US3386831A - Stabilizing of photographic silver halide emulsions with acyl phenyl hydrazides - Google Patents
Stabilizing of photographic silver halide emulsions with acyl phenyl hydrazides Download PDFInfo
- Publication number
- US3386831A US3386831A US435067A US43506765A US3386831A US 3386831 A US3386831 A US 3386831A US 435067 A US435067 A US 435067A US 43506765 A US43506765 A US 43506765A US 3386831 A US3386831 A US 3386831A
- Authority
- US
- United States
- Prior art keywords
- silver halide
- acid
- photographic
- emulsion
- emulsions
- 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
- 239000000839 emulsion Substances 0.000 title claims description 59
- -1 silver halide Chemical class 0.000 title claims description 48
- 229910052709 silver Inorganic materials 0.000 title claims description 41
- 239000004332 silver Substances 0.000 title claims description 41
- 230000000087 stabilizing effect Effects 0.000 title claims description 9
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 title description 6
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 claims description 8
- 238000000034 method Methods 0.000 description 13
- 108010010803 Gelatin Proteins 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 229920000159 gelatin Polymers 0.000 description 8
- 239000008273 gelatin Substances 0.000 description 8
- 235000019322 gelatine Nutrition 0.000 description 8
- 235000011852 gelatine desserts Nutrition 0.000 description 8
- 230000035945 sensitivity Effects 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 150000002429 hydrazines Chemical class 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000005070 ripening Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical class NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UIMIQJVANYZMKL-UHFFFAOYSA-N n-phenylacetohydrazide Chemical compound CC(=O)N(N)C1=CC=CC=C1 UIMIQJVANYZMKL-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 2
- NCNYEGJDGNOYJX-NSCUHMNNSA-N (e)-2,3-dibromo-4-oxobut-2-enoic acid Chemical compound OC(=O)C(\Br)=C(/Br)C=O NCNYEGJDGNOYJX-NSCUHMNNSA-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
- RLZCTRZKEDXPHT-UHFFFAOYSA-N 2-methyl-N-phenylprop-2-enehydrazide Chemical compound C(C(=C)C)(=O)N(C1=CC=CC=C1)N RLZCTRZKEDXPHT-UHFFFAOYSA-N 0.000 description 1
- JUTMSBPKIXTSNZ-UHFFFAOYSA-N 2-methyl-n-phenylpropanehydrazide Chemical compound CC(C)C(=O)N(N)C1=CC=CC=C1 JUTMSBPKIXTSNZ-UHFFFAOYSA-N 0.000 description 1
- XTXMTJJFYMPQSD-UHFFFAOYSA-N 5-(2,2-diphenylhydrazinyl)-5-oxopentanoic acid Chemical compound C1(=CC=CC=C1)N(NC(CCCC(=O)O)=O)C1=CC=CC=C1 XTXMTJJFYMPQSD-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101000913968 Ipomoea purpurea Chalcone synthase C Proteins 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 101000907988 Petunia hybrida Chalcone-flavanone isomerase C Proteins 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001408 amides 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
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- ZUIVNYGZFPOXFW-UHFFFAOYSA-N chembl1717603 Chemical compound N1=C(C)C=C(O)N2N=CN=C21 ZUIVNYGZFPOXFW-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- PKDBSOOYVOEUQR-UHFFFAOYSA-N mucobromic acid Natural products OC1OC(=O)C(Br)=C1Br PKDBSOOYVOEUQR-UHFFFAOYSA-N 0.000 description 1
- HXAKXFPOKDRNCQ-UHFFFAOYSA-N n'-phenylpropanehydrazide Chemical compound CCC(=O)NNC1=CC=CC=C1 HXAKXFPOKDRNCQ-UHFFFAOYSA-N 0.000 description 1
- QWOSOZMDGKDUJJ-UHFFFAOYSA-N n-phenylbutanehydrazide Chemical compound CCCC(=O)N(N)C1=CC=CC=C1 QWOSOZMDGKDUJJ-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/061—Hydrazine compounds
Definitions
- the invention relates to photographic emulsions and particularly to a process for stabilizing photographic silver halide emulsions by the addition of phenylhydrazides of aliphatic carboxylic acids.
- Silver halide emulsions prepared by the usual processes undergo a marked reduction in their sensitivity, a flattening in the graduation and increased fogging when stored under tropical conditions.
- the sensitivity nuclei and the latent image nuclei of exposed silver halide emulsions are not stable in storage. Stabilization of the latent image is of particular importance in multilayered color photography since the various additives in the individual layers, such as color components, sensitizers etc. cause varying degrees of alteration of the latent image on storage and thus cause a shift in the color balance.
- hydrazine compounds customarily employed in photographic emulsions show practically no stabilizing effect. They have even been used for fogging silver halide emulsions to render reversal exposure of the material unnecessary. Moreover, many hydrazine compounds impair or even completely prevent hardening of the gelatin by ordinary hardening agents.
- the compounds are characterized in that they contain at least once the following group wherein the phenyl nucleus can be substituted as desired by any groups that are photographically inert.
- groups that are photographically inert.
- alkyl radicals having up to 5 C- atoms
- alkoxy radicals preferably of the same type as 3,386,831 Patented June 4, 1968 See the alkyl radicals, halogen atoms such as chlorine or bromine and carboxyl groups.
- acetic acid phenylhydrazide acetic aoid-p-tolylhydrazide, propionic acid phenylhydrazide, butyric acid phenylhydrazide, methacrylic acid phenylhydrazide, isobutyric acid phenylhydrazide, maleic acid-bis-phenylhydrazide, fum'aric acid-bis-phenylhydrazide, itaconic acid-bis-phenylhydrazide, glutaric acid-bis-phenylhydrazide, citric acid-tri-phenylhydrazide, polyrnethacrylic acid phenylhydrazide, adipic :acid-bis-phenylhydrazide.
- the silver halide emulsions are produced in accordance with common practice.
- the preparation involves 3 separate steps: (1) precipitation of the silver halide and physical ripening in the presence of gelatin, (2) freeing of the emulsion of excess water-soluble salt usually by washing and (3) after-ripening or chemical ripening to obtain the desired speed or sensitivity.
- the substances can be added at any desired stage to the light-sensitive silver halide emulsion layer or if desired to auxiliary layers.
- the phenylhydrazides are advantageously incorporated in the finished emulsion after the chemical ripening. It is'convenient to add the stabilizers of the present invention from solutions in appropriate solvents.
- the solvent should, of course, be completely free from any deleterious effect on the silver halide emulsion. Water or lower aliphatic alcohols or admixtures thereof have proven satisfactory as solvents for the majority of the stabilizers of the invention.
- the concentration of the stabilizers in the emulsion can vary widely from about 0.1 to 20 g. per mol of silver halide, their specific concentration will vary according to the type of the light-sensitive emulsion and according to the effects desired. Preferred are concentrations of between 1 and 10 g. per mol of silver halide. The most suitable concentration for any given emulsion will be apparent upon making the test customarily used in the art.
- the emulsions for which the phenylhydrazides according to the invention are used are after-ripened in accordance with common practice.
- the emulsions essen-' tially form a latent image on the surface of the silver halide grain.
- the emulsions may contain the customarily employed silver halides such as silver chloride, silver bromide or mixtures thereof, which may contain a small amount of about up to mol percent of silver iodide.
- Suitable as binding agents for the light-sensitive layer are the usual hydrophilic binders such as carboxymethylcellulose, polyvinyl alcohol, vinyl pyrrolidone, alginic acid and its salts, esters or amides and especially gelatin.
- the emulsions stabilized in accordance with the present invention can be chemically sensitized by any of the accepted procedures.
- the emulsions can be treated with salts of the noble metals such as ruthenium, rhodium, palladium, iridium and platinum. Suitable compounds are well known in the art.
- the emulsions can also be sensitized with gold salts as described by R. Koslowsky Z. wiss. phot. 46, 65-72 (1951).
- the emulsions can also be chemically sensitized with reducing agents such as stannous salts, polyamines, sulfur compounds, such as described in the US. Patent 1,574,944, polyethylene oxides and the like.
- the emulsions can also be optically sensitized with the ordinary sensitizing dyes, cyanines or merocyanines.
- the emulsions can be stabilized with any of the known stabilizers such as mercury compounds, triazoles, azaindenes, such as disclosed by Birr in Z. wiss. phot., vol. 47 (1952), pages 2-28.
- the emulsions may be hardened by any suitable hardener, such as formaldehyde and halogen-substituted aliphatic acids such as mucobromic acid.
- Example 1 A highly sensitive silver iodobromide gelatin emulsion having an iodine content of 4 mols percent and a silver nitrate/gelatin ratio of 1:1 is produced by the usual method, washed and after-ripened to maximum sensitivity with the use of sulfurand gold sensitizers.
- the pH of the finished emulsion is 6.4.
- the customary stabilizers such as 200 mg. of 1,3,3a,7-tetraaza-4-hydroxy-6- methylindene per liter emulsion, wetting agents such as 30 ml. of a 7.5% aqueous solution of saponin per liter emulsion and hardening agents such as ml. of a 10% aqueous formaldehydre solution per liter emulsion are added to the emulsion.
- Example 3 Numerous hydrazine compounds which also do not prevent hardening of gelatin were added to a silver halide emulsion as described in Example 1 and their effect compared with phenylhydrazides according to the invention. Chloromucic acid was used as hardening agent. In all the samples, the melting point of the layer was above 100 C.
- the above table shows that only the phenylhydrazides of the present invention stabilize the latent image specks or the sensitivity of the silver halide emulsion. Other phenylhydrazides either have no stabilizing effect or cause a strong fogging of the silver halide emulsion layers.
- Example 4 A multilayer colorphotographic element is produced which includes a blue-sensitive silver halide emulsion layer containing 3-(p-stearyl-aminobenzoyl-acetamino) isophthalic acid as yellow coupler, a green-sensitive silver halide emulsion layer containing l-(3'-sulfo-4'- phenoxy)- phenyl-3-heptadecyl-pyrazolone-(5) as magenta coupler and a red-sensitive silver halide emulsion layer containing l-hydroxy 2 naphthoic acid-(2'-(methyl-n-octadecylamino)-5'-sulfonic acid)-anilide as cyan couple-r.
- the silver halide of the three light-sensitive layers essentially con sists of silver bromide.
- the usual casting additives as described by Glafkides: Photographic Chemistry, vol. 2 (Fountain Press, London), pages 564-568 for reverse color films are added to the three layers (Sample I).
- a second multilayer colorphotographic element is produced in the same way but 100 ml. of a 1% aqueous solution of acetic acid phenyl hydrazide is added per kg. of the emulsion containing the yellow coupler before the upper layer is cast (Sample II).
- the blue-sensitive emulsion layer was particularly subject to fading with respect to the latent image specks. This is clearly apparent from the yellowish color of the stored Sample I, which have a yellowish tint because of the reversal development. With stabilized Sample II a neutral grey image is obtained.
- phenylhydrazides utilized in accordance with the present invention are prepared by the conventional methods for the production of hydrazides of carboxylic acid. Suitable methods are disclosed in the handbook Methoden der organischen Chemie by Hou'ben-Weyl, 4th edition, volume 8, Part III, pages 676-680, published by Georg Thieme Verlag, Stuttgart 1952.
- An after-ripened photographic silver halide emulsion the silver halide grains of which are essentially surface-sensitive and which contains a stabilizing amount of a fl-mono-phenylhydrazde of an aliphatic carboxylic acid.
- a photographic silver halide emulsion as defined in claim 1, wherein the phenylhydrazide is characterized by the following formula:
- R is an aliphatic radical having up to 6 carbon atoms of the groups consisting of saturated alkyl and olefinically unsaturated alkyl, y stands for a whole number from 1 to 3 and X represents a substituent of the group consisting of hydrogen, alkyl, alkoxy, halogen and carboxyl.
- a process of making photographic images including the steps of exposing to the object to be reproduced a photographic element comprising a supported lightsensitive silver halide emulsion layer, developing and fixing the exposed element, the improvement consisting of performing the process with a photographic element containing a stabilizing amount of a p-mono-phenylhydrazide of an aliphatic carboxylic acid.
- R is an aliphatic radical having up to 6 carbon atoms of the group consisting of saturated alkyl and olefinically unsaturated alkyl and X represents a substituent of the group consisting of hydrogen, alkyl, alkoxy, halogen and carboxyl.
- a photographic silver halide emulsion containing from about 0.1 to about 20 grams per mole silver halide of a substituted or unsubstituted B-mono-phenylhydrazide of an aliphatic carboxylic acid, said B-mono-phenylhydrazide when substituted having a phenyl substituent selected from the group consisting of alkyl having up to 5 carbon atoms, alkoxy having up to 5 carbon atoms, halogen and carboxyl and said aliphatic carboxylic acid being a monocarboxylic or polycarboxylic, saturated or unsaturated acid.
- a method of stabilizing the latent image specks in a photographic silver halide emulsion comprising adding to said photographic silver halide emulsion from about 0.1 to about 20 grams per mole silver halide of a substituted or unsubstituted B-mono-phenylhydrazide of an aliphatic carboxylic acid, said fl-mono-phenylhydrazide when substituted having a phenyl substituent selected from the group consisting of alkyl having up to 5 carbon atoms, alkoxv having up to 5 carbon atoms, halogen and carboxyl and said aliphatic carboxylic acid being a monocarboxylic or polycarboxylic, saturated or unsaturated acid.
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEA45411A DE1199612B (de) | 1964-03-05 | 1964-03-05 | Verfahren zur Stabilisierung photographischer Halogensilber-Emulsionen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3386831A true US3386831A (en) | 1968-06-04 |
Family
ID=6934709
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US435067A Expired - Lifetime US3386831A (en) | 1964-03-05 | 1965-02-24 | Stabilizing of photographic silver halide emulsions with acyl phenyl hydrazides |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3386831A (en(2012)) |
| BE (1) | BE660667A (en(2012)) |
| DE (1) | DE1199612B (en(2012)) |
| FR (1) | FR1426573A (en(2012)) |
| GB (1) | GB1073546A (en(2012)) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5384714A (en) * | 1976-12-30 | 1978-07-26 | Fuji Photo Film Co Ltd | High sensitivity and high contrast photographic material |
| DE2758898A1 (de) * | 1977-08-30 | 1979-03-15 | Fuji Photo Film Co Ltd | Verfahren zur entwicklung photographischer lichtempfindlicher silberhalogenidmaterialien |
| US4166742A (en) * | 1976-10-18 | 1979-09-04 | Fuji Photo Film Co., Ltd. | Contrasty light-sensitive silver halide material containing a hydrazine derivative and a heterocyclic mercaptan |
| US4168977A (en) * | 1976-08-11 | 1979-09-25 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion |
| US4272606A (en) * | 1978-05-05 | 1981-06-09 | Fuji Photo Film Co., Ltd. | Method of forming a high-contrast photographic image |
| US4358531A (en) * | 1980-10-16 | 1982-11-09 | Agfa-Gevaert Aktiengesellschaft | Photographic material, process for the production thereof and process for the production of photographic images |
| US4377634A (en) * | 1977-09-06 | 1983-03-22 | Fuji Photo Film Co., Ltd. | Method for forming high contrast photographic image |
| US4650746A (en) * | 1978-09-22 | 1987-03-17 | Eastman Kodak Company | High contrast photographic emulsions and elements and processes for their development |
| US4756997A (en) * | 1986-07-23 | 1988-07-12 | Minnesota Mining And Manufacturing Company | Photographic silver halide developer compositions and process for forming photographic silver images |
| EP0338785A3 (en) * | 1988-04-21 | 1990-01-10 | Eastman Kodak Company (A New Jersey Corporation) | Photographic element containing scavenger for oxidized developing agent |
| US4937160A (en) * | 1988-08-27 | 1990-06-26 | E. I. Du Pont De Nemours And Company | Photographic silver halide elements containing aryl hydrazides |
| US5212045A (en) * | 1990-05-09 | 1993-05-18 | Mitsubishi Paper Mills Limited | Method for image formation |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5952815B2 (ja) * | 1976-12-21 | 1984-12-21 | 富士写真フイルム株式会社 | 硬調な画像を形成する方法 |
| JPS5952816B2 (ja) * | 1977-05-06 | 1984-12-21 | 富士写真フイルム株式会社 | 硬調写真画像を形成する方法 |
| DE4042595C2 (de) * | 1988-08-27 | 1996-06-13 | Du Pont Deutschland | Arylhydrazide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE603747A (en(2012)) | 1960-05-13 |
-
1964
- 1964-03-05 DE DEA45411A patent/DE1199612B/de active Pending
-
1965
- 1965-02-24 US US435067A patent/US3386831A/en not_active Expired - Lifetime
- 1965-03-04 GB GB9248/65A patent/GB1073546A/en not_active Expired
- 1965-03-05 BE BE660667D patent/BE660667A/xx unknown
- 1965-03-05 FR FR8195A patent/FR1426573A/fr not_active Expired
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4168977A (en) * | 1976-08-11 | 1979-09-25 | Fuji Photo Film Co., Ltd. | Silver halide photographic emulsion |
| US4166742A (en) * | 1976-10-18 | 1979-09-04 | Fuji Photo Film Co., Ltd. | Contrasty light-sensitive silver halide material containing a hydrazine derivative and a heterocyclic mercaptan |
| US4311781A (en) * | 1976-12-30 | 1982-01-19 | Fuji Photo Film Co., Ltd. | Highly-sensitive high-contrast photographic materials |
| FR2376437A1 (fr) * | 1976-12-30 | 1978-07-28 | Fuji Photo Film Co Ltd | Materiau photographique de haute sensibilite et contraste eleve |
| US4241164A (en) * | 1976-12-30 | 1980-12-23 | Fuji Photo Film Co., Ltd. | Highly-sensitive high-contrast photographic materials |
| JPS5384714A (en) * | 1976-12-30 | 1978-07-26 | Fuji Photo Film Co Ltd | High sensitivity and high contrast photographic material |
| DE2758898A1 (de) * | 1977-08-30 | 1979-03-15 | Fuji Photo Film Co Ltd | Verfahren zur entwicklung photographischer lichtempfindlicher silberhalogenidmaterialien |
| FR2402229A1 (fr) * | 1977-08-30 | 1979-03-30 | Fuji Photo Film Co Ltd | Procede de developpement d'une emulsion photographique procurant une image de contraste eleve |
| US4377634A (en) * | 1977-09-06 | 1983-03-22 | Fuji Photo Film Co., Ltd. | Method for forming high contrast photographic image |
| US4272606A (en) * | 1978-05-05 | 1981-06-09 | Fuji Photo Film Co., Ltd. | Method of forming a high-contrast photographic image |
| US4650746A (en) * | 1978-09-22 | 1987-03-17 | Eastman Kodak Company | High contrast photographic emulsions and elements and processes for their development |
| US4358531A (en) * | 1980-10-16 | 1982-11-09 | Agfa-Gevaert Aktiengesellschaft | Photographic material, process for the production thereof and process for the production of photographic images |
| US4756997A (en) * | 1986-07-23 | 1988-07-12 | Minnesota Mining And Manufacturing Company | Photographic silver halide developer compositions and process for forming photographic silver images |
| EP0338785A3 (en) * | 1988-04-21 | 1990-01-10 | Eastman Kodak Company (A New Jersey Corporation) | Photographic element containing scavenger for oxidized developing agent |
| JP2795674B2 (ja) | 1988-04-21 | 1998-09-10 | イーストマン コダック カンパニー | カラー写真要素 |
| US4937160A (en) * | 1988-08-27 | 1990-06-26 | E. I. Du Pont De Nemours And Company | Photographic silver halide elements containing aryl hydrazides |
| US5013844A (en) * | 1988-08-27 | 1991-05-07 | E. I. Du Pont De Nemours And Company | Pyridinium aryl hydrazide compounds |
| US5130480A (en) * | 1988-08-27 | 1992-07-14 | E. I. Du Pont De Nemours And Company | Ammonium aryl hydrazide compounds |
| US5212045A (en) * | 1990-05-09 | 1993-05-18 | Mitsubishi Paper Mills Limited | Method for image formation |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1426573A (fr) | 1966-01-28 |
| BE660667A (en(2012)) | 1965-09-06 |
| GB1073546A (en) | 1967-06-28 |
| DE1199612B (de) | 1965-08-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3386831A (en) | Stabilizing of photographic silver halide emulsions with acyl phenyl hydrazides | |
| US3220839A (en) | Photographic emulsions containing isothiourea derivatives | |
| US3447925A (en) | Anti-fogging and anti-plumming disulfide compound for use in silver halide photographs | |
| US3499761A (en) | Silver halide emulsions containing alkyl esters of benzimidazole carbamic acid antifogging agents | |
| US3266897A (en) | Antifoggant agents for photography | |
| US3765901A (en) | Spectral sensitization of light-sensitive silver halide emulsions | |
| US4330617A (en) | Photographic elements containing novel developing agent precursors | |
| US3506443A (en) | Color photographic elements and process | |
| US3779764A (en) | Silver halide emulsions for the production of reversal colorphotographic images | |
| US3650759A (en) | Silver halide emulsion containing 1.2-glycol as sensitizer and antifoggant | |
| JPS6122293B2 (en(2012)) | ||
| US4088495A (en) | Silver halide photographic element containing a gelatinous layer hardened with an aliphatic hydrocarbon having at least three vinylsulfonyl groups | |
| JPS60237078A (ja) | 写真記録材料、写真記録材料の安定化方法及び新規トリアゾ−ル | |
| US4366231A (en) | Photographic material containing a stabilizer, a process for its production, a development process, new pyrazoles, a process for their production and intermediate products | |
| US3622329A (en) | Photographic silver halide emulsions with increased sensitivity | |
| US4299913A (en) | Photographic reversal process without second exposure | |
| US3573915A (en) | Photographic silver halide emulsions containing nitrosubstituted or unisubstituted cinnamic acid or cinnamaldehyde | |
| US3148987A (en) | Photographic material | |
| JPS58176634A (ja) | ハロゲン化銀写真感光材料 | |
| US3598601A (en) | Alkyl esters or organic acids,such as stearyl malate,as antifoggants | |
| US3471296A (en) | Spirocyclic quaternary nitrogen compounds as silver halide sensitizers | |
| US3157509A (en) | Photographic emulsions containing novel fog-inhibiting addenda | |
| US5248586A (en) | Silver halide color photographic materials | |
| JPH10171060A (ja) | ハロゲン化銀写真乳剤及びそれを含む写真要素 | |
| JPH0453301B2 (en(2012)) |