US3674490A - Process for the production of photographic images - Google Patents
Process for the production of photographic images Download PDFInfo
- Publication number
- US3674490A US3674490A US881610A US3674490DA US3674490A US 3674490 A US3674490 A US 3674490A US 881610 A US881610 A US 881610A US 3674490D A US3674490D A US 3674490DA US 3674490 A US3674490 A US 3674490A
- Authority
- US
- United States
- Prior art keywords
- brown
- black
- silver
- color
- compounds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title abstract description 7
- 238000000034 method Methods 0.000 title description 20
- 150000001875 compounds Chemical class 0.000 abstract description 10
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 3
- 229910052709 silver Inorganic materials 0.000 description 48
- 239000004332 silver Substances 0.000 description 48
- -1 silver halide Chemical class 0.000 description 33
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 32
- 239000000243 solution Substances 0.000 description 30
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 29
- 239000000839 emulsion Substances 0.000 description 21
- 229910000510 noble metal Inorganic materials 0.000 description 19
- 239000000975 dye Substances 0.000 description 18
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 9
- 108010010803 Gelatin Proteins 0.000 description 8
- 239000008273 gelatin Substances 0.000 description 8
- 229920000159 gelatin Polymers 0.000 description 8
- 235000019322 gelatine Nutrition 0.000 description 8
- 235000011852 gelatine desserts Nutrition 0.000 description 8
- 150000002736 metal compounds Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 5
- 229960001922 sodium perborate Drugs 0.000 description 5
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 244000172533 Viola sororia Species 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- VTIIJXUACCWYHX-UHFFFAOYSA-L disodium;carboxylatooxy carbonate Chemical compound [Na+].[Na+].[O-]C(=O)OOC([O-])=O VTIIJXUACCWYHX-UHFFFAOYSA-L 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 3
- 229940045872 sodium percarbonate Drugs 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- DTFQULSULHRJOA-UHFFFAOYSA-N 2,3,5,6-tetrabromobenzene-1,4-diol Chemical compound OC1=C(Br)C(Br)=C(O)C(Br)=C1Br DTFQULSULHRJOA-UHFFFAOYSA-N 0.000 description 2
- DETXZQGDWUJKMO-UHFFFAOYSA-N 2-hydroxymethanesulfonic acid Chemical compound OCS(O)(=O)=O DETXZQGDWUJKMO-UHFFFAOYSA-N 0.000 description 2
- YNAKESQZGPZDDZ-UHFFFAOYSA-N 2-n,2-n-diethylbenzene-1,2-diamine Chemical compound CCN(CC)C1=CC=CC=C1N YNAKESQZGPZDDZ-UHFFFAOYSA-N 0.000 description 2
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 229960000583 acetic acid Drugs 0.000 description 2
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 2
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- IGDFDIZIHMFYGR-UHFFFAOYSA-N jineol Chemical compound OC1=CC=CC2=CC(O)=CN=C21 IGDFDIZIHMFYGR-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- YFOOEYJGMMJJLS-UHFFFAOYSA-N 1,8-diaminonaphthalene Chemical compound C1=CC(N)=C2C(N)=CC=CC2=C1 YFOOEYJGMMJJLS-UHFFFAOYSA-N 0.000 description 1
- VOSLIUIVGWBSOK-UHFFFAOYSA-N 1-n-phenylbenzene-1,2,4-triamine Chemical compound NC1=CC(N)=CC=C1NC1=CC=CC=C1 VOSLIUIVGWBSOK-UHFFFAOYSA-N 0.000 description 1
- BAXOFTOLAUCFNW-UHFFFAOYSA-N 1H-indazole Chemical compound C1=CC=C2C=NNC2=C1 BAXOFTOLAUCFNW-UHFFFAOYSA-N 0.000 description 1
- ZNPJJOJEIHFJQS-UHFFFAOYSA-N 1H-indazole pyrazol-3-one Chemical class N1=NC(C=C1)=O.N1N=CC2=CC=CC=C12 ZNPJJOJEIHFJQS-UHFFFAOYSA-N 0.000 description 1
- VEPOHXYIFQMVHW-XOZOLZJESA-N 2,3-dihydroxybutanedioic acid (2S,3S)-3,4-dimethyl-2-phenylmorpholine Chemical compound OC(C(O)C(O)=O)C(O)=O.C[C@H]1[C@@H](OCCN1C)c1ccccc1 VEPOHXYIFQMVHW-XOZOLZJESA-N 0.000 description 1
- VMFJRVFZHAPENO-UHFFFAOYSA-N 2,4-diaminobenzaldehyde Chemical compound NC1=CC=C(C=O)C(N)=C1 VMFJRVFZHAPENO-UHFFFAOYSA-N 0.000 description 1
- QAYVHDDEMLNVMO-UHFFFAOYSA-N 2,5-dichlorobenzene-1,4-diamine Chemical compound NC1=CC(Cl)=C(N)C=C1Cl QAYVHDDEMLNVMO-UHFFFAOYSA-N 0.000 description 1
- NFSOOPQRTBEFDR-UHFFFAOYSA-N 2-amino-5-(4-amino-3-sulfophenyl)benzenesulfonic acid Chemical compound C1=C(S(O)(=O)=O)C(N)=CC=C1C1=CC=C(N)C(S(O)(=O)=O)=C1 NFSOOPQRTBEFDR-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- HJXIRCMNJLIHQR-UHFFFAOYSA-N 2-n,2-n-dimethylbenzene-1,2-diamine Chemical compound CN(C)C1=CC=CC=C1N HJXIRCMNJLIHQR-UHFFFAOYSA-N 0.000 description 1
- GSSXLFACIJSBOM-UHFFFAOYSA-N 2h-pyran-2-ol Chemical compound OC1OC=CC=C1 GSSXLFACIJSBOM-UHFFFAOYSA-N 0.000 description 1
- OAUWOBSDSJNJQP-UHFFFAOYSA-N 3,4,5,6-tetrabromobenzene-1,2-diol Chemical compound OC1=C(O)C(Br)=C(Br)C(Br)=C1Br OAUWOBSDSJNJQP-UHFFFAOYSA-N 0.000 description 1
- XRZDIHADHZSFBB-UHFFFAOYSA-N 3-oxo-n,3-diphenylpropanamide Chemical class C=1C=CC=CC=1NC(=O)CC(=O)C1=CC=CC=C1 XRZDIHADHZSFBB-UHFFFAOYSA-N 0.000 description 1
- DHTAGNJCDJLZDX-UHFFFAOYSA-N 4,6,7-trihydroxynaphthalene-2-sulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C=C(O)C(O)=CC2=C1 DHTAGNJCDJLZDX-UHFFFAOYSA-N 0.000 description 1
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 1
- HCEYSAVOFADVMD-UHFFFAOYSA-N 4-amino-3-hydroxybenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1O HCEYSAVOFADVMD-UHFFFAOYSA-N 0.000 description 1
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical class NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 1
- XSFKCGABINPZRK-UHFFFAOYSA-N 4-aminopyrazol-3-one Chemical class NC1=CN=NC1=O XSFKCGABINPZRK-UHFFFAOYSA-N 0.000 description 1
- 125000002373 5 membered heterocyclic group Chemical group 0.000 description 1
- YPCNDGPUJSVBIV-UHFFFAOYSA-N 5-amino-2-(4-amino-2-hydroxyphenyl)phenol Chemical compound OC1=CC(N)=CC=C1C1=CC=C(N)C=C1O YPCNDGPUJSVBIV-UHFFFAOYSA-N 0.000 description 1
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 1
- BDDLHHRCDSJVKV-UHFFFAOYSA-N 7028-40-2 Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O BDDLHHRCDSJVKV-UHFFFAOYSA-N 0.000 description 1
- GWPGDZPXOZATKL-UHFFFAOYSA-N 9h-carbazol-2-ol Chemical compound C1=CC=C2C3=CC=C(O)C=C3NC2=C1 GWPGDZPXOZATKL-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- DSLZVSRJTYRBFB-UHFFFAOYSA-N Galactaric acid Natural products OC(=O)C(O)C(O)C(O)C(O)C(O)=O DSLZVSRJTYRBFB-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
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- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
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- 235000005811 Viola adunca Nutrition 0.000 description 1
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- 235000013487 Viola odorata Nutrition 0.000 description 1
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- 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
- 239000000654 additive Substances 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 235000013601 eggs Nutrition 0.000 description 1
- IINNWAYUJNWZRM-UHFFFAOYSA-L erythrosin B Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 IINNWAYUJNWZRM-UHFFFAOYSA-L 0.000 description 1
- DSLZVSRJTYRBFB-DUHBMQHGSA-N galactaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)[C@@H](O)[C@H](O)C(O)=O DSLZVSRJTYRBFB-DUHBMQHGSA-N 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- 229960001867 guaiacol Drugs 0.000 description 1
- 229940093915 gynecological organic acid Drugs 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
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical compound C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 description 1
- GBMMWPJEWMJGCK-UHFFFAOYSA-N naphthalene-1,6,7-triol Chemical compound C1=CC(O)=C2C=C(O)C(O)=CC2=C1 GBMMWPJEWMJGCK-UHFFFAOYSA-N 0.000 description 1
- ZUVBIBLYOCVYJU-UHFFFAOYSA-N naphthalene-1,7-diol Chemical compound C1=CC=C(O)C2=CC(O)=CC=C21 ZUVBIBLYOCVYJU-UHFFFAOYSA-N 0.000 description 1
- JRNGUTKWMSBIBF-UHFFFAOYSA-N naphthalene-2,3-diol Chemical compound C1=CC=C2C=C(O)C(O)=CC2=C1 JRNGUTKWMSBIBF-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000003111 oxaloamino group Chemical group C(=O)(C(=O)O)N* 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 150000004989 p-phenylenediamines Chemical class 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle 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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 150000003216 pyrazines Chemical class 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- JWVCLYRUEFBMGU-UHFFFAOYSA-N quinazoline Chemical compound N1=CN=CC2=CC=CC=C21 JWVCLYRUEFBMGU-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 229940083608 sodium hydroxide Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- UJMBCXLDXJUMFB-GLCFPVLVSA-K tartrazine Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)C1=NN(C=2C=CC(=CC=2)S([O-])(=O)=O)C(=O)C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 UJMBCXLDXJUMFB-GLCFPVLVSA-K 0.000 description 1
- 239000004149 tartrazine Substances 0.000 description 1
- 229960000943 tartrazine Drugs 0.000 description 1
- 235000012756 tartrazine Nutrition 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 239000000984 vat dye Substances 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/40—Chemically transforming developed images
- G03C5/42—Reducing; Intensifying
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/50—Compositions containing noble metal salts other than silver salts, as photosensitive substances
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/705—Compositions containing chalcogenides, metals or alloys thereof, as photosensitive substances, e.g. photodope systems
-
- 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/40—Chemically transforming developed images
-
- 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/40—Chemically transforming developed images
- G03C5/46—Toning
Definitions
- noble metal compounds are photochemically decomposed to form gold nuclei.
- the noble metal compounds are preferably salts of the noble metals with organic acids such as citric acid, tartaric acid, oxalic acid, salicylic acid, lactic acid, benzoic acid, mucic acid, etc., as well as halides, cyanides, thiocyanates and the like. See, for example, the relevant chapter in the work by J. Plotnikow Allegemeiue Photochemie, publishers W. de Gruyter & Co., Berlin- für, (1936), and the work by A.
- Layers which are particularly suitable are those which contain zinc oxide or titanium dioxide embedded in any binders but in particular in hydrophilic binders, such as silica gel, polyvinyl acetate, partially hydrolysed polyvinyl acetate, polyvinyl alcohol, cellulose esters, carbonymethyl cellulose or natural binders such as gelatin.
- hydrophilic binders such as silica gel, polyvinyl acetate, partially hydrolysed polyvinyl acetate, polyvinyl alcohol, cellulose esters, carbonymethyl cellulose or natural binders such as gelatin.
- the noble metal compounds are added to these layers before or after exposure.
- the noble metal compounds need not themselves to be light-sensitive.
- the noble metal compounds are reduced in the exposed areas of the layers so that noble metal nuclei which are capable of catalytically decomposing peroxy compounds are formed in imagewise distribution.
- the process of the invention exhibits particular utility for intensifying conventional photographic silver images which have been produced with conventional silver halide emulsion layers and in particular images in layers of this type which have a low silver content.
- the imagewise exposed silver salt emulsion layer is first developed in a conventional way.
- the silver image thus formed is capable of the catalytically decomposing the peroxy compound.
- the catalytic activity of the surface of the developed silver image may be still further increased by taking suitable measures after development and before treatment with the peroxy compound.
- Such increases in the catalytic activity of the developed silver image may be achieved, for example, by depositing traces of catalytically more active noble metals (e.g. Au, Pt, Pd, Ru, Os) on the surface of the image silver or by brief oxidative pretreatment of the image silver, for example with peroxy compounds preferably inorganic peroxy compounds, e.g. with dissolved or gaseous H 0 dissolved perborate, percarbonate or the like.
- noble metals e.g. Au, Pt, Pd, Ru, Os
- a certain increase in the catalytic activity of the developed image silver also occurs if additional silver ions are deposited on the surface of the silver image from the solution phase by brief physical after-development.
- the silver surface is then purified by displacement of adsorbed, inactivating substances (e.g. emulsion stabilizers), and its catalytic activity is increased.
- a low sensitivity fine grained silver halide emulsion layer which upon conventional processing has a sensitivity of about 13 DIN can be exposed as an emulsion with a sensitivity of 20 D'IN if processed according to the present invention, without any loss of details or density in the resulting image.
- the gain in photographic sensitivity by the process of the invention is particularly high if silver salt emulsion layers with the conventional higher silver content are used.
- images of high density and contrast can be obtained also using light-sensitive silver salt emulsion layers especially silver halide gelatin emulsion layers which have a silver content of only about 0.05-0.3 gram silver per square meter in the form of light-sensitive silver salt. Apart from the considerable economic advantage this leads to images of exceptionally high sharpness because light scattering in layers having a low silver halide content is reduced as compared with conventional silver halide layers, which have a much higher silver halide content.
- the fixing or bleach fixing process can be omitted for layers which have an extremely low silver halide content since the photolytic coloration in daylight of layers which have an exceptionally low silver content is much less than that of conventional layers which have a much higher silver content.
- the process of the invention can be performed with silver salt emulsion layers of common composition, for example silver halide, gelatin emulsion layers, which however may contain as already mentioned above for less silver salts.
- the silver salt emulsion layers used for the process of the present invention may contain the usual additives such as spectral or chemical sensitizers, accelerators, stabilizers, hardening agents, wetting agents, and so on.
- the process according to the invention may be used both for intensifying black-white silver images and for intensifying color photographic images.
- Peroxy compounds which are suitable for the process according to the invention are preferably inorganic peroxy compounds, e.g. hydrogen peroxide, perborates, percarbonates or persulfates, the last mentioned peroxy compounds preferably in the form of their alkali metal salts.
- Organic peroxy compounds, e.g. benzoyl peroxide, may also be used.
- the treatment with the peroxy compounds is perrformed in the presence of reagents which yield very deeply colored oxidation products so that the image which was previously invisible or hardly visible becomes clearly visible.
- These reagents may be organic compounds which yield an image dye on oxidation, preferably (1) amino and/or hydroxy substituted aryl compounds, in particular those of the benzene or naphthalene series or (2) amino and/or hydroxy substituted heterocyclic aromatic compounds, such as 5- or 6-membered heterocyclic rings, in particular rings with nitrogen as a ring member, for example rings of the pyrol, pyridine, pyrazole, imidazole, triazole, pyridazine, pyrimidine or pyrazine series, whereby these heterocyclic rings contain anellated benzene rings, such as indol, indazole, quinazoline, quinoxazaline, acridine or phenazine.
- the compounds are preferably water soluble.
- amino, hydroxy or aminohydroxy compounds may also be substituted, e.g. with halogen, sulfonic, alkyl, aryl, alkoxy or aroxy nitro, keto, aldehyde groups, carboxy or carbamoyl.
- mixtures of several such compounds show a much stronger dye formation on oxidation than the individual components.
- a mixture of o-phenylenediamine and pyrocatechol results in increased dye formation.
- a mixture of N,N-diethyl-phenylenediamine and pyrocatechol yields a deeper and more neutral black dye than the individual compounds.
- Even components which do not form a dye upon oxidation on their own, such as tetrabromohydroquinone or tetrabromopyrocatechol may enhance dye formation when added to other hydroxy, amino or aminohydroxy compounds.
- Oxidation of the aromatic amino, hydroxy and/ or aminohydroxy compounds yields monomeric or polymeric dyes which are related to quinonimines and azines.
- dye precursors Apart from dye precursors, one may, of course, also use leuco dye compounds and vat dyes which can be oxidized to dyes.
- leuco dye compounds and vat dyes which can be oxidized to dyes.
- Oxidisable organic compounds of the type which yield the image dye only in a sequence of reactions with other compounds are also suitable for use in the process of the invention.
- any reaction system which yields dyes on oxidative coupling may be used.
- Special reference may be made here to the so-called color-forming photographic developers of the phenylenediamine or aminopyrazolone series (see, e.g. C. E. K. Mees and T. H. James, The Theory of the Photographic Process," 3rd edition, MacMillan Co., New York (1966), page 382; H. R. Schweizer, Kiinstliche Organische Farbstofie und Struktur, Springer-Verlag, Berlin-Gottingen-Heidelberg (1964), page 295).
- Isocyclic and heterocyclic hydrazines can also be coupled oxidatively with suitable components to yield dyes ,(see e.g. H. Hiinig et al., Angew. Chem. 70 (1958) 215; S. Hiinig, Chimia 15 (1961) 133 and Angew. Chem. 74 (1962) 818).
- the color-forming photographic developed substances are catalytically oxidized on the imagewise distributed noble metal nuclei or noble metal particles by the peroxy compounds. Their oxidation products may then react with known photographic color couplers which are also present to form dyes.
- Any color couplers are suitable for this purpose, for example those of the phenol or naphthol series as cyan couplers, those of the pyrazolone indazol series as magenta couplers and those of the benzoyl-acetanilide series as yellow couplers.
- EXAMPLE 1 A gelatin layer (thickness of layer 25 m.) on a cellulose trlacetate support is treated with a saturated aqueous solution Of Na [Pd (C204) 2] 5 After drying and imagewise exposure with ultraviolet light, the layer is treated for two minutes at 20 C. in the following developer bath:
- Solution 1 5 cc. of glacial acetic acid are added to 500 cc. of water. 3 g. of S-aminobenzidene hydrochloride and 2 g. of pyrocatechol are then dissolved in this solution.
- Solution 2 10 g. of sodium acetate are dissolved in 500 cc. of water. 25 cc. of 30% aqueous H are then added.
- the two solutions are mixed before use.
- Nuclei of palladium metal are formed on the exposed areas of the layer during exposure. On development, these nuclei catalytically decompose the hydrogen peroxide present in solution 2 and the amine and phenol of solution 1 are imagewise oxidized to yield a brownish-black negative image of the original. The image dye is fast to diffusion.
- EXAMPLE 2 A transparent support of cellulose triacetate is coated with a solution which contains 6 ml. of a 10% aqueous solution of polyvinyl alcohol and 2 g. of TiO of particle size 0.3 to 0.4 m. and 0.1 mg. of erythrosin as spectral sensitizer in 400 cc. of water. The layer is then dried.
- the dry layer is exposed in a sensitometer customarily used in the art behind a grey step wedge and then treated for 10 minutes with a aqueous solution of NaAuCl It is then washed and treated for 2 minutes in a bath of the following solutions at 20 C.
- the three solutions are mixed before use.
- the developed material is washed for half a minute and dried. A blue-violet negative image of the original is obtained.
- a silver iodobromide gelatin emulsion layer (4.5 mols percent of Agl) which must be as free as possible from fog, is applied onto a support of polyethylene terephthalate. Conventional silver content of about g. silver per square meter. Layer thickness approximately 10 After imagewise exposure (0.5 second with X-rays between fluorescent intensifying foils), the layer is treated for 5 minutes in the following developer at 20 C.:
- the layer is treated for 5 minutes in a solution which contains 25 g. of sodium percarbonate and 200 cc. of 30% aqueous H 0 in 1 liter of H 0.
- the catalytic activity of the surface of the developed silver is thus increased.
- the layer is then treated for 2 minutes in the following bath:
- Solution 1 10 g. of pyrocatechol in 200 ml. water.
- Solution 2 10 g. of 1,7-dihydroxy naphthalene in 800 ml. water and added thereto 20 g. of sodium carbonate and 20 ml. of a S-N-sodium-hydroxide solution.
- Solultion 3 14 g. sodium perborate in 1 liter of water.
- the layer is finally rinsed and dried.
- the treatment with the last-mentioned bath may be performed in daylight.
- the contrast of the original silver image is greatly enhanced by the after treatment.
- the sensitivity of the material is apparently also strongly increased since one either obtains much more image detail for the same exposure followed by conventional photographic processing or the exposure time required to obtain the same quality of final image is much less (factor 10 to 100) than would be required if exposure were followed by conventional photographic processing.
- the intermediate treatment may be carried out e.g. with a 2% aqueous sodium perborate solution, a 1% aqueous PdCl solution, a 1% aqueous PtCl solution or a 1% aqueous AuCl solution.
- a brief treatment with gaseous H 0 at a temperature of about C. also increases the catalytic activity of the image silver.
- EXAMPLE 4 10 ml. of a silver bromide gelatin emulsion which is as free as possible from fog are added to 250 cc. of a 5% gelatin solution. 50 ml. of a 10% aqueous solution of the cyan color coupler:
- the layer After drying, the layer is exposed in a sensitometer for 1 second behind a grey step wedge and then treated with a color-forming developer for 2 minutes in the conventional manner in the following bath:
- the layer is then treated for 5 minutes in a solution which contains 20 g. of sodium perborate and cc. of 30% H 0 to 1 liter of H 0.
- the catalytic activity of the silver image surface is thereby increased.
- the layer is then treated for 5 minutes in the following bath:
- Solution 1 15 g. of phenylhydrazine-2-sulfonic acid sodium are dissolved in 500 cc. of 0.1% aqueous acetic acid.
- Solution 2 7 g. of sodium perborate and 40 g. of sodium acetate are dissolved in 500 cc. of water. 50 cc. of 30% of H are then added.
- the above layer is arranged between two intensifying foils of calcium tungstate and exposed to X-rays behind The two Solutions? mixed befPre a stepwedge of aluminum. Thereafter the exposed layer i cyan Image consldefably Increased is developed for one minute at a temperature of 20 C. tensity by this after treatment.
- phenylhydrazme-3- with the following developing bath: sulfonic acid sodium instead of the phenylhydrazine-Z- sulfonic acid sodium a red image is obtained.
- EXAMPLE 5 Fixation is not necessary since the coloration by photo- Acolor photographic lti-l d t i l hi h lytic formation of silver in the low silver halide content prises a red-sensitive silver halide emulsion layer conlayer p exposure to y t 1S neghgrbletaining a cyan color coupler, a green-sensitive silver halide Afte?
- development layer 18 "Ff 2 mmutes 1n emulsion layer containing a magenta coupler, a filter 20 a Solution of the followlng composltlon: layer containing tartrazine as yellow filter dye, and a blue- 50 f 30% aqueous H202 sensitive silver halide emulsion layer containing a yellow 20 of Sodium perborate (or g. Sodium percarbonate), coupler 1s exposed behmd a grey step wedge a sodium carbonate to adjust a pH-value of 10, water up light intensity which is about one-tenth of the amount reto 1 liter quired for conventional processing.
- Sodium perborate or g. Sodium percarbonate
- the material is then 25 developed for 8 minutes in the conventional manner in Thereafter the layer 15 contacted Y a the color-forming developer of Example 4. mg s fa F i f comams a $9
- the layer is treated three times in succession for 1 ppm] is e m e O owmg a 6 or m com minute each alternately with a 2.5% sodium percanbonate 22223 gg jg g fig g g i eacih i solution and the color development solution indicated 30 Per liter p e s e ea g soulon 223:1: gi t; i i ii r iie i gig 1s mtenslfied by this alter.
- a high speed silver bromo iodide gelatin emulsion con- The dye forming oxidation process can be stopped and taining 10% by weight of silver halide, silver iodide the image can be stabilized for storage by aftertreatment content 1 mol percent is applied onto a cellulose triwith an aqueous solution of Na SO NaHSO or acetate support and dried.
- the emulsion layer contains formaldehydebisulfite.
- Brownish black Brownish black
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19681813920 DE1813920C (de) | 1968-12-11 | Verfahren zur Herstellung photo graphischer Bilder |
Publications (1)
Publication Number | Publication Date |
---|---|
US3674490A true US3674490A (en) | 1972-07-04 |
Family
ID=5715873
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US881610A Expired - Lifetime US3674490A (en) | 1968-12-11 | 1969-12-02 | Process for the production of photographic images |
Country Status (6)
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US (1) | US3674490A (enrdf_load_stackoverflow) |
JP (1) | JPS4946419B1 (enrdf_load_stackoverflow) |
BE (1) | BE742768A (enrdf_load_stackoverflow) |
CH (1) | CH538711A (enrdf_load_stackoverflow) |
FR (1) | FR2025918A1 (enrdf_load_stackoverflow) |
GB (1) | GB1268126A (enrdf_load_stackoverflow) |
Cited By (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3765890A (en) * | 1970-11-17 | 1973-10-16 | Agfa Gevaert Ag | Organic hydrogen peroxide addition compounds for vesicular image formation processes |
US3841873A (en) * | 1973-05-21 | 1974-10-15 | Eastman Kodak Co | Cobalt (iii) complex amplifier baths in color photographic processes |
JPS5116023A (ja) * | 1974-07-12 | 1976-02-09 | Konishiroku Photo Ind | Harogenkaginshashinkankozairyono shorihoho |
JPS5136136A (ja) * | 1974-09-21 | 1976-03-26 | Konishiroku Photo Ind | Harogenkaginshashinkankozairyo no shorihoho |
US4002477A (en) * | 1973-11-28 | 1977-01-11 | Eastman Kodak Company | Diffusion transfer processes and elements using or containing inert transitional metal complex oxidizing agents |
DE2709054A1 (de) * | 1976-03-02 | 1977-09-08 | Fuji Photo Film Co Ltd | Verfahren zur erzeugung von bildern durch bildverstaerkung |
DE2736886A1 (de) * | 1976-08-18 | 1978-03-02 | Konishiroku Photo Ind | Verfahren zum behandeln lichtempfindlicher farbphotographischer silberhalogenid-aufzeichnungsmaterialien |
US4089685A (en) * | 1975-11-05 | 1978-05-16 | Eastman Kodak Company | Reversal imaging process including redox amplification |
US4094682A (en) * | 1975-10-24 | 1978-06-13 | Konishiroku Photo Industry Co., Ltd. | Method for processing light-sensitive silver halide photographic material |
US4113490A (en) * | 1974-07-12 | 1978-09-12 | Konishiroku Photo Industry Co., Ltd. | Method for processing light-sensitive silver halide photographic materials |
US4126461A (en) * | 1977-06-13 | 1978-11-21 | Eastman Kodak Company | Black-and-white photographic elements and processes |
US4146395A (en) * | 1976-10-08 | 1979-03-27 | Eastman Kodak Company | Reversal imaging process including redox amplification |
US4158565A (en) * | 1978-02-02 | 1979-06-19 | Eastman Kodak Company | Processes for producing positive or negative dye images using high iodide silver halide emulsions |
US4200466A (en) * | 1975-09-30 | 1980-04-29 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide photographic materials |
US4203767A (en) * | 1974-12-16 | 1980-05-20 | Konishiroku Photo Industry Co., Ltd. | Amplification process for light-sensitive color photographic material |
US4254213A (en) * | 1979-02-06 | 1981-03-03 | Konishiroku Photo Industry Co., Ltd. | Process for forming black dye images |
US4268616A (en) * | 1978-03-06 | 1981-05-19 | Fuji Photo Film Co., Ltd. | Process for forming photographic images |
US4371609A (en) * | 1980-07-19 | 1983-02-01 | Konishiroku Photo Industry Co., Ltd. | Forming method of a dye image |
EP0124795A2 (en) | 1983-04-11 | 1984-11-14 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion |
US4678740A (en) * | 1985-04-29 | 1987-07-07 | Catania James N | Method for making photographic mattes |
US5171658A (en) * | 1989-04-26 | 1992-12-15 | Eastman Kodak Company | Method of photographic processing |
US5244778A (en) * | 1990-01-18 | 1993-09-14 | Eastman Kodak Company | Thiosulphate fixing solutions |
US5364747A (en) * | 1992-11-25 | 1994-11-15 | Eastman Kodak Company | Color correcting layers consisting essentially of at least one dye-forming coupler and gelatin in chromogenic black-and-white photographic imaging systems |
US5380639A (en) * | 1991-08-23 | 1995-01-10 | Konica Corporation | Silver halide color photographic material |
US5411848A (en) * | 1993-08-16 | 1995-05-02 | Eastman Kodak Company | Photographic color couplers and photographic materials containing them |
US5418117A (en) * | 1993-07-24 | 1995-05-23 | Eastman Kodak Company | Method of photographic processing |
US5466562A (en) * | 1993-07-30 | 1995-11-14 | Eastman Kodak Company | Method of photographic processing |
US5477301A (en) * | 1993-04-13 | 1995-12-19 | Eastman Kodak Company | Photographic processing apparatus |
US5689753A (en) * | 1995-06-22 | 1997-11-18 | Eastman Kodak Company | Method of photographic processing with solution replenishment |
US5719010A (en) * | 1995-12-16 | 1998-02-17 | Eastman Kodak Company | Treatment method for treating effluents from a photographic development process |
US5736306A (en) * | 1994-12-24 | 1998-04-07 | Eastman Kodak Company | Photographic silver halide material having improved spectral characteristics |
US5747230A (en) * | 1994-12-24 | 1998-05-05 | Eastman Kodak Company | Photographic silver halide colour material having improved granularity and dye hue |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4526860A (en) * | 1983-07-28 | 1985-07-02 | Minnesota Mining And Manufacturing Company | Photographic process |
GB9008750D0 (en) * | 1990-04-18 | 1990-06-13 | Kodak Ltd | Method and apparatus for photographic processing solution replenishment |
GB9016472D0 (en) * | 1990-07-26 | 1990-09-12 | Kodak Ltd | Photographic bleach compositions |
GB9022779D0 (en) * | 1990-10-19 | 1990-12-05 | Kodak Ltd | Photographic processing apparatus |
GB9022781D0 (en) * | 1990-10-19 | 1990-12-05 | Kodak Ltd | Photographic processing apparatus |
GB9024783D0 (en) * | 1990-11-14 | 1991-01-02 | Kodak Ltd | Method of processing a photographic silver halide colour material |
GB9114090D0 (en) * | 1991-06-29 | 1991-08-14 | Kodak Ltd | Photographic processing apparatus |
GB9114933D0 (en) * | 1991-07-11 | 1991-08-28 | Kodak Ltd | Method for forming a photographic colour image |
GB9118299D0 (en) * | 1991-08-24 | 1991-10-09 | Kodak Ltd | Method of photographic processing |
US5702873A (en) * | 1991-12-03 | 1997-12-30 | Eastman Kodak Company | Redox amplification solutions containing metal ion sequestering agents |
GB9126386D0 (en) * | 1991-12-12 | 1992-02-12 | Kodak Ltd | Method of making stable colour photographic prints |
GB9423381D0 (en) | 1994-11-19 | 1995-01-11 | Kodak Ltd | Photographic developer/amplifier compositions |
GB9423382D0 (en) | 1994-11-19 | 1995-01-11 | Kodak Ltd | Photographic developer/amplifier compositions |
GB9516578D0 (en) | 1995-08-12 | 1995-10-11 | Kodak Ltd | Method of processing photographic silver halide materials |
GB9600112D0 (en) | 1996-01-04 | 1996-03-06 | Kodak Ltd | Improvements in or relating to photographic processsing apparatus |
-
1969
- 1969-12-02 US US881610A patent/US3674490A/en not_active Expired - Lifetime
- 1969-12-03 GB GB58935/69A patent/GB1268126A/en not_active Expired
- 1969-12-08 BE BE742768D patent/BE742768A/xx unknown
- 1969-12-08 CH CH1822169A patent/CH538711A/de not_active IP Right Cessation
- 1969-12-11 JP JP44099121A patent/JPS4946419B1/ja active Pending
- 1969-12-11 FR FR6943040A patent/FR2025918A1/fr not_active Withdrawn
Cited By (33)
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US3765890A (en) * | 1970-11-17 | 1973-10-16 | Agfa Gevaert Ag | Organic hydrogen peroxide addition compounds for vesicular image formation processes |
US3841873A (en) * | 1973-05-21 | 1974-10-15 | Eastman Kodak Co | Cobalt (iii) complex amplifier baths in color photographic processes |
US4002477A (en) * | 1973-11-28 | 1977-01-11 | Eastman Kodak Company | Diffusion transfer processes and elements using or containing inert transitional metal complex oxidizing agents |
JPS5116023A (ja) * | 1974-07-12 | 1976-02-09 | Konishiroku Photo Ind | Harogenkaginshashinkankozairyono shorihoho |
US4113490A (en) * | 1974-07-12 | 1978-09-12 | Konishiroku Photo Industry Co., Ltd. | Method for processing light-sensitive silver halide photographic materials |
JPS5136136A (ja) * | 1974-09-21 | 1976-03-26 | Konishiroku Photo Ind | Harogenkaginshashinkankozairyo no shorihoho |
US4203767A (en) * | 1974-12-16 | 1980-05-20 | Konishiroku Photo Industry Co., Ltd. | Amplification process for light-sensitive color photographic material |
US4200466A (en) * | 1975-09-30 | 1980-04-29 | Konishiroku Photo Industry Co., Ltd. | Light-sensitive silver halide photographic materials |
US4094682A (en) * | 1975-10-24 | 1978-06-13 | Konishiroku Photo Industry Co., Ltd. | Method for processing light-sensitive silver halide photographic material |
US4089685A (en) * | 1975-11-05 | 1978-05-16 | Eastman Kodak Company | Reversal imaging process including redox amplification |
DE2709054A1 (de) * | 1976-03-02 | 1977-09-08 | Fuji Photo Film Co Ltd | Verfahren zur erzeugung von bildern durch bildverstaerkung |
DE2736886A1 (de) * | 1976-08-18 | 1978-03-02 | Konishiroku Photo Ind | Verfahren zum behandeln lichtempfindlicher farbphotographischer silberhalogenid-aufzeichnungsmaterialien |
US4277556A (en) * | 1976-08-18 | 1981-07-07 | Konishiroku Photo Industry Co., Ltd. | Process for treating light-sensitive silver halide color photographic materials |
US4146395A (en) * | 1976-10-08 | 1979-03-27 | Eastman Kodak Company | Reversal imaging process including redox amplification |
US4126461A (en) * | 1977-06-13 | 1978-11-21 | Eastman Kodak Company | Black-and-white photographic elements and processes |
US4158565A (en) * | 1978-02-02 | 1979-06-19 | Eastman Kodak Company | Processes for producing positive or negative dye images using high iodide silver halide emulsions |
US4268616A (en) * | 1978-03-06 | 1981-05-19 | Fuji Photo Film Co., Ltd. | Process for forming photographic images |
US4254213A (en) * | 1979-02-06 | 1981-03-03 | Konishiroku Photo Industry Co., Ltd. | Process for forming black dye images |
US4371609A (en) * | 1980-07-19 | 1983-02-01 | Konishiroku Photo Industry Co., Ltd. | Forming method of a dye image |
EP0124795A2 (en) | 1983-04-11 | 1984-11-14 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion |
US4678740A (en) * | 1985-04-29 | 1987-07-07 | Catania James N | Method for making photographic mattes |
US5171658A (en) * | 1989-04-26 | 1992-12-15 | Eastman Kodak Company | Method of photographic processing |
US5244778A (en) * | 1990-01-18 | 1993-09-14 | Eastman Kodak Company | Thiosulphate fixing solutions |
US5380639A (en) * | 1991-08-23 | 1995-01-10 | Konica Corporation | Silver halide color photographic material |
US5364747A (en) * | 1992-11-25 | 1994-11-15 | Eastman Kodak Company | Color correcting layers consisting essentially of at least one dye-forming coupler and gelatin in chromogenic black-and-white photographic imaging systems |
US5477301A (en) * | 1993-04-13 | 1995-12-19 | Eastman Kodak Company | Photographic processing apparatus |
US5418117A (en) * | 1993-07-24 | 1995-05-23 | Eastman Kodak Company | Method of photographic processing |
US5466562A (en) * | 1993-07-30 | 1995-11-14 | Eastman Kodak Company | Method of photographic processing |
US5411848A (en) * | 1993-08-16 | 1995-05-02 | Eastman Kodak Company | Photographic color couplers and photographic materials containing them |
US5736306A (en) * | 1994-12-24 | 1998-04-07 | Eastman Kodak Company | Photographic silver halide material having improved spectral characteristics |
US5747230A (en) * | 1994-12-24 | 1998-05-05 | Eastman Kodak Company | Photographic silver halide colour material having improved granularity and dye hue |
US5689753A (en) * | 1995-06-22 | 1997-11-18 | Eastman Kodak Company | Method of photographic processing with solution replenishment |
US5719010A (en) * | 1995-12-16 | 1998-02-17 | Eastman Kodak Company | Treatment method for treating effluents from a photographic development process |
Also Published As
Publication number | Publication date |
---|---|
BE742768A (enrdf_load_stackoverflow) | 1970-06-08 |
CH538711A (de) | 1973-06-30 |
GB1268126A (en) | 1972-03-22 |
JPS4946419B1 (enrdf_load_stackoverflow) | 1974-12-10 |
FR2025918A1 (enrdf_load_stackoverflow) | 1970-09-11 |
DE1813920A1 (de) | 1970-06-25 |
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