DE1772375A1 - Silver bromide photographic emulsion with increased sensitivity - Google Patents
Silver bromide photographic emulsion with increased sensitivityInfo
- Publication number
- DE1772375A1 DE1772375A1 DE19681772375 DE1772375A DE1772375A1 DE 1772375 A1 DE1772375 A1 DE 1772375A1 DE 19681772375 DE19681772375 DE 19681772375 DE 1772375 A DE1772375 A DE 1772375A DE 1772375 A1 DE1772375 A1 DE 1772375A1
- Authority
- DE
- Germany
- Prior art keywords
- silver bromide
- thiazane
- alkyl
- carbon atoms
- following
- 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 34
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 title claims description 10
- 230000035945 sensitivity Effects 0.000 title description 17
- -1 cyano, carboxyl Chemical group 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- AJZGFFKDLABHDD-UHFFFAOYSA-N thiazinane Chemical compound C1CCSNC1 AJZGFFKDLABHDD-UHFFFAOYSA-N 0.000 claims description 5
- BRNULMACUQOKMR-UHFFFAOYSA-N thiomorpholine Chemical compound C1CSCCN1 BRNULMACUQOKMR-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 4
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 4
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 4
- 229920000159 gelatin Polymers 0.000 claims description 4
- 235000019322 gelatine Nutrition 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229940045105 silver iodide Drugs 0.000 claims description 4
- 108010010803 Gelatin Proteins 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 239000000126 substance Substances 0.000 description 28
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- 239000004332 silver Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 230000005070 ripening Effects 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- AYLDJQABCMPYEN-UHFFFAOYSA-N (4-azaniumylphenyl)-diethylazanium;sulfate Chemical compound OS(O)(=O)=O.CCN(CC)C1=CC=C(N)C=C1 AYLDJQABCMPYEN-UHFFFAOYSA-N 0.000 description 2
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-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
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 2
- 229930182490 saponin Natural products 0.000 description 2
- 150000007949 saponins Chemical class 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 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
- TUBQDCKAWGHZPF-UHFFFAOYSA-N 1,3-benzothiazol-2-ylsulfanylmethyl thiocyanate Chemical group C1=CC=C2SC(SCSC#N)=NC2=C1 TUBQDCKAWGHZPF-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
- ZMXYNJXDULEQCK-UHFFFAOYSA-N 2-amino-p-cresol Chemical compound CC1=CC=C(O)C(N)=C1 ZMXYNJXDULEQCK-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
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000001828 Gelatine Substances 0.000 description 1
- 241000562391 Limenitis arthemis Species 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- IEIREBQISNYNTN-UHFFFAOYSA-K [Ag](I)(Br)Cl Chemical compound [Ag](I)(Br)Cl IEIREBQISNYNTN-UHFFFAOYSA-K 0.000 description 1
- XUAJZOHXBBRXOX-UHFFFAOYSA-M [Ag]Br.[I] Chemical compound [Ag]Br.[I] XUAJZOHXBBRXOX-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- GRTOGORTSDXSFK-XJTZBENFSA-N ajmalicine Chemical compound C1=CC=C2C(CCN3C[C@@H]4[C@H](C)OC=C([C@H]4C[C@H]33)C(=O)OC)=C3NC2=C1 GRTOGORTSDXSFK-XJTZBENFSA-N 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
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- 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
- ZUIVNYGZFPOXFW-UHFFFAOYSA-N chembl1717603 Chemical compound N1=C(C)C=C(O)N2N=CN=C21 ZUIVNYGZFPOXFW-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- PBARJOQXHJCTKK-UHFFFAOYSA-L disodium;dibromide Chemical compound [Na+].[Na+].[Br-].[Br-] PBARJOQXHJCTKK-UHFFFAOYSA-L 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002433 hydrophilic molecules Chemical class 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
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- PKDBSOOYVOEUQR-UHFFFAOYSA-N mucobromic acid Natural products OC1OC(=O)C(Br)=C1Br PKDBSOOYVOEUQR-UHFFFAOYSA-N 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 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
- 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
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000005956 quaternization reaction Methods 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
- 230000001235 sensitizing effect Effects 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 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
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur 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
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical class [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—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
-
- 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
- G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (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)
- Plural Heterocyclic Compounds (AREA)
Description
LEVERKUSENLEVERKUSEN
Za/ax Neuschrift 26. November 1969Za / ax rewriting November 26, 1969
Photographische Silberbromidemulsion mit erhöhter EmpfindlichkeitSilver bromide photographic emulsion with increased sensitivity
Die vorliegende Erfindung betrifft ein Verfahren zur Steigerung der Empfindlichkeit photographischer Silberbromidemulsionen durch Zusatz von heterocyclischen Oniunverbindungen mit TMoäthergruppierungen. The present invention relates to a method of increasing the sensitivity of photographic silver bromide emulsions by adding heterocyclic onium compounds with TMoether groups.
Die Empfindlichkeit einer photographischen Emulsion läßt sich auf zweierlei V/eise beeinflussen. Zunächst ist es möglich, bei der sogenannten chemischen Reifung während der Emulsionsheretellung durch verlängerte Reifzeit oder durch Zusatz geeigneter Substanzen, wie Thiosulfat oder auch anderer, meist schwefelhaltiger Präparate, die Empfindlichkeit zu erhöhen. Die andereThe sensitivity of a photographic emulsion can be influenced in two ways. First of all, it is possible at the so-called chemical ripening during emulsion production by extending the ripening time or by adding suitable substances such as thiosulphate or other, mostly sulfur-containing substances Preparations to increase sensitivity. The other
A-O562- 109812/1632AO 562 - 109812/1632
177? υ177? υ
Art der Empfindlichkeitserhöhung einer photographischen Emulsion besteht im Zusatz sogenannter Entv/icklungsbeschleuniger oder chemischer Sensibilisatoren. Diese werden üblicherweise der bereits fertig gereiften Emulsion zugefügt.The way in which the sensitivity of a photographic emulsion is increased is the addition of so-called development accelerators or chemical sensitizers. These will usually be the already ready-ripened emulsion added.
Als Entv/icklungsbeschleuniger wurden dabei z. B. Verbindungen mit Oniumstruktur (wie etwa quaternäre Ammonium-, Phosphonium- und ternäre Sulfoniumsalze) sowie sehr häufig auch Polyalkylenoxide und Polyalkylenoxidderivate beschrieben. Gerade bei der zuletztgenannten Stoffklasse sind viele Versuche gemacht worden,um die erzielten Empfindlichkeitsgewinne durch Abwandlung der Derivate oder durch kombinierte Anwendung zusammen mit anderen Verbindungen zu erhöhen. Alle diese Verbindungen erfüllen jedoch nicht die von der Praxis geforderten Eigenschaften in vollem ; Maße, sei es, daß die Empfindlichkeitssteigerung unbefriedigend ist oder daß der mit der Sensibilisierung verbundene Schleier eine Anwendung verhindert.As a development accelerator, z. B. Compounds with an onium structure (such as quaternary ammonium, phosphonium and ternary sulfonium salts) and very often also polyalkylene oxides and polyalkylene oxide derivatives are described. With the last-mentioned class of substances in particular, many attempts have been made to increase the sensitivity gains achieved by modifying the derivatives or by combining them with other compounds. However, all of these compounds do not fully meet the properties required in practice ; To some extent, be it that the increase in sensitivity is unsatisfactory or that the fog associated with the sensitization prevents use.
Der Erfindung liegt die Aufgabe zugrunde, neue chemische Sensibilisatoren zu finden, die die obigen Nachteile nicht besitzen und mit deren Hilfe eine Steigerung der Empfindlichkeit photographischer Halogensilberemulsionen ohne Verursachung einer unerwünschten Schleierbildung möglich wird. The invention is based on the object of finding new chemical sensitizers which do not have the above disadvantages and with the aid of which it is possible to increase the sensitivity of photographic silver halide emulsions without causing undesirable fogging .
109812/1632 bad original109812/1632 bad original
A-B J62 - 2 - ' AB J62 - 2 - '
Es wurde nun gefunden, daß man bei Silberbroinidemulsionen besonders hohe Empfindliehkeitsgewinne bei relativ geringem Schleieranstieg er reichen kann, wenn man die Entwicklung in Gegenwart von 1,4-Thiazanen der folgenden Formel ausführt:It has now been found that with silver broinide emulsions in particular high gains in sensitivity with a relatively low increase in haze can be enough if you develop in the presence of 1,4-thiazanes of the following formula:
- R'- R '
worin bedeuten:where mean:
R = Wasserstoff oder Alkyl mit bis zu 5 C-Atomen, vorzugsweise Methyl;R = hydrogen or alkyl with up to 5 carbon atoms, preferably methyl;
R« = (l) Wasserstoff,(2 ) geradkettiges oder verzweigtes Alkyl mit bis zu 12. C-Atomen, vorzugsweise mit bis zu 5 C-Atomen, wobei die Alkylreste substituiert sein können mit Phenyl, Hydroxyl, Cyano, Carboxyl, verestertes Carboxyl oder Alkoxy, (3) Aryl, insbesondere Phenyl, wobei die Phenylreste ebenfalls substituiert sein können, (4) Acyl, insbesondere Acyl, das sich ableitet von aliphatischen Carbonsäuren mit vorzugs weise bis zu 5 C-Atomen, (5) Carbamyl, wobei die Amidgruppe substituiert sein kann mit Alkyl mit vorzugsweise bis zu 5 C-Atomen, Aralkyl wie Benzyl oder Aryl, insbesondere Phenyl und (6) eine Aminogruppe, wobei die Wasserstoffatome der Aminogruppe substituiert sein können mit Alkyl, vorzugsweise mit bis zu 5 C-Atomen, Aryl, insbesondere Phenyl oder Acylgruppen, inabesondere die der obenangegebenen Art; die Aminogruppe kann außerdem substituiert sein mit Carbanylgruppen, wobei diese wiederum alkyliert oder phenyliert sein können.R «= (1) hydrogen, (2) straight-chain or branched alkyl with up to 12 carbon atoms, preferably with up to 5 carbon atoms, it being possible for the alkyl radicals to be substituted by phenyl, Hydroxyl, cyano, carboxyl, esterified carboxyl or alkoxy, (3) aryl, especially phenyl, the phenyl radicals also can be substituted, (4) acyl, in particular acyl, which is derived from aliphatic carboxylic acids with preference wise up to 5 carbon atoms, (5) carbamyl, where the amide group can be substituted with alkyl with preferably up to 5 C atoms, aralkyl such as benzyl or aryl, in particular phenyl and (6) an amino group, the hydrogen atoms being the Amino groups can be substituted with alkyl, preferably with up to 5 carbon atoms, aryl, in particular phenyl or acyl groups, in particular those of the kind specified above; the amino group can also be substituted with carbanyl groups, which in turn can be alkylated or phenylated.
109812/1632109812/1632
Soweit das Stickstoffatom des Morpholinringes in der Lage ist, einfache Salze bzw. quaternäre Ammoniumsalze zu bilden, können selbstverständlich auch diese in der erfindungsgemäßen Weise eingesetzt werden. Als quaternäre Gruppen sind Alkyl mit bis zu 12 C-Atomen, vorzugsweise mit bis zu 5 C-Atomen geeignet, wobei diese Alkylgruppen substituiert sein können, z. B. mit Phenyl wie in den Benzylphenyläthylgruppen.As far as the nitrogen atom of the morpholine ring is able to To form simple salts or quaternary ammonium salts, these can of course also be formed in the manner according to the invention can be used. Suitable quaternary groups are alkyl with up to 12 carbon atoms, preferably with up to 5 carbon atoms, where these alkyl groups may be substituted, e.g. B. with phenyl as in the benzylphenylethyl groups.
Dabei können beliebige Anionen auftreten, z. B. Halogen, Halogenide, Perchlorate und ähnliche. Eine Quaternierung des Stickstoffatoms des Morpholinringes ist bekanntlich dann nicht möglich, wenn die basischen Eigenschaften des Stickstoffes durch negative Substituenten unterdrückt sind. Dies trifft z. B. zu, wenn R1 Phenyl, Carbamyl oder Acyl bedeutet.Any anions can occur, e.g. B. halogen, halides, perchlorates and the like. As is known, quaternization of the nitrogen atom of the morpholine ring is not possible if the basic properties of the nitrogen are suppressed by negative substituents. This applies e.g. B. to when R 1 is phenyl, carbamyl or acyl.
Einige besonders brauchbare Verbindungen sind im folgenden angegeben:Some particularly useful compounds are given below:
2. S"""^ . HCl2. S "" "^. HCl
3. S^^$ - NH2 3. S ^^ $ - NH 2
5. ST Ti - C2H8 5. ST Ti - C 2 H 8
6. ST N - CH2 - ß \\6. ST N - CH 2 - ß \\
7. S 7. S. N - ( J N - (J
~~~~ BAD ORIGINALBATH ORIGINAL
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A-G 362 - 4 -A-G 362 - 4 -
-■ CH2CH2-OH- ■ CH 2 CH 2 -OH
- CH2CH2 -C = N- CH 2 CH 2 -C = N
^N - CH2COOH bzw. © ^ N - CH 2 COOH or ©
S NS N
- CH2 - C(- CH 2 - C (
0 Il -C-NH-0 Il -C-NH-
Il
- C - CH, Il
- C - CH,
- NH- NH
- <5 - NH f~\ - <5 - NH f ~ \
IlIl
,G,G
- N- N
C U 0C U 0
NH. ITH—//NH. ITH - //
,NH2 , NH 2
GTTGTT
NH2 CH2 NH 2 CH 2
C2H6 C2H6 C 2 H 6 C 2 H 6
BiBi
ClCl
Die in. der erfindungagemäßen Weise zu verwendenden Substanzen werden in bekannter Weise aus Thiomorpholin hergeäbellt. Die Herstellung von Thiomorpholin ist beschrieben in J.Chem.Soc. 1920, S. 297 - 308} J.Am.Chem.Soc. 76, (1954), S. 1187-1188; US-Patent 2 761 860; DAS 1 104 513. Die Herstellung von C-substituierten 1,4-Thiazanen findet sich in J.Am.Chem.Soc. 76, (1954),S.2902 2906. The substances to be used in the manner according to the invention are produced in a known manner from thiomorpholine. The preparation of thiomorpholine is described in J. Chem. Soc. 1920, pp. 297-308} J.Am.Chem.Soc. 76, (1954), pp. 1187-1188; U.S. Patent 2,761,860; DAS 1 104 513. The preparation of C-substituted 1,4-thiazanes can be found in J.Am.Chem.Soc. 76, (1954), p . 2902 2906.
109812/1632109812/1632
BAD ORiG|NAL BAD ORiG | NAL
17723"E17723 "E.
Zur Herstellung der am Stickstoff substituierten 1,4-Thiazane .geht man von dem entsprechenden unsubstituierten Thiazan aus und setzt nach bekannten Verfahren mit einem geeigneten halogensubatituierten Präparat unter Hinzufügung säurebindender Mittel um..Andere der obigen Verbindungen lassen sich durch Reaktion des unsubstituiarten Thiazans mit Säurechlorideri oder mit Isocyanaten gewinnen.For the preparation of the 1,4-thiazanes substituted on the nitrogen . If you start from the corresponding unsubstituted thiazane and use a suitable one according to known methods Halogen-substituted preparation with the addition of acid-binding agents. Other of the above compounds can be by reaction of the unsubstituted thiazane with acid chlorides or win with isocyanates.
Das N-Amino-1,4-thiazan läßt sich durch Nitrosierung des Thiazans ^ und anschließende Reduktion darstellen.The N-amino-1,4-thiazane can be obtained by nitrosating the thiazane ^ and subsequent reduction.
Die Darstellung der Säuresalze und der Quaternärsalze gesohieht nach bekannten chemischen Methoden.The acid salts and the quaternary salts are represented using known chemical methods.
Die erfindungsgemäßen Substanzen könne der photographischen Emulsion in jedem Stadium ihrer Herstellung vor,>während oder , nach der chemischen Reifung zugesetzt werden. Man kann sie-auch der Gießlösung unmittelbar vor dem Vergießen zufügen. Die-zuge7 setete Menge hängt von dem gewünscht si Effekt-ab und kann von einem Fachmann jederzeit durch die üblichen Versucheermittelt; ; werden. - ■■■ ."■ ■ ■ . - . ..>··?·■ ν .;?- .··-/;■-.,,·■. -■, .■ <? ■ The substances according to the invention can be added to the photographic emulsion at any stage of its preparation before,> during or after chemical ripening. They can also be added to the casting solution immediately before casting. The fed-7 setete amount depends on the desired effect of si, and may by a skilled person at any time by the usual Versucheermittelt; ; will. - ■■■. "■ ■ ■. -. ..> ··? · ■ ν.;? -. ·· - /; ■ -. ,, · ■. - ■,. ■ <? ■
Im allgemeinen genügen Mengen von 0,003 bis 20 g, vorzugsweise von 0,003 bis 6 g pro Mol Halogensilber. :.In general, amounts of from 0.003 to 20 g are sufficient, preferably from 0.003 to 6 grams per mole of halosilver. :.
A-G 362 -ο AG 362 -ο
109812/1632 bad original109812/1632 bad original
Die Verbindungen können auch dem photographischen Entwickler zugesetzt werden.. In diesem Fall gelten die gleichen Mengenangaben wie für die Zugabe zur Emulsion, bezogen auf einen Liter Entwickler. The compounds can also be added to the photographic developer In this case, the same quantities apply as for the addition to the emulsion, based on one liter of developer.
Die erfindungegemäßen Substanzen können in beliebigen Halogensilberemulsionen angewendet werden. Als Silberhalogenid sind Silberbromid vorzugsweise mit einem geringen Gehalt an Silber- ^ jodid bis zu 10 Mol.-fo geeignet. Die Silberhalogenide können in den üblichen hydrophilen Verbindungen dispergiert sein, beispielsweise in Carboxymethylcellulose, Polyvinylalkohol, Polyvinylpyrrolidon, Alginsäure und deren Salzen, Estern oder Amiden oder vorzugsweise Gelatine.The substances according to the invention can be used in any halogen silver emulsions. Silver bromide preferably with a low content of silver iodide of up to 10 mol% are suitable as the silver halide. The silver halides can be dispersed in the customary hydrophilic compounds, for example in carboxymethyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, alginic acid and its salts, esters or amides or, preferably, gelatin.
Die Emulsionen können auch andere chemische Sensibilisatoren enthalten, z^. B. quaternäre Ammonium- una Phosphonium- sowie ternäre Sulfoniumsalze, Reduktionsmittel wie Zinn-II-Salze, Polyamine wie Diäthylentriamin oder Schwefelverbindungen, wie g in der amerikanischen Patentschrift 1 574 944 beschrieben. Zur chemischen Sensibilisierung können die angegebenen Emulsionen ferner Salze von Edelmetallen, wie Ehutenium, Rhodium, Palladium, Iridium, Platin oder Gold enthalten, wie dies in dem Artikel vonThe emulsions can also contain other chemical sensitizers included, z ^. B. quaternary ammonium and phosphonium as well ternary sulfonium salts, reducing agents such as tin (II) salts, Polyamines such as diethylenetriamine or sulfur compounds such as g in American Patent 1,574,944. To the chemical sensitization, the specified emulsions can also be salts of precious metals, such as ehutenium, rhodium, palladium, Contain iridium, platinum or gold, as described in the article by
R. Koslowsky., Z. Wiss. Phot. 46, 65 - 72 (1951) beschriebenR. Koslowsky., Z. Wiss. Phot. 46, 65-72 (1951)
worden ist. 'has been. '
A-G 362 - 7 - " AG 362 - 7 - "
BAD ORIGINAL 109812/1632BAD ORIGINAL 109812/1632
Weiterhin können die Emulsionen auch Polyalkylenoxide oder PoIyalkylenoxidderivate als Entwicklungsbeschleuniger oder chemische Sensibilisatoren enthalten.Furthermore, the emulsions can also contain polyalkylene oxides or polyalkylene oxide derivatives as development accelerators or chemical sensitizers.
Die Emulsionen können auch optisch eensibilisiert sein, z.B. mit den üblichen Polymethinfarbstoffe^ wie Neutrocyaninen, basischen oder sauren Carbocyanine^ Rhodacyaninen, Hemicyaninen, Styry!farbstoffen, Oxonolen und ähnlichen. Derartige Sensibilisatoren sind beschrieben in dem Werk von P.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 neutrocyanines, basic or acidic carbocyanines ^ rhodacyanines, hemicyanines, Styry! Dyes, oxonols and the like. Such Sensitizers are described in the work by P.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 (e.g. Mercaptotriazoles), simple mercury salts, sulfonium mercury double salts and other mercury compounds.
. - ■'■·■. - ■ '■ · ■
Als Stabilisatoren sind weiterhin geeignet Azaindene, vorzugsweise Tetra oder Pentaazaindene, insbesondere solche, die mit Hydroxyl- oder Aminogruppen substituiert sind. Derartige Verbindungen sind in dem Artikel von Birr, Z.Wies. Phot. 47, 2 -58, (1952) beschrieben. Weitere geeignete Stabilisatoren sind u.a. heterocyclische Mercaptoverbindungen, z.B. Phenylmercaptotetrazol, quaternäre Benthiazolderivate, Benztriazol und ähnliche.Azaindenes are also suitable as stabilizers, preferably Tetra or pentaazaindenes, especially those substituted with hydroxyl or amino groups. Such compounds are described in the article by Birr, Z.Wies. Phot. 47, 2-58, (1952). Other suitable stabilizers include heterocyclic mercapto compounds, e.g. phenyl mercaptotetrazole, quaternary benthiazole derivatives, Benzotriazole and the like.
A-G 362 - β - AG 362 - β -
109812/1832 BAD original109812/1832 BAD original
Die Emulsionen können in der üblichen Weise gehärtet sein, beispielsweise mit Formaldehyd oder halogensub'Btituierten Aldehyden, die eine Carboxylgruppe enthalten, wie Mucobromsäure, Diketonen, Methansulfoeäureester, Dialdehyden und dergleichen. The emulsions can be hardened in the usual way, for example with formaldehyde or halogen-substituted aldehydes which contain a carboxyl group, such as mucobromic acid, Diketones, methanesulfoic acid esters, dialdehydes and the like.
Die erfindungsgemäßen Substanzen besitzen ihre vorteilhafte Wirkung nicht nur in-Schwarz-Weiß-Emulsionen und Entwicklern, sondern sie zeigen ihre Effekte auch bei der Herstellung färb-■photographischer Bilder. Hier können sie sowohl farbkupplerhaltigen lichtempfindlichen Emulsionen als auch Farbentwicklern zugesetzt werden.The substances according to the invention have their advantageous properties Effect not only in black and white emulsions and developers, but they also show their effects in the production of color ■ photographic Pictures. Here you can use both color coupler-containing light-sensitive emulsions and color developers can be added.
Einer Silberbromidjodidgelatineemulsion, die pro Liter 60 g Silber in Form Ton Halogensilber mit einem Gehalt an Silberjodid von 6 Mol.-$ enthält, werden zugesetzt:A silver bromide iodide gelatin emulsion containing 60 g of silver per liter in the form of clay halogen silver with a content of silver iodide of 6 mol .- $ are added:
600 mg Saponin als Netzmittel, 200 mg 4-Hydroxy-6-methyl-l,3,3a,7-tetraazainden als Stabilisator und 10 ml einer 10 $igen wässrigen Lösung von Formaldehyd.600 mg saponin as a wetting agent, 200 mg 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene as a stabilizer and 10 ml of a 10% aqueous solution of formaldehyde.
Die Emulsion wurde in fünf gleiche -Teile geteilt und den einzelnen Proben pro Liter Emulsion die folgenden Substanzen zugesetzt:The emulsion was divided into five equal parts and each The following substances are added to samples per liter of emulsion:
Probe A ι Vergleichsprobe - ohne ZusatzSample A ι comparison sample - without addition
Probe B : 300 mg der Substanz I Sample B : 300 mg of substance I.
Probe -C : 600 mg der Substanz III Sample -C: 600 mg of substance III
A-G 362 - 9 - · AG 362 - 9 -
109812/1832109812/1832
177237.F177237.F
Die erhaltenen Gießlösungen werden auf einen Schichtträger aus Cellulosetriacetat vergossen, in einem Sensitometer hinter einem Graustufenkeil belichtet und in einem Entwickler der folgenden Zusammensetzung 10 Minuten lang entwickelt.:The casting solutions obtained are poured onto a layer support made of cellulose triacetate, in a sensitometer behind exposed to a grayscale wedge and developed in a developer of the following composition for 10 minutes:
Natriumsulfit sicc. 70,0 gSodium sulfite sicc. 70.0 g
Borax 7,0 gBorax 7.0 g
Hydrochinon 3,5 gHydroquinone 3.5 g
p-Monomethyl-aminophenol 3,5 gp-monomethyl aminophenol 3.5 g
Natriumeitrat 7,0 gSodium citrate 7.0 g
Kaliumbromid · 0,4 gPotassium bromide x 0.4 g
Mit Wasser auf einen Liter auffüllen.Make up to one liter with water.
Die Ergebnisse der sensitometrischen Prüfung sind in der folgenden Tabelle angegeben.:The results of the sensitometric test are in the given in the following table:
Eine Zunahme um 3° bedeutet einen Empfindlichkeitsgewinn von einer Blende bzw. die doppelte Empfindlichkeit.An increase of 3 ° means a gain in sensitivity of one aperture or twice the sensitivity.
A-G 362 - 10 - AG 362 - 10 -
BAD ORiGiNAlLBAD ORiGiNAlL
109812/1632109812/1632
Beispiel 2 " ' Example 2 "'
Eine Mi 3 cn emulsion, die sich aus 90 l/° einer Silberbromidjodidgeiatineemulsion und 10 $ einer Silberchloridbromidjodidgelatineemulsion zusammensetzt und die in bekannter .-/eise mit Gold- und Schwefelverbindungen bis zur optimalen Empfindlichkeit gereift wurde, wird durch Zusatz von 45 mg pro kg Emulsion des folgenden Sensibilisierungsfarbstoff es sens^ibilisiert.:A Mi 3 cn emulsion, which is composed of 90 l / ° of a silver bromide iodine diatine emulsion and 10 $ of a silver chloride bromide iodide gelatine emulsion and which has been ripened in the known manner with gold and sulfur compounds to the optimum sensitivity, is obtained by adding 45 mg per kg of emulsion of the following sensitizing dye it sensitizes:
Bei Emulsion werden ferner pro kg zugesetzt': In the case of emulsion, the following are also added per kg:
(1—(3'-sulf0-4'-phenoxy-)phenyl-3-heptadecyl-pyrazolon al^s Purpurkuppler(1- (3'-sulf0-4'-phenoxy) phenyl-3-heptadecyl-pyrazolone al ^ s purple coupler
1,3,3a,7-tetraaza-4-hydroxy-6-methyl-inden als Stabilisator " ■ '1,3,3a, 7-tetraaza-4-hydroxy-6-methyl-indene as a stabilizer "■ '
einer 5 ^igen wässrigen Lösuiig von Saponin als Näzmittela 5% aqueous solution of saponin as a nutrient
einer 30 folgen wässrigen Lösung von Formaldehyd als Härtungsmittel followed by an aqueous solution of formaldehyde as a hardening agent
Die Emulsion wird in Sieben, gleiche Teile, geteilt und den einzelnen Teilen pro kg Emulsion die folgenden Substanzen zugesetzt.:The emulsion is divided into seven, equal parts, and each one The following substances are added to parts per kg of emulsion:
A-G 362A-G 362
- 11 -·- 11 -
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177237F177237F
Probe A Probe B Probe C Probe D Probe E Probe P Probe GSample A Sample B Sample C Sample D Sample E Sample P Sample G.
Vergleichsprobe - ohne ZusatzComparative sample - without addition
1,0 g der Substanz I1.0 g of substance I.
3,0 g der Substanz III3.0 g of substance III
1,0 g der Substanz XII1.0 g of substance XII
1,0 g der Substanz IV1.0 g of substance IV
0,3 g der Substanz XI0.3 g of substance XI
1,0 g der Substanz XIV1.0 g of substance XIV
Die Proben werden auf einen Träger aus Celluloseacetat vergossen und getrocknet. Anschließend werden sie hinter einem Stufenkeil belichtet und in üblicher Weise verarbeitet. Der. Yerarbeitungsgang ist wie folgt: The samples are poured onto a cellulose acetate carrier and dried. They are then exposed behind a step wedge and processed in the usual way. Of the. The processing process is as follows:
Farbentwicklung Stoppbad Wässerung Bleichbad Wässerung Fixierbad Wässerung Color development stop bath watering bleach bath watering fixer bath watering
7 Minuten 5 Minuten 5 Minuten 5 Minuten 5 Minuten 5 Minuten 7 minutes 5 minutes 5 minutes 5 minutes 5 minutes 5 minutes
10 Minuten10 mins
A-G A-G 362362
- 12 -- 12 -
10 9 8 12/163210 9 8 12/1632
Kaliumcarbonat sice.Potassium carbonate sice.
KaliumbromidPotassium bromide
Auffüllen auf einen LiterMake up to one liter
75,0 g 2,0 g75.0 g 2.0 g
Die übrigen Verarbeitungsbäder hatten die folgende Zusammensetzung: The other processing baths had the following composition:
Stoppbad;Stop bath;
Natriumacetat 30,0 g Eisessig 6,0 gSodium acetate 30.0 g glacial acetic acid 6.0 g
Wasser auffüllen auf 1 1Fill up with water to 1 1
Die Farbdichte der Purpurschichten wurden mit dem Densitometer "Macbeth Quanta Log, Modell TD 102" unter Einschaltung des grünen Farbfilters in den Strahlengang des Meßlichtes gemessen. .The color density of the purple layers was measured with the "Macbeth Quanta Log, Model TD 102" densitometer with the inclusion of the green color filter measured in the beam path of the measuring light. .
A-G 362A-G 362
- 13 -- 13 -
BAD ORIGINALBATH ORIGINAL
109812/1632109812/1632
177237B177237B
Eine Zunahme um 3 bedeutet doppelte Empfindlichkeit oder einen Empfindlichiceitagewinn von einer Blende.·An increase of 3 means twice the sensitivity or an increase in sensitivity of one stop.
Die erfindungageinäßen Präparate haben auch in Farbentwicklern eine vorteilhafte 'Wirkung, wie da3 folgende Beiapiel zeigt. Einem Farbentwickler werden pro Liter je ein Gramm der folgenden Substanzen zugesetzt:The preparations according to the invention also have an advantageous effect in color developers, as the following example shows. One gram of the following substances is added per liter to a color developer:
Probe A : Vergleichsprobe - ohne Zusatz Probe B : Substanz ISample A: Comparative sample - without additive Sample B: Substance I
Probe C : Substanz IISample C: substance II
Probe D :· Substanz XV (0,5 g pro Liter) Der Farbentwickler hat die folgende Zusammensetzung:Sample D: Substance XV (0.5 g per liter) The color developer has the following composition:
Diäthyl-p-phenylendiamin-sulfat 2,75 gDiethyl p-phenylenediamine sulfate 2.75 g
Hydroxylaminsulfat . 1,2 g ··Hydroxylamine sulfate. 1.2 g
A-G 362 - 14 - ·. AG 362-14 -.
109812/1632 BAD 0RIGINAL 109812/1632 BATHROOM 0RIGINAL
Mit Wasser auf einen Liter auffüllen.Make up to one liter with water.
Es wird ein handelsübliches farbphotographisches Mehrschichtenmaterial hinter einem Stufenkeil belichtet und in üblicher Weise verarbeitet.It becomes a commercially available multilayer color photographic material exposed behind a step wedge and processed in the usual way.
Färbentwicklung 7 MinutenColor development 7 minutes
Zwischenbad 2 MinutenIntermediate bath 2 minutes
Wässerung 15 MinutenSoaking for 15 minutes
Bleichbad 5 MinutenBleach bath 5 minutes
Wässerung 5 MinutenSoaking for 5 minutes
Fixierbad 5 MinutenFixing bath 5 minutes
Wässerung 10 MinutenSoaking for 10 minutes
Zwiechenbad, Bleichbad und Fixierbad haben die üblichen Zusammen- " Setzungen.Intermediate bath, bleaching bath and fixing bath have the usual " Subsidence.
Die Farbdichten der einzelnen Schichten des Mehschichtenmaterials werden mit dem Densitometer "Macbeth Quanta Log, Modell TD 102" unter Einschaltung des jeweils notwendigen Farbfilters in den Strahlengang gemessen. 'The color densities of the individual layers of the multi-layer material are measured with the "Macbeth Quanta Log, Model TD 102" densitometer measured in the beam path by switching on the required color filter. '
A-G 362 - 15 - AG 362 - 15 -
&AD oniQ}NAL'- .i ■ ■■ , & AD oniQ} NAL ' - .i ■ ■■,
109812/1632 '109812/1632 '
Eine Zunahme um 3° bedeutet einen Empfindlichkeitsgewinn von einer Blende bzw. die doppelte Empfindlichkeit.An increase of 3 ° means a gain in sensitivity of one aperture or twice the sensitivity.
A-S 362 - 16 - AS 362 - 16 -
:'·Λ:ϊ. BAD: '· Λ: ϊ. BATH
1098 12/1632 .1098 12/1632.
Claims (10)
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19681772375 DE1772375A1 (en) | 1968-05-06 | 1968-05-06 | Silver bromide photographic emulsion with increased sensitivity |
| US818381A US3617280A (en) | 1968-05-06 | 1969-04-22 | Photopolymerization of ethylenically unsaturated organic compounds |
| CH623569A CH526794A (en) | 1968-05-06 | 1969-04-24 | Process for making photographic images |
| GB21930/69A GB1256393A (en) | 1968-05-06 | 1969-04-30 | Increasing the sensitivity of silver bromide emulsions |
| BE732547D BE732547A (en) | 1968-05-06 | 1969-05-06 | |
| FR6914464A FR2007937A1 (en) | 1968-05-06 | 1969-05-06 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19681772375 DE1772375A1 (en) | 1968-05-06 | 1968-05-06 | Silver bromide photographic emulsion with increased sensitivity |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1772375A1 true DE1772375A1 (en) | 1971-03-18 |
Family
ID=5701225
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19681772375 Pending DE1772375A1 (en) | 1968-05-06 | 1968-05-06 | Silver bromide photographic emulsion with increased sensitivity |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US3617280A (en) |
| BE (1) | BE732547A (en) |
| CH (1) | CH526794A (en) |
| DE (1) | DE1772375A1 (en) |
| FR (1) | FR2007937A1 (en) |
| GB (1) | GB1256393A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6047576B2 (en) | 1980-05-07 | 1985-10-22 | 富士写真フイルム株式会社 | Silver halide photographic material |
| US4419443A (en) * | 1980-11-11 | 1983-12-06 | Fuji Photo Film Co., Ltd. | Silver halide photographic light-sensitive material |
| JPS5969754A (en) | 1982-10-14 | 1984-04-20 | Fuji Photo Film Co Ltd | Color photosensitive silver halide material |
| JPS60143331A (en) | 1983-12-29 | 1985-07-29 | Fuji Photo Film Co Ltd | Silver halide photosensitive material |
| EP0209118B1 (en) | 1985-07-17 | 1991-10-23 | Konica Corporation | Silver halide photographic material |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3166539A (en) * | 1948-12-31 | 1965-01-19 | Degussa | Polymerization of acrylate mixtures of polymer/monomer using a catalyst system of a tertiary-amine and a quadrivalent sulfur compound |
| BE592259A (en) * | 1959-06-26 | |||
| BE610628A (en) * | 1960-11-14 | |||
| BE625542A (en) * | 1961-12-01 | |||
| GB1054125A (en) * | 1963-04-22 | |||
| GB1062884A (en) * | 1964-06-15 | 1967-03-22 | Agfa Gevaert Nv | Photochemical cross-linding of polymers |
-
1968
- 1968-05-06 DE DE19681772375 patent/DE1772375A1/en active Pending
-
1969
- 1969-04-22 US US818381A patent/US3617280A/en not_active Expired - Lifetime
- 1969-04-24 CH CH623569A patent/CH526794A/en not_active IP Right Cessation
- 1969-04-30 GB GB21930/69A patent/GB1256393A/en not_active Expired
- 1969-05-06 FR FR6914464A patent/FR2007937A1/fr not_active Withdrawn
- 1969-05-06 BE BE732547D patent/BE732547A/xx unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CH526794A (en) | 1972-08-15 |
| US3617280A (en) | 1971-11-02 |
| GB1256393A (en) | 1971-12-08 |
| FR2007937A1 (en) | 1970-01-16 |
| BE732547A (en) | 1969-11-06 |
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