US2405523A - Light-sensitive photographic compositions and elements - Google Patents
Light-sensitive photographic compositions and elements Download PDFInfo
- Publication number
- US2405523A US2405523A US548796A US54879644A US2405523A US 2405523 A US2405523 A US 2405523A US 548796 A US548796 A US 548796A US 54879644 A US54879644 A US 54879644A US 2405523 A US2405523 A US 2405523A
- Authority
- US
- United States
- Prior art keywords
- light
- water
- sensitive
- diazo
- 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.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title description 16
- 239000000243 solution Substances 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 238000000576 coating method Methods 0.000 description 17
- -1 aliphatic ester Chemical class 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 15
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 15
- 150000001989 diazonium salts Chemical class 0.000 description 12
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 150000008049 diazo compounds Chemical class 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 239000008199 coating composition Substances 0.000 description 9
- 229920002689 polyvinyl acetate Polymers 0.000 description 9
- 239000011118 polyvinyl acetate Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- 238000010168 coupling process Methods 0.000 description 7
- 238000005859 coupling reaction Methods 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 230000008878 coupling Effects 0.000 description 6
- 239000012954 diazonium Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 235000010288 sodium nitrite Nutrition 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 4
- 150000001241 acetals Chemical class 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920001290 polyvinyl ester Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- QPKNFEVLZVJGBM-UHFFFAOYSA-N 2-aminonaphthalen-1-ol Chemical class C1=CC=CC2=C(O)C(N)=CC=C21 QPKNFEVLZVJGBM-UHFFFAOYSA-N 0.000 description 2
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000006149 azo coupling reaction Methods 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- JTXUVYOABGUBMX-UHFFFAOYSA-N didodecyl hydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(=O)OCCCCCCCCCCCC JTXUVYOABGUBMX-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000005673 monoalkenes Chemical class 0.000 description 2
- 150000004780 naphthols Chemical class 0.000 description 2
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000033458 reproduction Effects 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- FRDZVVWYFHSMKP-UHFFFAOYSA-N (4-amino-2,5-dichlorophenyl)urea Chemical compound NC1=CC(=C(C=C1Cl)NC(=O)N)Cl FRDZVVWYFHSMKP-UHFFFAOYSA-N 0.000 description 1
- VNSGSGVPSPUXFV-UHFFFAOYSA-N (4-amino-2,5-dimethoxyphenyl)urea Chemical compound NC1=CC(=C(C=C1OC)NC(=O)N)OC VNSGSGVPSPUXFV-UHFFFAOYSA-N 0.000 description 1
- AYLDJQABCMPYEN-UHFFFAOYSA-N (4-azaniumylphenyl)-diethylazanium;sulfate Chemical compound OS(O)(=O)=O.CCN(CC)C1=CC=C(N)C=C1 AYLDJQABCMPYEN-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- NXVHEHXRZVQDCR-UHFFFAOYSA-N 1-n,1-n-diethyl-2-methylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C=C1C NXVHEHXRZVQDCR-UHFFFAOYSA-N 0.000 description 1
- HLOBBOUKIFEPGQ-UHFFFAOYSA-N 2,5-diethoxy-4-piperidin-1-ylaniline Chemical compound C1=C(N)C(OCC)=CC(N2CCCCC2)=C1OCC HLOBBOUKIFEPGQ-UHFFFAOYSA-N 0.000 description 1
- ARZSHPFMIADSPD-UHFFFAOYSA-N 2-aminoethyl 4-aminobenzoate Chemical compound NCCOC(=O)C1=CC=C(N)C=C1 ARZSHPFMIADSPD-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- 229940018563 3-aminophenol Drugs 0.000 description 1
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 description 1
- QHWDUJPWCGEBTH-UHFFFAOYSA-N 4-amino-n-phenylbenzamide Chemical compound C1=CC(N)=CC=C1C(=O)NC1=CC=CC=C1 QHWDUJPWCGEBTH-UHFFFAOYSA-N 0.000 description 1
- QNGVNLMMEQUVQK-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C=C1 QNGVNLMMEQUVQK-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- JDRXDAAQPPNBGU-UHFFFAOYSA-N COC(OC)OC(=O)CCCCC(O)=O Chemical compound COC(OC)OC(=O)CCCCC(O)=O JDRXDAAQPPNBGU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical class CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 1
- BZORFPDSXLZWJF-UHFFFAOYSA-N N,N-dimethyl-1,4-phenylenediamine Chemical compound CN(C)C1=CC=C(N)C=C1 BZORFPDSXLZWJF-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000004036 acetal group Chemical group 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 229960001748 allylthiourea Drugs 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003931 anilides Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- DMVOXQPQNTYEKQ-UHFFFAOYSA-N biphenyl-4-amine Chemical group C1=CC(N)=CC=C1C1=CC=CC=C1 DMVOXQPQNTYEKQ-UHFFFAOYSA-N 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- ZANNOFHADGWOLI-UHFFFAOYSA-N ethyl 2-hydroxyacetate Chemical compound CCOC(=O)CO ZANNOFHADGWOLI-UHFFFAOYSA-N 0.000 description 1
- JLEKJZUYWFJPMB-UHFFFAOYSA-N ethyl 2-methoxyacetate Chemical compound CCOC(=O)COC JLEKJZUYWFJPMB-UHFFFAOYSA-N 0.000 description 1
- LCHWYIIJDKDMII-UHFFFAOYSA-N ethyl butanoate ethyl propanoate Chemical compound C(CCC)(=O)OCC.C(CC)(=O)OCC LCHWYIIJDKDMII-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000001056 green pigment Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000266 injurious effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QDDUVLAJKGAIJX-UHFFFAOYSA-N n-(4-aminonaphthalen-1-yl)acetamide Chemical compound C1=CC=C2C(NC(=O)C)=CC=C(N)C2=C1 QDDUVLAJKGAIJX-UHFFFAOYSA-N 0.000 description 1
- CHMBIJAOCISYEW-UHFFFAOYSA-N n-(4-aminophenyl)acetamide Chemical compound CC(=O)NC1=CC=C(N)C=C1 CHMBIJAOCISYEW-UHFFFAOYSA-N 0.000 description 1
- 150000005002 naphthylamines Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000001052 yellow pigment Substances 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
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/52—Compositions containing diazo compounds as photosensitive substances
- G03C1/60—Compositions containing diazo compounds as photosensitive substances with macromolecular additives
Definitions
- This invention relates to photography and, more particularly, to light-sensitive photographic elements and to their preparation. Still more particularly, it relates to water-resistant supports bearing a water-permeable layer composed of a vinyl resin binder containing a light-sensitive diazonium salt, and to compositions for making such layers.
- An object of this invention is to provide new and useful light-sensitive diazo salt solutions which are stable, of low water content. and can be coated to form smooth, tough, mar-resistant surfaces.
- a related object is to provide such solutions which are fast drying, not softened by water, and have good adherence to water-resistant surfaces.
- a further object is to provide photographic elements with water-insoluble but water-permeable, light-sensitive layers which may be processed rapidly to yield reproductions of high contrast, resolving power, and definition. Still other objects will be apparent from the following description of the invention.
- the above objects are attained by the preparation and use of the novel coating compositions, layers and photographic elements described below.
- the coating solutions in their broader aspects consist of a solvent containing a waterpermeable, water-insoluble resinous lower aliphatic ester or acetal of a vinyl alcohol polymer which acts as a binding agent or medium for a light-sensitive diazonium compound.
- the novel light-sensitive layers and elements contain or comprise a stratum composed essentially of the aforesaid resinous ester or acetal and the diazoniulm salt.
- the solvent is completely or substantially removed during a coating operation. Since organic solvents may be used, the drying time may be greatly reduced. However, a small amount of water may be present in the solvent mixture to aid in dissolving the diazonium compound.
- the coating composition layers and elements further contain a stabilizing agent for the light-sensitive diazonium compound. This may advantageously be introduced during the preparation of the coat ing composition but'may be added just prior to coating if desired.
- the coating solutions may be prepared by dissolving the polyvinyl-ester or acetal and lightsensitive diazo compound in a suitable solvent or mixture of solvents, such as methanol, ethanol, dioxane, etc.
- a suitable solvent or mixture of solvents such as methanol, ethanol, dioxane, etc.
- the polyvinyl ester or acetal and diazo compound may be dissolved in the same solution separately or dissolved in different portions of the same solvent and admixed with stirring, if desired.
- the stabilizing agent can be added i like manner.
- the solutions may then be applied to a support and the resulting layers dried.
- the preparation of the solutions and coating operations should, of course, be carried out in the absence of actinic radiationswhich would affect the light-sensitive diazo compounds.
- the coupling components e. g., phenols, naphthols, reactive methylene compounds, etc.
- used to form the final dye image in the layer may be incorporated with the coating solutions in the same manner as the diazo compound.
- the development of the resulting elements may be carried out after exposure by treatment with ammonia vapor or an alkaline solution.
- the elements which are free from coupling components may be treated, after exposure, in an alkaline developer solution containing the coupling components.
- the preferred resinous lower aliphatic acetals and esters of vinyl alcohol polymers used in accordance with the teachings hereof have the following properties.
- the preferred resins having these properties are prepared by (1) polymerizing vinyl acetate or vinyl proplonate to such an extent that a solution of 86 g. of the polymer in 1000 cc. of benzene has a viscosity of between 50 and 150 centirepresented by the formula:
- radical represents approximately 25 to 40% of the total weight of the polymer and R is CH:; CH3CH2; CHsCHaCHa-; or (CI-l3) :CH.
- coating compositions are applied by dip- P 8. painting or spraying onto water-resistant surfaces such as metals, plastics, composition boards, glass, transparent film base, water-proofed paper, cellulose, or the like. After coating, the surface will dry in the air or may be warmed to 40 to 50 C. in a current of air to speed drying. Higher temperatures however are often injurious to the light-sensitive compound. The final element is then ready for use or may be stored for periods up to several months before use.
- diazo stabilizers are phosphate, dilaurylphosphate v aromatic phosphates, e. g., tricresylphosphate. These compounds are required in only very small amounts, i. e., 0.01 to 0.2% based on the total weight of binder used.
- a soluble stabilizer such as sodium nitrite is used and a wet processing step employed. it is desirable to add a small amount of the stabilizer to the final wash.
- Metal deactivators that contain amino groups are not practical in this process since they react with the diazo compound themselves.
- Example I Twenty-seven parts of p-aminodiethylaniline sulfate is dissolved in 100 parts of water containing 12.5 parts of concentrated hydrochloric acid and cooled to 0 C. To thi is added 20 parts of 5 molar sodium nitrite solution at 5 C. After five minutes 20 parts of zinc chloride is added and the solution stirred while adding 30 part of sodium chloride at 5 C. The resulting crystalline product, the zinc chloride double salt of p-diethylamlnobenzene diazonium chloride, is removed by filtration and washed with 10% sodium chloride solution and dried by suction for ten minutes.
- this moist diazo salt is dissolved in 80 parts of 95%; ethanol, filtered, and mixed with 320 parts of a solution prepared by dissolving 100 parts of polyvinyl acetate (viscosity 85-115 centipoises at 20 C. of a solution of 86 g. in 1000 cc. of benzene measured in a I-Ioeppler viscometer; melting range ISO-200 C.) in 500 partsof 95% ethanol 4 and the solution diluted with ethanol to 800 parts and used as a stock solution.
- polyvinyl acetate viscosity 85-115 centipoises at 20 C.
- Example II Glass, aluminum, stainless steel, and painted (alcohol-resistant lacquer) steel plates are dipped in a mixture of parts of the stock solution of Example I and 100 parts of ethyl acetate. The coating dries in about 5 minutes at 50 C. and the resulting plates are ready for use.
- ordinary steel plates are used in place of the above supports either, (If) two parts of 10% sodium nitrite or (B) one part of 10% sodium nitrite and two parts of 1% dilauryl phosphate in ethanol is added to the coating solution of Example 1 before dipping to prevent destruction of the diazo. salt.
- the dried plates are placed under a film containing a line drawing and exposed to sunlight for 15 seconds, then developed in a solution prepared by dissolving the ingredients in the following order:
- Example III To a solution containing 10 parts of polyvinyl acetate of the type described in Example I dissolved in parts of ethanol, 25 parts of ethyl acetate, 20 parts of butyl acetate, and 20 parts of p-ethoxyethanol there is added 10 parts of the diazo salt of Example I. Using a brush, this solution is spreadevenly on metal surfaces. e. g.,
- Example IV Example V In place of the polyvinyl acetate of Examples 1, II, III and IV is used a polyvinyl acetaldehyde acetai prepared by acetalizing 65% of the hydroxyl groups of a completely hydrolyzed polyvinyl alcohol which has a viscosity of 18-28 centi poises (4%aqueous solution at 20 (7.). Similar result are obtained.
- This invention is not limited to the use of the hydrolyzed- Interpolymers of vinyl acetate or vinyl pro- 1 pionat with terminally unsaturated mono-olefins, e. g., ethylene having an olefin content between about 2 and 40% which are not more than 50% hydrolyzed.
- Interpolymers of vinyl acetate with minor (mol ratio less than 1) parts of other unsaturated compounds e. g., vinyl chloride, vinylidene compounds, alkyl acrylates, alkylmethacrylates, etc.,
- mono-olefins such as ethylene, vinyl chloride, alkyl arcrylates, etc.
- lower aliphatic aldehydes e. g., CH3(CH2)nCHO where 12:0 to 2 to form acetal groups on between about 40 and 80% of the hydroxyl groups.
- Plasticizers though usually unnecessary may be used in the polyvinyl resinous esters, if desired. Suitable plasticizers including dibutyl sebacate, methylphthalate, methyl glycolate, N-ethyl-ptoluene-sulfonamide and dimethoxymethyl adipate may increase the flexibility of the resins. In general, they should be used in a small amount, e. g., 1 to 10% by weight based on the amount of polyvinyl ester.
- any organic solvent or mixture of solvents may be employed in preparing the solutions as long as they are not reactive with the diazo compounds.
- ketones such as acetone, methyl ethyl ketone, cyclohexanone, etc.
- alcohols e. g., methanol, ethanol, n-propanol, iso-propanol, n-butanol, secondary butanol, etc.
- glycols e. g., ethylene glycol, diethylene glycol, propylene glycol, ethylene glycol monomethyl and ethyl ethers; ethers, e.
- esters e. g., methyl acetate, ethyl acetate, ethyl propionate ethyl butyrate, ethyl glycolate, ethyl methoxyacetate
- hydrocarbons e. g., hexane
- chlorinated hydrocarbons e. g., chloroform,carbon tetrachloride, ethylene dichloride, etc.
- chlorinated hydrocarbons e. g., chloroform,carbon tetrachloride, ethylene dichloride, etc.
- the preferred solvents or solvent solutions are those which are water miscible to the extent that 10% or more'water can be dissolved therein.
- a small amount of water in the coating composition is desirable and aids in dissolving the diazonium compound and in securing an even lightsensitive' coating.
- portions (e. g., 525%) of solvent with a higher vapor pressure, e. g., boiling between 100 and 200 C are advantageous as an aid in securing even flow-outs and smooth coatings.
- an anti-foaming agent e. g., long chain aliphatic alcohol, e, g., decyl, dodecyl; tetradecyl, etc., so that an even coating free from bubbles may be obtained.
- R1 and R2 are organic radicals, e. g., aromatic hydrocarbon, aliphatic hydrocarbon, heterocyclic, etc.; also, R1 and R2 may together form a saturated, unsaturated, or heterocyclic ring.
- Ra may be the same as R1 or may be -SR1, 0R1, NI-ICOOR1, NHCONHR1.
- X and Y may be H, Cl, Br, alkyl, aryl, alkoxy, aryloxy, halogenoalkyl, etc.
- Z is hydrogen or, together with X, may form an aromatic or heterocyclic ring.
- Specific compounds of this type include p-aminoacetanilide, p-aminobenzanilide, 4-amino-2,5- dimethoxyacetanilide; 4 amino 2,5 dichlorobenzanilide; 1-amino-4 -acetaminonaphthalene; 4-aminodiethylaniline; 4 -aminodimethylaniline; 4-amino-2-methyldiethylaniline; N- (p aminophenyl)morpholine; N-(4-amino-2,5 diethoxyphenyl) piperidine; l-aminol-dimethylaminonaphthalene; 4-aminodiphenyl; 4-aminocarboethoxyaniline; 4-amino 2,5 dimethoxyphenyl urea; 4-amino-2,5-dichlorophenylurea.
- the light-sensitive solutions of this invention in general have a solids content, e. g., diazo plus binder, of between about 1 and 20%. However, it has been found that the best coatings are obtained with solutions in the range of about 2 to 7% solids content, depending upon the particular resin employed and the method used in applying the solution. Thus, for brushing or dipping,
- .Such compounds include aniiines, naphthylamines, aminophenols and aminonaphthols unsubstituted or having substituents in the ring or in the amino group, e. g., o-toluidine, m-aminophenol, 1-amino-8-naphthol-3,6-disulfonic acid.
- compositions of this invention can be prepared by use of the appropriate diazos for use according to the Frangialli process (see French Patent No. 853,868 and United States Patent No. 2,313,288) wherein the surface is exposed to a strong ultraviolet source, 1. e., a carbon light which destroys the diazo in the transparent portions of the drawing.
- a strong ultraviolet source 1. e., a carbon light which destroys the diazo in the transparent portions of the drawing.
- the drawing is then removed and the'light-sensitive surface moistened and exposed to a light of low ultraviolet intensity fora short period. This causes a conversion of a part of the diazo to a phenol and is followed by coupling with the unconverted diazo to form a dye image.
- Positive prints can also be obtained directly from negatives by the use of diazo sulfonate such as described in United States Patents 2,197,456 and 2,217,189.
- diazo sulfonate such as described in United States Patents 2,197,456 and 2,217,189.
- the process of United States Patents 2,034,508 and 2,067,690, wherein diazo compounds are converted to the colored oxidation products of phenols under the influence of light can be applied to the present invention.
- any of the various known sensitizers such as urea, thiourea, allyl thiourea, thiosulfate, etc., and/or compounds which form double salts with diazonium compounds such as tin, zinc, or cadmium salts of weak acids, e. g., tartaric, citric, succinic, boric, etc., may be employed in these compositions.
- weak acids e. g., tartaric, citric, succinic, boric, etc.
- pigments it is also desirable in some cases to add pigments to the compositions.
- a pigment is added which i complementary in color to that of the final azo dye produced in the drawing.
- a white pigment may be added such as titanium dioxide or barium sulfate pigment.
- the final colors are to be red. 3. green pigment may be used, or if they are to be blue, a yellow pigment may be used, or any other such combination.
- the light-sensitive coating compositions hereof have the advantages that they form water-permeable layers which are (a) not softened by water sufliciently to cause scratching or marring when handled wet, (b) resistant to dilute acids and alkalies at least for a short time, (c) capable of forming tough, strong, unsupported coherent films, having a tensile strength greater than 1000 lb./sq. in. when dry or wet, and are free from brittleness which will cause chippin or flaking terials to be used, such as metal, composition boards, etc., are coated with the light-sensitive compositions of this invention, dried, exposed through the master drawing and developed. The finished print which adheres firmly and is an exact duplicate of the original is used to cut out the template.
- Stencils or lettered transparencies may also be used to reproduce directions. identification numbers, etc., on parts or finished articles of manufacture.
- Elements may also be prepared by coating the light-sensitive solutions on flexible bases such as film base, waterproofed paper, plastic sheeting, and the like. Such elements may be used to prepare permanent records or may be fastened adhesively to permanent supports, e. g., metal, boards,'etc.
- a coating composition comprising a watermiscible organic solvent having dissolved therein a water-insoluble resinous polyvinyl acetate free from hydroxyl groups and having a water absorption of at least 10%, a light-sensitive diazonium salt, a diazo stabilizer, taken from the group consisting of water-soluble alkali metal nitrites, alkyl nitrites, and hydrocarbon phosphates, a diazo coupling component, and not more than 10% of water.
- a coating composition comprising a mixture of ethanol and ethyl acetatehaving dissolved therein a water-insoluble resinous polyvinyl acetate which is free from hydroxyl groups and has .a water absorption of at least 10%, from 0.01 to 0.2% of sodium nitrite based on the weight of said polyvinyl acetate. a light-sensitive diazonium salt, and not more than 10% of water.
- a photographic element comprising a ferrous metal support bearing a layer comprising a water-insoluble resinous polyvinyl acetate free from hydroxyl groups and having a water-absorption of at least 10% which ha intimately dispersed therethrough a light-sensitive xiiazonium salt, a diazo stabilizer taken from the group consisting of water-soluble alkali metal nitrites, alkyl nitrites, and hydrocarbon phosphates, and a diazo coupling component.
- a photographic element comprising a ferrous metal support bearing a layer comprising a water-insoluble resinous polyvinyl acetate free from hydroxyl groups and having a water-absorption of at least 10% which has intimately dispersed therethrough a light-sensitive diazonium salt and from 0.01 to 0.2% of sodium nitrite based on the weight of said polyvinyl acetate.
- VIRGIL B SEASE. DAVID W. WOODWARD.
Description
Patented Aug. 6, 1946 LIGHT-SENSITIVE PHOTOGRAPHIC COM- POSITIONS AND ELEIVIENTS Virgil B. Sease and David W. Woodward, Wilmlngton, Del., assignors to E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application August 9, 1944, Serial No. 548,796
4 Claims. (Cl. sis- 7) This invention relates to photography and, more particularly, to light-sensitive photographic elements and to their preparation. Still more particularly, it relates to water-resistant supports bearing a water-permeable layer composed of a vinyl resin binder containing a light-sensitive diazonium salt, and to compositions for making such layers.
An object of this invention is to provide new and useful light-sensitive diazo salt solutions which are stable, of low water content. and can be coated to form smooth, tough, mar-resistant surfaces. A related object is to provide such solutions which are fast drying, not softened by water, and have good adherence to water-resistant surfaces. A further object is to provide photographic elements with water-insoluble but water-permeable, light-sensitive layers which may be processed rapidly to yield reproductions of high contrast, resolving power, and definition. Still other objects will be apparent from the following description of the invention.
The above objects are attained by the preparation and use of the novel coating compositions, layers and photographic elements described below. The coating solutions in their broader aspects consist of a solvent containing a waterpermeable, water-insoluble resinous lower aliphatic ester or acetal of a vinyl alcohol polymer which acts as a binding agent or medium for a light-sensitive diazonium compound. The novel light-sensitive layers and elements contain or comprise a stratum composed essentially of the aforesaid resinous ester or acetal and the diazoniulm salt. The solvent is completely or substantially removed during a coating operation. Since organic solvents may be used, the drying time may be greatly reduced. However, a small amount of water may be present in the solvent mixture to aid in dissolving the diazonium compound.
In a preferred aspect of the invention the coating composition layers and elements further contain a stabilizing agent for the light-sensitive diazonium compound. This may advantageously be introduced during the preparation of the coat ing composition but'may be added just prior to coating if desired.
The coating solutions may be prepared by dissolving the polyvinyl-ester or acetal and lightsensitive diazo compound in a suitable solvent or mixture of solvents, such as methanol, ethanol, dioxane, etc. The polyvinyl ester or acetal and diazo compound may be dissolved in the same solution separately or dissolved in different portions of the same solvent and admixed with stirring, if desired. The stabilizing agent can be added i like manner. The solutions may then be applied to a support and the resulting layers dried. The preparation of the solutions and coating operations should, of course, be carried out in the absence of actinic radiationswhich would affect the light-sensitive diazo compounds.
The coupling components, e. g., phenols, naphthols, reactive methylene compounds, etc., used to form the final dye image in the layer may be incorporated with the coating solutions in the same manner as the diazo compound. The development of the resulting elements may be carried out after exposure by treatment with ammonia vapor or an alkaline solution. On the other hand, the elements which are free from coupling components may be treated, after exposure, in an alkaline developer solution containing the coupling components.
The preferred resinous lower aliphatic acetals and esters of vinyl alcohol polymers used in accordance with the teachings hereof have the following properties.
(A) They are soluble to the extent of at least 5% and preferably 10% in an organic solvent system which will dissolve the light-sensitive diazo compound without reaction therewith and are insoluble in water even when warmed to 80 C.
(B) They are permeable to aqueous processing solutions, i. e., they have a water absorption of at ,least 10% which permits rapid processing after exposure. The term water absorption of 10% means that an unsupported film about 0.002 inch thick which has been dried at 60 C. for 24 hours and placed in water at normal temperatures (20-25 C.) for one-half hour will absorb water equivalent to 10% of its weight.
(0) They have a softening point above 60 C. when dry.
The preferred resins having these properties are prepared by (1) polymerizing vinyl acetate or vinyl proplonate to such an extent that a solution of 86 g. of the polymer in 1000 cc. of benzene has a viscosity of between 50 and 150 centirepresented by the formula:
radical represents approximately 25 to 40% of the total weight of the polymer and R is CH:; CH3CH2; CHsCHaCHa-; or (CI-l3) :CH.
These coating compositions are applied by dip- P 8. painting or spraying onto water-resistant surfaces such as metals, plastics, composition boards, glass, transparent film base, water-proofed paper, cellulose, or the like. After coating, the surface will dry in the air or may be warmed to 40 to 50 C. in a current of air to speed drying. Higher temperatures however are often injurious to the light-sensitive compound. The final element is then ready for use or may be stored for periods up to several months before use.
Heretofore it has been impossible to apply diazonium compounds directly to ordinary untreated iron and steel surfaces which are not corrosion-resistant since a, rapid interaction oc curs between the metal and diazonium salt. This results in formation of rust and decomposition of the diazo salt. Now it has been found, n
this is an important feature of the present invention, that when certain diazo stabilizers are phosphate, dilaurylphosphate v aromatic phosphates, e. g., tricresylphosphate. These compounds are required in only very small amounts, i. e., 0.01 to 0.2% based on the total weight of binder used. When a soluble stabilizer such as sodium nitrite is used and a wet processing step employed. it is desirable to add a small amount of the stabilizer to the final wash.-
Metal deactivators that contain amino groups are not practical in this process since they react with the diazo compound themselves.
The following examples, in which an parts are by weight, are further illustrative of the nature of the invention. In the preparationand coating of these light-sensitive diazoniunf solutions all light is excluded which will decompose the diazonium compounds.
Example I Twenty-seven parts of p-aminodiethylaniline sulfate is dissolved in 100 parts of water containing 12.5 parts of concentrated hydrochloric acid and cooled to 0 C. To thi is added 20 parts of 5 molar sodium nitrite solution at 5 C. After five minutes 20 parts of zinc chloride is added and the solution stirred while adding 30 part of sodium chloride at 5 C. The resulting crystalline product, the zinc chloride double salt of p-diethylamlnobenzene diazonium chloride, is removed by filtration and washed with 10% sodium chloride solution and dried by suction for ten minutes. Eighteen parts of this moist diazo salt is dissolved in 80 parts of 95%; ethanol, filtered, and mixed with 320 parts of a solution prepared by dissolving 100 parts of polyvinyl acetate (viscosity 85-115 centipoises at 20 C. of a solution of 86 g. in 1000 cc. of benzene measured in a I-Ioeppler viscometer; melting range ISO-200 C.) in 500 partsof 95% ethanol 4 and the solution diluted with ethanol to 800 parts and used as a stock solution.
Example II Glass, aluminum, stainless steel, and painted (alcohol-resistant lacquer) steel plates are dipped in a mixture of parts of the stock solution of Example I and 100 parts of ethyl acetate. The coating dries in about 5 minutes at 50 C. and the resulting plates are ready for use. When ordinary steel plates are used in place of the above supports either, (If) two parts of 10% sodium nitrite or (B) one part of 10% sodium nitrite and two parts of 1% dilauryl phosphate in ethanol is added to the coating solution of Example 1 before dipping to prevent destruction of the diazo. salt. The dried plates are placed under a film containing a line drawing and exposed to sunlight for 15 seconds, then developed in a solution prepared by dissolving the ingredients in the following order:
Parts Water 300 Sodium hydroxide 5 Sodium sulfite 10 Sodium 'thiosulfate 40 Ethanol 80 2,3-hydroxynaphthoic anilide 5 Alpha-naphthol 0.3
Water to make 1,000
To this solution is added 5 parts of activated charcoal and the mixture filtered to yield a. clear, pale yellow solution. The plates. after being immersed in this developing solution for 30 seconds, followed by washing in water and drying, contained a positive reproduction of the original drawing with sharp, grainiess black lines. The surfaces are smooth, hard, and mar-resistant.
Example III To a solution containing 10 parts of polyvinyl acetate of the type described in Example I dissolved in parts of ethanol, 25 parts of ethyl acetate, 20 parts of butyl acetate, and 20 parts of p-ethoxyethanol there is added 10 parts of the diazo salt of Example I. Using a brush, this solution is spreadevenly on metal surfaces. e. g.,
aluminum, stainless steel, painted steel. In fivev minutes the coating has set, and after drying for 15 minutes at 40 C. a smooth even coating of the light-sensitive composition is ready for exposure and development as in Example II.
Example IV Example V In place of the polyvinyl acetate of Examples 1, II, III and IV is used a polyvinyl acetaldehyde acetai prepared by acetalizing 65% of the hydroxyl groups of a completely hydrolyzed polyvinyl alcohol which has a viscosity of 18-28 centi poises (4%aqueous solution at 20 (7.). Similar result are obtained.
This invention is not limited to the use of the hydrolyzed- Interpolymers of vinyl acetate or vinyl pro- 1 pionat with terminally unsaturated mono-olefins, e. g., ethylene having an olefin content between about 2 and 40% which are not more than 50% hydrolyzed.
Interpolymers of vinyl acetate with minor (mol ratio less than 1) parts of other unsaturated compounds, e. g., vinyl chloride, vinylidene compounds, alkyl acrylates, alkylmethacrylates, etc.,
which are not more than 50% hydrolyzed.
Polyvinyl alcohol and completely hydrolyzed interpolymers of vinyl acetate with less than 40% of an unsaturated polymerizable compound,
e. g., mono-olefins, such as ethylene, vinyl chloride, alkyl arcrylates, etc., which have been condensed with lower aliphatic aldehydes, e. g., CH3(CH2)nCHO where 12:0 to 2 to form acetal groups on between about 40 and 80% of the hydroxyl groups.
Plasticizers though usually unnecessary may be used in the polyvinyl resinous esters, if desired. Suitable plasticizers including dibutyl sebacate, methylphthalate, methyl glycolate, N-ethyl-ptoluene-sulfonamide and dimethoxymethyl adipate may increase the flexibility of the resins. In general, they should be used in a small amount, e. g., 1 to 10% by weight based on the amount of polyvinyl ester.
Any organic solvent or mixture of solvents may be employed in preparing the solutions as long as they are not reactive with the diazo compounds. Thus, ketones, such as acetone, methyl ethyl ketone, cyclohexanone, etc., cannot be used while alcohols, e. g., methanol, ethanol, n-propanol, iso-propanol, n-butanol, secondary butanol, etc., glycols, e. g., ethylene glycol, diethylene glycol, propylene glycol, ethylene glycol monomethyl and ethyl ethers; ethers, e. g., ethylene glycol dimethyl ether, tetrahydrofuran; esters, e. g., methyl acetate, ethyl acetate, ethyl propionate ethyl butyrate, ethyl glycolate, ethyl methoxyacetate; hydrocarbons, e. g., hexane,
benzene; chlorinated hydrocarbons, e. g., chloroform,carbon tetrachloride, ethylene dichloride, etc., can be used, providing that they. are solvents for all the constituents of the coating composition.
The preferred solvents or solvent solutions are those which are water miscible to the extent that 10% or more'water can be dissolved therein. A small amount of water in the coating composition is desirable and aids in dissolving the diazonium compound and in securing an even lightsensitive' coating. Further, it is usually desirable to use those with an appreciable vapor pressure at normal temperatures so that drying times will be as short as possible. However, in addition, portions (e. g., 525%) of solvent with a higher vapor pressure, e. g., boiling between 100 and 200 C, are advantageous as an aid in securing even flow-outs and smooth coatings.
In preparing solutions for application by spraying, it is often desirable to add an anti-foaming agent, e. g., long chain aliphatic alcohol, e, g., decyl, dodecyl; tetradecyl, etc., so that an even coating free from bubbles may be obtained.
Other light-sensitive diazo compounds than those of the above examples may be employed. The more commonly used diazo compounds include those prepared from the following amines:
a R, Ric ONH NH: /N NH:
I l R: z x z and Y I Ri-Q-NH: z x
where R1 and R2 are organic radicals, e. g., aromatic hydrocarbon, aliphatic hydrocarbon, heterocyclic, etc.; also, R1 and R2 may together form a saturated, unsaturated, or heterocyclic ring. Ra may be the same as R1 or may be -SR1, 0R1, NI-ICOOR1, NHCONHR1. X and Y may be H, Cl, Br, alkyl, aryl, alkoxy, aryloxy, halogenoalkyl, etc. Z is hydrogen or, together with X, may form an aromatic or heterocyclic ring. Specific compounds of this type include p-aminoacetanilide, p-aminobenzanilide, 4-amino-2,5- dimethoxyacetanilide; 4 amino 2,5 dichlorobenzanilide; 1-amino-4 -acetaminonaphthalene; 4-aminodiethylaniline; 4 -aminodimethylaniline; 4-amino-2-methyldiethylaniline; N- (p aminophenyl)morpholine; N-(4-amino-2,5 diethoxyphenyl) piperidine; l-aminol-dimethylaminonaphthalene; 4-aminodiphenyl; 4-aminocarboethoxyaniline; 4-amino 2,5 dimethoxyphenyl urea; 4-amino-2,5-dichlorophenylurea.
The light-sensitive solutions of this invention in general have a solids content, e. g., diazo plus binder, of between about 1 and 20%. However, it has been found that the best coatings are obtained with solutions in the range of about 2 to 7% solids content, depending upon the particular resin employed and the method used in applying the solution. Thus, for brushing or dipping,
higher solids contents may be employed, while for spraying it is usually desirable to use a more dilute solution containing a higher percentage of a solvent with a boiling point about C. In general, it has been found that the best results are obtained when the ratio of diazo to binder is in the order of about 1:1 to 1:3, although in certain cases a higher or lower ratio may be useful.
Other coupling components than those of the above examples may be employed. They are, in general, phenols and naphthols, typical of which are the following:
tion, they may be employed in the developer solution. .Such compounds include aniiines, naphthylamines, aminophenols and aminonaphthols unsubstituted or having substituents in the ring or in the amino group, e. g., o-toluidine, m-aminophenol, 1-amino-8-naphthol-3,6-disulfonic acid.
In addition, the compositions of this invention can be prepared by use of the appropriate diazos for use according to the Frangialli process (see French Patent No. 853,868 and United States Patent No. 2,313,288) wherein the surface is exposed to a strong ultraviolet source, 1. e., a carbon light which destroys the diazo in the transparent portions of the drawing. The drawing is then removed and the'light-sensitive surface moistened and exposed to a light of low ultraviolet intensity fora short period. This causes a conversion of a part of the diazo to a phenol and is followed by coupling with the unconverted diazo to form a dye image.
Positive prints can also be obtained directly from negatives by the use of diazo sulfonate such as described in United States Patents 2,197,456 and 2,217,189. Inaddition, the process of United States Patents 2,034,508 and 2,067,690, wherein diazo compounds are converted to the colored oxidation products of phenols under the influence of light, can be applied to the present invention.
Any of the other types of light-sensitive diazos, including those capable of elf-coupling, such as are prepared from aminonaphthols, can b employed in the present invention by using the appropriate processing steps.
Any of the various known sensitizers such as urea, thiourea, allyl thiourea, thiosulfate, etc., and/or compounds which form double salts with diazonium compounds such as tin, zinc, or cadmium salts of weak acids, e. g., tartaric, citric, succinic, boric, etc., may be employed in these compositions. The latter compounds prevent coupling prior to exposure.
It is also desirable in some cases to add pigments to the compositions. For instance, if the light-sensitive composition is to be applied to a surface which is dark in color or unpainted and it is desired to have the maximum contrast, a pigment is added which i complementary in color to that of the final azo dye produced in the drawing. Thus, if the dye formed is black, a white pigment may be added such as titanium dioxide or barium sulfate pigment. If the final colors are to be red. 3. green pigment may be used, or if they are to be blue, a yellow pigment may be used, or any other such combination.
The light-sensitive coating compositions hereof have the advantages that they form water-permeable layers which are (a) not softened by water sufliciently to cause scratching or marring when handled wet, (b) resistant to dilute acids and alkalies at least for a short time, (c) capable of forming tough, strong, unsupported coherent films, having a tensile strength greater than 1000 lb./sq. in. when dry or wet, and are free from brittleness which will cause chippin or flaking terials to be used, such as metal, composition boards, etc., are coated with the light-sensitive compositions of this invention, dried, exposed through the master drawing and developed. The finished print which adheres firmly and is an exact duplicate of the original is used to cut out the template. Stencils or lettered transparencies may also be used to reproduce directions. identification numbers, etc., on parts or finished articles of manufacture. Elements may also be prepared by coating the light-sensitive solutions on flexible bases such as film base, waterproofed paper, plastic sheeting, and the like. Such elements may be used to prepare permanent records or may be fastened adhesively to permanent supports, e. g., metal, boards,'etc.
What is claimed is:
1. A coating composition comprising a watermiscible organic solvent having dissolved therein a water-insoluble resinous polyvinyl acetate free from hydroxyl groups and having a water absorption of at least 10%, a light-sensitive diazonium salt, a diazo stabilizer, taken from the group consisting of water-soluble alkali metal nitrites, alkyl nitrites, and hydrocarbon phosphates, a diazo coupling component, and not more than 10% of water.
2. A coating composition comprising a mixture of ethanol and ethyl acetatehaving dissolved therein a water-insoluble resinous polyvinyl acetate which is free from hydroxyl groups and has .a water absorption of at least 10%, from 0.01 to 0.2% of sodium nitrite based on the weight of said polyvinyl acetate. a light-sensitive diazonium salt, and not more than 10% of water.
3. A photographic element comprising a ferrous metal support bearing a layer comprising a water-insoluble resinous polyvinyl acetate free from hydroxyl groups and having a water-absorption of at least 10% which ha intimately dispersed therethrough a light-sensitive xiiazonium salt, a diazo stabilizer taken from the group consisting of water-soluble alkali metal nitrites, alkyl nitrites, and hydrocarbon phosphates, and a diazo coupling component.
4. A photographic element comprising a ferrous metal support bearing a layer comprising a water-insoluble resinous polyvinyl acetate free from hydroxyl groups and having a water-absorption of at least 10% which has intimately dispersed therethrough a light-sensitive diazonium salt and from 0.01 to 0.2% of sodium nitrite based on the weight of said polyvinyl acetate.
VIRGIL B. SEASE. DAVID W. WOODWARD.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US548796A US2405523A (en) | 1944-08-09 | 1944-08-09 | Light-sensitive photographic compositions and elements |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US548796A US2405523A (en) | 1944-08-09 | 1944-08-09 | Light-sensitive photographic compositions and elements |
Publications (1)
Publication Number | Publication Date |
---|---|
US2405523A true US2405523A (en) | 1946-08-06 |
Family
ID=24190427
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US548796A Expired - Lifetime US2405523A (en) | 1944-08-09 | 1944-08-09 | Light-sensitive photographic compositions and elements |
Country Status (1)
Country | Link |
---|---|
US (1) | US2405523A (en) |
Cited By (55)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2467358A (en) * | 1946-06-15 | 1949-04-12 | Gen Aniline & Film Corp | Preparation of diazo prints utilizing resorcinol carbonamides as coupling components |
US2501874A (en) * | 1946-06-12 | 1950-03-28 | Gen Aniline & Film Corp | Photographic diazo-sensitized glassine paper |
US2531091A (en) * | 1945-08-03 | 1950-11-21 | Gevaert Photo Prod Nv | N-acetonyl-pyridinium chloride as an azo coupling component in diazotypes |
US2551133A (en) * | 1946-08-29 | 1951-05-01 | Du Pont | Photographic light-sensitive diazo element |
US2560137A (en) * | 1948-12-21 | 1951-07-10 | Gen Aniline & Film Corp | Diazotype photoprinting material |
US2576850A (en) * | 1945-04-26 | 1951-11-27 | Du Pont | Gelling of polymeric compounds |
US2598453A (en) * | 1946-12-27 | 1952-05-27 | Gen Aniline & Film Corp | Diazotype composition for siliceous surfaces |
US2603564A (en) * | 1948-09-21 | 1952-07-15 | Gen Aniline & Film Corp | Light sensitive diazotype layer containing a white opacifying pigment |
US2613149A (en) * | 1947-10-29 | 1952-10-07 | Gen Aniline & Film Corp | Diazotype photoprinting material |
US2617726A (en) * | 1947-07-10 | 1952-11-11 | Grinten Chem L V D | Light-sensitive diazotype materials |
US2672418A (en) * | 1950-01-17 | 1954-03-16 | Keuffel & Esser Co | Light-sensitive diazotype material |
US2720467A (en) * | 1951-09-11 | 1955-10-11 | Ozalid Co Ltd | Process for preparing photographic elements |
US2746863A (en) * | 1954-02-10 | 1956-05-22 | Gen Aniline & Film Corp | Light sensitive diazotype material |
US2772160A (en) * | 1952-03-21 | 1956-11-27 | Eastman Kodak Co | Light-detached resists or reliefs for printing plates |
US2801919A (en) * | 1953-02-19 | 1957-08-06 | Screen Engineering Co | Photographic method for making templates |
US2819164A (en) * | 1952-11-29 | 1958-01-07 | Philips Corp | Method of manufacturing metallic patterns |
US2822272A (en) * | 1954-02-10 | 1958-02-04 | Gen Aniline & Film Corp | Light sensitive diazotype material |
US3016298A (en) * | 1957-06-17 | 1962-01-09 | Grinten Chem L V D | One-component diazotype material |
US3028240A (en) * | 1958-01-18 | 1962-04-03 | Keuffel & Esser Co | Light sensitive diazotype materials |
US3032414A (en) * | 1956-11-19 | 1962-05-01 | Kalvar Corp | System of photographic reproduction |
US3113025A (en) * | 1960-03-02 | 1963-12-03 | Gen Aniline & Film Corp | Diazotype materials for the production of black images |
US3123472A (en) * | 1958-11-10 | 1964-03-03 | Material comprising a diazomum com- | |
US3149972A (en) * | 1960-08-16 | 1964-09-22 | Gen Aniline & Film Corp | Diazo and resinous coupler printing plates for photomechanical reproduction |
US3164469A (en) * | 1960-03-04 | 1965-01-05 | Keuffel & Esser Co | One-component diazo process |
US3164468A (en) * | 1960-06-06 | 1965-01-05 | Gen Aniline & Film Corp | Photomechanical reversal process and foil and dyes for use therein |
US3169869A (en) * | 1958-06-04 | 1965-02-16 | Grinten Chem L V D | Diazotype material |
US3174860A (en) * | 1959-02-26 | 1965-03-23 | Azoplate Corp | Light sensitive polymeric diazonium and azidoacrylamido reproduction material and process of making plates therewith |
US3230087A (en) * | 1959-02-26 | 1966-01-18 | Azoplate Corp | Light-sensitive polymeric diazonium and azidoacrylamido reproduction materials and process for making plates therefrom |
US3238044A (en) * | 1962-03-14 | 1966-03-01 | Grinten Chem L V D | One-component diazotype material |
US3261684A (en) * | 1961-08-31 | 1966-07-19 | Grinten Chem L V D | Process and developer for developing exposed one-component diazotype materials |
US3272629A (en) * | 1962-01-25 | 1966-09-13 | Nashua Corp | Photosensitive diazotype materials |
US3276876A (en) * | 1963-03-19 | 1966-10-04 | Gen Aniline & Film Corp | Photographic sheet material |
US3290150A (en) * | 1958-11-10 | 1966-12-06 | Grinten Chem L V D | Light-sensitive diazotype material and diazo compounds |
US3377165A (en) * | 1964-01-22 | 1968-04-09 | Minnesota Mining & Mfg | Process of copying utilizing a blush lacquer coating and a photodecomposable progenitor of a plasticizer |
US3397058A (en) * | 1958-11-10 | 1968-08-13 | Grinten Chem L V D | Diazotype material |
US3401038A (en) * | 1964-03-06 | 1968-09-10 | Gaf Corp | Diazotype materials containing polycyclic light-sensitive fluorene diazonium salts |
US3409434A (en) * | 1965-10-28 | 1968-11-05 | Gaf Corp | Resin precoated diazotype papers |
US3416925A (en) * | 1963-07-06 | 1968-12-17 | Keuffel & Esser Co | Diazotype reproduction material |
US3463639A (en) * | 1965-12-15 | 1969-08-26 | Addressograph Multigraph | Benzene diazonium salts useful in diazotype materials having ortho carboxamido substitution |
US3847614A (en) * | 1971-09-13 | 1974-11-12 | Scott Paper Co | Diazo photopolymer composition and article comprising carboxylated resin |
US3881931A (en) * | 1972-05-22 | 1975-05-06 | Fuji Photo Film Co Ltd | Method for developing black diazotype photographic light-sensitive materials |
US3954462A (en) * | 1972-04-07 | 1976-05-04 | Keuffel & Esser Company | Electrolytically induced polymerization utilizing diazotization of primary aromatic amines |
US4054456A (en) * | 1972-04-21 | 1977-10-18 | Fuji Photo Film Co., Ltd. | Diazo photographic materials containing 2-hydroxy 3-naphthanilide coupler |
US4374193A (en) * | 1980-05-16 | 1983-02-15 | Kimoto & Co., Ltd. | Photosensitive material and process for developing the same |
US4377630A (en) * | 1980-07-04 | 1983-03-22 | Hitachi, Ltd. | Photosensitive composition |
EP0080241A2 (en) * | 1981-11-23 | 1983-06-01 | Océ-Nederland B.V. | Diazotype material |
US4457997A (en) * | 1981-01-10 | 1984-07-03 | Hoechst Aktiengesellschaft | Two-component diazotype material |
US4495269A (en) * | 1982-09-22 | 1985-01-22 | Am International, Inc. | Waterborne two component diazo type coating composition with hydrolyzed polyvinyl acetate and hexamethoxy methylmelamine resin |
US4652604A (en) * | 1985-08-02 | 1987-03-24 | American Hoechst Corporation | Radiation-polymerizable composition and element containing a photopolymer composition |
US4707437A (en) * | 1985-08-02 | 1987-11-17 | Hoechst Celanese Corporation | Radiation-polymerizable composition and element containing a photopolymer composition |
US4772538A (en) * | 1985-08-02 | 1988-09-20 | American Hoechst Corporation | Water developable lithographic composition |
US4780392A (en) * | 1985-08-02 | 1988-10-25 | Hoechst Celanese Corporation | Radiation-polymerizable composition and element containing a photopolymerizable acrylic monomer |
US4822720A (en) * | 1985-08-02 | 1989-04-18 | Hoechst Celanese Corporation | Water developable screen printing composition |
US4849323A (en) * | 1986-08-12 | 1989-07-18 | Matsushita Electric Industrial Co., Ltd. | Pattern forming method using contrast enhanced material |
US5120772A (en) * | 1985-08-02 | 1992-06-09 | Walls John E | Radiation-polymerizable composition and element containing a photopolymerizable mixture |
-
1944
- 1944-08-09 US US548796A patent/US2405523A/en not_active Expired - Lifetime
Cited By (56)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2576850A (en) * | 1945-04-26 | 1951-11-27 | Du Pont | Gelling of polymeric compounds |
US2531091A (en) * | 1945-08-03 | 1950-11-21 | Gevaert Photo Prod Nv | N-acetonyl-pyridinium chloride as an azo coupling component in diazotypes |
US2501874A (en) * | 1946-06-12 | 1950-03-28 | Gen Aniline & Film Corp | Photographic diazo-sensitized glassine paper |
US2467358A (en) * | 1946-06-15 | 1949-04-12 | Gen Aniline & Film Corp | Preparation of diazo prints utilizing resorcinol carbonamides as coupling components |
US2551133A (en) * | 1946-08-29 | 1951-05-01 | Du Pont | Photographic light-sensitive diazo element |
US2598453A (en) * | 1946-12-27 | 1952-05-27 | Gen Aniline & Film Corp | Diazotype composition for siliceous surfaces |
US2617726A (en) * | 1947-07-10 | 1952-11-11 | Grinten Chem L V D | Light-sensitive diazotype materials |
US2613149A (en) * | 1947-10-29 | 1952-10-07 | Gen Aniline & Film Corp | Diazotype photoprinting material |
US2603564A (en) * | 1948-09-21 | 1952-07-15 | Gen Aniline & Film Corp | Light sensitive diazotype layer containing a white opacifying pigment |
US2560137A (en) * | 1948-12-21 | 1951-07-10 | Gen Aniline & Film Corp | Diazotype photoprinting material |
US2672418A (en) * | 1950-01-17 | 1954-03-16 | Keuffel & Esser Co | Light-sensitive diazotype material |
US2720467A (en) * | 1951-09-11 | 1955-10-11 | Ozalid Co Ltd | Process for preparing photographic elements |
US2772160A (en) * | 1952-03-21 | 1956-11-27 | Eastman Kodak Co | Light-detached resists or reliefs for printing plates |
US2819164A (en) * | 1952-11-29 | 1958-01-07 | Philips Corp | Method of manufacturing metallic patterns |
US2801919A (en) * | 1953-02-19 | 1957-08-06 | Screen Engineering Co | Photographic method for making templates |
US2822272A (en) * | 1954-02-10 | 1958-02-04 | Gen Aniline & Film Corp | Light sensitive diazotype material |
US2746863A (en) * | 1954-02-10 | 1956-05-22 | Gen Aniline & Film Corp | Light sensitive diazotype material |
US3032414A (en) * | 1956-11-19 | 1962-05-01 | Kalvar Corp | System of photographic reproduction |
US3016298A (en) * | 1957-06-17 | 1962-01-09 | Grinten Chem L V D | One-component diazotype material |
US3028240A (en) * | 1958-01-18 | 1962-04-03 | Keuffel & Esser Co | Light sensitive diazotype materials |
US3169869A (en) * | 1958-06-04 | 1965-02-16 | Grinten Chem L V D | Diazotype material |
US3123472A (en) * | 1958-11-10 | 1964-03-03 | Material comprising a diazomum com- | |
US3290150A (en) * | 1958-11-10 | 1966-12-06 | Grinten Chem L V D | Light-sensitive diazotype material and diazo compounds |
US3397058A (en) * | 1958-11-10 | 1968-08-13 | Grinten Chem L V D | Diazotype material |
US3174860A (en) * | 1959-02-26 | 1965-03-23 | Azoplate Corp | Light sensitive polymeric diazonium and azidoacrylamido reproduction material and process of making plates therewith |
US3230087A (en) * | 1959-02-26 | 1966-01-18 | Azoplate Corp | Light-sensitive polymeric diazonium and azidoacrylamido reproduction materials and process for making plates therefrom |
US3113025A (en) * | 1960-03-02 | 1963-12-03 | Gen Aniline & Film Corp | Diazotype materials for the production of black images |
US3164469A (en) * | 1960-03-04 | 1965-01-05 | Keuffel & Esser Co | One-component diazo process |
US3164468A (en) * | 1960-06-06 | 1965-01-05 | Gen Aniline & Film Corp | Photomechanical reversal process and foil and dyes for use therein |
US3149972A (en) * | 1960-08-16 | 1964-09-22 | Gen Aniline & Film Corp | Diazo and resinous coupler printing plates for photomechanical reproduction |
US3261684A (en) * | 1961-08-31 | 1966-07-19 | Grinten Chem L V D | Process and developer for developing exposed one-component diazotype materials |
US3272629A (en) * | 1962-01-25 | 1966-09-13 | Nashua Corp | Photosensitive diazotype materials |
US3238044A (en) * | 1962-03-14 | 1966-03-01 | Grinten Chem L V D | One-component diazotype material |
US3276876A (en) * | 1963-03-19 | 1966-10-04 | Gen Aniline & Film Corp | Photographic sheet material |
US3416925A (en) * | 1963-07-06 | 1968-12-17 | Keuffel & Esser Co | Diazotype reproduction material |
US3377165A (en) * | 1964-01-22 | 1968-04-09 | Minnesota Mining & Mfg | Process of copying utilizing a blush lacquer coating and a photodecomposable progenitor of a plasticizer |
US3401038A (en) * | 1964-03-06 | 1968-09-10 | Gaf Corp | Diazotype materials containing polycyclic light-sensitive fluorene diazonium salts |
US3409434A (en) * | 1965-10-28 | 1968-11-05 | Gaf Corp | Resin precoated diazotype papers |
US3463639A (en) * | 1965-12-15 | 1969-08-26 | Addressograph Multigraph | Benzene diazonium salts useful in diazotype materials having ortho carboxamido substitution |
US3847614A (en) * | 1971-09-13 | 1974-11-12 | Scott Paper Co | Diazo photopolymer composition and article comprising carboxylated resin |
US3954462A (en) * | 1972-04-07 | 1976-05-04 | Keuffel & Esser Company | Electrolytically induced polymerization utilizing diazotization of primary aromatic amines |
US4054456A (en) * | 1972-04-21 | 1977-10-18 | Fuji Photo Film Co., Ltd. | Diazo photographic materials containing 2-hydroxy 3-naphthanilide coupler |
US3881931A (en) * | 1972-05-22 | 1975-05-06 | Fuji Photo Film Co Ltd | Method for developing black diazotype photographic light-sensitive materials |
US4374193A (en) * | 1980-05-16 | 1983-02-15 | Kimoto & Co., Ltd. | Photosensitive material and process for developing the same |
US4377630A (en) * | 1980-07-04 | 1983-03-22 | Hitachi, Ltd. | Photosensitive composition |
US4457997A (en) * | 1981-01-10 | 1984-07-03 | Hoechst Aktiengesellschaft | Two-component diazotype material |
EP0080241A2 (en) * | 1981-11-23 | 1983-06-01 | Océ-Nederland B.V. | Diazotype material |
EP0080241B1 (en) * | 1981-11-23 | 1987-09-09 | Océ-Nederland B.V. | Diazotype material |
US4495269A (en) * | 1982-09-22 | 1985-01-22 | Am International, Inc. | Waterborne two component diazo type coating composition with hydrolyzed polyvinyl acetate and hexamethoxy methylmelamine resin |
US4652604A (en) * | 1985-08-02 | 1987-03-24 | American Hoechst Corporation | Radiation-polymerizable composition and element containing a photopolymer composition |
US4707437A (en) * | 1985-08-02 | 1987-11-17 | Hoechst Celanese Corporation | Radiation-polymerizable composition and element containing a photopolymer composition |
US4772538A (en) * | 1985-08-02 | 1988-09-20 | American Hoechst Corporation | Water developable lithographic composition |
US4780392A (en) * | 1985-08-02 | 1988-10-25 | Hoechst Celanese Corporation | Radiation-polymerizable composition and element containing a photopolymerizable acrylic monomer |
US4822720A (en) * | 1985-08-02 | 1989-04-18 | Hoechst Celanese Corporation | Water developable screen printing composition |
US5120772A (en) * | 1985-08-02 | 1992-06-09 | Walls John E | Radiation-polymerizable composition and element containing a photopolymerizable mixture |
US4849323A (en) * | 1986-08-12 | 1989-07-18 | Matsushita Electric Industrial Co., Ltd. | Pattern forming method using contrast enhanced material |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2405523A (en) | Light-sensitive photographic compositions and elements | |
US2980534A (en) | Photographic compositions and photographic elements | |
US2990281A (en) | Photosensitive resinous compositions and photographic elements | |
US2551133A (en) | Photographic light-sensitive diazo element | |
US2751296A (en) | Photosensitization of cinnamic acid esters of cellulose | |
US2099297A (en) | Photographic material and process | |
US2298444A (en) | Light sensitive diazotype material | |
US2182794A (en) | Photographic elements containing antihalation layers | |
DE1112403B (en) | Photosensitive material | |
DE1232020B (en) | Photopolymerizable recording material for the production of color images | |
DE1000688B (en) | Water-permeable photographic silver halide emulsion | |
US3048487A (en) | Basic mordants derived from the reaction between maleic anhydride interpolymers and disubstituted diamines | |
US2462151A (en) | Photographic elements having hydrophilic polyvinyl acetal colloid sublayers | |
US3573093A (en) | Method for the antistatic treatment of plastic films | |
DE1447747A1 (en) | Negative working copy material | |
US3143417A (en) | Light sensitive coatings for screen printing containing nu-alkoxymethylated poly-sigma-caprolactam | |
US2432593A (en) | Phloroglucide containing diazo photoprinting material | |
US2500099A (en) | Diazo sulfonate light-sensitive element containing a diketone azo component | |
US2916376A (en) | Light sensitive coating composition | |
US2536989A (en) | Diazotype layers containing resorcinol derivatives | |
US3164469A (en) | One-component diazo process | |
US4171222A (en) | Two-component diazotype material | |
US2448507A (en) | Photographic elements having antihalation layer composed of vinylpyridine polymer with vinylpyridine polymer sublayer and outer protective layer | |
US2516931A (en) | Diazotype layers containing resorcinol mono-ethers | |
US2326782A (en) | Photosensitive material |