US3471295A - Production of colored direct-positive images - Google Patents
Production of colored direct-positive images Download PDFInfo
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- US3471295A US3471295A US465254A US3471295DA US3471295A US 3471295 A US3471295 A US 3471295A US 465254 A US465254 A US 465254A US 3471295D A US3471295D A US 3471295DA US 3471295 A US3471295 A US 3471295A
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- Prior art keywords
- hydroxylamine
- carbon atoms
- alkyl
- color
- phenyl
- Prior art date
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- Expired - Lifetime
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- 238000004519 manufacturing process Methods 0.000 title description 4
- -1 silver halide Chemical class 0.000 description 28
- 125000004432 carbon atom Chemical group C* 0.000 description 19
- 239000000463 material Substances 0.000 description 18
- 229910052709 silver Inorganic materials 0.000 description 18
- 239000004332 silver Substances 0.000 description 18
- 239000000839 emulsion Substances 0.000 description 17
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- 150000002443 hydroxylamines Chemical class 0.000 description 7
- 108010010803 Gelatin Proteins 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 229920000159 gelatin Polymers 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 235000011852 gelatine desserts Nutrition 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 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 3
- 229910021612 Silver iodide Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004061 bleaching Methods 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
- 230000000694 effects Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- SYXUBXTYGFJFEH-UHFFFAOYSA-N oat triterpenoid saponin Chemical compound CNC1=CC=CC=C1C(=O)OC1C(C=O)(C)CC2C3(C(O3)CC3C4(CCC5C(C)(CO)C(OC6C(C(O)C(OC7C(C(O)C(O)C(CO)O7)O)CO6)OC6C(C(O)C(O)C(CO)O6)O)CCC53C)C)C4(C)CC(O)C2(C)C1 SYXUBXTYGFJFEH-UHFFFAOYSA-N 0.000 description 3
- 229940045105 silver iodide Drugs 0.000 description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PVJKFTUUDTYJJG-UHFFFAOYSA-N 1-[2,3-di(prop-2-enoyl)triazinan-1-yl]prop-2-en-1-one Chemical compound C=CC(=O)N1CCCN(C(=O)C=C)N1C(=O)C=C PVJKFTUUDTYJJG-UHFFFAOYSA-N 0.000 description 2
- INVVMIXYILXINW-UHFFFAOYSA-N 5-methyl-1h-[1,2,4]triazolo[1,5-a]pyrimidin-7-one Chemical compound CC1=CC(=O)N2NC=NC2=N1 INVVMIXYILXINW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- KHBQMWCZKVMBLN-UHFFFAOYSA-N Benzenesulfonamide Chemical compound NS(=O)(=O)C1=CC=CC=C1 KHBQMWCZKVMBLN-UHFFFAOYSA-N 0.000 description 2
- CKRZKMFTZCFYGB-UHFFFAOYSA-N N-phenylhydroxylamine Chemical class ONC1=CC=CC=C1 CKRZKMFTZCFYGB-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 159000000000 sodium salts 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
- 230000000087 stabilizing effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- AYLDJQABCMPYEN-UHFFFAOYSA-N (4-azaniumylphenyl)-diethylazanium;sulfate Chemical compound OS(O)(=O)=O.CCN(CC)C1=CC=C(N)C=C1 AYLDJQABCMPYEN-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical class C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-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
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002828 nitro derivatives Chemical class 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003142 primary aromatic amines Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 230000002226 simultaneous effect Effects 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D235/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings
- C07D235/02—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, condensed with other rings condensed with carbocyclic rings or ring systems
- C07D235/04—Benzimidazoles; Hydrogenated benzimidazoles
- C07D235/18—Benzimidazoles; Hydrogenated benzimidazoles with aryl radicals directly attached in position 2
-
- 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
- G03C7/39236—Organic compounds with a function having at least two elements among nitrogen, sulfur or oxygen
Definitions
- the object of the present invention is to provide photographic elements which contain the above 1,2-dihydrazones, but which are stable against the effects of heat and moisture.
- R represents (a) A linear or branched alkyl radical with up to 20 carbon atoms which may be substituted as desired, but preferably with phenyl, e.g. in a benzylor phenylethyl grouping, carboxy or sulfo,
- An aromatic ring grouping preferably aryl rings, in particular naphthyl or phenyl; these groups may in turn be substituted as desired, for example, with halogen, preferably chlorine or bromine, alkoxy groups with up to 18 carbon atoms, hydroxy, carboxy, esterified carboxy whereby the ester grouping is preferably derived from an aliphatic alcohol with up to 20 carbon atoms, sulfo, amino which may be substituted, for example, with acyl radicals, in particular those derived from aliphatic carboxylic acids 3,471,295 Patented Oct.
- phenyl-hydroxylamine derivatives particularly those containing water-solubilizing groups such as SO H or COOH and long-chain alkyl radicals with 7 to 20 carbon atoms. These substituents may be linked to the phenyl ring either directly or via any intermediate members, for example, a phenyl sulfonamide grouping.
- aromatic 1,2-dihydrazones described in British patent specification No. 916,657 are stabilized by the above hydroxylamines against the simultaneous effect of heat and moisture. This effect is unexpected inasmuch as the simple hydroxylamine or its salts do not produce any improvement in stability.
- other additives with a comparable reducing action such as aromatic hydrazines, hydroxamic acids, ascorbic acid and pyrocatechol, are practically ineffective.
- hydroxylamine derivatives are preferably added to the emulsions in amounts from 15% to 60% by weight, based on the aromatic 1,2-dihydrazone; that is about 10 to 750 mg. per square meter of the layer. They do not deleteriously affect the silver halide emulsion. According to British patent specification 916,657 or US.
- Patent 3,186,840 the aromatic dihydrazones are added in amounts of 1-20 g. per liter of silver halide emulsion; that is about 4.5 to g. per mol silver halide.
- the aromatic dihydrazones suitable for the photographic materials of the present invention are described in the above patent specification and patent as well as in British patent specification 916,658 and US. Patent 3,162,643.
- hydroxylamines may be prepared by methods described in the literature, starting from the corresponding nitro compounds. In cases where the water solubility is reduced, for example by fairly long alkyl radicals, it is EXAMPLE 1 Preparation of the hydroxylamine derivative:
- the above emulsion was applied onto a transparent support of celluloseacetobutyrate.
- the dried layer contained 0.55 g. of Ag per m. and had a thickness of 3 (Material A
- a comparison material B differed from material A in that 19 g. of 2-m(m-hydroxylaminophenyl)-l-octadecylbenzimidazole-S-sulfonic acid per mol of silver halide were added in the form of a 5% by weight solution in 0.1 N NaOH, and the pH then adjusted to 7.0 with citric acid.
- Samples of materials A and B were stored for 7 days at 40 C. and 85% relative humidity.
- Example 2 Two photographic materials (samples A and B were prepared as described in Example 1.
- Material B contained an equimolar quantity of compound II, instead of the hydroxylamine derivative referred to in Example 1. After storage, exposure and color-forming development as in Example 1, the following maximum color densities were otbained Material A; Material B 3 Cold-stored 1. 0 1. 01
- EXAMPLE 3 Layers containing the direct positive dihydrazone color component stabilized with an organic hydroxyl amine derivative according to the invention can also be used in multi-layer color photographic materials to correct the undesirable absorption of subtractive color couplers, in particular the undesirable absorption of magenta color couplers.
- Such a multilayer material can be composed as follows: on a transparent support, for example, of cellulose acetate or polyethylene glycol terephthalate having a subbing layer coated thereon are applied the following layers:
- the dried layer contains 0.75 g. silver in the form of silver halide per square meter,
- A.yellow filter layer consisting of colloidal distributed silver dispersed in gelatin
- a blue-sensitive silver iodobromide gelatin emulsion layer the silver halide of which contains 6 mol percent of silver iodide.
- the emulsion further contains per liter of casting solution 30 ml. of a 1% aqueous solution of 4-hydroxy-6-methyl-1,3,3a-7-tetraazaindene, 200 ml. of a 10% aqueous solution of the sodium salt of the yellow color coupler CODE COOH
- the dried layer contains per square meter 1.43 g. silver in the form of silver halide,
- the above material is exposed to a color original and processed according to common practice by developing and bleach-fixing the exposed material. A colored image of the original in true colors is obtained. An image of the same quality is obtained after storing the above material for several days at 40 C. and high humidity.
- a photographic light-sensitive silver halide emulsion containing an aromatic 1,2-hydrazone of an alpha dicarbonyl compound and forming a direct positive dye image upon exposure, color development and silver bleaching
- the improvement according to which the emulsion also contains an alkyl or aryl hydroxylamine in an amount that stabilizes the unprocessed emulsion against the loss of final color intensity resulting from storage at elevated temperatures.
- hydroxylamine is an alkyl hydroxylamine having up to 20 carbons.
- hydroxylamine is a phenylhydroxylamine, the phenyl ring of which carries an alkyl group having between 7 and 20 carbon atoms, and a water-solubilizing group.
- the hydroxylamine has the formula R--NHOH wherein R represents alkyl having up to 20 carbon atoms, phenyl-substituted alkyl having up to 20 carbon atoms in the alkyl, carboxy substituted alkyl having up to 20 carbon atoms in the alkyl, sulfo substituted alkyl having up to 20 carbon atoms in the alkyl, naphthyl, phenyl, or substitution products of naphthyl or phenyl wherein the substituents are halogen, alkoxy Ehaving up to 18 carbon atoms, hydroxy, carboxy, esterified carboxy having up to 21 carbon atoms, sulfo, amino, acylamino having up to 20 carbon atoms, phenylsulfoamino, alkylamino having up to 20 carbon atoms, sulfamido, acylsulfamide having up to 20 carbon atoms, phenyl
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Physics & Mathematics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
United States Patent Int. Cl. 603:! 1/40, 5/24 US. Cl. 96-100 15 Claims ABSTRACT OF THE DISCLOSURE This invention relates to the production of colored direct-positive images in light-sensitive silver halide emulsions containing aromatic 1,2-dihydrazones in soluble, diffusion-resistant form stabilized by an additional content of an aliphatic aromatic hydroxyl derivative.
The process for the production of direct positive colorphotographic images by means of photographic silver halide emulsion layers containing aromatic 1,2-dihydrazones is described in British patent specification 916,657. In this process the aromatic 1,2-dihydrazones remain un- I changed at the unexposed areas of the silver halide emulsion layers during color-forming development with primary aromatic amines of the p-phenylendiamine type, for example 4-aminodiethyl aniline, and are then oxidized to form colored compounds in a bleaching bath by means of alkali metal ferricyanide, while at the exposed areas the dihydrazones react with the oxidation products of the color-forming developer to form colorless or almost colorless compounds which are stable against oxidation by ferricyanide ions. The above process is of limited utility, since many formulations are not sufficiently stable when the photographic material is stored under the simultaneous influence of heat and moisture. This results in a decrease in the maximum color densities and in a corresponding flattening of the characteristic curve during color-forming development.
In the most unfavourable instances the above undesired effects even occur upon drying the photographic layer during their production.
The object of the present invention is to provide photographic elements which contain the above 1,2-dihydrazones, but which are stable against the effects of heat and moisture.
It has now been found that compounds of the following formula R-NHOH are particularly suitable for stabilizing the foregoing formulations. In this formula, R represents (a) A linear or branched alkyl radical with up to 20 carbon atoms which may be substituted as desired, but preferably with phenyl, e.g. in a benzylor phenylethyl grouping, carboxy or sulfo,
(b) An aromatic ring grouping, preferably aryl rings, in particular naphthyl or phenyl; these groups may in turn be substituted as desired, for example, with halogen, preferably chlorine or bromine, alkoxy groups with up to 18 carbon atoms, hydroxy, carboxy, esterified carboxy whereby the ester grouping is preferably derived from an aliphatic alcohol with up to 20 carbon atoms, sulfo, amino which may be substituted, for example, with acyl radicals, in particular those derived from aliphatic carboxylic acids 3,471,295 Patented Oct. 7, 1969 with up to 20 carbon atoms or from phenyl sulfonic acids, or with alkyl radicals of up to 2-0 carbon atoms, sulfamyl groupings, in which case the amide radical may be substituted as indicated above in respect of the amino groups, or with phenyl radicals or alkyl radicals with up to 20 carbon atoms.
a Preferred are phenyl-hydroxylamine derivatives particularly those containing water-solubilizing groups such as SO H or COOH and long-chain alkyl radicals with 7 to 20 carbon atoms. These substituents may be linked to the phenyl ring either directly or via any intermediate members, for example, a phenyl sulfonamide grouping.
The aromatic 1,2-dihydrazones described in British patent specification No. 916,657 are stabilized by the above hydroxylamines against the simultaneous effect of heat and moisture. This effect is unexpected inasmuch as the simple hydroxylamine or its salts do not produce any improvement in stability. In addition, other additives with a comparable reducing action such as aromatic hydrazines, hydroxamic acids, ascorbic acid and pyrocatechol, are practically ineffective.
The following compounds exhibit particular utility:
I (llnHm /N\ 0- NHOH H 03s C sHa'I III s 03H @NH-S OrQ-NH o H N H-C1BH31 1v HOOCCHz(|JH-NHOH v HOOC-CHr-(EH-NHOH NHOH -o 0 on V1 The hydroxylamine derivatives are preferably added to the emulsions in amounts from 15% to 60% by weight, based on the aromatic 1,2-dihydrazone; that is about 10 to 750 mg. per square meter of the layer. They do not deleteriously affect the silver halide emulsion. According to British patent specification 916,657 or US. Patent 3,186,840 the aromatic dihydrazones are added in amounts of 1-20 g. per liter of silver halide emulsion; that is about 4.5 to g. per mol silver halide. The aromatic dihydrazones suitable for the photographic materials of the present invention are described in the above patent specification and patent as well as in British patent specification 916,658 and US. Patent 3,162,643.
The hydroxylamines may be prepared by methods described in the literature, starting from the corresponding nitro compounds. In cases where the water solubility is reduced, for example by fairly long alkyl radicals, it is EXAMPLE 1 Preparation of the hydroxylamine derivative:
100 g. of 1-octadecyl-2(m-nitrophenyl)-benzimidazole- -sulfonic acid were dissolved in 500 ml. of pyridine. 130 ml. of S-N-hydrochloric acid were added to the solution and 25 g. of zinc powder were introduced with stirring at 25 to 30 C. over a period of 30 minutes. After stirring for another 15 minutes, the reaction mixture wa suctionfiltered. Ice was added to the filtrate and the reaction product was precipitated with hydrochloric acid, suctionfiltered, washed repeatedly with water and, finally, stirred with acetone and sucked dry.
Yield: 74 g. of 1-octadecyl-2-(m-hydroxyaminophenyl)-benzimidazole-S-sulfonic acid.
Photographic application:
To a gelatino-silver iodobromide emulsion of average sensitivity containing about 5 mol percent of silver iodide were added 40 ml. of a 7.5% aqueous solution of saponine, ml. of a 5% methanolic solution of tris-acroleylperhydrotriazine and 25 ml. of a 1% aqueous solution of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene and an aqueous solution of a dihydrazone of the following formula, so that the final layer contained 55 g. of that compound per mol silver halide.
The above emulsion was applied onto a transparent support of celluloseacetobutyrate. The dried layer contained 0.55 g. of Ag per m. and had a thickness of 3 (Material A A comparison material B differed from material A in that 19 g. of 2-m(m-hydroxylaminophenyl)-l-octadecylbenzimidazole-S-sulfonic acid per mol of silver halide were added in the form of a 5% by weight solution in 0.1 N NaOH, and the pH then adjusted to 7.0 with citric acid.
Samples of materials A and B were stored for 7 days at 40 C. and 85% relative humidity. The samples of A and B stored in this way, together with samples of A and B stored cold at +3 C. for the same period, were exposed behind a step wedge and developed for 8 minutes in a color-forming developer of the following composition:
Grams Sodium hexametaphosphate 2.0 p-Diethylaminoaniline sulfate 2.75 Sodium sulfite (anhydrous) 2.0 Potassium bromide 1.5 Potassium carbonate 75.0
Water, 1 liter.
The developed materials were washed, bleached in a potassium ferricyanide bleaching bath and then fixed and washed according to common practice. Sensitometric analysis of the following maximum color densities:
Material A; Material B1 Cold-stored 1. 0 1. 02 After storage at 40 0 0. 30 1. 04
The stabilizing effect of the hydroxylamine derivative is readily apparent.
EXAMPLE 2 Two photographic materials (samples A and B were prepared as described in Example 1. Material B contained an equimolar quantity of compound II, instead of the hydroxylamine derivative referred to in Example 1. After storage, exposure and color-forming development as in Example 1, the following maximum color densities were otbained Material A; Material B 3 Cold-stored 1. 0 1. 01
After storage at 40 C 0.32 1.03
EXAMPLE 3 EXAMPLE 4 Layers containing the direct positive dihydrazone color component stabilized with an organic hydroxyl amine derivative according to the invention can also be used in multi-layer color photographic materials to correct the undesirable absorption of subtractive color couplers, in particular the undesirable absorption of magenta color couplers.
Such a multilayer material can be composed as follows: on a transparent support, for example, of cellulose acetate or polyethylene glycol terephthalate having a subbing layer coated thereon are applied the following layers:
(a) A red-sensitive silver bromide gelatin emulsion which contains 6 mol percent of silver iodide and which further contains per liter emulsion 30 ml. of a 1% aqueous solution of 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene, 40 ml. of a 0.1% methanolic solution of the red-sensitizer of the following formula:
250 ml. of a 6% aqueous solution of the sodium salt of the cyanine coupler of the following formula:
CO-NH I 15E121 CH3 40 m1. of a 7.5% aqueous solution of saponin and 9 ml. of a 5% methanolic solution of tris(acryloyl)-perhydrotriazine. The dried layer contains 0.85 g. of silver in the form of silver halide per square meter.
(b) One of the emulsions described in Examples 1-3 sensitized to the green region of the spectrum by adding per liter of emulsion 50 ml. of 1% methanolic solution of the following sensitizing dye:
G=CHC CzHa (c) An intermediate layer of gelatin,
SOaH
40 ml. of a 7% aqueous solution of saponine and 12 ml. of a 5% methanolic solution of tris(acryloyl)perhydrotriazine. The dried layer contains 0.75 g. silver in the form of silver halide per square meter,
(e) A.yellow filter layer consisting of colloidal distributed silver dispersed in gelatin,
(f) A blue-sensitive silver iodobromide gelatin emulsion layer the silver halide of which contains 6 mol percent of silver iodide. The emulsion further contains per liter of casting solution 30 ml. of a 1% aqueous solution of 4-hydroxy-6-methyl-1,3,3a-7-tetraazaindene, 200 ml. of a 10% aqueous solution of the sodium salt of the yellow color coupler CODE COOH
ml. of a 5% methanolic solution of tris-(acroloyl)- perhydrotriazine and 50 ml. of a 7.5% aqueous solution of saponine.
The dried layer contains per square meter 1.43 g. silver in the form of silver halide,
(g) A protecting layer of hardened gelatin.
The above material is exposed to a color original and processed according to common practice by developing and bleach-fixing the exposed material. A colored image of the original in true colors is obtained. An image of the same quality is obtained after storing the above material for several days at 40 C. and high humidity.
What is claimed is:
1. In a photographic light-sensitive silver halide emulsion containing an aromatic 1,2-hydrazone of an alpha dicarbonyl compound and forming a direct positive dye image upon exposure, color development and silver bleaching, the improvement according to which the emulsion also contains an alkyl or aryl hydroxylamine in an amount that stabilizes the unprocessed emulsion against the loss of final color intensity resulting from storage at elevated temperatures.
2. The combination of claim 1 in which the hydroxylamine is an alkyl hydroxylamine having up to 20 carbons.
3. The combination of claim 1 in which the hydroxylamine is a phenyl or naphthyl hydroxylamine.
4. The combination of claim 1 in which the hydroxylamine contains a carboxy or sulfo group.
5. The combination of claim 1 in which the hydroxylamine contains an alkyl group having from 7 to 20 carbons.
6. The combination of claim 1 in which the hydroxylamine contains a carboxy or sulfo group and in addition an alkyl group having from 7 to 20' carbons.
7. The combination of claim 1, wherein the hydroxylamine is a phenylhydroxylamine, the phenyl ring of which carries an alkyl group having between 7 and 20 carbon atoms, and a water-solubilizing group.
8. The combination of claim 1 in which the hydroxylamine has the formula R--NHOH wherein R represents alkyl having up to 20 carbon atoms, phenyl-substituted alkyl having up to 20 carbon atoms in the alkyl, carboxy substituted alkyl having up to 20 carbon atoms in the alkyl, sulfo substituted alkyl having up to 20 carbon atoms in the alkyl, naphthyl, phenyl, or substitution products of naphthyl or phenyl wherein the substituents are halogen, alkoxy Ehaving up to 18 carbon atoms, hydroxy, carboxy, esterified carboxy having up to 21 carbon atoms, sulfo, amino, acylamino having up to 20 carbon atoms, phenylsulfoamino, alkylamino having up to 20 carbon atoms, sulfamido, acylsulfamide having up to 20 carbon atoms, phenylsulfamido, alkylsulfamido having up to 20 carbon atoms or alkyl having up to 20 carbon atoms.
9. The combination of claim 7 wherein the alkyl group is linlred to the phenyl ring via a phenyl sulfonamide grouping.
1 0. The combination of claim 1 wherein the hydroxylamine 1s o NHOH HOaS g N 11. The combination of claim 1 wherein the hydroxylamine is 12. The combination of claim 1 wherein the hydroxylamine is NH-CiaHgy 13. The combination of claim 1 wherein the hydroxylamine is HOOCCH2(|3HNH0H 14. The combination of claim 1 wherein the hydroxylamine is HOOC-CHr-(fJH-NHOH Cowden et a1. 9628 Trivelli et a1. 9695 Cowden et a1. 9695 Green et a1. 9695 NORMAN G. TORCHIN, Primary Examiner A. T. SURO PICO, Assistant Examiner References Cited UNITED STATES PATENTS 5/1947 Trivelli et a1. 9666 US. Cl. X.R.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEA0004638 | 1964-06-20 | ||
| DEA46380A DE1200678B (en) | 1964-06-20 | 1964-06-20 | Process for the stabilization of photographic materials for the production of colored direct positive images and photographic material for this |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3471295A true US3471295A (en) | 1969-10-07 |
Family
ID=25963057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US465254A Expired - Lifetime US3471295A (en) | 1964-06-20 | 1965-06-16 | Production of colored direct-positive images |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US3471295A (en) |
| BE (1) | BE665616A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3647463A (en) * | 1969-08-14 | 1972-03-07 | Eastman Kodak Co | Direct-positive photographic elements containing multiple layers |
| US4299913A (en) * | 1977-10-01 | 1981-11-10 | Agfa-Gevaert Ag | Photographic reversal process without second exposure |
| US4330606A (en) * | 1979-09-08 | 1982-05-18 | Agfa-Gevaert Ag | Color photographic materials and color photographic images |
| US4339515A (en) * | 1979-09-08 | 1982-07-13 | Agfa-Gevaert Aktiengesellschaft | Method of stabilizing color photographic materials and a color photographic material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2419975A (en) * | 1943-08-26 | 1947-05-06 | Eastman Kodak Co | Increasing speed and contrast of photographic emulsions |
| US2835575A (en) * | 1955-04-05 | 1958-05-20 | Eastman Kodak Co | Photographic reproduction process |
| US3293034A (en) * | 1963-06-26 | 1966-12-20 | Polaroid Corp | Alkoxy hydroxylamines as photographic developers |
-
1965
- 1965-06-16 US US465254A patent/US3471295A/en not_active Expired - Lifetime
- 1965-06-18 BE BE665616D patent/BE665616A/xx unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2419975A (en) * | 1943-08-26 | 1947-05-06 | Eastman Kodak Co | Increasing speed and contrast of photographic emulsions |
| US2835575A (en) * | 1955-04-05 | 1958-05-20 | Eastman Kodak Co | Photographic reproduction process |
| US3293034A (en) * | 1963-06-26 | 1966-12-20 | Polaroid Corp | Alkoxy hydroxylamines as photographic developers |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3647463A (en) * | 1969-08-14 | 1972-03-07 | Eastman Kodak Co | Direct-positive photographic elements containing multiple layers |
| US4299913A (en) * | 1977-10-01 | 1981-11-10 | Agfa-Gevaert Ag | Photographic reversal process without second exposure |
| US4330606A (en) * | 1979-09-08 | 1982-05-18 | Agfa-Gevaert Ag | Color photographic materials and color photographic images |
| US4339515A (en) * | 1979-09-08 | 1982-07-13 | Agfa-Gevaert Aktiengesellschaft | Method of stabilizing color photographic materials and a color photographic material |
Also Published As
| Publication number | Publication date |
|---|---|
| BE665616A (en) | 1965-12-20 |
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