US3396023A - Piazine antifoggants for silver halide emulsions - Google Patents
Piazine antifoggants for silver halide emulsions Download PDFInfo
- Publication number
- US3396023A US3396023A US482237A US48223765A US3396023A US 3396023 A US3396023 A US 3396023A US 482237 A US482237 A US 482237A US 48223765 A US48223765 A US 48223765A US 3396023 A US3396023 A US 3396023A
- Authority
- US
- United States
- Prior art keywords
- silver halide
- photographic
- piazine
- gelatin
- layer
- 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
- -1 silver halide Chemical class 0.000 title description 105
- 229910052709 silver Inorganic materials 0.000 title description 67
- 239000004332 silver Substances 0.000 title description 67
- 239000000839 emulsion Substances 0.000 title description 55
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 title description 31
- 239000003795 chemical substances by application Substances 0.000 description 44
- 229920000159 gelatin Polymers 0.000 description 33
- 235000019322 gelatine Nutrition 0.000 description 33
- 108010010803 Gelatin Proteins 0.000 description 32
- 239000008273 gelatin Substances 0.000 description 32
- 235000011852 gelatine desserts Nutrition 0.000 description 32
- 125000004008 6 membered carbocyclic group Chemical group 0.000 description 21
- 125000003373 pyrazinyl group Chemical group 0.000 description 18
- 229920000728 polyester Polymers 0.000 description 15
- 125000000217 alkyl group Chemical group 0.000 description 13
- 125000003118 aryl group Chemical group 0.000 description 12
- 229920006267 polyester film Polymers 0.000 description 12
- 239000002585 base Substances 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- ULNMZMBBJRBGLM-UHFFFAOYSA-N 5-methylphenazin-5-ium-1,3-diamine;chloride Chemical compound [Cl-].C1=C(N)C=C2[N+](C)=C(C=CC=C3)C3=NC2=C1N ULNMZMBBJRBGLM-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 125000004442 acylamino group Chemical group 0.000 description 7
- 150000001299 aldehydes Chemical class 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 125000002837 carbocyclic group Chemical group 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 125000004423 acyloxy group Chemical group 0.000 description 5
- 125000003172 aldehyde group Chemical group 0.000 description 5
- CXEPVDIXZYCMFU-UHFFFAOYSA-L disodium;hydrogen sulfite;pentanedial Chemical compound [Na+].[Na+].OS([O-])=O.OS([O-])=O.O=CCCCC=O CXEPVDIXZYCMFU-UHFFFAOYSA-L 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- RETSEGNZNUBJRB-UHFFFAOYSA-N 2-Hydroxyphenazine Chemical compound C1=CC=CC2=NC3=CC(O)=CC=C3N=C21 RETSEGNZNUBJRB-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 150000001450 anions Chemical group 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- IHCHZHPJQZVBKI-UHFFFAOYSA-N 5-phenylphenazin-5-ium-1,2-diamine chloride Chemical compound [Cl-].NC1=C(C2=NC3=CC=CC=C3[N+](=C2C=C1)C1=CC=CC=C1)N IHCHZHPJQZVBKI-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- LUMLZKVIXLWTCI-NSCUHMNNSA-N (e)-2,3-dichloro-4-oxobut-2-enoic acid Chemical compound OC(=O)C(\Cl)=C(/Cl)C=O LUMLZKVIXLWTCI-NSCUHMNNSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical class N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JGEMYUOFGVHXKV-OWOJBTEDSA-N fumaraldehyde Chemical compound O=C\C=C\C=O JGEMYUOFGVHXKV-OWOJBTEDSA-N 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- ZAKLKBFCSHJIRI-UHFFFAOYSA-N mucochloric acid Natural products OC1OC(=O)C(Cl)=C1Cl ZAKLKBFCSHJIRI-UHFFFAOYSA-N 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000002601 radiography Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- SEIXQDAQPVUUQG-UHFFFAOYSA-N 1-phenylphenazin-10-ium;chloride Chemical compound [Cl-].C1=CC=CC=C1C1=CC=CC2=NC3=CC=CC=C3[NH+]=C12 SEIXQDAQPVUUQG-UHFFFAOYSA-N 0.000 description 1
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- XPAZGLFMMUODDK-UHFFFAOYSA-N 6-nitro-1h-benzimidazole Chemical compound [O-][N+](=O)C1=CC=C2N=CNC2=C1 XPAZGLFMMUODDK-UHFFFAOYSA-N 0.000 description 1
- 208000032484 Accidental exposure to product Diseases 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229940090898 Desensitizer Drugs 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000001828 Gelatine Substances 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- YHFXJKYHUWPWSJ-UHFFFAOYSA-L [Na+].[Na+].OS([O-])=O.OS([O-])=O Chemical compound [Na+].[Na+].OS([O-])=O.OS([O-])=O YHFXJKYHUWPWSJ-UHFFFAOYSA-L 0.000 description 1
- 231100000818 accidental exposure Toxicity 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical class [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000000298 carbocyanine Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Chemical class 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000002012 dioxanes Chemical class 0.000 description 1
- 239000006185 dispersion Substances 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002988 phenazines Chemical class 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- UOULCEYHQNCFFH-UHFFFAOYSA-M sodium;hydroxymethanesulfonate Chemical compound [Na+].OCS([O-])(=O)=O UOULCEYHQNCFFH-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000004354 sulfur functional group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Chemical class 0.000 description 1
- 239000011701 zinc Chemical class 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
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B17/00—Azine dyes
Definitions
- a photographic element comprising piazine antifoggants for silver halide emulsions and processes for developing said element are disclosed.
- This invention relates to stabilizing photographic materials.
- this invention relates to photographic silver halide emulsions and elements containing piazines as stabilizing and antifoggin'g agents and to methods of preparing photographic materials containing such agents.
- this invention relates to photographic silver halide emulsions coated on polyester film base which emulsions are stabilized against fog caused by contaminants in the film base.
- photographic silver halide emulsions such as gelatin silver halide emulsions
- gelatin silver halide emulsions upon storage, tend to lose sensitivity and to become spontaneously developable without exposure to light.
- fog tends to increase with time and temperature in storage conditions.
- polyester supports which exhibit superior physical properties such as excellent dimensional stability in comparison to other supports.
- polyester supports commonly contain various side reaction products which may be formed during synthesis of the polyester as well as catalyst residue.
- One or all of these constituents may serve to fog photographic silver halide emulsions coated on polyester supports even though a barrier layer such as a conventional subbing layer is interposed between the support and the photographic silver halide emulsion coating.
- Another object of this invention is to provide a means for stabilizing photographic silver halide emulsions which are processed in the presence of hardening agents, particularly gelatin hardening agents.
- Another object of this invention is to provide photographic elements comprising photographic silver halide emulsion layers coated on polyester film base, which emulsion layers are protected against fog caused by contaminants in the base.
- Still another object of this invention is to provide photographic silver halide emulsions and elements which are stabilized against fog using a piazine.
- fog in photographic silver halide emulsions can be substantially inhibited by the use of at least one piazine containing a pyrazine ring to which two 6-membered carbocyclic rings are fused symmetrically.
- One embodiment of this invention relates to a photographic silver halide emulsion comprising a hardening agent and an antifog-gant concentration of a piazine containing a pyrazine ring to which two 6-membered carbocyclic rings are fused symmetrically.
- Another embodiment of this invention relates to a photographic element comprising a support, a photographic silver halide layer and, incorporated in at least one layer of said element, a hardening agent and an antifoggant concentration of a piazine containing a pyrazine ring to which two G-membered carbocyclic rings are fused symmetrically.
- Another embodiment of this invention relates to a photographic element comprising a polyester support, a photographic silver halide layer and, incorporated in at least one layer of said element an antifoggant concentration of a piazine containing a pyrazine ring to which two 6-membered carbocyclic rings are fused symmetrically.
- Still another embodiment of this invention relates to developing, in the presence of a gelatin hardening agent, a photographic element comprising a support, a photographic silver halide layer and, incorporated in at least one layer of said element, an antifoggant concentration of a piazine containing a pyrazine ring to which two 6-membered carbocyclic rings are fused symmetrically.
- Still another embodiment of this invention relates to developing, in a developer containing a hardening agent, a photographic element comprising a polyester support, a photographic silver halide layer, and incorporated in at least one layer of said element, an antifoggant concentration of a piazine containing a pyrazine ring to which two 6-rnembered carbocyclic rings are fused symmetrically.
- piazines employed in the practice of this invention have been used in the past as antioxidant or desensitizers in developing solution employed to develop photographic silver halide emulsion layers.
- the piazines described herein would function as useful antifoggants when incorporated into silver halide emulsion layers, particularly those processed in the presence of hardening agents or coated on polyester film base.
- many compounds, for example, tetraazaindene are excellent antifoggants for emulsions coated on cellulose acetate film base but they fail to substantially reduce fogging of the photographic silver halide emulsions coated on polyester film base.
- antifoggants such as 6-nitrobenzimidazole reduce the fog of photographic silver halide emulsions coated on polyester film base but they have the disadvantage of substantially lowering the photographic speed of the silver halide emulsion.
- photographic elements containing piazines, as described herein often exhibit no significant improvement in fog when processed in developer solutions containing no hardening agent, as shown in Example 3 which follows.
- the piazines employed in the practice of this invention are heterocyclic compounds having two nitrogen atoms in the para position.
- the piazines contain a pyrazine ring to which two 6-membered carbocyclic rings are fused symmetrically and can be in the free or quaternized form.
- a piazine containing a pyrazine ring to which two 6-membered carbocyclic rings are fused symmetrically it is intended to include the compound in its free or quaternized form.
- the pyrazine ring in the piazine is fused to two symmetrical carbocyclic rings which can be unsubstituted, as in phenazine, or substituted by a variety of substituents including one or more other carbocyclic rings, for example, one or two fused aromatic rings as in napthophenazine and napthazine.
- substituents which can be present to form the resulting substituted phenazines or napthazines include amino, hydroxy, methyl amino, ethyl amino, methyl, ethyl, dodecyl, carboxyethyl, sulfopropyl, sulf-obutyl, phenyl, benzyl, acetyl, and the like. It is obvious that the nature of the substitutents on the two 6-membered fused rings in the piazines is subject to wide variation. However, it can be seen that these piazines are characterized by a pyrazine ring to which two 6- membered carbocyclic rings are fused symmetrically.
- Piazines which are particularly useful in the practice of this invention can be represented by the following formulas:
- each of R and R is amino, hydroxy, hydrocarbyl amino, alkyl, aryl, acyloXy, acylamino or a fused 6- membered carbocyclic ring and each n is an integer of Ru I Rn X- III. I":
- R is alkyl, hydroxyalkyl or aryl
- z is an integer of 0 to 1
- X is an anion such as halogen, chlorate, sulfate, methyl sulfate, p-toluene sulfonate "and the like.
- concentration of piazine employed in the practice of this invention is subject to wide variation. In general, however, quite useful results can be obtained with concentrations in the range of about 1 to about 50, preferably about 2 to about 30 mg. per mole of silver halide.
- the piazines can be incorporated into the silver halide emulsion layer or some other layer, e.g., a gelatin layer which is contiguous to 2-hydroxyphenazine 2,3-dian1inophenazine 3,6-dlaminopl1enazlne gill...
- the photographic silver halides and other layers of the photographic elements can be hardened, i.e., made less soluble and more resistant to warm aqueous solutions using any of the hardening agents suitable for this purpose.
- Compounds which are often used in the photographic field for this purpose are hardening agents such as aldehyde hardening agents, aziridine hardening agents, hardening agents which are derivatives of dioxane, oxypolysaccharides such as oxy starch or oxy plant gums or other types of hardening agents for binding materials such as gelatin and hydrophilic colloids.
- aldehyde hardening agents e.g., monoaldehydes such as mucochloric acid or formaldehyde, dialdehydes, the aldehyde groups of which are separated by a linear chain of 23 carbon atoms, which chain can contain up to three substituents being alkyl and/or alkoxy of 1-4 carbon atoms, alkali soluble aldehyde-bisulfite addition compounds, particularly alkali metal bisulfite-dialdehyde addition products in which the aldehyde groups in the dialdehyde are separated by a linear chain of 2-3 carbon atoms, which chain preferably has no more than two alkyl or alkoxy substituents thereon.
- aldehyde hardening agents e.g., monoaldehydes such as mucochloric acid or formaldehyde, dialdehydes, the aldehyde groups of which are separated by a linear chain of 23 carbon atoms, which chain can contain up to three
- alkali metal bisulfites are bisulfite of alkali metals such as sodium, potassium and the like.
- Aldehyde-bisulfite derivatives of alkaline earth metal bisulfites, nitrogen base (ammonium, amines and the like) bisulfites and the like can also be employed.
- concentration of the hardening agent employed in the practice of this invention is subject to wide variation and will depend upon the degree of hardening desired, duration of hardening and the like. However, good results are generally obtained with concentrations in the range of about 0.1 to about 35%, preferably about 2 to about 30%, by weight, based on the total amount of vehicle employed in the layers.
- These hardening agents can conveniently be incorporated into the photographic silver halide emulsion layers and/or other layers, particularly gelatin containing layers of a photographic element, or they can be employed in developing compositions as is known in the art.
- Typical hardening agents that can be employed in the practice of this invention include formaldehyde, mucochloric acid, sodium formaldehyde bisulfite, glutaraldehyde, s-methyl glutaraldehyde, glutaraldehyde bis-sodium bisulfite, maleic dialdehyde, maleic dialdehyde bis-sodium bisulfite, methyl maleic dialdehyde, methyl succinic dialdehyde, u-methyl-a-ethoxy glutaraldehyde, a,n-butoxy glutaraldehyde, B-n-butyl glutaraldehyde, fl-isopropoxy succinic dialdehyde, butyl maleic dialdehyde and other bisulfite derivatives of dialdehydes, the aldehyde groups of which are separated by three carbon atoms and the like.
- the silver halides employed in the practice of this invention include any of the photographic silver halides, as exemplified by silver bromide, silver iodide, silver chloride or mixed silver halides such as silver chlorobromide, silver bromoiodide and the like.
- the silver halides used can be those which form latent images predominantly on the surface of the silver halide grains or those which form latent images inside the silver halide crystals, such as those described in Davey and Knott, US. Patent 2,592,250, issued Apr. 8, 1952.
- colloids can be used as vehicles or binding agents in the photographic emulsions and elements of this invention.
- gelatin or other colloidal materials such as colloidal albumin, cellulose derivatives, synthetic resins such as polyvinyl compounds, acrylamide polymers and the like.
- binding agents include, for example, mixtures of gelatin with aqueous dispersions of polymerized ethylenically unsaturated compounds, particularly polyvinyl compounds.
- the photographic compositions described herein can be coated on a wide variety of supports, but preferably supports which are transparent and flexible.
- Typical supports include polymeric films such as cellulose acetate film, polyvinyl acetal film, polystyrene film, polypropylene film and other polyolefin film, polycarbonate film as well as glass, paper and the like.
- Supports such as paper which are coated with a-olefin polymers, particularly polymers of u-olefins containing 2-10 carbon atoms, as exemplified by polyethylene, polypropylene, ethylene butene polymers and the like, can also be employed.
- the piazines are particularly effective for controlling fog in photographic elements employing polyester film supports.
- polyester film supports including polymers composed of bifunctional dicarboxylic acids and glycols such as polyesters prepared from 1,4-cyclohexanedimethanol and terephthalate acid.
- Especially useful polyester film supports are poly(alkylene terephthalates), poly(ethylene terephthalate) being particularly suitable.
- various side reaction products are formed which remain in the film and act as contaminants which have a tendency to cause fog when photographic silver halide emulsions are coated thereover.
- the use of the piazines in emulsions coated on such supports substantially inhibits fogging caused by contaminants in such polyester film supports.
- Preferred polyester film supports suitable for use in this invention have a thickness in the range of about 1 to about mils, preferably about 2 to about 11 mils.
- the photographic silver halide emulsions described herein can be chemically sensitized with compounds of the sulfur group, noble metal salts such as gold salts, reduction sensitized with reducing agents, and combinations of these.
- the emulsions can also contain additional additives, particularly those known to be beneficial in photographic emulsions, including, for example, stabilizers or antifoggants, particularly the water soluble inorganic acid salts of cadmium, cobalt, manganese and zinc as disclosed in US. Patent 2,829,404, the substituted triazaindolizines as disclosed in US. Patents 2,444,605 and 2,444,607, speed increasing materials, plasticizers, a bsorbing dyes and the like.
- Sensitizers which gave particularly good results in the photographic compositions disclosed herein are the alkylene oxide polymers which can be employed alone or in combination with other materials, such as quaternary ammonium 'salts, as disclosed in US. Patent 2,886,437 or with mercury compounds and nitrogen containing compounds, as disclosed in US. Patent 2,751,299.
- the emulsions used in practicing this invention can also be X-ray or other non-spectrally sensitized emulsions as well as orthochromatic, panchromatic and infrared sensitive emulsions, particularly those sensitized with merocyanine dyes, cyanine dyes, carbocyanine dyes and the like.
- Example 1 The photographic elements described herein exhibit improved resistance to fogging when processed in the presence of a hardening agent.
- samples of a gelatin, medium-grain silver bromoiodide (98:2) photographic emulsion of the type normally used in radiography are coated on on ordinary cellulose acetate film support at coverages of 494 mg. of silver per square foot and 635 mg. of gelatin per square foot.
- a control sample contains no piazine while several samples contain the piazines listed in the following Table 1 at the concentrations given.
- the samples are given an 80 kv. direct X-ray exposure and processed for six minutes at F. in a hardening developer solution having the following composition:
- Example 2 The procedure of Example 1 is repeated with a gelatin, medium-grain silver bromoiodide (98:2) photographic emulsion of the type normally used in radiography, but having a sensitivity which is difierent from the emulsion described in Example 1.
- the piazines employed and results obtained are as follows:
- Example 4 The piazines described herein are particularly effective antifoggants for photographic silver halide emulsions coated on polyester film base and do not adversely affect TABLE 2 other sensitometric characteristics.
- samples Plazme Per mole sllver hahde) g of a direct X-ray type gelatine medium-grain silver broi moiodide (98:2) photographic emulsion containing the lwwyqmxyphenelme (4O) piazones listed in the following table are coated on a 2 3'dlaml nophenazme (20) p0ly(ethylene terephthalate) film base.
- the emulsion is Lacetammos'aCFtOXYPheHaZme (40) coated at a coverage of 1025 mg. of silver per square foot zhydroxyphenazme (40) and 1805 mg. of gelatin per square foot.
- P p a Control Sample ing n0 PiaZ ne is also seen that the piazines described herein are effective to F0ated samples 0f the film Coatlngs when fresh, after reduce fog in photographic silver halide emulsions proclllcutlatlofl r two s at 120 F.
- Example 3 to a 250 kv. direct X-ray source and developed for six
- the piazines described herein mlnjltes at in a developer Solution having e are very effective antifoggants for photographic silver l W1ngf0rmula: halide emulsion layers processd in the presence of hardening agents although they often exhibit no antifoggant Grams activity in the absence of such hardening agents.
- photographic silver halide emulsions which are stabilized against fog, particularly when these emulsions are coated on polyester supports and/or processed in the presence of hardening agents.
- a photographic silver halide emulsion comprising a hardening agent and an antifoggant concentration of a piazine containing a pyrazine ring to which two 6-membered carbocyclic rings are fused symmetrically.
- a gelatin photographic silver halide emulsion comprising a gelatin hardening agent and an antifoggant concentration of a piazine containing a pyrazine ring to which two 6-membered carbocyclic rings are fused symmetrically.
- each of R and R is amino, hydroxy, hydrocarbyl amino, alkyl, aryl, acryloxy, acylamino or a fused 6-membered carbocyclic ring and each n is an integer of to 2.
- a gelatin photographic silver halide emulsion comprising a gelatin aldehyde hardening agent and an antifoggant concentration of a piazine having the formula:
- R and R is amino, hydroxy, hydrocarbyl amino, alkyl, aryl, acyloxy, acylamino or a fused 6-membered carbocyclic ring
- R is alkyl, hydroxyalkyl or aryl
- X is an anion
- each n is an integer of 0 to 2
- z is an integer of 0 to 1.
- a gelatin photographic silver halide emulsion comprising glutaraldehyde bis-sodium bisulfite gelatin hardening agent and an antifoggant concentration of 1,3-diamino- S-methyl phenazinium chloride.
- a photographic element comprising a support, a photographic silver halide layer and, incorporated in at least one layer of said element, a hardening agent and an antifoggant concentration of a piazine containing a pyrazine ring to which two 6-membered carbocyclic rings are fused symmetrically.
- a photographic element comprising a support, a gelatin photographic silver halide layer and, incorporated in at least one layer of said element, a gelatin hardening agent and an antifoggant concentration of a piazine containing a pyrazine ring to which two 6-membered carbocyclic rings are fused symmetrically.
- a photographic element comprising a support, a gelatin photographic silver halide layer and, incorporated in at least one layer of said element, a gelatin aldehyde hardening agent and an antifoggant concentration of a piazine having the formula:
- each of R and R' is amino, hydroxy, hydrocarbyl amino, alkyl, aryl, acyloxy, acylamino or a fused 6-membered carbocyclic ring and each n is an integer of 0 to 2.
- a photographic element comprising a support, a gelatin photographic silver halide layer and, incorporated in at least one layer of said element, a gelatin aldehyde hardening agent and an antifoggant concentration of a piazine having the formula:
- R and R is amino, hydroxy, hydrocarbyl amino, alkyl, aryl, acyloxy, acylamino or a fused 6-membered carbocyclic ring
- R is alkyl, hydroxyalkyl or aryl
- X is an anion
- each n is an integer of 0 to 2
- z is an integer of 0 to 1.
- the hardening agent is a dialdehyde in which the aldehyde groups are joined by a linear carbon chain of 2-3 carbon atoms.
- the hardening agent is an alkali soluble bisulfite-dialdehyde addition product in which the aldehyde groups are separated by a linear hydrocarbon chain of 2-3 carbon atoms.
- a photographic element comprising a support, a gelatin photographic silver halide layer and, incorporated in at least one layer of said element, a glutaraldehyde bissodium bisulfite hardening agent and an antifoggant concentration of 1,3-diamino-5-methyl phenazinium chloride.
- a photographic element comprising a polyester support, a photographic silver halide layer and, incorporated in at least one layer of said element an antifoggant concentration of a piazine containing a pyrazine ring to which two o-membered carbocyclic rings are fused symmetrically.
- a photographic element comprising a polyester support, a gelatin photographic silver halide layer and, incorporated in at least one layer of said element an antifoggant concentration of a piazine containing a pyrazine ring to which two G-membered carbocyclic rings are fused symmetrically.
- a photographic element comprising a polyester support, a gelatin photographic silver halide layer and, incorporated in at least one layer of said element, an antifoggant concentration of a piazine having the formula:
- each of R and R is amino, hydroxy, hydrocarbyl amino, alkyl, aryl, acyloxy, acylamino or a fused 6-membered carbocyclic ring and each n is an integer of 0 to 2.
- a photographic element comprising a polyester support, a gelatin photographic silver halide layer and, incorporated in at least one layer of said element, an antifoggant concentration of a piazine having the formula:
- R and R is amino, hydroxy, hydrocarbyl amino, alkyl, aryl, acyloxy, acylamino or a. fused 6-membered carbocyclic ring, R is alkyl, hydroxyalkyl or aryl, X is an anion, each n is an integer of O to 2 and z is an integer of 0 to 1.
- polyester support is a polyethylene terephthalate support.
- a photographic element comprising a polyethylene terephthalate support a gelatin photographic silver halide layer and, incorporated in at least one layer of said element, an antifoggant concentration of a 1,3-diamino-5- methyl phenazinium chloride.
- a process which comprises developing, in the presence of a gelatin hardening agent, a photographic element comprising a support, a photographic silver halide layer and, incorporated in at least one layer of said element, an antifoggant concentration of a piazine containing a pyrazine ring to which two 6-membered carbocyclic rings: are fused symmetrically.
- a process which comprises developing, in a developer containing a hardening agent, a photographic element comprising a polyester support, a photographic silver halide layer, and incorporated in at least one layer of said element, an antifoggant concentration of a piazine containing a pyrazine ring to which two 6-membered carbocyclic rings are fused symmetrically.
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Description
United States Patent 3,396,023 PIAZINE ANTIFOGGANTS FOR SILVER HALIDE EMULSIONS William W. Rees and William H. Russell, Rochester, N.Y.,
assignors to Eastman Kodak Company, Rochester, N.Y.,
a corporation of New Jersey No Drawing. Filed Aug. 24, 1965, Ser. No. 482,237 20 Claims. (CI. 96-67) ABSTRACT OF THE DISCLOSURE A photographic element comprising piazine antifoggants for silver halide emulsions and processes for developing said element are disclosed.
This invention relates to stabilizing photographic materials. In one of its aspects, this invention relates to photographic silver halide emulsions and elements containing piazines as stabilizing and antifoggin'g agents and to methods of preparing photographic materials containing such agents. In another of its aspects, this invention relates to photographic silver halide emulsions coated on polyester film base which emulsions are stabilized against fog caused by contaminants in the film base.
It is known that photographic silver halide emulsions such as gelatin silver halide emulsions, upon storage, tend to lose sensitivity and to become spontaneously developable without exposure to light. There is normally a detectable amount of the silver salt reduced during development in the area where no exposure is given; this is commonly called fog and sometimes called chemical fog where it is necessary to distinguish between it and the effects of accidental exposure to radiation. Such fog tends to increase with time and temperature in storage conditions. Furthermore, in many photographic applications it is necessary, or at least desirable, to harden a photographic silver halide emulsion layer during processing by incorporating a hard ening agent into the emulsion or a developing solution. Many of the hardening agents used for this purpose cause the photographic silver halide emulsion to fog. In addition, photographic silver halide emulsions are often coated on polyester supports which exhibit superior physical properties such as excellent dimensional stability in comparison to other supports. However, polyester supports commonly contain various side reaction products which may be formed during synthesis of the polyester as well as catalyst residue. One or all of these constituents may serve to fog photographic silver halide emulsions coated on polyester supports even though a barrier layer such as a conventional subbing layer is interposed between the support and the photographic silver halide emulsion coating.
It is evident, therefore, that the state of the photographic art will be enhanced by prowiding photographic silver halide emulsions which are stabilized against fog, particularly when coated on polyester supports and/or processed in the presence of hardening agents. Likewise, providing a means for preparing and processing such photographic silver halide emulsions and elements will represent an advance in the photographic art.
Accordingly, it is an object of this invention to provide photographic silver halide emulsions and elements which are stabilized against fog.
Another object of this invention is to provide a means for stabilizing photographic silver halide emulsions which are processed in the presence of hardening agents, particularly gelatin hardening agents.
Another object of this invention is to provide photographic elements comprising photographic silver halide emulsion layers coated on polyester film base, which emulsion layers are protected against fog caused by contaminants in the base.
Still another object of this invention is to provide photographic silver halide emulsions and elements which are stabilized against fog using a piazine.
Other objects of this invention will become apparent from an examination of the specification and claims which follow.
In accordance with this invention it has been found that fog in photographic silver halide emulsions can be substantially inhibited by the use of at least one piazine containing a pyrazine ring to which two 6-membered carbocyclic rings are fused symmetrically.
One embodiment of this invention relates to a photographic silver halide emulsion comprising a hardening agent and an antifog-gant concentration of a piazine containing a pyrazine ring to which two 6-membered carbocyclic rings are fused symmetrically.
Another embodiment of this invention relates to a photographic element comprising a support, a photographic silver halide layer and, incorporated in at least one layer of said element, a hardening agent and an antifoggant concentration of a piazine containing a pyrazine ring to which two G-membered carbocyclic rings are fused symmetrically.
Another embodiment of this invention relates to a photographic element comprising a polyester support, a photographic silver halide layer and, incorporated in at least one layer of said element an antifoggant concentration of a piazine containing a pyrazine ring to which two 6-membered carbocyclic rings are fused symmetrically.
Still another embodiment of this invention relates to developing, in the presence of a gelatin hardening agent, a photographic element comprising a support, a photographic silver halide layer and, incorporated in at least one layer of said element, an antifoggant concentration of a piazine containing a pyrazine ring to which two 6-membered carbocyclic rings are fused symmetrically.
Still another embodiment of this invention relates to developing, in a developer containing a hardening agent, a photographic element comprising a polyester support, a photographic silver halide layer, and incorporated in at least one layer of said element, an antifoggant concentration of a piazine containing a pyrazine ring to which two 6-rnembered carbocyclic rings are fused symmetrically.
Certain of the piazines employed in the practice of this invention have been used in the past as antioxidant or desensitizers in developing solution employed to develop photographic silver halide emulsion layers. However, it could not have been expected that the piazines described herein would function as useful antifoggants when incorporated into silver halide emulsion layers, particularly those processed in the presence of hardening agents or coated on polyester film base. Thus, many compounds, for example, tetraazaindene are excellent antifoggants for emulsions coated on cellulose acetate film base but they fail to substantially reduce fogging of the photographic silver halide emulsions coated on polyester film base. Also, antifoggants such as 6-nitrobenzimidazole reduce the fog of photographic silver halide emulsions coated on polyester film base but they have the disadvantage of substantially lowering the photographic speed of the silver halide emulsion. In addition, photographic elements containing piazines, as described herein, often exhibit no significant improvement in fog when processed in developer solutions containing no hardening agent, as shown in Example 3 which follows.
The piazines employed in the practice of this invention are heterocyclic compounds having two nitrogen atoms in the para position. The piazines contain a pyrazine ring to which two 6-membered carbocyclic rings are fused symmetrically and can be in the free or quaternized form. Where reference is made in the specification and claims to a piazine containing a pyrazine ring to which two 6-membered carbocyclic rings are fused symmetrically, it is intended to include the compound in its free or quaternized form. As shown in the formulas which follow, the pyrazine ring in the piazine is fused to two symmetrical carbocyclic rings which can be unsubstituted, as in phenazine, or substituted by a variety of substituents including one or more other carbocyclic rings, for example, one or two fused aromatic rings as in napthophenazine and napthazine. Examples of substituents which can be present to form the resulting substituted phenazines or napthazines include amino, hydroxy, methyl amino, ethyl amino, methyl, ethyl, dodecyl, carboxyethyl, sulfopropyl, sulf-obutyl, phenyl, benzyl, acetyl, and the like. It is obvious that the nature of the substitutents on the two 6-membered fused rings in the piazines is subject to wide variation. However, it can be seen that these piazines are characterized by a pyrazine ring to which two 6- membered carbocyclic rings are fused symmetrically.
Piazines having up to about 24 carbon atoms, preferably 12 to 20 carbon atoms, give particularly advantageous results in the practice of this invention. Piazines which are particularly useful in the practice of this invention can be represented by the following formulas:
where each of R and R is amino, hydroxy, hydrocarbyl amino, alkyl, aryl, acyloXy, acylamino or a fused 6- membered carbocyclic ring and each n is an integer of Ru I Rn X- III. I":
Z 8 I N I where each of a, b, c and d is an integer of 0 to 1 and each Z represents the non-metallic atoms necessary to form a 6-mem-bered carbocyclic ring,
where Z, a, b, c, and d are as defined above, R is alkyl, hydroxyalkyl or aryl, z is an integer of 0 to 1 and X is an anion such as halogen, chlorate, sulfate, methyl sulfate, p-toluene sulfonate "and the like. The concentration of piazine employed in the practice of this invention is subject to wide variation. In general, however, quite useful results can be obtained with concentrations in the range of about 1 to about 50, preferably about 2 to about 30 mg. per mole of silver halide. The piazines can be incorporated into the silver halide emulsion layer or some other layer, e.g., a gelatin layer which is contiguous to 2-hydroxyphenazine 2,3-dian1inophenazine 3,6-dlaminopl1enazlne gill...
3-amino-7-dimethylaminophenazlne (CH3) 2N NH:
2-metl1yl-3-amir10-7-dimethylamlnopheuazlno N f om (CHshN \N/ NH;
Naphtho-phenazine N aphtllazine Plienanthrophenazine 2,3-dihydroxyphenazine 2-acetarnino-3-acetoxyphenazine l,3-dia1nino-5-methylphenazinium chloride 1,3-diamino-o-phenylphenazinium chloride 3,7 -diamino-5-phenylphenazinium chloride 2,S-dimethyl-3,7-diamino-Bphenylphenazinium chloride 3-amin0-7-pl1enylamino-5-phenylphenazinium chloride N N Ck H 1% H2 l 2.3,7,S-phenylamino-5-phenylphenazinium chloride eHs 1,3-diamino-5-benzylphenazinium chloride I OH:
The photographic silver halides and other layers of the photographic elements can be hardened, i.e., made less soluble and more resistant to warm aqueous solutions using any of the hardening agents suitable for this purpose. Compounds which are often used in the photographic field for this purpose are hardening agents such as aldehyde hardening agents, aziridine hardening agents, hardening agents which are derivatives of dioxane, oxypolysaccharides such as oxy starch or oxy plant gums or other types of hardening agents for binding materials such as gelatin and hydrophilic colloids. It has been found that particularly good hardening agents for the practice of this invention are aldehyde hardening agents, e.g., monoaldehydes such as mucochloric acid or formaldehyde, dialdehydes, the aldehyde groups of which are separated by a linear chain of 23 carbon atoms, which chain can contain up to three substituents being alkyl and/or alkoxy of 1-4 carbon atoms, alkali soluble aldehyde-bisulfite addition compounds, particularly alkali metal bisulfite-dialdehyde addition products in which the aldehyde groups in the dialdehyde are separated by a linear chain of 2-3 carbon atoms, which chain preferably has no more than two alkyl or alkoxy substituents thereon. The bisulfite addition products release aldehyde and harden at pHs greater than 7. Suitable alkali metal bisulfites are bisulfite of alkali metals such as sodium, potassium and the like. Aldehyde-bisulfite derivatives of alkaline earth metal bisulfites, nitrogen base (ammonium, amines and the like) bisulfites and the like can also be employed.
The concentration of the hardening agent employed in the practice of this invention is subject to wide variation and will depend upon the degree of hardening desired, duration of hardening and the like. However, good results are generally obtained with concentrations in the range of about 0.1 to about 35%, preferably about 2 to about 30%, by weight, based on the total amount of vehicle employed in the layers. These hardening agents can conveniently be incorporated into the photographic silver halide emulsion layers and/or other layers, particularly gelatin containing layers of a photographic element, or they can be employed in developing compositions as is known in the art. Typical hardening agents that can be employed in the practice of this invention include formaldehyde, mucochloric acid, sodium formaldehyde bisulfite, glutaraldehyde, s-methyl glutaraldehyde, glutaraldehyde bis-sodium bisulfite, maleic dialdehyde, maleic dialdehyde bis-sodium bisulfite, methyl maleic dialdehyde, methyl succinic dialdehyde, u-methyl-a-ethoxy glutaraldehyde, a,n-butoxy glutaraldehyde, B-n-butyl glutaraldehyde, fl-isopropoxy succinic dialdehyde, butyl maleic dialdehyde and other bisulfite derivatives of dialdehydes, the aldehyde groups of which are separated by three carbon atoms and the like.
The silver halides employed in the practice of this invention include any of the photographic silver halides, as exemplified by silver bromide, silver iodide, silver chloride or mixed silver halides such as silver chlorobromide, silver bromoiodide and the like. The silver halides used can be those which form latent images predominantly on the surface of the silver halide grains or those which form latent images inside the silver halide crystals, such as those described in Davey and Knott, US. Patent 2,592,250, issued Apr. 8, 1952.
Various colloids can be used as vehicles or binding agents in the photographic emulsions and elements of this invention. Among such materials are gelatin or other colloidal materials such as colloidal albumin, cellulose derivatives, synthetic resins such as polyvinyl compounds, acrylamide polymers and the like. It is often advantageous to employ combinations of binding agents. Such combinations include, for example, mixtures of gelatin with aqueous dispersions of polymerized ethylenically unsaturated compounds, particularly polyvinyl compounds.
The photographic compositions described herein can be coated on a wide variety of supports, but preferably supports which are transparent and flexible. Typical supports include polymeric films such as cellulose acetate film, polyvinyl acetal film, polystyrene film, polypropylene film and other polyolefin film, polycarbonate film as well as glass, paper and the like. Supports such as paper which are coated with a-olefin polymers, particularly polymers of u-olefins containing 2-10 carbon atoms, as exemplified by polyethylene, polypropylene, ethylene butene polymers and the like, can also be employed. As already indicated, the piazines are particularly effective for controlling fog in photographic elements employing polyester film supports. Typical supports of this type are polyester film supports including polymers composed of bifunctional dicarboxylic acids and glycols such as polyesters prepared from 1,4-cyclohexanedimethanol and terephthalate acid. Especially useful polyester film supports are poly(alkylene terephthalates), poly(ethylene terephthalate) being particularly suitable. In the manufacture of such polyester film supports, for example, by the methods described in British Patent 578,079 or 740, 381, various side reaction products are formed which remain in the film and act as contaminants which have a tendency to cause fog when photographic silver halide emulsions are coated thereover. The use of the piazines in emulsions coated on such supports substantially inhibits fogging caused by contaminants in such polyester film supports. Preferred polyester film supports suitable for use in this invention have a thickness in the range of about 1 to about mils, preferably about 2 to about 11 mils.
The photographic silver halide emulsions described herein can be chemically sensitized with compounds of the sulfur group, noble metal salts such as gold salts, reduction sensitized with reducing agents, and combinations of these. The emulsions can also contain additional additives, particularly those known to be beneficial in photographic emulsions, including, for example, stabilizers or antifoggants, particularly the water soluble inorganic acid salts of cadmium, cobalt, manganese and zinc as disclosed in US. Patent 2,829,404, the substituted triazaindolizines as disclosed in US. Patents 2,444,605 and 2,444,607, speed increasing materials, plasticizers, a bsorbing dyes and the like. Sensitizers which gave particularly good results in the photographic compositions disclosed herein are the alkylene oxide polymers which can be employed alone or in combination with other materials, such as quaternary ammonium 'salts, as disclosed in US. Patent 2,886,437 or with mercury compounds and nitrogen containing compounds, as disclosed in US. Patent 2,751,299. The emulsions used in practicing this invention can also be X-ray or other non-spectrally sensitized emulsions as well as orthochromatic, panchromatic and infrared sensitive emulsions, particularly those sensitized with merocyanine dyes, cyanine dyes, carbocyanine dyes and the like.
This invention can be further illustrated by the following examples of preferred embodiments thereof although it will be understood that these examples are included merely for purposes of illustration and are not intended to limit the scope of the invention unless otherwise specifically indicated.
Example 1 The photographic elements described herein exhibit improved resistance to fogging when processed in the presence of a hardening agent. To illustrate, samples of a gelatin, medium-grain silver bromoiodide (98:2) photographic emulsion of the type normally used in radiography are coated on on ordinary cellulose acetate film support at coverages of 494 mg. of silver per square foot and 635 mg. of gelatin per square foot. A control sample contains no piazine while several samples contain the piazines listed in the following Table 1 at the concentrations given. The samples are given an 80 kv. direct X-ray exposure and processed for six minutes at F. in a hardening developer solution having the following composition:
Grams l-phenyl-3-pyrazolidone 1.5 Hydroquinone 25.0 Sodium sulfite, desiccated 60.0 Sodium metaborate, tetrahydrate 35.0 Tetra ammonium ethylene diamine acetate 5.0 Potassium bromide 15.0
Glutaraldehyde bis sodium bisulfite 15.0
Sodium hydroxide 2.0 Polyox WSR 301 (Union Carbide, water-soluble ethylene oxide polymer, average mol. wt. 4,000, 000) 0.01
Water to make 1 liter.
After development the samples are fixed, washed and dried in the usual manner. The fog determined on each of the samples is as follows:
TABLE 1 Piazine (mg/mol silver halide): Fog Control (0) 1.23 1,3 diamiuo 5 nethylphenazinium chloride (20) .14 1,3 diamino 5 ethylphenazinium chloride (20) .14 1,3 diamiuo 5 hydroxyethylphenazinium chloride (20) .15 1,3 diamino 5 benzylphenazinium chloride (10) .14 1,3 diamiuo 5 phenylphenazinium chloride Results similar to those reported above are obtained when the glutaraldehyde bis-sodium bisulfite is incorporated into the photographic element. In this case it is also convenient to incorporate developing agents such as 1-phenyl-3-pyrazolidone and hydroquinone into the element which can then be processed in an alkaline activator containing no developing agent.
Example 2 The procedure of Example 1 is repeated with a gelatin, medium-grain silver bromoiodide (98:2) photographic emulsion of the type normally used in radiography, but having a sensitivity which is difierent from the emulsion described in Example 1. The piazines employed and results obtained are as follows:
Example 4 The piazines described herein are particularly effective antifoggants for photographic silver halide emulsions coated on polyester film base and do not adversely affect TABLE 2 other sensitometric characteristics. To illustrate, samples Plazme Per mole sllver hahde) g of a direct X-ray type gelatine medium-grain silver broi moiodide (98:2) photographic emulsion containing the lwwyqmxyphenelme (4O) piazones listed in the following table are coated on a 2 3'dlaml nophenazme (20) p0ly(ethylene terephthalate) film base. The emulsion is Lacetammos'aCFtOXYPheHaZme (40) coated at a coverage of 1025 mg. of silver per square foot zhydroxyphenazme (40) and 1805 mg. of gelatin per square foot. For comparison From the results reported in Tables 1 and 2 it can be P p a Control Sample ing n0 PiaZ ne is also seen that the piazines described herein are effective to F0ated samples 0f the film Coatlngs when fresh, after reduce fog in photographic silver halide emulsions proclllcutlatlofl r two s at 120 F. and 15% relative essed i h presence f h d i agenm h umid1ty and after incubation for two weeks as 120 F. and 50% relative humidity are exposed for equal times Example 3 to a 250 kv. direct X-ray source and developed for six As previously indicated, the piazines described herein mlnjltes at in a developer Solution having e are very effective antifoggants for photographic silver l W1ngf0rmula: halide emulsion layers processd in the presence of hardening agents although they often exhibit no antifoggant Grams activity in the absence of such hardening agents. To illusy -p ph ol Sulfate 2.2 trate, the procedures of Examples 1 and 2 are repeated Hydr q mone 8.8 except that the samples are developed in Kodak Devel- Sodi m sulfate (anhydrous) 72.0 oper D 19b having the following composition: Sodium carbonate (anhydrous) 48,0 (37mmS Potassium bromide 4,0 N methy1-p-amin0pher101 sulfate 2.2 Water to make hter' Hydroquinone 8.8 Sodium sulfate, anhydrous 72.0 After fiXlng, Washmg and drymg 1n the usual manner, Sodium carbonate, crystanine 130.0 h p e (measu ed at a density of 0.85 above fog with Potassium bromide 2 4.0 the Il r l speed eing taken at 100 in each case), gamma Water to make 1 liter. ('y) and fog are as follows:
TABLE 4 2Wceks 120 F. 2 weeks 120 F. Piazine (mg.,lsilver mole) Fresh (15% RH) RH) Speed Fog Speed A Fog Speed x Fog Control (0 100 2. .07 105 2.70 .18 07 2.75 .14 Phenazino (4) 97 2.80 .05 105 2.75 .12 04 2. .10 2-hydroxyphenazine (16 100 2.75 .04 105 2.75 .12 91 2.80 .10 2,3-diaminophenezine 4) 95 2.75 .04 95 2.75 .11 29 2.80 .10 3-amino-2-hydroxy-pl1enazine 95 2 s0 .00 2.75 .13 95 2.80 .11 3diamino-5-methylphenazinium chloride (4) 97 2.80 .05 97 2.75 .11 91 2.80 10 3 diamino-5phenyl phenazinium chloride (4).-.. 07 2.80 .05 100 2.75 .11 91 2. 86 .10 3,7-diamiuo-5-phenylphenaziniurn chloride (8) 97 2.80 .05 102 2. s5 .12 04 2.80 .11
After development the samples are fixed, washed and dried in the usual manner. The fog determined on each of the samples is as follows:
TABLE 3 Procedure of Example 1 (Table 1) Piazine (mg./ mole silver halide): Fog Control (0) .01
1,3 diamino 5 methylphenazinium chloride (20) .02 1,3-diamino-5ethylphenaziniurn chloride (20)-- .01
1,3 diamino 5 hydroxyethylphenazinium 2,3-dihydroxyp-henazine (40) .02 2,3-diaminophenazine (20) .02 2-acetamino-3-acetoxyphenazine (40) .Ol 2-hydroxyphenazine (40) -2 .01
Thus, by the practice of this invention there is provided photographic silver halide emulsions which are stabilized against fog, particularly when these emulsions are coated on polyester supports and/or processed in the presence of hardening agents.
Although the invention has been described in considerable detail with reference to certain preferred embodiments thereof, it will be understood that variations and modifications can be effected without departing from the spirit and scope of the invention as described hereinabove and as defined in the appended claims.
We claim:
1. A photographic silver halide emulsion comprising a hardening agent and an antifoggant concentration of a piazine containing a pyrazine ring to which two 6-membered carbocyclic rings are fused symmetrically.
2. A gelatin photographic silver halide emulsion comprising a gelatin hardening agent and an antifoggant concentration of a piazine containing a pyrazine ring to which two 6-membered carbocyclic rings are fused symmetrically.
3. A gelatin photographic silver halide emulsion comprising a gelatin aldehyde hardening agent and an antifoggant concentration of a piazine having the formula:
1 1 where each of R and R is amino, hydroxy, hydrocarbyl amino, alkyl, aryl, acryloxy, acylamino or a fused 6-membered carbocyclic ring and each n is an integer of to 2.
4. A gelatin photographic silver halide emulsion comprising a gelatin aldehyde hardening agent and an antifoggant concentration of a piazine having the formula:
where each of R and R is amino, hydroxy, hydrocarbyl amino, alkyl, aryl, acyloxy, acylamino or a fused 6-membered carbocyclic ring, R is alkyl, hydroxyalkyl or aryl, X is an anion, each n is an integer of 0 to 2 and z is an integer of 0 to 1.
5. A gelatin photographic silver halide emulsion comprising glutaraldehyde bis-sodium bisulfite gelatin hardening agent and an antifoggant concentration of 1,3-diamino- S-methyl phenazinium chloride.
6. A photographic element comprising a support, a photographic silver halide layer and, incorporated in at least one layer of said element, a hardening agent and an antifoggant concentration of a piazine containing a pyrazine ring to which two 6-membered carbocyclic rings are fused symmetrically.
7. A photographic element comprising a support, a gelatin photographic silver halide layer and, incorporated in at least one layer of said element, a gelatin hardening agent and an antifoggant concentration of a piazine containing a pyrazine ring to which two 6-membered carbocyclic rings are fused symmetrically.
8. A photographic element comprising a support, a gelatin photographic silver halide layer and, incorporated in at least one layer of said element, a gelatin aldehyde hardening agent and an antifoggant concentration of a piazine having the formula:
where each of R and R' is amino, hydroxy, hydrocarbyl amino, alkyl, aryl, acyloxy, acylamino or a fused 6-membered carbocyclic ring and each n is an integer of 0 to 2.
9. A photographic element comprising a support, a gelatin photographic silver halide layer and, incorporated in at least one layer of said element, a gelatin aldehyde hardening agent and an antifoggant concentration of a piazine having the formula:
where each of R and R is amino, hydroxy, hydrocarbyl amino, alkyl, aryl, acyloxy, acylamino or a fused 6-membered carbocyclic ring, R is alkyl, hydroxyalkyl or aryl, X is an anion, each n is an integer of 0 to 2 and z is an integer of 0 to 1.
10. The photographic element of claim 8 in which the hardening agent is a dialdehyde in which the aldehyde groups are joined by a linear carbon chain of 2-3 carbon atoms.
11. The photographic element of claim 8 in which the hardening agent is an alkali soluble bisulfite-dialdehyde addition product in which the aldehyde groups are separated by a linear hydrocarbon chain of 2-3 carbon atoms.
12. A photographic element comprising a support, a gelatin photographic silver halide layer and, incorporated in at least one layer of said element, a glutaraldehyde bissodium bisulfite hardening agent and an antifoggant concentration of 1,3-diamino-5-methyl phenazinium chloride.
13. A photographic element comprising a polyester support, a photographic silver halide layer and, incorporated in at least one layer of said element an antifoggant concentration of a piazine containing a pyrazine ring to which two o-membered carbocyclic rings are fused symmetrically.
14. A photographic element comprising a polyester support, a gelatin photographic silver halide layer and, incorporated in at least one layer of said element an antifoggant concentration of a piazine containing a pyrazine ring to which two G-membered carbocyclic rings are fused symmetrically.
15. A photographic element comprising a polyester support, a gelatin photographic silver halide layer and, incorporated in at least one layer of said element, an antifoggant concentration of a piazine having the formula:
where each of R and R is amino, hydroxy, hydrocarbyl amino, alkyl, aryl, acyloxy, acylamino or a fused 6-membered carbocyclic ring and each n is an integer of 0 to 2.
16. A photographic element comprising a polyester support, a gelatin photographic silver halide layer and, incorporated in at least one layer of said element, an antifoggant concentration of a piazine having the formula:
where each of R and R is amino, hydroxy, hydrocarbyl amino, alkyl, aryl, acyloxy, acylamino or a. fused 6-membered carbocyclic ring, R is alkyl, hydroxyalkyl or aryl, X is an anion, each n is an integer of O to 2 and z is an integer of 0 to 1.
17. The photographic element of claim 13 in which the polyester support is a polyethylene terephthalate support.
18. A photographic element comprising a polyethylene terephthalate support a gelatin photographic silver halide layer and, incorporated in at least one layer of said element, an antifoggant concentration of a 1,3-diamino-5- methyl phenazinium chloride.
19. A process which comprises developing, in the presence of a gelatin hardening agent, a photographic element comprising a support, a photographic silver halide layer and, incorporated in at least one layer of said element, an antifoggant concentration of a piazine containing a pyrazine ring to which two 6-membered carbocyclic rings: are fused symmetrically.
20. A process which comprises developing, in a developer containing a hardening agent, a photographic element comprising a polyester support, a photographic silver halide layer, and incorporated in at least one layer of said element, an antifoggant concentration of a piazine containing a pyrazine ring to which two 6-membered carbocyclic rings are fused symmetrically.
References Cited UNITED STATES PATENTS 2,270,118 1/1942 Gaspar 96-53 2,410,025 10/1946 Gaspar 96--53 NORMAN G. TORCHIN, Primary Examiner.
I. R. EVERETT, Assistant Examiner.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US482237A US3396023A (en) | 1965-08-24 | 1965-08-24 | Piazine antifoggants for silver halide emulsions |
DE19661547712 DE1547712A1 (en) | 1965-08-24 | 1966-07-22 | Use of piazines as antifoggants in photographic silver halide emulsion layers |
FR73399A FR1491636A (en) | 1965-08-24 | 1966-08-18 | New photographic products stabilized against haze |
BE685778D BE685778A (en) | 1965-08-24 | 1966-08-19 | |
GB37939/66A GB1158802A (en) | 1965-08-24 | 1966-08-24 | Antifoggants for Silver Halide Photographic Materials |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US482237A US3396023A (en) | 1965-08-24 | 1965-08-24 | Piazine antifoggants for silver halide emulsions |
Publications (1)
Publication Number | Publication Date |
---|---|
US3396023A true US3396023A (en) | 1968-08-06 |
Family
ID=23915278
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US482237A Expired - Lifetime US3396023A (en) | 1965-08-24 | 1965-08-24 | Piazine antifoggants for silver halide emulsions |
Country Status (4)
Country | Link |
---|---|
US (1) | US3396023A (en) |
BE (1) | BE685778A (en) |
DE (1) | DE1547712A1 (en) |
GB (1) | GB1158802A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3642481A (en) * | 1968-08-03 | 1972-02-15 | Fuji Photo Film Co Ltd | Processing of photographic silver halide light-sensitive materials |
US3655391A (en) * | 1969-05-16 | 1972-04-11 | Paoli Merli | Azodicarbonamide fog inhibitors |
US3718469A (en) * | 1969-10-17 | 1973-02-27 | Fuji Photo Film Co Ltd | Making of a photographic image |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2270118A (en) * | 1936-12-14 | 1942-01-13 | Chromogen Inc | Production of colored photographic pictures |
US2410025A (en) * | 1936-12-14 | 1946-10-29 | Chromogen Inc | Production of colored photographic pictures |
-
1965
- 1965-08-24 US US482237A patent/US3396023A/en not_active Expired - Lifetime
-
1966
- 1966-07-22 DE DE19661547712 patent/DE1547712A1/en active Pending
- 1966-08-19 BE BE685778D patent/BE685778A/xx unknown
- 1966-08-24 GB GB37939/66A patent/GB1158802A/en not_active Expired
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2270118A (en) * | 1936-12-14 | 1942-01-13 | Chromogen Inc | Production of colored photographic pictures |
US2410025A (en) * | 1936-12-14 | 1946-10-29 | Chromogen Inc | Production of colored photographic pictures |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3642481A (en) * | 1968-08-03 | 1972-02-15 | Fuji Photo Film Co Ltd | Processing of photographic silver halide light-sensitive materials |
US3655391A (en) * | 1969-05-16 | 1972-04-11 | Paoli Merli | Azodicarbonamide fog inhibitors |
US3718469A (en) * | 1969-10-17 | 1973-02-27 | Fuji Photo Film Co Ltd | Making of a photographic image |
Also Published As
Publication number | Publication date |
---|---|
DE1547712A1 (en) | 1971-12-16 |
BE685778A (en) | 1967-02-01 |
GB1158802A (en) | 1969-07-23 |
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