EP0563638A1 - Photographic recording material - Google Patents
Photographic recording material Download PDFInfo
- Publication number
- EP0563638A1 EP0563638A1 EP93103858A EP93103858A EP0563638A1 EP 0563638 A1 EP0563638 A1 EP 0563638A1 EP 93103858 A EP93103858 A EP 93103858A EP 93103858 A EP93103858 A EP 93103858A EP 0563638 A1 EP0563638 A1 EP 0563638A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkyl
- aryl
- color
- layer
- alkoxy
- 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
- 239000000463 material Substances 0.000 title claims description 19
- -1 R<2> is -OH Chemical group 0.000 claims abstract description 56
- 150000001875 compounds Chemical class 0.000 claims abstract description 47
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 30
- 125000003118 aryl group Chemical group 0.000 claims abstract description 29
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 19
- 238000011161 development Methods 0.000 claims abstract description 15
- GZTPJDLYPMPRDF-UHFFFAOYSA-N pyrrolo[3,2-c]pyrazole Chemical compound N1=NC2=CC=NC2=C1 GZTPJDLYPMPRDF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 125000004442 acylamino group Chemical group 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 229910006069 SO3H Inorganic materials 0.000 claims abstract description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 5
- 125000000547 substituted alkyl group Chemical group 0.000 claims abstract description 5
- 125000001054 5 membered carbocyclic group Chemical group 0.000 claims abstract description 3
- 125000004008 6 membered carbocyclic group Chemical group 0.000 claims abstract description 3
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 239000000839 emulsion Substances 0.000 claims description 43
- 229910052709 silver Inorganic materials 0.000 claims description 36
- 239000004332 silver Substances 0.000 claims description 36
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 7
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims description 5
- 125000004391 aryl sulfonyl group Chemical group 0.000 claims description 5
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 4
- 125000004414 alkyl thio group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000005110 aryl thio group Chemical group 0.000 claims description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 3
- 239000000975 dye Substances 0.000 abstract description 25
- 239000004611 light stabiliser Substances 0.000 abstract description 9
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 99
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 42
- 229920000159 gelatin Polymers 0.000 description 31
- 235000019322 gelatine Nutrition 0.000 description 31
- 108010010803 Gelatin Proteins 0.000 description 27
- 239000008273 gelatin Substances 0.000 description 27
- 235000011852 gelatine desserts Nutrition 0.000 description 27
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 22
- 230000003595 spectral effect Effects 0.000 description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 11
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 8
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 7
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000011241 protective layer Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- 239000001828 Gelatine Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 3
- QVLXDGDLLZYJAM-UHFFFAOYSA-N 2,5-dioctylbenzene-1,4-diol Chemical compound CCCCCCCCC1=CC(O)=C(CCCCCCCC)C=C1O QVLXDGDLLZYJAM-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000005840 aryl radicals Chemical class 0.000 description 3
- 238000004061 bleaching Methods 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- QWDQYHPOSSHSAW-UHFFFAOYSA-N 1-isocyanatooctadecane Chemical compound CCCCCCCCCCCCCCCCCCN=C=O QWDQYHPOSSHSAW-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- ZEUDGVUWMXAXEF-UHFFFAOYSA-L bromo(chloro)silver Chemical compound Cl[Ag]Br ZEUDGVUWMXAXEF-UHFFFAOYSA-L 0.000 description 2
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000008569 process Effects 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
- 150000003839 salts Chemical class 0.000 description 2
- 230000001235 sensitizing effect Effects 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- FTNJQNQLEGKTGD-UHFFFAOYSA-N 1,3-benzodioxole Chemical class C1=CC=C2OCOC2=C1 FTNJQNQLEGKTGD-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N 1,4-Benzenediol Natural products OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 1
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- LTIKIBFTASQKMM-UHFFFAOYSA-N 1-[bis(4-isocyanatophenyl)methyl]-4-isocyanatobenzene Chemical compound C1=CC(N=C=O)=CC=C1C(C=1C=CC(=CC=1)N=C=O)C1=CC=C(N=C=O)C=C1 LTIKIBFTASQKMM-UHFFFAOYSA-N 0.000 description 1
- HHIRBXHEYVDUAM-UHFFFAOYSA-N 1-chloro-3-isocyanatobenzene Chemical compound ClC1=CC=CC(N=C=O)=C1 HHIRBXHEYVDUAM-UHFFFAOYSA-N 0.000 description 1
- PTSIWTZNEIAHHQ-UHFFFAOYSA-N 1-isocyanato-2,4-bis[(4-isocyanatophenyl)methyl]benzene Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C(CC=2C=CC(=CC=2)N=C=O)=C1 PTSIWTZNEIAHHQ-UHFFFAOYSA-N 0.000 description 1
- YIDSTEJLDQMWBR-UHFFFAOYSA-N 1-isocyanatododecane Chemical compound CCCCCCCCCCCCN=C=O YIDSTEJLDQMWBR-UHFFFAOYSA-N 0.000 description 1
- GFLXBRUGMACJLQ-UHFFFAOYSA-N 1-isocyanatohexadecane Chemical compound CCCCCCCCCCCCCCCCN=C=O GFLXBRUGMACJLQ-UHFFFAOYSA-N 0.000 description 1
- DYQFCTCUULUMTQ-UHFFFAOYSA-N 1-isocyanatooctane Chemical compound CCCCCCCCN=C=O DYQFCTCUULUMTQ-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
- QTLHLXYADXCVCF-UHFFFAOYSA-N 2-(4-amino-n-ethyl-3-methylanilino)ethanol Chemical compound OCCN(CC)C1=CC=C(N)C(C)=C1 QTLHLXYADXCVCF-UHFFFAOYSA-N 0.000 description 1
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 description 1
- ZMXYNJXDULEQCK-UHFFFAOYSA-N 2-amino-p-cresol Chemical compound CC1=CC=C(O)C(N)=C1 ZMXYNJXDULEQCK-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-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
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 101100493713 Caenorhabditis elegans bath-45 gene Proteins 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 229920001174 Diethylhydroxylamine Polymers 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- VHXACVCTXWUSGG-UHFFFAOYSA-N [2-[(3-isocyanato-4-methylphenyl)carbamoyloxy]-2-[(3-isocyanato-4-methylphenyl)carbamoyloxymethyl]butyl] n-(3-isocyanato-4-methylphenyl)carbamate Chemical compound C=1C=C(C)C(N=C=O)=CC=1NC(=O)OCC(OC(=O)NC=1C=C(C(C)=CC=1)N=C=O)(CC)COC(=O)NC1=CC=C(C)C(N=C=O)=C1 VHXACVCTXWUSGG-UHFFFAOYSA-N 0.000 description 1
- DCSCINQIKHMFEN-UHFFFAOYSA-N [3-(6-isocyanatohexanoyloxy)-2,2-bis(6-isocyanatohexanoyloxymethyl)propyl] 6-isocyanatohexanoate Chemical compound O=C=NCCCCCC(=O)OCC(COC(=O)CCCCCN=C=O)(COC(=O)CCCCCN=C=O)COC(=O)CCCCCN=C=O DCSCINQIKHMFEN-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- UMEAURNTRYCPNR-UHFFFAOYSA-N azane;iron(2+) Chemical compound N.[Fe+2] UMEAURNTRYCPNR-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- OIPQUBBCOVJSNS-UHFFFAOYSA-L bromo(iodo)silver Chemical compound Br[Ag]I OIPQUBBCOVJSNS-UHFFFAOYSA-L 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000298 carbocyanine Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- GZCJJOLJSBCUNR-UHFFFAOYSA-N chroman-6-ol Chemical class O1CCCC2=CC(O)=CC=C21 GZCJJOLJSBCUNR-UHFFFAOYSA-N 0.000 description 1
- 150000001843 chromanes Chemical class 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 108700039708 galantide Proteins 0.000 description 1
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical class OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000000687 hydroquinonyl group Chemical group C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 125000002887 hydroxy group Chemical class [H]O* 0.000 description 1
- VGYYSIDKAKXZEE-UHFFFAOYSA-L hydroxylammonium sulfate Chemical compound O[NH3+].O[NH3+].[O-]S([O-])(=O)=O VGYYSIDKAKXZEE-UHFFFAOYSA-L 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- CLJDCQWROXMJAZ-UHFFFAOYSA-N n-[2-(4-amino-n-ethyl-3-methylanilino)ethyl]methanesulfonamide;sulfuric acid Chemical compound OS(O)(=O)=O.CS(=O)(=O)NCCN(CC)C1=CC=C(N)C(C)=C1 CLJDCQWROXMJAZ-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001308 pyruvoyl group Chemical group O=C([*])C(=O)C([H])([H])[H] 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- AQRYNYUOKMNDDV-UHFFFAOYSA-M silver behenate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O AQRYNYUOKMNDDV-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-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
- 239000002356 single layer Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- RYEZERQIMITWHD-UHFFFAOYSA-K trisodium;5,6-dihydroxybenzene-1,2,4-trisulfonate Chemical compound [Na+].[Na+].[Na+].OC1=C(O)C(S([O-])(=O)=O)=C(S([O-])(=O)=O)C=C1S([O-])(=O)=O RYEZERQIMITWHD-UHFFFAOYSA-K 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/392—Additives
- G03C7/39208—Organic compounds
- G03C7/39232—Organic compounds with an oxygen-containing function
-
- 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
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/3003—Materials characterised by the use of combinations of photographic compounds known as such, or by a particular location in the photographic element
- G03C7/3005—Combinations of couplers and photographic additives
- G03C7/3008—Combinations of couplers having the coupling site in rings of cyclic compounds and photographic additives
- G03C7/301—Combinations of couplers having the coupling site in pyrazoloazole rings and photographic additives
Definitions
- the invention relates to a photographic recording material having at least one silver halide emulsion layer, which contains novel light stabilizers for the purple azomethine dyes of the pyrazoloazole type produced in the chromogenic development.
- magenta dyes produced from pyrazoloazole couplers bleach particularly strongly, while the cyan dyes produced from phenolic couplers proved to be particularly unaffected in this regard.
- Suitable light-stabilizing agents are essentially phenolic compounds, in particular derivatives of hydroquinone, which are either added to the couplers or linked to the coupler molecules in the form of substituents (DE-B-1 547 803, DE-A-26 17 826, DE-A -29 52 511, JP-N 53 070 822, JP-N 54 070 830, JP-N 54 073 032).
- substituents DE-B-1 547 803, DE-A-26 17 826, DE-A -29 52 511, JP-N 53 070 822, JP-N 54 070 830, JP-N 54 073 032).
- the known light stabilizers do not yet meet the requirements placed on them in every respect.
- the invention is based on the object of specifying novel light stabilizers for photographic recording materials, in particular those which are suitable for improving the light stability of the magenta colored image dyes produced from magenta couplers of the pyrazoloazole type.
- a radical which can be split off under alkaline conditions and is represented by R 1 is, for example, an acyl radical which is derived from aliphatic or aromatic carboxylic acids;
- Examples of radicals which can be eliminated under alkaline conditions are acetyl, dichloroacetyl, alkoxycarbonyl and pyruvoyl.
- An alkyl radical represented by R2 to R6 preferably contains 1 to 4 carbon atoms; Examples are methyl, ethyl, propyl, isopropyl, butyl, t-butyl.
- An aryl radical represented by R2 to R6 contains 6 to 10 C atoms; Examples are phenyl and naphthyl.
- the alkyl or aryl radicals can be further substituted, for example with halogen or alkyl.
- An alkoxy radical represented by R2 to R6 can contain 1 to 18 carbon atoms.
- the acyl radical in an acylamino radical represented by R2 to R6 is derived from aliphatic or aromatic carboxylic or sulfonic acids.
- An alkyl, cycloalkyl or aryl radical represented by R8 can be substituted one or more times, for example with a group of the formula wherein R1 to R7, A and n have the meanings already given.
- Suitable isocyanates for the preparation of compounds of the formula I are all aromatic and aliphatic isocyanates having 1 to 4 isocyanate groups, such as 3-chlorophenyl isocyanate, phenyl isocyanate, 1,3-phenylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-diphenyl methane diisocyanate, the isomers of tolylene diisocyanate, optionally a mixture, 2,4-bis (4-isocyanatobenzyl) -1-isocyanato-benzene, tris (4-isocyanatophenyl) methane, 2-ethyl-1,2,3-tris- (3- isocyanato-4-methyl-anilinocarbonyloxy) propane, tetrakis (5-isocyanatopentylcarbonyloxy-methyl) -methane, preferably the aliphatic mono- and diisocyanates such as dodecy
- the compounds S-2 to S-14 are prepared in an analogous manner from the corresponding compounds of the formula II and isocyanates.
- the color photographic recording material according to the invention contains at least one light-sensitive silver halide emulsion layer and preferably a sequence of several such light-sensitive silver halide emulsion layers and optionally further auxiliary layers such as, in particular, protective layers and non-light-sensitive binder layers arranged between the light-sensitive layers, according to the present invention at least one of the light-sensitive silver halide emulsion layers present in combination with a compound according to the invention is associated with a magenta coupler of the pyrazoloazole coupler type.
- the compounds of the invention act primarily as light stabilizers, i.e.
- the azomethine dyes formed from the color coupler in the chromogenic development have a considerably increased stability against the action of light in the presence of the compounds according to the invention.
- some of the compounds according to the invention also take on the function of an oil former for the color coupler, i.e. they can be used together with other known oil formers as coupler solvents.
- the compounds according to the invention preferably make up 10 to 60% by weight of the total amount of oil former in the respective layer. The fact that further oil formers may only be required in a smaller amount has a favorable effect on the layer loading and / or the total layer thickness of the recording materials according to the invention.
- the compounds according to the invention are usually obtained in the preparation (reaction of the compounds containing active hydrogen atoms with isocyanates) as low-melting solids and are used as a solution in aprotic (hydrophobic) solvents, for example ethyl acetate, when incorporated into the casting solution for the layer in question, if appropriate together with the respective color coupler.
- aprotic (hydrophobic) solvents for example ethyl acetate
- the silver halide present as a light-sensitive component in the photographic recording material according to the invention can contain chloride, bromide or iodide or mixtures thereof as the halide.
- the halide content of at least one layer can consist 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 with a high chloride content are used up to pure silver chloride emulsions.
- It can be predominantly compact crystals, e.g. are regular 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, e.g. 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, are different.
- the average grain size of the emulsions is preferably between 0.2 ⁇ m and 2.0 ⁇ m, the grain size distribution can be both homo- and heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ⁇ 30%.
- the emulsions can also contain other silver salts, for example organic silver salts, such as silver benzotriazolate or silver behenate.
- Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
- the emulsions can be chemically and or spectrally sensitized in the usual way; they can also be stabilized by suitable additives. Suitable chemical sensitizers, spectral sensitizing dyes and stabilizers are described, for example, in Research Disclosure 17643 (December 1978); Reference is made in particular to chapters III, IV and VI.
- the color photographic recording material according to the invention preferably contains, in addition to the combination of pyrazoloazole coupler and compound of the formula I, which is normally green-sensitized, silver halide emulsion layer containing further silver halide emulsion layers for recording light of the other spectral ranges red and blue.
- the light-sensitive layers are spectrally sensitized in a known manner by means of suitable sensitizing dyes.
- Suitable green sensitizers are, for example, 9-ethyl carbocyanines with benzoxazole, naphthoxasol or a benzoxazole and a benzthiazole as basic end groups, and also benzimidazocarbocyanines, which may also be further substituted and must likewise contain at least one sulfoalkyl group on the heterocyclic nitrogen.
- Color photographic recording materials according to the invention usually contain, in spatial and spectral assignment to the silver halide emulsion layers of different spectral sensitivity, color couplers for producing the different partial color images cyan, magenta and yellow, the compounds according to the invention, together with the respective color coupler, preferably being assigned to a green-sensitive silver halide emulsion layer.
- Color coupler is in such a spatial relationship to the silver halide emulsion layer that an interaction between them is possible, which is an image-like correspondence between the silver image formed during development and the image allows the color coupler generated color image. This is usually achieved by the fact that the color coupler is contained in the silver halide emulsion layer itself or in a possibly non-light-sensitive binder layer adjacent to it.
- Spectral assignment is understood to mean that the spectral sensitivity of each of the light-sensitive silver halide emulsion layers and the color of the partial color image generated from the spatially assigned color coupler are in a specific relationship to one another, with each of the spectral sensitivities (red, green, blue) having a different color of the relevant partial color image (in general, for example, the colors cyan, purple or yellow in this order).
- the recording material according to the invention may contain further couplers in the layer in question, in particular magenta couplers, which do not have to belong to the pyrazoloazole class.
- These further 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 inherent color, that of color coupling disappears or is replaced by the color of the image dye produced (mask coupler), but also the white couplers which, when reacted with color developer oxidation products, essentially give colorless products.
- the 2-equivalent couplers also include those couplers that contain a cleavable residue in the coupling site, which is released upon reaction with color developer oxidation products and thereby either directly or after one or more further groups have been cleaved from the primarily cleaved residue (e.g. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic activity unfolds, 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.
- the couplers used in particular the pyrazoloazole-type magenta couplers used according to the invention, for example of the formulas IV and V, can also be in polymeric form, e.g. are used as polymer latex.
- 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.
- the color couplers used can also be those which provide dyes with poor or restricted mobility.
- Weak or restricted mobility means mobility that is dimensioned such that the contours of the discrete dye spots formed in the chromogenic development run and are smeared into one another.
- This degree of mobility is to be distinguished on the one hand from the usual case of complete immobility in photographic layers, which is sought in conventional photographic recording materials for the color couplers or the dyes produced therefrom, in order to achieve the highest possible sharpness, and on the other hand from the case of complete mobility of the dyes, which is sought for example in color diffusion processes.
- the last-mentioned dyes usually have at least one group that make them soluble in the alkaline medium.
- the extent of the weak mobility sought according to the invention can be controlled by varying substituents, for example the solubility in the organic medium of the oil former or to influence the affinity for the binder matrix in a targeted manner.
- the color photographic recording material of the present invention can contain further additives, for example antioxidants, dye-stabilizing agents and agents for influencing the mechanical and electrostatic properties and UV absorbers.
- additional compounds are advantageously combined with the compounds according to the invention, i.e. used in the same binder layer or in adjacent binder layers.
- Additives to improve dye, coupler and whiteness stability and to reduce the color fog can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromanes, spiroindanes , p-alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, sterically hindered amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.
- R -c8H17-t
- R1 -CH3
- R -C8H17
- R1 -C3H7-i
- R1 -C4H9-t
- R1 -C5H11-t
- 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. Connections of different structures are usually used for the two tasks.
- Examples are aryl-substituted benzotriazole compounds (US-A-3 533 794), 4-thiazolidone compounds (USA-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).
- the color photographic recording material according to the invention which contains a color coupler and a compound of the formula I associated with at least one silver halide emulsion layer, is developed with a color developer compound.
- All developer compounds which have the ability in the form of their oxidation product to react with color couplers to form azomethine 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-methylsulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl-3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.
- N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methylsulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-eth
- the material is usually bleached and fixed. Bleaching and fixing can be carried out separately or together.
- the usual compounds can be used as bleaching agents, for example Fe3+ salts and Fe3+ complex salts such as ferricyanides, dichromates, water-soluble Cobalt complexes, etc.
- Particularly preferred are iron III complexes of aminopolycarboxylic acids, in particular, for example, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids.
- Persulphates are also suitable as bleaching agents.
- Samples 2 to 12 were prepared in the same way as sample 1, with the difference that the tricresyl phosphate used in sample 1 was replaced in sample 2 (also compare samples 6-9) and that a light stabilizer was additionally used in samples 3-12 , namely in samples 3-11 a compound of formula I (according to the invention) and in sample 12 the comparison compound of formula: Samples 1-12 contained either tricresyl phosphate or dibutyl phthalate as oil formers (see Table 1).
- the samples obtained were then exposed behind a graduated gray wedge.
- the materials were then processed in the following manner using the processing baths listed below: Development: 210 s, 33 ° C Bleaching: 50 s, 20 ° C Fix: 60 s, 20 ° C Water: 120 s, 20 ° Dry.
- the example shows that high maximum color densities are achieved by the compounds according to the invention and at the same time the light stability of the image dye is improved.
- the compound VP-1 used as a comparison according to GB 2 135 788 brings about a minor improvement in the light stability.
- a layer structure is produced as described in Example 1, with the difference that the magenta coupler M-14 is used instead of the magenta coupler M-5 in the green-sensitive layer.
- Sample 13 (comparison) is obtained in this way.
- Samples 14-18 are prepared in the same manner as sample 13, with the difference that layer 3 in sample 13 has been added to one of the compounds according to the invention. In the same manner, sample 19 is prepared using comparative compound VP-1. Processing and testing are carried out as described in Example 1.
- the example shows that the light stability of the image dyes is improved by using the compounds according to the invention.
- the compound VP-1 used as a comparison according to GB 2 135 788 brings about a lower improvement in light stability.
- a color photographic recording material suitable for a rapid processing process was produced by applying the following layers in the order given to a support made of paper coated on both sides with polyethylene.
- the quantities given relate to 1 m2.
- the corresponding amounts of AgNO3 are given.
- Samples 21 to 27 were produced in the same way as sample 20, with the difference that the fourth layer (sensitive to green) is a light stabilizer according to the invention of the formula I (samples 21 to 25) or the comparative compounds VP-1 and VP-2 (samples 26 or 27) were added.
- the samples obtained were processed behind a graduated gray wedge and then with the processing baths listed below as follows:
- the example shows a clear improvement in the light stability of the image dyes by the compounds according to the invention in contrast to the compounds VP-1 and VP-2 used as a comparison.
- a color photographic recording material suitable for reversal processing was produced by applying the following layers in the order given to a transparent cellulose triacetate support provided with an adhesive layer.
- the quantities given relate to 1 m2.
- the corresponding amounts of AgNO3 are given.
- Samples 29-33 are prepared in the same way as sample 28, with the difference that the 6th and 7th layers (green-sensitive layers) are a compound of the formula I according to the invention (samples 29-32) and the compound VP- 2 (sample 33) is added.
- the maximum color density was then measured (Tab. 4) and the samples were exposed to the light of a xenon lamp standardized for daylight and exposed to 7.2 x 106 lx ⁇ h; the percentage decrease in density was then measured.
- the example shows that the compounds according to the invention improve the light stability of the image dyes.
- the connection VP-2 set as a comparison results in less improvement.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
Description
Die Erfindung betrifft ein fotografisches Aufzeichnungsmaterial mit mindestens einer Silberhalogenidemulsionsschicht, das neuartige Lichtschutzmittel für die bei der chromogenen Entwicklung erzeugten purpurfarbenen Azomethinfarbstoffe von Pyrazoloazol-Typ enthält.The invention relates to a photographic recording material having at least one silver halide emulsion layer, which contains novel light stabilizers for the purple azomethine dyes of the pyrazoloazole type produced in the chromogenic development.
Es ist bekannt, farbige fotografische Bilder durch chromogene Entwicklung herzustellen, d.h. dadurch, daß man bildmäßig belichtete Silberhalogenidemulsionsschichten in Gegenwart geeigneter Farbkuppler mittels geeigneter farbbildender Entwicklersubstanzen - sogenannter Farbentwickler - entwickelt, wobei das in Übereinstimmung mit dem Silberbild entstehende Oxidationsprodukt der Entwicklersubstanzen mit dem Farbkuppler unter Bildung eines Farbstoffbildes reagiert. Als Farbentwickler werden gewohnlich aromatische, primäre Aminogruppen enthaltende Verbindungen, insbesondere solche vom p-Phenylendiamintyp, verwendet.It is known to produce colored photographic images by chromogenic development, that is to say by developing imagewise exposed silver halide emulsion layers in the presence of suitable color couplers by means of suitable color-forming developer substances - so-called color developers - the oxidation product of the developer substances with the color coupler which is formed in accordance with the silver image being formed of a dye image reacts. Aromatic compounds containing primary amino groups, in particular those of the p-phenylenediamine type, are usually used as color developers.
Es ist auch bekannt, daß die durch chromogene Entwicklung erzeugten Bildfarbstoffe in unterschiedlichem Ausmaß unter dem Einfluß der Umweltbedingungen gewisse Veränderungen erleiden. Besonders auffällig ist dies, was die Einwirkung von Licht betrifft. Bekanntlich bleichen hierbei die aus Pyrazoloazolkupplern erzeugten Magentafarbstoffe besonders stark aus, während sich die aus phenolischen Kupplern erzeugte Blaugrünfarbstoffe in dieser Hinsicht als besonders wenig anfällig erwiesen.It is also known that the image dyes produced by chromogenic development undergo certain changes to varying degrees under the influence of environmental conditions. This is particularly noticeable when it comes to the effects of light. As is known, the magenta dyes produced from pyrazoloazole couplers bleach particularly strongly, while the cyan dyes produced from phenolic couplers proved to be particularly unaffected in this regard.
Es hat nicht an Versuchen gefehlt, diesem Mangel durch besondere Maßnahmen abzuhelfen. Namentlich im Fall der Magentakuppler ist es gelungen, durch lichtstabilisierende Zusätze oder besondere Ausgestaltung der Kuppler zu verbesserter Lichtbeständigkeit zu gelangen. Als lichtstabilisierende Mittel eignen sich im wesentlichen phenolische Verbindungen, insbesondere Derivate des Hydrochinons, die entweder den Kupplern beigemischt oder in Form von Substituenten mit den Kupplermolekülen verknüpft werden (DE-B-1 547 803, DE-A-26 17 826, DE-A-29 52 511, JP-N 53 070 822, JP-N 54 070 830, JP-N 54 073 032). Die bekannten Lichtschutzmittel genügen jedoch noch nicht in jeder Hinsicht den an sie gestellten Anforderungen.There has been no shortage of attempts to remedy this deficiency through special measures. In the case of the magenta couplers in particular, it has been possible to achieve improved light resistance through light stabilizing additives or special design of the couplers. Suitable light-stabilizing agents are essentially phenolic compounds, in particular derivatives of hydroquinone, which are either added to the couplers or linked to the coupler molecules in the form of substituents (DE-B-1 547 803, DE-A-26 17 826, DE-A -29 52 511, JP-N 53 070 822, JP-N 54 070 830, JP-N 54 073 032). However, the known light stabilizers do not yet meet the requirements placed on them in every respect.
Der Erfindung liegt die Aufgabe zugrunde, für fotografische Aufzeichnungsmaterialien neuartige Lichtschutzmittel anzugeben, insbesondere solche, die für die Verbesserung der Lichtstabilität der aus Magentakupplern, vom Typ der Pyrazoloazole erzeugten purpurfarbigen Bildfarbstoffe geeignet sind.The invention is based on the object of specifying novel light stabilizers for photographic recording materials, in particular those which are suitable for improving the light stability of the magenta colored image dyes produced from magenta couplers of the pyrazoloazole type.
Gegenstand der Erfindung ist ein farbfotografisches Aufzeichnungsmaterial mit mindestens einer Silberhalogenidemulsionsschicht und einem dieser zugeordneten Farbkuppler, dadurch gekennzeichnet, daß es in einer Silberhalogenidemulsionsschicht oder in einer hierzu benachbarten nicht lichtempfindlichen Bindemittelschicht eine Kombination aus einem Pyrazoloazolkuppler und einer Verbindung der allgemeinen Formel I enthält:
worin bedeuten
- R¹
- H, einen unter alkalischen Bedingungen abspaltbaren Rest, Alkyl oder Aryl;
- R²
- -OH, Alkyl, Aryl, Alkoxy oder
- R³, R⁴, R⁵ und R⁶
- H, -OH, -COOH, -SO₃H, -SO₂H, Alkyl, Aryl, Alkoxy, Alkylsulfonyl, Arylsulfonyl, gegebenenfalls z.B. durch Alkyl und/oder Aryl substituiertes Sulfamoyl, Acylamino oder
wobei mindestens einer der Reste R², R³, R⁴, R⁵ und R⁶ ein Rest der Formel
ist,
- A
- Alkylen mit 1-6 C-Atomen;
- n
- O oder 1;
- R⁷
- H oder gegebenenfalls beispielsweise mit -COOH oder -SO₃H substituiertes Alkyl, z.B. Carboxymethyl;
- R⁸
- gegebenenfalls substituiertes Alkyl, Cycloalkyl, oder Aryl mit 4 bis 20 C-Atomen, insbesondere 10 bis 18 C-Atomen;
- R¹ und R³
- können einen 5- oder 6-gliedrigen Ring bilden, wobei R² = -OH oder Alkoxy;
- R² und R⁴
- können einen 5- oder 6-gliedrigen carbocyclischen Ring bilden.
in what mean
- R¹
- H, a radical which can be split off under alkaline conditions, alkyl or aryl;
- R²
- -OH, alkyl, aryl, alkoxy or
- R³, R⁴, R⁵ and R⁶
- H, -OH, -COOH, -SO₃H, -SO₂H, alkyl, aryl, alkoxy, alkylsulfonyl, arylsulfonyl, optionally substituted, for example, by alkyl and / or aryl Sulfamoyl, acylamino or
wherein at least one of the radicals R², R³, R⁴, R⁵ and R⁶ is a radical of the formula
is
- A
- Alkylene with 1-6 C atoms;
- n
- O or 1;
- R⁷
- H or optionally alkyl, for example substituted with -COOH or -SO₃H, for example carboxymethyl;
- R⁸
- optionally substituted alkyl, cycloalkyl or aryl with 4 to 20 C atoms, in particular 10 to 18 C atoms;
- R¹ and R³
- can form a 5- or 6-membered ring, wherein R² = -OH or alkoxy;
- R² and R⁴
- can form a 5- or 6-membered carbocyclic ring.
Ein durch R¹ dargestellter unter alkalischen Bedingungen abspaltbarer Rest ist beispielsweise ein Acylrest, der sich ableitet von aliphatischen oder aromatischen Carbonsäuren; Beispiele für unter alkalischen Bedingungen abspaltbare Reste sind Acetyl, Dichloracetyl, Alkoxycarbonyl, Pyruvoyl.A radical which can be split off under alkaline conditions and is represented by R 1 is, for example, an acyl radical which is derived from aliphatic or aromatic carboxylic acids; Examples of radicals which can be eliminated under alkaline conditions are acetyl, dichloroacetyl, alkoxycarbonyl and pyruvoyl.
Ein durch R² bis R⁶ dargestellter Alkylrest enthält vorzugsweise 1 bis 4 C-Atome; Beispiele sind Methyl, Ethyl, Propyl, Isopropyl, Butyl, t-Butyl. Ein durch R² bis R⁶ dargestellter Arylrest enthält 6 bis 10 C-Atome; Beispiele sind Phenyl und Naphthyl. Die Alkyl- bzw. Arylreste können weiter substituiert sein, z.B. mit Halogen oder Alkyl. Ein durch R² bis R⁶ dargestellter Alkoxyrest kann 1 bis 18 C-Atome enthalten. Der Acylrest in einem durch R² bis R⁶ dargestellten Acylaminorest leitet sich ab von aliphatischen oder aromatischen Carbon- oder Sulfonsäuren. Ein durch R⁸ dargestellter Alkyl-, Cycloalkyl- oder Arylrest kann ein- oder mehrfach substituiert sein, z.B. mit einer Gruppe der Formel
worin R¹ bis R⁷, A und n die bereits angegebenen Bedeutungen haben.An alkyl radical represented by R² to R⁶ preferably contains 1 to 4 carbon atoms; Examples are methyl, ethyl, propyl, isopropyl, butyl, t-butyl. An aryl radical represented by R² to R⁶ contains 6 to 10 C atoms; Examples are phenyl and naphthyl. The alkyl or aryl radicals can be further substituted, for example with halogen or alkyl. An alkoxy radical represented by R² to R⁶ can contain 1 to 18 carbon atoms. The acyl radical in an acylamino radical represented by R² to R⁶ is derived from aliphatic or aromatic carboxylic or sulfonic acids. An alkyl, cycloalkyl or aryl radical represented by R⁸ can be substituted one or more times, for example with a group of the formula
wherein R¹ to R⁷, A and n have the meanings already given.
Beispiele für erfindungsgemäße Stabilisierungsmittel sind im folgenden angegeben.
Die Herstellung der erfindungsgemäßen Verbindungen kann auf einfache Weise durch Umsetzung von Aminen der Formel II mit monomeren Mono-, Di- oder Polyisocyanaten erfolgen.
In Formel II haben R¹, A und n die bei Formel I angegebene Bedeutung;
- R2'
- steht für -OH, Alkyl, Aryl, Alkoxy oder -(A)n-NH₂;
- R3', R4', R5' und R6'
- stehen für H, -OH, -COOH, -SO₃H, -SO₂H, Alkyl, Aryl, Alkoxy, Alkylsulfonyl, Arylsulfonyl, gegebenenfalls durch Alkyl und/oder Aryl substituiertes Sulfamoyl, Acylamino oder -A)n-NH₂,
The compounds according to the invention can be prepared in a simple manner by reacting amines of the formula II with monomeric mono-, di- or polyisocyanates.
In formula II, R 1, A and n have the meaning given for formula I;
- R 2 '
- represents -OH, alkyl, aryl, alkoxy or - (A) n -NH₂;
- R 3 ' , R 4' , R 5 ' and R 6'
- stand for H, -OH, -COOH, -SO₃H, -SO₂H, alkyl, aryl, alkoxy, alkylsulfonyl, arylsulfonyl, sulfamoyl, acylamino or -A) n -NH₂, optionally substituted by alkyl and / or aryl,
Als Isocyanate zur Herstellung von Verbindungen der Formel I eignen sich alle aromatischen und aliphatischen Isocyanate mit 1 bis 4 Isocyanatgruppen wie z.B. 3-Chlorphenylisocyanat, Phenylisocyanat, 1,3-Phenylendiisocyanat, 1,5-Naphthylendiisocyanat, 4,4'-Diphenylmethandiisocyanat, die Isomere des Toluylendiisocyanat, gegebenenfalls eine Mischung, 2,4-Bis-(4-isocyanatobenzyl)-1-isocyanato-benzol, Tris-(4-isocyanatophenyl)-methan, 2-Ethyl-1,2,3-tris-(3-isocyanato-4-methyl-anilinocarbonyloxy)-propan, Tetrakis-(5-isocyanatopentylcarbonyloxy-methyl)-methan, vorzugsweise die aliphatischen Mono- und Diisocyanate wie Dodecylisocyanat, Cyclohexylisocyanat, Stearylisocyanat, Octylisocyanat, Hexadecylisocyanat, Hexan-1,6-diisocyanat, Dicyclohexylmethandiisocyanat, Cyclohexan-1,4-diisocyanat, Isophorondiisocyanat.Suitable isocyanates for the preparation of compounds of the formula I are all aromatic and aliphatic isocyanates having 1 to 4 isocyanate groups, such as 3-chlorophenyl isocyanate, phenyl isocyanate, 1,3-phenylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-diphenyl methane diisocyanate, the isomers of tolylene diisocyanate, optionally a mixture, 2,4-bis (4-isocyanatobenzyl) -1-isocyanato-benzene, tris (4-isocyanatophenyl) methane, 2-ethyl-1,2,3-tris- (3- isocyanato-4-methyl-anilinocarbonyloxy) propane, tetrakis (5-isocyanatopentylcarbonyloxy-methyl) -methane, preferably the aliphatic mono- and diisocyanates such as dodecyl isocyanate, cyclohexyl isocyanate, stearyl isocyanate, octyl isocyanate, hexadecyl isocyanate, hexane-1,6-diisocyanate, diisocyanate , Cyclohexane-1,4-diisocyanate, isophorone diisocyanate.
Eine Lösung von 67,7 g 2-Hydroxy-5-methylanilin in 1000 ml Aceton wird bei 20°C langsam mit einer Lösung von 147,5 g Stearylisocyanat in 500 ml Aceton versetzt. Nach 6-stündigem Rühren destilliert man das Aceton am Rotationsverdampfer ab und löst den Rückstand in Essigester. Die organische Phase wird gründlich mit 10%iger Salzsäure gewaschen und über Na₂SO₄ getrocknet. Abdestillieren des Essigesters liefert 199 g S-1. Die Ausbeute beträgt 98 %.A solution of 67.7 g of 2-hydroxy-5-methylaniline in 1000 ml of acetone is slowly mixed with a solution of 147.5 g of stearyl isocyanate in 500 ml of acetone at 20 ° C. After stirring for 6 hours, the acetone is distilled off on a rotary evaporator and the residue is dissolved in ethyl acetate. The organic phase is washed thoroughly with 10% hydrochloric acid and dried over Na₂SO₄. Distilling off the ethyl acetate gives 199 g of S-1. The yield is 98%.
Die Verbindungen S-2 bis S-14 werden in analoger Weise aus den entsprechenden Verbindungen der Formel II und Isocyanaten hergestellt.The compounds S-2 to S-14 are prepared in an analogous manner from the corresponding compounds of the formula II and isocyanates.
Das erfindungsgemäße farbfotografische Aufzeichnungsmaterial enthält mindestens eine lichtempfindliche Silberhalogenidemulsionsschicht und vorzugsweise eine Abfolge mehrerer solcher lichtempfindlichen Silberhalogenidemulsionsschichten und gegebenenfalls weitere Hilfsschichten wie insbesondere Schutzschichten und zwischen den lichtempfindlichen Schichten angeordnete nicht lichtempfindliche Bindemittelschichten, wobei nach vorliegender Erfindung mindestens einer der vorhandenen lichtempfindlichen Silberhalogenidemulsionsschichten eine erfindungsgemäße Verbindung in Kombination mit einem Magentakuppler vom Typ der Pyrazoloazolkuppler, zugeordnet ist.The color photographic recording material according to the invention contains at least one light-sensitive silver halide emulsion layer and preferably a sequence of several such light-sensitive silver halide emulsion layers and optionally further auxiliary layers such as, in particular, protective layers and non-light-sensitive binder layers arranged between the light-sensitive layers, according to the present invention at least one of the light-sensitive silver halide emulsion layers present in combination with a compound according to the invention is associated with a magenta coupler of the pyrazoloazole coupler type.
Die erfindungsgemäßen Verbindungen wirken dabei in erster Linie als Lichtstabilisierungsmittel, d.h. die aus dem Farbkuppler bei der chromogenen Entwicklung gebildeten Azomethinfarbstoffe weisen in Gegenwart der erfindungsgemäßen Verbindungen eine beträchtlich erhöhte Stabilität gegenüber der Einwirkung von Licht auf. Daneben übernehmen die erfindungsgemäßen Verbindungen teilweise auch die Funktion eines Ölbildners für den Farbkuppler, d.h. sie können zusammen mit anderen bekannten Ölbildnern als Kupplerlösungsmittel verwendet werden. Dabei machen die erfindungsgemäßen Verbindungen vorzugsweise 10 bis 60 Gew.-% der gesamten Ölbildnermenge in der jeweiligen Schicht aus. Der Umstand, daß weitere Ölbildner gegebenenfalls nur in geringerer Menge erforderlich sind, wirkt sich günstig auf die Schichtbelastung und/oder die Gesamtschichtdicke der erfindungsgemäßen Aufzeichnungsmaterialien aus.The compounds of the invention act primarily as light stabilizers, i.e. The azomethine dyes formed from the color coupler in the chromogenic development have a considerably increased stability against the action of light in the presence of the compounds according to the invention. In addition, some of the compounds according to the invention also take on the function of an oil former for the color coupler, i.e. they can be used together with other known oil formers as coupler solvents. The compounds according to the invention preferably make up 10 to 60% by weight of the total amount of oil former in the respective layer. The fact that further oil formers may only be required in a smaller amount has a favorable effect on the layer loading and / or the total layer thickness of the recording materials according to the invention.
Die erfindungsgemäßen Verbindungen fallen bei der Herstellung (Umsetzung der aktive Wasserstoffatome enthaltenden Verbindungen mit Isocyanaten) meist als niedrigschmelzende Feststoffe an und werden als Lösung in aprotischen (hydrophoben) Lösungsmitteln, z.B. Ethylacetat, bei der Einarbeitung in die Gießlösung für die betreffende Schicht, gegebenenfalls zusammen mit dem jeweiligen Farbkuppler, eingesetzt. Die Einarbeitung erfolgt in der üblichen Weise, wobei gegebenenfalls weitere Hilfslösungsmittel und/oder hochsiedende Kupplerlösungsmittel, sogenannte Ölbildner, verwendet werden können.The compounds according to the invention are usually obtained in the preparation (reaction of the compounds containing active hydrogen atoms with isocyanates) as low-melting solids and are used as a solution in aprotic (hydrophobic) solvents, for example ethyl acetate, when incorporated into the casting solution for the layer in question, if appropriate together with the respective color coupler. The incorporation takes place in the usual manner, it being possible, if appropriate, to use further auxiliary solvents and / or high-boiling coupler solvents, so-called oil formers.
Das als lichtempfindlicher Bestandteil in dem erfindungsgemäßen fotografischen Aufzeichnungsmaterial 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.The silver halide present as a light-sensitive component in the photographic recording material according to the invention can contain chloride, bromide or iodide or mixtures thereof as the halide. For example, the halide content of at least one layer can consist of 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% of bromide.
Im Falle von Farbnegativ- und Farbumkehrfilmen werden üblicherweise Silberbromidiodidemulsionen, im Falle von Farbnegativ-und Farbumkehrpapier üblicherweise Silberchloridbromidemulsionen mit hohem Chloridanteil bis zu reinen Silberchloridemulsionen 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.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 with a high chloride content are used up to pure silver chloride emulsions. It can be predominantly compact crystals, e.g. are regular 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, e.g. 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 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 andere Silbersalze, z.B. organische Silbersalze enthalten, wie etwa 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, are different. The average grain size of the emulsions is preferably between 0.2 μm and 2.0 μm, the grain size distribution can be both homo- and heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ± 30%. In addition to the silver halide, the emulsions can also contain other silver salts, for example organic silver salts, such as 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 Emulsionen können in der üblichen Weise chemisch und oder spektral sensibilisiert sein; sie können auch durch geeignete Zusätze stabilisiert sein. Geeignete chemische Sensibilisatoren, spektrale Sensibilisierungsfarbstoffe und Stabilisatoren sind beispielsweise in Research Disclosure 17643 (Dezember 1978) beschrieben; verwiesen wird insbesondere auf die Kapitel III, IV und VI.The emulsions can be chemically and or spectrally sensitized in the usual way; they can also be stabilized by suitable additives. Suitable chemical sensitizers, spectral sensitizing dyes and stabilizers are described, for example, in Research Disclosure 17643 (December 1978); Reference is made in particular to chapters III, IV and VI.
Das erfindungsgemäße farbfotografische Aufzeichnungsmaterial enthält bevorzugt außer der die erfindungsgemäße Kombination aus Pyrazoloazolkuppler und Verbindung der Formel I enthaltenden, im Normalfall grünsensibilisierten Silberhalogenidemulsionsschicht weitere Silberhalogenidemulsionsschichten für die Aufzeichnung von Licht der anderen Spektralbereiche Rot und Blau. Zu diesem Zweck sind die lichtempfindlichen Schichten in bekannter Weise durch geeignete Sensibilisierungsfarbstoffe spektral sensibilisiert.The color photographic recording material according to the invention preferably contains, in addition to the combination of pyrazoloazole coupler and compound of the formula I, which is normally green-sensitized, silver halide emulsion layer containing further silver halide emulsion layers for recording light of the other spectral ranges red and blue. To this For this purpose, the light-sensitive layers are spectrally sensitized in a known manner by means of suitable sensitizing dyes.
Eine Übersicht über die als Spektralsensibilisatoren geeigneten Polymethinfarbstoffe, deren geeignete Kombinationen und supersensibilisierend wirkenden Kombinationen enthalt Research Disclosure 17643 (Dez. 1978),Kapitel IV.Research Disclosure 17643 (Dec. 1978), Chapter IV, provides an overview of the polymethine dyes suitable as spectral sensitizers, their suitable combinations and combinations having a super-sensitizing effect.
Als Grünsensibilisatoren sind beispielsweise geeignet 9-Ethylcarbocyanine mit Benzoxazol, Naphthoxasol 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.Suitable green sensitizers are, for example, 9-ethyl carbocyanines with benzoxazole, naphthoxasol or a benzoxazole and a benzthiazole as basic end groups, and also benzimidazocarbocyanines, which may also be further substituted and must likewise contain at least one sulfoalkyl group on the heterocyclic nitrogen.
Als Beispiele seien, insbesondere für Negativ- und Umkehrfilm, die nachfolgend aufgeführen Grünsensibilisatoren GS genannt, die jeweils einzeln oder in Kombination miteinander eingesetzt werden können, z.B. GS-1 und GS-2.
- GS-1:
- R¹, R³, R⁷, R⁹ = H; R² = Phenyl;
R⁴ =
R⁸ = Cl; m = 2; n = 3; x, Y = O; - GS-2:
- R¹, R², R⁷, R⁸ = Cl; R³, R⁵, R⁶, R⁹ = H;
R⁴ =
- GS-3:
- R¹, R⁷ = H; R², R³ sowie R⁸, R⁹ zusammen -CH=CH-CH=CH-; R⁴ = SO₃⊖Na⊕; R⁵ = C₂H₅; R⁶ = SO₃⊖; m, n = 3; X, Y = O;
- GS-4:
- R¹, R³, R⁴, R⁷, R⁸, R⁹ = H; R² = -OCH₃; R⁵ = -C₂H₅;
R⁶ = SO₃⊖; m = 2; n = 4; X = O; Y = S;
- GS-1:
- R¹, R³, R⁷, R⁹ = H; R² = phenyl;
R⁴ =
R⁸ = Cl; m = 2; n = 3; x, Y = O; - GS-2:
- R¹, R², R⁷, R⁸ = Cl; R³, R⁵, R⁶, R⁹ = H;
R⁴ = - GS-3:
- R¹, R⁷ = H; R², R³ and R⁸, R⁹ together -CH = CH-CH = CH-; R⁴ = SO₃ ⊖ Na ⊕ ; R⁵ = C₂H₅; R⁶ = SO₃ ⊖ ; m, n = 3; X, Y = O;
- GS-4:
- R¹, R³, R⁴, R⁷, R⁸, R⁹ = H; R² = -OCH₃; R⁵ = -C₂H₅;
R⁶ = SO₃ ⊖ ; m = 2; n = 4; X = O; Y = S;
Erfindungsgemäße farbfotografische Aufzeichnungsmaterialien enthalten üblicherweise in räumlicher und spektraler Zuordnung zu den Silberhalogenidemulsionsschichten unterschiedlicher Spektralempfindlichkeit Farbkuppler zur Erzeugung der unterschiedlichen Teilfarbenbilder Cyan, Magenta und Gelb, wobei die erfindungsgemäßen Verbindungen zusammen mit dem jeweiligen Farbkuppler bevorzugt einer grünempfindlichen Silberhalogenidemulsionsschicht zugeordnet sind.Color photographic recording materials according to the invention usually contain, in spatial and spectral assignment to the silver halide emulsion layers of different spectral sensitivity, color couplers for producing the different partial color images cyan, magenta and yellow, the compounds according to the invention, together with the respective color coupler, preferably being assigned to a green-sensitive silver halide emulsion layer.
Unter räumlicher Zuordnung ist dabei zu verstehen, daß der Farbkuppler sich in einer solchen räumlichen Beziehung zu der Silberhalogenidemulsionsschicht befindet, daß eine Wechselwirkung zwischen ihnen möglich ist, die eine bildgemäße Übereinstimmung zwischen dem bei der Entwicklung gebildeten Silberbild und dem aus dem Farbkuppler erzeugten Farbbild zuläßt. Dies wird in der Regel dadurch erreicht, daß der Farbkuppler in der Silberhalogenidemulsionsschicht selbst enthalten ist oder in einer hierzu benachbarten gegebenenfalls nichtlichtempfindlichen Bindemittelschicht.Spatial assignment is to be understood to mean that the color coupler is in such a spatial relationship to the silver halide emulsion layer that an interaction between them is possible, which is an image-like correspondence between the silver image formed during development and the image allows the color coupler generated color image. This is usually achieved by the fact that the color coupler is contained in the silver halide emulsion layer itself or in a possibly non-light-sensitive binder layer adjacent to it.
Unter spektraler Zuordnung ist zu verstehen, daß die Spektralempfindlichkeit jeder der lichtempfindlichen Silberhalogenidemulsionsschichten und die Farbe des aus dem jeweils räumlich zugeordneten Farbkuppler erzeugten Teilfarbenbildes in einer bestimmten Beziehung zueinander stehen, wobei jeder der Spektralempfindlichkeiten (Rot, Grün, Blau) eine andere Farbe des betreffenden Teilfarbenbildes (im allgemeinen z.B. die Farben Cyan, Purpur bzw. Gelb in dieser Reihenfolge) zugeordnet ist.Spectral assignment is understood to mean that the spectral sensitivity of each of the light-sensitive silver halide emulsion layers and the color of the partial color image generated from the spatially assigned color coupler are in a specific relationship to one another, with each of the spectral sensitivities (red, green, blue) having a different color of the relevant partial color image (in general, for example, the colors cyan, purple or yellow in this order).
Jeder der unterschiedlich spektral sensibilisierten Silberhalogenidemulsionsschichten kann ein oder können auch mehrere Farbkupper zugeordnet sein. Wenn mehrere Silberhalogenidemulsionsschichten gleicher Spektralempfindlichkeit vorhanden sind, kann jeder von ihnen einen Farbkuppler enthalten, wobei diese Farbkuppler nicht notwendigerweise identisch zu sein brauchen. Sie sollen lediglich bei der Farbentwicklung wenigstens anähernd die gleiche Farbe ergeben, normalerweise eine Farbe, die komplementär ist zu der Farbe des Lichtes, für das die betreffenden Silberhalogenidemulsionsschichten überwiegend empfindlich sind. Die erfindungsgemäß verwendeten Farbkuppler zur Erzeugung des Teilfarbenbildes Magenta sind Kuppler vom Typ der Pyrazoloazole; geeignete Beispiele hierfür sind:
- M-1:
- R¹ =
- M-2:
- R¹ =
- M-3:
- R¹ =
- M-4:
- R¹ =
- M-5:
- R¹ =
- M-6:
- R¹ =
- M-7:
- R¹ =
- M-8:
- R¹ =
- M-9:
- R¹ =
- M-10:
- R¹ =
- M-11:
- R¹ =
- M-12:
- R¹ = -C₃H₇-i R² =
- M-13:
Pyrazoloazolkuppler der allgemeinen Formeln IV und V
sind beispielsweise in US-A-3 725 067 und US-A-4 540 654 beschrieben. In den Formeln IV und V bedeuten:
- X
- H oder eine unter den Bedingungen der Farbentwicklung freisetzbare Gruppe;
- R¹, R², H,
- Alkyl, Aralkyl, Aryl, Alkoxy, Aroxy, Alkylthio, Arylthio, Amino, Anilino, Acylamino, Cyano, Alkoxycarbonyl, Carbamoyl, Sulfamoyl, wobei diese Reste weiter substituiert sein können.
- M-1:
- R¹ =
- M-2:
- R¹ =
- M-3:
- R¹ =
- M-4:
- R¹ =
- M-5:
- R¹ =
- M-6:
- R¹ =
- M-7:
- R¹ =
- M-8:
- R¹ =
- M-9:
- R¹ =
- M-10:
- R¹ =
- M-11:
- R¹ =
- M-12:
- R¹ = -C₃H₇-i R² =
- M-13:
Pyrazoloazole couplers of the general formulas IV and V
are described, for example, in US-A-3,725,067 and US-A-4,540,654. In formulas IV and V:
- X
- H or a group releasable under the conditions of color development;
- R¹, R², H,
- Alkyl, aralkyl, aryl, alkoxy, aroxy, alkylthio, arylthio, amino, anilino, acylamino, cyano, alkoxycarbonyl, carbamoyl, sulfamoyl, where these radicals can be further substituted.
Außer der erfindungsgemäß verwendeten Kombination aus Pyrazoloazolkuppler und Verbindung der Formel I kann das erfindungsgemäße Aufzeichnungsmaterial in der betreffenden Schicht weitere Kuppler enthalten, insbesondere Magentakuppler, die nicht der Klasse der Pyrazoloazole angehören müssen.In addition to the combination of pyrazoloazole coupler and compound of the formula I used according to the invention, the recording material according to the invention may contain further couplers in the layer in question, in particular magenta couplers, which do not have to belong to the pyrazoloazole class.
Bei diesen weiteren Kupplern 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, wie auch solche, die eine intensive Eigenfarbe aufweisen, die bei der Farbkupplung verschwindet bzw. durch die Farbe des erzeugten Bildfarbstoffes ersetzt wird (Maskenkuppler), aber auch 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.These further 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 inherent color, that of color coupling disappears or is replaced by the color of the image dye produced (mask coupler), but also the white couplers which, when reacted with color developer oxidation products, essentially give colorless products. The 2-equivalent couplers also include those couplers that contain a cleavable residue in the coupling site, which is released upon reaction with color developer oxidation products and thereby either directly or after one or more further groups have been cleaved from the primarily cleaved residue ( e.g. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic activity unfolds, 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.
Die verwendeten Kuppler, insbesondere die erfindungsgemäß verwendeten Magentakuppler vom Typ der Pyrazoloazole, beispielsweise der Formeln IV und V, können auch in polymerer Form, z.B. als Polymerisatlatex zur Anwendung gelangen.The couplers used, in particular the pyrazoloazole-type magenta couplers used according to the invention, for example of the formulas IV and V, can also be in polymeric form, e.g. are used as polymer latex.
Hochmolekulare Farbkuppler sind beispielsweise beschrieben 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.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.
Die hochmolekularen Farbkuppler werden in der Regel durch Polymerisation von ethylenisch ungesättigten monomeren Farbkupplern hergestellt.The high molecular weight color couplers are usually produced by polymerizing ethylenically unsaturated monomeric color couplers.
Die verwendeten Farbkuppler können auch solche sein, die Farbstoffe mit einer schwachen bzw. eingeschränkten Beweglichkeit liefern.The color couplers used can also be those which provide dyes with poor or restricted mobility.
Unter einer schwachen bzw. eingeschränkten Beweglichkeit ist eine Beweglichkeit zu verstehen, die so bemessen ist, daß die Konturen der bei der chromogenen Entwicklung gebildeten diskreten Farbstoffflecken verlaufen und ineinander verschmiert werden. Dieses Ausmaß der Beweglichkeit ist einerseits zu unterscheiden von dem üblichen Fall der völligen Unbeweglichkeit in fotografischen Schichten, der in herkömmlichen fotografischen Aufzeichnungsmaterialien für die Farbkuppler bzw. die daraus hergestellten Farbstoffe angestrebt wird, um eine möglichst hohe Schärfe zu erzielen, und andererseits von dem Fall der völligen Beweglichkeit der Farbstoffe, der beispielsweise bei Farbdiffusionsverfahren angestrebt wird. Die letztgegenannten Farbstoffe verfügen meist über mindestens eine Gruppe, die sie im alkalischen Medium löslich machen. Das Ausmaß der erfindungsgemäß angestrebten schwachen Beweglichkeit kann gesteuert werden durch Variation von Substituenten, um beispielsweise die Löslichkeit im organischen Medium des Ölbildners oder die Affinität zur Bindemittelmatrix in gezielter Weise zu beeinflussen.Weak or restricted mobility means mobility that is dimensioned such that the contours of the discrete dye spots formed in the chromogenic development run and are smeared into one another. This degree of mobility is to be distinguished on the one hand from the usual case of complete immobility in photographic layers, which is sought in conventional photographic recording materials for the color couplers or the dyes produced therefrom, in order to achieve the highest possible sharpness, and on the other hand from the case of complete mobility of the dyes, which is sought for example in color diffusion processes. The last-mentioned dyes usually have at least one group that make them soluble in the alkaline medium. The extent of the weak mobility sought according to the invention can be controlled by varying substituents, for example the solubility in the organic medium of the oil former or to influence the affinity for the binder matrix in a targeted manner.
Über die genannten Bestandteile hinaus kann das farbfotografische Aufzeichnungsmaterial der vorliegenden Erfindung weitere Zusätze enthalten, wie zum Beispiel Antioxidantien, farbstoffstabilisierende Mittel und Mittel zur Beeinflussung der mechanischen und elektrostatischen Eigenschaften sowie UV-Absorber. Vorteilhaft werden solche zusätzlichen Verbindungen kombiniert mit den erfindungsgemäßen Verbindungen, d.h. in derselben Bindungsmittelschicht oder in zueinander benachbarten Bindemittelschichten verwendet.In addition to the constituents mentioned, the color photographic recording material of the present invention can contain further additives, for example antioxidants, dye-stabilizing agents and agents for influencing the mechanical and electrostatic properties and UV absorbers. Such additional compounds are advantageously combined with the compounds according to the invention, i.e. used in the same binder layer or in adjacent binder layers.
Zusätze zur Verbesserung der Farbstoff-, Kuppler- und Weißenstabilität sowie zur Verringerung des Farbschleiers (Research Disclosure 17 643 (Dez. 1978), Kapitel VII) können den folgenden chemischen Stoffklassen 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 Hydroxylgruppen, Metallkomplexe.Additives to improve dye, coupler and whiteness stability and to reduce the color fog (Research Disclosure 17 643 (Dec. 1978), Chapter VII) can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromanes, 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 von gelben Farbbildern als Folge der Entwicklung von Wärme, Feuchtigkeit und Licht. Um die Beeinträchtigung von purpurroten Farbbildern, insbesondere ihre Beeinträchtigung als Folge der Einwirkung von Licht, zu verhindern, sind Spiroindane (JP-A-159 644/81) und Chromane, die durch Hydrochinondiether oder -monoether substituiert sind (JP-A-89 835/80) besonders wirksam.Compounds that have both a hindered amine partial structure and a hindered phenol partial structure in one molecule (US-A-4,268,593) are particularly effective in preventing the deterioration of yellow color images due to the development of heat, moisture and light. To the To prevent deterioration of magenta color images, especially their impairment as a result of exposure to light, are spiroindanes (JP-A-159 644/81) and chromanes, which are substituted by hydroquinone diethers or monoethers (JP-A-89 835/80 ) particularly effective.
Beispiele besonders geeigneter Verbindungen sind:
R = -c₈H₁₇-t; R¹ = -CH₃ R = -C₈H₁₇ ; R¹ = -C₃H₇-i
R, R¹ = -C₄H₉-t R, R¹ = -C₅H₁₁-t
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 (USA-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).Examples of particularly suitable compounds are:
R = -c₈H₁₇-t; R¹ = -CH₃ R = -C₈H₁₇; R¹ = -C₃H₇-i
R, R¹ = -C₄H₉-t R, R¹ = -C₅H₁₁-t
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. Connections of different structures are usually used for the two tasks. Examples are aryl-substituted benzotriazole compounds (US-A-3 533 794), 4-thiazolidone compounds (USA-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).
Beispiele besonders geeigneter Verbindungen sind
R, R¹ = H; R² = -C₄H₉-t
R = H; R¹, R² = -C₄H₉-t
R = H; R¹, R² = -C₅H₁₁-t
R = H; R¹ = -C₄H₉-s; R² = -C₄H₉-t
R = Cl; R¹ = -C₄H₉-t; R² = -C₄H₉-s
R = Cl; R¹, R² = -C₄H₉-t
R = Cl; R¹ = -C₄H₉-t; R² = -CH₂-CH₂-COOC₈H₁₇
R = H; R = -C₁₂H₂₅-i; R² = -CH₃
R, R¹, R² = -C₄H₉-t
R¹, R² = -C₆H₁₃ ; R³, R⁴ = -CN
R¹, R² = -C₂H₅; R³ =
R⁴ = -CO-OC₈H₁₇
R¹, R² = -C₂H₅; R³ =
R₄ = -COO-C₁₂H₂₅
R¹, R² = -CH₂=CH-CH₂; R³, R⁴ = -CN
R¹, R² = H; R³ = -CN; R⁴ = -CO-NHC₁₂H₂₅
R¹, R² = -CH₃; R³ = -CN; R⁴ = -CO-NHC₁₂H₂₅
Es können auch ultraviolettabsorbierende Kuppler (wie Blaugrünkuppler des α-Naphtholtyps) und ultraviolettabsorbierende Polymere verwendet werden Diele Ultraviolettabsorbentien können durch Beizen in einer speziellen Schicht fixiert sein.Examples of particularly suitable compounds are
R, R1 = H; R² = -C₄H₉-t
R = H; R¹, R² = -C₄H₉-t
R = H; R¹, R² = -C₅H₁₁-t
R = H; R¹ = -C₄H₉-s; R² = -C₄H₉-t
R = Cl; R¹ = -C₄H₉-t; R² = -C₄H₉-s
R = Cl; R¹, R² = -C₄H₉-t
R = Cl; R¹ = -C₄H₉-t; R² = -CH₂-CH₂-COOC₈H₁₇
R = H; R = -C₁₂H₂₅-i; R² = -CH₃
R, R¹, R² = -C₄H₉-t
R¹, R² = -C₆H₁₃; R³, R⁴ = -CN
R¹, R² = -C₂H₅; R³ =
R⁴ = -CO-OC₈H₁₇
R¹, R² = -C₂H₅; R³ =
R₄ = -COO-C₁₂H₂₅
R¹, R² = -CH₂ = CH-CH₂; R³, R⁴ = -CN
R1, R2 = H; R³ = -CN; R⁴ = -CO-NHC₁₂H₂₅
R¹, R² = -CH₃; R³ = -CN; R⁴ = -CO-NHC₁₂H₂₅
Ultraviolet-absorbing couplers (such as cyan couplers of the α-naphthol type) and ultraviolet-absorbing polymers can also be used. Floorboards Ultraviolet absorbents can be fixed in a special layer by pickling.
Zur Herstellung farbfotografischer Bilder wird das erfindungsgemäße farbfotografische Aufzeichnungsmaterial, das zugeordnet zu mindestens einer Silberhalogenidemulsionsschicht einen Farbkuppler und eine Verbindung der Formel I enthält, mit einer Farbentwicklerverbindung entwickelt. Als Farbentwicklerverbindung lassen sich sämtliche Entwicklerverbindungen verwenden, die die Fähigkeit haben in Form ihres Oxidationsproduktes mit Farbkupplern zu Azomethinfarbstoffen 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-methylsulfonamidoethyl)-3-methyl-p-phenylendiamin, 1-(N-ethyl-N-hydroxyethyl-3-methyl-p-phenylendiamin und 1-(N-ethyl-N-methoxyethyl)-3-methyl-p-phenylendiamin.To produce color photographic images, the color photographic recording material according to the invention, which contains a color coupler and a compound of the formula I associated with at least one silver halide emulsion layer, is developed with a color developer compound. All developer compounds which have the ability in the form of their oxidation product to react with color couplers to form azomethine 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-methylsulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl-3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.
Weitere brauchbare Farbentwickler sind beispielsweise beschrieben in J. Amer. Chem. Soc. 73, 3100 (1951) und in G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, Seiten 545 ff.Other useful color developers are described, for example, in J. Amer. Chem. Soc. 73 , 3100 (1951) and in G. Haist, Modern Photographic Processing, 1979, John Wiley and Sons, New York, pages 545 ff.
Nach der Farbentwicklung wird das Material üblicherweise gebleicht und fixiert. Bleichung und Fixierung können getrennt voneinander oder auch zusammen durchgeführt werden. Als Bleichmittel können die üblichen Verbindungen verwendet werden, z.B. Fe³⁺-Salze und Fe³⁺-Komplexsalze wie Ferricyanide, Dichromate, wasserlösliche Kobaltkomplexe usw. Besonders bevorzugt sind Eisen-III-Komplexe von Aminopolycarbonsäuren insbesondere z.B. Ethylendiamintetraessigsäure, N-Hydroxyethylethylendiamintriessigsäure, Alkyliminodicarbonsäuren und von entsprechenden Phosphonsäuren. Geeignet als Bleichmittel sind weiterhin Persulfate.After color development, the material is usually bleached and fixed. Bleaching and fixing can be carried out separately or together. The usual compounds can be used as bleaching agents, for example Fe³⁺ salts and Fe³⁺ complex salts such as ferricyanides, dichromates, water-soluble Cobalt complexes, etc. Particularly preferred are iron III complexes of aminopolycarboxylic acids, in particular, for example, ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, alkyliminodicarboxylic acids and corresponding phosphonic acids. Persulphates are also suitable as bleaching agents.
Ein Schichtträger aus beidseitig mit Polyethylen beschichtetem Papier wurde mit folgenden Schichten versehen. Die Mengenangaben beziehen sich auf 1 m².
- Schicht 1
- Eine Substratschicht aus 200 mg Gelatine mit KNO₃- und Chromalaunzusatz.
- Schicht 2
- Eine Haftschicht aus 320 mg Gelatine.
- Schicht 3
- Eine grünempfindliche Silberbromidchloridemulsionsschicht (20 mol-% Chlorid) aus
530 mg AgNO₃ mit 750 mg Gelatine,
0,61 g Magentakuppler M-5, emulgiert mit
0,61 g Trikresylphosphat (TKP) - Schicht 4
- Eine Schutzschicht aus 1 g Gelatine und 16 mg eines Netzmittels der Formel
C₈F₁₇ SO₃⊖ N(C₂H₅)₄⊕ (NM-1)
Auf diese Schicht trägt man eine Härtungsschicht auf, die pro m² 120 mg Härtungsmittel der Formel
enthält.A layer support made of paper coated on both sides with polyethylene was provided with the following layers. The quantities refer to 1 m².
- Layer 1
- A substrate layer made of 200 mg of gelatin with KNO₃- and Chromalaunzusatz.
- Layer 2
- An adhesive layer made of 320 mg gelatin.
- Layer 3
- A green sensitive silver bromide chloride emulsion layer (20 mol% chloride)
530 mg AgNO₃ with 750 mg gelatin,
0.61 g magenta coupler M-5, emulsified with
0.61 g tricresyl phosphate (CPM) - Layer 4
- A protective layer of 1 g gelatin and 16 mg of a wetting agent of the formula
C₈F₁₇ SO₃ ⊖ N (C₂H₅) ₄ ⊕ (NM-1)
A hardening layer is applied to this layer, 120 mg hardening agent per m² of the formula
contains.
Proben 2 bis 12 wurden in der gleichen Weise wie Probe 1 hergestellt mit dem Unterschied, daß das in Probe 1 verwendete Trikresylphosphat bei Probe 2 (vergleiche auch Proben 6-9) ersetzt wurde und daß bei den Proben 3-12 zusätzlich ein Lichtschutzmittel verwendet wurde, und zwar bei den Proben 3-11 eine Verbindung der Formel I (gemäß der Erfindung) und bei Probe 12 die Vergleichsverbindung der Formel:
Als Ölbildner enthielten die Proben 1-12 entweder Trikresylphosphat oder Dibutylphthalat (s. Tabelle 1).Samples 2 to 12 were prepared in the same way as sample 1, with the difference that the tricresyl phosphate used in sample 1 was replaced in sample 2 (also compare samples 6-9) and that a light stabilizer was additionally used in samples 3-12 , namely in samples 3-11 a compound of formula I (according to the invention) and in sample 12 the comparison compound of formula:
Samples 1-12 contained either tricresyl phosphate or dibutyl phthalate as oil formers (see Table 1).
Die erhaltenen Proben wurden anschließend hinter einem graduierten Graukeil belichtet. Anschließend wurden die Materialien mit den nachfolgend aufgeführten Verarbeitungsbädern in folgender Weise verarbeitet:
Entwickler:
pH = 10,4
Auffüllen mit Wasser aus 1 Liter
pH = 10.4
Fill up with water from 1 liter
Danach wurde die maximale Farbdichte gemessen (Tabelle 1).The maximum color density was then measured (Table 1).
Außerdem wurden die Proben dem Licht einer für Tageslicht normierten Xenonlampe ausgesetzt und mit 4,2 x 106 lx.h belichtet; danach wurde die prozentuale Dichteabnahme gemessen (Tabelle 1).
Das Beispiel zeigt, daß durch die erfindungsgemäßen Verbindungen hohe maximale Farbdichten erzielt werden und gleichzeitig die Lichtstabilität des Bildfarbstoffs verbessert wird, Die als Vergleich eingesetzte Verbindung VP-1 gemäß GB 2 135 788 bewirkt eine geringere Verbesserung der Lichtstabilität.The example shows that high maximum color densities are achieved by the compounds according to the invention and at the same time the light stability of the image dye is improved. The compound VP-1 used as a comparison according to GB 2 135 788 brings about a minor improvement in the light stability.
Es wird wie in Beispiel 1 beschrieben ein Schichtaufbau hergestellt mit dem Unterschied, daß in der grünempfindlichen Schicht anstelle des Magentakupplers M-5 der Magentakuppler M-14 verwendet wird, Man erhält so die Probe 13 (Vergleich).A layer structure is produced as described in Example 1, with the difference that the magenta coupler M-14 is used instead of the magenta coupler M-5 in the green-sensitive layer. Sample 13 (comparison) is obtained in this way.
Die Proben 14-18 werden in der gleichen Weise wie Probe 13 hergestellt mit dem Unterschied, daß die Schicht 3 in Probe 13 eine der erfindungsgemäßen Verbindungen zugesetzt wurde, In gleicher Weise wird Probe 19 unter Verwendung der Vergleichsverbindung VP-1 hergestellt. Die Verarbeitung und Prüfung erfolgt wie in Beispiel 1 beschrieben.
Das Beispiel zeigt, daß durch den Einsatz der erfindungsgemäßen Verbindungen die Lichtstabilität der Bildfarbstoffe verbessert wird. Die als Vergleich eingesezte Verbindung VP-1 gemäß GB 2 135 788 bewirkt eine geringere Verbesserung der Lichtstabilität.The example shows that the light stability of the image dyes is improved by using the compounds according to the invention. The compound VP-1 used as a comparison according to GB 2 135 788 brings about a lower improvement in light stability.
Ein für einen Schnellverarbeitungsprozeß geeignetes farbfotografisches Aufzeichnungsmaterial wurde hergestellt, indem auf einen Schichtträger aus beidseitig mit Polyethylen beschichtetem Papier die folgenden Schichten in der angegebenen Reihenfolge aufgetragen wurden. Die Mengenangaben beziehen sich jeweils auf 1 m². Für den Silberhalogenidauftrag werden die entsprechenden Mengen AgNO₃ angegeben.A color photographic recording material suitable for a rapid processing process was produced by applying the following layers in the order given to a support made of paper coated on both sides with polyethylene. The quantities given relate to 1 m². For the silver halide application, the corresponding amounts of AgNO₃ are given.
- Schicht 1:Layer 1:
-
(Substratschicht)
0,2 g Gelatine(Substrate layer)
0.2 g gelatin - Schicht 2:Layer 2:
-
(blauempfindliche Schicht)
blauempfindliche Silberhalogenidemulsion (99,5 mol-% Chlorid, 0,5 mol-% Bromid, mittlerer Korndurchmesser 0,8 µm) aus 0,63 g
AgNO₃ mit
1,38 g Gelatine
0,95 g Gelbkuppler Y-1
0,2 g Weißkuppler W-1
0,29 g Trikresylphosphat (TKP)(blue sensitive layer)
Blue-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.8 µm) from 0.63 g
AgNO₃ with
1.38 g gelatin
0.95 g yellow coupler Y-1
0.2 g white coupler W-1
0.29 g tricresyl phosphate (CPM) - Schicht 3:Layer 3:
-
(Schutzschicht)
1,1 g Gelatine
0,06 g 2,5-Dioctylhydrochinon
0,06 g Dibutylphthalat (DBP)(Protective layer)
1.1 g gelatin
0.06 g 2,5-dioctylhydroquinone
0.06 g dibutyl phthalate (DBP) - Schicht 4:Layer 4:
-
(grünempfindliche Schicht)
grünsensibilisierte Silberhalogenidemulsion (99,5 mol-% Chlorid, 0,5 mol-% Bromid, mittlerer Korndurchmesser 0,6 µm) aus 0,45 g
AgNO₃ mit
1,08 g Gelatine
0,40 g Magentakuppler M-15
0,16 g α-(3-t-Butyl-4-hydroxyphenoxy)-myristinsäure-ethylester
0,08 g 2,5-Dioctylhydrochinon
0,34 g DBP
0,04 g TKP(green sensitive layer)
Green-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.6 µm) from 0.45 g
AgNO₃ with
1.08 g gelatin
0.40 g magenta coupler M-15
0.16 g of ethyl α- (3-t-butyl-4-hydroxyphenoxy) myristic acid
0.08 g 2,5-dioctyl hydroquinone
0.34 g DBP
0.04 g CPM - Schicht 5:Layer 5:
-
(UV-Schutzschicht)
1,15 g Gelatine
0,6 g UV-Absorber der Formel
0,04 g TKP(UV protective layer)
1.15 g gelatin
0.6 g UV absorber of the formula
0.04 g CPM - Schicht 6:Layer 6:
-
(rotempfindliche Schicht)
rotsensibilisierte Silberhalogenidemulsion (99,5 mol-% Chlorid, 0,5 mol-% Bromid, mittlerer Korndurchmesser 0,5 µm) aus
0,3 g AgNO₃ mit
0,75 g Gelatine
0,36 g Cyankuppler C-1
0,36 g TKP(red sensitive layer)
red-sensitized silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.5 µm)
0.3 g of AgNO₃ with
0.75 g gelatin
0.36 g cyan coupler C-1
0.36 g CPM - Schicht 7:Layer 7:
-
(UV-Schutzschicht)
0,35 g Gelatine
0,15 g UV-Absorber wie in Schicht 5
0,2 g TKP(UV protective layer)
0.35 g gelatin
0.15 g UV absorber as in layer 5
0.2 g CPM - Schicht 8:Layer 8:
-
(Schutzschicht)
0,9 g Gelatine
0,3 g Härtungsmittel Carbamoylpyridiniumsalz (CAS Reg.No. 65411-60-1)(Protective layer)
0.9 g gelatin
0.3 g carbamoyl pyridinium salt hardener (CAS Reg.No. 65411-60-1)
Proben 21 bis 27 wurden in gleicher Weise hergestellt wie Probe 20 mit dem Unterschied, daß der 4. Schicht (grünempfindlich) ein erfindungsgemäßes Lichtschutzmittel der Formel I (Proben 21 bis 25) bzw. die Vergleichsverbindungen VP-1 und VP-2 (Proben 26 bzw. 27) zugesetzt wurden.
Die erhaltenen Proben wurden hinter einem graduierten Graukeil und danach mit den nachfolgend aufgeführten Verarbeitungsbädern wie folgt verarbeitet:Samples 21 to 27 were produced in the same way as sample 20, with the difference that the fourth layer (sensitive to green) is a light stabilizer according to the invention of the formula I (samples 21 to 25) or the comparative compounds VP-1 and VP-2 (samples 26 or 27) were added.
The samples obtained were processed behind a graduated gray wedge and then with the processing baths listed below as follows:
Danach wurde die maximale Farbdichte gemessen (Tabelle 3); die Proben wurden dem Licht eine für Tageslicht normierten Xenonlampe ausgesetzt und mit 9.6 x 10⁶ lx'h belichtet; anschließend wurde die prozentuale Dichteabmahme gemessen.
Das Beispiel zeigt eine deutliche Verbesserung der Lichtstabilität der Bildfarbstoffe durch die erfindungsgemäßen Verbindungen in Gegensatz zu den als Vergleich eingesetzten Verbindungen VP-1 und VP-2.The example shows a clear improvement in the light stability of the image dyes by the compounds according to the invention in contrast to the compounds VP-1 and VP-2 used as a comparison.
Ein für die Umkehrverarbeitung geeignetes farbfotografisches Aufzeichnungsmaterial wurde hergestellt, indem auf einen mit einer Haftschicht versehenen transparenten Schichtträger aus Cellulosetriacetat die folgenden Schichten in der angegebenen Reihenfolge aufgetragen wurden. Die Mengenangaben beziehen sich jeweils auf 1 m². Für den Silberhalogenidauftrag werden die entsprechenden Mengen AgNO₃ angegeben.A color photographic recording material suitable for reversal processing was produced by applying the following layers in the order given to a transparent cellulose triacetate support provided with an adhesive layer. The quantities given relate to 1 m². For the silver halide application, the corresponding amounts of AgNO₃ are given.
- Schicht 1Layer 1
-
(Antihaloschicht)
schwarzes kolloidales Silbersol mit
0,25 g Ag
1,60 g Gelatine
0,24 g UV-Absorber UV-1(Antihalation layer)
black colloidal silver sol with
0.25 g Ag
1.60 g gelatin
0.24 g UV absorber UV-1 - Schicht 2Layer 2
-
(Zwischenschicht)
0,64 g Gelatine(Intermediate layer)
0.64 g gelatin - Schicht 3Layer 3
-
(1. rotempfindliche Schicht)
rotsensibilisierte Silberbromidiodidemulsion
(2,5 mol-% Iodid; mittlerer Korndurchmesser 0,25 µm)
aus 0,60 g AgNO₃, mit
0,59 g Gelatine
0,24 g Cyankuppler C-2
0,12 g TKP(1st red sensitive layer)
red-sensitized silver bromoiodide emulsion
(2.5 mol% iodide; average grain diameter 0.25 µm)
from 0.60 g AgNO₃, with
0.59 g gelatin
0.24 g cyan coupler C-2
0.12 g CPM - Schicht 4Layer 4
-
(2. rotempfindliche Schicht)
rotsensibilisierte Silberbromidiodidemulsion
(3,0 mol-% Iodid; mittlerer Korndurchmesser 0,43 µm)
aus 0,95 g AgNO₃, mit
1,96 g Gelatine
0,95 g Cyankuppler C-2
0,48 g TKP(2nd red sensitive layer)
red-sensitized silver bromoiodide emulsion
(3.0 mol% iodide; average grain diameter 0.43 µm)
from 0.95 g AgNO₃, with
1.96 g gelatin
0.95 g cyan coupler C-2
0.48 g CPM - Schicht 5Layer 5
-
(Zwischenschicht)
1,78 g Gelatine
0,24 g Verbindung SC-1
0,12 g TKP(Intermediate layer)
1.78 g gelatin
0.24 g of compound SC-1
0.12 g CPM - Schicht 6Layer 6
-
(1. grünempfindliche Schicht)
Mischung 3:1 aus
einer Silberbromidiodidemulsion
(1,0 mol-% Iodid; mittlerer Korndurchmesser 0,26 µm)
und einer Silberbromidiodidemulsion
(4,0 mol-% Iodid; mittlerer Korndurchmesser 0,21 µm),
beide grünsensibilisiert,
aus 0,67 g AgNO₃, mit
1,13 g Gelatine
0,14 g Magentakuppler M-16
0,10 g TKP(1st green sensitive layer)
Mix 3: 1
a silver bromoiodide emulsion
(1.0 mol% iodide; average grain diameter 0.26 µm)
and a silver bromoiodide emulsion
(4.0 mol% iodide; average grain diameter 0.21 µm),
both green-sensitized,
from 0.67 g AgNO₃, with
1.13 g gelatin
0.14 g magenta coupler M-16
0.10 g CPM - Schicht 7Layer 7
-
(2. grünempfindliche Schicht)
grünsensibilisierte Silberbromidiodidemulsion
(1,5 mol-% Iodid; mittlerer Korndurchmesser 0,42 µm)
aus 1,05 g AgNO₃, mit
2,72 g Gelatine
0,68 g Magentakuppler M-16
0,45 g TKP(2nd green sensitive layer)
green-sensitized silver bromoiodide emulsion
(1.5 mol% iodide; average grain diameter 0.42 µm)
from 1.05 g AgNO₃, with
2.72 g gelatin
0.68 g M-16 magenta coupler
0.45 g CPM - Schicht 8Layer 8
-
(Zwischenschicht)
0,55 g Gelatine
0,10 g Verbindung SC-1(Intermediate layer)
0.55 g gelatin
0.10 g compound SC-1 - Schicht 9Layer 9
-
(Gelbfilterschicht)
gelbes kolloidales Silbersol mit
0,11 g Ag,
0,45 g Gelatine(Yellow filter layer)
yellow colloidal silver sol with
0.11 g Ag,
0.45 g gelatin - Schicht 10Layer 10
-
(Zwischenschicht)
0,71 g Gelatine(Intermediate layer)
0.71 g gelatin - Schicht 11Layer 11
-
(1. blauempfindliche Schicht)
blausensibilisierte Silberbromidiodidemulsion
(4,0 mol-% Iodid; mittlerer Korndurchmesser 0,28 µm)
aus 0,58 g AgNO₃, mit
1,31 g Gelatine
0,24 g Gelbkuppler Y-2
0,12 g TKP(1st blue sensitive layer)
blue-sensitized silver bromoiodide emulsion
(4.0 mol% iodide; average grain diameter 0.28 µm)
from 0.58 g AgNO₃, with
1.31 g gelatin
0.24 g yellow coupler Y-2
0.12 g CPM - Schicht 12Layer 12
-
(2. blauempfindliche Schicht)
blausensibilisierte Silberbromidiodidemulsion
(3,0 mol-% Iodid; mittlerer Korndurchmesser 0,66 µm)
aus 0,66 g AgNO₃, mit
2,04 g Gelatine
0,83 g Gelbkuppler Y-2
0,41 g TKP(2nd blue sensitive layer)
blue-sensitized silver bromoiodide emulsion
(3.0 mol% iodide; average grain diameter 0.66 µm)
from 0.66 g AgNO₃, with
2.04 g gelatin
0.83 g yellow coupler Y-2
0.41 g CPM - Schicht 13Layer 13
-
(Zwischenschicht)
0,76 g Gelatine
0,54 g Verbindung SC-1
0,50 g UV-Absorber UV-2
0,02 g TKP(Intermediate layer)
0.76 g gelatin
0.54 g compound SC-1
0.50 g UV absorber UV-2
0.02 g CPM - Schicht 14Layer 14
-
(Zwischenschicht)
Mikrat-Silberbromidiodidemulsion
(4,0 mol-% Iodid; mittlerer Korndurchmesser 0,15 µm)
aus 0,20 g AgNO₃, mit
0,57 g Gelatine(Intermediate layer)
Mikrat-silver bromide iodide emulsion
(4.0 mol% iodide; average grain diameter 0.15 µm)
from 0.20 g AgNO₃, with
0.57 g gelatin - Schicht 15Layer 15
-
(Härtungsschicht)
0,25 g Gelatine
0,87 g Härtungsmittel Carbamoylpyridiniumsalz (CAS Reg. No. 65411-60-1)(Hardening layer)
0.25 g gelatin
0.87 g hardening agent carbamoylpyridinium salt (CAS Reg. No. 65411-60-1)
Die Proben 29-33 werden in der gleichen Weise hergestell wie die Probe 28 mit dem Unterschied, daß der 6. und der 7. Schicht (grünempfindliche Schichten) eine erfindungsgemäße Verbindung der Formel I (Proben 29-32) bzw. die Verbindung VP-2 (Probe 33) zugesetzt wird.Samples 29-33 are prepared in the same way as sample 28, with the difference that the 6th and 7th layers (green-sensitive layers) are a compound of the formula I according to the invention (samples 29-32) and the compound VP- 2 (sample 33) is added.
Die auf diese Weise hergestellten Proben wurden unter einem graduierten Graukeil belichtet und einer Colorumkehrentwicklung unterzogen, wie beschrieben in "Manual for PROCESSING Kodak Ektachrome Film using Process E7", Eastman Kodak Company, 1977 (vgl. Kodak Publikation Nr. 7-119).The samples prepared in this manner were exposed under a graduated gray wedge and subjected to color reversal development as described in "Manual for PROCESSING Kodak Ektachrome Film using Process E7", Eastman Kodak Company, 1977 (see Kodak Publication No. 7-119).
Anschließend wurde die maximale Farbdichte gemessen (Tab. 4) und die Proben dem Licht einer für Tageslicht normierten Xenonlampe ausgesetzt und mit 7.2 x 10⁶ lx·h belichtet; danach wurde die prozentuale Dichteabnahme gemessen.
Das Beispiel zeigt, daß die erfindungsgemäßen Verbindungen die Lichtstabilität der Bildfarbstoffe verbessern. Die als Vergleich eigensetzte Verbindung VP-2 bewirkt eine geringere Verbesserung.The example shows that the compounds according to the invention improve the light stability of the image dyes. The connection VP-2 set as a comparison results in less improvement.
Claims (2)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4209346A DE4209346A1 (en) | 1992-03-23 | 1992-03-23 | Photographic recording material |
| DE4209346 | 1992-03-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0563638A1 true EP0563638A1 (en) | 1993-10-06 |
| EP0563638B1 EP0563638B1 (en) | 1998-06-17 |
Family
ID=6454766
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP93103858A Expired - Lifetime EP0563638B1 (en) | 1992-03-23 | 1993-03-10 | Photographic recording material |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5340709A (en) |
| EP (1) | EP0563638B1 (en) |
| JP (1) | JPH0643614A (en) |
| DE (2) | DE4209346A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10111655A1 (en) * | 2001-03-12 | 2002-10-02 | Agfa Gevaert Ag | Inkjet ink |
| JP5892327B2 (en) | 2012-03-15 | 2016-03-23 | Ｊｆｅスチール株式会社 | Method for producing non-oriented electrical steel sheet |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0176845A2 (en) * | 1984-09-27 | 1986-04-09 | Agfa-Gevaert AG | Photographic recording material |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3501722A1 (en) * | 1985-01-19 | 1986-07-24 | Agfa-Gevaert Ag, 5090 Leverkusen | LIGHT SENSITIVE, STABILIZED PHOTOGRAPHIC RECORDING MATERIAL |
| JPH0762759B2 (en) * | 1986-01-22 | 1995-07-05 | コニカ株式会社 | Silver halide photographic light-sensitive material |
| JPH0648372B2 (en) * | 1986-11-13 | 1994-06-22 | 富士写真フイルム株式会社 | Silver halide color photographic light-sensitive material |
| DE4136965A1 (en) * | 1991-11-11 | 1993-05-13 | Agfa Gevaert Ag | PHOTOGRAPHIC RECORDING MATERIAL |
-
1992
- 1992-03-23 DE DE4209346A patent/DE4209346A1/en not_active Withdrawn
-
1993
- 1993-03-10 EP EP93103858A patent/EP0563638B1/en not_active Expired - Lifetime
- 1993-03-10 DE DE59308679T patent/DE59308679D1/en not_active Expired - Fee Related
- 1993-03-10 US US08/028,815 patent/US5340709A/en not_active Expired - Fee Related
- 1993-03-22 JP JP5085160A patent/JPH0643614A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0176845A2 (en) * | 1984-09-27 | 1986-04-09 | Agfa-Gevaert AG | Photographic recording material |
Non-Patent Citations (1)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN vol. 12, no. 12 (P-655)(2859) 14. Januar 1988 & JP-A-62 169 160 ( KONISHIROKU ) 25. Juli 1987 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0643614A (en) | 1994-02-18 |
| DE4209346A1 (en) | 1993-09-30 |
| EP0563638B1 (en) | 1998-06-17 |
| DE59308679D1 (en) | 1998-07-23 |
| US5340709A (en) | 1994-08-23 |
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