EP0324180B1 - Electrophotographical recording material - Google Patents
Electrophotographical recording material Download PDFInfo
- Publication number
- EP0324180B1 EP0324180B1 EP88121872A EP88121872A EP0324180B1 EP 0324180 B1 EP0324180 B1 EP 0324180B1 EP 88121872 A EP88121872 A EP 88121872A EP 88121872 A EP88121872 A EP 88121872A EP 0324180 B1 EP0324180 B1 EP 0324180B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- recording material
- polyvinylphenol
- layer
- photoconductive layer
- binder
- 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
- 239000000463 material Substances 0.000 title claims description 22
- 229920001665 Poly-4-vinylphenol Polymers 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 11
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- JESXATFQYMPTNL-UHFFFAOYSA-N 2-ethenylphenol Chemical group OC1=CC=CC=C1C=C JESXATFQYMPTNL-UHFFFAOYSA-N 0.000 description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- -1 Hydroxy, amino Chemical group 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- KETQAJRQOHHATG-UHFFFAOYSA-N 1,2-naphthoquinone Chemical compound C1=CC=C2C(=O)C(=O)C=CC2=C1 KETQAJRQOHHATG-UHFFFAOYSA-N 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LORKUZBPMQEQET-UHFFFAOYSA-M (2e)-1,3,3-trimethyl-2-[(2z)-2-(1-methyl-2-phenylindol-1-ium-3-ylidene)ethylidene]indole;chloride Chemical compound [Cl-].CC1(C)C2=CC=CC=C2N(C)\C1=C/C=C(C1=CC=CC=C1[N+]=1C)/C=1C1=CC=CC=C1 LORKUZBPMQEQET-UHFFFAOYSA-M 0.000 description 1
- ZOMLUNRKXJYKPD-UHFFFAOYSA-N 1,3,3-trimethyl-2-[2-(2-methylindol-3-ylidene)ethylidene]indole;hydrochloride Chemical compound [Cl-].C1=CC=C2C(C)(C)C(/C=C/C=3C4=CC=CC=C4NC=3C)=[N+](C)C2=C1 ZOMLUNRKXJYKPD-UHFFFAOYSA-N 0.000 description 1
- ZPANWZBSGMDWON-UHFFFAOYSA-N 1-[(2-hydroxynaphthalen-1-yl)methyl]naphthalen-2-ol Chemical compound C1=CC=C2C(CC3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 ZPANWZBSGMDWON-UHFFFAOYSA-N 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- HTQNYBBTZSBWKL-UHFFFAOYSA-N 2,3,4-trihydroxbenzophenone Chemical compound OC1=C(O)C(O)=CC=C1C(=O)C1=CC=CC=C1 HTQNYBBTZSBWKL-UHFFFAOYSA-N 0.000 description 1
- QAMCXJOYXRSXDU-UHFFFAOYSA-N 2,4-dimethoxy-n-[2-(1,3,3-trimethylindol-1-ium-2-yl)ethenyl]aniline;chloride Chemical compound [Cl-].COC1=CC(OC)=CC=C1NC=CC1=[N+](C)C2=CC=CC=C2C1(C)C QAMCXJOYXRSXDU-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- TZXATTMVGZDPHM-UHFFFAOYSA-N 2-[4-[(2-chloro-4-nitrophenyl)diazenyl]-n-ethylanilino]ethyl-trimethylazanium Chemical compound C1=CC(N(CC[N+](C)(C)C)CC)=CC=C1N=NC1=CC=C([N+]([O-])=O)C=C1Cl TZXATTMVGZDPHM-UHFFFAOYSA-N 0.000 description 1
- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 1
- ZRUOTKQBVMWMDK-UHFFFAOYSA-N 2-hydroxy-6-methylbenzaldehyde Chemical compound CC1=CC=CC(O)=C1C=O ZRUOTKQBVMWMDK-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- AXDJCCTWPBKUKL-UHFFFAOYSA-N 4-[(4-aminophenyl)-(4-imino-3-methylcyclohexa-2,5-dien-1-ylidene)methyl]aniline;hydron;chloride Chemical compound Cl.C1=CC(=N)C(C)=CC1=C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 AXDJCCTWPBKUKL-UHFFFAOYSA-N 0.000 description 1
- WTQZSMDDRMKJRI-UHFFFAOYSA-N 4-diazoniophenolate Chemical compound [O-]C1=CC=C([N+]#N)C=C1 WTQZSMDDRMKJRI-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DOLKKDJAWDNAMU-UHFFFAOYSA-N [4-[bis[4-(diethylamino)phenyl]methylidene]naphthalen-1-ylidene]-(4-methylphenyl)azanium;chloride Chemical compound [Cl-].C1=CC(N(CC)CC)=CC=C1C(C=1C=CC(=CC=1)N(CC)CC)=C(C=C1)C2=CC=CC=C2C1=[NH+]C1=CC=C(C)C=C1 DOLKKDJAWDNAMU-UHFFFAOYSA-N 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical group C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229920001727 cellulose butyrate Polymers 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 150000007978 oxazole derivatives Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- QBDSZLJBMIMQRS-UHFFFAOYSA-N p-Cumylphenol Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=CC=C1 QBDSZLJBMIMQRS-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical group 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- DNXIASIHZYFFRO-UHFFFAOYSA-N pyrazoline Chemical compound C1CN=NC1 DNXIASIHZYFFRO-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 150000005691 triesters Chemical class 0.000 description 1
- 150000001651 triphenylamine derivatives Chemical class 0.000 description 1
- JEVGKYBUANQAKG-UHFFFAOYSA-N victoria blue R Chemical compound [Cl-].C12=CC=CC=C2C(=[NH+]CC)C=CC1=C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 JEVGKYBUANQAKG-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- G03G5/02—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
- G03G5/0528—Macromolecular bonding materials
- G03G5/0532—Macromolecular bonding materials obtained by reactions only involving carbon-to-carbon unsatured bonds
- G03G5/0535—Polyolefins; Polystyrenes; Waxes
Definitions
- the invention relates to an electrophotographic recording material comprising an electrically conductive layer support, particularly suitable for the production of printing forms or printed circuits, and a photoconductive layer which contains organic photoconductor, phenolic resin as a binder, sensitizer and conventional additives.
- Recording material of the type described is known (DE-PS 25 26 720 corresponding to US-PS 4,063,948). It contains binders in the photoconductive layer which are soluble in aqueous or alkaline solvent systems. These include high molecular weight substances which carry alkali-solubilizing groups such as acid, anhydride, carboxyl, phenol, sulfonic acid, sulfonamide or sulfonimide groups. Binders with high acid numbers are particularly suitable. With good electrophotographic properties, however, the solubility of the layer is not yet adjusted to meet the highest requirements for reproducing small details.
- mixtures which contain photosensitive compounds such as o-quinonediazides and phenol condensation products such as novolak. After UV exposure, they experience a change in their solubility in an aqueous alkaline solution through the decomposition reaction of the photosensitive compounds.
- photosensitive compounds such as o-quinonediazides and phenol condensation products such as novolak.
- novolak component polymers or copolymers can be used which have vinylphenol units (DE-PS 23 22 230 corresponding to US-PS 3,869,292). Their use for electrophotographic purposes could not be deduced from this.
- the solution to this problem is based on a material of the type mentioned at the outset, and it is characterized in that an optionally substituted polyvinylphenol is present in the photoconductive layer as a binder.
- an optionally substituted polyvinylphenol is present in the photoconductive layer as a binder.
- a polyvinylphenol with a molecular weight between 1500 and 60,000 is present.
- the polyvinylphenol according to the invention is preferably a polymer of p-vinylphenol.
- the polyvinylphenol can preferably be halogen-substituted.
- chlorinated or brominated, in particular brominated, polymers are preferably used as halogenated vinylphenol polymers.
- copolymers of vinylphenols and other vinyl compounds such as styrene or acrylic acid esters can also be used.
- the homopolymers of p-vinylphenol are preferred.
- the halogen content of the halogenated polyvinylphenol is generally between 20 and 60, preferably 40-60 percent by weight.
- an o-quinonediazide is preferred in the photoconductive layer according to the invention an o-naphthoquinonediazide is present. It is hereby achieved that the photoconductive layer can be subjected to a post-exposure with UV light after the development (emphasis), which results in a particularly good solubility of the exposed areas during the stripping. The applied toner image can not be fixed. It was completely surprising that the addition of the light-sensitive substance does not adversely change the electrophotographic properties of the photoconductive layer and exhibits good charging behavior with little dark discharge. The recording material also has a good shelf life.
- the photoconductive layer can generally contain 5-40 percent by weight of o-quinonediazide. Preferably 15 to 25 percent by weight is present.
- the reproduction of fine picture elements, such as fine raster, is made possible in excellent quality.
- cellulose products such as special papers, cellulose hydrate, cellulose acetate
- plastics such as polyamides in film form or metal-coated films, are also suitable as layer supports.
- the surface refinement consists in mechanical or electrochemical roughening and, if appropriate, in a subsequent anodization and treatment with polyvinylphosphonic acid according to DE-OS 16 21 478 in accordance with US Pat. No. 4,153,461. This results in a higher print run and less susceptibility to oxidation.
- the organic photoconductors used for the photoconductive layer can be regarded as known in principle.
- Triphenylamine derivatives more highly condensed aromatic compounds, such as anthracene, benzo-fused heterocycles, such as benzothiazoles, pyrazoline, imidazole or triazole derivatives, oxdiazole derivatives such as 2,5-bis- (4'-diethylaminophenyl) oxdiazole-1,3,4), oxazole derivatives such as 2 -Phenyl-4- (2'-chlorophenyl) -5- (4 ⁇ -diethylaminophenyl) oxazole, further vinyl aromatic polymers such as polyvinylanthracene, polyacenaphthylene or polyvinyl carbazole and their copolymers, provided that they are compatible with polyvinylphenol and are suitable for differentiation in solubility.
- Preferred o-quinonediazides to be added are preferably o-naphthoquinonediazides, such as the di- or tri-esters of 2,3,4-trihydroxybenzophenone and naphthoquinone- (1,2) -diazide- (2) -5-or 4-sulfonic acid, esters , especially the diester of bis (2-hydroxynaphthyl) methane and naphthoquinone (1,2) diazide- (2) -5-sulfonic acid and esters from 2-phenyl-2- (4'-hydroxyphenyl) propane and naphthoquinone- (1,2) diazide- (2) -4 -sulfonic acid.
- Esters from hydroxyl-containing polymers and naphthoquinonediazide sulfonic acids are also suitable. Mixtures of the quinonediazide sulfonic acid esters mentioned can also be used with good success.
- Additional binders can also be contained in the photoconductive layer. Their addition serves to improve the film properties of the layer, its adhesive strength on the substrate and to increase the print run.
- Suitable binders are, for example, copolymers of styrene and maleic anhydride and their partial esterification products, polyvinyl acetates and copolymers with crotonic acid, phenolic resins, coumarone-indene resins, polyacrylates and copolymers with acrylic acid, rosin and its conversion products, maleate resins and phthalate resins.
- Electrophotographic recording material contains at least one sensitizing dye to expand the spectral sensitivity range.
- Suitable sensitizing dyes are, for example, malachite green (Color Index (CI) 42,000), crystal violet (CI 42 555), methyl violet (CI No. 42 535), night blue (CI No. 44 085), Victoria blue (CI No. 44 045 or No. 52595: 2), Rhodamine B, Rhodamine FB (CI No. 45 170), Capri Blue (CI No. 51 015), methylene blue (CI No. 52 015), Fuchsin (CI No. 42 500), Rose Bengal (CI No. 45 440), polymethine dyes such as Astrazonorange G (CI No.
- Astrazonorange R (CI 48 040), Astrazonyellow 3G (CI No. 48 055), Astrazon Yellow 5G (CI No. 48 065), Basic Yellow (CI No. 48 060), or Astrazon Red Violet (CI No. 48 013).
- the recording material according to the invention can contain leveling agents and plasticizers and / or between layer support and layer adhesion promoter as usual additives in the photoconductive layer.
- the presence of the additive does not significantly affect the interaction between the photoconductor and any o-quinonediazide present.
- the solution is applied to a 300 ⁇ m thick electrochemically roughened, anodized and pretreated with polyvinylphosphonic acid aluminum plate in such a way that that after evaporation of the solvent, a photoconductor layer with a thickness of 5.5 microns is formed.
- the light sensitivity of the layer is determined by charging it to -500 V and exposing it to white incandescent light until it is discharged to a residual voltage of -60 V.
- the energy density required for this is 320 ⁇ J / cm2.
- the photoconductor layer is charged with a corona to a surface potential of -500 V and exposed to images in a repro camera with 8 halogen lamps of 500 watts for 20 seconds.
- the resulting latent charge image is developed using a magnetic roller with a commercially available toner / carrier development mixture.
- the developed image is fixed with the help of heat radiation.
- the plate For conversion into a printing form, the plate is immersed for 2 minutes in a solution which is obtained by dissolving 20 g Na2SiO3 ⁇ 9H2O and 2 g NaOH in a mixture of 728 g water, 100 g n-propanol and 150 g ethylenediglycol.
- the layer parts not covered by the toner image are removed with a water jet with gentle rubbing.
- the printing form obtained is characterized by good raster and full tone reproduction.
- the plate prints well over 100,000 prints in a sheetfed offset press.
- the 50 g poly-p-vinylphenol resin is replaced by a novolak made from m-cresol and Formaldehyde (Alnovol® 429 K from HOECHST AG) gives a printing plate which requires an energy density of 520 ⁇ J / cm2 to discharge from -500 V to -60V and which has to be exposed in the repro camera for 30 seconds.
- the residence time in the stripping solution described above is 6 minutes.
- 35 g of 2-vinyl-4- (2'-chlorophenyl) -5- (4 ⁇ -diethylaminophenyl) oxazole and 40 g of polyvinylphenol are dissolved in a mixture of 160 ml of ethylene glycol monomethyl ether, 270 ml of tetrahydrofuran and 60 ml of butyl acetate and the solution is added 440 mg astrazone orange R (CI 48 040) and 350 mg astrazone red violet 3 RN (CI 48 013).
- the solution is used to coat an anodized aluminum plate which has been roughened by wet brushing and pretreated with polyvinylphosphonic acid in such a way that the photoconductor layer has a weight per unit area of 5.5 g / m 2.
- the plate is charged (-500 V) and exposed as described in Example 1, the exposure time being only 14 seconds in order to achieve a high-contrast, base-free image.
- the latent electrostatic image has been made visible with a dry developer and the toner image has been fixed by means of heat radiation
- the plate is passed through a commercially available stripping device to remove the non-image areas at a throughput speed of 1.1 m / min.
- the plate is charged to -500 V and imagewise exposed in a repro camera for 18 seconds with 10 halogen lamps of 600 watts each, developed and fixed in a known manner.
- the photoconductor layer is removed at the areas not covered by toner with the solution described in Example 1.
- the printing result achieved with the plate is excellent.
- a 300 ⁇ m thick, electrochemically roughened, anodized aluminum foil treated with polyvinylphosphonic acid is coated with the solution in such a way that a 5 ⁇ m thick photoconductor layer remains after the solvents have evaporated.
- the layer is charged to -500 V and exposed in a repro camera as described in Example 1.
- the toner image created after development is not fixed.
- the concrete plate is exposed for 2 minutes in a commercial automatic copying machine under a 5 KW metal halogen lamp (Violight).
- the toner image is then removed by rinsing with water and the plate is immersed for 1/2 minute in a stripping solution described in Example 1, rinsed with water and rubbed off.
- a printing form is obtained in which, in particular, a rastered image is reproduced better than with the plates described in Examples 1-3.
- An anodized aluminum foil is coated with the solution as described in Example 4.
- a toner image that is not fixed is produced on the coated film by electrophotography.
- the toner image is rinsed off with water.
- the plate is immersed in a decoater solution described in Example 1 for 30 seconds and rinsed with water while rubbing. You get a planographic printing form with very good image reproduction and high print run quality.
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Photoreceptors In Electrophotography (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
Description
Die Erfindung betrifft ein elektrophotographisches Aufzeichnungsmaterial aus einem elektrisch leitenden, insbesondere zur Herstellung von Druckformen oder gedruckten Schaltungen geeigneten Schichtträger und einer photoleitfähigen Schicht, die organischen Photoleiter, Phenolharz als Bindemittel, Sensibilisator und übliche Zusätze enthält.The invention relates to an electrophotographic recording material comprising an electrically conductive layer support, particularly suitable for the production of printing forms or printed circuits, and a photoconductive layer which contains organic photoconductor, phenolic resin as a binder, sensitizer and conventional additives.
Aufzeichnungsmaterial der beschriebenen Art ist bekannt (DE-PS 25 26 720 entsprechend US-PS 4,063,948). Es enthält in der photoleitfähigen Schicht Bindemittel, die in wäßrigen oder alkalischen Lösungsmittelsystemen löslich sind. Hierzu gehören hochmolekulare Substanzen, die alkalilöslich machende Gruppen, wie Säure, Anhydrid-, Carboxyl-, Phenol-, Sulfonsäure-, Sulfonamid- oder Sulfonimid-gruppen tragen. Bindemittel mit hohen Säurezahlen sind besonders geeignet. Bei guten elektrophotographischen Eigenschaften ist die Löslichkeit der Schicht jedoch noch nicht so eingestellt, daß sie höchsten Anforderungen nach Wiedergabe kleiner Details entspricht.Recording material of the type described is known (DE-PS 25 26 720 corresponding to US-PS 4,063,948). It contains binders in the photoconductive layer which are soluble in aqueous or alkaline solvent systems. These include high molecular weight substances which carry alkali-solubilizing groups such as acid, anhydride, carboxyl, phenol, sulfonic acid, sulfonamide or sulfonimide groups. Binders with high acid numbers are particularly suitable. With good electrophotographic properties, however, the solubility of the layer is not yet adjusted to meet the highest requirements for reproducing small details.
Es ist auch bekannt bei einem Verfahren zur Herstellung einer Druckform auf elektrophotographischem Wege für die photoleitfähige Schicht ein Material zu verwenden, das neben anorganischem oder organischem Photoleiter ein o-Chinondiazid enthält (DE-PS 14 47 008 entsprechend GB-PS 996 315). Als Bindemittel enthält die Schicht organisches Natur- oder Kunstharz, vorteilhaft eine Mischung aus Polyvinylacetat und m-Kresolformaldehyd-Novolak. Materialien dieser Art sind jedoch in ihrer Wechselwirkung aufeinander nicht ausreichend abgestimmt, so daß sich das Verfahren nicht durchsetzen konnte.It is also known in a method for producing a printing form by electrophotography to use a material for the photoconductive layer which contains an o-quinonediazide in addition to inorganic or organic photoconductor (DE-PS 14 47 008 corresponding to GB-PS 996 315). The layer contains organic as a binder Natural or synthetic resin, advantageously a mixture of polyvinyl acetate and m-cresol formaldehyde novolak. The interaction of materials of this type, however, is not sufficiently coordinated with one another, so that the process has not been able to establish itself.
Es ist ferner bekannt, substituierte Phenolharze als Bindemittel in photoleitfähigen Schichten für zum Druck geeignete elektrophotographische Aufzeichnungsmaterialien zu verwenden (DE-AS 29 04 183 entsprechend GB-PS 2,014,748). Die Harze werden durch Kondensation von Aldehyden oder Ketonen mit längerkettig substituierten Phenolen hergestellt. Aufgrund ihrer hydrophoben Beschaffenheit sind zusätzlich hydrophile Substituenten am Phenolkern wie z.B. Hydroxy-, Amino- oder Carboxy-Gruppen notwendig. Es zeigte sich jedoch, daß die Löslichkeit ungenügend und die anschließende Entschichtung nur bedingt und mit stark basischen Entschichtern möglich war.It is also known to use substituted phenolic resins as binders in photoconductive layers for electrophotographic recording materials suitable for printing (DE-AS 29 04 183 corresponding to GB-PS 2,014,748). The resins are produced by condensation of aldehydes or ketones with phenols substituted by longer chains. Due to their hydrophobic nature, there are additional hydrophilic substituents on the phenol core, e.g. Hydroxy, amino or carboxy groups are necessary. However, it was found that the solubility was insufficient and the subsequent stripping was only possible to a limited extent and with strongly basic strippers.
Es sind andererseits Gemische bekannt, die lichtempfindliche Verbindungen, wie o-Chinondiazide und Phenolkondensationsprodukte, wie Novolak enthalten. Sie erfahren nach UV-Belichtung eine Änderung ihrer Löslichkeit in einer wäßrig-alkalischen Lösung durch Zersetzungsreaktion der lichtempfindlichen Verbindungen. Anstelle der Novolakkomponente können Polymerisate oder Mischpolymerisate verwendet werden, die Vinylphenoleinheiten besitzen (DE-PS 23 22 230 entsprechend US-PS 3,869,292). Ihr Einsatz für elektrophotographische Zwecke war hieraus nicht zu entnehmen.On the other hand, mixtures are known which contain photosensitive compounds such as o-quinonediazides and phenol condensation products such as novolak. After UV exposure, they experience a change in their solubility in an aqueous alkaline solution through the decomposition reaction of the photosensitive compounds. Instead of the novolak component, polymers or copolymers can be used which have vinylphenol units (DE-PS 23 22 230 corresponding to US-PS 3,869,292). Their use for electrophotographic purposes could not be deduced from this.
Es ist auch bekannt in lichtempfindlichen Schichten, die für die Bestrahlung mit Elektronenstrahlen geeignet sind, Gemische von lichtempfindlichen Verbindungen mit Poly-(p-vinylphenol) als Bindemittel zu verwenden. In Form bromsubstituierter Verbindungen sind solche Gemische besonders für Vernetzungsreaktionen bei Bestrahlung und damit für negativ arbeitende lichtempfindliche Verfahren geeignet (IBM Technical Disclosure Bulletin, Band 23, Nr.2, Juli 1980, Seite 773, EP-PS 0 045 639).It is also known to use mixtures of photosensitive compounds with poly (p-vinylphenol) as a binder in photosensitive layers which are suitable for irradiation with electron beams. In the form of bromine-substituted compounds, such mixtures are particularly suitable for crosslinking reactions when irradiated and thus for negative-working photosensitive processes (IBM Technical Disclosure Bulletin, Volume 23, No. 2, July 1980, page 773, EP-PS 0 045 639).
Es war Aufgabe der Erfindung ein elektrophotographisches Aufzeichnungsmaterial zur Verfügung zu stellen, das höchsten Ansprüchen genügt, die bekannten Nachteile nicht besitzt, das bei einer großen Hellentladung und geringen Dunkelentladung mit Trocken- oder Flüssigentwickler durch Betonern entwickelt werden kann und das zur Herstellung von hochwertigen Druckformen mit umweltfreundlichen wäßrig-alkalischen Lösungen leicht entschichtet werden kann.It was an object of the invention to provide an electrophotographic recording material which meets the highest demands, does not have the known disadvantages, which can be developed by dryers or liquid developers by a developer with a large bright discharge and low dark discharge and which can be used to produce high-quality printing forms environmentally friendly aqueous alkaline solutions can be easily stripped.
Die Lösung dieser Aufgabe geht aus von einem Material der eingangs erwähnten Art, und sie ist dadurch gekennzeichnet, daß als Bindemittel ein gegebenenfalls substituiertes Polyvinylphenol in der photoleitfähigen Schicht vorhanden ist. Vorzugsweise ist ein Polyvinylphenol mit einem Molekulargewicht zwischen 1500 und 60 000 vorhanden. Bevorzugt ist das erfindungsgemäße Polyvinylphenol ein Polymerisat des p-Vinylphenols. Das Polyvinylphenol kann vorzugsweise halogensubstituiert sein.The solution to this problem is based on a material of the type mentioned at the outset, and it is characterized in that an optionally substituted polyvinylphenol is present in the photoconductive layer as a binder. Preferably a polyvinylphenol with a molecular weight between 1500 and 60,000 is present. The polyvinylphenol according to the invention is preferably a polymer of p-vinylphenol. The polyvinylphenol can preferably be halogen-substituted.
Hierdurch wird erreicht, daß ein Aufzeichnungsmaterial zur Herstellung von Druckformen oder gedruckten Schaltungen zur Verfügung gestellt werden kann, das in seinen elektrophotographischen Eigenschaften, insbesondere in der Aufladbarkeit, seiner Lichtempfindlichkeit und in seinem Löslichkeitsverhalten gegenüber wäßrig-alkalischen Lösungen verbessert ist, kleine Bildelemente gut wiedergibt und eine hohe Druckauflage ermöglicht.This ensures that a recording material for the production of printing forms or printed circuits for Can be provided, which is improved in its electrophotographic properties, in particular in the chargeability, its photosensitivity and in its solubility behavior compared to aqueous alkaline solutions, reproduces small picture elements well and enables a large print run.
Die Herstellung von Vinylphenolpolymerisaten ist bekannt (DE-OS 26 08 407) und "Journal of Polymer Science" Teil A-1, Bd. 7 (1969), Seiten 2175 bis 2184 und 2405 bis 2410 oder in "Journal of Organic Chemistry", Bd. 24 (1959), Seiten 1345 bis 1347, bei der man Ethylphenol zur Umwandlung in Vinylphenol dehydriert und das entstehende Rohprodukt radikalisch oder kationsich polymerisiert und das Polymersationsprodukt reinigt. Die halogensubstituierten Polymerisate werden z.B. durch Bromieren des Vinylphenolpolymerisats hergestellt.The production of vinylphenol polymers is known (DE-OS 26 08 407) and "Journal of Polymer Science" Part A-1, Vol. 7 (1969), pages 2175 to 2184 and 2405 to 2410 or in "Journal of Organic Chemistry", Vol. 24 (1959), pages 1345 to 1347, in which ethylphenol is dehydrated for conversion into vinylphenol and the resulting crude product is polymerized by radical or cationic means and the polymerization product is purified. The halogen-substituted polymers are e.g. prepared by brominating the vinyl phenol polymer.
Als halogenierte Vinylphenolpolymerisate werden erfindungsgemäß vorzugsweise chlorierte oder bromierte, insbesondere bromierte Polymerisate verwendet.According to the invention, chlorinated or brominated, in particular brominated, polymers are preferably used as halogenated vinylphenol polymers.
Außer Homopolymerisaten können auch Mischpolymerisate von Vinylphenolen und anderen Vinylverbindungen wie Styrol oder Acrylsäureester eingesetzt werden. Im allgemeinen werden die Homopolymerisate des p-Vinylphenols bevorzugt. Der Halogengehalt des halogenierten Polyvinylphenols liegt im allgemeinen zwischen 20 und 60, vorzugsweise 40 - 60 Gewichtsprozent.In addition to homopolymers, copolymers of vinylphenols and other vinyl compounds such as styrene or acrylic acid esters can also be used. In general, the homopolymers of p-vinylphenol are preferred. The halogen content of the halogenated polyvinylphenol is generally between 20 and 60, preferably 40-60 percent by weight.
In besonderer Ausführungsform ist in der erfindungsgemäßen photoleitfähigen Schicht ein o-Chinondiazid, vorzugsweise ein o-Naphthochinondiazid vorhanden. Hierdurch wird erreicht, daß die photoleitfähige Schicht nach der Entwicklung (Betonerung) einer Nachbelichtung mit UV-Licht unterzogen werden kann, was eine besonders gute Löslichkeit der belichteten Bereiche bei der Entschichtung bewirkt. Eine Fixierung des aufgebrachten Tonerbildes kann unterbleiben. Es war völlig überraschend, daß die photoleitfähige Schicht durch Zusatz der lichtempfindlichen Substanz in ihren elektrophotographischen Eigenschaften nicht nachteilig verändert wird und ein gutes Aufladungsverhalten bei geringer Dunkelentladung aufweist. Das Aufzeichnungsmaterial besitzt darüber hinaus eine gute Lagerfähigkeit.In a particular embodiment, an o-quinonediazide is preferred in the photoconductive layer according to the invention an o-naphthoquinonediazide is present. It is hereby achieved that the photoconductive layer can be subjected to a post-exposure with UV light after the development (emphasis), which results in a particularly good solubility of the exposed areas during the stripping. The applied toner image can not be fixed. It was completely surprising that the addition of the light-sensitive substance does not adversely change the electrophotographic properties of the photoconductive layer and exhibits good charging behavior with little dark discharge. The recording material also has a good shelf life.
Die photoleitfähige Schicht kann im allgemeinen 5 - 40 Gewichtsprozent an o-Chinondiazid enthalten. Vorzugsweise sind 15 bis 25 Gewichtsprozent vorhanden. Die Wiedergabe feiner Bildelemente, wie feiner Raster wird hierdurch in hervorragender Qualität ermöglicht.The photoconductive layer can generally contain 5-40 percent by weight of o-quinonediazide. Preferably 15 to 25 percent by weight is present. The reproduction of fine picture elements, such as fine raster, is made possible in excellent quality.
Als Schichtträger für das erfindungsgemäße Aufzeichnungsmaterial zur Herstellung von Druckformen und gedruckten Schaltungen können sämtliche für diesen Zweck bekannten Materialien eingesetzt werden, wie z.B. Aluminium-, Zink-, Magnesium-, Kupferplatten oder Mehrmetallplatten, aber auch Celluloseprodukte, wie z.B. Spezialpapiere, Cellulosehydrat-, Celluloseacetat-oder Cellulosebutyrat-Folien, letztere besonders in teilweise verseifter Form. In beschränktem Umfange kommen auch Kunststoffe, wie z.B. Polyamide in Folienform oder metallbedampfte Folien als Schichtträger in Frage.All materials known for this purpose, such as aluminum, zinc, magnesium, copper plates or multi-metal plates, but also cellulose products, such as special papers, cellulose hydrate, cellulose acetate, can be used as layer supports for the recording material according to the invention for the production of printing forms and printed circuits or cellulose butyrate films, the latter especially in partially saponified form. To a limited extent, plastics, such as polyamides in film form or metal-coated films, are also suitable as layer supports.
Besonders bewährt haben sich oberflächenveredelte Aluminiumfolien. Die Oberflächenveredelung besteht in einer mechanischen oder elektrochemischen Aufrauhung und gegebenenfalls in einer anschließenden Anodisierung und Behandlung mit Polyvinylphosphonsäure gemäß DE-OS 16 21 478 entsprechend US-PS 4,153,461. Hierdurch wird eine höhere Druckauflage und eine geringere Anfälligkeit gegen Oxidation erzielt.Surface-coated aluminum foils have proven particularly useful. The surface refinement consists in mechanical or electrochemical roughening and, if appropriate, in a subsequent anodization and treatment with polyvinylphosphonic acid according to DE-OS 16 21 478 in accordance with US Pat. No. 4,153,461. This results in a higher print run and less susceptibility to oxidation.
Die für die photoleitfähige Schicht verwendeten organischen Photoleiter sind als im Prinzip bekannt anzusehen. Hierfür kommen in Frage:
Triphenylaminderivate, höher kondensierte aromatische Verbindungen, wie Anthracen, benzokondensierte Heterocyclen, wie Benzthiazole, Pyrazolin-, Imidazol- oder Triazolderivate, Oxdiazolderivate wie 2,5-Bis-(4′-diethylaminophenyl)oxdiazol-1,3,4), Oxazolderivate wie 2-Phenyl-4-(2′-chlorphenyl)-5-(4˝-diethylaminophenyl)-oxazol, ferner vinylaromatische Polymerisate wie Polyvinylanthracen, Polyacenaphthylen oder Polyvinylcarbazol und dessen Mischpolymerisate, sofern sie mit Polyvinylphenol verträglich sind und zu einer Löslichkeitsdifferenzierung geeignet sind.The organic photoconductors used for the photoconductive layer can be regarded as known in principle. The following are possible:
Triphenylamine derivatives, more highly condensed aromatic compounds, such as anthracene, benzo-fused heterocycles, such as benzothiazoles, pyrazoline, imidazole or triazole derivatives, oxdiazole derivatives such as 2,5-bis- (4'-diethylaminophenyl) oxdiazole-1,3,4), oxazole derivatives such as 2 -Phenyl-4- (2'-chlorophenyl) -5- (4˝-diethylaminophenyl) oxazole, further vinyl aromatic polymers such as polyvinylanthracene, polyacenaphthylene or polyvinyl carbazole and their copolymers, provided that they are compatible with polyvinylphenol and are suitable for differentiation in solubility.
Als gegebenenfalls zuzusetzende o-Chinondiazide werden vorzugsweise o-Naphthochinondiazide verwendet, wie die Di- oder Trisester aus 2,3,4-Trihydroxybenzophenon und Naphthochinon-(1,2)-diazid-(2)-5-oder 4-sulfonsäure, Ester, insbesondere der Diester aus Bis(2-hydroxynaphthyl)-methan und Naphthochinon(1,2)-diazid-(2)-5-sulfonsäure und Ester aus 2-Phenyl-2-(4′-hydroxyphenyl)-propan und Naphthochinon-(1,2)-diazid-(2)-4-sulfonsäure. Ferner kommen Ester aus hydroxylgruppenhaltigen Polymerisaten und Napthochinondiazidsulfonsäuren in Frage. Auch Mischungen der genannten Chinondiazidsulfonsäureester können mit gutem Erfolg eingesetzt werden.Preferred o-quinonediazides to be added are preferably o-naphthoquinonediazides, such as the di- or tri-esters of 2,3,4-trihydroxybenzophenone and naphthoquinone- (1,2) -diazide- (2) -5-or 4-sulfonic acid, esters , especially the diester of bis (2-hydroxynaphthyl) methane and naphthoquinone (1,2) diazide- (2) -5-sulfonic acid and esters from 2-phenyl-2- (4'-hydroxyphenyl) propane and naphthoquinone- (1,2) diazide- (2) -4 -sulfonic acid. Esters from hydroxyl-containing polymers and naphthoquinonediazide sulfonic acids are also suitable. Mixtures of the quinonediazide sulfonic acid esters mentioned can also be used with good success.
In der photoleitfähigen Schicht können zusätzlich weitere Bindemittel enthalten sein. Ihr Zusatz dient der Verbesserung der Filmeigenschaften der Schicht, ihrer Haftfestigkeit auf dem Schichtträger und der Steigerung der Druckauflage.Additional binders can also be contained in the photoconductive layer. Their addition serves to improve the film properties of the layer, its adhesive strength on the substrate and to increase the print run.
Als Bindemittel eignen sich beispielsweise Copolymerisate aus Styrol und Maleinsäureanhydrid und deren Teilveresterungsprodukte, Polyvinylacetate und Copolymerisate mit Crotonsäure, Phenolharze, Cumaron-Inden-Harze, Polyacrylate und Copolymerisate mit Acrylsäure, Kolophonium und seine Umwandlungsprodukte, Maleinatharze und Phthalatharze.Suitable binders are, for example, copolymers of styrene and maleic anhydride and their partial esterification products, polyvinyl acetates and copolymers with crotonic acid, phenolic resins, coumarone-indene resins, polyacrylates and copolymers with acrylic acid, rosin and its conversion products, maleate resins and phthalate resins.
Erfindungsgemäßes elektrophotographisches Aufzeichnungsmaterial enthält zur Erweiterung des spektralen Empfindlichkeitsbereiches mindestens einen Sensibilisierungsfarbstoff. Geeignete Sensibilisierungsfarbstoffe sind beispielsweise Malachitgrün (Color-Index (C.I.) 42 000), Kristallviolett (C.I. 42 555), Methylviolett (C.I. Nr. 42 535), Nachtblau (C.I. Nr. 44 085), Viktoriablau (C.I. Nr. 44 045 bzw. Nr. 52595:2), Rhodamin B, Rhodamin FB (C.I. Nr. 45 170), Capriblau (C.I. Nr. 51 015), Methylenblau (C.I. Nr. 52 015), Fuchsin (C.I. Nr. 42 500), Rose Bengal (C.I. Nr. 45 440), Polymethinfarbstoffe, wie Astrazonorange G (C.I. Nr. 48 035), Astrazonorange R (C.I. 48 040), Astrazongelb 3G (C.I. Nr. 48 055), Astrazongelb 5G (C.I. Nr. 48 065), Basic Yellow (C.I. Nr. 48 060), oder Astrazonrotviolett (C.I. Nr. 48 013).Electrophotographic recording material according to the invention contains at least one sensitizing dye to expand the spectral sensitivity range. Suitable sensitizing dyes are, for example, malachite green (Color Index (CI) 42,000), crystal violet (CI 42 555), methyl violet (CI No. 42 535), night blue (CI No. 44 085), Victoria blue (CI No. 44 045 or No. 52595: 2), Rhodamine B, Rhodamine FB (CI No. 45 170), Capri Blue (CI No. 51 015), methylene blue (CI No. 52 015), Fuchsin (CI No. 42 500), Rose Bengal (CI No. 45 440), polymethine dyes such as Astrazonorange G (CI No. 48 035), Astrazonorange R (CI 48 040), Astrazonyellow 3G (CI No. 48 055), Astrazon Yellow 5G (CI No. 48 065), Basic Yellow (CI No. 48 060), or Astrazon Red Violet (CI No. 48 013).
Das erfindungsgemäße Aufzeichnungsmaterial kann als übliche Zusätze in der photoleitfähigen Schicht Verlaufmittel und Weichmacher und/oder zwischen Schichtträger und Schicht Haftvermittler enthalten.The recording material according to the invention can contain leveling agents and plasticizers and / or between layer support and layer adhesion promoter as usual additives in the photoconductive layer.
Die Anwesenheit des Zusatzes beeinflußt die Wechselwirkung zwischen dem Photoleiter und dem gegebenenfalls vorhandenen o-Chinondiazid nicht wesentlich.The presence of the additive does not significantly affect the interaction between the photoconductor and any o-quinonediazide present.
Anhand der folgenden Beispiele wird die Herstellung und Verarbeitung des erfindungsgemäßen Materials näher beschrieben.The production and processing of the material according to the invention is described in more detail using the following examples.
In einem Gemisch aus 225 ml Ethylenglykolmonomethylether, 360 ml Tetrahydrofuran und 90 ml Butylacetat werden 50 g 2,5-Bis-(4′-diethylaminophenyl)-oxadiazol-1,3,4, 50 g Poly-p-vinylphenolharz (Resin M der Maruzen Oil Co., Ltd. Osaka, Japan) und 250 mg Rhodamin FB (Color Index C.I. 45 170) gelöst. Die Lösung wird auf eine 300 µm dicke elektrochemisch aufgerauhte, anodisierte und mit Polyvinylphosphonsäure vorbehandelte Aluminiumplatte so aufgetragen, daß nach dem Verdunsten des Lösungsmittels eine Photoleiterschicht mit einer Dicke von 5,5 µm entsteht.In a mixture of 225 ml of ethylene glycol monomethyl ether, 360 ml of tetrahydrofuran and 90 ml of butyl acetate, 50 g of 2,5-bis (4'-diethylaminophenyl) -oxadiazole-1,3,4, 50 g of poly-p-vinylphenol resin (Resin M der Maruzen Oil Co., Ltd. Osaka, Japan) and 250 mg Rhodamine FB (Color Index CI 45 170) dissolved. The solution is applied to a 300 μm thick electrochemically roughened, anodized and pretreated with polyvinylphosphonic acid aluminum plate in such a way that that after evaporation of the solvent, a photoconductor layer with a thickness of 5.5 microns is formed.
Die Lichtempfindlichkeit der Schicht bestimmt man, indem man sie auf -500 V auflädt und mit weißem Glühlampenlicht so lange belichtet bis sie auf eine Restspannung von -60 V entladen ist. Die dazu erforderliche Energiedichte beträgt 320 µJ/cm².The light sensitivity of the layer is determined by charging it to -500 V and exposing it to white incandescent light until it is discharged to a residual voltage of -60 V. The energy density required for this is 320 µJ / cm².
Zur Bebilderung wird die Photoleiterschicht mit einer Corona auf ein Oberflächenpotential von -500 V aufgeladen und in einer Reprocamera mit 8 Halogenlampen à 500 Watt 20 Sekunden lang bildmäßig belichtet. Das entstandene latente Ladungsbild wird mit Hilfe einer Magnetwalze mit einem handelsüblichen Toner/Träger-Entwicklungsgemisch entwickelt. Das entwickelte Bild wird mit Hilfe von Wärmestrahlung fixiert.For imaging, the photoconductor layer is charged with a corona to a surface potential of -500 V and exposed to images in a repro camera with 8 halogen lamps of 500 watts for 20 seconds. The resulting latent charge image is developed using a magnetic roller with a commercially available toner / carrier development mixture. The developed image is fixed with the help of heat radiation.
Zur Umwandlung in eine Druckform taucht man die Platte 2 Minuten in eine Lösung, die man erhält, wenn man 20 g Na₂SiO₃·9H₂O und 2 g NaOH in einem Gemisch aus 728 g Wasser, 100 g n-Propanol und 150 g Ethylendiglykol löst. Die nicht vom Tonerbild bedeckten Schichtteile werden mit einem Wasserstrahl unter leichtem Reiben entfernt. Die erhaltene Druckform zeichnet sich durch eine gute Raster-und Volltonwiedergabe aus. In einer Bogenoffsetmaschine druckt die Platte weit über 100 000 Drucke.For conversion into a printing form, the plate is immersed for 2 minutes in a solution which is obtained by dissolving 20 g Na₂SiO₃ · 9H₂O and 2 g NaOH in a mixture of 728 g water, 100 g n-propanol and 150 g ethylenediglycol. The layer parts not covered by the toner image are removed with a water jet with gentle rubbing. The printing form obtained is characterized by good raster and full tone reproduction. The plate prints well over 100,000 prints in a sheetfed offset press.
Ersetzt man im oben beschriebenen Ansatz die 50 g Poly-p-vinylphenolharz durch einen Novolak aus m-Kresol und Formaldehyd (Alnovol® 429 K der HOECHST AG) so erhält man eine Druckplatte, die zur Entladung von -500 V auf -60V eine Energiedichte von 520 µJ/cm² erfordert, und die in der Reprocamera 30 Sekunden belichtet werden muß. Die Verweilzeit in der oben beschriebenen Entschichtungslösung beträgt 6 Minuten.In the approach described above, the 50 g poly-p-vinylphenol resin is replaced by a novolak made from m-cresol and Formaldehyde (Alnovol® 429 K from HOECHST AG) gives a printing plate which requires an energy density of 520 µJ / cm² to discharge from -500 V to -60V and which has to be exposed in the repro camera for 30 seconds. The residence time in the stripping solution described above is 6 minutes.
Man löst 35 g 2-Vinyl-4-(2′-chlorphenyl)-5-(4˝-diethylaminophenyl)-oxazol und 40 g Polyvinylphenol in einer Mischung aus 160 ml Ethylenglykolmonomethylether, 270 ml Tetrahydrofuran und 60 ml Butylacetat und setzt der Lösung 440 mg Astrazonorange R (C.I. 48 040) und 350 mg Astrazonrotviolett 3 RN (C.I. 48 013) zu. Mit der Lösung beschichtet man eine oberflächlich durch Naßbürstung aufgerauhte, anodisierte, mit Polyvinylphosphonsäure vorbehandelte Aluminiumplatte so, daß die Photoleiterschicht ein Flächengewicht von 5,5 g/m² aufweist. Die Platte wird wie in Beispiel 1 beschrieben aufgeladen (-500 V) und belichtet, wobei die Belichtungszeit zur Erzielung eines kontrastreichen grundfreien Bildes nur 14 Sekunden beträgt. Nach Sichtbarmachen des latenten elektrostatischen Bildes mit einem Trockenentwickler und Fixierung des Tonerbildes mittels Wärmestrahlung wird die Platte zur Entfernung der bildfreien Bereiche durch ein handelsübliches Entschichtungsgerät, bei einer Durchlaufgeschwindigkeit von 1,1 m/min geführt.35 g of 2-vinyl-4- (2'-chlorophenyl) -5- (4˝-diethylaminophenyl) oxazole and 40 g of polyvinylphenol are dissolved in a mixture of 160 ml of ethylene glycol monomethyl ether, 270 ml of tetrahydrofuran and 60 ml of butyl acetate and the solution is added 440 mg astrazone orange R (CI 48 040) and 350 mg astrazone red violet 3 RN (CI 48 013). The solution is used to coat an anodized aluminum plate which has been roughened by wet brushing and pretreated with polyvinylphosphonic acid in such a way that the photoconductor layer has a weight per unit area of 5.5 g / m 2. The plate is charged (-500 V) and exposed as described in Example 1, the exposure time being only 14 seconds in order to achieve a high-contrast, base-free image. After the latent electrostatic image has been made visible with a dry developer and the toner image has been fixed by means of heat radiation, the plate is passed through a commercially available stripping device to remove the non-image areas at a throughput speed of 1.1 m / min.
30 g eines bromierten Polyvinylphenolharzes (Resin MB, Maruzen Oil, Japan) , 30 g eines Copolymerisates aus Styrol und Maleinsäureanhydrid, 40 g 2,5-Bis-(4′-diethylaminophenyl)-oxadiazol-1,3,4, 10 g eines Kondensationsproduktes aus Benzophenon-2-carbonsäure und Diethylanilin und 250 mg Rhodamin FB (C.I. 45 170) werden in einem Gemisch aus 280 ml Propylenglykolmonomethylether, 100 ml Tetrahydrofuran und 200 ml Butylacetat gelöst. Mit der Lösung wird eine Aluminiumfolie wie in Beispiel 1 beschrieben beschichtet und getrocknet.30 g of a brominated polyvinylphenol resin (Resin MB, Maruzen Oil, Japan), 30 g of a copolymer of styrene and maleic anhydride, 40 g of 2,5-bis (4'-diethylaminophenyl) oxadiazole-1,3,4, 10 g of one Condensation product of benzophenone-2-carboxylic acid and diethylaniline and 250 mg of rhodamine FB (CI 45 170) are dissolved in a mixture of 280 ml of propylene glycol monomethyl ether, 100 ml of tetrahydrofuran and 200 ml of butyl acetate. An aluminum foil is coated with the solution as described in Example 1 and dried.
Die Platte wird auf -500 V aufgeladen und in einer Reprocamera 18 Sekunden lang mit 10 Halogenlampen à 600 Watt bildmäßig belichtet, in bekannter Weise entwickelt und fixiert. Die Photoleiterschicht wird an den nicht von Toner bedeckten Stellen mit der in Beispiel 1 beschriebenen Lösung entfernt. Das mit der Platte erzielte Druckergebnis ist ausgezeichnet.The plate is charged to -500 V and imagewise exposed in a repro camera for 18 seconds with 10 halogen lamps of 600 watts each, developed and fixed in a known manner. The photoconductor layer is removed at the areas not covered by toner with the solution described in Example 1. The printing result achieved with the plate is excellent.
Man löst 40 g Polyvinylphenol mit einem mittleren Molekulargewicht von 1700, 40 g 2,5-Bis-(4′-diethylaminophenyl)-oxadiazol-1,3,4, 20 g 2,3,4-Trihydroxybenzophenon-naphthochinon-(1,2)-diazid-(2)-5-sulfonsäure-trisester, 500 mg Astrazonorange R (C.I. 48 040) und 200 mg Rhodamin FB (C.I. 45 170) in einem Lösungsmittelgemisch aus 200 ml Propylenglykolmonomethylether, 100 ml Tetrahydrofuran und 200 ml Butylacetat. Mit der Lösung beschichtet man eine 300 µm dicke, elektrochemisch aufgerauhte, anodisierte und mit Polyvinylphosphonsäure behandelte Aluminiumfolie so, daß nach dem Verdunsten der Lösungsmittel eine Photoleiterschicht von 5 µm Dicke zurückbleibt. Die Schicht wird auf -500 V aufgeladen und in einer Reprokamera wie in Beispiel 1 beschrieben belichtet. Das nach dem Entwickeln entstandene Tonerbild wird nicht fixiert. Die betonerte Platte wird in einer handelsüblichen Automatik-Kopieranlage unter einer 5 KW Metall-Halogen-Lampe (Violight) 2 Minuten lang belichtet. Anschließend wird das Tonerbild durch Abspülen mit Wasser entfernt und die Platte 1/2 Minute lang in eine in Beispiel 1 beschriebene Entschichterlösung getaucht, mit Wasser gespült und ausgerieben. Man erhält eine Druckform, bei der insbesondere ein gerastertes Bild besser wiedergegeben wird als mit den in den Beispielen 1-3 beschriebenen Platten.40 g of polyvinylphenol with an average molecular weight of 1700, 40 g of 2,5-bis- (4'-diethylaminophenyl) -oxadiazole-1,3,4, 20 g of 2,3,4-trihydroxybenzophenone-naphthoquinone- (1, 2) -diazide- (2) -5-sulfonic acid trisester, 500 mg astrazone orange R (CI 48 040) and 200 mg rhodamine FB (CI 45 170) in a solvent mixture of 200 ml Propylene glycol monomethyl ether, 100 ml of tetrahydrofuran and 200 ml of butyl acetate. A 300 μm thick, electrochemically roughened, anodized aluminum foil treated with polyvinylphosphonic acid is coated with the solution in such a way that a 5 μm thick photoconductor layer remains after the solvents have evaporated. The layer is charged to -500 V and exposed in a repro camera as described in Example 1. The toner image created after development is not fixed. The concrete plate is exposed for 2 minutes in a commercial automatic copying machine under a 5 KW metal halogen lamp (Violight). The toner image is then removed by rinsing with water and the plate is immersed for 1/2 minute in a stripping solution described in Example 1, rinsed with water and rubbed off. A printing form is obtained in which, in particular, a rastered image is reproduced better than with the plates described in Examples 1-3.
Verwendet man anstelle des Polyvinylphenols einen Novolak aus Kresol und Formaldehyd, so ist bei der Bebilderung in der Reprocamera eine Belichtungszeit von 30 statt 20 Sekunden erforderlich. Die Verweilzeit im Entschichter beträgt 2 Minuten.If a novolak of cresol and formaldehyde is used instead of the polyvinylphenol, an exposure time of 30 instead of 20 seconds is required for the imaging in the repro camera. The residence time in the stripper is 2 minutes.
In einem Gemisch aus 250 ml Propylenglykolmonomethylether, 125 ml Tetrahydrofuran und 250 ml Butylacetat werden 24 g eines bromierten Polyvinylphenols (Resin MB, der Maruzen Oil Co., Ltd., JP), 24 g eines mit Isobutanol teilveresterten Copolymerisates aus Styrol und Maleinsäureanhydrid, 42 g 2-Phenyl-4-(2′-chlorphenyl)-5(4˝-diethylaminophenyl)oxazol, 30 g 2,3,4-Trihydroxybenzophenonnaphthochinon-(1,2)-diazid-(2)-5-sulfonsäuretrisester, 525 mg Astrazonorange R und 210 mg Rhodamin FB gelöst. Mit der Lösung wird eine anodisierte Aluminiumfolie wie in Beispiel 4 beschrieben beschichtet. Auf der beschichteten Folie erzeugt man auf elektrophotographischem Wege ein Tonerbild, das nicht fixiert wird. Nach einer wie in Beispiel 4 beschriebenen Belichtung zur Zersetzung des in der Schicht enthaltenen Chinondiazids wird das Tonerbild mit Wasser abgespült. Zur Umwandlung in eine Druckform wird die Platte 30 Sekunden in eine in Beispiel 1 beschriebene Entschichterlösung getaucht und unter Reiben mit Wasser abgespült. Man erhält eine Flachdruckform mit sehr guter Bildwiedergabe und hoher Auflagenqualität beim Drucken.In a mixture of 250 ml propylene glycol monomethyl ether, 125 ml of tetrahydrofuran and 250 ml of butyl acetate are mixed with 24 g of a brominated polyvinylphenol (Resin MB, from Maruzen Oil Co., Ltd., JP), 24 g with a copolymer of styrene and maleic anhydride partially esterified with isobutanol, 42 g with 2-phenyl-4- ( 2'-chlorophenyl) -5 (4˝-diethylaminophenyl) oxazole, 30 g 2,3,4-trihydroxybenzophenonaphthoquinone- (1,2) -diazide- (2) -5-sulfonic acid trisester, 525 mg astrazone orange R and 210 mg rhodamine FB solved. An anodized aluminum foil is coated with the solution as described in Example 4. A toner image that is not fixed is produced on the coated film by electrophotography. After exposure as described in Example 4 to decompose the quinonediazide contained in the layer, the toner image is rinsed off with water. To convert it into a printing form, the plate is immersed in a decoater solution described in Example 1 for 30 seconds and rinsed with water while rubbing. You get a planographic printing form with very good image reproduction and high print run quality.
Claims (7)
- An electrophotographic recording material comprised of an electrically conducting layer support being in particular suitable for the production of printing plates of printed circuits, and of a photoconductive layer comprising an organic photoconductor, a phenolic resin as the binder, a sensitizer and customary additives, characterized in that an optionally substituted polyvinylphenol is present as binder.
- A recording material as claimed in claim 1, characterized in that a polyvinylphenol having a molecular weight of between 1,500 and 60,000 is present as binder.
- A recording material as claimed in claim 1 or 2, characterized in that the polyvinylphenol is a polymer of p-vinylphenol.
- A recording material as claimed in claims 1 to 3, characterized in that the polyvinylphenol is halogenated.
- A recording material as claimed in claim 4, characterized in that the polyvinylphenol is brominated.
- A recording material as claimed in claim 1, characterized in that the photoconductive layer contains an o-quinonediazide.
- A recording material as claimed in claims 1 and 6, characterized in that the photoconductive layer contains an o-naphthoquinonediazide.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3800617A DE3800617A1 (en) | 1988-01-12 | 1988-01-12 | ELECTROPHOTOGRAPHIC RECORDING MATERIAL |
DE3800617 | 1988-01-12 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0324180A2 EP0324180A2 (en) | 1989-07-19 |
EP0324180A3 EP0324180A3 (en) | 1990-01-17 |
EP0324180B1 true EP0324180B1 (en) | 1993-07-21 |
Family
ID=6345116
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88121872A Expired - Lifetime EP0324180B1 (en) | 1988-01-12 | 1988-12-30 | Electrophotographical recording material |
Country Status (4)
Country | Link |
---|---|
US (1) | US4933248A (en) |
EP (1) | EP0324180B1 (en) |
JP (1) | JPH01216362A (en) |
DE (2) | DE3800617A1 (en) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69127668T2 (en) * | 1990-07-26 | 1998-01-15 | Matsushita Electric Ind Co Ltd | Photosensitive material for electrophotography and its manufacture |
US5437952A (en) * | 1992-03-06 | 1995-08-01 | Konica Corporation | Lithographic photosensitive printing plate comprising a photoconductor and a naphtho-quinone diazide sulfonic acid ester of a phenol resin |
JPH05323682A (en) * | 1992-05-18 | 1993-12-07 | Konica Corp | Method for making printing plate |
TW403972B (en) * | 1993-01-18 | 2000-09-01 | Semiconductor Energy Lab | Method of fabricating mis semiconductor device |
DE4445820A1 (en) | 1994-12-21 | 1996-06-27 | Hoechst Ag | Process for developing irradiated, radiation-sensitive recording materials |
DE19803564A1 (en) | 1998-01-30 | 1999-08-05 | Agfa Gevaert Ag | Polymers with units of N-substituted maleimide and their use in radiation-sensitive mixtures |
US6214502B1 (en) | 1998-07-21 | 2001-04-10 | Lexmark International, Inc. | Charge generation layers comprising binder blends and photoconductors including the same |
US6376144B1 (en) | 2000-08-03 | 2002-04-23 | Kodak Polychrome Graphics, Llc | Organic photoconductive composition |
US20040043314A1 (en) * | 2002-08-30 | 2004-03-04 | Nusrallah Jubran | Organophotoreceptors with a fluoran-based compound |
KR100916656B1 (en) * | 2002-10-22 | 2009-09-08 | 삼성전자주식회사 | laser irradiation apparatus and manufacturing method for polysilicon thin film transistor using the apparatus |
JP4506583B2 (en) * | 2005-06-24 | 2010-07-21 | 富士ゼロックス株式会社 | Coating agent composition, electrophotographic photoreceptor, method for producing the same, and image forming apparatus |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE625567A (en) * | 1961-12-04 | |||
BE637605A (en) * | 1962-09-22 | |||
ZA6807938B (en) * | 1967-12-04 | |||
GB1375461A (en) * | 1972-05-05 | 1974-11-27 | ||
JPS51105389A (en) * | 1975-03-01 | 1976-09-17 | Kenji Kanezaki | Kojundo pp binirufuenoorujugotaino seizohoho |
AU507694B2 (en) * | 1975-06-14 | 1980-02-21 | Hoechst Aktiengesellschaft | Electrophotographic reproduction |
GB2014748B (en) * | 1978-02-07 | 1982-06-16 | Konishiroku Photo Ind | Electrophotographic material for obtaining toner image and process for forming printing plate by using the same |
JPS5730829A (en) * | 1980-08-01 | 1982-02-19 | Hitachi Ltd | Micropattern formation method |
US4439516A (en) * | 1982-03-15 | 1984-03-27 | Shipley Company Inc. | High temperature positive diazo photoresist processing using polyvinyl phenol |
DE3313798A1 (en) * | 1983-04-15 | 1984-10-18 | Hoechst Ag, 6230 Frankfurt | ELECTROPHOTOGRAPHIC RECORDING MATERIAL |
-
1988
- 1988-01-12 DE DE3800617A patent/DE3800617A1/en not_active Withdrawn
- 1988-12-30 DE DE8888121872T patent/DE3882509D1/en not_active Expired - Fee Related
- 1988-12-30 EP EP88121872A patent/EP0324180B1/en not_active Expired - Lifetime
-
1989
- 1989-01-11 US US07/295,759 patent/US4933248A/en not_active Expired - Fee Related
- 1989-01-12 JP JP1003883A patent/JPH01216362A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
DE3882509D1 (en) | 1993-08-26 |
EP0324180A2 (en) | 1989-07-19 |
US4933248A (en) | 1990-06-12 |
JPH01216362A (en) | 1989-08-30 |
DE3800617A1 (en) | 1989-07-20 |
EP0324180A3 (en) | 1990-01-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0157241B1 (en) | Photosensitive recording material and its use in a process for the production of a printing plate or a printed circuit | |
DE1058836B (en) | Material for electrophotographic reproduction | |
EP0324180B1 (en) | Electrophotographical recording material | |
EP0198488B1 (en) | Electrophotographic recording material | |
DE2322046C3 (en) | Process for the production of printing forms | |
DE2904183B2 (en) | Electrophotographic recording material and use of the same for the production of a printing form | |
AT392852B (en) | ELECTROPHOTOGRAPHIC RECORDING MATERIAL | |
DE3307613C2 (en) | ||
EP0131215B1 (en) | Recording materials with improved photosensitivity | |
EP0093330B1 (en) | Electrographic recording materials with special compounds transporting charge carriers | |
EP0031481B1 (en) | Material for electrographical reproduction | |
DE3210577A1 (en) | ELECTROPHOTOGRAPHIC RECORDING MATERIAL | |
DE3310804A1 (en) | PROCESS AND LIGHT-SENSITIVE MATERIALS FOR THE PRODUCTION OF FLAT PRINTING FORMS | |
EP0125481B1 (en) | Electrophotographic recording material | |
EP0093329B1 (en) | Electrographic recording materials with special compounds transporting charge carriers | |
EP0133469B1 (en) | Electrophotographic recording materials with improved photosensitivity | |
EP0733955B1 (en) | Electrophotographic recording material for the production of printing plates | |
DE4034623C2 (en) | Printing plate for electrophotographic process | |
DE1811209C3 (en) | Process for the production of printing forms by electrophotographic means | |
DE3338903C2 (en) | ||
DE2726116A1 (en) | Electrophotographic printing plate - contg. photoconductive insulating layer comprising formaldehyde and aromatic carboxylic polycondensate, binder and activator | |
DE2322047C3 (en) | Process for the production of printing forms | |
DE3911405A1 (en) | Printing plate for electrophotographic plate production | |
DE2322047B2 (en) | PROCESS FOR PRODUCING PRINTING FORMS | |
JPH0561276A (en) | Electrophotographic printing plate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): DE FR GB NL |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): DE FR GB NL |
|
17P | Request for examination filed |
Effective date: 19900625 |
|
17Q | First examination report despatched |
Effective date: 19920925 |
|
RBV | Designated contracting states (corrected) |
Designated state(s): DE GB |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): DE GB |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Effective date: 19930721 |
|
REF | Corresponds to: |
Ref document number: 3882509 Country of ref document: DE Date of ref document: 19930826 |
|
GBV | Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed] |
Effective date: 19930721 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Effective date: 19940901 |