DE2160207A1 - PHOTOGRAPHIC SILVER SALT EMULSION WITH INCREASED SENSITIVITY - Google Patents
PHOTOGRAPHIC SILVER SALT EMULSION WITH INCREASED SENSITIVITYInfo
- Publication number
- DE2160207A1 DE2160207A1 DE2160207A DE2160207A DE2160207A1 DE 2160207 A1 DE2160207 A1 DE 2160207A1 DE 2160207 A DE2160207 A DE 2160207A DE 2160207 A DE2160207 A DE 2160207A DE 2160207 A1 DE2160207 A1 DE 2160207A1
- Authority
- DE
- Germany
- Prior art keywords
- silver salt
- halogen
- emulsions
- phosphoric acid
- emulsion
- 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.)
- Pending
Links
- 239000000839 emulsion Substances 0.000 title claims description 38
- 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 title claims description 15
- 230000035945 sensitivity Effects 0.000 title description 11
- 239000000126 substance Substances 0.000 claims description 26
- 230000005070 ripening Effects 0.000 claims description 15
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005189 flocculation Methods 0.000 claims description 3
- 230000016615 flocculation Effects 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 4
- -1 Silver halide Chemical class 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- 229920000159 gelatin Polymers 0.000 description 7
- 235000019322 gelatine Nutrition 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 108010010803 Gelatin Proteins 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000008273 gelatin Substances 0.000 description 6
- 235000011852 gelatine desserts Nutrition 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000000975 dye Substances 0.000 description 5
- 150000003012 phosphoric acid amides Chemical class 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229920000233 poly(alkylene oxides) Chemical class 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 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 3
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003464 sulfur compounds Chemical class 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-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
- 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
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- 206010070834 Sensitisation Diseases 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
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 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
- 125000000623 heterocyclic group Chemical group 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
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 2
- 230000036211 photosensitivity Effects 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
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 230000035807 sensation Effects 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 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
- 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
- LLCOQBODWBFTDD-UHFFFAOYSA-N 1h-triazol-1-ium-4-thiolate Chemical class SC1=CNN=N1 LLCOQBODWBFTDD-UHFFFAOYSA-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
- CBHTTYDJRXOHHL-UHFFFAOYSA-N 2h-triazolo[4,5-c]pyridazine Chemical class N1=NC=CC2=C1N=NN2 CBHTTYDJRXOHHL-UHFFFAOYSA-N 0.000 description 1
- INVVMIXYILXINW-UHFFFAOYSA-N 5-methyl-1h-[1,2,4]triazolo[1,5-a]pyrimidin-7-one Chemical compound CC1=CC(=O)N2NC=NC2=N1 INVVMIXYILXINW-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- 239000001828 Gelatine Substances 0.000 description 1
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 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
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 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
- 239000011230 binding agent Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- OIPQUBBCOVJSNS-UHFFFAOYSA-L bromo(iodo)silver Chemical compound Br[Ag]I OIPQUBBCOVJSNS-UHFFFAOYSA-L 0.000 description 1
- 239000000298 carbocyanine Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229940125904 compound 1 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
- 238000002474 experimental method Methods 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
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 150000004820 halides Chemical class 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
- 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
- VLGWYKOEXANHJT-UHFFFAOYSA-N methylsulfanol Chemical class CSO VLGWYKOEXANHJT-UHFFFAOYSA-N 0.000 description 1
- PKDBSOOYVOEUQR-UHFFFAOYSA-N mucobromic acid Natural products OC1OC(=O)C(Br)=C1Br PKDBSOOYVOEUQR-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 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
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 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
- 239000010970 precious metal Substances 0.000 description 1
- 230000001376 precipitating effect Effects 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
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003378 silver Chemical class 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
- 229910001923 silver oxide Inorganic materials 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
- 235000010265 sodium sulphite Nutrition 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
- 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
Landscapes
- 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)
Description
AGFA-GEVAERTAGAGFA-GEVAERTAG
PATENTABTEILUNGPATENT DEPARTMENT
za-mka Leverkusen - 3. DEZ. 1971za-mka Leverkusen - DEC 3. 1971
Photographische Silbersalzemulsion mit erhöhter EmpfindlichkeitSilver salt photographic emulsion with increased sensitivity
Die vorliegende Erfindung betrifft eine photographische Silbersalzemulsion mit erhöhter Empfindlichkeit, die durch einen Zusatz von Phosphorsäureamiden erzielt wird.The present invention relates to a silver salt photographic emulsion with increased sensitivity, which is achieved by adding phosphoric acid amides.
Die Lichtempfindlichkeit einer photographischen Silbersalzemulsion
läßt sich auf zweierlei Weise beeinflussen. Zunächst kann
man durch geeignete Wahl der Fällungsbedingungen und der sogenannten physikalischen Reifung mit physikalischen Mitteln eine Steigerung
der Empfindlichkeit erreichen. In der Praxis sind dieserThe photosensitivity of a photographic silver salt emulsion can be influenced in two ways. First of all, can
an increase in sensitivity can be achieved by a suitable choice of the precipitation conditions and the so-called physical ripening with physical means. In practice these are
A-G 905A-G 905
309824/0989309824/0989
Möglichkeit jedoch dadurch Grenzen gesetzt, daß mit der Erhöhung der Empfindlichkeit eine Vergrößerung des Silbersalzkornes parallel geht, durch die die Qualität des endgültigen Bildes nachteilhaft beeinflußt wird. Gewünscht sind daher Silbersalzemulsionen mit möglichst hoher Empfindlichkeit, aber möglichst kleinem Korn. Es ist ferner möglich, die Empfindlichkeit der photographischen Emulsionen auf chemischem Wege zu erhöhen durch Zusatz von chemischen Verbindungen, die im allgemeinen als chemische Sensibilisatoren bezeichnet werden. Im Prinzip können solche Verbindungen in jedem Stadium der Herstellung der Emulsion zugefügt werden, z.B. vor der chemischen Reifung als Reif zusätze oder nach der chemischen Reifung zu der fertigen Gießlösung. Als Reifzusät-Possibility, however, is limited by the fact that the increase in sensitivity is accompanied by an increase in the size of the grain of silver salt which adversely affects the quality of the final image. Silver salt emulsions are therefore desired with the highest possible sensitivity, but the smallest possible grain. It is also possible to increase the sensitivity of the photographic Emulsions increase chemically by adding chemical compounds, generally called chemical sensitizers are designated. In principle, such compounds can be added to the emulsion at any stage of preparation e.g. before chemical ripening as ripening additives or after chemical ripening to the finished casting solution. As a frosting additive
^ ze sind z.B. Edelmetallsalze, insbesondere Goldsalze und Schwefelverbindungen wie Thiosulfate oder organische, insbesondere heterocyclische Schwefelverbindungen geeignet. Nachteilhaft bei der chemischen Sensibilisierung ist, daß parallel mit der Erhöhung der Empfindlichkeit eine verstärkte Neigung der Emulsion, einen entwickelbaren uniformen Schleier zu bilden, zu beobachten ist. Aus diesem Grunde können hochwirksame chemische Sensibilisatoren wie Verbindungen mit Oniumstruktur, z.b. quaternäre Ammonium-, Phosphonium- oder ternäre Sulfoniumsalze, ferner Polyalkylenoxide und Polyalkylenoxyd-Derivate nur nach der chemischen Reifung zu der fertigen Gießlösung zugefügt werden. Bei einem Zusatz dieser Substanzen vor der chemischen Reifung würden die photographischen Silbersalzemulsionen so stark verschleiert wer-^ ze are e.g. precious metal salts, especially gold salts and sulfur compounds such as thiosulfates or organic, especially heterocyclic, sulfur compounds are suitable. Disadvantageous with the chemical sensitization is that, in parallel with the increase in sensitivity, there is an increased tendency of the emulsion to form a Developable uniforms to form a veil is observed. Because of this, you can use highly effective chemical sensitizers such as compounds with an onium structure, e.g. quaternary ammonium, phosphonium or ternary sulfonium salts, and also polyalkylene oxides and polyalkylene oxide derivatives are only added to the finished casting solution after chemical ripening. With an addition of these substances before chemical ripening would so severely obscure the silver salt photographic emulsions
W den, daß sie praktisch nicht mehr brauchbar sind. W den that they are practically no longer usable.
Alle die bekannten chemischen Sensibilisatoren erfüllen die von der Praxis geforderten Eigenschaften nicht in ausreichendem Maße, sei es, daß die Empfindlichkeitssteigerung unbefriedigend ist, oder daß der mit der Sensibilisierung verbundene Schleier eine Anwendung verhindert.All of the known chemical sensitizers do not adequately meet the properties required in practice Measures, be it that the increase in sensitivity is unsatisfactory or that the fog associated with the sensitization prevents an application.
Der Erfindung liegt die Aufgabe zugrunde, neue chemische Sensibilisatoren zu finden, die die obigen Nachteile nicht besitzenThe invention is based on the object of new chemical sensitizers to find that do not have the above disadvantages
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und mit deren Hilfe eine Steigerung der Lichtempfindlichkeit photographischer Sirbersalzemulsionen, insbesondere photographischer Silberhalogenidemulsionen ohne unerwünschte Schleierbildung möglich ist.and with their help an increase in photosensitivity photographic syrber salt emulsions, especially photographic Silver halide emulsions without undesired fogging is possible.
Es wurde nun ein photographisches Material mit mindestens einer Silbersalzemulsionsschicht gefunden, die als chemischen Sensibilisator ein wasserlösliches Ehosphorsäureamid der folgenden Formel enthält:We have now found a photographic material with at least one silver salt emulsion layer, which acts as a chemical sensitizer contains a water-soluble phosphoric acid amide of the following formula:
R^ 0
N - PR ^ 0
N - P
R1SO2 R 1 SO 2
worin bedeutenin which mean
R = (1) eine gesättigte oder olefinisch ungesättigte aliphatische Gruppe, vorzugsweise Alkyl, insbesondere Alkyl mit 1-3 C-Atomen, (2) Aryl, insbesondere Phenyl, das gegebenenfalls substituiert sein kann, z.B. mit Alkyl, Alkoxy, beide mit vorzugsweise bis zu 3 C-Atomen, Carboxyl, SuIfο, Sulfonamido, Alkylsulfonyl, Halogen wie Fluor, Chlor oder Brom, oder Nitril oder (3) Cycloalkyl wie Cyclopentyl oder Cyclohexyl;R = (1) a saturated or olefinically unsaturated one aliphatic group, preferably alkyl, in particular alkyl with 1-3 carbon atoms, (2) aryl, in particular Phenyl, which can optionally be substituted, e.g. with alkyl, alkoxy, both preferably with up to 3 carbon atoms, Carboxyl, sulfo, sulfonamido, alkylsulfonyl, halogen such as Fluorine, chlorine or bromine, or nitrile or (3) cycloalkyl such as cyclopentyl or cyclohexyl;
R = (1) Wasserstoff, (2) eine gesättigte oder olefinisch ungesättigte aliphatische Gruppe, vorzugsweise Alkyl, insbesondere Alkyl mit 1-3 C-Atomen, (3) Aryl, insbesondere Phenyl, das gegebenenfalls substituiert sein kann, z.B. mit Alkyl, Alkoxy, beide mit vorzugsweise bis zu 3 C-Atomen, Carboxyl, SuIfο, Sulfonamido, Alkylsulfonyl, Halogen wie Fluor, Chlor oder Brom, oder Nitril oder (4) Cycloalkyl wie Cyclopentyl oder Cyclohexyl;R = (1) hydrogen, (2) a saturated or olefinically unsaturated one aliphatic group, preferably alkyl, in particular alkyl with 1-3 carbon atoms, (3) aryl, in particular Phenyl, which can optionally be substituted, e.g. with alkyl, alkoxy, both preferably with up to 3 carbon atoms, Carboxyl, sulfo, sulfonamido, alkylsulfonyl, halogen such as Fluorine, chlorine or bromine, or nitrile or (4) cycloalkyl such as cyclopentyl or cyclohexyl;
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X = Halogen, insbesondere Chlor, oder Hydroxyl undX = halogen, especially chlorine, or hydroxyl and
ρ X = Halogen, insbesondere Chlor, oder Hydroxyl oder eine Aminogruppe, die substituiert sein kann mit einer gesättigten oder olefinisch ungesättigten aliphatischen Gruppe mit vorzugsweise bis zu 3 C-Atomen, Aryl, insbesondere Phenyl oder Cycloalkyl wie Cyclopentyl oder Cyclohexyl.ρ X = halogen, especially chlorine, or hydroxyl or an amino group, which can be substituted with a saturated or olefinically unsaturated aliphatic group with preferably up to 3 carbon atoms, aryl, in particular phenyl or cycloalkyl such as cyclopentyl or cyclohexyl.
Geeignet sind z.B. die folgenden Verbindungen:The following compounds, for example, are suitable:
IlIl
ClCl
SO2-NH-SO 2 -NH-
IlIl
OHOH
ClCH2-CH2 ClCH 2 -CH 2
0 .Cl0 .Cl
ClCH2-CH2 ClCH 2 -CH 2
SO2NH-P(Cl)2 SO 2 NH-P (Cl) 2
0 OH0 OH
H,CH, C
SO2NH-P(Cl)2 SO 2 NH-P (Cl) 2
A-GA-G
> 4 309824/0989 > 4 309824/0989
OHOH
Die Herstellung der in der erfindungsgemäßen Weise zu verwendenden Verbindungen ist "bekannt. Es sei verwiesen auf folgende Veröffentlichungen :The preparation of those to be used in the manner according to the invention Compounds is "known. Reference is made to the following publications :
HOUBEN-WEYL XII/2 (1964), Seiten 525 ff. A.V. KIRSANOV, Izv. Akad. SSSR, 1952, 710 A.V. KIRSANOV und E.A. ABRAZHANOVA, Sbοmik State! Obshchei Khim. Z,HOUBEN-WEYL XII / 2 (1964), pages 525 ff. A.V. KIRSANOV, Izv. Akad. SSSR, 1952, 710 A.V. KIRSANOV and E.A. ABRAZHANOVA, Sbοmik State! Obshchei Khim. Z,
1048 (1953)1048 (1953)
Die Herstellung einiger Verbindungen ist im folgenden im einzelnen beschrieben:The preparation of some compounds is detailed below described:
Phosphorsäure- (N-phenylsulfonylamid)-dichloridPhosphoric acid (N-phenylsulfonylamide) dichloride
0,01 Mol Phosphorsäure-phenylsulfonylimino-trichlorid werden in 50 ml trockenem Benzol mit 0,01 Mol wasserfreier Ameisensäure verrührt. Nach kurzer Zeit beginnen Kohlenmonoxid und Chlorwasserstoff zu entweichen. Man läßt so lange rühren, bis keine Gasentwicklung mehr zu beobachten ist. Das ausfallende Reaktionsprodukt wird abgesaugt und aus Tetrachlorkohlenstoff oder Petroläther umkristallisiert.0.01 mol of phosphoric acid phenylsulfonylimino trichloride is mixed with 0.01 mol of anhydrous formic acid in 50 ml of dry benzene stirred. After a short time, carbon monoxide and hydrogen chloride begin to escape. The mixture is left to stir until no gas evolution is more observable. The precipitating reaction product is filtered off and made of carbon tetrachloride or Recrystallized petroleum ether.
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Verbindung 2:
Fhosphorsäure-mono-(N-phenylsulfonyl-aniid) Connection 2:
Phosphoric acid mono- (N-phenylsulfonyl aniide)
0,01 Mol Phosphorsäure-(N-phenylsulfonyl-amid)-dichlorid werden mit 0,02 Mol wasserfreier Ameisensäure in 50 ml trockenem Benzol oder Dioxan 12 Stunden auf 80 - 1000C erwärmt und das ausgeschiedene Reaktionsprodukt abgesaugt und mit Benzol gewaschen.0.01 moles of phosphoric acid (N-phenylsulfonyl-amide) dichloride is containing 0.02 mole of anhydrous formic acid in 50 ml of dry benzene or dioxane 12 hours 80 - heated 100 0 C and filtered with suction the precipitated reaction product and washed with benzene.
Die in der erfindungsgemäßen Weise chemisch sensibilisierten photographischen Silbersalzemulsionen werden in üblicher Weise hergestellt. Die Herstellung umfaßt die folgenden Schritte:The silver salt photographic emulsions chemically sensitized in the manner of the present invention are processed in a conventional manner manufactured. The production consists of the following steps:
1. Fällung der Silbersalze, insbesondere der Silberhalogenide φ in Gegenwart eines Schutzkolloids und physikalische Reifung;1. Precipitation of the silver salts, in particular the silver halides φ in the presence of a protective colloid and physical ripening;
2. Erstarrung und Flockung der Emulsion sowie Auswaschen der bei der Fällung entstandenen wasserlöslichen Salze und2. Solidification and flocculation of the emulsion and washing out of the water-soluble salts formed during the precipitation and
3. Redispergierung der gewaschenen Emulsion und chemische Reifung,3. Redispersion of the washed emulsion and chemical ripening,
Die erfindungsgemäßen Substanzen werden der photographischen Silbersalzemulsion vor der chemischen Reifung, vorzugsweise bereits bei der Fällung zugesetzt. Die zugesetzte Menge hängt von dem gewünschten Effekt ab und kann mit wenigen einfachen Versuchen in üblicher Weise ermittelt werden. Im allgemeinen genügen Mengen von 1 - 50 g, bezogen auf je 100 g eingesetzter Ansatzgelatine; bezogen auf zu fällendes Silberhalogenid sind α es 150 mg - 8 g, vorzugsweise 300 mg - 4 g pro Mol AgX.The substances of the present invention are preferably added to the silver salt photographic emulsion before chemical ripening added during the precipitation. The amount added depends on the desired effect and can be achieved with a few simple Experiments can be determined in the usual way. In general, amounts of 1-50 g are sufficient, based on 100 g used Batch gelatine; Based on the silver halide to be precipitated, it is 150 mg - 8 g, preferably 300 mg - 4 g per mole of AgX.
Die in der erfindungsgemäßen Weise zu verwendenden Substanzen werden vorzugsweise in Form ihrer wässrigen Lösung zugesetzt. Die Konzentration der Substanzen in dieser Lösung ist nicht kritisch und kann innerhalb weiter Grenzen schwanken. Die Fhosphorsäureamide haben insoweit wasserlöslich zu sein, daß eine wässrige Lösung hergestellt werden kann, die eine ausreichende Menge wirksamer Substanzen enthalt. Es genügt z.B. bereits, eine 1-5 %ige Lösung einzusetzen. Selbstverständlich kann bei besonders gut löslichen Substanzen die Lösung auch konzentrierter sein. Im allgemeinen werden die Lösungen bei einem pH von etwa gelöst werden. Es ist jedoch auch möglich, den pH-Wert der Lösung schwach sauer zu halten, z.B. bei pH-Werten zwischen 5 undThe substances to be used in the manner according to the invention are preferably added in the form of their aqueous solution. The concentration of the substances in this solution is not critical and can fluctuate within wide limits. The phosphoric acid amides have to be water-soluble to the extent that an aqueous solution can be prepared which is in a sufficient amount contains active substances. For example, it is sufficient to use a 1-5% solution. Of course, especially Well soluble substances make the solution more concentrated. In general, the solutions will be at a pH of about be solved. However, it is also possible to keep the pH value of the solution slightly acidic, e.g. at pH values between 5 and
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309 8 24/0989309 8 24/0989
7 oder bei sogenannten Ammoniakemul'sionen können die pH-Werte der Lösung auch zwischen 5 und 9 liegen. 2160207 Die erfindungsgemäßen Substanzen können in beliebigen Silbersalz-, vorzugsweise Silberhalogenidemulsionen angewendet werden. Als SiI-berhalogenide sind Silberchlorid, Silberbromid oder Gemische davon, evtl. mit einem geringen Gehalt an Silberjpdid bis zu 10 Mol-% geeignet. Die Silberhalogenide können in den üblichen hydrophilen Bindemitteln dispergiert sein, beispielsweise in Carboxymethylcellulose, Polyvinylalkohol, Polyvinylpyrrolidon, Alginsäure und deren Salze, Estern oder Amiden oder Proteinen, vorzugsweise Gelatine.7 or in the case of so-called ammonia emulsions, the pH values the solution can also be between 5 and 9. 2160207 The substances according to the invention can be used in any silver salt, preferably silver halide, emulsions. As SiI superhalides are silver chloride, silver bromide or mixtures thereof, possibly with a low content of silver oxide up to 10 mol% is suitable. The silver halides can be used in the usual hydrophilic binders be dispersed, for example in carboxymethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, Alginic acid and its salts, esters or amides or proteins, preferably gelatin.
Die Emulsionen können auch andere chemische Sensibilisatoren enthalten, z.B. quaternäre Ammonium- und Phosphonium- sowie ternäre SuIfoniumsalze, Reduktionsmittel wie Zinn-II-Salze, Polyamine wie Diäthylentriamin oder Schwefelverbindungen, wie in der amerikanischen Patentschrift 1,574,944 beschrieben. Zur chemischen Sensibilisierung können die angegebenen Emulsionen ferner Salze von Edelmetallen, wie Rhutenium, Rhodium, Palladium, Iridium, Platin oder Gold enthalten, wie dies in dem Artikel von R. KOSLOWSKY, Z.Wiss.Phot. 46, 65 - 72 (1951) beschrieben worden ist. Weiterhin können die Emulsionen auch Polyalkylenoxide oder Polyalkylenoxidderivate als Entwicklungsbeschleuniger oder chemische Sensibilisatoren enthalten. Dabei wird ein zusätzlicher Empfindlichkeitsgewinn erzielt.The emulsions may also contain other chemical sensitizers, e.g. quaternary ammonium and phosphonium as well as ternary sulfonium salts, reducing agents such as tin-II salts, polyamines such as diethylenetriamine or sulfur compounds as described in US Pat. No. 1,574,944. For chemical The specified emulsions can also sensitize salts of noble metals, such as ruthenium, rhodium, palladium, iridium, Contain platinum or gold, as described in the article by R. KOSLOWSKY, Z.Wiss.Phot. 46, 65-72 (1951) is. Furthermore, the emulsions can also contain polyalkylene oxides or polyalkylene oxide derivatives as development accelerators or chemical agents Contain sensitizers. An additional gain in sensitivity is achieved.
Die Emulsionen können auch optisch sensibilisiert sein, z.B. mit den üblichen Polymethinfarbstoffen wie Neutrocyanin, basischen oder sauren Carbocyaninen, Rhodacyaninen, Hemicyaninen, Styrylfarbstoffen, Oxonolen und ähnlichen. Derartige Sensibilisatoren sind beschrieben in dem Werk von F.M. HAMER "The Cyanine Dyes and related Compounds" (1964).The emulsions can also be optically sensitized, e.g. with the usual polymethine dyes such as neutrocyanin, basic or acidic carbocyanines, rhodacyanines, hemicyanines, styryl dyes, Oxonols and the like. Such sensitizers are described in the work of F.M. HAMER "The Cyanine Dyes and related Compounds "(1964).
Die Emulsionen können die üblichen Stabilisatoren enthalten, wie z.B. homöopolare oder salzartige Verbindungen des Quecksilbers mit aromatischen oder heterocyclischen Ringen (etwa Mercaptotriazolen), einfache Quecksilbersalze, Sulfoniumquecksilberdoppelsalze und andere Quecksilberverbindungen„The emulsions can contain the usual stabilizers, such as homopolar or salt-like compounds of mercury with aromatic or heterocyclic rings (such as mercaptotriazoles), simple mercury salts, sulfonium mercury double salts and other mercury compounds "
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ORIGINAL INSPECTEDORIGINAL INSPECTED
Als Stabilisatoren sind weiterhin geeignet Azaindene, vorzugsweise Tetra- oder Pentaazaindene, insbesondere solche, die mit Hydroxyl- oder Aminogruppen substituiert sind.Azaindenes are also suitable as stabilizers, preferably Tetra- or Pentaazaindenes, especially those with Hydroxyl or amino groups are substituted.
Derartige Verbindungen sind in dem Artikel von BIRR, Z.Wiss.Phot. 47, 2-58 (1952) beschrieben. Weitere geeignete Stabilisatoren sind u.a. heterocyclische Mercaptoverbindungen, z.B. Phenylmercaptotetrazol, quaternäre Benzthiazolderivate, Benztriazol und ähnliche.Such compounds are described in the article by BIRR, Z.Wiss.Phot. 47 , 2-58 (1952). Other suitable stabilizers include heterocyclic mercapto compounds, for example phenyl mercaptotetrazole, quaternary benzothiazole derivatives, benzotriazole and the like.
Die Emulsionen können in der üblichen Weise gehärtet sein, beispielsweise mit Formaldehyd oder halogensubstituierten Aldehyden, die eine Carboxylgruppe enthalten, wie Mucobromsäure, Diketonen, Methansulfensäureester, Dialdehyden und dergleichen oder polyfunktionellen Triazinderivaten wie Trisacrylotylhexahydrotriazin oder Halogen- bzw. Alkoxy-substituierten Hexahydrotriazinderivateri. The emulsions can be hardened in the usual way, for example with formaldehyde or halogen-substituted aldehydes that contain a carboxyl group, such as mucobromic acid, diketones, Methanesulfenic acid esters, dialdehydes and the like or polyfunctional Triazine derivatives such as trisacrylotylhexahydrotriazine or halogen- or alkoxy-substituted hexahydrotriazine derivatives.
Die erfindungsgemäßen Substanzen besitzen ihre vorteilhafte Wirkung nicht nur in Schwarz-Weiß-Emulsionen, sondern sei zeigen ihre Effekte auch bei der Herstellung farbphotographischer Bilder. Sie besitzen eine gute Verträglichkeit mit den üblichen Farbkupplern. Ebenso können die Phosphorsäureamide auch bei Direktpositivemulsionen, z.B. solchen mit geschichtetem Kornaufbau gemäß französischer Patentschrift 1,585,791 eingesetzt werden. Sie sind ferner geeignet für Emulsionen für das Silberfarbbleichverfahren oder Farbstoffdiffusionsverfahren.The substances according to the invention have their advantageous effect not only in black and white emulsions, but also show their effects in the production of color photographic images. They have good compatibility with the usual color couplers. The phosphoric acid amides can also be used in Direct positive emulsions, e.g. those with a layered grain structure according to French patent 1,585,791, can be used. They are also suitable for emulsions for the silver dye bleaching process or dye diffusion process.
Eine besonders gute Wirkung wird mit den Phosphorsäureamiden bei solchen Silbersalzemulsionen erzielt, die in Gegenwart von Kieselsolen gefällt werden. Die Herstellung solcher Emulsionen ist in der deutschen Offenlegungsschrift 1 797 254 bzw. der US-Anmeldung Ser.No. 61,001 beschrieben.A particularly good effect is achieved with the phosphoric acid amides achieved such silver salt emulsions which are precipitated in the presence of silica sols. The production of such emulsions is in German Offenlegungsschrift 1,797,254 and US application Ser.No. 61,001.
Gemäß einer weiteren bevorzugten Ausführungsform werden die Phosphorsäureamide in Kombination mit Polymeren verwendet, die Disulfonimidgruppen enthalten. Solche Verbindungen sind in der deutschen Patentschrift 1 089 548 bzw. der US-Patentschrift Nr. 3,052,656 beschrieben. Die polymeren Disulfonimide werden vor der chemischen Reifung, insbesondere bei der Fällung oder derAccording to a further preferred embodiment, the phosphoric acid amides are used in combination with polymers which Contain disulfonimide groups. Such compounds are described in German Patent 1,089,548 and US Patent No. 3,052,656. The polymeric disulfonimides are before the chemical ripening, in particular during the precipitation or the
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Flockung zugesetzt. Die Konzentration der Disulfonimide kann innerhalb weiter Grenzen schwanken. Im allgemeinen haben sich Mengen von 1 bis 10 %, bezogen auf die Ansatzgelatine, als ausreichend erwiesen.Flocculation added. The concentration of disulfonimides can be within further limits fluctuate. In general, amounts of 1 to 10%, based on the batch gelatin, have proven to be sufficient proven.
Probe 1:Sample 1:
Man fällt eine neutrale Silberbromidjodidgelatine-Emulsion mit 6 Mol-% an Silberjodid (mittlere Korngröße von 0,9 Mikron). Zur Fällung von 1 kg Silberhalogenid werden 100 g Gelatine eingesetzt. Nach Fällung und physikalischer Reifung des Silberhalogenids wird die Emulsion auf 350C abgekühlt. Man flockt in üblicher Weise mit Polystyrolsulfonsäure und säuert auf pH 3,0 mit 25 %iger Schwefelsäure an. Man läßt das Flockulat absitzen und zieht die überstehende Lösung ab. Anschließend wird zweimal mit 20 1 Wasser gewaschen, in dem das Flockulat 5 Minuten lang durch Rühren aufgewirbelt wird. Nach dem letzten Abzug des Wassers wird das Flockulat in einer entsprechenden Wasser- und Gelatinemenge bei pH 7 und 400C gelöst, mit Gold-III-chlorid und Natriumthiosulfat als Reifzusätzen versehen und nach Einstellen des pAg-Wertes auf 8,9 bei einer Reiftemperatür von 400C ausgereift.A neutral gelatin silver bromide iodide emulsion containing 6 mol% of silver iodide (mean grain size 0.9 micron) is precipitated. 100 g of gelatin are used to precipitate 1 kg of silver halide. After precipitation and physical ripening of the silver halide, the emulsion is cooled to 35 0 C. It is flocculated in the usual way with polystyrene sulfonic acid and acidified to pH 3.0 with 25% sulfuric acid. The flocculate is allowed to settle and the supernatant solution is drawn off. It is then washed twice with 20 l of water, in which the flocculate is whirled up by stirring for 5 minutes. After the last withdrawal of the water, the flocculate is dissolved in a corresponding amount of water and gelatin at pH 7 and 40 0 C, provided with gold (III) chloride and sodium thiosulfate as frosting additives and after adjusting the pAg to 8.9 at a ripening temperature matured from 40 0 C.
Probe 2:Sample 2:
Die Emulsion wird in der gleichen Weise hergestellt. Bei der Fällung werden jedoch zur vorgelegten Gelatine-Alkalihalogenidlösung noch 50 ml einer 7 %igen wässrigen Lösung der Verbindung 1 zugegeben.The emulsion is made in the same way. During the felling however, 50 ml of a 7% aqueous solution of compound 1 are added to the gelatin alkali halide solution admitted.
Beide Proben werden nach Zusatz pro kg Emulsion von 10 ml einer 5 #igen wässrigen Lösung von Saponin als Netzmittel, 10 ml einer 10 %igen wässrigen Lösung von Formaldehyd als Härtungsmittel und 2o ml einer 1 %igen methanolischen Lösung von 4-Hydroxy-6-methyl-1,3,3a,7-Tetraazainden als Stabilisator auf einen Celluloseacetatschichtträger vergossen. Nach Belichtung in einem üblichen Sensitometer hinter einem Stufenkeil und Entwicklung (7 und 16 Minuten bei 20 C) in einem Entwickler der folgenden ZusammensetzungAfter adding, per kg of emulsion, 10 ml of a 5% aqueous solution of saponin as a wetting agent, 10 ml of a 10% aqueous solution of formaldehyde as a hardening agent and 20 ml of a 1 % methanolic solution of 4-hydroxy-6- methyl-1,3,3a, 7-tetraazaindene poured onto a cellulose acetate support as a stabilizer. After exposure in a conventional sensitometer behind a step wedge and development (7 and 16 minutes at 20 ° C.) in a developer of the following composition
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wird sensitometrisch ausgewertet. Aus der anschließenden Tabelle ist zu ersehen, daß die Emulsionen 2-9 eine höhere Empfindlichkeit besitzen als die Vergleichsemulsion 1.is evaluated sensitometrically. From the table below it can be seen that emulsions 2-9 have a higher sensitivity have as the comparative emulsion 1.
2
3
4
5
6
7
8
91
2
3
4th
5
6th
7th
8th
9
lichkeitSensation
opportunity
0,65
0,60
0,70
0,65
0,60
0,65
0,60
0,750.60
0.65
0.60
0.70
0.65
0.60
0.65
0.60
0.75
0,18
0,15
0,14
0,16
0,13
0,15
0,12
0,15 '0.16
0.18
0.15
0.14
0.16
0.13
0.15
0.12
0.15 '
lichkeitSensation
opportunity
0,85
0,80
0,95
0,85
0,75
0,80
0,70
0,950.90
0.85
0.80
0.95
0.85
0.75
0.80
0.70
0.95
0,25
0,18
0,16
0,19
0,16
0,17
0,15
0,20
I0.21
0.25
0.18
0.16
0.19
0.16
0.17
0.15
0.20
I.
+ 1,5°
+ 1°
+ 1,5°
+ 1,5°
+ 1°
+ 1°
+ 0,5°
+ 1.5°Type
+ 1.5 °
+ 1 °
+ 1.5 °
+ 1.5 °
+ 1 °
+ 1 °
+ 0.5 °
+ 1.5 °
+ 1°
+ 0,5°
+ 1°
+ 1°
+ 1°
+ 1°
+ 1°
+ 1°Type
+ 1 °
+ 0.5 °
+ 1 °
+ 1 °
+ 1 °
+ 1 °
+ 1 °
+ 1 °
3 = 1 Blende3 = 1 aperture
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Claims (1)
RSO2
RSO
X = Halogen, Hydroxy oder eine Aminogruppe.ρ
X = halogen, hydroxy or an amino group.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE792091D BE792091A (en) | 1971-12-04 | PHOTOGRAPHIC SILVER SALT EMULSIONS WITH INCREASED SENSITIVITY | |
| DE2160207A DE2160207A1 (en) | 1971-12-04 | 1971-12-04 | PHOTOGRAPHIC SILVER SALT EMULSION WITH INCREASED SENSITIVITY |
| US00310635A US3850644A (en) | 1971-12-04 | 1972-11-29 | Silver halide grains precipitated in the presence of a phosphoric acid amide sensitizer |
| GB5548372A GB1390540A (en) | 1971-12-04 | 1972-12-01 | Process for the production of a material containing a photo graphic silver salt emulsion with increased sensitivity |
| FR7243088A FR2162231A1 (en) | 1971-12-04 | 1972-12-04 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2160207A DE2160207A1 (en) | 1971-12-04 | 1971-12-04 | PHOTOGRAPHIC SILVER SALT EMULSION WITH INCREASED SENSITIVITY |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE2160207A1 true DE2160207A1 (en) | 1973-06-14 |
Family
ID=5826988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2160207A Pending DE2160207A1 (en) | 1971-12-04 | 1971-12-04 | PHOTOGRAPHIC SILVER SALT EMULSION WITH INCREASED SENSITIVITY |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3850644A (en) |
| BE (1) | BE792091A (en) |
| DE (1) | DE2160207A1 (en) |
| FR (1) | FR2162231A1 (en) |
| GB (1) | GB1390540A (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1472792B2 (en) * | 1965-12-28 | 1976-09-23 | Agfa-Gevaert Ag, 5090 Leverkusen | LIGHT SENSITIVE PHOTOGRAPHIC RECORDING MATERIAL |
| 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/en unknown
-
1971
- 1971-12-04 DE DE2160207A patent/DE2160207A1/en 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
Also Published As
| Publication number | Publication date |
|---|---|
| FR2162231A1 (en) | 1973-07-13 |
| US3850644A (en) | 1974-11-26 |
| BE792091A (en) | 1973-05-30 |
| GB1390540A (en) | 1975-04-16 |
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