂が、表面保護層において、内部応
力を低減させる緩衝体として作用するので、上記特定エ
ーテル化メラミン・ホルムアルデヒド樹脂を、より多量
に層中に配合してもクラック等の発生する虞がなく、樹
脂中に含まれる多量の芳香族π電子と、層中に含まれる
導電性付与剤とによって層の導電性をさらに向上させる
ことができる。したがって、この発明の電子写真感光体
は感光特性に優れたものとなる。また、上記のように、
層を構成する主成分が、硬化によって３次元構造を形成
する熱硬化性シリコーン樹脂と特定エーテル化メラミン
・ホルムアルデヒド樹脂であるため、硬化後の表面保護
層は表面硬度が高くなる。しかも、前述したように両樹
脂は相溶性が高く、硬化後の３次元構造が複雑に入り組
んだものとなって、熱可塑性樹脂による弾力性の付与と
相俟って、熱硬化性シリコーン樹脂単独の場合に比べて
摺動摩擦に対する脆さ等が改善されたものとなる。In the electrophotographic photoreceptor of the present invention having the above-mentioned constitution, the specific etherified melamine / formaldehyde resin contained in the coating liquid has a higher crosslinkability than the conventional butyl etherified melamine / formaldehyde resin, and when cured, Although it does not form a covalent bond with the Si-OH group of the thermosetting silicone resin, it has a sufficiently large molecular interaction with the above Si-OH group, and therefore the compatibility between the silicone site and the melamine site in the layer is high. Is improved, and a dense film with few structural traps is formed. Further, since the thermoplastic resin contained in the coating liquid acts as a buffer for reducing internal stress in the surface protective layer, a larger amount of the specific etherified melamine / formaldehyde resin is blended in the layer. Also, there is no risk of cracks and the like, and the conductivity of the layer can be further improved by the large amount of aromatic π electrons contained in the resin and the conductivity imparting agent contained in the layer. Therefore, the electrophotographic photoreceptor of the present invention has excellent photosensitivity. Also, as mentioned above,
Since the main constituents of the layer are a thermosetting silicone resin that forms a three-dimensional structure by curing and a specific etherified melamine-formaldehyde resin, the surface hardness of the surface protective layer after curing is high. Moreover, as described above, both resins have high compatibility, and the three-dimensional structure after curing becomes complicated and complicated, and in combination with the elasticity imparted by the thermoplastic resin, the thermosetting silicone resin alone is used. Compared with the case of 1, the brittleness against sliding friction is improved.
なお、塗布液中における、熱硬化性シリコーン樹脂の非
揮発性固形分100重量部に対する、特定エーテル化メラ
ミン・ホルムアルデヒド樹脂の含有量が５〜50重量部の
範囲内、熱可塑性樹脂の含有割合が、シリコーン樹脂の
非揮発性固形分と特定エーテル化メラミン・ホルムアル
デヒド樹脂との合計量の１〜11重量％の範囲内に、それ
ぞれ限定されるのは、下記の理由による。In the coating liquid, the content of the specific etherified melamine / formaldehyde resin is in the range of 5 to 50 parts by weight, and the content ratio of the thermoplastic resin is 100 parts by weight of the nonvolatile solid content of the thermosetting silicone resin. The reason for limiting each to within the range of 1 to 11% by weight of the total amount of the nonvolatile solid content of the silicone resin and the specific etherified melamine-formaldehyde resin is as follows.
すなわち、特定エーテル化メラミン・ホルムアルデヒド
樹脂の含有量が５重量部未満では、熱可塑性樹脂の含有
割合に関係なく、硬化後の表面保護層に、摺動摩擦に対
する脆さ等の問題が生じる他、層中の芳香族π電子が不
足して感光特性が悪化する。That is, when the content of the specific etherified melamine / formaldehyde resin is less than 5 parts by weight, the surface protective layer after curing causes problems such as brittleness against sliding friction regardless of the content ratio of the thermoplastic resin. There is a shortage of aromatic π-electrons, and the photosensitivity is deteriorated.
一方、特定エーテル化メラミン・ホルムアルデヒド樹脂
の含有量が50重量部を超えると、熱硬化性シリコーン樹
脂に対する相互作用が強すぎて、熱可塑性樹脂の配合割
合に関係なく、表面保護層に内部応力が生じ、クラック
等が発生して、きれいな表面保護層が得られなくなる。On the other hand, if the content of the specific etherified melamine / formaldehyde resin exceeds 50 parts by weight, the interaction with the thermosetting silicone resin is too strong, and the internal stress is generated in the surface protective layer regardless of the blending ratio of the thermoplastic resin. If it occurs, cracks or the like will occur, and a clean surface protective layer cannot be obtained.
また、熱可塑性樹脂の含有割合が１重量％未満では、特
定エーテル化メラミン・ホルムアルデヒド樹脂の含有量
が多いほど、表面保護層に内部応力が生じ、クラック等
が発生して、きれいな表面保護層が得られなくなる。When the content of the thermoplastic resin is less than 1% by weight, the larger the content of the specific etherified melamine / formaldehyde resin is, the more internal stress is generated in the surface protective layer, cracks and the like occur, and a clean surface protective layer is formed. You won't get it.
そして、熱可塑性樹脂の含有割合が11重量％を超える
と、表面保護層の軟化を生じる上、特定エーテル化メラ
ミン・ホルムアルデヒド樹脂の含有量が少ないほど、白
濁や感光特性の悪化等を生じる。When the content of the thermoplastic resin exceeds 11% by weight, the surface protective layer is softened, and the smaller the content of the specific etherified melamine / formaldehyde resin is, the more the white turbidity and the deterioration of the photosensitivity occur.
塗布液中に含有される熱硬化性シリコーン樹脂は、テト
ラアルコキシシラン、トリアルコキシアルキルシラン、
ジアルコキシジアルキルシラン等のオルガノシラン、ト
リクロルアルキルシラン、ジクロルジアルキルシラン等
のオルガノハロゲンシランなど、シラン系化合物の、単
独または２種以上の混合物の加水分解物（いわゆるオル
ガノポリシロキサン）、またはその初期縮合反応物を非
揮発性固形分として、溶媒中に溶解または分散させたも
ので、シラン化合物のアルコキシ基、アルキル基として
は、メトキシ基、エトキシ基、イソプロポキシ基、ｔ−
ブトキシ基、グリシドキシ基、メチル、エチル等の、炭
素数１〜４程度の低級基が挙げられる。The thermosetting silicone resin contained in the coating liquid is tetraalkoxysilane, trialkoxyalkylsilane,
A hydrolyzate (so-called organopolysiloxane) of a silane compound such as an organosilane such as dialkoxydialkylsilane, a trichloroalkylsilane, an organohalogensilane such as a dichlorodialkylsilane, or a mixture thereof (so-called organopolysiloxane), or an initial stage thereof. The condensation reaction product is dissolved or dispersed in a solvent as a non-volatile solid content, and the alkoxy group and the alkyl group of the silane compound include a methoxy group, an ethoxy group, an isopropoxy group, and t-
Examples thereof include lower groups having about 1 to 4 carbon atoms such as butoxy group, glycidoxy group, methyl and ethyl.
上記熱硬化性シリコーン樹脂と併用される特定エーテル
化メラミン・ホルムアルデヒド樹脂のうち、メチルエー
テル化メラミン・ホルムアルデヒド樹脂は、メラミンと
ホルムアルデヒドとの反応物であるモノないしヘキサの
各種メチロールメラミンにおけるメチロール基の一部ま
たは全部がメチルエーテル化したもの、またはその初期
縮合反応物であり、液状ないしシロップ状等の状態で供
給されるものが好ましく用いられる。Among the specific etherified melamine / formaldehyde resins used together with the thermosetting silicone resin, the methyl etherified melamine / formaldehyde resin is one of the methylol groups in various mono- or hexamethylol melamine which is a reaction product of melamine and formaldehyde. Partly or wholly methyl etherified, or an initial condensation reaction product thereof, which is supplied in a liquid or syrup state, is preferably used.
上記メチルエーテル化メラミン・ホルムアルデヒド樹脂
の数平均分子量はこの発明では特に限定されないが、15
00を超えると反応性が低下するので、上記数平均分子量
は1500以下であることが好ましい。また、上記樹脂は、
メラミン核１個当たりの結合ホルムアルデヒド数が３〜
６個であり、そのうちの３〜６個がメチルエーテル化し
たものであることが好ましい。メラミン核１個当たりの
結合ホルムアルデヒド数が３個未満では、表面保護層が
機械的強度に劣ったものとなる虞がある。また、上記ホ
ルムアルデヒドのうちメチルエーテル化した個数が３個
未満では、表面保護層用の塗布液が安定性に欠けたもの
となる虞がある。The number average molecular weight of the methyl etherified melamine formaldehyde resin is not particularly limited in the present invention,
When it exceeds 00, the reactivity decreases, so the number average molecular weight is preferably 1500 or less. Further, the above resin is
The number of bound formaldehyde per melamine nucleus is 3 ~
It is preferably 6 and 3 to 6 of them are methyl etherified. If the number of bound formaldehydes per melamine nucleus is less than 3, the surface protective layer may be inferior in mechanical strength. Further, if the number of methyl etherified formaldehyde is less than 3, the coating solution for the surface protective layer may lack stability.
一方、メチル−ブチル混合エーテル化メラミン・ホルム
アルデヒド樹脂は、上記モノないしヘキサの各種メチロ
ールメラミンにおけるメチロール基の少なくとも１つが
メチルエーテル化し、残余のメチロール基の少なくとも
１つがブチルエーテル化したもの、またはその初期縮合
反応物であり、同じく液状ないしシロップ状等の状態で
供給されるものが好ましく用いられる。On the other hand, the methyl-butyl mixed etherified melamine-formaldehyde resin is a resin in which at least one of the methylol groups in the above-mentioned various mono- or hexamethylol melamine is methyl etherified and at least one of the remaining methylol groups is butyl etherified, or its initial condensation. A reactant, which is also supplied in a liquid or syrup state, is preferably used.
上記メチル−ブチル混合エーテル化メラミン・ホルムア
ルデヒド樹脂の数平均分子量はこの発明では特に限定さ
れないが、1500を超えると反応性が低下するので、上記
数平均分子量は1500以下であることが好ましい。また、
上記樹脂は、メラミン核１個当たりの結合ホルムアルデ
ヒド数が３〜６個であり、そのうちの２〜５個がメチル
エーテル化し、１〜２個がブチルエーテル化したもので
あることが好ましい。メラミン核１個当たりの結合ホル
ムアルデヒド数が３個未満では表面保護層が機械的強度
に劣ったものとなる虞がある。また、上記ホルムアルデ
ヒドのうちメチルエーテル化した個数が２個未満では繰
り返し露光による表面電位の低下が大きくなり、５個を
超えると、クラックが発生し易くなる虞がある。また、
ブチルエーテル化した個数が１個未満ではクラックが発
生し易くなり、３個を超えると繰り返し露光による表面
電位の低下が大きくなる虞がある。The number average molecular weight of the methyl-butyl mixed etherified melamine-formaldehyde resin is not particularly limited in the present invention, but if it exceeds 1500, the reactivity decreases, so the number average molecular weight is preferably 1500 or less. Also,
The resin preferably has 3 to 6 bound formaldehydes per melamine nucleus, of which 2 to 5 are methyl etherified and 1 to 2 are butyl etherified. If the number of bound formaldehydes per melamine nucleus is less than 3, the surface protective layer may be inferior in mechanical strength. If the number of methyl etherified formaldehyde is less than 2, the surface potential will be greatly reduced by repeated exposure, and if it exceeds 5, cracks will be likely to occur. Also,
If the number of butyl etherified is less than 1, cracks are likely to occur, and if the number exceeds 3, the decrease in surface potential due to repeated exposure may be large.
なお、上記各硬化性樹脂は、条件によっては触媒を用い
なくても、加熱するだけで硬化させることができるが、
通常、硬化反応をスムーズ且つ均一に完結させるために
触媒を用いる場合が多い。The above curable resins can be cured only by heating without using a catalyst depending on the conditions,
Usually, a catalyst is often used in order to complete the curing reaction smoothly and uniformly.
硬化用触媒としては、無機酸または有機酸、アミン類な
どのアルカリ等、種々のものを使用することができる。
また、必要に応じて、従来公知の硬化助剤等を併用する
こともできる。As the curing catalyst, various ones such as inorganic acids or organic acids, alkalis such as amines, etc. can be used.
Further, if necessary, a conventionally known curing aid and the like can be used in combination.
上記熱硬化性シリコーン樹脂および特定エーテル化メラ
ミン・ホルムアルデヒド樹脂と共に表面保護層中に含有
される熱可塑性樹脂としては、スチレン系重合体；アク
リル系重合体；スチレン−アクリル系共重合体；ポリエ
チレン、エチレン−酢酸ビニル共重合体、塩素化ポリエ
チレン、ポリプロピレン、アイオノマー等のオレフィン
系重合体；ポリ塩化ビニル；塩化ビニル−酢酸ビニル共
重合体；ポリ酢酸ビニル；飽和ポリエステル；ポリアミ
ド；熱可塑性ポリウレタン樹脂；ポリカーボネート；ポ
リアリレート；ポリスルホン；ケトン樹脂；ポリビニル
ブチラール樹脂；ポリエーテル樹脂等の、種々の合成樹
脂材料が使用できるが、特に、ポリ酢酸ビニルとアクリ
ル系重合体が好適に使用される。Examples of the thermoplastic resin contained in the surface protective layer together with the thermosetting silicone resin and the specific etherified melamine / formaldehyde resin include styrene-based polymers; acrylic-based polymers; styrene-acrylic-based copolymers; polyethylene and ethylene. -Olefin polymers such as vinyl acetate copolymer, chlorinated polyethylene, polypropylene and ionomer; polyvinyl chloride; vinyl chloride-vinyl acetate copolymer; polyvinyl acetate; saturated polyester; polyamide; thermoplastic polyurethane resin; polycarbonate; Various synthetic resin materials such as polyarylate; polysulfone; ketone resin; polyvinyl butyral resin; polyether resin can be used, but polyvinyl acetate and an acrylic polymer are particularly preferably used.
熱可塑性樹脂としてポリ酢酸ビニルを用いた系では、ポ
リ酢酸ビニルの持つ柔軟性により、表面保護層の脆さが
改善されて、機械的強度が向上し、長寿命化が可能にな
る。In a system using polyvinyl acetate as the thermoplastic resin, the flexibility of polyvinyl acetate improves the brittleness of the surface protective layer, improves the mechanical strength, and prolongs the service life.
一方、熱可塑性樹脂としてポリメチルメタクリレート
（PMMA）等のアクリル系重合体を用いた系では、上記ア
クリル系重合体の持つ高い光学特性に基づいて、より一
層の光感度化が可能になる。On the other hand, in a system using an acrylic polymer such as polymethylmethacrylate (PMMA) as the thermoplastic resin, it is possible to further increase the photosensitivity based on the high optical characteristics of the acrylic polymer.
なお、上記ポリ酢酸ビニルおよびアクリル系重合体は、
それぞれ単独で使用できる他、両者を併用することもで
き、さらに、その他の熱可塑性樹脂を配合することも可
能である。The polyvinyl acetate and the acrylic polymer are
Each of them can be used alone, both can be used in combination, and further, other thermoplastic resins can be blended.
上記各成分を溶解または分散して、表面保護層用の塗布
液を構成する溶媒としては、例えばイソプロピルアルコ
ール;n−ヘキサン、オクタン、シクロヘキサン等の脂肪
族系炭化水素；ベンゼン、トルエン、キシレン等の芳香
族炭化水素；ジクロロメタン、ジクロロエタン、四塩化
炭素、クロロベンゼン等のハロゲン化炭化水素；ジメチ
ルエーテル、ジエチルエーテル、テトラヒドロフラン、
エチレングリコールジメチルエーテル、エチレングリコ
ールジエチルエーテル、ジエチレングリコールジメチル
エーテル等のエーテル類；アセトン、メチルエチルケト
ン、シクロヘキサノン等のケトン類；酢酸エチル、酢酸
メチル等のエステル類；ジメチルホルムアミド；ジメチ
ルスルホキシド等が挙げられ、これらが単独で、または
二種以上混合して使用される。Examples of the solvent that constitutes the coating liquid for the surface protective layer by dissolving or dispersing the above components include isopropyl alcohol; aliphatic hydrocarbons such as n-hexane, octane, and cyclohexane; benzene, toluene, xylene, and the like. Aromatic hydrocarbons; halogenated hydrocarbons such as dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene; dimethyl ether, diethyl ether, tetrahydrofuran,
Ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, cyclohexanone; esters such as ethyl acetate, methyl acetate; dimethylformamide; dimethyl sulfoxide, etc. , Or a mixture of two or more.
画像形成プロセスにおける下層への電荷の注入を容易に
する目的で、塗布液中に配合される導電性付与剤として
は、酸化スズ、酸化チタン、酸化インジウム、酸化アン
チモン等の単体金属酸化物や、酸化スズと酸化アンチモ
ンとの固溶体等の導電性金属酸化物が挙げられる。上記
導電性金属酸化物は、一般に、微粒子状態で、硬化前の
塗布液中に攪拌、混合され、塗膜の硬化によって表面保
護層中に分散されるが、微粒子の状態では凝集し易く、
塗布液中に均一に分散させるための長時間の攪拌が必要
となるため、前述したように、コロイド溶液の状態で、
塗布液中に混和させることが好ましい。上記コロイド溶
液においては、導電性金属酸化物の微粒子は、それぞれ
の持つ表面電荷によって互いに反発して、塗布液中にお
ける凝集が防止されるので、短時間の攪拌、混合によ
り、塗布液中に均一に分散させることができる。For the purpose of facilitating the injection of charges into the lower layer in the image forming process, as the conductivity-imparting agent to be mixed in the coating liquid, tin oxide, titanium oxide, indium oxide, a simple metal oxide such as antimony oxide, or the like, A conductive metal oxide such as a solid solution of tin oxide and antimony oxide can be used. The conductive metal oxide is generally in the form of fine particles, stirred and mixed in the coating liquid before curing, and dispersed in the surface protective layer by the curing of the coating film, but easily aggregates in the form of fine particles,
As long-term stirring is required to uniformly disperse in the coating liquid, as described above, in the state of colloid solution,
It is preferable to mix it in the coating solution. In the colloidal solution, the fine particles of the conductive metal oxide repel each other due to the surface charge of each, and the aggregation in the coating liquid is prevented. Can be dispersed in.
導電性金属酸化物粒子のコロイド溶液の製造方法は、導
電性金属酸化物の種類によって異なり、例えば、五酸化
アンチモン（Sb2O5）のコロイド溶液は、無水三酸化ア
ンチモンと硝酸とを混合し、加熱後、α−ヒドロキシカ
ルボン酸と、N,N−ジメチルホルムアミド（DMF）等の有
機溶媒とをこの順に添加し、副生成物としての水を蒸留
によって除去する方法（特開昭47-11382号公報参照）
や、塩化水素等のハロゲン化水素に、エチレングリコー
ルに代表される１価或いは２価以上のアルコール、DMF
等の親水性有機溶媒およびα−ヒドロキシカルボン酸を
加え、そこへ三酸化アンチモンを分散させた状態で、過
酸化水素水によって酸化させる方法（特開昭52-38495号
公報、特開昭52-38496号公報参照）等により調製するこ
とができる。The method for producing a colloidal solution of conductive metal oxide particles depends on the type of conductive metal oxide. For example, a colloidal solution of antimony pentoxide (Sb 2 O 5 ) is prepared by mixing anhydrous antimony trioxide and nitric acid. After heating, α-hydroxycarboxylic acid and an organic solvent such as N, N-dimethylformamide (DMF) are added in this order, and water as a by-product is removed by distillation (JP-A-47-11382). (See issue)
Or hydrogen halide such as hydrogen chloride, monovalent or divalent alcohol represented by ethylene glycol, DMF
A method in which a hydrophilic organic solvent such as α-hydroxycarboxylic acid is added, and antimony trioxide is dispersed therein and then oxidized with hydrogen peroxide solution (Japanese Patent Laid-Open No. 38395/52/38495). (See Japanese Patent No. 38496) and the like.
上記五酸化アンチモンコロイド溶液を調製するための分
散媒としては、下層の感光層を侵すことがないように、
有機性の小さいメチルアルコール、エチルアルコール、
ｎ−プロピルアルコール、イソプロピルアルコール、ブ
チルアルコール等のアルコール類を用いることが好まし
い。As a dispersion medium for preparing the antimony pentoxide colloidal solution, so as not to attack the lower photosensitive layer,
Organic small methyl alcohol, ethyl alcohol,
It is preferable to use alcohols such as n-propyl alcohol, isopropyl alcohol and butyl alcohol.
また、酸化スズ（SnO2、SnO等）と酸化アンチモン（Sb2
O5、Sb2O3等）との固溶体のコロイド溶液の場合には、例
えば第１図に示すように、固溶体粒子１の表面に、粒径
5nm以下程度の酸化ケイ素粒子２…を吸着させる方法等
により調製することができる。そして、第１図の構造に
おいては、固溶体粒子１の表面に吸着された酸化ケイ素
粒子２…が、分散媒との接触によりOH基を生じて負に帯
電することで、固溶体粒子１の表面に電荷を持たせるよ
うになっている。In addition, tin oxide (SnO 2 , SnO, etc.) and antimony oxide (Sb 2
In the case of a colloidal solution of a solid solution with O 5 , Sb 2 O 3 etc.), for example, as shown in FIG.
It can be prepared by a method of adsorbing silicon oxide particles 2 ... In the structure shown in FIG. 1, the silicon oxide particles 2 adsorbed on the surface of the solid solution particles 1 generate OH groups upon contact with the dispersion medium and are negatively charged, so that the surfaces of the solid solution particles 1 are charged. It is designed to have an electric charge.
上記酸化スズと酸化アンチモンとの固溶体粒子は、通
常、酸化スズの微粒子にアンチモンをドープして形成さ
れるもので、特に限定されないが、固溶体粒子中におけ
るアンチモンの含有割合が0.001〜30重量％であること
が好ましく、５〜20重量％であることがより好ましい。
固溶体粒子中におけるアンチモンの含有割合が0.001重
量％未満の場合や、30重量％を超えた場合には、十分な
導電性が得られなくなる虞がある。The solid solution particles of tin oxide and antimony oxide are usually formed by doping tin oxide fine particles with antimony, and are not particularly limited, but the content ratio of antimony in the solid solution particles is 0.001 to 30% by weight. It is preferably present, and more preferably 5 to 20% by weight.
When the content ratio of antimony in the solid solution particles is less than 0.001% by weight or exceeds 30% by weight, sufficient conductivity may not be obtained.
また、上記固溶体粒子の粒径は特に限定されないが、10
〜20nmであることが好ましい。固溶体粒子の粒径が10nm
未満では、表面保護層の電気抵抗が大きくなり、20nmを
超えると、表面保護層の光透過率が低下する虞がある。The particle size of the solid solution particles is not particularly limited, but 10
It is preferably ˜20 nm. Particle size of solid solution particles is 10 nm
If it is less than 20 nm, the electric resistance of the surface protective layer increases, and if it exceeds 20 nm, the light transmittance of the surface protective layer may decrease.
固溶体粒子に対する酸化ケイ素の割合も特に限定されな
いが、固溶体粒子100重量部に対し10重量部以下である
ことが好ましい。固溶体粒子100重量部に対する酸化ケ
イ素の割合が10重量部を超えた場合には、十分な導電性
が得られなくなる虞がある。The ratio of silicon oxide to solid solution particles is not particularly limited, but is preferably 10 parts by weight or less with respect to 100 parts by weight of solid solution particles. When the ratio of silicon oxide to 100 parts by weight of the solid solution particles exceeds 10 parts by weight, sufficient conductivity may not be obtained.
上記固溶体粒子と共にコロイド溶液を構成する分散媒と
しては、前述したように、酸化ケイ素を負に帯電させる
ために極性溶媒が使用され、特に、保護層用塗布液との
相溶性に優れ、且つ下地層としての感光層を侵す虞のな
い、メチルアルコール、エチルアルコール、ｎ−プロピ
ルアルコール、イソプロピルアルコール、ブチルアルコ
ール等のアルコール類が好適に使用される。As the dispersion medium that forms the colloidal solution with the solid solution particles, as described above, a polar solvent is used to negatively charge silicon oxide, and particularly, the compatibility with the protective layer coating liquid is excellent, and Alcohols, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, and butyl alcohol, which do not damage the photosensitive layer as the base layer, are preferably used.
上記表面保護層を構成する結着樹脂には、膜の特性を損
なわない範囲で、前記以外の熱硬化性樹脂を併用するこ
とができる。前記以外の他の熱硬化性樹脂としては、硬
化性アクリル樹脂；アルキッド樹脂；不飽和ポリエステ
ル樹脂；ジアリルフタレート樹脂；フェノール樹脂；尿
素樹脂；ベンゾグアナミン樹脂；特定エーテル化系およ
びブチルエーテル化系以外のメラミン樹脂が例示され
る。A thermosetting resin other than the above can be used in combination with the binder resin constituting the surface protective layer as long as the characteristics of the film are not impaired. Other thermosetting resins other than the above, curable acrylic resins; alkyd resins; unsaturated polyester resins; diallyl phthalate resins; phenol resins; urea resins; benzoguanamine resins; melamine resins other than specific etherified and butyl etherified resins Is exemplified.
上記表面保護層には、ターフェニル、ハロナフトキノン
類、アセナフチレン等従来公知の増感剤;9−（N,N−ジ
フェニルヒドラジノ）フルオレン、９−カルバゾリルイ
ミノフルオレン等のフルオレン系化合物；導電性付与
剤；アミン系、フェノール系等の酸化防止剤、ベンゾフ
ェノン系等の紫外線吸収剤などの劣化防止剤；可塑剤な
ど、種々の添加剤を含有させることができる。In the surface protective layer, conventionally known sensitizers such as terphenyl, halonaphthoquinones, and acenaphthylene; fluorene compounds such as 9- (N, N-diphenylhydrazino) fluorene and 9-carbazolyliminofluorene; conductive materials Various additives such as a property-imparting agent; an antioxidant such as an amine-based or phenol-based agent; a deterioration inhibitor such as an ultraviolet absorber such as a benzophenone-based agent; and a plasticizer can be contained.
上記表面保護層の膜厚は、0.1〜10μｍ、特に２〜５μ
ｍの範囲内であることが好ましい。The thickness of the surface protective layer is 0.1 to 10 μm, especially 2 to 5 μm.
It is preferably within the range of m.
なお、この発明感光体は、表面保護層以外の構成につい
ては、従来と同様の材料を用い、従来同様の構成とする
ことができる。The photoreceptor of the present invention can have the same structure as the conventional one by using the same material as the conventional material except for the surface protective layer.
まず、導電性基材について述べる。First, the conductive base material will be described.
導電性基材は、電子写真感光体が組み込まれる画像形成
装置の機構、構造に対応してシート状あるいはドラム状
など、適宜の形状に形成される。また、上記導電性基材
は、全体を金属などの導電性材料で構成しても良く、基
材自体は導電性を有しない構造材料で形成し、その表面
に導電性を付与しても良い。The conductive base material is formed into an appropriate shape such as a sheet shape or a drum shape according to the mechanism and structure of the image forming apparatus in which the electrophotographic photosensitive member is incorporated. Further, the conductive base material may be entirely composed of a conductive material such as metal, or the base material itself may be formed of a structural material having no conductivity, and the surface thereof may be provided with conductivity. .
なお、前者の構造を有する導電性基材において使用され
る導電性材料としては、表面がアルマイト処理された、
または未処理のアルミニウム、銅、スズ、白金、金、
銀、バナジウム、モリブデン、クロム、カドミウム、チ
タン、ニッケル、パラジウム、インジウム、ステンレス
銅、真鍮等の金属材料が好ましい。As the conductive material used in the conductive base material having the former structure, the surface was anodized,
Or untreated aluminum, copper, tin, platinum, gold,
Metal materials such as silver, vanadium, molybdenum, chromium, cadmium, titanium, nickel, palladium, indium, stainless copper, and brass are preferable.
一方、後者の構造としては、合成樹脂製基材またはガラ
ス基材の表面に、上記例示の金属や、ヨウ化アルミニウ
ム、酸化スズ、酸化インジウム等の導電性材料からなる
薄膜が、真空蒸着法または湿式めっき法などの公知の膜
形成方法によって積層された構造、上記合成樹脂成形品
やガラス基材の表面に上記金属材料等のフィルムがラミ
ネートされた構造、上記合成樹脂成形品やガラス基材の
表面に、導電性を付与する物質が注入された構造が例示
される。On the other hand, as the latter structure, on the surface of a synthetic resin base material or a glass base material, a thin film made of a conductive material such as the above-exemplified metals or aluminum iodide, tin oxide, indium oxide, a vacuum deposition method or Structures laminated by a known film forming method such as a wet plating method, structures in which a film such as the metal material is laminated on the surface of the synthetic resin molded product or the glass substrate, the synthetic resin molded product or the glass substrate A structure in which a substance imparting conductivity is injected into the surface is exemplified.
なお、導電性基材は、必要に応じて、シランカップリン
グ剤やチタンカップリング剤などの表面処理剤で表面処
理を施し、感光層との密着性を高めても良い。The conductive base material may be subjected to a surface treatment with a surface treatment agent such as a silane coupling agent or a titanium coupling agent, if necessary, to enhance the adhesion to the photosensitive layer.
次に、導電性基材上に形成される感光層について述べ
る。Next, the photosensitive layer formed on the conductive substrate will be described.
感光層は、半導体材料や有機材料、またはこれらの複合
材料からなる下記構成のものが使用できる。The photosensitive layer may be made of a semiconductor material, an organic material, or a composite material thereof, having the following structure.
半導体材料からなる単層型の感光層。A single layer type photosensitive layer made of a semiconductor material.
結着樹脂中に電荷発生材料と電荷輸送材料とを含有す
る単層型の有機感光層。A single-layer type organic photosensitive layer containing a charge generating material and a charge transporting material in a binder resin.
結着樹脂中に電荷発生材料を含有する電荷発生層と、
結着樹脂中に電荷輸送材料を含有する電荷輸送層とから
なる積層型の有機感光層。A charge generation layer containing a charge generation material in a binder resin,
A laminated organic photosensitive layer comprising a charge transport layer containing a charge transport material in a binder resin.
半導体材料からなる電荷発生層と、上記有機の電荷輸
送層とが積層された複合型の感光層。A composite type photosensitive layer in which a charge generation layer made of a semiconductor material and the organic charge transport layer are laminated.
複合型感光層において電荷発生層として用いられると共
に、単独でも感光層を形成できる半導体材料としては、
例えばａ−As2Se3、ａ−SeAsTe等のアモルファスカルコ
ゲン化物やアモルファスセレン（ａ−Se）、アモルファ
スシリコン（ａ−Si）が例示される。上記半導体材料か
らなる感光層または電荷発生層は、真空蒸着法、グロー
放電分解法等の公知の薄膜形成方法によって形成するこ
とができる。As a semiconductor material that can be used alone as a charge generation layer in a composite type photosensitive layer to form a photosensitive layer,
Examples thereof include amorphous chalcogenides such as a-As 2 Se 3 , a-SeAsTe, amorphous selenium (a-Se), and amorphous silicon (a-Si). The photosensitive layer or charge generating layer made of the above semiconductor material can be formed by a known thin film forming method such as a vacuum vapor deposition method or a glow discharge decomposition method.
単層型または積層型の有機感光層における電荷発生層に
使用される、有機または無機の電荷発生材料としては、
例えば前記例示の半導体材料の粉末;ZnO、CdS等のII-VI
族微結晶；ピリリウム塩；アゾ系化合物；ビスアゾ系化
合物；フタロシアニン系化合物；アンサンスロン系化合
物；ペリレン系化合物；インジゴ系化合物；トリフェニ
ルメタン系化合物；スレン系化合物；トルイジン系化合
物；ピラゾリン系化合物；キナクリドン系化合物；ピロ
ロピロール系化合物が例示される。そして、上記例示の
化合物の中でも、フタロシアニン系化合物に属する、α
型，β型，γ型など種々の結晶型を有するアルミニウム
フタロシアニン、銅フタロシアニン、メタルフリーフタ
ロシアニン、オキソチタニルフタロシアニン等が好まし
く用いられ、特に、上記メタルフリーフタロシアニンお
よび／またはオキソチタニルフタロシアニンがより好ま
しく用いられる。なお、上記電荷発生材料は、それぞれ
単独で用いられる他、複数種を併用しても良い。As the organic or inorganic charge generating material used for the charge generating layer in the single-layer type or laminated type organic photosensitive layer,
For example, the powder of the semiconductor material exemplified above; ZnO, CdS, etc. II-VI
Group crystallites; pyrylium salts; azo compounds; bisazo compounds; phthalocyanine compounds; ansanthrone compounds; perylene compounds; indigo compounds; triphenylmethane compounds; threnic compounds; toluidine compounds; pyrazoline compounds; Examples include quinacridone compounds; pyrrolopyrrole compounds. And among the above-exemplified compounds, α belonging to a phthalocyanine-based compound
Phthalocyanine, copper phthalocyanine, metal-free phthalocyanine, oxotitanyl phthalocyanine, and the like having various crystal types such as γ-type, β-type, and γ-type are preferably used, and particularly, the above metal-free phthalocyanine and / or oxotitanyl phthalocyanine is more preferably used. . The charge generating materials may be used alone or in combination of plural kinds.
また、上記単層型または積層型の有機感光層や、複合型
の感光層における電荷輸送層中に含まれる電荷輸送材料
としては、例えばテトラシアノエチレン;2,4,7−トリニ
トロ−９−フルオレノン等のフルオレノン系化合物；ジ
ニトロアントラセン等のニトロ化化合物；無水コハク
酸；無水マレイン酸；ジブロモ無水マレイン酸；トリフ
ェニルメタン系化合物;2,5−ジ（４−ジメチルアミノフ
ェニル）−1,3,4−オキサジアゾール等のオキサジアゾ
ール系化合物;9−（４−ジエチルアミノスチリル）アン
トラセン等のスチリル系化合物；ポリ−Ｎ−ビニルカル
バゾール等のカルバゾール系化合物;1−フェニル−３−
（ｐ−ジメチルアミノフェニル）ピラゾリン等のピラゾ
リン系化合物;4,4′,4″−トリス（N,N−ジフェニルア
ミノ）トリフェニルアミン等のアミン誘導体;1,1−ビス
（４−ジエチルアミノフェニル）−4,4−ジフェニル−
1,3−ブタジエン等の共役不飽和化合物;4−（N,N−ジエ
チルアミノ）ベンズアルデヒド−N,N−ジフェニルヒド
ラゾン等のヒドラゾン系化合物；インドール系化合物、
オキサゾール系化合物、イソオキサゾール系化合物、チ
アゾール系化合物、チアジアゾール系化合物、イミダゾ
ール系化合物、ピラゾール系化合物、ピラゾリン系化合
物、トリアゾール系化合物等の含窒素環式化合物；縮合
多環族化合物が例示される。上記電荷輸送材料も単独
で、あるいは、複数種併用して用いることができる。な
お、上記電荷輸送材料の中でも、前記ポリ−Ｎ−ビニル
カルバゾール等の光導電性を有する高分子材料は、感光
層の結着樹脂としても使用することができる。Examples of the charge transport material contained in the charge transport layer in the single-layer type or multilayer type organic photosensitive layer or the composite type photosensitive layer include tetracyanoethylene; 2,4,7-trinitro-9-fluorenone. Fluorenone compounds such as; nitration compounds such as dinitroanthracene; succinic anhydride; maleic anhydride; dibromomaleic anhydride; triphenylmethane compounds; 2,5-di (4-dimethylaminophenyl) -1,3, Oxadiazole compounds such as 4-oxadiazole; styryl compounds such as 9- (4-diethylaminostyryl) anthracene; carbazole compounds such as poly-N-vinylcarbazole; 1-phenyl-3-
Pyrazoline compounds such as (p-dimethylaminophenyl) pyrazolin; amine derivatives such as 4,4 ′, 4 ″ -tris (N, N-diphenylamino) triphenylamine; 1,1-bis (4-diethylaminophenyl) -4,4-diphenyl-
Conjugated unsaturated compounds such as 1,3-butadiene; hydrazone compounds such as 4- (N, N-diethylamino) benzaldehyde-N, N-diphenylhydrazone; indole compounds,
Nitrogen-containing cyclic compounds such as oxazole-based compounds, isoxazole-based compounds, thiazole-based compounds, thiadiazole-based compounds, imidazole-based compounds, pyrazole-based compounds, pyrazoline-based compounds, and triazole-based compounds; and condensed polycyclic compounds are exemplified. The above charge transport materials can be used alone or in combination of two or more. Among the above charge transport materials, the photoconductive polymer material such as poly-N-vinylcarbazole can also be used as the binder resin for the photosensitive layer.
また、前記単層型または積層型の有機感光層、複合型感
光層における電荷輸送層などの層には、前記増感剤、フ
ルオレン系化合物、酸化防止剤、紫外線吸収剤等の劣化
防止剤、可塑剤などの添加剤を含有させることができ
る。Further, the single-layer type or laminated type organic photosensitive layer, the layer such as the charge transport layer in the composite type photosensitive layer, the sensitizer, a fluorene compound, an antioxidant, a deterioration inhibitor such as an ultraviolet absorber, Additives such as plasticizers may be included.
単層型の有機感光層における、結着樹脂100重量部に対
する電荷発生材料の含有割合は、２〜20重量部の範囲
内、特に３〜15重量部の範囲内であることが好ましく、
一方、結着樹脂100重量部に対する電荷輸送材料の含有
割合は、40〜200重量部の範囲内、特に50〜100重量部の
範囲内であることが好ましい。電荷発生材料が２重量部
未満、または、電荷輸送材料が40重量部未満では、感光
体の感度が不充分になったり残留電位が大きくなったり
するからであり、電荷発生材料が20重量部を超え、また
は、電荷輸送材料が200重量部を超えると、感光体の耐
摩耗性が十分に得られなくなるからである。In the single-layer organic photosensitive layer, the content ratio of the charge generation material to 100 parts by weight of the binder resin is preferably in the range of 2 to 20 parts by weight, particularly preferably 3 to 15 parts by weight,
On the other hand, the content ratio of the charge transport material to 100 parts by weight of the binder resin is preferably in the range of 40 to 200 parts by weight, and particularly preferably in the range of 50 to 100 parts by weight. If the charge generating material is less than 2 parts by weight or the charge transporting material is less than 40 parts by weight, the sensitivity of the photoconductor becomes insufficient and the residual potential becomes large. This is because if the amount exceeds or the amount of the charge transport material exceeds 200 parts by weight, the abrasion resistance of the photoreceptor cannot be sufficiently obtained.
上記単層型感光層は、適宜の厚みに形成できるが、通常
は、10〜50μｍ、特に15〜25μｍの範囲内に形成される
ことが好ましい。The single-layer type photosensitive layer can be formed to have an appropriate thickness, but it is usually preferably formed in the range of 10 to 50 μm, particularly 15 to 25 μm.
一方、積層型の有機感光層を構成する層のうち、電荷発
生層における、結着樹脂100重量部に対する電荷発生材
料の含有割合は、５〜500重量部の範囲内、特に10〜250
重量部の範囲内であることが好ましい。電荷発生材料が
５重量部未満では電荷発生能が小さ過ぎ、500重量部を
超えると隣接する他の層や基材との密着性が低下するか
らである。On the other hand, in the layers constituting the laminated organic photosensitive layer, the content ratio of the charge generating material to the binder resin 100 parts by weight in the charge generating layer is in the range of 5 to 500 parts by weight, particularly 10 to 250 parts by weight.
It is preferably within the range of parts by weight. This is because if the amount of the charge generating material is less than 5 parts by weight, the charge generating ability is too small, and if it exceeds 500 parts by weight, the adhesiveness with other adjacent layers or substrates is deteriorated.
上記電荷発生層の膜厚は、0.01〜３μｍ、特に0.1〜２
μｍの範囲内であることが好ましい。The thickness of the charge generation layer is 0.01 to 3 μm, particularly 0.1 to 2 μm.
It is preferably in the range of μm.
また、積層型の有機感光層および複合型感光層を構成す
る層のうち、電荷輸送層における、結着樹脂100重量部
に対する電荷輸送材料の含有割合は、10〜500重量部の
範囲内、特に25〜200重量部の範囲内であることが好ま
しい。電荷輸送材料が10重量部未満では電荷輸送能が十
分でなく、500重量部を超えると電荷輸送層の機械的強
度が低下するからである。Further, among the layers constituting the laminated organic photosensitive layer and the composite type photosensitive layer, in the charge transport layer, the content ratio of the charge transport material relative to 100 parts by weight of the binder resin is in the range of 10 to 500 parts by weight, and particularly, It is preferably in the range of 25 to 200 parts by weight. This is because if the charge transport material is less than 10 parts by weight, the charge transport ability is insufficient, and if it exceeds 500 parts by weight, the mechanical strength of the charge transport layer is lowered.
上記電荷輸送層の膜厚は、２〜100μｍ、特に５〜30μ
ｍの範囲内であることが好ましい。The thickness of the charge transport layer is 2 to 100 μm, particularly 5 to 30 μm.
It is preferably within the range of m.
以上に説明した、単層型や積層型の有機感光層、複合型
感光層のうちの電荷輸送層、および表面保護層などの有
機の層は、前述した各成分を含有する各層用の塗布液を
調製し、これら塗布液を、前述した層構成を形成し得る
ように、各層毎に順次導電性基材上に塗布し、乾燥また
は硬化させることで積層形成することができる。As described above, the organic layer such as the single-layer type or laminated type organic photosensitive layer, the charge transport layer of the composite type photosensitive layer, and the surface protective layer is a coating liquid for each layer containing the above-mentioned components. Is prepared, and each of these layers is sequentially coated on a conductive base material so that the above-mentioned layer constitution can be formed, and dried or cured to form a laminate.
なお、上記塗布液の調製に際しては、使用される結着樹
脂等の種類に応じて種々の溶剤を使用することができ
る。上記溶剤としては、ｎ−ヘキサン、オクタン、シク
ロヘキサン等の脂肪族炭化水素；ベンゼン、キシレン、
トルエン等の芳香族炭化水素；ジクロロメタン、四塩化
炭素、クロロベンゼン、塩化メチレン等のハロゲン化炭
化水素；メチルアルコール、エチルアルコール、イソプ
ロピルアルコール、アリルアルコール、シクロペンタノ
ール、ベンジルアルコール、フルフリルアルコール、ジ
アセトンアルコール等のアルコール類；ジメチルエーテ
ル、ジエチルエーテル、テトラヒドロフラン、エチレン
グリコールジメチルエーテル、エチレングリコールジエ
チルエーテル、ジエチレングリコールジメチルエーテル
等のエーテル類；アセトン、メチルエチルケトン、メチ
ルイソブチルケトン、シクロヘキサノン等のケトン類；
酢酸エチル、酢酸メチル等のエステル類；ジメチルホル
ムアミド；ジメチルスルホキシド等、種々の溶剤が例示
され、これらが一種または二種以上混合して用いられ
る。また、上記塗布液を調製する際、分散性、塗工性等
を向上させるため、界面活性剤やレベリング剤等を併用
しても良い。When preparing the above-mentioned coating liquid, various solvents can be used depending on the type of binder resin or the like used. Examples of the solvent include aliphatic hydrocarbons such as n-hexane, octane and cyclohexane; benzene, xylene,
Aromatic hydrocarbons such as toluene; halogenated hydrocarbons such as dichloromethane, carbon tetrachloride, chlorobenzene, methylene chloride; methyl alcohol, ethyl alcohol, isopropyl alcohol, allyl alcohol, cyclopentanol, benzyl alcohol, furfuryl alcohol, diacetone Alcohols such as alcohols; ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone;
Examples of various solvents include esters such as ethyl acetate and methyl acetate; dimethylformamide; dimethylsulfoxide and the like, and these are used alone or in combination of two or more. In addition, a surfactant, a leveling agent, or the like may be used together in order to improve dispersibility, coatability, and the like when preparing the coating liquid.
また、上記塗布液は従来慣用の方法、例えばミキサー、
ボールミル、ペイントシェーカー、サンドミル、アトラ
イター、超音波分散機等を用いて調製することができ
る。Further, the coating solution is a conventional method, for example, a mixer,
It can be prepared using a ball mill, paint shaker, sand mill, attritor, ultrasonic disperser, or the like.
〈実施例〉 以下に、実施例に基づき、この発明をより詳細に説明す
る。<Examples> Hereinafter, the present invention will be described in more detail with reference to Examples.
実施例１〜６、比較例１〜16 結着樹脂としてのポリアリレート（ユニチカ社製，商品
名Ｕ−100）100重量部、電荷輸送材料としての４−（N,
N−ジエチルアミノ）ベンズアルデヒド−N,N−ジフェニ
ルヒドラゾン100重量部および溶媒としての塩化メチレ
ン（CH2Cl2）900重量部からなる電荷輸送用塗布液を調
製し、この塗布液を外径78mm×長さ340mmのアルミニウ
ム管上に塗布した後、90℃で30分間加熱乾燥させて、膜
厚約20μｍの電荷輸送層を形成した。Examples 1 to 6 and Comparative Examples 1 to 16 100 parts by weight of polyarylate (manufactured by Unitika Ltd., trade name U-100) as a binder resin, 4- (N,
N-diethylamino) benzaldehyde-N, N-diphenylhydrazone 100 parts by weight and methylene chloride (CH 2 Cl 2 ) as a solvent 900 parts by weight to prepare a charge-transporting coating liquid, and this coating liquid was prepared to have an outer diameter of 78 mm × length. After coating on a 340 mm aluminum tube, it was heated and dried at 90 ° C. for 30 minutes to form a charge transport layer having a film thickness of about 20 μm.
次に、上記電荷輸送層上に、電荷発生材料としての2,7
−ジブロモアンサンスロン（ICI社製）80重量部および
メタルフリーフタロシアニン（BASF社製）20重量部、結
着樹脂としてのポリ酢酸ビニル（日本合成化学社製，商
品名Y5−Ｎ）50重量部および溶媒としてのジアセトンア
ルコール2000重量部からなる電荷発生層用塗布液を塗布
し、110℃で30分間加熱乾燥させて、膜厚約0.5μｍの電
荷発生層を形成した。Next, on the charge transport layer, 2,7 as a charge generating material
-80 parts by weight of dibromoanthanthurone (manufactured by ICI) and 20 parts by weight of metal-free phthalocyanine (manufactured by BASF), 50 parts by weight of polyvinyl acetate (manufactured by Nippon Gohsei Co., Ltd., trade name Y5-N) as a binder resin, and A charge generation layer coating solution consisting of 2000 parts by weight of diacetone alcohol as a solvent was applied and dried by heating at 110 ° C. for 30 minutes to form a charge generation layer having a thickness of about 0.5 μm.
次に、0.02N塩酸57.4重量部とイソプロピルアルコール3
6重量部とを混合し、上記混合液の液温を20〜25℃に保
ちつつ攪拌しながら、メチルトリメトキシシラン80重量
部およびグリシドキシプロピルトリメトキシシラン20重
量部を徐々に滴下した後、室温に１時間放置することに
よってシラン加水分解物溶液を得た。そして、このシラ
ン加水分解物溶液に、同溶液中の非揮発性固形分に対
し、表１に示す配合量の特定エーテル化メラミン・ホル
ムアルデヒド樹脂と、上記熱硬化性シリコーン樹脂の非
揮発性固形分および特定エーテル化メラミン・ホルムア
ルデヒド樹脂の合計量に対し、同表に示す配合割合のポ
リビニルブチラール（電気化学社製、商品名デンカブチ
ラール5000A）とを配合して表面保護層用の塗布液を調
製した。Next, 57.4 parts by weight of 0.02N hydrochloric acid and isopropyl alcohol 3
After mixing with 6 parts by weight, 80 parts by weight of methyltrimethoxysilane and 20 parts by weight of glycidoxypropyltrimethoxysilane were gradually added dropwise while stirring while maintaining the liquid temperature of the mixed solution at 20 to 25 ° C. A silane hydrolyzate solution was obtained by leaving it at room temperature for 1 hour. Then, in this silane hydrolyzate solution, the non-volatile solid content of the thermosetting silicone resin and the specific etherified melamine-formaldehyde resin in the compounding amounts shown in Table 1 with respect to the non-volatile solid content in the solution. And, with respect to the total amount of the specific etherified melamine / formaldehyde resin, polyvinyl butyral (manufactured by Denki Kagaku Co., Ltd., trade name Denka Butyral 5000A) in a mixing ratio shown in the same table was mixed to prepare a coating solution for the surface protective layer. .
次に、アンチモンドープ酸化スズ微粉末（住友セメント
社製、酸化スズと酸化アンチモンとの固溶体粒子、アン
チモンを10重量％含有）を、上記塗布液中の樹脂固形分
100重量部に対し、60重量部配合して、ボールミルによ
り150時間攪拌、混合した。そして、上記塗布液とアン
チモンドープ酸化スズ微粉末との混合物を前記電荷発生
層上に塗布し、110℃で１時間加熱硬化させて、膜厚約
2.5μｍの表面保護層を形成し、積層形感光層を有する
ドラム型の電子写真感光体を作製した。Next, antimony-doped tin oxide fine powder (manufactured by Sumitomo Cement Co., containing solid solution particles of tin oxide and antimony oxide, containing 10% by weight of antimony) was used as a resin solid content in the coating liquid.
60 parts by weight was mixed with 100 parts by weight, and the mixture was stirred and mixed for 150 hours by a ball mill. Then, a mixture of the coating liquid and antimony-doped tin oxide fine powder is applied on the charge generation layer, and cured by heating at 110 ° C. for 1 hour to give a film thickness of about
A 2.5 μm surface protective layer was formed to prepare a drum-type electrophotographic photosensitive member having a laminated photosensitive layer.
実施例７〜10 アンチモンドープ酸化スズ微粉末に代えて、五酸化アン
チモンの微粒子がイソプロピルアルコール中に分散され
たコロイド溶液（日産化学社製、商品名サンコロイド、
固形分含量20重量％）を使用し、このコロイド溶液を、
塗布液中の樹脂固形分（Ｐ）と、コロイド溶液中の固形
分（Ｍ）とが、P:M＝100:60（重量比）となるように、
上記シリコーン樹脂系塗布液中に配合し、ボールミルで
１時間攪拌、混合したこと以外は、上記実施例１〜６と
同様にして、電子写真感光体を作製した。Examples 7 to 10 Instead of the antimony-doped tin oxide fine powder, a colloidal solution in which fine particles of antimony pentoxide were dispersed in isopropyl alcohol (manufactured by Nissan Kagaku Co., Ltd., Sun colloid,
Solid content of 20% by weight)
The resin solid content (P) in the coating liquid and the solid content (M) in the colloid solution are P: M = 100: 60 (weight ratio),
An electrophotographic photosensitive member was produced in the same manner as in Examples 1 to 6 except that the silicone resin-based coating liquid was blended and stirred and mixed in a ball mill for 1 hour.
実施例11〜18 アンチモンドープ酸化スズ微粉末に代えて、酸化スズと
酸化アンチモンとの固溶体粒子（アンチモンを10重量％
含有、粒径10〜20nm）が、当該固溶体粒子100重量部に
対して９重量部の酸化ケイ素粒子により負に帯電された
状態で、分散媒としてのイソプロピルアルコール中に分
散されたコロイド溶液（日産化学社製）を使用し、この
コロイド溶液を、塗布液中の樹脂固形分（Ｐ）と、コロ
イド溶液中の固形分（Ｍ）とが、P:M＝100:60（重量
比）となるように、上記シリコーン樹脂系塗布液中に配
合し、ボールミルで１時間攪拌、混合したこと以外は、
上記実施例１〜６と同様にして、電子写真感光体を作製
した。Examples 11 to 18 Instead of antimony-doped tin oxide fine powder, solid solution particles of tin oxide and antimony oxide (10% by weight of antimony were used.
Colloidal solution (Nissan, Inc., particle size 10 to 20 nm) dispersed in isopropyl alcohol as a dispersion medium in a state of being negatively charged by 9 parts by weight of silicon oxide particles with respect to 100 parts by weight of the solid solution particles. (Chemical Co., Ltd.) is used, and the resin solid content (P) in the coating solution and the solid content (M) in the colloid solution of this colloidal solution become P: M = 100: 60 (weight ratio) As described above, except that it was blended in the above silicone resin-based coating liquid and stirred and mixed in a ball mill for 1 hour.
Electrophotographic photoreceptors were prepared in the same manner as in Examples 1 to 6 above.
比較例17 表面保護層用塗布液として、市販のシリコーン樹脂系塗
布液（東芝シリコン社製、商品名トスガード520）を使
用したこと以外は、上記実施例１〜６と同様にして、電
子写真感光体を作製した。Comparative Example 17 Electrophotographic sensitization was performed in the same manner as in Examples 1 to 6 except that a commercially available silicone resin-based coating liquid (Toshiba Silicon Co., trade name Tosgard 520) was used as the surface protective layer coating liquid. The body was made.
実施例19〜28、比較例18〜33 ポリビニルブチラールに代えて、表２に示す配合割合の
ポリ酢酸ビニル（日本合成化学社製、商品名Y5−Ｎ）を
使用したこと以外は、上記実施例１〜６と同様にして、
電子写真感光体を作製した。Examples 19 to 28, Comparative Examples 18 to 33 The above examples except that polyvinyl acetate (manufactured by Nippon Gohsei Kagaku Co., Ltd., trade name Y5-N) having a blending ratio shown in Table 2 was used in place of polyvinyl butyral. In the same way as 1-6,
An electrophotographic photoreceptor was produced.
実施例29〜32 アンチモンドープ酸化スズ微粉末に代えて、五酸化アン
チモンの微粒子がイソプロピルアルコール中に分散され
たコロイド溶液（日産化学社製、商品名サンコロイド、
固形分含量20重量％）を使用し、このコロイド溶液を、
塗布液中の樹脂固形分（Ｐ）と、コロイド溶液中の固形
分（Ｍ）とが、P:M＝100:60（重量比）となるように、
上記シリコーン樹脂系塗布液中に配合し、ボールミルで
１時間攪拌、混合したこと以外は、上記実施例19〜28と
同様にして、電子写真感光体を作製した。Examples 29 to 32 Instead of the antimony-doped tin oxide fine powder, fine particles of antimony pentoxide were dispersed in isopropyl alcohol in a colloidal solution (manufactured by Nissan Kagaku Co., Ltd., Sun colloid,
Solid content of 20% by weight)
The resin solid content (P) in the coating liquid and the solid content (M) in the colloid solution are P: M = 100: 60 (weight ratio),
Electrophotographic photoreceptors were prepared in the same manner as in Examples 19 to 28, except that the silicone resin-based coating liquid was blended, stirred and mixed in a ball mill for 1 hour.
実施例33〜40 アンチモンドープ酸化スズ微粉末に代えて、酸化スズと
酸化アンチモンとの固溶体粒子（アンチモンを10重量％
含有、粒径10〜20nm）が、当該固溶体粒子100重量部に
対して９重量部の酸化ケイ素粒子により負に帯電された
状態で、分散媒としてのイソプロピルアルコール中に分
散されたコロイド溶液（日産化学社製）を使用し、この
コロイド溶液を、塗布液中の樹脂固形分（Ｐ）と、コロ
イド溶液中の固形分（Ｍ）とが、P:M＝100:60（重量
比）となるように、上記シリコーン樹脂系塗布液中に配
合し、ボールミルで１時間攪拌、混合したこと以外は、
上記実施例19〜28と同様にして、電子写真感光体を作製
した。Examples 33 to 40 Instead of the antimony-doped tin oxide fine powder, solid solution particles of tin oxide and antimony oxide (10% by weight of antimony were used.
Colloidal solution (Nissan, Inc., particle size 10 to 20 nm) dispersed in isopropyl alcohol as a dispersion medium in a state of being negatively charged by 9 parts by weight of silicon oxide particles with respect to 100 parts by weight of the solid solution particles. (Chemical Co., Ltd.) is used, and the resin solid content (P) in the coating solution and the solid content (M) in the colloid solution of this colloidal solution become P: M = 100: 60 (weight ratio) As described above, except that it was blended in the above silicone resin-based coating liquid and stirred and mixed in a ball mill for 1 hour.
Electrophotographic photoreceptors were prepared in the same manner as in Examples 19 to 28 above.
実施例41〜52、比較例34〜49 ポリビニルブチラールに代えて、表３に示す配合割合の
アクリル系重合体（三菱レイヨン社製、商品名BR−10
5）を使用したこと以外は、上記実施例１〜６と同様に
して、電子写真感光体を作製した。Examples 41 to 52, Comparative Examples 34 to 49 Instead of polyvinyl butyral, an acrylic polymer having a blending ratio shown in Table 3 (manufactured by Mitsubishi Rayon Co., Ltd., trade name BR-10
Electrophotographic photoreceptors were produced in the same manner as in Examples 1 to 6 except that 5) was used.
実施例53〜56 アンチモンドープ酸化スズ微粉末に代えて、五酸化アン
チモンの微粒子がイソプロピルアルコール中に分散され
たコロイド溶液（日産化学社製、商品名サイコロイド、
固形分含量20重量％）を使用し、このコロイド溶液を、
塗布液中の樹脂固形分（Ｐ）と、コロイド溶液中の固形
分（Ｍ）とが、P:M＝100:60（重量比）となるように、
上記シリコーン樹脂系塗布液中に配合し、ボールミルで
１時間攪拌、混合したこと以外は、上記実施例41〜52と
同様にして、電子写真感光体を作製した。Examples 53 to 56 Instead of the antimony-doped tin oxide fine powder, fine particles of antimony pentoxide are dispersed in isopropyl alcohol in a colloidal solution (manufactured by Nissan Kagaku Co., Ltd., trade name Cycolloid,
Solid content of 20% by weight)
The resin solid content (P) in the coating liquid and the solid content (M) in the colloid solution are P: M = 100: 60 (weight ratio),
Electrophotographic photoreceptors were produced in the same manner as in Examples 41 to 52 except that the silicone resin-based coating liquid was blended and stirred and mixed in a ball mill for 1 hour.
実施例57〜64 アンチモンドープ酸化スズ微粉末に代えて、酸化スズと
酸化アンチモンとの固溶体粒子（アンチモンを10重量％
含有、粒径10〜20nm）が、当該固溶体粒子100重量部に
対して９重量部の酸化ケイ素粒子により負に帯電された
状態で、分散媒としてのイソプロピルアルコール中に分
散されたコロイド溶液（日産化学社製）を使用し、この
コロイド溶液を、塗布液中の樹脂固形分（Ｐ）と、コロ
イド溶液中の固形分（Ｍ）とが、P:M＝100:60（重量
比）となるように、上記シリコーン樹脂系塗布液中に配
合し、ボールミルで１時間攪拌、混合したこと以外は、
上記実施例41〜52と同様にして、電子写真感光体を作製
した。Examples 57 to 64 Instead of the antimony-doped tin oxide fine powder, solid solution particles of tin oxide and antimony oxide (10% by weight of antimony were used.
Colloidal solution (Nissan, Inc., particle size 10 to 20 nm) dispersed in isopropyl alcohol as a dispersion medium in a state of being negatively charged by 9 parts by weight of silicon oxide particles with respect to 100 parts by weight of the solid solution particles. (Chemical Co., Ltd.) is used, and the resin solid content (P) in the coating solution and the solid content (M) in the colloid solution of this colloidal solution become P: M = 100: 60 (weight ratio) As described above, except that it was blended in the above silicone resin-based coating liquid and stirred and mixed in a ball mill for 1 hour.
Electrophotographic photoreceptors were produced in the same manner as in Examples 41 to 52 above.
上記各実施例並びに比較例で作製した電子写真感光体に
ついて、下記の各試験を行った。The following tests were carried out on the electrophotographic photosensitive members produced in the above-mentioned Examples and Comparative Examples.
表面電位測定 上記各電子写真感光体を、静電複写試験装置（ジェンテ
ック社製，ジェンテックシンシア30M型機）に装填し、
その表面を正に帯電させて、表面電位V1s.p.（Ｖ）を測
定した。Surface potential measurement Each of the above electrophotographic photoconductors was loaded into an electrostatic copying tester (Gentec Cynthia 30M model, manufactured by Gentec),
The surface was positively charged and the surface potential V 1 sp (V) was measured.
半減露光量、残留電位測定 上記帯電状態の各電子写真感光体を、上記静電複写試験
装置の露光光源であるハロゲンランプを用いて、露光強
度0.92mW/cm2、露光時間60m秒の条件で露光し、前記表
面電位V1s.p.が1/2になるのに要する時間を求め、半減
露光量E1/2（lux・Sec）を算出した。Half-dose exposure, residual potential measurement Each electrophotographic photosensitive member in the charged state was exposed under the conditions of an exposure intensity of 0.92 mW / cm 2 and an exposure time of 60 msec using a halogen lamp which is an exposure light source of the electrostatic copying test apparatus. After exposure, the time required for the surface potential V 1 sp to become 1/2 was determined, and the half-exposure amount E1 / 2 (lux · Sec) was calculated.
また、上記露光開始時から0.4秒経過後の表面電位を、
残留電位Vr.p.（Ｖ）として測定した。Further, the surface potential after 0.4 seconds has elapsed from the start of the exposure,
It was measured as the residual potential Vr.p. (V).
耐摩耗試験 各電子写真感光体をドラム研磨試験機（三田工業社製）
に装填すると共に、このドラム研磨試験機に設けられ
た、感光体が1000回転する間に１回転する研磨試験紙装
着リングに研磨試験紙（住友スリーエム社製，商品名イ
ンペリアルラッピングフィルム，粒径12μｍの酸化アル
ミニウム粉末を表面に付着させたもの）を装填し、この
研磨試験紙を感光体表面に線圧10g/mmで押圧しながら、
感光体を100回回転させた時の摩耗量（μｍ）を測定し
た。Abrasion resistance test Drum polishing tester (manufactured by Mita Kogyo) for each electrophotographic photoreceptor
And a drum tester installed on this drum polishing tester, which rotates once during 1000 revolutions of the photoconductor, has a polishing test paper (Sumitomo 3M, trade name Imperial Wrapping Film, particle size 12 μm) Aluminum oxide powder on the surface) was loaded and the polishing test paper was pressed against the surface of the photoconductor at a linear pressure of 10 g / mm,
The amount of wear (μm) when the photoconductor was rotated 100 times was measured.
外観 表面保護層の外観を目視により観察した。Appearance The appearance of the surface protective layer was visually observed.
以上の結果を表１〜３に示す。なお、表１〜３、並び
に、後述する表４における＊１〜＊５は下記の通り。The above results are shown in Tables 1-3. In addition, Tables 1 to 3 and * 1 to * 5 in Table 4 described later are as follows.
＊１ MBEMH:メチル−ブチル混合エーテル化メラミン・ホルム
アルデヒド樹脂 MEMH:メチルエーテル化メラミン・ホルムアルデヒド樹
脂 BEMH:ブチルエーテル化メラミン・ホルムアルデヒド樹
脂 ＊２ PVB:ポリビニルブチラール PVAc:ポリ酢酸ビニル AC:アクリル系重合体 ＊３ A:アンチモンドープ酸化スズ微粉末 B:五酸化アンチモンコロイド溶液 C:酸化スズと酸化アンチモンとの固溶体のコロイド溶液 ＊４ クラック発生のため測定できなかった。* 1 MBEMH: Methyl-butyl mixed etherified melamine formaldehyde resin MEMH: Methyl etherified melamine formaldehyde resin BEMH: Butyl etherified melamine formaldehyde resin * 2 PVB: Polyvinyl butyral PVAc: Polyvinyl acetate AC: Acrylic polymer * 3 A: Antimony-doped tin oxide fine powder B: Antimony pentoxide colloidal solution C: Solid solution colloidal solution of tin oxide and antimony oxide * 4 It could not be measured because of cracks.
＊５ 白濁発生のため測定できなかった。* 5 Measurement could not be performed due to cloudiness.
上記表１〜３の結果より、熱可塑性樹脂としてポリビニ
ルブチラール、ポリ酢酸ビニルおよびアクリル系重合体
を用いた３つの併用系の何れにおいても、熱硬化性シリ
コーン樹脂の非揮発性固形分100重量部に対する、特定
エーテル化メラミン・ホルムアルデヒド樹脂の含有量が
５〜50重量部の範囲内で、且つ、熱可塑性樹脂の含有割
合が、シリコーン樹脂の非揮発性固形分と特定エーテル
化メラミン・ホルムアルデヒド樹脂との合計量の１〜11
重量％の範囲内である場合にのみ、感光特性、物性等に
優れ、且つ摺動摩擦に対する脆さ等が改善されており、
しかも、より導電性に優れた表面保護層を有する電子写
真感光体を製造し得ることが判明した。 From the results of Tables 1 to 3 above, in any of the three combined systems using polyvinyl butyral, polyvinyl acetate and an acrylic polymer as the thermoplastic resin, 100 parts by weight of the nonvolatile solid content of the thermosetting silicone resin is used. , The content of the specific etherified melamine / formaldehyde resin is within the range of 5 to 50 parts by weight, and the content ratio of the thermoplastic resin is the non-volatile solid content of the silicone resin and the specific etherified melamine / formaldehyde resin. 1 to 11 of the total amount of
Only when the content is within the range of weight%, the photosensitivity and the physical properties are excellent, and the brittleness against sliding friction is improved.
Moreover, it has been found that it is possible to manufacture an electrophotographic photosensitive member having a surface protective layer having more excellent conductivity.
また、各系を比較すると、熱可塑性樹脂としてポリ酢酸
ビニルを用いた系は、他の系に比べて耐摩耗性に優れ、
アクリル系重合体を用いた系は、他の系に比べて半減露
光量、残留電位が小さい等、感光特性に優れていること
が判明した。Also, comparing each system, the system using polyvinyl acetate as the thermoplastic resin is superior in abrasion resistance compared to other systems,
It has been found that the system using the acrylic polymer has excellent photosensitivity such as a half-exposure amount and a small residual potential as compared with other systems.
一方、同じ系の中では、導電性付与剤として、導電性金
属酸化物のコロイド溶液を使用した場合、１時間の攪拌
により、導電性金属酸化物を微粉末の状態で使用した場
合の150時間の攪拌混合以上の分散性が得られることが
判明した。On the other hand, in the same system, when a colloidal solution of a conductive metal oxide is used as a conductivity-imparting agent, 150 hours when the conductive metal oxide is used in a fine powder state by stirring for 1 hour. It was found that a dispersibility equal to or higher than that of stirring and mixing was obtained.
そして、比較例17と、上記各系とを比較すると、上記各
系は、何れも、熱硬化性シリコーン樹脂単独に比べて、
感光特性、耐摩耗性共に優れたものであることが判明し
た。Then, when comparing Comparative Example 17 and each of the above systems, each of the above systems is compared with the thermosetting silicone resin alone,
It was found that the photosensitivity and abrasion resistance were excellent.
実施例65,66、比較例50 実施例１〜６で作製したシラン加水分解物溶液に、同溶
液中の非揮発性固形分に対して10重量部のエーテル化メ
ラミン・ホルムアルデヒド樹脂と、上記熱硬化性シリコ
ーン樹脂の非揮発性固形分およびエーテル化メラミン・
ホルムアルデヒド樹脂の合計量に対して9.09重量％のア
クリル系重合体（三菱レイヨン社製、商品名BR-105）と
を配合して表面保護層用の塗布液を調製し、あとは、上
記実施例１〜６と同様にして、電子写真感光体を作製し
た。Examples 65 and 66, Comparative Example 50 The silane hydrolyzate solutions prepared in Examples 1 to 6 were mixed with 10 parts by weight of an etherified melamine-formaldehyde resin based on the non-volatile solid content in the solution and the above heat. Non-volatile solid content of curable silicone resin and etherified melamine
An acrylic polymer (manufactured by Mitsubishi Rayon Co., Ltd., trade name BR-105) of 9.09% by weight relative to the total amount of formaldehyde resin was blended to prepare a coating solution for the surface protective layer. An electrophotographic photosensitive member was produced in the same manner as in 1 to 6.
上記実施例並びに比較例の電子写真感光体について、前
述した表面電位測定、半減露光量測定、並びに外観の観
察の各試験と、以下に示す、繰返し露光後の表面電位変
化測定を行った。With respect to the electrophotographic photosensitive members of the above Examples and Comparative Examples, the above-described surface potential measurement, half-exposure amount measurement, and external appearance observation tests, and the following surface potential change measurement after repeated exposure were performed.
繰返し露光後の表面電位変化測定 上記各電子写真感光体を複写機（三田工業社製，DC-111
型機）に装填して500枚の複写処理を行った後、表面電
位を、繰返し露光後の表面電位V2s.p.（Ｖ）として測定
した。Measurement of change in surface potential after repeated exposure Each of the above electrophotographic photoconductors was copied by a copying machine (manufactured by Mita Kogyo Co., Ltd., DC-111
After performing a copying process on 500 sheets, the surface potential was measured as the surface potential V 2 sp (V) after repeated exposure.
また、前記表面電位測定値V1s.p.値と、繰返し露光後の
表面電位測定値V2s.p.値とから、下記式〔Ｉ〕により、
表面電位変化値−ΔＶ（Ｖ）を算出した。Further, from the surface potential measurement value V 1 sp value and the surface potential measurement value V 2 sp value after repeated exposure, according to the following formula [I],
The surface potential change value-ΔV (V) was calculated.
−ΔＶ（Ｖ）＝ V2s.p.（Ｖ）−V1s.p.（Ｖ）…〔Ｉ〕 以上の結果を表４に示す。-ΔV (V) = V 2 sp (V) -V 1 sp (V) ... [I] The above results are shown in Table 4.
上記表４の結果より、特定エーテル化メラミン・ホルム
アルデヒド樹脂に含まれない、ブチルエーテル化メラミ
ン・ホルムアルデヒド樹脂を使用した系では、繰返し露
光によって感光特性が著しく悪化することが判明した。 From the results in Table 4 above, it was found that the system using a butyl etherified melamine-formaldehyde resin, which is not included in the specific etherified melamine-formaldehyde resin, remarkably deteriorates the photosensitivity by repeated exposure.
〈発明の効果〉 この発明の電子写真感光体は以上のように構成されてい
るため、電子写真感光体の感光特性、物性等に悪影響を
与えることなく、且つ熱硬化性シリコーン樹脂単独の場
合に比べて摺動摩擦に対する脆さ等が改善されており、
しかも、より導電性に優れた表面保護層を有するものと
なる。<Effects of the Invention> Since the electrophotographic photosensitive member of the present invention is configured as described above, it does not adversely affect the photosensitive characteristics, physical properties and the like of the electrophotographic photosensitive member, and when the thermosetting silicone resin is used alone. In comparison, the brittleness against sliding friction has been improved,
In addition, it has a surface protective layer having more excellent conductivity.
また、熱可塑性樹脂としてポリ酢酸ビニルを用いた場合
には、ポリ酢酸ビニルの持つ柔軟性により、表面保護層
の脆さが改善されて、機械的強度が向上し、長寿命化が
可能になる。Further, when polyvinyl acetate is used as the thermoplastic resin, the flexibility of polyvinyl acetate improves the brittleness of the surface protective layer, improves the mechanical strength, and enables a longer life. .
一方、熱可塑性樹脂としてポリメチルメタクリレート
（PMMA）等のアクリル系重合体を用いた場合には、上記
アクリル系重合体の持つ高い光学特性に基づいて、より
一層の高感度化が可能になる。On the other hand, when an acrylic polymer such as polymethylmethacrylate (PMMA) is used as the thermoplastic resin, the sensitivity can be further increased due to the high optical properties of the acrylic polymer.
第１図は酸化スズと酸化アンチモンとの固溶体粒子の表
面に酸化ケイ素粒子を吸着させることで、上記固溶体粒
子を帯電させた状態を示す模式図である。 １……固溶体粒子、２……酸化ケイ素粒子。FIG. 1 is a schematic diagram showing a state where the solid solution particles of tin oxide and antimony oxide are charged by adsorbing the silicon oxide particles on the surface of the solid solution particles. 1 ... Solid solution particles, 2 ... Silicon oxide particles.
Claims (3)
シリコーン樹脂の非揮発性固形分100重量部に対して５
〜50重量部のメチルエーテル化メラミン・ホルムアルデ
ヒド樹脂および／またはメチル−ブチル混合エーテル化
メラミン・ホルムアルデヒド樹脂と、上記熱硬化性シリ
コーン樹脂の非揮発性固形分およびエーテル化メラミン
・ホルムアルデヒド樹脂の合計量に対して１〜11重量％
の熱可塑性樹脂と、導電性付与剤とを含有する塗布液を
感光層上に塗布し、硬化させてなる表面保護層を有する
ことを特徴とする電子写真感光体。1. A thermosetting silicone resin and 5 per 100 parts by weight of non-volatile solid content of the thermosetting silicone resin.
-50 parts by weight of methyl etherified melamine-formaldehyde resin and / or methyl-butyl mixed etherified melamine-formaldehyde resin, and the total amount of the nonvolatile solid content of the thermosetting silicone resin and the etherified melamine-formaldehyde resin. 1 to 11% by weight
An electrophotographic photoreceptor having a surface protective layer formed by applying a coating solution containing the thermoplastic resin of 1. and a conductivity-imparting agent onto the photosensitive layer and curing the coating solution.
項１記載の電子写真感光体。2. The electrophotographic photosensitive member according to claim 1, wherein the thermoplastic resin is polyvinyl acetate.
シリコーン樹脂の非揮発性固形分100重量部に対して５
〜50重量部のメチルエーテル化メラミン・ホルムアルデ
ヒド樹脂および／またはメチル−ブチル混合エーテル化
メラミン・ホルムアルデヒド樹脂と、上記熱硬化性シリ
コーン樹脂の非揮発性固形分およびエーテル化メラミン
・ホルムアルデヒド樹脂の合計量に対して１〜11重量％
のアクリル系重合体と、導電性付与剤とを含有する塗布
液を感光層上に塗布し、硬化させてなる表面保護層を有
することを特徴とする電子写真感光体。3. A thermosetting silicone resin and 5 to 100 parts by weight of non-volatile solid content of the thermosetting silicone resin.
-50 parts by weight of methyl etherified melamine-formaldehyde resin and / or methyl-butyl mixed etherified melamine-formaldehyde resin, and the total amount of the nonvolatile solid content of the thermosetting silicone resin and the etherified melamine-formaldehyde resin. 1 to 11% by weight
An electrophotographic photoreceptor having a surface protective layer obtained by applying a coating solution containing the acrylic polymer of 1. and a conductivity-imparting agent onto the photosensitive layer and curing the coating solution.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27441489A JPH0690538B2 (en) | 1989-10-20 | 1989-10-20 | Electrophotographic photoreceptor |
| CA002027998A CA2027998A1 (en) | 1989-10-20 | 1990-10-18 | Electrophotographic photosensitive element |
| EP90120124A EP0423823B1 (en) | 1989-10-20 | 1990-10-19 | Electrophotographic photosensitive element |
| US07/599,858 US5260157A (en) | 1989-10-20 | 1990-10-19 | Electrophotographic photosensitive element comprising a surface protective layer comprising an etherified melamine-formaldehyde resin |
| DE69024592T DE69024592T2 (en) | 1989-10-20 | 1990-10-19 | Electrophotographic photosensitive member |
| ES90120124T ES2080775T3 (en) | 1989-10-20 | 1990-10-19 | PHOTOSENSITIVE ELECTROPHOTOGRAPHIC ELEMENT. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27441489A JPH0690538B2 (en) | 1989-10-20 | 1989-10-20 | Electrophotographic photoreceptor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03135574A JPH03135574A (en) | 1991-06-10 |
| JPH0690538B2 true JPH0690538B2 (en) | 1994-11-14 |
Family
ID=17541341
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP27441489A Expired - Lifetime JPH0690538B2 (en) | 1989-10-20 | 1989-10-20 | Electrophotographic photoreceptor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0690538B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5532905A (en) * | 1994-07-19 | 1996-07-02 | Analog Devices, Inc. | Thermally enhanced leadframe for packages that utilize a large number of leads |
-
1989
- 1989-10-20 JP JP27441489A patent/JPH0690538B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03135574A (en) | 1991-06-10 |
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