JPH0255363A - Electrophotographic sensitive body - Google Patents
Electrophotographic sensitive bodyInfo
- Publication number
- JPH0255363A JPH0255363A JP20626388A JP20626388A JPH0255363A JP H0255363 A JPH0255363 A JP H0255363A JP 20626388 A JP20626388 A JP 20626388A JP 20626388 A JP20626388 A JP 20626388A JP H0255363 A JPH0255363 A JP H0255363A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- surface layer
- charge
- antioxidant
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010410 layer Substances 0.000 claims abstract description 79
- 239000002344 surface layer Substances 0.000 claims abstract description 35
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 26
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 24
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 11
- 239000002356 single layer Substances 0.000 claims abstract description 6
- 108091008695 photoreceptors Proteins 0.000 claims description 40
- 229920005989 resin Polymers 0.000 abstract description 27
- 239000011347 resin Substances 0.000 abstract description 27
- 238000000576 coating method Methods 0.000 abstract description 14
- 239000011248 coating agent Substances 0.000 abstract description 13
- 238000012546 transfer Methods 0.000 abstract description 4
- 229920000515 polycarbonate Polymers 0.000 abstract description 3
- 239000004417 polycarbonate Substances 0.000 abstract description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 abstract description 3
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 abstract 1
- 238000003475 lamination Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 39
- 239000006185 dispersion Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 13
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 11
- 239000011737 fluorine Substances 0.000 description 11
- 229910052731 fluorine Inorganic materials 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000000049 pigment Substances 0.000 description 10
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 229930185605 Bisphenol Natural products 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- -1 trifluorochloroethylene, ethylene Chemical group 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000003618 dip coating Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011241 protective layer Substances 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 125000004076 pyridyl group Chemical group 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920006026 co-polymeric resin Polymers 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- XXWVEJFXXLLAIB-UHFFFAOYSA-N 4-[[4-(diethylamino)-2-methylphenyl]-phenylmethyl]-n,n-diethyl-3-methylaniline Chemical compound CC1=CC(N(CC)CC)=CC=C1C(C=1C(=CC(=CC=1)N(CC)CC)C)C1=CC=CC=C1 XXWVEJFXXLLAIB-UHFFFAOYSA-N 0.000 description 1
- DMZJGPXZLVUMIN-UHFFFAOYSA-N 5-(2-chlorophenyl)-1,3-oxazole Chemical compound ClC1=CC=CC=C1C1=CN=CO1 DMZJGPXZLVUMIN-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 235000003899 Brassica oleracea var acephala Nutrition 0.000 description 1
- 235000012905 Brassica oleracea var viridis Nutrition 0.000 description 1
- IFCRTUXRONMDOY-UHFFFAOYSA-N C=C.Cl.Cl.Cl.Cl Chemical compound C=C.Cl.Cl.Cl.Cl IFCRTUXRONMDOY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004716 Ethylene/acrylic acid copolymer Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 235000000177 Indigofera tinctoria Nutrition 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- ZTWQZJLUUZHJGS-UHFFFAOYSA-N Vat Yellow 4 Chemical compound C12=CC=CC=C2C(=O)C2=CC=C3C4=CC=CC=C4C(=O)C4=C3C2=C1C=C4 ZTWQZJLUUZHJGS-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 229940097275 indigo Drugs 0.000 description 1
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- VPKVQYMSVYDZPL-UHFFFAOYSA-N n,n-diethyl-4-[2-(2-phenyl-1,3-dihydropyrazol-5-yl)ethenyl]aniline Chemical class C1=CC(N(CC)CC)=CC=C1C=CC1=CCN(C=2C=CC=CC=2)N1 VPKVQYMSVYDZPL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- LLBIOIRWAYBCKK-UHFFFAOYSA-N pyranthrene-8,16-dione Chemical compound C12=CC=CC=C2C(=O)C2=CC=C3C=C4C5=CC=CC=C5C(=O)C5=C4C4=C3C2=C1C=C4C=C5 LLBIOIRWAYBCKK-UHFFFAOYSA-N 0.000 description 1
- WVIICGIFSIBFOG-UHFFFAOYSA-N pyrylium Chemical compound C1=CC=[O+]C=C1 WVIICGIFSIBFOG-UHFFFAOYSA-N 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/14—Inert intermediate or cover layers for charge-receiving layers
- G03G5/147—Cover layers
- G03G5/14708—Cover layers comprising organic material
- G03G5/14713—Macromolecular material
- G03G5/14717—Macromolecular material obtained by reactions only involving carbon-to-carbon unsaturated bonds
- G03G5/14726—Halogenated polymers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/02—Charge-receiving layers
- G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
- G03G5/05—Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
- G03G5/0503—Inert supplements
- G03G5/051—Organic non-macromolecular compounds
- G03G5/0514—Organic non-macromolecular compounds not comprising cyclic groups
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G5/00—Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
- G03G5/14—Inert intermediate or cover layers for charge-receiving layers
- G03G5/147—Cover layers
- G03G5/14708—Cover layers comprising organic material
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Photoreceptors In Electrophotography (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は電子写真感光体に関し、より詳しくは表面層が
含フッ素樹脂粉体を含み、その下の感、光層が酸化防止
剤を含む電子写真感光体に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an electrophotographic photoreceptor, and more specifically, the present invention relates to an electrophotographic photoreceptor, and more specifically, a surface layer containing fluorine-containing resin powder, and an underlying photoreceptor layer containing an antioxidant. Related to electrophotographic photoreceptors.
電子写真感光体は、適用される電子写真グロｔスに応じ
た所定の感度、電気物性、光学特性をυ１１えているこ
とが要求され、更にくり返し使用される電子写真感光体
にあっては、その電子写真感光体の表面層、即ち支持体
より最も離隔する層にはコロナ帯電、トナー現像、紙へ
の転写、りＩＪ’ ｉング処理などの電気的、機械的
外力が直接に加えられるため、それらに対する耐久性が
要求される。Electrophotographic photoreceptors are required to have specified sensitivity, electrical properties, and optical properties according to the electrophotographic gloss to which they are applied, and furthermore, for electrophotographic photoreceptors that are used repeatedly, Electrical and mechanical external forces such as corona charging, toner development, transfer to paper, and IJ'ing processing are directly applied to the surface layer of the electrophotographic photoreceptor, that is, the layer furthest from the support. Durability against them is required.
具体的には摺擦による表面の摩耗やキズの発生、また高
湿下においてコロナ帯電時に発生するオゾンによる表面
の劣化等に対する耐久性が要求されている。さらにトナ
ー現像、クリーニングのくり返しによる表面層へのトナ
ー付着という問題もあり、これに対しては表面層のクリ
ーニング性を向上させることが求められている。上記の
ような表面層に要求される緒特性を満足させるために種
々の方法が検討されており、その中でも含フッ素樹脂粉
体を分散させた樹脂層を電子写真感光体の表面に設ける
ことが特に効果的である。Specifically, durability is required against surface wear and scratches due to rubbing, and surface deterioration due to ozone generated during corona charging under high humidity. Furthermore, there is a problem of toner adhesion to the surface layer due to repeated toner development and cleaning, and to solve this problem, it is required to improve the cleaning properties of the surface layer. Various methods have been studied to satisfy the above-mentioned properties required for the surface layer, and among them, it is possible to provide a resin layer in which fluorine-containing resin powder is dispersed on the surface of the electrophotographic photoreceptor. Particularly effective.
含フッ素樹脂粉体を分散させた樹脂層を電子写真感光体
の表面に設けることにより、キズ、表面クリーニング性
、摩耗等における耐久性が向上し、又電子写真感光体表
面の撥水性、離型性が向上するので高湿下での表面劣化
の防止に対しても有効である。By providing a resin layer in which fluorine-containing resin powder is dispersed on the surface of the electrophotographic photoreceptor, durability against scratches, surface cleaning, abrasion, etc. is improved, and water repellency and mold release of the surface of the electrophotographic photoreceptor are improved. It is also effective in preventing surface deterioration under high humidity conditions.
一方、電子写真感光体は、その適用される電子写真プロ
セスに従がって使用される際に、そのプロセスから受け
る物理的な衝激の他に、くり返し露光による疲労を受け
、あるいはコロナ放電により生成したオゾンや窒素酸化
物等にさらされている。特にオゾンや窒素酸化物は電子
写真感光体表面の電荷輸送材料に直接化学的に作用して
表面の抵抗力を低下させ、画像に影響を与える。これを
防止する為には、酸化電位の高い電荷輸送材料を用いて
、前記のオゾンや窒素酸化物と反応しにくいようにして
やることが効果的である。On the other hand, when an electrophotographic photoreceptor is used in accordance with the electrophotographic process to which it is applied, in addition to the physical shock it receives from the process, it is also subject to fatigue due to repeated exposure or due to corona discharge. Exposed to generated ozone and nitrogen oxides. In particular, ozone and nitrogen oxides directly chemically act on the charge transport material on the surface of the electrophotographic photoreceptor, lowering the resistance of the surface and affecting images. In order to prevent this, it is effective to use a charge transport material with a high oxidation potential to make it difficult to react with the ozone and nitrogen oxides.
しかし、特に窒素酸化物について言うならば、ガス状態
で電子写真感光体に作用するほかに、空気中の水分と結
合して硝酸の形態で電子写真感光体に作用する。However, especially regarding nitrogen oxides, in addition to acting on the electrophotographic photoreceptor in a gaseous state, it also acts on the electrophotographic photoreceptor in the form of nitric acid when combined with moisture in the air.
特にコロナ帯電器付近においては硝酸の発生量が多く、
これがコロナ帯電器に付着し、機械を長時間休止してい
る間に電子写真感光体上に移動し、さらに電子写真感光
体内部に進入し、支持体まで達するためこの帯電器下の
部分では帯電能の低下や感度変化を起こし、他の部分と
は異なる特性を持ってしまうという現象を引き起こして
いた。Especially near the corona charger, a large amount of nitric acid is generated.
This adheres to the corona charger, moves onto the electrophotographic photoreceptor while the machine is stopped for a long time, enters the electrophotographic photoreceptor, and reaches the support, so the area under the charger becomes electrically charged. This caused a decrease in performance, a change in sensitivity, and a phenomenon in which the parts had different characteristics from those of other parts.
これらの現象が生じないようにするために従来から表面
層中に酸化防止剤を添加して電子写真感光体内部に侵入
してくるオゾンあるいは硝酸等を不活性化させる検討が
なされてきており、良い効果をあげてきた。In order to prevent these phenomena from occurring, studies have been made to add antioxidants to the surface layer to inactivate ozone, nitric acid, etc. that enter the electrophotographic photoreceptor. It has had good effects.
前記二種類の技術を組み合わせるならば、機械的特性、
表面潤滑性、耐湿性に優れた電子写真感光体ができあが
るはずである。゛しかし現実には必ずしも良いものがで
きるとは限らない。なぜならば、ここで取りあげている
含フッ素樹脂粉体はバインダー樹脂中に分散させる際に
極めて分散性が悪く、均一に分散させる為には分散助剤
として界面活性剤等を使用することがほぼ不可欠である
といりて良い。If the above two types of technologies are combined, mechanical properties,
An electrophotographic photoreceptor with excellent surface lubricity and moisture resistance should be completed. ``However, in reality, it is not always possible to produce something good. This is because the fluororesin powder discussed here has extremely poor dispersibility when dispersed in a binder resin, and it is almost essential to use a surfactant as a dispersion aid to ensure uniform dispersion. It is good to say that it is.
ところが電子写真感光体の同一層内に、この界面活性剤
と、酸化防止剤の両者が混在する場合にはそれらの相互
作用により電子写真感光体の電子写真特性に悪影響を及
ぼして、例えば、感度の低下、残留電位の増加、耐久に
よる態位変動量の増加等を引き起こす。However, when both a surfactant and an antioxidant coexist in the same layer of an electrophotographic photoreceptor, their interaction adversely affects the electrophotographic properties of the electrophotographic photoreceptor, resulting in a decrease in sensitivity, for example. This causes a decrease in energy consumption, an increase in residual potential, and an increase in posture fluctuation due to durability.
本発明の目的は、上記の欠点を克服し、くり返し使用の
際の摺擦による表面の摩耗やキズの発生に対する耐久性
、耐湿性を有し、かつ前記の硝酸等に起因する部分的な
帯電能ムラ、感度ムラによる画像ムラを生じることのな
い電子写真感光体を提供することである。It is an object of the present invention to overcome the above-mentioned drawbacks, to have durability and moisture resistance against surface abrasion and scratches caused by rubbing during repeated use, and to be able to resist partial electrification caused by the above-mentioned nitric acid, etc. An object of the present invention is to provide an electrophotographic photoreceptor that does not cause image unevenness due to unevenness in performance or unevenness in sensitivity.
また本発明の他の目的は、くり返し電子写真プロセスに
おいて高品位で、特に高感度の電子写真感光体を提供す
ることである。Another object of the present invention is to provide an electrophotographic photoreceptor with high quality and particularly high sensitivity in repeated electrophotographic processes.
本発明では、このような目的に従がって検討を重ねた結
果、含フッ素樹脂粉体を含有するが酸化防止剤を含有し
ない表面層と、サルファイド系酸化防止剤を含有する次
層との積層構造から成る電子写真感光体を提供すること
により前記課題のｙμ決が可能となった。In the present invention, as a result of repeated studies in accordance with these objectives, the surface layer containing fluorine-containing resin powder but no antioxidant, and the next layer containing a sulfide antioxidant. By providing an electrophotographic photoreceptor having a laminated structure, it has become possible to solve the above problem.
即ち本発明は導電性支持体、感光層及び表面層を有する
電子写真感光体であって、該表面層がバインダー及びそ
の中に分散した含フッ素樹脂粉体を含むが酸化防止剤を
含まず、また積層型感光層の該表面層と接する側の層又
は単層型感光層がサルファイド系酸化防止剤を含む電子
写真感光体である。That is, the present invention provides an electrophotographic photoreceptor having a conductive support, a photosensitive layer, and a surface layer, wherein the surface layer contains a binder and fluorine-containing resin powder dispersed therein, but does not contain an antioxidant; Further, the electrophotographic photoreceptor is one in which the layer on the side of the laminated photosensitive layer in contact with the surface layer or the single layer photosensitive layer contains a sulfide antioxidant.
本発明においては含フッ素樹脂粉体として四フッ化エチ
レン、三フッ化塩化エチレン、エチレン・六フッ化プロ
ピレン、フッ化ビニル、フッ化ピ二リデン、ニフッ化二
塩化エチレン、トリフルオロプロピルメチルジクロルシ
ラン等の重合体、又はとれらの共重合体、あるいはこれ
らと塩化ビニルとの共重合体の樹脂粉体を適宜用いるこ
とができ、特に、四フッ化エチレン樹脂、フッ化ビニリ
デン樹脂が好ましい。樹脂の分子量や粉体の粒径は形成
する塗膜の均一性に影響を与えない範囲において選択さ
れる。具体的には平均粒径２μ以下、好ましくは１μ以
下である。In the present invention, fluorine-containing resin powders include tetrafluoroethylene, trifluorochloroethylene, ethylene/hexafluoropropylene, vinyl fluoride, pynylidene fluoride, ethylene dichloride dichloride, and trifluoropropylmethyl dichloride. Resin powders of polymers such as silane, copolymers thereof, or copolymers of these and vinyl chloride can be used as appropriate, and tetrafluoroethylene resins and vinylidene fluoride resins are particularly preferred. The molecular weight of the resin and the particle size of the powder are selected within a range that does not affect the uniformity of the coating film formed. Specifically, the average particle diameter is 2 μ or less, preferably 1 μ or less.
分散される含フッ素樹脂粉体の含有率は適当には表面層
の全固形分基準で１〜５０重量％である。The content of the dispersed fluororesin powder is suitably 1 to 50% by weight based on the total solid content of the surface layer.
含有率が１チより少ない場合は十分な効果が得られず、
又５０％を越える場合は電子写真特性に悪影響が出る。If the content is less than 1 t, sufficient effect will not be obtained,
If it exceeds 50%, electrophotographic properties will be adversely affected.
分散に用いるバインダー樹脂は成膜性のある高分子であ
ればいかなるものでもよいが、単独で用いてもある程度
の硬さを有すること、中ヤリア輸送を妨害しないこと等
の点から、ポリメタクリル酸エステル、デリカーデネー
ト、ボリアリレート、ポリエステル、ポリサルホン、塩
化ビニル・酢酸ビニル共重合体、−リスチレン等が好ま
しい。The binder resin used for dispersion may be any polymer as long as it has film-forming properties, but polymethacrylic acid is used because it has a certain degree of hardness even when used alone and does not interfere with media transport. Preferred are esters, delicadenates, polyarylates, polyesters, polysulfones, vinyl chloride/vinyl acetate copolymers, -ristyrene, and the like.
との含フッ素樹脂粉体をバインダー中に分散させた表面
層は必ずしも保護層としてだけ扱う必要はない。すなわ
ちこの表面層は電荷輸送材料を含有して電荷輸送層の一
部として、または電荷発生材料を含有して電荷発生層の
一部として機能することが可能であり、この表面層のす
ぐ下の電荷輸送層又は電荷発生層と同じ電荷輸送材料／
バインダーの比率又は電荷発生材料／バインダーの比率
とすることもできる。含有させる電荷輸送材料又は電荷
発生材料の量は電子写真感光体の性能によって適宜選択
することができる。表面層に電荷輸送材料又は電荷発生
材料を含有させた場合でも含フッ素樹脂粉体の効果は十
分に発揮される。The surface layer made of fluororesin powder dispersed in a binder does not necessarily need to be treated only as a protective layer. That is, this surface layer can contain a charge transport material and function as part of the charge transport layer, or it can contain a charge generation material and function as part of the charge generation layer, and the surface layer can contain a charge transport material and function as part of the charge generation layer. Same charge transport material as the charge transport layer or charge generation layer/
It can also be a binder ratio or a charge generating material/binder ratio. The amount of charge transporting material or charge generating material to be included can be appropriately selected depending on the performance of the electrophotographic photoreceptor. Even when the surface layer contains a charge transporting material or a charge generating material, the effect of the fluororesin powder is fully exhibited.
本発明の電子写真感光体においては、感光層は単層型で
あってもよく、また電荷発生層と電荷輸送層に機能分離
した積層型であってもよい。また積層型の場合には導電
性支持体、電荷発生層、電荷輸送層及び表面層がこの順
序で積層されていても、あるいは電荷発生層と電荷輸送
層の順序が逆になっていてもよい。In the electrophotographic photoreceptor of the present invention, the photosensitive layer may be of a single-layer type, or may be of a laminated type with functions separated into a charge generation layer and a charge transport layer. In the case of a laminated type, the conductive support, the charge generation layer, the charge transport layer, and the surface layer may be laminated in this order, or the order of the charge generation layer and the charge transport layer may be reversed. .
本発明においてはサルファイド系酸化防止剤は。In the present invention, sulfide antioxidants are.
感光層が単層型の場合には感光層全体に含有され。When the photosensitive layer is a single layer type, it is contained in the entire photosensitive layer.
積ノー型の場合には表面層と接する側の層、例えば導電
性支持体、電荷発生層、電荷輸送層、表面層の順序で積
層されている時には電荷輸送層中に含有される。しかし
電荷輸送層及び電荷発生層の両方に含有されていてもよ
い。In the case of a stacked type, the layer in contact with the surface layer, for example, when the conductive support, charge generation layer, charge transport layer, and surface layer are laminated in this order, it is contained in the charge transport layer. However, it may be contained in both the charge transport layer and the charge generation layer.
サルファイド系酸化防止剤の添加量は添加される層中の
電荷輸送材料に基づいて０．１〜１０モルチであること
が好ましい。０．１モルチより少ない場合は十分な効果
が得られず、１０モルチを越える場合には電子写真特性
に悪影響を及ぼす。The amount of the sulfide antioxidant added is preferably 0.1 to 10 molty based on the charge transport material in the layer to which it is added. If it is less than 0.1 molty, sufficient effects cannot be obtained, and if it exceeds 10 molty, it will adversely affect electrophotographic properties.
本発明で用いることのできるサルファイド系酸化防止剤
としては次にあげるものがある：本発明の電子写真感光
体を製造する場合、導電性支持体としては導電性を有す
るものであれば何れのものでもよく、例えばアルミニウ
ム、ステンレスなどの金属の、あるいは導電性物質を単
独で又は適当なバインダー樹脂と共に、塗布して導電層
を設けたグラスチック、紙などの円筒状シリンダーまた
はフィルムが用いられる。これらの導電性支持体の上に
はバリヤー機能と下引機能をもつ下引層（接着層）を設
けることもできる。下引層は感光層の接着性改良、塗工
性改良、支持体の保護、支持体上の欠陥の被覆、基体か
らの電荷注入性改良、感光層の電気的破壊に対する保護
などのために形成することができる。Sulfide antioxidants that can be used in the present invention include the following: When producing the electrophotographic photoreceptor of the present invention, any conductive support can be used as long as it has conductivity. For example, a cylindrical cylinder or film made of metal such as aluminum or stainless steel, or made of glass, paper, etc., coated with a conductive material alone or together with a suitable binder resin to provide a conductive layer can be used. A subbing layer (adhesive layer) having a barrier function and a subbing function can also be provided on these conductive supports. The undercoat layer is formed to improve adhesion of the photosensitive layer, improve coating properties, protect the support, cover defects on the support, improve charge injection from the substrate, protect the photosensitive layer from electrical breakdown, etc. can do.
下引層の材料としては、ポリビニルアルコール、ｙ！”
）−Ｎ−ヒニルイミダゾール、？リエチレンオキシト″
＋エチルセルロース、メチルセルロース、エチレン・ア
クリル酸コポリマー カゼイン、？リアミド、共重合ナ
イロン、ニカワ、ゼラチン等が知られている。これらは
それぞれに適した溶剤に溶解されて、支持体上に塗布さ
れる。その膜厚は０．２〜２．０μ程度である。The material for the undercoat layer is polyvinyl alcohol, y! ”
)-N-hinyl imidazole, ? Liethylene oxide
+ Ethyl cellulose, methyl cellulose, ethylene/acrylic acid copolymer casein, ? Lyamide, copolymerized nylon, glue, gelatin, etc. are known. These are each dissolved in a suitable solvent and applied onto a support. The film thickness is about 0.2 to 2.0 μm.
電荷発生材料としてはピリリウム系、チアピリリウム系
染料、フタロシアニン系顔料、アントアントロン顔料、
ジベンズピレンキノン顔料、ピラントロン顔料、トリス
アゾ顔料、ソスアゾ顔料、アゾ顔料、インジゴ顔料、キ
ナクリドン系顔料、非対称キノシアニン、キノシアニン
などを用いることができる。Charge-generating materials include pyrylium dyes, thiapyrylium dyes, phthalocyanine pigments, anthoanthrone pigments,
Dibenzpyrenequinone pigments, pyranthrone pigments, trisazo pigments, sosazo pigments, azo pigments, indigo pigments, quinacridone pigments, asymmetric quinocyanine, quinocyanine, and the like can be used.
電荷輸送物質としてはピレン、Ｎ−エチルカル”シーｋ
、Ｎ−イアｆロピルカルパソＡ／ ： Ｎ −メチル−
Ｎ−フェニルヒドラゾノ−３−メチリアン−９−エチル
カルバゾール、Ｎ、Ｎ−ゾブエニルヒドラジノー３−メ
チリアン−９−エチルカルバゾール、Ｎ、Ｎ−ジフェニ
ルヒドラゾノー３−メチリアン−１０−エチルフェノチ
アジン、Ｎ、Ｎ−ジフェニルヒドラジノー３−メチリア
ン−１０−エチルフェノキサシン、Ｐ−ジエチルアミノ
ベンズアルデヒドーＮ、Ｎ−ジフェニルヒドラゾノ、Ｐ
−ジエチルアミノベンズアルデヒド−Ｎ−α−すメチル
−Ｎ−７エニルヒドラゾン ｐ ＋ ヒロリゾノペンズ
アルデヒドーＮ、Ｎ−ジフェニルヒドラゾン、１．３．
３− ） ＩＪ メチルインドレニン−α−７ルア”
ヒトーＮ、Ｎ−ジフェニルヒドラゾン、Ｐ−ジエチルベ
ンズアルデヒド−３−メチルベンズチアゾリノン−２−
ヒト２シン等のヒドラゾン類：２，５−ビｘ（ｐ−ｐエ
チルアミノフェニル） −１，３，４−、ｔオキサジア
ゾール、１−フェニル−３−（Ｐ−ジエチルアミノスチ
リル）−５−（Ｐ−ジエチルアミンフェニル）ピラゾリ
ン、１−〔キノリル（２））−３−（Ｐ−ジエチルアミ
ノスチリル）−ｓ−（ｐ−ジエチルアミノフェニル）ピ
ラゾリン、１−〔ピリジル（２） ’ｌ −３−（ｐ−
ジエチルアミノスチリル）−５−（Ｐ−ジエチルアミノ
フェニル）ピラゾリン、１−〔６−メドキシーピリジル
（２）−３−（ｐ−ジエチルアミノスチリル）−５−（
Ｐ−ジエチルアミノフェニル）ピラゾリン、１−〔ピリ
ジル（３））−３−（Ｐ−ジエチルアミノスチリル）−
５−（Ｐ−ジエチルアミノフェニル）ピラゾリン、１−
〔レビジル（２） ） −３−（ｐ−ジエチルアミノス
チリル）−５−（Ｐ−ジエチルアミノフェニル）ピラゾ
リン、１−〔ピリジル（２） ） −３−（ｐ−ジエチ
ルアミノスチリル）−４−メチル−５−（Ｐ−ジエチル
アミノフェニル）ピラゾリン、１−〔ピリゾル（２）
） −３−（α−メチル−Ｐ−ジエチルアミノスチリル
）−５−（Ｐ−ジエチルアミノフェニル）ピラゾリン、
１−フェニル−３−（ｐ−ジエチルアミノスチリル）−
４−メチル−５−（Ｐ−−／エチルアミノフェニル）ピ
ラゾリン、１−７エニルー３−（α−ベンゾルーＰ−ジ
エチルアミノスチリル）−５−（Ｐ−ジエチルアミノフ
ェニル）ピラゾリン、スピロピラゾリン等のピラゾリン
類：２−（Ｐ−ジエチルアミノスチリル）−６−ノエチ
ルアミノペンズオキサゾール、２−（Ｐ−ジエチルアミ
ノフェニル）−４−（Ｐ−ジメチルアミノフェニル）−
５−（２−クロロフェニル）オキサゾール等のオキサゾ
ール系化合物；２−（Ｐ−ジエチルアミノスチリル）−
６−ジニチルアミノペンゾチアゾール等のチアゾール系
化合物；ビス（４−ジエチルアミノ−２−メチルフェニ
ル）−フェニルメタン等のトリアリールメタン系化合物
：１，１−ビス（４−Ｎ、Ｎ−ジエチルアミノ−２−メ
チルフェニル）へブタン、１，１，２．２−テトラキス
（４−Ｎ、Ｎ−ジメチルアミン−２−メチルフェニル）
エタン等のポリアリールアルカン類等を用いることがで
きる。Pyrene, N-ethylcal"C" is used as a charge transport material.
, N-iaflopylcarpatho A/: N-methyl-
N-phenylhydrazono-3-methylan-9-ethylcarbazole, N,N-zobuenylhydrazino-3-methylan-9-ethylcarbazole, N,N-diphenylhydrazono-3-methylan-10-ethylphenothiazine, N, N-diphenylhydrazino 3-methylian-10-ethylphenoxacin, P-diethylaminobenzaldehyde N, N-diphenylhydrazono, P
-diethylaminobenzaldehyde-N-α-sumethyl-N-7enylhydrazone p + hylorisonopenzaldehyde N,N-diphenylhydrazone, 1.3.
3-) IJ methylindolenine-α-7lua”
Human N,N-diphenylhydrazone, P-diethylbenzaldehyde-3-methylbenzthiazolinone-2-
Hydrazones such as human 2-syn: 2,5-bix(pp-ethylaminophenyl)-1,3,4-, t-oxadiazole, 1-phenyl-3-(P-diethylaminostyryl)-5- (P-diethylaminophenyl)pyrazoline, 1-[quinolyl(2))-3-(P-diethylaminostyryl)-s-(p-diethylaminophenyl)pyrazoline, 1-[pyridyl(2)'l -3-(p −
diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, 1-[6-medoxypyridyl(2)-3-(p-diethylaminostyryl)-5-(
P-diethylaminophenyl)pyrazoline, 1-[pyridyl(3))-3-(P-diethylaminostyryl)-
5-(P-diethylaminophenyl)pyrazoline, 1-
[Levidyl (2)) -3-(p-diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, 1-[pyridyl (2)) -3-(p-diethylaminostyryl)-4-methyl-5- (P-diethylaminophenyl)pyrazoline, 1-[pyrisol (2)
) -3-(α-methyl-P-diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline,
1-phenyl-3-(p-diethylaminostyryl)-
Pyrazolines such as 4-methyl-5-(P--/ethylaminophenyl)pyrazoline, 1-7enyl-3-(α-benzo-P-diethylaminostyryl)-5-(P-diethylaminophenyl)pyrazoline, and spiropyrazoline: 2 -(P-diethylaminostyryl)-6-noethylaminopenzoxazole, 2-(P-diethylaminophenyl)-4-(P-dimethylaminophenyl)-
Oxazole compounds such as 5-(2-chlorophenyl)oxazole; 2-(P-diethylaminostyryl)-
Thiazole compounds such as 6-dinithylaminopenzothiazole; triarylmethane compounds such as bis(4-diethylamino-2-methylphenyl)-phenylmethane: 1,1-bis(4-N,N-diethylamino- 2-methylphenyl)hebutane, 1,1,2,2-tetrakis(4-N,N-dimethylamine-2-methylphenyl)
Polyarylalkane such as ethane can be used.
本発明においてフッ素樹脂粉体を樹脂溶液中に分散させ
る方法としては、ホモジナイザー、ケールミル、振動ゾ
ールミル、サンドミル、アトライター ロールミル等の
方法を用いることができる。In the present invention, methods such as a homogenizer, kale mill, vibrating sol mill, sand mill, and attritor roll mill can be used to disperse the fluororesin powder in the resin solution.
手順としては有機溶剤に・ぐイングー樹脂を溶解し、こ
れに含フッ素樹脂粉体及び分散助剤を必要量混合し、上
記の分散方法によ、って分散し、できあがった分散液中
に電荷輸送材料や電荷発生材料を混合すれば良い。電荷
発生材料が顔料である場合は別途電荷発生材料の分散条
件にあわせて電荷発生材料のみの分散液を作成し、その
後に含フッ素樹脂粉体の分散液と混合すれば良く、また
条件が許すのであればこの電荷発生材料を含フッ素樹脂
粉体と同時に分散させても良い。The procedure is to dissolve Guingu resin in an organic solvent, mix the required amount of fluororesin powder and dispersion aid, and disperse using the above dispersion method. What is necessary is to mix a transport material and a charge generation material. If the charge-generating material is a pigment, it is sufficient to separately prepare a dispersion of only the charge-generating material according to the dispersion conditions of the charge-generating material, and then mix it with a dispersion of fluorine-containing resin powder, as conditions permit. If so, this charge generating material may be dispersed simultaneously with the fluororesin powder.
本発明の電子写真感光体を製造する際に、各層を塗布す
る方法としては例えば浸漬コーティング法、スプレーコ
ーティング法、スピンナーコーティング法、ビードコー
ティング法、ブレードコーティング法、カーテンコーテ
ィング法等のコーティング法を用いることができる。こ
こで特にフッ素樹脂粉体を分散させた表面層を塗工する
際に、その下の層とバインダーが同系樹脂の場合又は同
系でなくても一方に使用している溶剤が他方を溶解する
ような場合は、浸漬コーティング法等は使用できない可
能性があシ、その場合にはスプレーコーティング法等が
適している。表面層の塗工乾燥後の膜厚は目的に応じて
適当な厚さとすることができる。特に電荷輸送材料又は
電荷発生材料を含有する系においては表面層がそれぞれ
電荷輸送層又は電荷発生層の働きもするため、一般の保
護層等と比較して、厚く塗工しても電子写真特性を劣化
させることはない。When manufacturing the electrophotographic photoreceptor of the present invention, coating methods such as dip coating, spray coating, spinner coating, bead coating, blade coating, and curtain coating are used to coat each layer. be able to. Especially when coating a surface layer in which fluororesin powder is dispersed, if the layer below and the binder are of the same type of resin, or even if they are not of the same type, the solvent used for one will dissolve the other. In such cases, it may not be possible to use dip coating methods, in which case spray coating methods are suitable. The thickness of the surface layer after coating and drying can be adjusted to an appropriate thickness depending on the purpose. In particular, in systems containing a charge transport material or a charge generation material, the surface layer also functions as a charge transport layer or a charge generation layer, respectively, so compared to a general protective layer, it has electrophotographic properties even when coated thickly. will not deteriorate.
以下実施例を示す。Examples are shown below.
実施例１
直径８０ｗφ、長さ３６０ｍのアルミニウムシリンダー
支持体上に、６−６．６−６．１０−１．２の四元系ポ
リアミド共重合体樹脂の５％メタノール溶液を浸漬法で
塗布して０．５μ厚の下引き層を設けた。Example 1 A 5% methanol solution of a quaternary polyamide copolymer resin of 6-6.6-6.10-1.2 was applied by dipping onto an aluminum cylinder support with a diameter of 80 wφ and a length of 360 m. A subbing layer with a thickness of 0.5 μm was provided.
次に構造式
次に式
の電荷発生材料１２部、ポリビニルベンプール樹脂６部
及びシクロヘキサノン６０部、１１φがラスビーズを用
い念サンドミル装置で２０時間分散させた。この分散液
にテトラヒドロフラン１２０部を加えて混合し、この混
合液を下引き層上に塗布して０．２μの電荷発生層を形
成した。Next, 12 parts of a charge generating material having the structural formula: 6 parts of polyvinyl benpool resin, 60 parts of cyclohexanone, and 11 φ were dispersed in a sand mill apparatus using lath beads for 20 hours. 120 parts of tetrahydrofuran was added to this dispersion and mixed, and this mixed solution was applied onto the undercoat layer to form a 0.2 μm charge generation layer.
で示される電荷輸送材料１０部及びビスフェノル２型ぽ
リカーボネート樹脂１０部をモノクロルベンゼンとジク
ロルメタンとの混合溶媒７０部に溶解し、更にこれに前
記の表中のＡ Ｉのサルファイド系酸化防止剤を電荷輸
送材基準で１モルチ量添加溶解させた。10 parts of the charge transport material shown by and 10 parts of bisphenol type 2 polycarbonate resin were dissolved in 70 parts of a mixed solvent of monochlorobenzene and dichloromethane, and a sulfide antioxidant of A I in the above table was added to this. An amount of 1 molty based on the charge transport material was added and dissolved.
この溶解液を電荷発生層上に浸漬塗布（てよシ塗布し、
１２０℃で熱風乾燥して１７μ厚の電荷輸送層を形成し
た。This solution is applied by dip coating on the charge generation layer.
A charge transport layer having a thickness of 17 μm was formed by drying with hot air at 120° C.
次に、平均−欠粒径０．３μの低分子量ポリ四フッ化エ
チレン粉体５部、分散助剤としてフルオロアルキレート
を側鎖に持つフッ素系のくシ展ダラフトポリマ−０，５
部、及びバインダーとして数平均分子量的２００００の
ビスフェノール２型ｎｆ ’）カーボネート５部をモノ
クロルベンゼン３５部と混合し、？−ルミルにて５０時
間分散させた。この分散液に、前記の電荷輸送材料５２
部、ポリカーボ、ｉ−ト５０部、モノクロルベンゼン７
００部、及びジクロルメタン１００部を加え、その生成
液をエアスプレー塗布装置にて電荷輸送層上に塗布し、
１２０℃にて乾燥して５μの表面層を形成した。この電
子写真感光体を試料１とする。Next, 5 parts of low molecular weight polytetrafluoroethylene powder with an average particle diameter of 0.3 μm and 0.5 parts of a fluorine-based comb-extended duraft polymer having fluoroalkylate in the side chain as a dispersion aid were added.
and 5 parts of bisphenol type 2 nf') carbonate having a number average molecular weight of 20,000 as a binder are mixed with 35 parts of monochlorobenzene, and ? -Dispersed for 50 hours using Lumil. The charge transport material 52 described above is added to this dispersion.
parts, polycarbon, i-to 50 parts, monochlorobenzene 7 parts
00 parts and 100 parts of dichloromethane were added, and the resulting solution was applied onto the charge transport layer using an air spray coating device.
It was dried at 120° C. to form a 5 μm surface layer. This electrophotographic photoreceptor will be referred to as Sample 1.
また、表面層を塗布せずに電荷輸送層を２２μ厚とした
ものを試料２、試料１の表面層塗工液を調合する際に後
から加える溶剤の量をモノクロルベンゼン３００部、ゾ
クロルメタン５０部として調合し、さらにこれに加えた
電荷輸送材料の１モル％量の前記表中のＡ１のサルファ
イド係酸化防止剤を加えて溶解し、この分散調合液を電
荷発生層上に塗布し、１２０℃で乾燥させて２２μ厚の
電荷輸送層としたものを試料３、試料３において電荷輸
送層に酸化防止剤を添加しなかったものを試料４とする
。In addition, sample 2 was prepared with a charge transport layer having a thickness of 22 μm without coating the surface layer, and the amount of solvents added later when preparing the surface layer coating solution of sample 1 was 300 parts of monochlorobenzene and 50 parts of zochloromethane. Further, the sulfide antioxidant A1 in the above table was added and dissolved in an amount of 1 mol% of the charge transport material added, and this dispersion mixture was applied on the charge generation layer and heated at 120°C. A charge transport layer having a thickness of 22 μm was obtained by drying the charge transport layer, and a sample 4 was obtained by adding no antioxidant to the charge transport layer.
これらの試料１〜４を乾式普通砥複写機に設置し、暗部
電位６５０Ｖ明部亀位１３０Ｖとなるように条件を設定
し、ｅコロナ帯電、画像露光、乾式トナー現像、普通舐
へのトナー転写、ゴムブレードによるクリーニングから
なる′１コ子写真プロセスを実施し、３００００枚耐久
後の画像の評価を行なった。結果は次の通りであった。These samples 1 to 4 were installed in a dry type normal abrasive copying machine, and conditions were set so that the dark area potential was 650V and the bright area potential was 130V. A '1-copy photographic process consisting of cleaning with a rubber blade was carried out, and the images were evaluated after being used for 30,000 sheets. The results were as follows.
次に、耐久使用後のこれらの電子写真感光体を複写機中
で２４時間放置した後再び画像の評価を行なったところ
、試料１〜３については放置前と同様の画像が得られた
が、試料４においてはコロナ帯電器に相対する部分が見
かけ上感度が上がり、ハーフトーン画像を出し九ところ
、その部分が帯状に白くなってしまった。Next, after long-term use, these electrophotographic photoreceptors were left in a copying machine for 24 hours and the images were evaluated again. As for Samples 1 to 3, images similar to those before being left were obtained, but In sample 4, the sensitivity apparently increased in the area facing the corona charger, producing a halftone image, but that area turned white in the form of a band.
すなわち３００００枚耐久後にキズ、白地部分カプリ及
び帯状の白ヌケ状態のいずれも発生しなかったのは、試
料１のみであった。That is, Sample 1 was the only sample in which no scratches, no white portions, and no band-like white spots occurred after running 30,000 sheets.
実施例２
実施例１の方法において、含フッ素樹脂粉体としてポリ
フッ化ビニリデン粉体を用い、分散助剤としてパーフル
オロアルキル基部分とアクリル樹脂とからなるフッ素系
ブロックポリマーを用い、酸化防止剤として前記表中の
Ａ７のサルファイド系酸化防止剤を用いた場合にも同様
の結果が得られた。Example 2 In the method of Example 1, polyvinylidene fluoride powder was used as the fluororesin powder, a fluorine-based block polymer consisting of a perfluoroalkyl group moiety and an acrylic resin was used as the dispersion aid, and as the antioxidant Similar results were obtained when the sulfide antioxidant A7 in the table above was used.
実施例３
８０ｗφ×３６０のアルミニウムシリンダーを支持体と
し、これに実施例１で用いた？リアミド樹脂の５チメタ
ノール溶液を浸漬塗布して１μの下引層を設けた。Example 3 An 80 wφ x 360 aluminum cylinder was used as a support in Example 1. A 1 μm subbing layer was provided by dip coating a 5-timemethanol solution of Lyamide resin.
次に構造式
で示される電荷発生材料１部及びビスフェノール２型ポ
リカーデネート１０部をモノクロルベンゼン６０部に加
え、この混合物をステンレス製ボールミルにて７２時間
分散させ、さらにこれに実施例１で用いた電荷輸送材料
６部を加えて溶解した。Next, 1 part of the charge generating material represented by the structural formula and 10 parts of bisphenol 2 type polycarbonate were added to 60 parts of monochlorobenzene, and this mixture was dispersed in a stainless steel ball mill for 72 hours. 6 parts of charge transport material was added and dissolved.
さらにこの溶液に前記表中ＡＩＯのサルファイド系酸化
防止剤を電荷輸送材基準で２．０モルチ添加した。この
溶液を下引き層上に浸漬塗布して１５μの感光層を設け
た。Furthermore, 2.0 molt of the sulfide antioxidant indicated by AIO in the table above was added to this solution based on the charge transport material. This solution was dip coated onto the undercoat layer to provide a 15 micron photosensitive layer.
次に酸化防止剤を添加しなかった以外はこの感光層塗工
液を作る方法と同じ方法及び同じ成分を用い、そしてス
テンレス製ボールミルで分散させる際に更にポリ四７ツ
化エチレン樹脂粉体４部及び分散助剤としてノーフルオ
ロアルキル基とスチレン樹脂とからなるフッ素系クシ型
グラフトポリマー０．４部を同時に加えて分散させ、電
荷輸送材料を含む分散液を作成した。この分散液に更忙
モノクロルベンゼンを加えて固、型分率１０％の溶液と
し、これをスプレー塗布装置にて感光層上に塗布し、１
２０℃で乾燥して５μの表面層を形成した。このように
して作成した電子写真感光体を試料５とする。Next, except that no antioxidant was added, the same method and the same ingredients as in the preparation of this photosensitive layer coating solution were used, and when dispersing with a stainless steel ball mill, polytetra7ethylene resin powder was added and 0.4 parts of a fluorine-based comb-shaped graft polymer consisting of a non-fluoroalkyl group and a styrene resin as a dispersion aid were simultaneously added and dispersed to prepare a dispersion containing a charge transporting material. A solid monochlorobenzene was added to this dispersion to form a solid solution with a type fraction of 10%, and this was applied onto the photosensitive layer using a spray coating device.
It was dried at 20° C. to form a 5 μm surface layer. The electrophotographic photoreceptor thus produced is designated as sample 5.
又感光層を設ける際に２０μ厚とし、表面層を設けない
ものを試料６、試料５に″おいて感光層中に酸化防止剤
を添加しなかった庵のを試料７とする。さらに感光層を
設ける際に感光層中にポリ四フフ化エチレン樹脂粉体と
酸化防止剤の両者を含有させたものを試料８とする。In addition, when providing the photosensitive layer, the thickness was 20 μm and no surface layer was provided, as sample 6, and sample 5'', in which no antioxidant was added to the photosensitive layer, was referred to as sample 7. Sample 8 is a photosensitive layer containing both a polytetrafluoroethylene resin powder and an antioxidant.
これらの試料５〜８の電子写真感光体を実施例１の場合
と同様に普通紙複写機に設置し、ｅコロナ帯電、画像露
光、乾式トナー現像、普通紙への転写、ゴムブレードに
よるクリーニング強露光による表面電位除去の工程によ
シ画像出し耐久試験を行なった。３００００枚後の画像
評価を下に示す。These electrophotographic photoreceptors of Samples 5 to 8 were placed in a plain paper copying machine in the same manner as in Example 1, and subjected to e-corona charging, image exposure, dry toner development, transfer to plain paper, and cleaning with a rubber blade. An image formation durability test was conducted using the process of removing the surface potential by exposure to light. The image evaluation after 30,000 sheets is shown below.
これらの感光体の強露光後の残留電位を測定したところ
次の通υであった。The residual potential of these photoreceptors after strong exposure was measured and was found to be as follows.
さらに実施例１と同様にこれらの電子写真感光体を４８
時間機械内に放置した後に再び画像出しを行なったとこ
ろ試料５，６．８については放置前と同様の画像が得ら
れたが、試料７に関してはコロナ帯電器と対応する部分
が、ハーフトーン画像において白く帯状になっていた。Furthermore, in the same manner as in Example 1, these electrophotographic photoreceptors were
When images were taken again after being left in the machine for a time, images similar to those before being left were obtained for samples 5 and 6.8, but for sample 7, the part corresponding to the corona charger was a halftone image. It was white and band-like.
実施例４
８０ＷＩφ、３６０＋ｍ長のアルミニウムシリンダー支
持体上に６−６．６−６．１０−１．２の四元素ポリア
ミド共重合体樹脂の５チメタノール溶液を浸漬法で塗布
して０．５μ厚の下引き層を設けた。Example 4 A 5-th methanol solution of a 6-6.6-6.10-1.2 four-element polyamide copolymer resin was applied by dipping onto a 80WIφ, 360+m long aluminum cylinder support to form a 0.5μ A thick undercoat layer was provided.
次に式
基準で１，５モルチの量の前記の表中のＡ８で示される
酸化防止剤をモノクロルベンゼンに溶解し、上記下引き
層上に浸漬塗布して１８μ厚の電荷輸送層を形成した。Next, an amount of 1.5 molty of the antioxidant represented by A8 in the above table based on the formula was dissolved in monochlorobenzene, and the solution was dip coated onto the undercoat layer to form a charge transport layer with a thickness of 18 μm. .
次に式
で示される電荷輸送材料１２部、ビスフェノール２型ポ
リカーゴネート１０部及び該電荷輸送材料で示される電
荷発生材料１０部及びビスフェノール２型Ｉリカーボネ
ート１０部をテトラヒドロ７ラン／シクロヘキサノン＝
１７１の混合溶媒Ｉｏ。Next, 12 parts of a charge transporting material represented by the formula, 10 parts of bisphenol 2 type polycargonate, 10 parts of a charge generating material represented by the charge transporting material, and 10 parts of bisphenol 2 type I recarbonate were added to tetrahydro7rane/cyclohexanone=
171 mixed solvent Io.
部に加え、サンドミルにて電荷発生材料の平均分散粒径
がＯ０１μ以下になるまで分散した。この分散液に前記
電荷輸送材料５部及び該電荷輸送材料基準で１．５モル
チの量の前記の表中の屋８の酸化防止剤を溶解し、溶解
後、スプレー塗布法にて電荷輸送層上に塗布して３μ厚
の電荷発生層を形成した。さらにポリ四フフ化エチレン
粉体２部、実施例１で用いたフッ素系グラフト？リマー
０．２部及びビスフェノール２型ボリカーデネート８部
をモノクロルベンゼン／ジクロルメタン＝７７３（７）
ｆｉ合溶媒１００部と混合し、ボールミルにて５０時間
分散した。この分散液をスプレー塗布法により電荷発生
層上に塗布して３μ厚の保護層を形成した。このように
して作成した感光体を試料９とする。さらに試料９の保
護層を有していないものを試料１０、また試料９におい
て電荷輸送層、電荷発生層中に酸化防止剤を含まないも
のを試料１１とした。これらの試料９〜１１に対してｅ
コロナ帯電、画像露光による潜像形成、乾式トナーによ
る現像、普通紙へのトナー転写、ウレタンプムブレード
によるクリーニング工程、強請光による残留電位の除去
の工程からなる電子写真プロセスにより１ｏｏｏｏ枚の
画像出し耐久を行ない耐久後の画像の評価及び電位の評
価を行なった。The charge generating material was then dispersed in a sand mill until the average dispersed particle size of the charge generating material became 001 μm or less. In this dispersion, 5 parts of the charge transporting material and 1.5 molti of the antioxidant listed in the table above, based on the charge transporting material, were dissolved, and after dissolving, a charge transporting layer was formed by spray coating. A charge generation layer having a thickness of 3 μm was formed by coating on top. Furthermore, 2 parts of polytetrafluoroethylene powder, the fluorine-based graft used in Example 1? 0.2 parts of reamer and 8 parts of bisphenol 2 type polycarbonate in monochlorobenzene/dichloromethane = 773 (7)
The mixture was mixed with 100 parts of fi mixed solvent and dispersed in a ball mill for 50 hours. This dispersion was applied onto the charge generation layer by a spray coating method to form a 3 μm thick protective layer. The photoreceptor thus produced is designated as sample 9. Furthermore, Sample 10 was Sample 9 which did not have the protective layer, and Sample 11 was Sample 9 which did not contain an antioxidant in the charge transport layer and charge generation layer. e for these samples 9-11
The electrophotographic process consists of corona charging, formation of a latent image by image exposure, development with dry toner, toner transfer to plain paper, cleaning process with a urethane blade, and removal of residual potential with forced light. The image and potential after durability were evaluated.
さらに１００００枚耐久後の試料９〜１１を２４時間機
械内に放置後再度画像出しを行ない／・−フトーン画像
の比較を行なったところ、試料１１において放置時コロ
ナ帯電器の下になっていた場所と対応する部分が帯電器
とほぼ同じ幅で白く帯状になっていた。これは帯電器に
付着していた硝酸が放置している間に感光体上に移動し
て支持体まで達したために白く帯状になりたものと考え
られる。Furthermore, after the 10,000-sheet durability test, Samples 9 to 11 were left in the machine for 24 hours and then imaged again. - When comparing the tone images, it was found that in Sample 11, the area that was under the corona charger when left was The corresponding part was a white band with approximately the same width as the charger. This is thought to be because the nitric acid adhering to the charger migrated onto the photoreceptor and reached the support while the charger was left standing, resulting in the white band-like appearance.
この結果から試料９の耐久性が優れていることがわかり
た。From this result, it was found that Sample 9 had excellent durability.
本発明の電子写真感光体は、以上に説明したように構成
されているので、機械的特性、表面潤滑性、耐湿性、耐
久性に優れている。Since the electrophotographic photoreceptor of the present invention is constructed as described above, it has excellent mechanical properties, surface lubricity, moisture resistance, and durability.
代理人 弁理士 山 下 積 平Agent Patent Attorney Sekihei Yamashita
Claims (1)
感光体であって、該表面層がバインダー及びその中に分
散した含フッ素樹脂粉体を含むが酸化防止剤を含まず、
また積層型感光層の該表面層と接する側の層又は単層型
感光層がサルファイド系酸化防止剤を含むことを特徴と
する電子写真感光体。1. An electrophotographic photoreceptor having a conductive support, a photosensitive layer and a surface layer, the surface layer containing a binder and fluororesin powder dispersed therein, but containing no antioxidant;
Further, an electrophotographic photoreceptor characterized in that a layer of the laminated photosensitive layer in contact with the surface layer or a single layer photosensitive layer contains a sulfide antioxidant.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20626388A JP2637494B2 (en) | 1988-08-22 | 1988-08-22 | Electrophotographic photoreceptor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20626388A JP2637494B2 (en) | 1988-08-22 | 1988-08-22 | Electrophotographic photoreceptor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0255363A true JPH0255363A (en) | 1990-02-23 |
| JP2637494B2 JP2637494B2 (en) | 1997-08-06 |
Family
ID=16520434
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20626388A Expired - Fee Related JP2637494B2 (en) | 1988-08-22 | 1988-08-22 | Electrophotographic photoreceptor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2637494B2 (en) |
-
1988
- 1988-08-22 JP JP20626388A patent/JP2637494B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2637494B2 (en) | 1997-08-06 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |