EP0355568A2 - Preparation of a silver halide emulsion - Google Patents
Preparation of a silver halide emulsion Download PDFInfo
- Publication number
- EP0355568A2 EP0355568A2 EP89114620A EP89114620A EP0355568A2 EP 0355568 A2 EP0355568 A2 EP 0355568A2 EP 89114620 A EP89114620 A EP 89114620A EP 89114620 A EP89114620 A EP 89114620A EP 0355568 A2 EP0355568 A2 EP 0355568A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- gelatin
- silver halide
- compounds
- color
- 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.)
- Granted
Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 66
- -1 silver halide Chemical class 0.000 title claims abstract description 65
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 54
- 239000004332 silver Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 4
- 229920000159 gelatin Polymers 0.000 claims abstract description 83
- 235000019322 gelatine Nutrition 0.000 claims abstract description 83
- 238000001556 precipitation Methods 0.000 claims abstract description 20
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052737 gold Inorganic materials 0.000 claims abstract description 16
- 239000010931 gold Substances 0.000 claims abstract description 16
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000018417 cysteine Nutrition 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000005189 flocculation Methods 0.000 claims abstract description 4
- 230000016615 flocculation Effects 0.000 claims abstract description 4
- 108010010803 Gelatin Proteins 0.000 claims description 76
- 235000011852 gelatine desserts Nutrition 0.000 claims description 76
- 239000008273 gelatin Substances 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 10
- 239000001828 Gelatine Substances 0.000 abstract 7
- 239000010410 layer Substances 0.000 description 68
- 150000001875 compounds Chemical class 0.000 description 38
- 239000000975 dye Substances 0.000 description 31
- 238000011161 development Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 13
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 10
- 230000008878 coupling Effects 0.000 description 9
- 238000010168 coupling process Methods 0.000 description 9
- 238000005859 coupling reaction Methods 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 8
- 206010070834 Sensitisation Diseases 0.000 description 8
- 150000004820 halides Chemical class 0.000 description 8
- 239000003112 inhibitor Substances 0.000 description 8
- 230000008313 sensitization Effects 0.000 description 8
- 230000003595 spectral effect Effects 0.000 description 8
- 239000000123 paper Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000004061 bleaching Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000004848 polyfunctional curative Substances 0.000 description 6
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 5
- 238000005266 casting Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 4
- KIUMMUBSPKGMOY-UHFFFAOYSA-N 3,3'-Dithiobis(6-nitrobenzoic acid) Chemical compound C1=C([N+]([O-])=O)C(C(=O)O)=CC(SSC=2C=C(C(=CC=2)[N+]([O-])=O)C(O)=O)=C1 KIUMMUBSPKGMOY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 210000000988 bone and bone Anatomy 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 4
- 230000005070 ripening Effects 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000006850 spacer group Chemical group 0.000 description 4
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 3
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000001565 benzotriazoles Chemical class 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- ZEUDGVUWMXAXEF-UHFFFAOYSA-L bromo(chloro)silver Chemical compound Cl[Ag]Br ZEUDGVUWMXAXEF-UHFFFAOYSA-L 0.000 description 3
- 239000000872 buffer Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011241 protective layer Substances 0.000 description 3
- 238000009877 rendering Methods 0.000 description 3
- 150000003378 silver Chemical class 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000004964 sulfoalkyl group Chemical group 0.000 description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 3
- WNWHHMBRJJOGFJ-UHFFFAOYSA-N 16-methylheptadecan-1-ol Chemical compound CC(C)CCCCCCCCCCCCCCCO WNWHHMBRJJOGFJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- BZVZOFXXJNWFDY-UHFFFAOYSA-N CCCCCCCCCCCCCOOP(=O)(O)O Chemical compound CCCCCCCCCCCCCOOP(=O)(O)O BZVZOFXXJNWFDY-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-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
- 238000001016 Ostwald ripening Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- UYXTWWCETRIEDR-UHFFFAOYSA-N Tributyrin Chemical compound CCCC(=O)OCC(OC(=O)CCC)COC(=O)CCC UYXTWWCETRIEDR-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- JEHKKBHWRAXMCH-UHFFFAOYSA-N benzenesulfinic acid Chemical compound O[S@@](=O)C1=CC=CC=C1 JEHKKBHWRAXMCH-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 150000003014 phosphoric acid esters Chemical class 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- UGZVCHWAXABBHR-UHFFFAOYSA-O pyridin-1-ium-1-carboxamide Chemical class NC(=O)[N+]1=CC=CC=C1 UGZVCHWAXABBHR-UHFFFAOYSA-O 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- LUMLZKVIXLWTCI-NSCUHMNNSA-N (e)-2,3-dichloro-4-oxobut-2-enoic acid Chemical compound OC(=O)C(\Cl)=C(/Cl)C=O LUMLZKVIXLWTCI-NSCUHMNNSA-N 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- IAUKWGFWINVWKS-UHFFFAOYSA-N 1,2-di(propan-2-yl)naphthalene Chemical compound C1=CC=CC2=C(C(C)C)C(C(C)C)=CC=C21 IAUKWGFWINVWKS-UHFFFAOYSA-N 0.000 description 1
- IRFSXVIRXMYULF-UHFFFAOYSA-N 1,2-dihydroquinoline Chemical class C1=CC=C2C=CCNC2=C1 IRFSXVIRXMYULF-UHFFFAOYSA-N 0.000 description 1
- FTNJQNQLEGKTGD-UHFFFAOYSA-N 1,3-benzodioxole Chemical class C1=CC=C2OCOC2=C1 FTNJQNQLEGKTGD-UHFFFAOYSA-N 0.000 description 1
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical compound C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 1
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical class C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical class C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical compound O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 description 1
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 1
- FCTDKZOUZXYHNA-UHFFFAOYSA-N 1,4-dioxane-2,2-diol Chemical compound OC1(O)COCCO1 FCTDKZOUZXYHNA-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- MZFSRQQVIKFYON-UHFFFAOYSA-N 1-(3-acetyl-5-prop-2-enoyl-1,3,5-triazinan-1-yl)prop-2-en-1-one Chemical compound CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 MZFSRQQVIKFYON-UHFFFAOYSA-N 0.000 description 1
- YGDWUQFZMXWDKE-UHFFFAOYSA-N 1-oxido-1,3-thiazole Chemical class [O-]S1=CN=C=C1 YGDWUQFZMXWDKE-UHFFFAOYSA-N 0.000 description 1
- VQNVPKIIYQJWCF-UHFFFAOYSA-N 1-tetradecylpyrrolidin-2-one Chemical compound CCCCCCCCCCCCCCN1CCCC1=O VQNVPKIIYQJWCF-UHFFFAOYSA-N 0.000 description 1
- RWKSBJVOQGKDFZ-UHFFFAOYSA-N 16-methylheptadecyl 2-hydroxypropanoate Chemical compound CC(C)CCCCCCCCCCCCCCCOC(=O)C(C)O RWKSBJVOQGKDFZ-UHFFFAOYSA-N 0.000 description 1
- CARFETJZUQORNQ-UHFFFAOYSA-N 1h-pyrrole-2-thiol Chemical class SC1=CC=CN1 CARFETJZUQORNQ-UHFFFAOYSA-N 0.000 description 1
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical class SC1=NN=NN1 JAAIPIWKKXCNOC-UHFFFAOYSA-N 0.000 description 1
- PRAJOOPKIIUZRM-UHFFFAOYSA-N 2,2-dichloro-1,4-dioxane Chemical compound ClC1(Cl)COCCO1 PRAJOOPKIIUZRM-UHFFFAOYSA-N 0.000 description 1
- HGQDBHBWRAYRMJ-UHFFFAOYSA-N 2,2-diethyldodecanamide Chemical compound CCCCCCCCCCC(CC)(CC)C(N)=O HGQDBHBWRAYRMJ-UHFFFAOYSA-N 0.000 description 1
- WMVJWKURWRGJCI-UHFFFAOYSA-N 2,4-bis(2-methylbutan-2-yl)phenol Chemical compound CCC(C)(C)C1=CC=C(O)C(C(C)(C)CC)=C1 WMVJWKURWRGJCI-UHFFFAOYSA-N 0.000 description 1
- YKUDHBLDJYZZQS-UHFFFAOYSA-N 2,6-dichloro-1h-1,3,5-triazin-4-one Chemical compound OC1=NC(Cl)=NC(Cl)=N1 YKUDHBLDJYZZQS-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- VTIMKVIDORQQFA-UHFFFAOYSA-N 2-Ethylhexyl-4-hydroxybenzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=C(O)C=C1 VTIMKVIDORQQFA-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- BITBMHVXCILUEX-UHFFFAOYSA-N 2-chloroethylurea Chemical compound NC(=O)NCCCl BITBMHVXCILUEX-UHFFFAOYSA-N 0.000 description 1
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 1
- KRTDQDCPEZRVGC-UHFFFAOYSA-N 2-nitro-1h-benzimidazole Chemical compound C1=CC=C2NC([N+](=O)[O-])=NC2=C1 KRTDQDCPEZRVGC-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
- LJGHYPLBDBRCRZ-UHFFFAOYSA-N 3-(3-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC(S(=O)(=O)C=2C=C(N)C=CC=2)=C1 LJGHYPLBDBRCRZ-UHFFFAOYSA-N 0.000 description 1
- OWIRCRREDNEXTA-UHFFFAOYSA-N 3-nitro-1h-indazole Chemical compound C1=CC=C2C([N+](=O)[O-])=NNC2=C1 OWIRCRREDNEXTA-UHFFFAOYSA-N 0.000 description 1
- XRZDIHADHZSFBB-UHFFFAOYSA-N 3-oxo-n,3-diphenylpropanamide Chemical compound C=1C=CC=CC=1NC(=O)CC(=O)C1=CC=CC=C1 XRZDIHADHZSFBB-UHFFFAOYSA-N 0.000 description 1
- NYYSPVRERVXMLJ-UHFFFAOYSA-N 4,4-difluorocyclohexan-1-one Chemical compound FC1(F)CCC(=O)CC1 NYYSPVRERVXMLJ-UHFFFAOYSA-N 0.000 description 1
- XVEPKNMOJLPFCN-UHFFFAOYSA-N 4,4-dimethyl-3-oxo-n-phenylpentanamide Chemical compound CC(C)(C)C(=O)CC(=O)NC1=CC=CC=C1 XVEPKNMOJLPFCN-UHFFFAOYSA-N 0.000 description 1
- QNGVNLMMEQUVQK-UHFFFAOYSA-N 4-n,4-n-diethylbenzene-1,4-diamine Chemical compound CCN(CC)C1=CC=C(N)C=C1 QNGVNLMMEQUVQK-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 241000252095 Congridae Species 0.000 description 1
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 1
- PGIBJVOPLXHHGS-UHFFFAOYSA-N Di-n-decyl phthalate Chemical compound CCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCC PGIBJVOPLXHHGS-UHFFFAOYSA-N 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical class NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical class OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- HSHXDCVZWHOWCS-UHFFFAOYSA-N N'-hexadecylthiophene-2-carbohydrazide Chemical compound CCCCCCCCCCCCCCCCNNC(=O)c1cccs1 HSHXDCVZWHOWCS-UHFFFAOYSA-N 0.000 description 1
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- 239000006224 matting agent Substances 0.000 description 1
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- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
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- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
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- 150000003222 pyridines Chemical class 0.000 description 1
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical class SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
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- 239000012088 reference solution Substances 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical group O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
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- AQRYNYUOKMNDDV-UHFFFAOYSA-M silver behenate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O AQRYNYUOKMNDDV-UHFFFAOYSA-M 0.000 description 1
- MCKXPYWOIGMEIZ-UHFFFAOYSA-M silver;2h-benzotriazole-4-carboxylate Chemical compound [Ag+].[O-]C(=O)C1=CC=CC2=NNN=C12 MCKXPYWOIGMEIZ-UHFFFAOYSA-M 0.000 description 1
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- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
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- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- JJJPTTANZGDADF-UHFFFAOYSA-N thiadiazole-4-thiol Chemical class SC1=CSN=N1 JJJPTTANZGDADF-UHFFFAOYSA-N 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- IELLVVGAXDLVSW-UHFFFAOYSA-N tricyclohexyl phosphate Chemical compound C1CCCCC1OP(OC1CCCCC1)(=O)OC1CCCCC1 IELLVVGAXDLVSW-UHFFFAOYSA-N 0.000 description 1
- 150000003639 trimesic acids Chemical class 0.000 description 1
- APVVRLGIFCYZHJ-UHFFFAOYSA-N trioctyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound CCCCCCCCOC(=O)CC(O)(C(=O)OCCCCCCCC)CC(=O)OCCCCCCCC APVVRLGIFCYZHJ-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
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Images
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
- G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
-
- 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
- G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
- G03C1/047—Proteins, e.g. gelatine derivatives; Hydrolysis or extraction products of proteins
Definitions
- the invention relates to a process for the preparation of a light-sensitive silver halide emulsion by precipitation of the silver halide in the presence of gelatin, flocculation and washing of the silver halide precipitated in the presence of the gelatin and redispersion with the addition of further gelatin.
- the oxidation of gelatins for inertization i.e. to destroy photographically active substances, but also to remove bacterial contaminants or to brighten the color of the gelatin, is known, using as the oxidizing agent hydrogen peroxide, peracids such as performic acid, peracetic acid, periodic acid, chloramine T (N-chloro-p-toluenesulfonic acid amide sodium) and the like .ä. be used.
- the object of the invention was therefore to modify the production of a silver halide emulsion so that on the one hand improved grain growth is achieved and on the other hand an undesirably high haze is avoided.
- this object can be achieved in that in the process described at the outset the precipitation in the presence of a gelatin with a gold number of at most 10 ⁇ mol / g gelatin and a cysteine content of at most 6 ppm and the redispersion with a gelatin with a Gold number of at least 23 ⁇ mol / g gelatin is carried out.
- the redispersion gelatin can have cysteine contents of 6 to 16 ppm.
- Gelatins with a gold value of at least 23 ⁇ mol / g are obtained in the usual alkaline or acidic liming.
- Gelatins with a gold value of at most 10 ⁇ mol / g and a cysteine content of at most 6 ppm are obtained from the usual gelatins by oxidation with the oxidizing agents specified above.
- the gelatin-to-silver weight ratio (Ge-Si) of the finished emulsion is preferably 1: 1 to 1: 5, silver being used as silver nitrate in the mixture.
- the weight ratio of the amount of gelatin during the precipitation to the amount of gelatin that is added during the redispersion is in particular 1: 1 to 1:10, preferably 1: 1 to 1: 5.
- the oxidized gelatin can be acidic or alkaline.
- the raw material can be bone or skin. Bone as the raw material is preferred, however, because it is easier to make inert gelatins, i.e. Gelatins with low levels of photographically active contaminants, such as thiosulfate or sulfite, can be produced.
- the gelatin can be oxidized at any time during the production of the gelatin.
- the oxidation can also take place in the gelatin solution before the beginning of the emulsion precipitation.
- the pH during the oxidation can fluctuate within wide limits and is preferably between pH 2 and pH 8. Higher and lower pH values are possible, but the physical properties of the gelatin will then deteriorate.
- the oxidation of the gelatin can be checked by determining the gold value or the cysteine content and terminated according to the desired values.
- the gelatin is titrated potentiometrically with tetrachloroauric acid at pH 2.
- the Gold consumption gives the gold number.
- non-oxidized gelatins show gold numbers of ⁇ 23 ⁇ mol / g. This corresponds approximately to a methionine content of ⁇ 50 ⁇ mol / g.
- the cysteine content of the gelatin is determined by a method described by H. Meichelbeck, AGhack and Chr. Sentler in Z. Ges. Textilindustrie 70 , 242 (1968).
- TRIS tris (hydroxymethyl) aminomethane
- DTNB 5,5′-dithiobis (2-nitrobenzoic acid)
- the measurement is carried out at 412 nm.
- the same solution as the measurement solution, but without hydrolyzate, is used as the reference solution.
- the gelatin hydrolyzates have different colors, which absorb in this area, the hydrolyzate with all additives except DTNB must also be measured and subtracted from the absorbance of the measurement solution.
- the buffer is prepared as follows: 121 g of TRIS are dissolved in 500 ml of water and the pH is adjusted to 7.4 with HCl. The solution is then made up to 1000 ml.
- Reagent solution 10 ml of TRIS / HCl buffer are diluted to about 50 ml with water, containing 25 mg of reagent (DTNB) and 20 mg EDTA salt dissolved. The pH is adjusted to 4 with HCl. The solution is made up to 100 ml.
- the fluctuation range of the measurements must not be greater than ⁇ 1 ppm.
- the cysteine content results from the measured value using a previously defined calibration curve. As with H. Meichelbeck et al, loc. cit. specified, the cysteine content can also be obtained arithmetically from the measured value without a calibration curve.
- the gelatins can be desalinated or not. Inert gelatins are preferred which are characterized in that they contain only a few photographically active compounds. Non-desalted inert gelatins often have a high content of Ca ions.
- the silver halide present in the photographic emulsion as a light-sensitive component can contain chloride, bromide or iodide or mixtures thereof as the halide.
- the halide content at least one layer consists of 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% of bromide.
- silver bromide iodide emulsions are usually used; in the case of color negative and color reversal paper, silver chloride bromide emulsions are usually used.
- the crystals can be predominantly compact, which are, for example, regularly cubic or octahedral or can have transitional forms.
- platelet-shaped crystals can preferably also be present, the average ratio of diameter to thickness of which is preferably at least 5: 1, the diameter of a grain being defined as the diameter of a circle with a circle content corresponding to the projected area of the grain.
- the layers can also have tabular silver halide crystals in which the ratio of diameter to thickness is substantially greater than 5: 1, for example 12: 1 to 30: 1.
- the silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as doping of the individual grain areas, being different.
- the average grain size of the emulsions is preferably between 0.2 .mu.m and 5.0 .mu.m, particularly preferably 0.2 .mu.m and 2.0 .mu.m the grain size distribution can be both homo- and heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not exceed ⁇ 30% of deviate from the average grain size.
- the emulsions can also contain organic silver salts, for example silver benzotriazolate or silver behenate.
- Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
- the photographic emulsions can be prepared using various methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.
- various methods e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.
- the silver halide can be precipitated in the acidic, neutral or alkaline pH range, silver halide complexing agents preferably being additionally used.
- the latter include, for example, ammonia, thioether, imidazole, ammonium thiocyanate or excess halide.
- the water-soluble silver salts and the halides are combined either in succession by the single-jet process or simultaneously by the double-jet process or by any combination of the two processes. Dosing with increasing inflow rates is preferred, the "critical" feed rate at which just yet no new germs arise, should not be exceeded.
- the pAg range can vary within wide limits during the precipitation, preferably the so-called pAg-controlled method is used, in which a certain pAg value is kept constant or a defined pAg profile is traversed during the precipitation.
- so-called inverse precipitation with an excess of silver ions is also possible.
- the silver halide crystals can also grow through physical ripening (Ostwald ripening), in the presence of excess halide and / or silver halide complexing agent. The growth of the emulsion grains can even take place predominantly by Ostwald ripening, a fine-grained, so-called Lippmann emulsion preferably being mixed with a less soluble emulsion and being redissolved on the latter.
- Salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe can also be present during the precipitation and / or physical ripening of the silver halide grains.
- the precipitation can also be carried out in the presence of sensitizing dyes.
- Complexing agents and / or dyes can be rendered ineffective at any time, for example by changing the pH or by an oxidative treatment.
- the soluble salts are removed from the emulsion by flocculation and washing.
- the silver halide emulsion is generally subjected to chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until the optimum sensitivity and fog are reached.
- the procedure is e.g. described by H. Frieser "The basics of photographic processes with silver halides" page 675-734, Akademische Verlagsgesellschaft (1968).
- Chemical sensitization can be carried out with the addition of compounds of sulfur, selenium, tellurium and / or noble metal compounds (e.g. gold, platinum, palladium, iridium), thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic nitrogen compounds (e.g. imidazoles, azaindenes) or also spectral sensitizers (described, for example, by F. Hamer "The Cyanine Dyes and Related Compounds", 1964, or Ullmanns Encyclopedia of Industrial Chemistry, 4th edition, vol. 18, pp. 431 ff. and Research Disclosure No. 17643, section III) are added.
- noble metal compounds e.g. gold, platinum, palladium, iridium
- thiocyanate compounds e.g. gold, platinum, palladium, iridium
- surface-active compounds such as thioethers
- heterocyclic nitrogen compounds e.g. imidazoles, azaindenes
- a reduction sensitization with the addition of reducing agents can be carried out by hydrogen, by low pAg (eg less than 5) and / or high pH (eg above 8) .
- the photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.
- Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are for example from Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. Salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can also be used as antifoggants.
- metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can also be used as antifoggants.
- Heterocycles containing mercapto groups for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, are particularly suitable, these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
- mercaptobenzthiazoles for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines
- these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group.
- a water-solubilizing group for example a carboxyl group or sulfo group.
- the stabilizers can be added to the silver halide emulsions before, during or after their ripening.
- the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.
- the photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can contain surface-active agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics (eg acceleration of development, high contrast, sensitization etc.).
- surface-active agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics (eg acceleration of development, high contrast, sensitization etc.).
- surface-active compounds e.g. Saponin
- non-ionic surfactants e.g. Alkylene oxide compounds, glycerin compounds or glycidol compounds
- cationic surfactants e.g.
- alkyl amines quaternary ammonium salts, pyridine compounds and other heterocyclic compounds, sulfonium compounds or phosphonium compounds, anionic surfactants containing an acid group, e.g. Carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants, e.g. Amino acid and aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters of an amino alcohol.
- an acid group e.g. Carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group
- ampholytic surfactants e.g. Amino acid and aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters of an amino alcohol.
- the photographic emulsions can be spectrally sensitized using methine dyes or other dyes.
- Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.
- 9-ethyl carbocyanines with benzthiazole, benzselenazole or naphthothiazole as basic end groups which can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy, carbalkoxy, aryl, and 9-ethyl-naphthoxathia or -selencarbocyanines and 9- Ethyl-naphthothiaoxa- or -benzimidazocarbocyanine, provided that the dyes carry at least one sulfoalkyl group on the heterocyclic nitrogen.
- the emulsions can contain additional binders, such as synthetic or natural, layer-forming polymers.
- the emulsions according to the invention are suitable for all types of photographic materials, such as X-ray films, black and white film, black and white paper, but in particular for color photographic materials.
- color photographic materials are color negative films, color reversal films, color positive films, color photographic paper, color reversal photographic paper, color sensitive materials for the color diffusion transfer process or the silver color bleaching process.
- Suitable supports for the production of color photographic materials are, for example, films and foils of semisynthetic and synthetic polymers, such as cellulose nitrate, Cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate and paper laminated with a baryta layer or ⁇ -olefin polymer layer (eg polyethylene).
- These supports can be colored with dyes and pigments, for example titanium dioxide. They can also be colored black for the purpose of shielding light.
- the surface of the support is generally subjected to a treatment in order to improve the adhesion of the photographic emulsion layer, for example a corona discharge with subsequent application of a substrate layer.
- the color photographic materials usually contain at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer and, if appropriate, intermediate layers and protective layers.
- the color couplers are essential components of the photographic emulsion layers.
- the differently sensitized emulsion layers are assigned non-diffusing monomeric or polymeric color couplers, which can be located in the same layer or in a layer adjacent to it.
- cyan couplers are assigned to the red-sensitive layers, purple couplers to the green-sensitive layers and yellow couplers to the blue-sensitive layers.
- Color couplers for producing the blue-green partial color image are usually couplers of the phenol or ⁇ -naphthol type.
- Color couplers for generating the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrauoloazole type.
- Color couplers for producing the yellow partial color image are generally couplers with an open-chain ketomethylene group, in particular couplers of the ⁇ -acylacetamide type; Suitable examples are ⁇ -benzoylacetanilide couplers and ⁇ -pivaloylacetanilide couplers.
- the color couplers can be 4-equivalent couplers, but also 2-equivalent couplers.
- the latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site which is split off during the coupling.
- the 2-equivalent couplers include those that are colorless, as well as those that have an intense intrinsic color that disappears when the color is coupled or is replaced by the color of the image dye produced (mask coupler), and the white couplers that react with color developer oxidation products yield essentially colorless products.
- the 2-equivalent couplers also include those couplers which contain a detachable residue in the coupling point, which in reaction with color developer oxidation products Freedom is set, either directly or after one or more further groups have been split off from the primarily split off remainder (e.g. DE-A-27 03-145, DE-A-28 55 697, DE-A-31 05 026, DE -A-33 19 428), develops a certain desired photographic effectiveness, for example as a development inhibitor or accelerator.
- Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or. FAR coupler.
- DIR couplers which release development inhibitors of the azole type, for example triazoles and benzotriazoles, are described in DE-A-24 14 006, 26 10 546, 26 59 417, 27 54 281, 27 26 180, 36 26 219, 36 30 564, 36 36 824, 36 44 416 and 28 42 063. Further advantages for color reproduction, that is, color separation and color purity, and for detail reproduction, that is, sharpness and granularity, can be achieved with those DIR couplers which, for example, do not split off the development inhibitor directly as a result of coupling with an oxidized color developer, but only after a further follow-up reaction, which is achieved, for example, with a timing group.
- DIR couplers which release a development inhibitor which is decomposed into essentially photographically ineffective products in the developer bath are described, for example, in DE-A-32 09 486 and in EP-A-167 168 and 219 713. This measure ensures trouble-free development and processing consistency.
- the DIR couplers can be added to a wide variety of layers in a multilayer photographic material, for example also light-insensitive or intermediate layers. However, they are preferably added to the light-sensitive silver halide emulsion layers, the characteristic properties of the silver halide emulsion, for example its iodide content, the structure of the silver halide grains or their grain size distribution having an influence on the photographic properties achieved.
- the influence of the inhibitors released can be limited, for example, by incorporating an inhibitor scavenger layer in accordance with DE-A-24 31 223. For reasons of reactivity or stability, it may be advantageous to insert a DIR coupler set, which forms in the respective layer in which it is introduced, a color different from the color to be generated in this layer in the coupling.
- DAR or FAR couplers can be used, which release a development accelerator or an fogger.
- Compounds of this type are, for example, in DE-A-25 34 466, 32 09 110, 33 33 355, 34 10 616, 34 29 545, 34 41 823, in EP-A-89 834, 110 511, 118 087, 147 765 and described in US-A-4,618,572 and 4,656,123.
- DIR, DAR or FAR couplers Since with DIR, DAR or FAR couplers the effectiveness of the residue released during coupling is mainly desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also suitable, which give essentially colorless products on coupling (DE-A-15 47 640).
- the cleavable residue can also be a ballast residue, so that upon reaction with color developer oxidation products coupling products are obtained which are diffusible or at least have a weak or restricted mobility (US Pat. No. 4,420,556).
- the material may further contain compounds other than couplers, which can, for example, release a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a fogging agent or an antifoggant, for example so-called DIR-hydroquinones and other compounds, as described for example in US-A-4 636 546, 4 345 024, 4 684 604 and in DE-A-31 45 640, 25 15 213, 24 47 079 and in EP-A-198 438. These compounds perform the same function as the DIR, DAR or FAR couplers, except that they do not form coupling products.
- couplers can, for example, release a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a fogging agent or an antifoggant, for example so-called DIR-hydroquinones and other compounds, as described for example in US-A-4 636 546, 4 345 024, 4 684 604 and in DE
- High molecular weight color couplers are described, for example, in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211.
- the high molecular weight color couplers are usually produced by polymerizing ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation.
- the couplers or other compounds can be incorporated into silver halide emulsion layers by first preparing a solution, a dispersion or an emulsion from the compound in question and then adding it to the casting solution for the layer in question.
- the selection of the suitable solvent or dispersing agent depends on the solubility of the compound.
- Hydrophobic compounds can also be introduced into the casting solution using high-boiling solvents, so-called oil formers. Corresponding methods are described for example in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 and EP-A-O 043 037.
- oligomers or polymers instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers, can be used.
- the compounds can also be introduced into the casting solution in the form of loaded latices.
- anionic water-soluble compounds e.g. dyes
- pickling polymers e.g. acrylic acid
- Suitable oil formers are e.g. Alkyl phthalates, phosphonic acid esters, phosphoric acid esters, citric acid esters, benzoic acid esters, amides, fatty acid esters, trimesic acid esters, alcohols, phenols, aniline derivatives and hydrocarbons.
- oil formers examples include dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecoxy phosphate, 2-ethylhexyl phosphate, tridecoxy phosphate, 2-ethylhexyl phylate, , 2-ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-tert-amylphenol, dioctyl acylate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N,
- Each of the differently sensitized, light-sensitive layers can consist of a single layer or can also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470).
- Red-sensitive silver halide emulsion layers are Layer supports are often arranged closer than green-sensitive silver halide emulsion layers and these in turn are closer than blue-sensitive layers, a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.
- the green or Red-sensitive layers can be chosen without the yellow filter layer, other layer arrangements in which e.g. the blue-sensitive, then the red-sensitive and finally the green-sensitive layers follow.
- the non-light-sensitive intermediate layers which are generally arranged between layers of different spectral sensitivity, can contain agents which prevent undesired diffusion of developer oxidation products from one light-sensitive layer into another light-sensitive layer with different spectral sensitization.
- Suitable agents which are also called scavengers or EOP-catchers, are described in Research Disclosure 17 643 (Dec. 1978), Chapter VII, 17 842/1979, pages 94-97 and 18.716 / 1979, page 650 and in EP-A- 69,070, 98,072, 124,877, 125,522 and in US-A-463,226.
- sub-layers of the same spectral sensitization can differ with regard to their composition, in particular with regard to the type and amount of the silver halide grains.
- the sublayer with higher sensitivity will be located further from the support than the sublayer with lower sensitivity.
- Partial layers of the same spectral sensitization can be adjacent to one another or through other layers, e.g. separated by layers of other spectral sensitization.
- all highly sensitive and all low-sensitive layers can be combined to form a layer package (DE-A-19 58 709, DE-A-25 30 645, DE-A-26 22 922).
- the photographic material can also contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D min dyes, additives to improve dye, coupler and white stabilization and to reduce the color fog, plasticizers (latices), Contain biocides and others.
- Examples are aryl-substituted benzotriazole compounds (US-A-3 533 794), 4-thiazolidone compounds (US-A-3 314 794 and 3 352 681), benzophenone compounds (JP-A-2784/71), cinnamic acid ester compounds (US-A-3 705 805 and 3,707,375), butadiene compounds (US-A-4,045,229) or benzoxazole compounds (US-A-3,700,455).
- Ultraviolet absorbing couplers such as ⁇ -naphthol type cyan couplers
- ultraviolet absorbing polymers can also be used. These ultraviolet absorbents can be fixed in a special layer by pickling.
- Filter dyes suitable for visible light include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are used particularly advantageously.
- Suitable white toners are e.g. in Research Disclosure 17,643 (Dec. 1978), Chapter V, in US-A-2,632,701, 3,269,840 and in GB-A-852,075 and 1,319,763.
- Certain layers of binder in particular the layer furthest from the support, but also occasionally intermediate layers, especially if they represent the most distant layer from the support during production, can contain photographically inert particles of inorganic or organic nature, for example as matting agents or as spacers (DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, Dec. 1978, Chapter XVI).
- the average particle diameter of the spacers is in particular in the range from 0.2 to 10 ⁇ m.
- the spacers are water-insoluble and can be alkali-insoluble or alkali-soluble, the alkali-soluble ones generally being removed from the photographic material in the alkaline development bath.
- suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.
- Additives to improve dye, coupler and whiteness stability and to reduce the color haze can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromans, spiroindanes, p- Alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, sterically hindered amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.
- Compounds that have both a hindered amine partial structure and a hindered one Phenol partial structure in a molecule are particularly effective for preventing the deterioration (deterioration or degradation) of yellow color images as a result of the development of heat, moisture and light.
- Spiroindane JP-A-159 644/81
- chromanes are caused by Hydroquinone diethers or monoethers are particularly effective (JP-A-89 835/80).
- the layers of the photographic material can be hardened with the usual hardening agents.
- Suitable curing agents are, for example, formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethyl urea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and other compounds, the reactive halogen included (US-A-3 288 775, US-A-2 732 303, GB-A-974 723 and GB-A-1 167 207) divinyl sulfone compounds, 5-acetyl-1,3-diacryloylhexahydro-1,3,5 triazine and other compounds containing a reactive olefin bond (US-A-3 635 718, US-A-3 232 763 and GB-A-994 869); N-hydroxymethylphthalimide and other N-methylol compounds (US-A-2 7
- the hardening can be effected in a known manner by adding the hardening agent to the casting solution for the layer to be hardened or by overlaying the layer to be hardened with a layer which contains a diffusible hardening agent.
- Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that hardening is completed to the extent that no further crosslinking takes place immediately after casting, at the latest after 24 hours, preferably at the latest after 8 hours reaction-related change in the sensitometry and the swelling of the layer structure occurs.
- Swelling is understood to mean the difference between the wet film thickness and the dry film thickness during the aqueous processing of the film (Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).
- hardening agents that react very quickly with gelatin are e.g. to carbamoylpyridinium salts, which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin to form peptide bonds and crosslink the gelatin.
- Color photographic negative materials are usually processed by developing, bleaching, fixing and washing or by developing, bleaching, fixing and stabilizing without subsequent washing, with bleaching and fixing can be combined into one processing step.
- All developer compounds which have the ability to react in the form of their oxidation product with color couplers to form azomethine or indophenol dyes can be used as the color developer compound.
- Suitable color developer compounds are aromatic compounds of the p-phenylenediamine type containing at least one primary amino group, for example N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methanesulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl) -3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.
- Further useful color developers are described, for example, in J. Amer. Chem. Soc. 73 , 3106 (1951) and G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, page 545 ff.
- Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used as bleaching agents.
- Iron (III) complexes of aminopolycarboxylic acids in particular, for example, ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethyl are particularly preferred ethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids.
- Persulphates and peroxides for example hydrogen peroxide, are also suitable as bleaching agents.
- the bleach-fixing bath or fixing bath is usually followed by washing, which is designed as countercurrent washing or consists of several tanks with their own water supply.
- the washing can be completely replaced by a stabilizing bath, which is usually carried out in countercurrent.
- this stabilizing bath also functions as a final bath.
- development is initially carried out using a black and white developer whose oxidation product is not capable of reacting with the color couplers. This is followed by a diffuse second exposure and then development with a color developer, bleaching and fixing.
- a silver bromide chloride emulsion with 10 mol% silver chloride was prepared by the double-jet method at 56 ° C.
- the GeSi was 0.15.
- the emulsion was flocculated by adding a flocculant and lowering the pH to 3.5 and then washing. The pH was then adjusted to 4.5 again, further gelatin 1 was added, and the emulsion was redispersed with heating. After redispersion, the GeSi was 0.65.
- the emulsion was then matured with the addition of thiosulfate for optimal sensitivity (emulsion A).
- emulsion B Another emulsion with gelatin 2 was prepared by precipitation and redispersion using the same process (emulsion B).
- the emulsions were provided per 100 g AgNO3 180 mg of a blue sensitizer and 120 g of a yellow coupler and poured onto a PE-coated paper base. One was placed over the emulsion layer Gelatin layer pulled with a hardener. After drying, the layers were exposed in a sensitometer and developed using the EP 2 process.
- the latent image was determined 6 hours after the exposure, the exposed strip being stored at room temperature.
- E latent image [log it]. emulsion Grain evaluation Sensitometry V distribution E S Gamma 1 ⁇ E latent image log it A 0.96 strong new germ formation 100 0.112 1.65 -0.02 B 0.91 very monodisperse 90 0.195 1.60 -0.06 C. 1.01 very monodisperse 120 0.115 1.68 -0.03 V: Center of volume in ⁇ m of all measured silver halide grains E: relative sensitivity S: veil Gamma 1: increase in the characteristic curve between points 0.1 over veil and 0.85 over veil.
- oxidized gelatin in the batch has an improved grain distribution, i.e. very monodisperse emulsions.
- oxidized gelatin in the post-ripening, however, there is a higher haze.
- the decline in the latent picture is noticeably stronger. If, on the other hand, the non-oxidized gelatin is used in the post-ripening, a better haze and a more stable latent image with an unchanged good grain distribution are obtained.
- Example 1 was repeated with gelatin 3 instead of gelatin 1 and gelatin 4 instead of gelatin 2.
- the silver chloride bromide emulsion contained 95 mol% of silver chloride, the ripening for optimum sensitivity was carried out with the addition of gold salts and thiosulfate. All other parameters remained unchanged.
- Emulsions D (only gelatin 3), E (only gelatin 4) and F (gelatin 4 during precipitation, gelatin 3 during redispersion) resulted.
- the emulsions were provided with a blue sensitizer and a yellow coupler and then poured onto a PE-coated paper backing. A layer of gelatin with a hardening agent is applied over the emulsion.
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Abstract
Description
Die Erfindung betrifft ein Verfahren zur Herstellung einer lichtempfindlichen Silberhalogenidemulsion durch Fällung des Silberhalogenids in Gegenwart von Gelatine, Ausflocken und Waschen des in Gegenwart der Gelatine gefällten Silberhalogenids und Redispergieren unter Zusatz weiterer Gelatine.The invention relates to a process for the preparation of a light-sensitive silver halide emulsion by precipitation of the silver halide in the presence of gelatin, flocculation and washing of the silver halide precipitated in the presence of the gelatin and redispersion with the addition of further gelatin.
Die Oxidation von Gelatinen zur Inertisierung, d.h. zur Zerstörung photographisch aktiver Substanzen, aber auch zur Entfernung bakterieller Verunreinigungen oder zur Aufhellung der Farbe der Gelatine, ist bekannt, wobei als Oxidationsmittel Wasserstoffperoxid, Persäuren wie Perameisensäure, Peressigsäure, Periodsäure, Chloramin T (N-Chlor-p-toluolsulfonsäureamid-Natrium) u.ä. verwendet werden.The oxidation of gelatins for inertization, i.e. to destroy photographically active substances, but also to remove bacterial contaminants or to brighten the color of the gelatin, is known, using as the oxidizing agent hydrogen peroxide, peracids such as performic acid, peracetic acid, periodic acid, chloramine T (N-chloro-p-toluenesulfonic acid amide sodium) and the like .ä. be used.
Aus EP-A-0 227 444 und EP-A-0 228 256 ist bekannt, daß die Verwendung oxidierter Gelatine für die Herstellung tafelförmiger Silberhalogenidemulsionen, insbesondere bei großem Chloridanteil der Emulsion vorteilhaft ist. Nachteilig ist aber, daß solche Gelatinen zu einem intolerablen Anstieg des Schleiers führen.From EP-A-0 227 444 and EP-A-0 228 256 it is known that the use of oxidized gelatin for the production of tabular silver halide emulsions, in particular if the emulsion contains a large proportion of chloride. However, it is disadvantageous that such gelatins lead to an intolerable increase in the haze.
Aufgabe der Erfindung war es daher, die Herstellung einer Silberhalogenidemulsion so zu modifizieren, daß einerseits ein verbessertes Kornwachstum erzielt, andererseits ein unerwünscht hoher Schleier vermieden wird.The object of the invention was therefore to modify the production of a silver halide emulsion so that on the one hand improved grain growth is achieved and on the other hand an undesirably high haze is avoided.
Es wurde nun gefunden, daß sich diese Aufgabe dadurch lösen läßt, daß bei dem eingangs beschriebenen Verfahren die Fällung in Gegenwart einer Gelatin mit einer Goldzahl von höchstens 10 µMol/g Gelatine und einem Cysteingehalt von höchstens 6 ppm und die Redispergierung mit einer Gelatine mit einer Goldzahl von mindestens 23 µMol/g Gelatine durchgeführt wird. Die Gelatine zur Redispergierung kann Cysteingehalte von 6 bis 16 ppm haben.It has now been found that this object can be achieved in that in the process described at the outset the precipitation in the presence of a gelatin with a gold number of at most 10 μmol / g gelatin and a cysteine content of at most 6 ppm and the redispersion with a gelatin with a Gold number of at least 23 µmol / g gelatin is carried out. The redispersion gelatin can have cysteine contents of 6 to 16 ppm.
Gelatinen mit einem Goldwert von mindestens 23 µMol/g werden beider üblichen alkalischen oder sauren Äscherung erhalten. Gelatinen mit einem Goldwert von höchstens 10 µMol/g und einem Cysteingehalt von höchstens 6 ppm erhält man aus den üblichen Gelatinen durch Oxidation mit den vorstehend angegebenen Oxidationsmitteln.Gelatins with a gold value of at least 23 µmol / g are obtained in the usual alkaline or acidic liming. Gelatins with a gold value of at most 10 µmol / g and a cysteine content of at most 6 ppm are obtained from the usual gelatins by oxidation with the oxidizing agents specified above.
Vorzugsweise beträgt das Gelatine-zu-Silber-Gewichtsverhältnis (Ge-Si) der fertigen Emulsion 1:1 bis 1:5, wobei Silber als Silbernitrat in die Recnung eingesetzt wird.The gelatin-to-silver weight ratio (Ge-Si) of the finished emulsion is preferably 1: 1 to 1: 5, silver being used as silver nitrate in the mixture.
Das Gewichtsverhältnis der Gelatinemenge bei der Fällung zur Gelatinemenge, die bei der Redispergierung zugesetzt wird, beträgt insbesondere 1:1 bis 1:10, vorzugsweise 1:1 bis 1:5.The weight ratio of the amount of gelatin during the precipitation to the amount of gelatin that is added during the redispersion is in particular 1: 1 to 1:10, preferably 1: 1 to 1: 5.
Die oxidierte Gelatine kann sauer oder alkalisch aufgeschlossen sein. Das Rohmaterial kann Knochen oder Haut sein. Knochen als Rohmaterial wird jedoch bevorzugt, da hieraus leichter Inertgelatinen, d.h. Gelatinen mit geringen Anteilen an fotografisch aktiven Verunreinigungen, wie Thiosulfat oder Sulfit, hergestellt werden können.The oxidized gelatin can be acidic or alkaline. The raw material can be bone or skin. Bone as the raw material is preferred, however, because it is easier to make inert gelatins, i.e. Gelatins with low levels of photographically active contaminants, such as thiosulfate or sulfite, can be produced.
Die Oxidation der Gelatine kann zu jedem beliebigen Zeitpunkt der Herstellung der Gelatine erfolgen. Die Oxidation kann auch in der Gelatinelösung vor Beginn der Emulsionsfällung erfolgen.The gelatin can be oxidized at any time during the production of the gelatin. The oxidation can also take place in the gelatin solution before the beginning of the emulsion precipitation.
Der pH-Wert während der Oxidation kann in weiten Grenzen schwanken und liegt vorzugsweise zwischen pH 2 und pH 8. Höhere und niedrigere pH-Werte sind möglich, jedoch werden dann die physikalischen Eigenschaften der Gelatine verschlechtert.The pH during the oxidation can fluctuate within wide limits and is preferably between pH 2 and pH 8. Higher and lower pH values are possible, but the physical properties of the gelatin will then deteriorate.
Die Oxidation der Gelatine kann durch Bestimmung des Goldwertes oder des Cysteingehaltes kontrolliert und entsprechend den gewünschten Werten beendet werden.The oxidation of the gelatin can be checked by determining the gold value or the cysteine content and terminated according to the desired values.
Zur Bestimmung der Goldzahl wird die Gelatine mit Tetrachlorogoldsäure bei pH 2 potentiometrisch titriert. Der Goldverbrauch ergibt die Goldzahl. Nicht oxidierte Gelatinen zeigen nach dieser Methode Goldzahlen von ≧23 µMol/g. Dies entspricht etwa einem Methioningehalt von ≧50 µMol/g.To determine the gold number, the gelatin is titrated potentiometrically with tetrachloroauric acid at pH 2. The Gold consumption gives the gold number. According to this method, non-oxidized gelatins show gold numbers of ≧ 23 µmol / g. This corresponds approximately to a methionine content of ≧ 50 µmol / g.
Die Bestimmung des Cysteingehaltes der Gelatine erfolgt nach einem von H. Meichelbeck, A.G. Hack und Chr. Sentler in Z. Ges. Textilindustrie 70, 242 (1968) beschriebenen Verfahren. Hierbei wird 1 g Gelatine unter Zugabe von 1 ml Wasser und 1 ml 30 gew.-%iger H₂SO₄ 60 Minuten im siedenden Wasserbad hydrolysiert und nach dem Abkühlen mit 3 m Tris(hydroxymethyl)-aminomethan (TRIS) und einem TRIS/HCl-Puffer auf pH 7,4 eingestellt.The cysteine content of the gelatin is determined by a method described by H. Meichelbeck, AG Hack and Chr. Sentler in Z. Ges. Textilindustrie 70 , 242 (1968). Here, 1 g of gelatin with the addition of 1 ml of water and 1 ml of 30 wt .-% H₂SO₄ hydrolyzed for 60 minutes in a boiling water bath and after cooling with 3 m of tris (hydroxymethyl) aminomethane (TRIS) and a TRIS / HCl buffer adjusted to pH 7.4.
Als Farbreagens dient 5,5′-Dithiobis-(2-nitrobenzoesäure) (DTNB). Ausgemessen wird bei 412 nm. Als Vergleichslösung wird die gleiche Lösung wie die Meßlösung, aber ohne Hydrolysat verwendet. Da jedoch die Gelatinehydrolysate unterschiedliche Färbungen aufweisen, die in diesem Bereich absorbieren, muß das Hydrolysat mit allen Zusätzen außer DTNB ebenfalls gemessen und von der Extinktion der Meßlösung abgezogen werden.5,5′-dithiobis (2-nitrobenzoic acid) (DTNB) is used as the color reagent. The measurement is carried out at 412 nm. The same solution as the measurement solution, but without hydrolyzate, is used as the reference solution. However, since the gelatin hydrolyzates have different colors, which absorb in this area, the hydrolyzate with all additives except DTNB must also be measured and subtracted from the absorbance of the measurement solution.
Der Puffer wird wie folgt hergestellt: 121 g TRIS werden in 500 ml Wasser gelöst und der pH-Wert mit HCl auf 7,4 eingestellt. Die Lösung wird dann auf 1000 ml aufgefüllt.The buffer is prepared as follows: 121 g of TRIS are dissolved in 500 ml of water and the pH is adjusted to 7.4 with HCl. The solution is then made up to 1000 ml.
Reagenslösung: 10 ml TRIS/HCl-Puffer werden mit Wasser auf etwa 50 ml verdünnt, darin werden 25 mg Reagens (DTNB) und 20 mg EDTA-Salz gelöst. Der pH-Wert wird mit HCl auf 4 eingestellt. Die Lösung wird auf 100 ml aufgefüllt.Reagent solution: 10 ml of TRIS / HCl buffer are diluted to about 50 ml with water, containing 25 mg of reagent (DTNB) and 20 mg EDTA salt dissolved. The pH is adjusted to 4 with HCl. The solution is made up to 100 ml.
Zur Einstellung des pH-Wertes des Gelatinehydrolysates wird außerdem 3 m TRIS benötigt.3 m TRIS is also required to adjust the pH of the gelatin hydrolyzate.
Um exakte Werte zu erhalten, ist eine Doppelbestimmung unerläßlich. Die Schwankungsbreite der Messungen darf nicht größer als ±1 ppm sein.In order to obtain exact values, a double determination is essential. The fluctuation range of the measurements must not be greater than ± 1 ppm.
Aus dem Meßwert ergibt sich der Cysteingehalt mittels einer zuvor festgelegten Eichkurve. Wie bei H. Meichelbeck et al, loc. cit. angegeben, kann auch ohne Eichkurve aus dem Meßwert der Cysteingehalt rechnerisch erhalten werden.The cysteine content results from the measured value using a previously defined calibration curve. As with H. Meichelbeck et al, loc. cit. specified, the cysteine content can also be obtained arithmetically from the measured value without a calibration curve.
Sowohl Goldzahlbestimmung als auch Cysteinanalyse sind ausgezeichnet reproduzierbar.Both the gold number determination and cysteine analysis are extremely reproducible.
Die Gelatinen können entsalzt oder nicht entsalzt sein. Bevorzugt werden Inertgelatinen, die dadurch gekennzeichnet sind, daß diese nur wenig photographisch aktive Verbindungen enthalten. Nicht entsalzte Inert-Gelatinen weisen oftmals einen hohen Gehalt an Ca-Ionen auf.The gelatins can be desalinated or not. Inert gelatins are preferred which are characterized in that they contain only a few photographically active compounds. Non-desalted inert gelatins often have a high content of Ca ions.
Das als lichtempfindlicher Bestandteil in der fotografischen Emulsion befindliche Silberhalogenid kann als Halogenid Chlorid, Bromid oder Iodid bzw. Mischungen davon enthalten. Beispielsweise kann der Halogenidanteil wenigstens einer Schicht zu 0 bis 15 Mol-% aus Iodid, zu 0 bis 100 Mol-% aus Chlorid und zu 0 bis 100 Mol-% aus Bromid bestehen. Im Falle von Farbnegativ- und Farbumkehrfilmen werden üblicherweise Silberbromidiodidemulsionen, im Falle von Farbnegativ- und Farbumkehrpapier üblicherweise Silberchloridbromidemulsionen verwendet. Es kann sich um überwiegend kompakte Kristalle handeln, die z.B. regulär kubisch oder oktaedrisch sind oder Übergangsformen aufweisen können. Vorzugsweise können aber auch plättchenförmige Kristalle vorliegen, deren durchschnittliches Verhältnis von Durchmesser zu Dicke bevorzugt wenigstens 5:1 ist, wobei der Durchmesser eines Kornes definiert ist als der Durchmesser eines Kreises mit einem Kreisinhalt entsprechend der projizierten Fläche des Kornes. Die Schichten können aber auch tafelförmige Silberhalogenidkristalle aufweisen, bei denen das Verhältnis von Durchmesser zu Dicke wesentlich größer als 5:1 ist, z.B. 12:1 bis 30:1.The silver halide present in the photographic emulsion as a light-sensitive component can contain chloride, bromide or iodide or mixtures thereof as the halide. For example, the halide content at least one layer consists of 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% of bromide. In the case of color negative and color reversal films, silver bromide iodide emulsions are usually used; in the case of color negative and color reversal paper, silver chloride bromide emulsions are usually used. The crystals can be predominantly compact, which are, for example, regularly cubic or octahedral or can have transitional forms. However, platelet-shaped crystals can preferably also be present, the average ratio of diameter to thickness of which is preferably at least 5: 1, the diameter of a grain being defined as the diameter of a circle with a circle content corresponding to the projected area of the grain. However, the layers can also have tabular silver halide crystals in which the ratio of diameter to thickness is substantially greater than 5: 1, for example 12: 1 to 30: 1.
Die Silberhalogenidkörner können auch einen mehrfach geschichteten Kornaufbau aufweisen, im einfachsten Fall mit einem inneren und einem äußeren Kornbereich (core/shell), wobei die Halogenidzusammensetzung und/oder sonstige Modifizierungen, wie z.B. Dotierungen der einzelnen Kornbereiche unterschiedlich sind. Die mittlere Korngröße der Emulsionen liegt vorzugsweise zwischen 0,2 µm und 5,0 µm, besonders bevorzugt 0,2 µm und 2,0 µm die Korngrößenverteilung kann sowohl homo- als auch heterodispers sein. Homodisperse Korngrößenverteilung bedeutet, daß 95 % der Körner nicht mehr als ± 30 % von der mittleren Korngröße abweichen. Die Emulsionen können neben dem Silberhalogenid auch organische Silbersalze enthalten, z.B. Silberbenztriazolat oder Silberbehenat.The silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as doping of the individual grain areas, being different. The average grain size of the emulsions is preferably between 0.2 .mu.m and 5.0 .mu.m, particularly preferably 0.2 .mu.m and 2.0 .mu.m the grain size distribution can be both homo- and heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not exceed ± 30% of deviate from the average grain size. In addition to the silver halide, the emulsions can also contain organic silver salts, for example silver benzotriazolate or silver behenate.
Es können zwei oder mehrere Arten von Silberhalogenidemulsionen, die getrennt hergestellt werden, als Mischung verwendet werden.Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
Die fotografischen Emulsionen können nach verschiedenen Methoden (z.B. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), G.F. Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), V.L. Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) aus löslichen Silbersalzen und löslichen Halogeniden hergestellt werden.The photographic emulsions can be prepared using various methods (e.g. P. Glafkides, Chimie et Physique Photographique, Paul Montel, Paris (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press, London (1966), VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press, London (1966) from soluble silver salts and soluble halides.
Die Fällung des Silberhalogenids kann im sauren, neutralen oder alkalischen pH-Bereich durchgeführt werden, wobei vorzugsweise Silberhalogenidkomplexbildner zusätzlich verwendet werden. Zu letzteren gehören z.B. Ammoniak, Thioether, Imidazol, Ammoniumthiocyanat oder überschüssiges Halogenid. Die Zusammenführung der wasserlöslichen Silbersalze und der Halogenide erfolgt wahlweise nacheinander nach dem single-jet- oder gleichzeitig nach dem double-jet-Verfahren oder nach beliebiger Kombination beider Verfahren. Bevorzugt wird die Dosierung mit steigenden Zuflußraten, wobei die "kritische" Zufuhrgeschwindigkeit, bei der gerade noch keine Neukeime entstehen, nicht überschritten werden sollte. Der pAg-Bereich kann während der Fällung in weiten Grenzen variieren, vorzugsweise wird das sogenannte pAg-gesteuerte Verfahren benutzt, bei dem ein bestimmter pAg-Wert konstant gehalten oder ein definiertes pAg-Profil während der Fällung durchfahren wird. Neben der bevorzugten Fällung bei Halogenidüberschuß ist aber auch die sogenannte inverse Fällung bei Silberionenüberschluß möglich. Außer durch Fällung können die Silberhalogenidkristalle auch durch physikalische Reifung (Ostwaldreifung), in Gegenwart von überschüssigem Halogenid und/oder Silberhalogenidkomplexierungsmittel wachsen. Das Wachstum der Emulsionskörner kann sogar überwiegend durch Ostwaldreifung erfolgen, wobei vorzugsweise eine feinkörnige, sogenannte Lippmann-Emulsion, mit einer schwerer löslichen Emulsion gemischt und auf letzterer umgelöst wird.The silver halide can be precipitated in the acidic, neutral or alkaline pH range, silver halide complexing agents preferably being additionally used. The latter include, for example, ammonia, thioether, imidazole, ammonium thiocyanate or excess halide. The water-soluble silver salts and the halides are combined either in succession by the single-jet process or simultaneously by the double-jet process or by any combination of the two processes. Dosing with increasing inflow rates is preferred, the "critical" feed rate at which just yet no new germs arise, should not be exceeded. The pAg range can vary within wide limits during the precipitation, preferably the so-called pAg-controlled method is used, in which a certain pAg value is kept constant or a defined pAg profile is traversed during the precipitation. In addition to the preferred precipitation with an excess of halide, so-called inverse precipitation with an excess of silver ions is also possible. In addition to precipitation, the silver halide crystals can also grow through physical ripening (Ostwald ripening), in the presence of excess halide and / or silver halide complexing agent. The growth of the emulsion grains can even take place predominantly by Ostwald ripening, a fine-grained, so-called Lippmann emulsion preferably being mixed with a less soluble emulsion and being redissolved on the latter.
Während der Fällung und/oder der physikalischen Reifung der Silberhalogenidkörner können auch Salze oder Komplexe von Metallen, wie Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe vorhanden sein.Salts or complexes of metals such as Cd, Zn, Pb, Tl, Bi, Ir, Rh, Fe can also be present during the precipitation and / or physical ripening of the silver halide grains.
Ferner kann die Fällung auch in Gegenwart von Sensibilisierungsfarbstoffen erfolgen. Komplexierungsmittel und/oder Farbstoffe lassen sich zu jedem beliebigen Zeitpunkt unwirksam machen, z.B. durch Änderung des pH-Wertes oder durch eine oxidative Behandlung.The precipitation can also be carried out in the presence of sensitizing dyes. Complexing agents and / or dyes can be rendered ineffective at any time, for example by changing the pH or by an oxidative treatment.
Nach abgeschlossener Kristallbildung oder auch schon zu einem früheren Zeitpunkt werden durch das Flocken und Waschen die löslichen Salze aus der Emulsion entfernt.After crystal formation has been completed or at an earlier point in time, the soluble salts are removed from the emulsion by flocculation and washing.
Die Silberhalogenidemulsion wird im allgemeinen einer chemischen Sensibilisierung unter definierten Bedingungen - pH, pAg, Temperatur, Gelatine-, Silberhalogenid- und Sensibilisatorkonzentration - bis zum Erreichen des Empfindlichkeits- und Schleieroptimums unterworfen. Die Verfahrensweise ist z.B. bei H. Frieser "Die Grundlagen der Photographischen Prozesse mit Silberhalogeniden" Seite 675-734, Akademische Verlagsgesellschaft (1968) beschrieben.The silver halide emulsion is generally subjected to chemical sensitization under defined conditions - pH, pAg, temperature, gelatin, silver halide and sensitizer concentration - until the optimum sensitivity and fog are reached. The procedure is e.g. described by H. Frieser "The basics of photographic processes with silver halides" page 675-734, Akademische Verlagsgesellschaft (1968).
Dabei kann die chemische Sensibilisierung unter Zusatz von Verbindungen von Schwefel, Selen, Tellur und/oder Edelmetallverbindungen (z.B. Gold, Platin, Palladium, Iridium) erfolgen, weiterhin können Thiocyanatverbindungen, oberflächenaktive Verbindungen, wie Thioether, heterocyclische Stickstoffverbindungen (z.B. Imidazole, Azaindene) oder auch spektrale Sensibilisatoren (beschrieben z.B. bei F. Hamer "The Cyanine Dyes and Related Compounds", 1964, bzw. Ullmanns Encyclopädie der technischen Chemie, 4. Auflage, Bd. 18, S. 431 ff. und Research Disclosure Nr. 17643, Abschnitt III) zugegeben werden. Ersatzweise oder zusätzlich kann eine Reduktionssensibilisierung unter Zugabe von Reduktionsmitteln (Zinn-II-Salze, Amine, Hydrazinderivate, Aminoborane, Silane, Formamidinsulfinsäure) durch Wasserstoff, durch niedrigen pAg (z.B. kleiner 5) und/oder hohen pH (z.B. über 8) durchgeführt werden.Chemical sensitization can be carried out with the addition of compounds of sulfur, selenium, tellurium and / or noble metal compounds (e.g. gold, platinum, palladium, iridium), thiocyanate compounds, surface-active compounds such as thioethers, heterocyclic nitrogen compounds (e.g. imidazoles, azaindenes) or also spectral sensitizers (described, for example, by F. Hamer "The Cyanine Dyes and Related Compounds", 1964, or Ullmanns Encyclopedia of Industrial Chemistry, 4th edition, vol. 18, pp. 431 ff. and Research Disclosure No. 17643, section III) are added. Alternatively or additionally, a reduction sensitization with the addition of reducing agents (tin-II salts, amines, hydrazine derivatives, aminoboranes, silanes, formamidinesulfinic acid) can be carried out by hydrogen, by low pAg (eg less than 5) and / or high pH (eg above 8) .
Die fotografischen Emulsionen können Verbindungen zur Verhinderung der Schleierbildung oder zur Stabilisierung der fotografischen Funktion während der Produktion, der Lagerung oder der fotografischen Verarbeitung enthalten.The photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.
Besonders geeignet sind Azaindene, vorzugsweise Tetra- und Pentaazaindene, insbesondere solche, die mit Hydroxyl- oder Aminogruppen substituiert sind. Derartige Verbindungen sind z.B. von Birr, Z. Wiss. Phot. 47 (1952), S. 2-58 beschrieben worden. Weiter können als Antischleiermittel Salze von Metallen wie Quecksilber oder Cadmium, aromatische Sulfon- oder Sulfinsäuren wie Benzolsulfinsäure, oder stickstoffhaltige Heterocyclen wie Nitrobenzimidazol, Nitroindazol, gegebenenfalls substituierte Benztriazole oder Benzthiazoliumsalze eingesetzt werden. Besonders geeignet sind Mercaptogruppen enthaltende Heterocyclen, z.B. Mercaptobenzthiazole, Mercaptobenzimidazole, Mercaptotetrazole, Mercaptothiadiazole, Mercaptopyrimidine, wobei diese Mercaptoazole auch eine wasserlöslichmachende Gruppe, z.B. eine Carboxylgruppe oder Sulfogruppe, enthalten können. Weitere geeignete Verbindungen sind in Research Disclosure Nr. 17643 (1978), Abschnitt VI, veröffentlicht.Azaindenes are particularly suitable, preferably tetra- and penta-azaindenes, in particular those which are substituted by hydroxyl or amino groups. Such connections are for example from Birr, Z. Wiss. Phot. 47 (1952), pp. 2-58. Salts of metals such as mercury or cadmium, aromatic sulfonic or sulfinic acids such as benzenesulfinic acid, or nitrogen-containing heterocycles such as nitrobenzimidazole, nitroindazole, optionally substituted benzotriazoles or benzothiazolium salts can also be used as antifoggants. Heterocycles containing mercapto groups, for example mercaptobenzthiazoles, mercaptobenzimidazoles, mercaptotetrazoles, mercaptothiadiazoles, mercaptopyrimidines, are particularly suitable, these mercaptoazoles also being able to contain a water-solubilizing group, for example a carboxyl group or sulfo group. Other suitable compounds are published in Research Disclosure No. 17643 (1978), Section VI.
Die Stabilisatoren können den Silberhalogenidemulsionen vor, während oder nach deren Reifung zugesetzt werden. Selbstverständlich kann man die Verbindungen auch anderen fotografischen Schichten, die einer Halogensilberschicht zugeordnet sind, zusetzen.The stabilizers can be added to the silver halide emulsions before, during or after their ripening. Of course, the compounds can also be added to other photographic layers which are assigned to a halogen silver layer.
Es können auch Mischungen aus zwei oder mehreren der genannten Verbindungen eingesetzt werden.Mixtures of two or more of the compounds mentioned can also be used.
Die fotografischen Emulsionsschichten oder andere hydrophile Kolloidschichten des erfindungsgemäß hergestellten lichtempfindlichen Materials können oberflächenaktive Mittel für verschiedene Zwecke enthalten, wie Überzugshilfen, zur Verhinderung der elektrischen Aufladung, zur Verbesserung der Gleiteigenschaften, zum Emulgieren der Dispersion, zur Verhinderung der Adhäsion und zur Verbesserung der fotografischen Charakteristika (z.B. Entwicklungsbeschleunigung, hoher Kontrast, Sensibilisierung usw.). Neben natürlichen oberflächenaktiven Verbindungen, z.B. Saponin, finden hauptsächlich synthetische oberflächenaktive Verbindungen (Tenside) Verwendung: nicht-ionische Tenside, z.B. Alkylenoxidverbindungen, Glycerinverbindungen oder Glycidolverbindungen, kationische Tenside, z.B. höhere Alkylamine, quartäre Ammoniumsalze, Pyridinverbindungen und andere heterocyclische Verbindungen, Sulfoniumverbindungen oder Phosphoniumverbindungen, anionische Tenside, enthaltend eine Säuregruppe, z.B. Carbonsäure-, Sulfonsäure-, eine Phosphorsäure-, Schwefelsäureester- oder Phosphorsäureestergruppe, ampholytische Tenside, z.B. Aminosäure- und Aminosulfonsäureverbindungen sowie Schwefel- oder Phosphorsäureester eines Aminoalkohols.The photographic emulsion layers or other hydrophilic colloid layers of the light-sensitive material produced according to the invention can contain surface-active agents for various purposes, such as coating aids, to prevent electrical charging, to improve the sliding properties, to emulsify the dispersion, to prevent adhesion and to improve the photographic characteristics ( eg acceleration of development, high contrast, sensitization etc.). In addition to natural surface-active compounds, e.g. Saponin, mainly synthetic surface-active compounds (surfactants) are used: non-ionic surfactants, e.g. Alkylene oxide compounds, glycerin compounds or glycidol compounds, cationic surfactants, e.g. higher alkyl amines, quaternary ammonium salts, pyridine compounds and other heterocyclic compounds, sulfonium compounds or phosphonium compounds, anionic surfactants containing an acid group, e.g. Carboxylic acid, sulfonic acid, a phosphoric acid, sulfuric acid ester or phosphoric acid ester group, ampholytic surfactants, e.g. Amino acid and aminosulfonic acid compounds as well as sulfuric or phosphoric acid esters of an amino alcohol.
Die fotografischen Emulsionen können unter Verwendung von Methinfarbstoffen oder anderen Farbstoffen spektral sensibilisiert werden. Besonders geeignete Farbstoffe sind Cyaninfarbstoffe, Merocyaninfarbstoffe und komplexe Merocyaninfarbstoffe.The photographic emulsions can be spectrally sensitized using methine dyes or other dyes. Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.
Eine Übersicht über die als Spektralsensibilisatoren geeigneten Polymethinfarbstoffe, deren geeignete Kombinationen und supersensibilisierend wirkenden Kombinationen enthält Research Disclosure 17643/1978 in Abteilung IV.Research Disclosure 17643/1978 in Department IV contains an overview of the polymethine dyes suitable as spectral sensitizers, their suitable combinations and combinations with a super-sensitizing effect.
Insbesondere sind die folgenden Farbstoffe - geordnet nach Spektralgebieten - geeignet:The following dyes, sorted by spectral range, are particularly suitable:
9-Ethylcarbocyanine mit Benzthiazol, Benzselenazol oder Naphthothiazol als basische Endgruppen, die in 5- und/oder 6-Stellung durch Halogen, Methyl, Methoxy, Carbalkoxy, Aryl substituiert sein können sowie 9-Ethyl-naphthoxathia- bzw. -selencarbocyanine und 9-Ethyl-naphthothiaoxa- bzw. -benzimidazocarbocyanine, vorausgesetzt, daß die Farbstoffe mindestens eine Sulfoalkylgruppe am heterocyclischen Stickstoff tragen.9-ethyl carbocyanines with benzthiazole, benzselenazole or naphthothiazole as basic end groups, which can be substituted in the 5- and / or 6-position by halogen, methyl, methoxy, carbalkoxy, aryl, and 9-ethyl-naphthoxathia or -selencarbocyanines and 9- Ethyl-naphthothiaoxa- or -benzimidazocarbocyanine, provided that the dyes carry at least one sulfoalkyl group on the heterocyclic nitrogen.
9-Ethylcarbocyanine mit Benzoxazol, Naphthoxazol oder einem Benzoxazol und einem Benzthiazol als basische Endgruppen sowie Benzimidazocarbocyanine, die ebenfalls weiter substituiert sein können und ebenfalls mindestens eine Sulfoalkylgruppe am heterocyclischen Stickstoff enthalten müssen.9-ethylcarbocyanines with benzoxazole, naphthoxazole or a benzoxazole and a benzthiazole as basic end groups, and also benzimidazocarbocyanines, which may also be further substituted and must also contain at least one sulfoalkyl group on the heterocyclic nitrogen.
symmetrische oder asymmetrische Benzimidazo-, Oxa-, Thia- oder Selenacyanine mit mindestens einer Sulfoalkylgruppe am heterocyclischen Stickstoff und gegebenenfalls weiteren Substituenten am aromatischen Kern, sowie Apomerocyanine mit einer Rhodaningruppe.symmetrical or asymmetrical benzimidazo-, oxa-, thia- or selenacyanines with at least one sulfoalkyl group on the heterocyclic nitrogen and optionally further substituents on the aromatic nucleus, and apomerocyanines with a rhodanine group.
Die Emulsionen können außer den erfindungsgemäßen Gelatinen zusätzliche Bindemittel, wie synthetische oder natürliche, schichtbildende Polymere enthalten.In addition to the gelatins according to the invention, the emulsions can contain additional binders, such as synthetic or natural, layer-forming polymers.
Die erfindungsgemäßen Emulsionen eignen sich für alle Arten von fotografischen Materialien, wie Röntgenfilmen, Schwarz-Weiß-Film, Schwarz-Weiß-Papier, insbesondere aber für farbfotografische Materialien.The emulsions according to the invention are suitable for all types of photographic materials, such as X-ray films, black and white film, black and white paper, but in particular for color photographic materials.
Beispiele für farbfotografische Materialien sind Farbnegativfilme, Farbumkehrfilme, Farbpositivfilme, farbfotografisches Papier, farbumkehrfotografisches Papier, farbempfindliche Materialien für das Farbdiffusionstransfer-Verfahren oder das Silberfarb-Bleichverfahren.Examples of color photographic materials are color negative films, color reversal films, color positive films, color photographic paper, color reversal photographic paper, color sensitive materials for the color diffusion transfer process or the silver color bleaching process.
Geeignete Träger zur Herstellung farbfotografischer Materialien sind z.B. Filme und Folien von halbsynthetischen und synthetischen Polymeren, wie Cellulosenitrat, Celluloseacetat, Cellulosebutyrat, Polystyrol, Polyvinylchlorid, Polyethylenterephthalat und Polycarbonat und mit einer Barytschicht oder α-Olefinpolymerschicht (z.B. Polyethylen) laminiertes Papier. Diese Träger können mit Farbstoffen und Pigmenten, beispielsweise Titandioxid, gefärbt sein. Sie können auch zum Zwecke der Abschirmung von Licht schwarz gefärbt sein. Die Oberfläche des Trägers wird im allgemeinen einer Behandlung unterzogen, um die Adhäsion der fotografischen Emulsionsschicht zu verbessern, beispielsweise einer Corona-Entladung mit nachfolgendem Antrag einer Substratschicht.Suitable supports for the production of color photographic materials are, for example, films and foils of semisynthetic and synthetic polymers, such as cellulose nitrate, Cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate and paper laminated with a baryta layer or α-olefin polymer layer (eg polyethylene). These supports can be colored with dyes and pigments, for example titanium dioxide. They can also be colored black for the purpose of shielding light. The surface of the support is generally subjected to a treatment in order to improve the adhesion of the photographic emulsion layer, for example a corona discharge with subsequent application of a substrate layer.
Die farbfotografischen Materialien enthalten üblicherweise mindestens je eine rotempfindliche, grünempfindliche und blauempfindliche Silberhalogenidemulsionsschicht sowie gegebenenfalls Zwischenschichten und Schutzschichten.The color photographic materials usually contain at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer and, if appropriate, intermediate layers and protective layers.
Wesentliche Bestandteile der fotografischen Emulsionsschichten sind neben Bindemittel und Silberhalogenidkörnchen die Farbkuppler.In addition to binders and silver halide grains, the color couplers are essential components of the photographic emulsion layers.
Den unterschiedlich sensibilisierten Emulsionsschichten werden nicht diffundierende monomere oder polymere Farbkuppler zugeordnet, die sich in der gleichen Schicht oder in einer dazu benachbarten Schicht befinden können. Gewöhnlich werden den rotempfindlichen Schichten Blaugrünkuppler, den grünempfindlichen Schichten Purpurkuppler und den blauempfindlichen Schichten Gelbkuppler zugeordnet.The differently sensitized emulsion layers are assigned non-diffusing monomeric or polymeric color couplers, which can be located in the same layer or in a layer adjacent to it. Usually, cyan couplers are assigned to the red-sensitive layers, purple couplers to the green-sensitive layers and yellow couplers to the blue-sensitive layers.
Farbkuppler zur Erzeugung des blaugrünen Teilfarbenbildes sind in der Regel Kuppler vom Phenol- oder α-Naphtholtyp.Color couplers for producing the blue-green partial color image are usually couplers of the phenol or α-naphthol type.
Farbkuppler zur Erzeugung des purpurnen Teilfarbenbildes sind in der Regel Kuppler vom Typ des 5-Pyrazolons, des Indazolons oder Pyrauoloazole.Color couplers for generating the purple partial color image are generally couplers of the 5-pyrazolone, indazolone or pyrauoloazole type.
Farbkuppler zur Erzeugung des gelben Teilfarbenbildes sind in der Regel Kuppler mit einer offenkettigen Ketomethylengruppierung, insbesondere Kuppler vom Typ des α-Acylacetamids; geeignete Beispiele hierfür sind α-Benzoylacetanilidkuppler und α-Pivaloylacetanilidkuppler.Color couplers for producing the yellow partial color image are generally couplers with an open-chain ketomethylene group, in particular couplers of the α-acylacetamide type; Suitable examples are α-benzoylacetanilide couplers and α-pivaloylacetanilide couplers.
Bei den Farbkupplern kann es sich um 4-Äquivalentkuppler, aber auch um 2-Äquivalentkuppler handeln. Letztere leiten sich von den 4-Äquivalentkupplern dadurch ab, daß sie in der Kupplungsstelle einen Substituenten enthalten, der bei der Kupplung abgespalten wird. Zu den 2-Äquivalentkupplern sind solche zu rechnen, die farblos sind, als auch solche, die eine intensive Eigenfarbe aufweisen, die bei der Farbkupplung verschwindet bzw. durch die Farbe des erzeugten Bildfarbstoffes ersetzt wird (Maskenkuppler), und die Weißkuppler, die bei Reaktion mit Farbentwickleroxidationsprodukten im wesentlichen farblose Produkte ergeben. Zu den 2-Äquivalentkupplern sind ferner solche Kuppler zu rechnen, die in der Kupplungsstelle einen abspaltbaren Rest enthalten, der bei Reaktion mit Farbentwickleroxidationsprodukten in Freiheit gesetzt wird und dabei entweder direkt oder nachdem aus dem primär abgespaltenen Rest eine oder mehrere weitere Gruppen abgespalten worden sind (z.B. DE-A-27 03-145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), eine bestimmte erwünschte fotografische Wirksamkeit entfaltet, z.B. als Entwicklungsinhibitor oder -accelerator. Beispiele für solche 2-Äquivalentkuppler sind die bekannten DIR-Kuppler wie auch DAR-bzw. FAR-Kuppler.The color couplers can be 4-equivalent couplers, but also 2-equivalent couplers. The latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site which is split off during the coupling. The 2-equivalent couplers include those that are colorless, as well as those that have an intense intrinsic color that disappears when the color is coupled or is replaced by the color of the image dye produced (mask coupler), and the white couplers that react with color developer oxidation products yield essentially colorless products. The 2-equivalent couplers also include those couplers which contain a detachable residue in the coupling point, which in reaction with color developer oxidation products Freedom is set, either directly or after one or more further groups have been split off from the primarily split off remainder (e.g. DE-A-27 03-145, DE-A-28 55 697, DE-A-31 05 026, DE -A-33 19 428), develops a certain desired photographic effectiveness, for example as a development inhibitor or accelerator. Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or. FAR coupler.
DIR-Kuppler, die Entwicklungsinhibitoren vom Azoltyp, z.B. Triazole und Benzotriazole freisetzen, sind in DE-A-24 14 006, 26 10 546, 26 59 417, 27 54 281, 27 26 180, 36 26 219, 36 30 564, 36 36 824, 36 44 416 und 28 42 063 beschrieben. Weitere Vorteile für die Farbwiedergabe, d.h., Farbtrennung und Farbreinheit, und für die Detailwiedergabe, d.h., Schärfe und Körnigkeit, sind mit solchen DIR-Kupplern zu erzielen, die z.B. den Entwicklungsinhibitor nicht unmittelbar als Folge der Kupplung mit einem oxidierten Farbentwickler abspalten, sondern erst nach einer weiteren Folgereaktion, die beispielsweise mit einer Zeitsteuergruppe erreicht wird. Beispiele dafür sind in DE-A-28 55 697, 32 99 671, 38 18 231, 35 18 797, in EP-A-157 146 und 204 175, in US-A-4 146 396 und 4 438 393 sowie in GB-A-2 072 363 be schrieben.DIR couplers which release development inhibitors of the azole type, for example triazoles and benzotriazoles, are described in DE-A-24 14 006, 26 10 546, 26 59 417, 27 54 281, 27 26 180, 36 26 219, 36 30 564, 36 36 824, 36 44 416 and 28 42 063. Further advantages for color reproduction, that is, color separation and color purity, and for detail reproduction, that is, sharpness and granularity, can be achieved with those DIR couplers which, for example, do not split off the development inhibitor directly as a result of coupling with an oxidized color developer, but only after a further follow-up reaction, which is achieved, for example, with a timing group. Examples of these are in DE-A-28 55 697, 32 99 671, 38 18 231, 35 18 797, in EP-A-157 146 and 204 175, in US-A-4 146 396 and 4 438 393 and in GB -A-2,072,363.
DIR-Kuppler, die einen Entwicklungsinhibitor freisetzen, der im Entwicklerbad zu im wesentlichen fotografisch unwirksamen Produkten zersetzt wird, sind beispielsweise in DE-A-32 09 486 und in EP-A-167 168 und 219 713 beschrieben. Mit dieser Maßnahme wird eine störungsfreie Entwicklung und Verarbeitungskonstanz erreicht.DIR couplers which release a development inhibitor which is decomposed into essentially photographically ineffective products in the developer bath are described, for example, in DE-A-32 09 486 and in EP-A-167 168 and 219 713. This measure ensures trouble-free development and processing consistency.
Bei Einsatz von DIR-Kupplern, insbesondere von solchen, die einen gut diffundierbaren Entwicklungsinhibitor abspalten, lassen sich durch geeignete Maßnahmen bie der optischen Sensibilisierung Verbesserungen der Farbwiedergabe, z.B. eine differenziertere Farbwiedergabe, erzielen, wie beispielsweise in EP-A-115 304, 167 173, GB-A-2 165 058, DE-A-37 00 419 und US-A-4 707 436 beschrieben.When using DIR couplers, especially those that release a well-diffusible development inhibitor, improvements in color rendering, e.g. achieve a more differentiated color rendering, as described, for example, in EP-A-115 304, 167 173, GB-A-2 165 058, DE-A-37 00 419 and US-A-4 707 436.
Die DIR-Kuppler können in einem mehrschichtigen fotografischen Material den unterschiedlichsten Schichten zugesetzt werden, z.B. auch lichtunempfindlichen oder Zwischenschichten. Vorzugsweise werden sie jedoch den lichtempfindlichen Silberhalogenidemulsionsschichten zugesetzt, wobei die charakteristischen Eigenschaften der Silberhalogenidemulsion, z.B. deren Iodidgehalt, die Struktur der Silberhalogenidkörner oder deren Korngrößenverteilung von Einfluß auf die erzielten fotografischen Eigenschaften sind. Der Einfluß der freigesetzten Inhibitoren kann beispielsweise durch den Einbau einer Inhibitorfängerschicht gemäß DE-A-24 31 223 begrenzt werden. Aus Gründen der Reaktivität oder Stabilität kann es vorteilhaft sein, einen DIR-Kuppler einzu setzen, der in der jeweiligen Schicht, in der er eingebracht ist, eine von der in dieser Schicht zu erzeugenden Farbe abweichende Farbe bei der Kupplung bildet.The DIR couplers can be added to a wide variety of layers in a multilayer photographic material, for example also light-insensitive or intermediate layers. However, they are preferably added to the light-sensitive silver halide emulsion layers, the characteristic properties of the silver halide emulsion, for example its iodide content, the structure of the silver halide grains or their grain size distribution having an influence on the photographic properties achieved. The influence of the inhibitors released can be limited, for example, by incorporating an inhibitor scavenger layer in accordance with DE-A-24 31 223. For reasons of reactivity or stability, it may be advantageous to insert a DIR coupler set, which forms in the respective layer in which it is introduced, a color different from the color to be generated in this layer in the coupling.
Zur Steigerung der Empfindlichkeit, des Kontrastes und der maximalen Dichte können vor allem DAR- bzw. FAR-Kuppler eingesetzt werden, die einen Entwicklungsbeschleuniger oder ein Schleiermittel abspalten. Verbindungen dieser Art sind beispielsweise in DE-A-25 34 466, 32 09 110, 33 33 355, 34 10 616, 34 29 545, 34 41 823, in EP-A-89 834, 110 511, 118 087, 147 765 und in US-A-4 618 572 und 4 656 123 beschrieben.To increase the sensitivity, the contrast and the maximum density, DAR or FAR couplers can be used, which release a development accelerator or an fogger. Compounds of this type are, for example, in DE-A-25 34 466, 32 09 110, 33 33 355, 34 10 616, 34 29 545, 34 41 823, in EP-A-89 834, 110 511, 118 087, 147 765 and described in US-A-4,618,572 and 4,656,123.
Als Beispiel für den Einsatz von BAR-Kuppler (Bleach Accelerator Releasing Coupler) wird auf EP-A-193 389 verwiesen.As an example for the use of BAR couplers (Bleach Accelerator Releasing Coupler), reference is made to EP-A-193 389.
Es kann vorteilhaft sein, die Wirkung einer aus einem Kuppler abgespaltenen fotografisch wirksamen Gruppe dadurch zu modifizieren, daß eine intermolekulare Reaktion dieser Gruppe nach ihrer Freisetzung mit einer anderen Gruppe gemäß DE-A-35 06 805 eintritt.It can be advantageous to modify the effect of a photographically active group which is split off from a coupler in that an intermolecular reaction of this group occurs after its release with another group according to DE-A-35 06 805.
Da bei den DIR-, DAR- bzw. FAR-Kupplern hauptsächlich die Wirksamkeit des bei der Kupplung freigesetzten Restes erwünscht ist und es weniger auf die farbbildenden Eigenschaften dieser Kuppler ankommt, sind auch solche DIR-, DAR- bzw. FAR-Kuppler geeignet, die bei der Kupplung im wesentlichen farblose Produkte ergeben (DE-A-15 47 640).Since with DIR, DAR or FAR couplers the effectiveness of the residue released during coupling is mainly desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also suitable, which give essentially colorless products on coupling (DE-A-15 47 640).
Der abspaltbare Rest kann auch ein Ballastrest sein, so daß bei der Reaktion mit Farbentwickleroxidationsprodukten Kupplungsprodukte erhalten werden, die diffusionsfähig sind oder zumindest eine schwache bzw. eingeschränkte Beweglichkeit aufweisen (US-A-4 420 556).The cleavable residue can also be a ballast residue, so that upon reaction with color developer oxidation products coupling products are obtained which are diffusible or at least have a weak or restricted mobility (US Pat. No. 4,420,556).
Das Material kann weiterhin von Kupplern verschiedene Verbindungen enthalten, die beispielsweise einen Entwicklungsinhibitor, einen Entwicklungsbeschleuniger, einen Bleichbeschleuniger, einen Entwickler, ein Silberhalogenidlösungsmittel, ein Schleiermittel oder ein Antischleiermittel in Freiheit setzen können, beispielsweise sogenannte DIR-Hydrochinone und andere Verbindungen, wie sie beispielsweise in US-A-4 636 546, 4 345 024, 4 684 604 und in DE-A-31 45 640, 25 15 213, 24 47 079 und in EP-A-198 438 beschrieben sind. Diese Verbindungen erfüllen die gleiche Funktion wie die DIR-, DAR- oder FAR-Kuppler, außer daß sie keine Kupplungsprodukte bilden.The material may further contain compounds other than couplers, which can, for example, release a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a fogging agent or an antifoggant, for example so-called DIR-hydroquinones and other compounds, as described for example in US-A-4 636 546, 4 345 024, 4 684 604 and in DE-A-31 45 640, 25 15 213, 24 47 079 and in EP-A-198 438. These compounds perform the same function as the DIR, DAR or FAR couplers, except that they do not form coupling products.
Hochmolekulare Farbkuppler sind beispielsweise in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211 beschrieben. Die hochmolekularen Farbkuppler werden in der Regel durch Polymerisation von ethylenisch ungesättigten monomeren Farbkupplern hergestellt. Sie können aber auch durch Polyaddition oder Polykondensation erhalten werden.High molecular weight color couplers are described, for example, in DE-C-1 297 417, DE-A-24 07 569, DE-A-31 48 125, DE-A-32 17 200, DE-A-33 20 079, DE-A-33 24 932, DE-A-33 31 743, DE-A-33 40 376, EP-A-27 284, US-A-4 080 211. The high molecular weight color couplers are usually produced by polymerizing ethylenically unsaturated monomeric color couplers. However, they can also be obtained by polyaddition or polycondensation.
Die Einarbeitung der Kuppler oder anderer Verbindungen in Silberhalogindemulsionsschichten kann in der Weise erfolgen, daß zunächst von der betreffenden Verbindung eine Lösung, eine Dispersion oder eine Emulsion hergestellt und dann der Gießlösung für die betreffende Schicht zugefügt wird. Die Auswahl des geeigneten Lösungs- oder Dispersionsmittel hängt von der jeweiligen Löslichkeit der Verbindung ab.The couplers or other compounds can be incorporated into silver halide emulsion layers by first preparing a solution, a dispersion or an emulsion from the compound in question and then adding it to the casting solution for the layer in question. The selection of the suitable solvent or dispersing agent depends on the solubility of the compound.
Methoden zum Einbringen von in Wasser im wesentlichen unlöslichen Verbindungen durch Mahlverfahren sind beispielsweise in DE-A-26 09 741 und DE-A-26 09 742 beschrieben.Methods for introducing compounds which are essentially insoluble in water by grinding processes are described, for example, in DE-A-26 09 741 and DE-A-26 09 742.
Hydrophobe Verbindungen können auch unter Verwendung von hochsiedenden Lösungsmitteln, sogenannten Ölbildnern, in die Gießlösung eingebracht werden. Entsprechende Methoden sind beispielsweise in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 und EP-A-O 043 037 beschrieben.Hydrophobic compounds can also be introduced into the casting solution using high-boiling solvents, so-called oil formers. Corresponding methods are described for example in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 and EP-A-O 043 037.
Anstelle der hochsiedenden Lösungsmitteln können Oligomere oder Polymere, sogenannte polymere Ölbildner Verwendung finden.Instead of the high-boiling solvents, oligomers or polymers, so-called polymeric oil formers, can be used.
Die Verbindungen können auch in Form beladener Latices in die Gießlösung eingebracht werden. Verwiesen wird beispielsweise auf DE-A-25 41 230, DE-A-25 41 274, DE-A-28 35 856, EP-A-O 014 921, EP-A-0 069 671, EP-A-O 130 115, US-A-4 291 113.The compounds can also be introduced into the casting solution in the form of loaded latices. Reference is made, for example, to DE-A-25 41 230, DE-A-25 41 274, DE-A-28 35 856, EP-AO 014 921, EP-A-0 069 671, EP-AO 130 115, US Pat. A-4 291 113.
Die diffusionsfeste Einlagerung anionischer wasserlöslicher Verbindungen (z.B. von Farbstoffen) kann auch mit Hilfe von kationischen Polymeren, sogenannten Beizenpolymeren erfolgen.The diffusion-resistant incorporation of anionic water-soluble compounds (e.g. dyes) can also be carried out using cationic polymers, so-called pickling polymers.
Geeignete Ölbildner sind z.B. Phthalsäurealkylester, Phosphonsäureester, Phosphorsäureester, Citronensäureester, Benzoesäureester, Amide, Fettsäureester, Trimesinsäureester, Alkohole, Phenole, Anilinderivate und Kohlenwasserstoffe.Suitable oil formers are e.g. Alkyl phthalates, phosphonic acid esters, phosphoric acid esters, citric acid esters, benzoic acid esters, amides, fatty acid esters, trimesic acid esters, alcohols, phenols, aniline derivatives and hydrocarbons.
Beispiele für geeignete Ölbildner sind Dibutylphthalat, Dicyclohexylphthalat, Di-2-ethylhexylphthalat, Decylphthalat, Triphenylphosphat, Tricresylphosphat, 2-Ethylhexyldiphenylphosphat, Tricyclohexylphosphat, Tri-2-ethylhexylphosphat, Tridecylphosphat, Tributoxyethylphosphat, Trichlorpropylphosphat, Di-2-ethylhexylphenylphosphat, 2-Ethylhexylbenzoat, Dodecylbenzoat, 2-Ethylhexyl-p-hydroxybenzoat, Diethyldodecanamid, N-Tetradecylpyrrolidon, Isostearylalkohol, 2,4-Di-tert.-amylphenol, Dioctylacelat, Glycerintributyrat, Isostearyllactat, Trioctylcitrat, N,N-Dibutyl-2-butoxy-5-tert.-octylanilin, Paraffin, Dodecylbenzol und Diisopropylnaphthalin.Examples of suitable oil formers are dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridecoxy phosphate, 2-ethylhexyl phosphate, tridecoxy phosphate, 2-ethylhexyl phylate, , 2-ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-tert-amylphenol, dioctyl acylate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, N, N-doxy-5-butyl-2-. -octylaniline, paraffin, dodecylbenzene and diisopropylnaphthalene.
Jede der unterschiedlich sensibilisierten, lichtempfindlichen Schichten kann aus einer einzigen Schicht bestehen oder auch zwei oder mehr Silberhalogenidemulsionsteilschichten umfassen (DE-C-1 121 470). Dabei sind rotempfindliche Silberhalogenidemulsionsschichten dem Schichtträger häufig näher angeordnet als grünempfindliche Silberhalogenidemulsionsschichten und diese wiederum näher als blauempfindliche, wobei sich im allgemeinen zwischen grünempfindlichen Schichten und blauempfindlichen Schichten eine nicht lichtempfindliche gelbe Filterschicht befindet.Each of the differently sensitized, light-sensitive layers can consist of a single layer or can also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470). Red-sensitive silver halide emulsion layers are Layer supports are often arranged closer than green-sensitive silver halide emulsion layers and these in turn are closer than blue-sensitive layers, a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.
Bei geeignet geringer Eigenempfindlichkeit der grün-bzw. rotempfindlichen Schichten kann man unter Verzicht auf die Gelbfilterschicht andere Schichtanordnungen wählen, bei denen auf den Träger z.B. die blauempfindlichen, dann die rotempfindlichen und schließlich die grünempfindlichen Schichten folgen.With a suitably low intrinsic sensitivity of the green or Red-sensitive layers can be chosen without the yellow filter layer, other layer arrangements in which e.g. the blue-sensitive, then the red-sensitive and finally the green-sensitive layers follow.
Die in der Regel zwischen Schichten unterschiedlicher Spektralempfindlichkeit angeordneten nicht lichtempfindlichen Zwischenschichten können Mittel enthalten, die eine unerwünschte Diffusion von Entwickleroxidationsprodukten aus einer lichtempfindlichen in eine andere lichtempfindliche Schicht mit unterschiedlicher spektraler Sensibilisierung verhindern.The non-light-sensitive intermediate layers, which are generally arranged between layers of different spectral sensitivity, can contain agents which prevent undesired diffusion of developer oxidation products from one light-sensitive layer into another light-sensitive layer with different spectral sensitization.
Geeignete Mittel, die auch Scavenger oder EOP-Fänger genannt werden, werden in Research Disclosure 17 643 (Dez. 1978), Kapitel VII, 17 842/1979, Seite 94-97 und 18.716/ 1979, Seite 650 sowie in EP-A-69 070, 98 072, 124 877, 125 522 und in US-A-463 226 beschrieben.Suitable agents, which are also called scavengers or EOP-catchers, are described in Research Disclosure 17 643 (Dec. 1978), Chapter VII, 17 842/1979, pages 94-97 and 18.716 / 1979, page 650 and in EP-A- 69,070, 98,072, 124,877, 125,522 and in US-A-463,226.
Liegen mehrere Teilschichten gleicher spektraler Sensibilisierung vor, so können sich diese hinsichtlich ihrer Zusammensetzung, insbesondere was Art und Menge der Silberhalogenidkörnchen betrifft unterscheiden. Im allgemeinen wird die Teilschicht mit höherer Empfindlichkeit von Träger entfernter angeordnet sein als die Teilschicht mit geringerer Empfindlichkeit. Teilschichten gleicher spektraler Sensibilisierung können zueinander benachbart oder durch andere Schichten, z.B. durch Schichten anderer spektraler Sensibilisierung getrennt sein. So können z.B. alle hochempfindlichen und alle niedrigempfindlichen Schichten jeweils zu einem Schichtpaket zusammengefaßt sein (DE-A-19 58 709, DE-A-25 30 645, DE-A-26 22 922).If there are several sub-layers of the same spectral sensitization, these can differ with regard to their composition, in particular with regard to the type and amount of the silver halide grains. In general, the sublayer with higher sensitivity will be located further from the support than the sublayer with lower sensitivity. Partial layers of the same spectral sensitization can be adjacent to one another or through other layers, e.g. separated by layers of other spectral sensitization. For example, all highly sensitive and all low-sensitive layers can be combined to form a layer package (DE-A-19 58 709, DE-A-25 30 645, DE-A-26 22 922).
Das fotografische Material kann weiterhin UV-Licht absorbierende Verbindungen, Weißtöner, Abstandshalter, Filterfarbstoffe, Formalinfänger, Lichtschutzmittel, Antioxidantien, DMin-Farbstoffe, Zusätze zur Verbesserung der Farbstoff-, Kuppler- und Weißenstabilisierung sowie zur Verringerung des Farbschleiers, Weichmacher (Latices), Biocide und anderes enthalten.The photographic material can also contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D min dyes, additives to improve dye, coupler and white stabilization and to reduce the color fog, plasticizers (latices), Contain biocides and others.
UV-Licht absorbierende Verbindungen sollen einerseits die Bildfarbstoffe vor dem Ausbleichen durch UV-reiches Tageslicht schützen und andererseits als Filterfarbstoffe das UV-Licht im Tageslicht bei der Belichtung absorbieren und so die Farbwiedergabe eines Films verbessern. Üblicherweise werden für die beiden Aufgaben Verbindungen unterschiedlicher Struktur eingesetzt. Beispiele sind arylsubstituierte Benzotriazolverbindungen (US-A-3 533 794), 4-Thiazolidonverbindungen (US-A-3 314 794 und 3 352 681), Benzophenonverbindungen (JP-A-2784/71), Zimtsäureesterverbindungen (US-A-3 705 805 und 3 707 375), Butadienverbindungen (US-A-4 045 229) oder Benzoxazolverbindungen (US-A-3 700 455).Compounds that absorb UV light are intended on the one hand to protect the image dyes from fading by UV-rich daylight and, on the other hand, as filter dyes to absorb the UV light in daylight upon exposure and thus improve the color rendering of a film. Usually for the two tasks Connections of different structures used. Examples are aryl-substituted benzotriazole compounds (US-A-3 533 794), 4-thiazolidone compounds (US-A-3 314 794 and 3 352 681), benzophenone compounds (JP-A-2784/71), cinnamic acid ester compounds (US-A-3 705 805 and 3,707,375), butadiene compounds (US-A-4,045,229) or benzoxazole compounds (US-A-3,700,455).
Es können auch ultraviolettabsorbierende Kuppler (wie Blaugrünkuppler des α-Naphtholtyps) und ultraviolettabsorbierende Polymere verwendet werden. Diese Ultraviolettabsorbentien können durch Beizen in einer speziellen Schicht fixiert sein.Ultraviolet absorbing couplers (such as α-naphthol type cyan couplers) and ultraviolet absorbing polymers can also be used. These ultraviolet absorbents can be fixed in a special layer by pickling.
Für sichtbares Licht geeignete Filterfarbstoffe umfassen Oxonolfarbstoffe, Hemioxonolfarbstoffe, Styrylfarbstoffe, Merocyaninfarbstoffe, Cyaninfarbstoffe und Azofarbstoffe. Von diesen Farbstoffen werden Oxonolfarbstoffe, Hemioxonolfarbstoffe und Merocyaninfarbstoffe besonders vorteilhaft verwendet.Filter dyes suitable for visible light include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are used particularly advantageously.
Geeignete Weißtöner sind z.B. in Research Disclosure 17 643 (Dez. 1978), Kapitel V, in US-A-2 632 701, 3 269 840 und in GB-A-852 075 und 1 319 763 beschrieben.Suitable white toners are e.g. in Research Disclosure 17,643 (Dec. 1978), Chapter V, in US-A-2,632,701, 3,269,840 and in GB-A-852,075 and 1,319,763.
Bestimmte Bindemittelschichten, insbesondere die vom Träger am weitesten entfernte Schicht, aber auch gelegentlich Zwischenschichten, insbesondere, wenn sie während der Herstellung die vom Träger am weitesten entfernte Schicht darstellen, können fotografisch inerte Teilchen anorganischer oder organischer Natur enthalten, z.B. als Mattierungsmittel oder als Abstandshalter (DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, Dez. 1978, Kapitel XVI).Certain layers of binder, in particular the layer furthest from the support, but also occasionally intermediate layers, especially if they represent the most distant layer from the support during production, can contain photographically inert particles of inorganic or organic nature, for example as matting agents or as spacers (DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, Dec. 1978, Chapter XVI).
Der mittlere Teilchendurchmesser der Abstandshalter liegt insbesondere im Bereich von 0,2 bis 10 µm. Die Abstandshalter sind wasserunlöslich und können alkaliunlöslich oder alkalilöslich sein, wobei die alkalilöslichen im allgemeinen im alkalischen Entwicklungsbad aus dem fotografischen Material entfernt werden. Beispiele für geeignete Polymere sind Polymethylmethacrylat, Copolymere aus Acrylsäure und Methylmethacrylat sowie Hydroxypropylmethylcellulosehexahydrophthalat.The average particle diameter of the spacers is in particular in the range from 0.2 to 10 μm. The spacers are water-insoluble and can be alkali-insoluble or alkali-soluble, the alkali-soluble ones generally being removed from the photographic material in the alkaline development bath. Examples of suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.
Zusätze zur Verbesserung der Farbstoff-, Kuppler- und Weißenstabilität sowie zur Verringerung des Farbschleiers (Research Disclosure 17 643/1978, Kapitel VII) können den folgenden chemischen Stoffklasen angehören: Hydrochinone, 6-Hydroxychromane, 5-Hydroxycumarane, Spirochromane, Spiroindane, p-Alkoxyphenole, sterische gehinderte Phenole, Gallussäurederivate, Methylendioxybenzole, Aminophenole, sterisch gehinderte Amine, Derivate mit veresterten oder verätherten phenolischen Hydroxylgurppen, Metallkomplexe.Additives to improve dye, coupler and whiteness stability and to reduce the color haze (Research Disclosure 17 643/1978, Chapter VII) can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromans, spiroindanes, p- Alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, sterically hindered amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.
Verbindungen, die sowohl eine sterisch gehinderte Amin-Partialstruktur als auch eine sterisch gehinderte Phenol-Partialstruktur in einem Molekül aufweisen (US-A-4 268 593), sind besonders wirksam zur Verhinderung der Beeinträchtigung (Verschlechterung bzw. Abbau) von gelben Farbbildern als Folge der Entwicklung von Wärme, Feuchtigkeit und Licht. Um die Beeinträchtigung (Verschlechterung bzw. den Abbau) von purpurroten Farbbildern, insbesondere ihre Beeinträchtigung (Verschlechterung bzw. Abbau) als Folge der Einwirkung von Licht, zu verhindern, sind Spiroindane (JP-A-159 644/81) und Chromane, die durch Hydrochinondiether oder -monoether substiutiert sind (JP-A-89 835/80) besonders wirksam.Compounds that have both a hindered amine partial structure and a hindered one Phenol partial structure in a molecule (US-A-4 268 593), are particularly effective for preventing the deterioration (deterioration or degradation) of yellow color images as a result of the development of heat, moisture and light. In order to prevent the deterioration (deterioration or degradation) of crimson color images, in particular their impairment (deterioration or degradation) as a result of exposure to light, Spiroindane (JP-A-159 644/81) and chromanes are caused by Hydroquinone diethers or monoethers are particularly effective (JP-A-89 835/80).
Die Schichten des fotografischen Materials können mit den üblichen Härtungsmitteln gehärtet werden. Geeignete Härtungsmittel sind z.B. Formaldehyd, Glutaraldehyd und ähnliche Aldehydverbindungen, Diacetyl, Cyclopentadion und ähnliche Ketonverbindungen, Bis-(2-chlorethylharnstoff), 2-Hydroxy-4,6-dichlor-1,3,5-triazin und andere Verbindungen, die reaktives Halogen enthalten (US-A-3 288 775, US-A-2 732 303, GB-A-974 723 und GB-A-1 167 207) Divinylsulfonverbindungen, 5-Acetyl-1,3-diacryloylhexahydro-1,3,5-triazin und andere Verbindungen, die eine reaktive Olefinbindung enthalten (US-A-3 635 718, US-A-3 232 763 und GB-A-994 869); N-Hydroxymethylphthalimid und andere N-Methylolverbindungen (US-A-2 732 316 und US-A-2 586 168); Isocyanate (US-A-3 103 437); Aziridinverbindungen (US-A-3 017 280 und US-A-2 983 611); Säurederivate (US-A-2 725 294 und US-A-2 725 295); Verbindungen vom Carbodiimidtyp (US-A- 3 100 704); Carbamoylpyridiniumsalze (DE-A-22 25 230 und DE-A-24 39 551); Carbamoyloxypyridiniumverbindungen (DE-A-24 08 814); Verbindungen mit einer Phosphor-Halogen-Bindung (JP-A-113 929/83); N-Carbonyloximid-Verbindungen (JP-A-43353/81); N-Sulfonyloximido-Verbindungen (US-A-4 111 926), Dihydrochinolinverbindungen (US-A-4 013 468), 2-Sulfonyloxypyridiniumsalze (JP-A-110 762/81), Formamidiniumsalze (EP-A-0 162 308), Verbindungen mit zwei order mehr N-Acyloximino-Gruppen (US-A-4 052 373), Epoxyverbindungen (US-A-3 091 537), Verbindungen vom Isoxazoltyp (US-A-3 321 313 und US-A-3 543 292); Halogencarboxyaldehyde, wie Mucochlorsäure; Dioxanderivate, wie Dihydroxydioxan und Di-chlordioxan; und anorganische Härter, wie Chromalaun und Zirkonsulfat.The layers of the photographic material can be hardened with the usual hardening agents. Suitable curing agents are, for example, formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethyl urea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and other compounds, the reactive halogen included (US-A-3 288 775, US-A-2 732 303, GB-A-974 723 and GB-A-1 167 207) divinyl sulfone compounds, 5-acetyl-1,3-diacryloylhexahydro-1,3,5 triazine and other compounds containing a reactive olefin bond (US-A-3 635 718, US-A-3 232 763 and GB-A-994 869); N-hydroxymethylphthalimide and other N-methylol compounds (US-A-2 732 316 and US-A-2 586 168); Isocyanates (US-A-3 103 437); Aziridine compounds (US-A-3 017 280 and US-A-2 983 611); Acid derivatives (US-A-2 725 294 and US-A-2 725 295); Carbodiimide type compounds (US-A- 3 100 704); Carbamoylpyridinium salts (DE-A-22 25 230 and DE-A-24 39 551); Carbamoyloxypyridinium compounds (DE-A-24 08 814); Compounds with a phosphorus-halogen bond (JP-A-113 929/83); N-carbonyloximide compounds (JP-A-43353/81); N-sulfonyloximido compounds (US-A-4 111 926), dihydroquinoline compounds (US-A-4 013 468), 2-sulfonyloxypyridinium salts (JP-A-110 762/81), formamidinium salts (EP-A-0 162 308) , Compounds having two or more N-acyloximino groups (US-A-4 052 373), epoxy compounds (US-A-3 091 537), isoxazole-type compounds (US-A-3 321 313 and US-A-3 543 292); Halocarboxyaldehydes such as mucochloric acid; Dioxane derivatives such as dihydroxydioxane and di-chlorodioxane; and inorganic hardeners such as chrome alum and zirconium sulfate.
Die Härtung kann in bekannter Weise dadurch bewirkt werden, daß das Härtungsmittel der Gießlösung für die zu härtende Schicht zugesetzt wird, oder dadurch, daß die zu härtende Schicht mit einer Schicht überschichtet wird, die ein diffusionsfähiges Härtungsmittel enthält.The hardening can be effected in a known manner by adding the hardening agent to the casting solution for the layer to be hardened or by overlaying the layer to be hardened with a layer which contains a diffusible hardening agent.
Unter den aufgeführten Klassen gibt es langsam wirkende und schnell wirkende Härtungsmittel sowie sogenannte Soforthärter, die besonders vorteilhaft sind. Unter Soforthärtern werden verbindungen verstanden, die geeignete Bindemittel so vernetzen, daß unmittelbar nach Beguß, spätestens nach 24 Stunden, vorzugsweise spätestens nach 8 Stunden die Härtung so weit abgeschlossen ist, daß keine weitere durch die Vernetzungs reaktion bedingte Änderung der Sensitometrie und der Quellung des Schichtverbandes auftritt. Unter Quellung wird die Differenz von Naßschichtdicke und Trockenschichtdicke bei der wäßrigen Verarbeitung des Films verstanden (Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).There are slow-acting and fast-acting hardeners and so-called instant hardeners, which are particularly advantageous, in the classes listed. Immediate hardeners are understood to mean compounds which crosslink suitable binders in such a way that hardening is completed to the extent that no further crosslinking takes place immediately after casting, at the latest after 24 hours, preferably at the latest after 8 hours reaction-related change in the sensitometry and the swelling of the layer structure occurs. Swelling is understood to mean the difference between the wet film thickness and the dry film thickness during the aqueous processing of the film (Photogr. Sci., Eng. 8 (1964), 275; Photogr. Sci. Eng. (1972), 449).
Bei diesen mit Gelatine sehr schnell reagierenden Härtungsmitteln handelt es sich z.B. um Carbamoylpyridiniumsalze, die mit freien Carboxylgruppen der Gelatine zu reagieren vermögen, so daß letztere mit freien Aminogruppen der Gelatine unter Ausbildung von Peptidbindungen und Vernetzung der Gelatine reagieren.These hardening agents that react very quickly with gelatin are e.g. to carbamoylpyridinium salts, which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin to form peptide bonds and crosslink the gelatin.
Es gibt diffusionsfähige Härtungsmittel, die auf alle Schichten innerhalb eines Schichtverbandes in gleicher Weise härtend wirken. Es gibt aber auch schichtbegrenzt wirkende, nicht diffundierende, niedermolekulare und hochmolekulare Härter. Mit ihnen kann man einzelnen Schichten, z.B. die Schutzschicht besonders stark vernetzen. Dies ist wichtig, wenn mann die Silberhalogenid-Schicht wegen der Silberdeckkrafterhöhung wenig härtet und mit der Schutzschicht die mechanischen Eigenschaften verbessern muß (EP-A 0 114 699).There are diffusible curing agents that have the same curing effect on all layers within a layer structure. There are also layer-limited, non-diffusing, low-molecular and high-molecular hardeners. They can be used to separate individual layers, e.g. crosslink the protective layer particularly strongly. This is important if the silver halide layer is hardened little because of the increase in silver opacity and the protective layer has to improve the mechanical properties (EP-
Farbfotografische Negativmaterialien werden üblicherweise durch Entwickeln, Bleichen, Fixieren und Wässern oder durch Entwickeln, Bleichen, Fixieren und Stabilisieren ohne nachfolgende Wässerung verarbeitet, wobei Bleichen und Fixieren zu einem Verarbeitungsschritt zusammengefaßt sein können. Als Farbentwicklerverbindung lassen sich sämtliche Entwicklerverbindungen verwenden, die die Fähigkeit besitzen, in Form ihres Oxidationsproduktes mit Farbkupplern zu Azomethin- bzw. Indophenolfarbstoffen zu reagieren. Geeignete Farbentwicklerverbindungen sind aromatische, mindestens eine primäre Aminogruppe enthaltende Verbindungen vom p-Phenylendiamintyp, beispielsweise N,N-Dialkyl-p-phenylendiamine wie N,N-Diethyl-p-phenylendiamin, 1-(N-Ethyl-N-methansulfonamidoethyl)-3-methyl-p-phenylendiamin, 1-(N-Ethyl-N-hydroxyethyl)-3-methyl-p-phenylendiamin und 1-(N-Ethyl-N-methoxyethyl)-3-methyl-p-phenylendiamin. Weitere brauchbare Farbentwickler sind beispielsweise in J. Amer. Chem. Soc. 73, 3106 (1951) und G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, Seite 545 ff. beschrieben.Color photographic negative materials are usually processed by developing, bleaching, fixing and washing or by developing, bleaching, fixing and stabilizing without subsequent washing, with bleaching and fixing can be combined into one processing step. All developer compounds which have the ability to react in the form of their oxidation product with color couplers to form azomethine or indophenol dyes can be used as the color developer compound. Suitable color developer compounds are aromatic compounds of the p-phenylenediamine type containing at least one primary amino group, for example N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methanesulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl) -3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine. Further useful color developers are described, for example, in J. Amer. Chem. Soc. 73 , 3106 (1951) and G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, page 545 ff.
Nach der Farbentwicklung kann ein saures Stoppbad oder eine Wässerung folgen.After the color development, an acidic stop bath or watering can follow.
Üblicherweise wird das Material unmittelbar nach der Farbentwicklung gebleicht und fixiert. Als Bleichmittel können z.B. Fe(III)-Salze und Fe(III)-Komplexsalze wie Ferricyanide, Dichromate, wasserlösliche Kobaltkomplexe verwendet werden. Besonders bevorzugt sind Eisen-(III)-Komplexe von Aminopolycarbonsäuren, insbesondere z.B. von Ethylendiamintetraessigsäure, Propylendiamintetraessigsäure, Diethylentriaminpentaessigsäure, Nitrilotriessigsäure, Iminodiessigsäure, N-Hydroxyethyl ethylendiamintriessigsäure, Alkyliminodicarbonsäuren und von entsprechenden Phosphonsäuren. Geeignete als Bleichmittel sind weiterhin Persulfate und Peroxide, z.B. Wasserstoffperoxid.Usually the material is bleached and fixed immediately after color development. For example, Fe (III) salts and Fe (III) complex salts such as ferricyanides, dichromates, water-soluble cobalt complexes can be used as bleaching agents. Iron (III) complexes of aminopolycarboxylic acids, in particular, for example, ethylenediaminetetraacetic acid, propylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, iminodiacetic acid, N-hydroxyethyl are particularly preferred ethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids. Persulphates and peroxides, for example hydrogen peroxide, are also suitable as bleaching agents.
Auf das Bleichfixierbad oder Fixierbad folgt meist eine Wässerung, die als Gegenstromwässerung ausgeführt ist oder aus mehreren Tanks mit eigener Wasserzufuhr besteht.The bleach-fixing bath or fixing bath is usually followed by washing, which is designed as countercurrent washing or consists of several tanks with their own water supply.
Günstige Ergebnisse können bei Verwendung eines darauf folgenden Schlußbades, das keinen oder nur wenig Formaldehyd enthält, erhalten werden.Favorable results can be obtained using a subsequent final bath which contains little or no formaldehyde.
Die Wässerung kann aber durch ein Stabilisierbad vollständig ersetzt werden, das üblicherweise im Gegenstrom geführt wird. Dieses Stabilisierbad übernimmt bei Formaldehydzusatz auch die Funktion eines Schlußbades.However, the washing can be completely replaced by a stabilizing bath, which is usually carried out in countercurrent. When formaldehyde is added, this stabilizing bath also functions as a final bath.
Bei Farbumkehrmaterialien erfolgt zunächst eine Entwicklung mit einem Schwarz-Weiß-Entwickler, dessen Oxidationsprodukt nicht zur Reaktion mit den Farbkupplern befähigt ist. Es schließt sich eine diffuse Zweitbelichtung und dann Entwicklung mit einem Farbentwickler, Bleichen und Fixieren an.In the case of color reversal materials, development is initially carried out using a black and white developer whose oxidation product is not capable of reacting with the color couplers. This is followed by a diffuse second exposure and then development with a color developer, bleaching and fixing.
Für die Beispiele wurden die folgenden alkalisch geäscherten Knochengelatinen verwendet.
Mit Gelatine 1 wurde nach dem double-jet-Verfahren bei 56°C eine Silberbromidchloridemulsion mit 10 Mol-% Silberchlorid hergestellt. Am Ende der Silberhalogenidfällung betrug das GeSi 0,15. Die Emulsion wurde durch Zugabe eines Flockmittels und Erniedrigung des pH-Wertes auf 3,5 geflockt und anschließend gewaschen. Danach wurde der pH-Wert wieder auf 4,5 eingestellt, weitere Gelatine 1 zugesetzt, und die Emulsion unter Erwärmen redispergiert. Nach der Redispergierung betrug das GeSi 0,65. Die Emulsion wurde anschließend unter Zusatz von Thiosulfat zur optimalen Empfindlichkeit gereift (Emulsion A).With
Nach dem gleichen Verfahren wurde eine weitere Emulsion mit Gelatine 2 bei Fällung und Redispergierung hergestellt (Emulsion B).Another emulsion with gelatin 2 was prepared by precipitation and redispersion using the same process (emulsion B).
Nach dem gleichen Verfahren wurde eine weitere Emulsion mit Gelatine 2 bei der Fällung und Gelatine 1 bei der Redispergierung hergestellt (Emulsion C).Another emulsion with gelatin 2 during precipitation and
Die Korngrößenverteilungen wurden mit dem Möllerzähler bestimmt (G. Möller Int. Congr. Phot. Sci. Moscow 1970, p.125).The grain size distributions were determined with the Möller counter (G. Möller Int. Congr. Phot. Sci. Moscow 1970 , p.125).
Die Emulsionen wurden pro 100 g AgNO₃ 180 mg eines Blausensibilisators und 120 g eines Gelbkupplers versehen und auf eine PE-beschichtete Papierunterlage vergossen. Über die Emulsionsschicht wurde eine Gelatineschicht mit einem Härtungsmittel gezogen. Die Schichten wurden nach dem Trocknen in einem Sensitometer belichtet und nach dem EP 2-Prozeß entwickelt.The emulsions were provided per 100 g AgNO₃ 180 mg of a blue sensitizer and 120 g of a yellow coupler and poured onto a PE-coated paper base. One was placed over the emulsion layer Gelatin layer pulled with a hardener. After drying, the layers were exposed in a sensitometer and developed using the EP 2 process.
Die Bestimmung des latenten Bildes erfolgte 6 Stunden nach der Belichtung, wobei der belichtete Streifen bei Raumtemperatur gelagert wurde.The latent image was determined 6 hours after the exposure, the exposed strip being stored at room temperature.
Die direkt entwickelten und die nach 6-stündiger Lagerung entwickelten Materialien wurden miteinander verglichen und ergaben E Latentbild [log I.t].
Die Kornverteilungen sind in Fig. 1 (Emulsion A), Fig. 2 (B) und Fig. 3 (C) dargestellt.The grain distributions are shown in Fig. 1 (Emulsion A), Fig. 2 (B) and Fig. 3 (C).
Die Beispiele zeigen, daß die Verwendung von oxidierter Gelatine im Ansatz eine verbesserte Kornverteilung, d.h. sehr monodisperse Emulsionen, ergibt. Bei der Verwendung von oxidierter Gelatine in der Nachreifung ergibt sich jedoch ein höherer Schleier. Außerdem ist der Rückgang des latenten Bildes merklich stärker. Wird dagegen die nicht oxidierte Gelatine in der Nachreifung verwendet, wird ein besserer Schleier und ein stabileres latentes Bild bei unverändert guter Kornverteilung erhalten.The examples show that the use of oxidized gelatin in the batch has an improved grain distribution, i.e. very monodisperse emulsions. When using oxidized gelatin in the post-ripening, however, there is a higher haze. In addition, the decline in the latent picture is noticeably stronger. If, on the other hand, the non-oxidized gelatin is used in the post-ripening, a better haze and a more stable latent image with an unchanged good grain distribution are obtained.
Beispiel 1 wurde wiederholt mit Gelatine 3 anstelle von Gelatine 1 und Gelatine 4 anstelle von Gelatine 2. Die Silberchloridbromidemulsion enthielt 95 Mol-% Silberchlorid, die Reifung zur optimalen Empfindlichkeit erfolgte unter Zusatz von Goldsalzen und Thiosulfat. Alle anderen Parameter blieben unverändert. Es resultierten die Emulsionen D (nur Gelatine 3), E (nur Gelatine 4) und F (Gelatine 4 bei der Fällung, Gelatine 3 bei der Redispergierung).Example 1 was repeated with gelatin 3 instead of
Die Emulsionen wurden wie in Beispiel 1 beschrieben mit einem Blausensibilisator und einem Gelbkuppler versehen und dann auf einen PE-beschichteten Papierträger vergossen. Über der Emulsion wird eine Gelatineschicht mit einem Härtungsmittel angebracht.As described in Example 1, the emulsions were provided with a blue sensitizer and a yellow coupler and then poured onto a PE-coated paper backing. A layer of gelatin with a hardening agent is applied over the emulsion.
Die Emulsionen wurden wie in Beispiel 1 geprüft.
Es zeigt sich auch, daß mit dieser entsalzten, inerten Knochengelatine durch die Oxidation zwar ein verbessertes Kornwachstum, aber ein höherer Schleier entsteht. Bei Verwendung der oxidierten Gelatine nur bei der Fällung und Verwendung der nicht oxidierten Gelatine in der Nachreifung wird ein gutes Kornwachstum bei gutem Schleier und guter Latentbildstabilität erreicht.It is also shown that with this desalted, inert bone gelatin the oxidation does improve grain growth, but creates a higher haze. If the oxidized gelatin is used only when the unoxidized gelatin is precipitated and used after-ripening, good grain growth is achieved with good fog and good latent image stability.
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Application Number | Priority Date | Filing Date | Title |
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DE3828312A DE3828312A1 (en) | 1988-08-20 | 1988-08-20 | PRODUCTION OF A SILVER HALOGENID EMULSION |
DE3828312 | 1988-08-20 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0355568A2 true EP0355568A2 (en) | 1990-02-28 |
EP0355568A3 EP0355568A3 (en) | 1991-01-23 |
EP0355568B1 EP0355568B1 (en) | 1995-01-11 |
Family
ID=6361251
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89114620A Expired - Lifetime EP0355568B1 (en) | 1988-08-20 | 1989-08-08 | Preparation of a silver halide emulsion |
Country Status (4)
Country | Link |
---|---|
US (1) | US4992362A (en) |
EP (1) | EP0355568B1 (en) |
JP (1) | JPH02111940A (en) |
DE (2) | DE3828312A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5412075A (en) * | 1992-03-11 | 1995-05-02 | Eastman Kodak Company | Control of methionine content in photographic grade gelatin |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2614929A (en) * | 1947-08-13 | 1952-10-21 | Eastman Kodak Co | Method of preparing photographic emulsions |
EP0228256A2 (en) * | 1985-12-19 | 1987-07-08 | EASTMAN KODAK COMPANY (a New Jersey corporation) | A process for precipitating a tabular grain emulsion in the presence of a gelatino-peptizer and an emulsion produced thereby |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE231430C (en) * | ||||
US3888676A (en) * | 1973-08-27 | 1975-06-10 | Du Pont | Silver halide films with wide exposure latitude and low gradient |
US4131467A (en) * | 1977-11-23 | 1978-12-26 | E. I. Du Pont De Nemours And Company | 4,7-Dihydroxybenzimidazole hydrobromide as antifogger |
US4496652A (en) * | 1978-12-26 | 1985-01-29 | E. I. Du Pont De Nemours And Company | Silver halide crystals with two surface types |
CA1284051C (en) * | 1985-12-19 | 1991-05-14 | Joe E. Maskasky | Chloride containing emulsion and a process for emulsion preparation |
-
1988
- 1988-08-20 DE DE3828312A patent/DE3828312A1/en not_active Withdrawn
-
1989
- 1989-08-04 US US07/389,544 patent/US4992362A/en not_active Expired - Fee Related
- 1989-08-08 EP EP89114620A patent/EP0355568B1/en not_active Expired - Lifetime
- 1989-08-08 DE DE58908871T patent/DE58908871D1/en not_active Expired - Fee Related
- 1989-08-18 JP JP1211565A patent/JPH02111940A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2614929A (en) * | 1947-08-13 | 1952-10-21 | Eastman Kodak Co | Method of preparing photographic emulsions |
EP0228256A2 (en) * | 1985-12-19 | 1987-07-08 | EASTMAN KODAK COMPANY (a New Jersey corporation) | A process for precipitating a tabular grain emulsion in the presence of a gelatino-peptizer and an emulsion produced thereby |
Non-Patent Citations (2)
Title |
---|
CHEMICAL ABSTRACTS, vol. 91, no. 26, 24 Dezember 1979 Columbus, Ohio, USA W.Wojciak et al.: "Evaluation of criteria use for quantitative characterization of the protective properties of lyophilic colloids" Seite 378; rechte Spalte; ref. no. 217326Z * |
JOURNAL OF PHOTOGRAPHIC SCIENCE. vol. 37, no. 1, Januar 1989, LONDON GB Seiten 19 - 22; F.J.Moll, K.Wagner: "Determination of Cysteine/Cystine in Gelatin" * |
Also Published As
Publication number | Publication date |
---|---|
DE3828312A1 (en) | 1990-03-01 |
US4992362A (en) | 1991-02-12 |
EP0355568A3 (en) | 1991-01-23 |
DE58908871D1 (en) | 1995-02-23 |
JPH02111940A (en) | 1990-04-24 |
EP0355568B1 (en) | 1995-01-11 |
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