US3850644A - Silver halide grains precipitated in the presence of a phosphoric acid amide sensitizer - Google Patents
Silver halide grains precipitated in the presence of a phosphoric acid amide sensitizer Download PDFInfo
- Publication number
- US3850644A US3850644A US00310635A US31063572A US3850644A US 3850644 A US3850644 A US 3850644A US 00310635 A US00310635 A US 00310635A US 31063572 A US31063572 A US 31063572A US 3850644 A US3850644 A US 3850644A
- Authority
- US
- United States
- Prior art keywords
- emulsion
- silver halide
- phosphoric acid
- emulsions
- acid amide
- 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
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- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 title claims abstract description 7
- -1 Silver halide Chemical class 0.000 title claims description 21
- 229910052709 silver Inorganic materials 0.000 title claims description 16
- 239000004332 silver Substances 0.000 title claims description 16
- 239000000839 emulsion Substances 0.000 claims abstract description 48
- 230000005070 ripening Effects 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 11
- 108010010803 Gelatin Proteins 0.000 claims description 9
- 229920000159 gelatin Polymers 0.000 claims description 9
- 239000008273 gelatin Substances 0.000 claims description 9
- 235000019322 gelatine Nutrition 0.000 claims description 9
- 235000011852 gelatine desserts Nutrition 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 150000001408 amides Chemical class 0.000 claims description 4
- 229910000510 noble metal Inorganic materials 0.000 claims description 4
- 150000003464 sulfur compounds Chemical class 0.000 claims description 4
- 230000003311 flocculating effect Effects 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 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 abstract description 11
- 206010034960 Photophobia Diseases 0.000 abstract description 4
- 208000013469 light sensitivity Diseases 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 description 23
- 150000001875 compounds Chemical class 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 150000003012 phosphoric acid amides Chemical class 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 5
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- MYNVYOSPXMTLKD-UHFFFAOYSA-N n-dichlorophosphorylbenzenesulfonamide Chemical compound ClP(Cl)(=O)NS(=O)(=O)C1=CC=CC=C1 MYNVYOSPXMTLKD-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 2
- NCNYEGJDGNOYJX-NSCUHMNNSA-N (e)-2,3-dibromo-4-oxobut-2-enoic acid Chemical compound OC(=O)C(\Br)=C(/Br)C=O NCNYEGJDGNOYJX-NSCUHMNNSA-N 0.000 description 1
- OYWRDHBGMCXGFY-UHFFFAOYSA-N 1,2,3-triazinane Chemical class C1CNNNC1 OYWRDHBGMCXGFY-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- FYBFGAFWCBMEDG-UHFFFAOYSA-N 1-[3,5-di(prop-2-enoyl)-1,3,5-triazinan-1-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 FYBFGAFWCBMEDG-UHFFFAOYSA-N 0.000 description 1
- LLCOQBODWBFTDD-UHFFFAOYSA-N 1h-triazol-1-ium-4-thiolate Chemical class SC1=CNN=N1 LLCOQBODWBFTDD-UHFFFAOYSA-N 0.000 description 1
- CBHTTYDJRXOHHL-UHFFFAOYSA-N 2h-triazolo[4,5-c]pyridazine Chemical class N1=NC=CC2=C1N=NN2 CBHTTYDJRXOHHL-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical class CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- QMJDEXCUIQJLGO-UHFFFAOYSA-N [4-(methylamino)phenyl] hydrogen sulfate Chemical compound CNC1=CC=C(OS(O)(=O)=O)C=C1 QMJDEXCUIQJLGO-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- BVWNPRDRJALPDQ-UHFFFAOYSA-N benzenesulfonamidophosphonic acid Chemical compound OP(O)(=O)NS(=O)(=O)C1=CC=CC=C1 BVWNPRDRJALPDQ-UHFFFAOYSA-N 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical group C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical group C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Chemical group 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000298 carbocyanine Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002730 mercury Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- XCGQJCSSCTYHDV-UHFFFAOYSA-N mercury(1+);sulfane Chemical compound S.[Hg+] XCGQJCSSCTYHDV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PKDBSOOYVOEUQR-UHFFFAOYSA-N mucobromic acid Natural products OC1OC(=O)C(Br)=C1Br PKDBSOOYVOEUQR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- QWYZFXLSWMXLDM-UHFFFAOYSA-M pinacyanol iodide Chemical class [I-].C1=CC2=CC=CC=C2N(CC)C1=CC=CC1=CC=C(C=CC=C2)C2=[N+]1CC QWYZFXLSWMXLDM-UHFFFAOYSA-M 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
- C07F9/2479—Compounds containing the structure P(=X)n-N-acyl, P(=X)n-N-heteroatom, P(=X)n-N-CN (X = O, S, Se; n = 0, 1)
- C07F9/2483—Compounds containing the structure P(=X)n-N-acyl, P(=X)n-N-heteroatom, P(=X)n-N-CN (X = O, S, Se; n = 0, 1) containing the structure P(=X)n-N-S (X = O, S, Se; n = 0, 1)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
-
- 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
- G03C1/08—Sensitivity-increasing substances
- G03C1/10—Organic substances
Definitions
- This invention relates to a photographic silver salt emulsion with increased sensitivity which is achieved by the addition of phosphoric acid amides.
- the sensitivity to light'of a photographic silver salt emulsion can be influenced in two ways. Firstly, it can be increased by suitable choice of the precipitation conditions and of the so-called physical ripening. In practice, the possibility of increasing the sensitivity in this way is limited by the fact that the increase in sensitivity is accompanied by an increase of the grain size, which deleteriously effects the quality of the final image. lt is therefore desired to obtain silver salt emulsions with a very high light-sensitivity but fine grain.
- the sensitivity of photographic emulsions can be increased by chemical methods by adding compounds which are generally known as chemical sensitizers.
- these compounds could be added at any stage of the preparation of the emulsion, e.g., as ripening additives before chemical ripening or to the finished casting solution after chemical ripening.
- Ripening agents are e.g., noble metal salts, particularly gold salts, and sulfur compounds such as thiosulfates or organic and particularly heterocyclic sulfur compounds.
- a disadvantage of the chemical sensitization method is that the increase in sensitivity is accompanied by an increased tendency of the emulsion to form an uniform fog which is capable of being developed.
- lt is among objects of the present invention to provide new chemical sensitizers which do not have the above disadvantages and which increase the lightsensitivity of photographic silver salt emulsions, and particularly of photographic silver halide emulsions without unwanted fogging.
- v R (l) a saturated or olefinically unsaturated aliphatic group, preferably alkyl, in particular alkyl having one to three carbon atoms, (2) aryl, in particular phenyl, which may be substituted, e.g,, with alkyl or alkoxy, both of which preferably have up to three carbon atoms, or with carboxyl, sulfo, sulfonamido, alkyl, sulfonyl, halogen such as fluorine, chlorine orbromine, or nitrile, or (3) cycloalkyl such as cyclopentyl or cyclohexyl;
- the photographic silver salt emulsions chemically sensitized in accordance with the invention are prepared by the usual methods.
- the method of preparation comprises the following steps:
- the chemical sensitizer of the present invention are added to the photographic silver salt emulsion before chemical ripening, preferably at the precipitation stage.
- the quantity to be added depends on the desired effect and can be determined by a few simple tests in the usual manner. Quantities of from 1 to 50 g. based on 100 g of gelatin. are generally sufficient. Based on the quantity of silver halide to be precipitated. the quantities to be used are 150 mg 8 g, preferably 300 mg 4 g, per mol of silver halide.
- the substances to be used according to the invention are preferably added in the form of their aqueous solutions.
- concentration of substances in these solutions is not critical and may vary within wide limits.
- the phosphoric acid amides should be water-soluble to the extent that it is possible to prepare an aqueous solution which contains a sufficient quantity of active substance. It is sufficient, for example, to prepare a 1 5 percent solution. If the substances are particularly easily soluble the solutions may, of course, be more concentrated.
- the solutions are generally prepared at a pH of about 7 but the pH may also be kept slightly acid, e.g., between 5 and 7, or in the case of so-called ammoniacal emulsions the pH of the solution may be between -5 and 9.
- the emulsions may also contain other chemical sensitizers, e.g., quaternary ammonium and phosphonium salts or ternary sulfonium salts, reducing agents such as tin-(ll) salts, polyamines such as diethylenetriamine or sulfur compounds as described in US. Pat. No. 1,574,944.
- the emulsions may also contain salts of noble metals such as ruthenium, rhodium, palladium, iridium, platinum or gold as chemical sensitizers as described in the article by R. KOSLOWSKY, Z. Wis- -s.Phot. 46, 72 1951 They may also contain polyalkylene oxides or polyalkylene oxide derivatives as development accelerators or chemical sensitizers. An additional increase in sensitivity is thereby achieved.
- the emulsions may also be optically sensitized, e.g., with the usual polymethine dyes such as neutrocyanine,
- the emulsions may contain the usual stabilizers, e.g., homopolar or salt-type compounds of mercury containing aromatic or heterocyclic rings (for example mercaptotriazoles), simple mercury salts, sulfonium mercury double salts and other mercury compounds.
- stabilizers e.g., homopolar or salt-type compounds of mercury containing aromatic or heterocyclic rings (for example mercaptotriazoles), simple mercury salts, sulfonium mercury double salts and other mercury compounds.
- Azaindenes are also suitable stabilizers. especially tetraor penta-azaindenes, particularly those which are substituted with hydroxyl or amino groups. Compounds of this kind have been described in the article by BlRR, Z.Wiss.Phot. 47, 2 58 (1952).
- Other suitable stabilizers include heterocyclic mercapto compounds, e.g. phenyl mercaptotetrazole, quaternary benzothiazole derivatives and benzotriazole.
- the emulsions may be hardened in the usual manner, for example with formaldehyde or halogenated aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methane sulfonic acid esters and dialdehydes or polyfunctional triazine derivatives such as tri-acryloyl-hexahydrotriazine or halogenated or alkoxy-substituted hexahydrotriazine derivatives.
- formaldehyde or halogenated aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methane sulfonic acid esters and dialdehydes or polyfunctional triazine derivatives such as tri-acryloyl-hexahydrotriazine or halogenated or alkoxy-substituted hexahydrotriazine derivatives.
- the substances according to the invention produce their advantageous effect not only in black and white emulsions but also in the production of color photographic images. They are readily compatible with the usual color couplers.
- the phosphoric acid amides may also be used with direct positive emulsions, e.g., those which have a composite grain structure in accordance with French Pat. No. 1,585,791. They are also suitable for emulsions used for the silver dye bleaching process or dye diffusion process.
- the phosphoric acid amides are used in combination with polymers which contain disulfonimide groups.
- Such compounds have been described in German Pat. No. 1,089,548 and in U.S. Pat. No.
- concentration of the disulfonimides may vary within wide limits. Quantities of l to percent, based on the gelatin originally put into the process, have generally been found to be sufficient.
- the flocculate is left to settle and the supernatant solution is drawn off.
- the flocculate is then twice washed with litres of water in which it is agitated by stirring for 5 minutes. After the final removal of supernatant water, the flocculate is dissolved in the appropriate quantity of water; gelatin at pH 7 at C,. gold-(Ill) chloride and sodium thiosulfate are added as ripening additives and, after adjustment of the pAg to 8.9, the emulsion is ripened at a ripening temperature of 48C.
- Sample 2 The emulsion is prepared in the same way as in sample l above but during precipitation, ml of a 7 percent aqueous solution of compound] are added to the given gelatin/alkali metal halide solution.
- Samples 3 9 are prepared accordingly by the addition of the same amount of compounds 2 5 and 7 9.
- the samples are cast on a cellulose acetate support after the addition, per kg of emulsion, of 10 ml, of a 5 percent aqueous solution of saponin as wetting agent, 10 ml of a 10 percent aqueous solution of formaldehyde as hardener and 20 ml of a 1 percent methanolic solution of 4-hydroxy-6-methyl-l,3,3a,7- tetraazaindene as stabilizer.
- a conventional sensitometer behind a step wedge and development (7 and 16 minutes at 20) in a developer of the following composition Sodium sult'ile sicc. Borax 7 Hydroquinone 3.. p-monomethylaminophenol sulfate 3 Sodium citrate 7.
- Potassium bromide 0. made up to 1 litre with water the emulsions are assessed sensitometrically. From the following table it will be seen that emulsions 2 9 have a higher sensitivity than comparison emulsion l.
- a process for the preparation of photographic silver halide emulsions comprising the steps of precipitating the silver halide in a gelatin emulsion, physically ripening, flocculating and solidifying the precipitated silver halide emulsion, and then chemically ripening the emulsion, including adding a sensitizer from the group consisting of noble metal salts and sulfur compounds after the solidifying step wherein the improvement comprises in the preparation of the emulsion adding to the gelatin emulsion during precipitation of silver halide a phosphoric acid amide to sensitize the emulsion said amide is of the following formula:
- R is (l) a saturated or olefinically unsaturated alkyl group, (2) phenyl, (3) cyclopentyl or cyclohexyl;
- R represents (1) hydrogen, (2) a saturated or olefinically unsaturated alkyl group, (3) phenyl or (4) cyclopentyl or cyclohexyl;
- X stands for halogen or unsubstituted hydroxyl
- X represents halogen, unsubstituted hydroxyl or an unsubstituted amino group, said amide being added in an amount in the range of mg 8 g per mol of silver halide and then chemically ripening the emulsion in the presence of said phosphoric acid amide.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Health & Medical Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2160207A DE2160207A1 (de) | 1971-12-04 | 1971-12-04 | Photographische silbersalzemulsion mit erhoehter empfindlichkeit |
Publications (1)
Publication Number | Publication Date |
---|---|
US3850644A true US3850644A (en) | 1974-11-26 |
Family
ID=5826988
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00310635A Expired - Lifetime US3850644A (en) | 1971-12-04 | 1972-11-29 | Silver halide grains precipitated in the presence of a phosphoric acid amide sensitizer |
Country Status (5)
Country | Link |
---|---|
US (1) | US3850644A (nl) |
BE (1) | BE792091A (nl) |
DE (1) | DE2160207A1 (nl) |
FR (1) | FR2162231A1 (nl) |
GB (1) | GB1390540A (nl) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3471296A (en) * | 1965-12-28 | 1969-10-07 | Agfa Gevaert Ag | Spirocyclic quaternary nitrogen compounds as silver halide sensitizers |
US3567587A (en) * | 1967-03-03 | 1971-03-02 | Eastman Kodak Co | Phosphorous-halogen fog stabilizers for photographic emulsions |
US3615612A (en) * | 1968-01-12 | 1971-10-26 | Gaf Corp | Photographic element containing a phosphoric acid ester of a butynediol-alkylene oxide condensate |
-
0
- BE BE792091D patent/BE792091A/nl unknown
-
1971
- 1971-12-04 DE DE2160207A patent/DE2160207A1/de active Pending
-
1972
- 1972-11-29 US US00310635A patent/US3850644A/en not_active Expired - Lifetime
- 1972-12-01 GB GB5548372A patent/GB1390540A/en not_active Expired
- 1972-12-04 FR FR7243088A patent/FR2162231A1/fr not_active Withdrawn
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3471296A (en) * | 1965-12-28 | 1969-10-07 | Agfa Gevaert Ag | Spirocyclic quaternary nitrogen compounds as silver halide sensitizers |
US3567587A (en) * | 1967-03-03 | 1971-03-02 | Eastman Kodak Co | Phosphorous-halogen fog stabilizers for photographic emulsions |
US3615612A (en) * | 1968-01-12 | 1971-10-26 | Gaf Corp | Photographic element containing a phosphoric acid ester of a butynediol-alkylene oxide condensate |
Also Published As
Publication number | Publication date |
---|---|
FR2162231A1 (nl) | 1973-07-13 |
BE792091A (nl) | 1973-05-30 |
DE2160207A1 (de) | 1973-06-14 |
GB1390540A (en) | 1975-04-16 |
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