US3287125A - Aminoalkyl hydroxylamines as photographic developers - Google Patents
Aminoalkyl hydroxylamines as photographic developers Download PDFInfo
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- US3287125A US3287125A US290618A US29061863A US3287125A US 3287125 A US3287125 A US 3287125A US 290618 A US290618 A US 290618A US 29061863 A US29061863 A US 29061863A US 3287125 A US3287125 A US 3287125A
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- Prior art keywords
- silver halide
- hydroxylamine
- methyl
- percent
- developing
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- -1 Aminoalkyl hydroxylamines Chemical class 0.000 title claims description 39
- 239000004332 silver Substances 0.000 claims description 46
- 229910052709 silver Inorganic materials 0.000 claims description 46
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 125000000217 alkyl group Chemical group 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- CREXVNNSNOKDHW-UHFFFAOYSA-N azaniumylideneazanide Chemical group N[N] CREXVNNSNOKDHW-UHFFFAOYSA-N 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 8
- 150000002443 hydroxylamines Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- RGZRSLKIOCHTSI-UHFFFAOYSA-N hydron;n-methylhydroxylamine;chloride Chemical compound Cl.CNO RGZRSLKIOCHTSI-UHFFFAOYSA-N 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 235000019645 odor Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 2
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- VDUIPQNXOQMTBF-UHFFFAOYSA-N n-ethylhydroxylamine Chemical compound CCNO VDUIPQNXOQMTBF-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LQLJZSJKRYTKTP-UHFFFAOYSA-N 2-dimethylaminoethyl chloride hydrochloride Chemical compound Cl.CN(C)CCCl LQLJZSJKRYTKTP-UHFFFAOYSA-N 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- VMESOKCXSYNAKD-UHFFFAOYSA-N n,n-dimethylhydroxylamine Chemical compound CN(C)O VMESOKCXSYNAKD-UHFFFAOYSA-N 0.000 description 1
- CPQCSJYYDADLCZ-UHFFFAOYSA-N n-methylhydroxylamine Chemical compound CNO CPQCSJYYDADLCZ-UHFFFAOYSA-N 0.000 description 1
- ZUZQXHSOEZUAIS-UHFFFAOYSA-N nitric acid;6-nitro-1h-benzimidazole Chemical compound O[N+]([O-])=O.[O-][N+](=O)C1=CC=C2N=CNC2=C1 ZUZQXHSOEZUAIS-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000000837 restrainer Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 description 1
- 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 1
- 239000007787 solid Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
- C07D213/42—Radicals substituted by singly-bound nitrogen atoms having hetero atoms attached to the substituent nitrogen atom
-
- 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
- G03C5/29—Development processes or agents therefor
- G03C5/30—Developers
- G03C5/3014—Hydrazine; Hydroxylamine; Urea; Derivatives thereof
Definitions
- Another object of the present invention is to provide novel developer compositions and processes employing such novel developer compositions for the development of silver halide emulsions.
- a fiurther object of this invention is to provide novel developer compositions usetul in diffusion transfer processes.
- the invention accordingly comprises the several steps and the relation and order of one or more of such steps with respect to each of the others, and the compositions possessing the features, properties and the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will. be indicated in the claims.
- the present invention relates to novel N-substit-uted hydroxylamines corresponding to the zforrnula:
- R -N-R wherein at least one of R and R is an alkyl group containing an intralinear amino nitrogen atom, either cyclic or acyclic, and the other of R and R is selected from the group consisting of alkyl groups and alkyl groups containing an intralinear amino nitrogen atom, either cyclic or acyclic.
- R and R preferably contain from 1 to 7 carbons, but may contain more carbons provided the resulting compound is soluble in aqueous sodium hydroxide.
- the preferred hydroxylamines of this invention include:
- novel hydroxylamines of this invention may be prepared by an addition reaction ibetween a hydroxylamine and an appropriate compound, mg, a pyridine or acrylamide, containing an activated double bond.
- an addition reaction ibetween a hydroxylamine and an appropriate compound, mg, a pyridine or acrylamide, containing an activated double bond.
- cooling means e.g., addition of ice
- Isolation of the product preferably is accomplished by vacuum fractionatiug or by recrystallization of a suitable solvent, though in some cases extraction or other purification procedures may be desirable before distillation.
- Example 1 A flask was charged with 72 g. (0.5 mole) of dimethyl aminoethylchloride hydrochloride and 41.75 :g. (0.5 mole) of N-methylhydroxylamine hydrochloride in 300 cc. of methanol. 53 g. (0.5 mole) of sodium bicarbonate in ml. of water was added gradually to the mixture in the flask. The reaction mixture was refluxed for 4 hours, after which the inonganic salts were filtered off, the filtrate evaporated. Extraction of the residue with chloroform gave 14 :g. (18.2% yield) of Nmethyl-N-Z-dimethylamino ethyl-hydroxylamine hydrochloride melting at 126- 127 C. Sodium hydroxide was added to the water layer and extraction with chloroform gave 11 g. (18.7%) of the free amine, boiling at 43 C. at a pressure of 0.5 mm. Elemental analysis of the hydrochloride gave the following results:
- Example 2 To a flask charged with 15.7 g. of methylhydroxylamine hydrochloride suspended in 32.8 g. of morpholine, 15 g. of 37% formaldehyde was added dropwise with stirring and ice cooling. During the addition the reaction mixture became homogeneous and after stirring for about 30 minutes no formaldehyde odor could be noted. After standing, the top oily layer of the reaction mixture was removed and vacuum distilled to yield 8.4 g. (31% yield) of the desired N-methyl-N-(N'unorpholino)-methyl-hydroxylamine as a colorless oil easily soluble in 5% NaOH and boiling at 60-65" C.
- Example 10.5 g. of 2-vinylpyridine were added in one portion to 3.45 g. of hydroxy-lamine hydrochloride in 40 cc. of Warm methanol, and the reaction mixture was refluxed for 10 minutes and allowed to stand overnight. 3 g. of sodium carbonate and a few drops of water were added with stirring. The reaction mixture was filtered andthe filtrate was evaporated. Recrystallization of the residue from benzene gave 6.9 g. (57% yield) of N,Nbis-[2- (2'pyridyl)-ethyl]-hydroxylamine melting at 110-111 C. Nitrogen analysis gave 17.26% compared with 17.27% calculated for C14H17N3O.
- Example 6 N methyl-N-2- (4-pyridyl) ethyl-hydroxylamine was synthesized from 36.75 g. (0.35 mole) of 4-vinylpyridine and 41.75 g. (0.5 mole) of N-methylhydroxylamine hydrochloride in a manner similar to that set forth in Example 4. The crude product was purified by dissolving it in hot benzene and adding ligroin until a turbidity was observed. 36.8 g. (69.5% yield) of pale yellow crystals were obtained. After further recrystallization from ligroin, the product melted at 78 C., and gave the following elemental analysis:
- Example 7 N,N-bis-[2-(4'-pyridyl) -ethy1] -hydroxylamine was synthesized from 36.75 g. (0.35 mole) of 4-vinylpyridine and 34.75 g. (0.5 mole) of hydroxylamine hydrochloride in a manner similar to that set forth in Example 5. The solid reaction product was recrystallized from benzene to give white needles melting at 148-149- C.
- novel silver halide developing agents of this invention are useful in conventional or wet development of silver halide emulsions, diffusion transfer processes, both dye and silver, and many of them are especially useful in such photographic processes wherein it is desired to eliminate or minimize the need for washing or stabilizing operations in liquid baths subsequent to the formation of the silver print. Examples of such processes are disclosed in US. Patent No. 2,647,056 to Edwin H. Land.
- an exposed .silver halide emulsion is treated with a liquid processing composition while in superposed relationship with an image-receiving mate-.
- the liquid processing composition develops exposed silver halide to silver and reacts with unexposed rial.
- the processing composition includes a silver halide solvent, such as sodium thiosulfate, and may also contain a film-forming mate rial for increasing the viscosity of the composition.
- silver halide solven refers to reagents which will form a soluble complex with silver. halide, as is well known in the art of forming silver images .by transfer.
- Example 8 A silver iodobromide emulsion sold .by E. I du Pont de Nemours & Co., Wilmington, Delaware, was exposed and processed with a processing solution preparedby.
- the image-receiving element comprised a silver-receptive stratum containing silver-precipitating nuclei dispersed .in
- N,N-diethyl-hydroxylamine is characterized by substantial volatility at room temperatures. While this is a desirable property. for many purposes, e.g., to remove unreacted developing agent without washing operations,
- the induction periods of the novel developing agents of this invention were tested by applying an approximately 1 molar solution of the hydroxylarnine in 5% sodium hydroxide to a fogged silver iodobromide emulsion and 1 noting the elapsed time before strong developing starts.
- Example 1 The compounds preparedin Examples 1, 4, 5 and 6 all showed induction periods of from 1 to 2 seconds, and that of Example 3 showed an induction period of 3 seconds, as compared with 2.5 to 3 seconds for N,N-diethyl-hydroxylamine and 8 seconds for N,N-dimethyl-hydroxylamine.
- novel developing agents may be employed in solution or they may be initially incorporated in a layer of the photosensitive or image-receiving elements; in the latter case they are preferably employed as acid salts, e.g., as the hydrochloride or hydrobromide.
- an aqueous solution comprising an alkaline material, a silver halide solvent, and a silver halide developing agent selected from the group consisting of compounds within the formula:
- R and R is selected from the group consisting of alkyl groups containing an intralinear amino nitrogen atom, and the other of said R and R is selected from the group consisting of alkyl groups and alkyl groups containing an intralinear amino nitrogen atom.
- a method of developing a silver halide emulsion which comprises treating an exposed silver halide emulsion with an aqueous solution comprising an alkaline material and a silver halide developing agent selected from the group consisting of compounds represented b the formula:
- R and R is selected from the group consisting of alkyl groups containing an intralinear amino nitrogen atom, and the other of said R and R is selected from the group consisting of alkyl groups and alkyl groups containing an intralinear amino nitrogen atom.
- a method of developing a silver halide emulsion which comprises treating an exposed silver halide emulsion with an aqueous solution comprising an alkaline material and N-methyl-N-2-dimethylaminoethyl-hydroxylamine for a suflicient time to develop said exposed silver halide emulsion.
- a method of developing a silver halide emulsion which comprises treating an exposed silver halide emulsion with an aqueous solution comprising an alkaline material and N-methyl-N-(N'-m0rpholino)-methyl-hydroxylamine for a sufficient time to develop said exposed silver halide emulsion.
- a method of developing a silver halide emulsion which comprises treating an exposed silver halide emulsion with an aqueous solution comprising an alkaline material and N-methyl-N-Z-carboxamidoethyl-hydroxylamine for a sufficient time to develop said exposed silver halide emulsion.
- a method of developing a silver halide emulsion which comprises treating an exposed silver halide emul- 5 sion with an aqueous solution comprising an alkaline material and Namethyl-N-Z-(Z-pyridyl)ethyl-hydroxylamine for a sufiicient time to develop said exposed silver halide emulsion.
- a method of developing a silver halide emulsion 10 which comprises treating an exposed silver halide emulsion with an aqueous solution comprising an alkaline material and N,N bis-[2-(2'-pyridyl) -ethyl] -hydroxylamine for a suflioient time to develop said exposed silver halide emulsion.
- a photographic process comprising the steps of developing an exposed silver halide emulsion with an aqueous alkaline solution comprising a silver halide develop ing agent and a silver halide solvent in the presence of an image-receiving material superposed on said silver halide emulsion, said developing agent being selected from the goup consisting of compounds represented by the formula:
- IRA-N-R wherein at least one of R and R is selected from the group consisting of alkyl groups containing an intralinear amino nitrogen atom, and the other of said R and R is selected from the group consisting of alkyl groups and alkyl groups containing an intralinear amino nitrogen atom to form a positive silver print on said image-receiving material.
- a process as defined in claim 8, wherein said developing agent is N-methyl-N-Z-carboxamidoethyl-hydroxylamine.
- a process as defined in claim 8, wherein said developing agent is N-methyl-N-2-(4-pyridy-l)-ethyl-hydroxylamine.
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- Pyridine Compounds (AREA)
Description
United States Patent 3,287,125 AMINOALKYL HYDROXYLAMINES AS PHOTOGRAPHIC DEVELOPERS Milton Green, Newton Highlands, Mass., and Adnan A. Sayigh, North Haven, and Henri Ulrich, Northford, Conn., assignors to Polaroid Corporation, Cambridge, Mass., a corporation of Delaware No Drawing. Filed June 26, 1963, Ser. No. 290,618 15 Claims. (Cl. 96-29) This invention relates to photography and more particularly to novel chemical compounds usefiul in the development of photosensitive silver halide elements.
It is one object of the present invention to provide novel chemical compounds which may be employed in the development of silver halide emulsions.
Another object of the present invention is to provide novel developer compositions and processes employing such novel developer compositions for the development of silver halide emulsions.
A fiurther object of this invention is to provide novel developer compositions usetul in diffusion transfer processes.
The invention accordingly comprises the several steps and the relation and order of one or more of such steps with respect to each of the others, and the compositions possessing the features, properties and the relation of elements which are exemplified in the following detailed disclosure, and the scope of the application of which will. be indicated in the claims.
Other objects of this invention will in part be obvious and will in part appear hereinafter.
The present invention relates to novel N-substit-uted hydroxylamines corresponding to the zforrnula:
R -N-R wherein at least one of R and R is an alkyl group containing an intralinear amino nitrogen atom, either cyclic or acyclic, and the other of R and R is selected from the group consisting of alkyl groups and alkyl groups containing an intralinear amino nitrogen atom, either cyclic or acyclic. R and R preferably contain from 1 to 7 carbons, but may contain more carbons provided the resulting compound is soluble in aqueous sodium hydroxide.
The preferred hydroxylamines of this invention include:
(1) OH CH 0 H I IC Hz-C H2 I C H 'NmethylN-2-dimethy1aminoethykhydroxylamine 0 BAH: Ear X N-methyl-N- (N-morpl1o1ino) methyl-hydroxylamine O H -bI-C H2O Evil-NH:
N-rne thyl-N-2-carboxamid oethyl-hydroxylamine [-3- (iN-methyl) -hydroxylaminopropionamide] CH l ICHzOH N N-methyl-N-2- (2-pyridyl) ethyl-hydroxylamine N ,N-bis-[2-'(4 -pyridyl) -ethyl] hydroxylamine The use of hydroxylamines in developing silver halide emulsions is disclosed, e.'g., by Land et al., US. Patents Nos. 2,857,274; 2,857,275; and 2,857,276. A particularly useful :hydroxylamine has been N,N-diethy-lhydroxylamine. The novel chemical compounds of the present invention exhibit many properties making them more desirable as silver halide developing agents than hydroxylamines previously used, as will be noted hereinafter.
Many of the novel hydroxylamines of this invention may be prepared by an addition reaction ibetween a hydroxylamine and an appropriate compound, mg, a pyridine or acrylamide, containing an activated double bond. Where the reaction is exothermic, use of cooling means, e.g., addition of ice, may be desirable to hold the to perature below the critical point. Isolation of the product preferably is accomplished by vacuum fractionatiug or by recrystallization of a suitable solvent, though in some cases extraction or other purification procedures may be desirable before distillation.
The following detailed examples are given only to illustrate the preparation of preferred compounds the scope of this invention, and are not intended to be in any Way limiting.
Example 1 A flask was charged with 72 g. (0.5 mole) of dimethyl aminoethylchloride hydrochloride and 41.75 :g. (0.5 mole) of N-methylhydroxylamine hydrochloride in 300 cc. of methanol. 53 g. (0.5 mole) of sodium bicarbonate in ml. of water was added gradually to the mixture in the flask. The reaction mixture was refluxed for 4 hours, after which the inonganic salts were filtered off, the filtrate evaporated. Extraction of the residue with chloroform gave 14 :g. (18.2% yield) of Nmethyl-N-Z-dimethylamino ethyl-hydroxylamine hydrochloride melting at 126- 127 C. Sodium hydroxide was added to the water layer and extraction with chloroform gave 11 g. (18.7%) of the free amine, boiling at 43 C. at a pressure of 0.5 mm. Elemental analysis of the hydrochloride gave the following results:
Calculated cfor C H ClN O: Percent C, 38.83; percent H, 9.77; percent N, 18.11. Found: percent C, 39.10; percent H, 9.85; percent N, 18.28.
Example 2 To a flask charged with 15.7 g. of methylhydroxylamine hydrochloride suspended in 32.8 g. of morpholine, 15 g. of 37% formaldehyde was added dropwise with stirring and ice cooling. During the addition the reaction mixture became homogeneous and after stirring for about 30 minutes no formaldehyde odor could be noted. After standing, the top oily layer of the reaction mixture was removed and vacuum distilled to yield 8.4 g. (31% yield) of the desired N-methyl-N-(N'unorpholino)-methyl-hydroxylamine as a colorless oil easily soluble in 5% NaOH and boiling at 60-65" C. at a pressure of 1 Nitrogen analysis of the product gave 19.0% compared with the calculated value of 191% for c -H N O Example 3 To 20 g. of N-methylhydroxylamine hydrochloride in cc. of methanol, 7 g. of anhydrous sodium carbonate and 14.2 g. of acrylamide were added with stirring.
After 5 minutes a slight exothermic reaction was observed. The reaction mixture was refluxed for 30 minutes, filtered, and the filtrate was evaporated in vacuo.
Recrystallization of the crude crystalline residue gave.
14.3 g. (60.5% yield) of N-methyl-N-Z-carboxamidoethyl-hydroxylamine product, melting at 94-95 C. The infrared spectrum (KBr) showed major bands at 3.03 (NH); 3.18 (OH); 5.98 (CO); 695 Nitrogen analysis of the product gave 23.41% compared with the calculated f! C H N O Example 4 A 36.75 g. (0.35 mole) portion of 2-vinylpyridine was added dropwise, with cooling, to 41.75 g. (0.5 mole) of N-methyLhydroxylamine hydrochloride. The reaction mixture was stirred at room temperature and an exothermic reaction took place causing the temperature to rise to 50' C. After stirring for 3 0 minutes at 50 C., aqueous sodium carbonate was added and the alkaline reaction mixture was extracted with chloroform. Rectification in vacuo gave 41.8 g. (79% yield) of N-methyl-N-2-(2'-pyridyl)-ethyl-hydroxylamine boiling at 95- 97 C. at a pressure of 0.15 mm. Elemental analysis of the methiodide, melting at 113-1 14 C., gave:
Calculated for C H N O: Percent C, 36.73; percent H, 5.13; percent N, 9.52. Found: Percent C, 36.88; percent H, 5.41; percent N, 9.82.
Example 10.5 g. of 2-vinylpyridine were added in one portion to 3.45 g. of hydroxy-lamine hydrochloride in 40 cc. of Warm methanol, and the reaction mixture was refluxed for 10 minutes and allowed to stand overnight. 3 g. of sodium carbonate and a few drops of water were added with stirring. The reaction mixture was filtered andthe filtrate was evaporated. Recrystallization of the residue from benzene gave 6.9 g. (57% yield) of N,Nbis-[2- (2'pyridyl)-ethyl]-hydroxylamine melting at 110-111 C. Nitrogen analysis gave 17.26% compared with 17.27% calculated for C14H17N3O.
Example 6 N methyl-N-2- (4-pyridyl) ethyl-hydroxylamine was synthesized from 36.75 g. (0.35 mole) of 4-vinylpyridine and 41.75 g. (0.5 mole) of N-methylhydroxylamine hydrochloride in a manner similar to that set forth in Example 4. The crude product was purified by dissolving it in hot benzene and adding ligroin until a turbidity was observed. 36.8 g. (69.5% yield) of pale yellow crystals were obtained. After further recrystallization from ligroin, the product melted at 78 C., and gave the following elemental analysis:
Calculated for C H N O: Percent C, 63.13; percent H, 7.95; percent N, 18.41. Found: percent C, 63.24; percent H, 8.05; percent N, 18.10.
Example 7 N,N-bis-[2-(4'-pyridyl) -ethy1] -hydroxylamine was synthesized from 36.75 g. (0.35 mole) of 4-vinylpyridine and 34.75 g. (0.5 mole) of hydroxylamine hydrochloride in a manner similar to that set forth in Example 5. The solid reaction product was recrystallized from benzene to give white needles melting at 148-149- C.
As previously mentioned, the novel silver halide developing agents of this invention are useful in conventional or wet development of silver halide emulsions, diffusion transfer processes, both dye and silver, and many of them are especially useful in such photographic processes wherein it is desired to eliminate or minimize the need for washing or stabilizing operations in liquid baths subsequent to the formation of the silver print. Examples of such processes are disclosed in US. Patent No. 2,647,056 to Edwin H. Land.
In diffusion transfer processes of this type, as is well known in the art, an exposed .silver halide emulsion is treated with a liquid processing composition while in superposed relationship with an image-receiving mate-. The liquid processing composition develops exposed silver halide to silver and reacts with unexposed rial.
silver halide to form a complex silver salt which is transferred to the image-receiving material and there reduced 1 to silver to form a positive print. The processing composition includes a silver halide solvent, such as sodium thiosulfate, and may also contain a film-forming mate rial for increasing the viscosity of the composition. As used herein, the term silver halide solven refers to reagents which will form a soluble complex with silver. halide, as is well known in the art of forming silver images .by transfer.
The following example is intended to illustrate the use of the novel developing agents of this invention in diffusion transfer processes, and is intended to, be illus-' trative only.
Example 8 A silver iodobromide emulsion sold .by E. I du Pont de Nemours & Co., Wilmington, Delaware, was exposed and processed with a processing solution preparedby.
adding 0.4 g. of N-methyl-N-2-dimethylaminoethyl-hydroxylamine to 10 cc. of a composition comprising:
Sodium carboxymethyl cellulose g 38.1 Sodium hydroxide g 34.2 6-nitrobenzimidazole nitrate g 60 Sodium sulfite g 53.6 Sodium thiosulfate g 20.0 Water cc 850 The image-receiving element comprised a silver-receptive stratum containing silver-precipitating nuclei dispersed .in
molar equivalents of the other novel hydroxylamines prepared in the above examples also gave good diffusion transfer images.
N,N-diethyl-hydroxylamine is characterized by substantial volatility at room temperatures. While this is a desirable property. for many purposes, e.g., to remove unreacted developing agent without washing operations,
there results a strong fishy. or amine odor which is objectionable in many applications, e.g., where a number of prints are to be made in a short time in the same room. In contrast, many'of the novel developing agents of this invention do not exhibit strong odors at room temperature because their vapor pressures are appreciably lower than that of N,N-diethy1-hydroxylamine. Although N-methyl- N-2-dimethylaminoethylhydroxyl-amine does have appreciable volatility at room temperature, ithas a shorter development induction period than N;N-diethyl-hydroxylamine. The compounds containing a heterocyclic nitrogen atom may be less desirablethan the others in certain applications, since they tend to form coloredoxidation products instead of the colorless or substantially colorless oxidation products of the other compounds.
The induction periods of the novel developing agents of this invention were tested by applying an approximately 1 molar solution of the hydroxylarnine in 5% sodium hydroxide to a fogged silver iodobromide emulsion and 1 noting the elapsed time before strong developing starts.
The compounds preparedin Examples 1, 4, 5 and 6 all showed induction periods of from 1 to 2 seconds, and that of Example 3 showed an induction period of 3 seconds, as compared with 2.5 to 3 seconds for N,N-diethyl-hydroxylamine and 8 seconds for N,N-dimethyl-hydroxylamine.
The novel developing agents may be employed in solution or they may be initially incorporated in a layer of the photosensitive or image-receiving elements; in the latter case they are preferably employed as acid salts, e.g., as the hydrochloride or hydrobromide.
It will be apparent that the relative proportions of the novel developing agents of the developer compositions set forth above may be varied to suit the requirements of the operator. Thus, it is within the scope of this invention to modify the above developer compositions by the substitution of preservatives, alkalies, silver halide solvents, anti-foggants, etc., other than those specifically mentioned. Where desirable, it is also contemplated to include in the developer composition common components such as restrainers, accelerators, etc.
Since certain changes may be made in the above compositions and processes without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.
What is claimed is:
1. As a new developer composition, an aqueous solution comprising an alkaline material, a silver halide solvent, and a silver halide developing agent selected from the group consisting of compounds within the formula:
wherein at least one of R and R is selected from the group consisting of alkyl groups containing an intralinear amino nitrogen atom, and the other of said R and R is selected from the group consisting of alkyl groups and alkyl groups containing an intralinear amino nitrogen atom.
2. A method of developing a silver halide emulsion which comprises treating an exposed silver halide emulsion with an aqueous solution comprising an alkaline material and a silver halide developing agent selected from the group consisting of compounds represented b the formula:
wherein at least one of R and R is selected from the group consisting of alkyl groups containing an intralinear amino nitrogen atom, and the other of said R and R is selected from the group consisting of alkyl groups and alkyl groups containing an intralinear amino nitrogen atom.
3. A method of developing a silver halide emulsion which comprises treating an exposed silver halide emulsion with an aqueous solution comprising an alkaline material and N-methyl-N-2-dimethylaminoethyl-hydroxylamine for a suflicient time to develop said exposed silver halide emulsion.
4. A method of developing a silver halide emulsion which comprises treating an exposed silver halide emulsion with an aqueous solution comprising an alkaline material and N-methyl-N-(N'-m0rpholino)-methyl-hydroxylamine for a sufficient time to develop said exposed silver halide emulsion.
5. A method of developing a silver halide emulsion which comprises treating an exposed silver halide emulsion with an aqueous solution comprising an alkaline material and N-methyl-N-Z-carboxamidoethyl-hydroxylamine for a suficient time to develop said exposed silver halide emulsion.
6. A method of developing a silver halide emulsion which comprises treating an exposed silver halide emul- 5 sion with an aqueous solution comprising an alkaline material and Namethyl-N-Z-(Z-pyridyl)ethyl-hydroxylamine for a sufiicient time to develop said exposed silver halide emulsion.
7. A method of developing a silver halide emulsion 10 which comprises treating an exposed silver halide emulsion with an aqueous solution comprising an alkaline material and N,N bis-[2-(2'-pyridyl) -ethyl] -hydroxylamine for a suflioient time to develop said exposed silver halide emulsion.
8. A photographic process comprising the steps of developing an exposed silver halide emulsion with an aqueous alkaline solution comprising a silver halide develop ing agent and a silver halide solvent in the presence of an image-receiving material superposed on said silver halide emulsion, said developing agent being selected from the goup consisting of compounds represented by the formula:
IRA-N-R wherein at least one of R and R is selected from the group consisting of alkyl groups containing an intralinear amino nitrogen atom, and the other of said R and R is selected from the group consisting of alkyl groups and alkyl groups containing an intralinear amino nitrogen atom to form a positive silver print on said image-receiving material.
9. A process as defined in claim 8, wherein said developing agent is N-methyl-N-Z-dimethylaminoethyl-hydroxylamine.
10. A process as defined in claim 8, wherein saiddeveloping agent is N-methyl-N-(N'-morpholino)-methy1- hydroxylamine.
11. A process as defined in claim 8, wherein said developing agent is N-methyl-N-Z-carboxamidoethyl-hydroxylamine.
12. A process as defined in claim 8, wherein said developing agent is N-rnethyl-N-2-(2-pyridyl) ethyl-hydroxylamine.
13. A process as defined in claim 8, wherein said developing agent is N,N- bis- [2-(2'-pyridyl)-ethyl] -hydroxylamine.
14. A process as defined in claim 8, wherein said developing agent is N-methyl-N-2-(4-pyridy-l)-ethyl-hydroxylamine.
15. A process as defined in claim 8, wherein said developing agent is N,N-bis- [2- (4'-pyridyl) -ethyl] -hydroxylamine.
References Cited by the Examiner UNITED STATES PATENTS 2,169,976 8/1939 Guenther 260-583 2,857,276 10/ 1958 Land et a1. 9629 3,137,705 6/ 1964 Prelog et a1 260583 X OTHER REFERENCES Agwada: J. Org. Chem, vol. 7, 1962., pp. 3153-3155. Reich et 21.: J. Amer. Chem. Soc., vol. 77, pp. 5434- 5436 NORMAN G. TORCHIN, Primary Examiner.
DONALD LEVY, Examiner.
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,287,125 November 22, 1966 Milton Green et al.
It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 3, line 25, for "C H N O" read CgH15IN2O column 4, line 28, for "60" read 6.0
Signed and sealed this 28th day of November 1967.
(SEAL) Attest:
EDWARD J. BRENNER EDWARD M. FLETCHER,JR. Attesting Officer Commissioner of Patents
Claims (1)
1. AS A NEW DEVELOPER COMPOSITION, AN AQUEOUS SOLUTION COMPRISING AN ALKALINE MATERIAL, A SILVER HALIDE SOLVENT, AND A SILVER HALIDE DEVELOPING AGENT SELECTED FROM THE GROUP CONSISTING OF COMPOUNDS WITHIN THE FORMULA:
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| US290618A US3287125A (en) | 1963-06-26 | 1963-06-26 | Aminoalkyl hydroxylamines as photographic developers |
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| Application Number | Priority Date | Filing Date | Title |
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| US290618A US3287125A (en) | 1963-06-26 | 1963-06-26 | Aminoalkyl hydroxylamines as photographic developers |
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Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3619185A (en) * | 1968-04-29 | 1971-11-09 | Polaroid Corp | Photographic processing compositions and processes using same |
| JPS4811039B1 (en) * | 1970-10-16 | 1973-04-10 | ||
| US3867445A (en) * | 1971-04-13 | 1975-02-18 | Ciba Geigy Corp | Substituted hydroxylamine anti-oxidants |
| JPS513219B1 (en) * | 1969-10-27 | 1976-02-02 | ||
| US4526857A (en) * | 1983-04-20 | 1985-07-02 | Fuji Photo Film Co., Ltd. | Image formation by silver salt diffusion transfer process comprising mercaptotriazole and thiouracil |
| US4699868A (en) * | 1984-03-02 | 1987-10-13 | Minnesota Mining And Manufacturing Company | Photographic tanning developer formulation |
| EP0266797A2 (en) | 1986-11-07 | 1988-05-11 | Fuji Photo Film Co., Ltd. | Method of processing silver halide color photographic material and photographic color developing composition |
| US4797350A (en) * | 1986-04-16 | 1989-01-10 | Konishiroku Photo Industry Co., Ltd. | Process for forming dye-image using a developer comprising an image stabilizer, a hydroxylamine and not containing benzyl alcohol |
| US4800153A (en) * | 1986-07-18 | 1989-01-24 | Fuji Photo Film Co., Ltd. | Method for processing silver halide color photographic materials and a color photographic developer composition comprising hydroxylamine and stabilizer |
| US4801516A (en) * | 1986-06-25 | 1989-01-31 | Fuji Photo Film Co., Ltd. | Method of processing silver halide color photographic material using a developer comprising a hydroxylamine and an antifoggant |
| US4851325A (en) * | 1986-07-12 | 1989-07-25 | Fuji Photo Film Co., Inc. | Process for producing silver halide color photographic materials comprising a heterocyclic developing agent |
| US4876174A (en) * | 1986-06-24 | 1989-10-24 | Fuji Photo Film Co., Ltd. | Method of processing silver halide color photosensitive material using developer comprising dialkyl hydroxylamine and no benzyl alcohol |
| JPH0218556A (en) * | 1988-07-06 | 1990-01-22 | Fuji Photo Film Co Ltd | Method of processing silver halide color photographic sensitive material |
| US4897339A (en) * | 1986-08-08 | 1990-01-30 | Fuji Photo Film Co., Ltd. | Method for processing a silver halide color photographic material and a color developing composition comprising hydroxylamines and stabilizing agents |
| JPH0251155A (en) * | 1988-08-12 | 1990-02-21 | Fuji Photo Film Co Ltd | Image forming method by silver salt diffusion transfer |
| JPH02146542A (en) * | 1988-11-29 | 1990-06-05 | Fuji Photo Film Co Ltd | Image forming method by silver salt diffusion transfer |
| US5290661A (en) * | 1991-07-31 | 1994-03-01 | Fuji Photo Film Co., Ltd. | Method for forming images by silver salt diffusion transfer |
| US5354646A (en) * | 1986-03-26 | 1994-10-11 | Konishiroku Photo Industry Co., Ltd. | Method capable of rapidly processing a silver halide color photographic light-sensitive material |
| US5362610A (en) * | 1991-10-28 | 1994-11-08 | Konica Corporation | Photographic processing agent |
| US5366853A (en) * | 1991-11-06 | 1994-11-22 | Konica Corporation | Tablet-shaped processing agent and method for processing silver halide photographic light sensitive materials |
| US5409805A (en) * | 1993-07-29 | 1995-04-25 | Konica Corporation | Solid processing agent for silver halide photographic light-sensitive materials |
| US5646327A (en) * | 1995-12-08 | 1997-07-08 | Eastman Kodak Company | Method for preparing hydroxylamines using vinylic compounds without base neutralization and reaction mixture produced thereby |
| US6383726B1 (en) | 2000-11-03 | 2002-05-07 | Eastman Kodak Company | Method for formulating a photographic developer composition and process conditions to optimize developed images for digital scanning |
| US6649331B2 (en) | 2000-11-03 | 2003-11-18 | Eastman Kodak Company | Developer composition and method of development for photographic color negative films |
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| US2169976A (en) * | 1934-01-26 | 1939-08-15 | Ig Farbenindustrie Ag | Process of producing assistants in the textile and related industries |
| US2857276A (en) * | 1954-11-23 | 1958-10-21 | Polaroid Corp | Photographic processes and compositions useful therein |
| US3137705A (en) * | 1960-04-08 | 1964-06-16 | Ciba Geigy Corp | Hydroxylamino compounds |
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1963
- 1963-06-26 US US290618A patent/US3287125A/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2169976A (en) * | 1934-01-26 | 1939-08-15 | Ig Farbenindustrie Ag | Process of producing assistants in the textile and related industries |
| US2857276A (en) * | 1954-11-23 | 1958-10-21 | Polaroid Corp | Photographic processes and compositions useful therein |
| US3137705A (en) * | 1960-04-08 | 1964-06-16 | Ciba Geigy Corp | Hydroxylamino compounds |
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3619185A (en) * | 1968-04-29 | 1971-11-09 | Polaroid Corp | Photographic processing compositions and processes using same |
| JPS513219B1 (en) * | 1969-10-27 | 1976-02-02 | ||
| JPS4811039B1 (en) * | 1970-10-16 | 1973-04-10 | ||
| US3867445A (en) * | 1971-04-13 | 1975-02-18 | Ciba Geigy Corp | Substituted hydroxylamine anti-oxidants |
| US4526857A (en) * | 1983-04-20 | 1985-07-02 | Fuji Photo Film Co., Ltd. | Image formation by silver salt diffusion transfer process comprising mercaptotriazole and thiouracil |
| US4699868A (en) * | 1984-03-02 | 1987-10-13 | Minnesota Mining And Manufacturing Company | Photographic tanning developer formulation |
| US5354646A (en) * | 1986-03-26 | 1994-10-11 | Konishiroku Photo Industry Co., Ltd. | Method capable of rapidly processing a silver halide color photographic light-sensitive material |
| US4797350A (en) * | 1986-04-16 | 1989-01-10 | Konishiroku Photo Industry Co., Ltd. | Process for forming dye-image using a developer comprising an image stabilizer, a hydroxylamine and not containing benzyl alcohol |
| US4876174A (en) * | 1986-06-24 | 1989-10-24 | Fuji Photo Film Co., Ltd. | Method of processing silver halide color photosensitive material using developer comprising dialkyl hydroxylamine and no benzyl alcohol |
| US4801516A (en) * | 1986-06-25 | 1989-01-31 | Fuji Photo Film Co., Ltd. | Method of processing silver halide color photographic material using a developer comprising a hydroxylamine and an antifoggant |
| US4851325A (en) * | 1986-07-12 | 1989-07-25 | Fuji Photo Film Co., Inc. | Process for producing silver halide color photographic materials comprising a heterocyclic developing agent |
| US4800153A (en) * | 1986-07-18 | 1989-01-24 | Fuji Photo Film Co., Ltd. | Method for processing silver halide color photographic materials and a color photographic developer composition comprising hydroxylamine and stabilizer |
| US4897339A (en) * | 1986-08-08 | 1990-01-30 | Fuji Photo Film Co., Ltd. | Method for processing a silver halide color photographic material and a color developing composition comprising hydroxylamines and stabilizing agents |
| EP0266797A2 (en) | 1986-11-07 | 1988-05-11 | Fuji Photo Film Co., Ltd. | Method of processing silver halide color photographic material and photographic color developing composition |
| JPH0218556A (en) * | 1988-07-06 | 1990-01-22 | Fuji Photo Film Co Ltd | Method of processing silver halide color photographic sensitive material |
| JPH0251155A (en) * | 1988-08-12 | 1990-02-21 | Fuji Photo Film Co Ltd | Image forming method by silver salt diffusion transfer |
| JPH0830882B2 (en) | 1988-08-12 | 1996-03-27 | 富士写真フイルム株式会社 | Image forming method by silver salt diffusion transfer |
| JPH0830883B2 (en) | 1988-11-29 | 1996-03-27 | 富士写真フイルム株式会社 | Image forming method by silver salt diffusion transfer |
| JPH02146542A (en) * | 1988-11-29 | 1990-06-05 | Fuji Photo Film Co Ltd | Image forming method by silver salt diffusion transfer |
| US5290661A (en) * | 1991-07-31 | 1994-03-01 | Fuji Photo Film Co., Ltd. | Method for forming images by silver salt diffusion transfer |
| US5362610A (en) * | 1991-10-28 | 1994-11-08 | Konica Corporation | Photographic processing agent |
| US5366853A (en) * | 1991-11-06 | 1994-11-22 | Konica Corporation | Tablet-shaped processing agent and method for processing silver halide photographic light sensitive materials |
| US5409805A (en) * | 1993-07-29 | 1995-04-25 | Konica Corporation | Solid processing agent for silver halide photographic light-sensitive materials |
| US5646327A (en) * | 1995-12-08 | 1997-07-08 | Eastman Kodak Company | Method for preparing hydroxylamines using vinylic compounds without base neutralization and reaction mixture produced thereby |
| US6383726B1 (en) | 2000-11-03 | 2002-05-07 | Eastman Kodak Company | Method for formulating a photographic developer composition and process conditions to optimize developed images for digital scanning |
| US6589722B2 (en) | 2000-11-03 | 2003-07-08 | Eastman Kodak Company | Method for formulating a photographic developer composition and process conditions to optimize developed images for digital scanning |
| US6649331B2 (en) | 2000-11-03 | 2003-11-18 | Eastman Kodak Company | Developer composition and method of development for photographic color negative films |
| US6696231B2 (en) | 2000-11-03 | 2004-02-24 | Eastman Kodak Company | Method for formulating a photographic developer composition and process conditions to optimize developed images for digital scanning |
| US20040126716A1 (en) * | 2000-11-03 | 2004-07-01 | Arcus Robert A. | Developer composition and method of development for photographic color negative films |
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