US2915394A - Stabilizer for single powder photographic developer - Google Patents
Stabilizer for single powder photographic developer Download PDFInfo
- Publication number
- US2915394A US2915394A US556042A US55604255A US2915394A US 2915394 A US2915394 A US 2915394A US 556042 A US556042 A US 556042A US 55604255 A US55604255 A US 55604255A US 2915394 A US2915394 A US 2915394A
- Authority
- US
- United States
- Prior art keywords
- single powder
- anhydrous
- oxalic acid
- stabilizer
- alkali
- 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
- 239000003381 stabilizer Substances 0.000 title claims description 8
- 239000000843 powder Substances 0.000 title description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- 229960001484 edetic acid Drugs 0.000 claims description 7
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- -1 SILVER HALIDE Chemical class 0.000 claims description 4
- 229940079877 pyrogallol Drugs 0.000 claims description 4
- 150000001642 boronic acid derivatives Chemical class 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 10
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 10
- 239000003513 alkali Substances 0.000 description 7
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 5
- 239000012964 benzotriazole Substances 0.000 description 5
- 235000010265 sodium sulphite Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- RWPGFSMJFRPDDP-UHFFFAOYSA-L potassium metabisulfite Chemical compound [K+].[K+].[O-]S(=O)S([O-])(=O)=O RWPGFSMJFRPDDP-UHFFFAOYSA-L 0.000 description 3
- 229940043349 potassium metabisulfite Drugs 0.000 description 3
- 235000010263 potassium metabisulphite Nutrition 0.000 description 3
- CYXJEHCKVOQFOV-UHFFFAOYSA-N (4-amino-2-methylphenyl) hydrogen sulfate Chemical compound CC1=CC(N)=CC=C1OS(O)(=O)=O CYXJEHCKVOQFOV-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 2
- 239000003755 preservative agent Substances 0.000 description 2
- 230000002335 preservative effect Effects 0.000 description 2
- HDZHNYWSJFVZIO-UHFFFAOYSA-N 2,3-diaminophenol;hydrochloride Chemical compound Cl.NC1=CC=CC(O)=C1N HDZHNYWSJFVZIO-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 150000003022 phthalic acids Chemical class 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical class C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 239000000837 restrainer Substances 0.000 description 1
- 150000003870 salicylic acids Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
- G03C5/265—Supplying of photographic processing chemicals; Preparation or packaging thereof of powders, granulates, tablets
Definitions
- the present invention relates to single powder photographic developers, and more particularly to compositions containing organic stabilizers for eifectively preventing reaction between the developing agent and the alkaline ingredients of such compositions.
- the invention is components for photographic developers such as the developing agents, anti-oxidant or preservative, alkali energizer and an anti-fogging agent. It has been found, however, that when these components are blended in the form of a dry powder there is a marked tendency for the organic developing agent to react with the alkali, causing deterioration of the photographic properties of the composition. It is, therefore, necessary to incorporate in the powder a substance which will preclude such reaction and operate to stabilize the developer.
- Example IV Grams Ethylene diamine tetra acetic acid 0.8 Sodium carbonate, monohydrate 27.0 Oxalic acid, anhydrous 1.0 Potassium metabisulfite 2.5 Sodium sulfite 10.0 Phenidone 0.10 Hydroquinone 6.0 Benzotriazole 0.006 Potassium bromide 0.3
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
United States Pat t 2 Claims. (31. 96-66) The present invention relates to single powder photographic developers, and more particularly to compositions containing organic stabilizers for eifectively preventing reaction between the developing agent and the alkaline ingredients of such compositions.
The advantages of single powder photographic developers are readily recognized in that such powders may be blended in one operation and packaged in a simple, singlecomponent container. Such powders contain the usual Patented Dec. 1 1959 presence of benzotriazole and, hence, this component may b'e'used in the compositions hereof, either as a restraineror to produce blue-black tones. .Itis also recommended that-a sequestering agent be added to take care'of salts present in hard water and, to this end, ethylene diamine tetra acetic acid may be effectively employed.
The following examples will serve to illustrate the invention, but it is to be understood that the invention is components for photographic developers such as the developing agents, anti-oxidant or preservative, alkali energizer and an anti-fogging agent. It has been found, however, that when these components are blended in the form of a dry powder there is a marked tendency for the organic developing agent to react with the alkali, causing deterioration of the photographic properties of the composition. It is, therefore, necessary to incorporate in the powder a substance which will preclude such reaction and operate to stabilize the developer.
Recognition of this fact has led the art to select as stabilizers, such substances as benzoic, maleic, boric and phthalic anhydrides and metaboric, salicylic and phthalic acids. Optimum results, however, are not secured by utilization of any of these components. Thus, many are only moderately effective and display properties which lead to additional problems. For example, they cannot be employed with any degree of success where anhydrous sodium carbonate is employed as the alkali. Similarly, they are of little use should it be desired to employ benzotriazole as a blue-black toner or as a restrainer. Again, they dissolve relatively slowly in water, thereby greatly prolonging the mixing operation designed to produce the active developing solutions. Finally, these acidic substances have a tendency to react with sulfite and carbonate, thereby forming gases which may build up objectionable pressures in hermetically sealed containers.
It has now been discovered that the disadvantages of the previously suggested stabilizers may be overcome while obtaining single powder developers, readily soluble in water with little tendency to gas formation during storage, by employing anhydrous oxalic acid as the stabilizer. Single powder developers containing anhydrous oxalic acid as a stabilizer constitute the purposes and objects of the present invention.
The single powder developers contemplated herein contain the usual developer components, such as the developing agent, i.e., metol, phenidone, hydroquinone, p-aminophenol, hydrochloride, pyrogallol and the like; a preservative or anti-oxidant such as an alkali metal sulfite, i.e.,
potassium sulfite, potassium metabisulfite and the like; an
not restricted thereto. The components ofthe various examples may be packaged as single powder mixtures for dissolution in one liter of water to prepare the-developer solution.
Example I i v i" Grams Ethylene diamine tetra acetic acid- Q 0.8 Borax I 4.0 Oxalic acid, anhydrous 0.6 Sodium sulfite 80.0 Metol 1.5 Hydroquinone 3.0 Potassium bromide 0.5
Example II Grams Ethylene diamine tetra acetic acid 0.5 Sodium sulfite 44.0 Oxalic acid, anhydrous 0.6 Diamino phenol hydrochloride 6.6 Potassium bromide 0.55
Example III Grams Ethylene diamine tetra acetic acid 0.8 Sodium carbonate, monohydrate 25.0 Oxalic acid, anhydrous 1.0 Potassium metabisulfite 2.5 Sodium sulfite 13.0
Metol 1.3 Hydroquinone 3 .7 Benzotriazole 0.006 Potassium bromide 0.3
Example IV Grams Ethylene diamine tetra acetic acid 0.8 Sodium carbonate, monohydrate 27.0 Oxalic acid, anhydrous 1.0 Potassium metabisulfite 2.5 Sodium sulfite 10.0 Phenidone 0.10 Hydroquinone 6.0 Benzotriazole 0.006 Potassium bromide 0.3
Example V Grams Ethylenediamine tetra acetic acid 1.0 Sodium carbonate, anhydrous 23.0 Oxalic acid, anhydrous 1.0 Potassium metabisulfite 2.5 Sodium sulfite 10.0 Phenidone 0.10 Hydroquinone 6.0 Benzotriazole 0.006 Potassium bromide 0.3
Example VI Grams Ethylene diamine tetra acetic acid 1.0 Sodium carbonate, monohydrate 75.0 Oxalic acid, anhydrous 3.0 Sodium sulfite 55.0 Potassium bromide 10.0 Hydroquinone 35.0
Developers constituted according to the examples,
after storage for prolonged periods at 120 F showed no significant decomposition and evidenced no gas formation when placed in hermetically sealed cans. However, omission of the oxalic acid caused the mixtures of the examples to become'badly discolored after one days storage with a marked deterioration in their photographic activity.
All of the compositions of the examples dissolved readily in water to form developing solutions photographically equal to those freshly prepared from the individual chemical constituents. 3
I claim: v .1. A stabilized single powder developing composition consisting essentially of an organic silver halide developer selected from the group consisting of methyl-p-amino phenol sulfate, 1-phenyl-3-pyrazolidone, hydroquinone, paminophenol hydrochloride, pyrogallol and mixtures thereof, an alkali selected from the group consisting of alkali carbonates, sulfites, borates and mixtures thereof, a stabilizing'agent consisting essentially of anhydrous oxalic acid, an'antifogging' agent and ethylene diamine tetracetic' acid.
2. A stabilized single powder developing composition 4 consisting essentially of an organic silver halide developer selected from the group consisting of methyl-p-aminophenol sulfate, 1-phenyl-3-pyrazolidone, hydroquinone, paminophenyl hydrochloride, pyrogallol and mixture thereof, an alkali selected from. the group consisting of alkali carbonates, sulfites, borates and mixtures thereof, ethylene diamine tetra acetic acid, benzotriazole, an antifoggant and a stabilizing agent consisting essentially of anhydrous oxalic acid.
References Cited in the file of this patent UNITED STATES PATENTS 2,162,765 Tarnofi June 20, 1939 2,649,376 Rasch et al Aug. 18, 1953 .FOREIGN PATENTS 16,537 Great Britain Aug. 3, 1889 of 1888 I 725,892 Great Britain Mar. 9, 1955 OTHER REFERENCES Chemistry of Carbon Compounds, Rodd, vol. I, part B (1952), page 955. (Copy in Div. 38.) v
Claims (1)
1. A STABILIZED SINGLE POWER DEVELOPING COMPOSITION CONSISTING ESSENTIALLY OF AN ORGANIC SILVER HALIDE DEVELOPER SELECTED FROM THE GROUP CONSISTING OF METHYL-P-AMINO PHENOL SULFATE, 1-PHENYL-3-PYRAZOLIDONE, HYDROQUINONE, PAMINOPHENOL HYDROCHLORIDE, PYROGALLOL AND MIXTURES THEREOF, AN ALKALI SELECTED FROM THE GROUP CONSISTING OF ALKALI CARBONATE, SULFITES, BORATES, AND MIXTURE THEREOF, A STABILIZING AGENT CONSISTING ESSENTIALLY OF ANHYDROUS OXALIC ACID, AN ANTIFOGGING AGENT AND ETHYLENE DIAMINE TETRACETIC ACID.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| BE553777D BE553777A (en) | 1955-12-29 | ||
| US556042A US2915394A (en) | 1955-12-29 | 1955-12-29 | Stabilizer for single powder photographic developer |
| DEG21176A DE1036638B (en) | 1955-12-29 | 1956-12-24 | Photographic developer in powder form |
| GB39333/56A GB798678A (en) | 1955-12-29 | 1956-12-27 | Stabilizer for single powder photographic developer |
| FR1163679D FR1163679A (en) | 1955-12-29 | 1956-12-28 | Unique powder photographic developer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US556042A US2915394A (en) | 1955-12-29 | 1955-12-29 | Stabilizer for single powder photographic developer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2915394A true US2915394A (en) | 1959-12-01 |
Family
ID=24219653
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US556042A Expired - Lifetime US2915394A (en) | 1955-12-29 | 1955-12-29 | Stabilizer for single powder photographic developer |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US2915394A (en) |
| BE (1) | BE553777A (en) |
| DE (1) | DE1036638B (en) |
| FR (1) | FR1163679A (en) |
| GB (1) | GB798678A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3467521A (en) * | 1965-05-03 | 1969-09-16 | Agfa Gevaert Ag | Developer compositions containing sequestering agents |
| US5155014A (en) * | 1989-09-04 | 1992-10-13 | Agfa-Gevaert, N.V. | Method of developing direct positive silver halide material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2162765A (en) * | 1937-10-28 | 1939-06-20 | Tarnoff Louis | Nonoxidizing and nondeteriorating developer for off-set or contrast film and plate negatives |
| US2649376A (en) * | 1952-06-26 | 1953-08-18 | Eastman Kodak Co | Single powder developers containing stabilized alkali hydroxides |
| GB725892A (en) * | 1952-06-26 | 1955-03-09 | Kodak Ltd | Improvements in single powder photographic developers |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2660528A (en) * | 1952-03-25 | 1953-11-24 | Bobbie J Schultz | Hypersensitizing photographic film developer |
-
0
- BE BE553777D patent/BE553777A/xx unknown
-
1955
- 1955-12-29 US US556042A patent/US2915394A/en not_active Expired - Lifetime
-
1956
- 1956-12-24 DE DEG21176A patent/DE1036638B/en active Pending
- 1956-12-27 GB GB39333/56A patent/GB798678A/en not_active Expired
- 1956-12-28 FR FR1163679D patent/FR1163679A/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2162765A (en) * | 1937-10-28 | 1939-06-20 | Tarnoff Louis | Nonoxidizing and nondeteriorating developer for off-set or contrast film and plate negatives |
| US2649376A (en) * | 1952-06-26 | 1953-08-18 | Eastman Kodak Co | Single powder developers containing stabilized alkali hydroxides |
| GB725892A (en) * | 1952-06-26 | 1955-03-09 | Kodak Ltd | Improvements in single powder photographic developers |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3467521A (en) * | 1965-05-03 | 1969-09-16 | Agfa Gevaert Ag | Developer compositions containing sequestering agents |
| US5155014A (en) * | 1989-09-04 | 1992-10-13 | Agfa-Gevaert, N.V. | Method of developing direct positive silver halide material |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1163679A (en) | 1958-09-30 |
| BE553777A (en) | |
| GB798678A (en) | 1958-07-23 |
| DE1036638B (en) | 1958-08-14 |
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