US3266899A - Photographic developers - Google Patents
Photographic developers Download PDFInfo
- Publication number
- US3266899A US3266899A US338015A US33801564A US3266899A US 3266899 A US3266899 A US 3266899A US 338015 A US338015 A US 338015A US 33801564 A US33801564 A US 33801564A US 3266899 A US3266899 A US 3266899A
- Authority
- US
- United States
- Prior art keywords
- developing
- composition
- hydroquinone
- solution
- water
- 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
- 239000000203 mixture Substances 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- KKLMJYDGZSAIQX-UHFFFAOYSA-N 2-(n-hydroxyanilino)acetic acid Chemical compound OC(=O)CN(O)C1=CC=CC=C1 KKLMJYDGZSAIQX-UHFFFAOYSA-N 0.000 description 2
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 2
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- -1 silver halide Chemical class 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 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
- G03C5/29—Development processes or agents therefor
- G03C5/30—Developers
Definitions
- a developing composition which comprises a developing substance of the general formula:
- a second developing substance preferably hydroquinone which with the compound of the said formula exerts a superadditive effect, the composition when dissolved in water affording an alkaline solution.
- the invention includes the compositions in solid form suitable for dilution with water and optionally addition of other ingredients to make a developer solution suitable for use, concentrated aqueous solutions of the normally solid constituents and the aqueous solutions ready for use. It further includes the process of making photographic records by developing, with such solutions, photographic materials having layers containing developable silver salts.
- the values of x, y, Z and Z may be selected to be such that the nitrogen ring systems may be, for example, pyridine, pyrroline, quinoline or thiazoline systems.
- hydroquinone there may be employed chlorhydroquinone or other developers, e.g. those known from the literature to afford a superadditive effect with l-phenyl- 3-pyrazolidone.
- the developer solutions for use should be alkaline and it is often desirable to provide that the pH value is above 9 and preferably above 11.
- a typical compound of the foregoing general formula for use in the present invention is 5,5-hydrazo-2,2-2',2 tetramethyl-l,1'-pyrroline-l,1-dioxide, of the formula:
- Example 1 The following developing composition is formulated:
- Dcvelop- Speed increase Compound ment time, log exposure Gamma mins. units 2: 2 hydrazo-l,1'-pyridine-1,1'-dioxide, may be prepared by the following method.
- Z-nitropyridine-l-oxide (0.5 g.) is dissolved in absolute alcohol (50 ml.) and hydrogenated at 20 C. over a 2% palladiurn/ strontium carbonate catalyst (0.2 g.) at a pressure of 1 atmosphere, the reduction is stopped when the theoretical volume of hydrogen (215 ml.) has been absorbed.
- the catalyst is removed from the solution by filtration and the filtrates evaporated to dryness under reduced pressure. The residue is slurried in dry acetone and the crude 2:2'-hydrazo-1,1-pyridine-1,1'-dioxide collected.
- a developing composition which comprises essentially a developing substance of the formula:
- x and y are each selected from nought and one and Z and Z are each the residues necessary to complete a heterocyclic nitrogen ring and, as a second developing substance, a substance known to exert a superadditive effeet on l-phenyl-3-pyrazolidone, the composition when dissolved in water affording an alkaline solution.
- heterocyelic nitrogen ring is selected from the class consisting of pyridine, pyrroline, quinoline and thiazoline.
- a developing composition as in claim 1 wherein the second developing substance is selected from the class consisting of hydroquinone, chlorhydroquinone, hydroxyphenyl glycine and ascorbic acid.
- a developing composition which comprises 5,5'-hydrazo-2,2-2,2-tetramethyl-l,1'-pyrr0line-l,1'-dioxide and hydroquinone, the composition when dissolved in water affording an alkaline solution.
- a developing composition which comprises 2:2'-hydrazo-1,1-pyridine-l,l'-dioxide and hydroquinone, the composition when dissolved in water affording an alkaline solution.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pyridine Compounds (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
United States Patent Oflice 3,255,890 Patented August 16, 1966 3,266,899 PHQTQGRAPHEC DEVELGPERS David William Crichton Ramsay, Sale, England, assignor to Ilford Limited, llford, England, a British company No Drawing. Filed Jan. 16, 1964, Ser. No. 338,015 Claims priority, application Great Britain, Jan. 21, 1963,
8 Claims. (Cl. 96-66) This invention relates to photographic developing compositions.
It is known that certain chemical compounds which used alone are poor developers for photographic silver halide emulsions become much more effective when used in conjunction with other developers, the effect being known as supera-dditivity. Thus, for example p-methylaminophenol and 1-phenyl-3-pyraz0lidone show the phenomenon of superadditivity when either is used in conjunction with hydroquinone, hydroxyphenyl glycine, ascorbic acid or other photographic developing substances.
It is an object of the present invention to provide new photographic developing compositions which exhibit the said phenomenon of superadditivity.
According to the present invention there is provided a developing composition which comprises a developing substance of the general formula:
where x and y are the same or different and each is nought or one and Z and Z are the same or different and are each the atoms or groups necessary to complete a heterocyclic nitrogen ring, or an acid addition salt thereof, a second developing substance (preferably hydroquinone) which with the compound of the said formula exerts a superadditive effect, the composition when dissolved in water affording an alkaline solution.
The invention includes the compositions in solid form suitable for dilution with water and optionally addition of other ingredients to make a developer solution suitable for use, concentrated aqueous solutions of the normally solid constituents and the aqueous solutions ready for use. It further includes the process of making photographic records by developing, with such solutions, photographic materials having layers containing developable silver salts.
In the foregoing general formula the values of x, y, Z and Z may be selected to be such that the nitrogen ring systems may be, for example, pyridine, pyrroline, quinoline or thiazoline systems.
Instead of hydroquinone there may be employed chlorhydroquinone or other developers, e.g. those known from the literature to afford a superadditive effect with l-phenyl- 3-pyrazolidone.
The developer solutions for use should be alkaline and it is often desirable to provide that the pH value is above 9 and preferably above 11.
A typical compound of the foregoing general formula for use in the present invention is 5,5-hydrazo-2,2-2',2 tetramethyl-l,1'-pyrroline-l,1-dioxide, of the formula:
which may be prepared by the method described in Proceedings of the Chemical Society, 1962, p. 360.
The following examples will serve to illustrate the invention:
Example 1 The following developing composition is formulated:
. G. 5:5 hydrazo-Z 2-2 2'-tetramethyl-1 l'-pyrroline- 1: 1-dioxide 3.9 Hydroquinone 8.0 Sodium sulphite (an-hydrous) Sodium carbonate (anhydrous) 37.5 Potassium bromide 2.0 Potassium hydroxide 60 Water to make 1 litre.
The compounds CH2CH2 GHQ-CH2 3 I I I! Naphthalene disulplionie acid salt m J. NH-NH were each dissolved at a concentration of 0.04 centimole per litre in a solution of the following composition:
Hydroquinone g 1.46 Sodium sulphite (anhydrous) g 6.75 Sodium hydroxide g 1.30 Potassium bromide g 0.25 Ethylene diamine tetra-acetic acid, disodium salt g 0.60 Benzotriazole (1% solution) ml 0.95 Water to make ml 1000 The pH of this solution was 12.
Sensitometrically exposed high speed panchromatic negative material was processed for 4 and 7 minutes at 20 C. in these solutions. Comparison of the characteristic curves obtained with curves from the material similarly processed in the solution without compound (1) or (2), showed that the addition of these compounds had produced increases in speed over the valve obtained with hydroquinone alone. The differences are shown in the following table:
Dcvelop- Speed increase Compound ment time, log exposure Gamma mins. units 2: 2 hydrazo-l,1'-pyridine-1,1'-dioxide, may be prepared by the following method.
Z-nitropyridine-l-oxide (0.5 g.) is dissolved in absolute alcohol (50 ml.) and hydrogenated at 20 C. over a 2% palladiurn/ strontium carbonate catalyst (0.2 g.) at a pressure of 1 atmosphere, the reduction is stopped when the theoretical volume of hydrogen (215 ml.) has been absorbed. The catalyst is removed from the solution by filtration and the filtrates evaporated to dryness under reduced pressure. The residue is slurried in dry acetone and the crude 2:2'-hydrazo-1,1-pyridine-1,1'-dioxide collected.
After recrystallisation from absolute ethanol 2:2'-hydrazo-l,1-pyridine-1,1'-dioxide (0.1 g.) is obtained, melting point 158-161 C. (decomp.).
I claim as my invention:
1. A developing composition which comprises essentially a developing substance of the formula:
where x and y are each selected from nought and one and Z and Z are each the residues necessary to complete a heterocyclic nitrogen ring and, as a second developing substance, a substance known to exert a superadditive effeet on l-phenyl-3-pyrazolidone, the composition when dissolved in water affording an alkaline solution.
2. A developing composition as in claim 1 wherein the heterocyelic nitrogen ring is selected from the class consisting of pyridine, pyrroline, quinoline and thiazoline.
3. A developing composition as in claim 1 wherein the second developing substance is selected from the class consisting of hydroquinone, chlorhydroquinone, hydroxyphenyl glycine and ascorbic acid.
4. A developing composition as in claim 1 wherein the composition is in solid form suitable for dilution with water to make a developer solution.
5. A developing composition as in claim 1 wherein the composition is in the form of a concentrated aqueous solution suitable for dilution with water to make a developer solution.
6. A developing composition as in claim 1 wherein the pH of the composition dissolved in water is above 11.
7. A developing composition which comprises 5,5'-hydrazo-2,2-2,2-tetramethyl-l,1'-pyrr0line-l,1'-dioxide and hydroquinone, the composition when dissolved in water affording an alkaline solution.
8. A developing composition which comprises 2:2'-hydrazo-1,1-pyridine-l,l'-dioxide and hydroquinone, the composition when dissolved in water affording an alkaline solution.
No references cited.
NORMAN G. TORCHIN, Primary Examiner.
CAROLYN DAVIS, Assistant Examiner.
Claims (1)
1. A DEVELOPING COMPOSITION WHICH COMPRISES ESSENTIALLY A DEVELOPING SUBSTANCE OF THE FORMULA:
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB2583/63A GB1013447A (en) | 1963-01-21 | 1963-01-21 | Photographic developers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3266899A true US3266899A (en) | 1966-08-16 |
Family
ID=9742132
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US338015A Expired - Lifetime US3266899A (en) | 1963-01-21 | 1964-01-16 | Photographic developers |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3266899A (en) |
| BE (1) | BE642789A (en) |
| CH (1) | CH442002A (en) |
| DE (1) | DE1447716A1 (en) |
| GB (1) | GB1013447A (en) |
-
1963
- 1963-01-21 GB GB2583/63A patent/GB1013447A/en not_active Expired
-
1964
- 1964-01-16 US US338015A patent/US3266899A/en not_active Expired - Lifetime
- 1964-01-20 DE DE19641447716 patent/DE1447716A1/en active Pending
- 1964-01-21 CH CH66164A patent/CH442002A/en unknown
- 1964-01-21 BE BE642789A patent/BE642789A/xx unknown
Non-Patent Citations (1)
| Title |
|---|
| None * |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1013447A (en) | 1965-12-15 |
| DE1447716A1 (en) | 1968-11-28 |
| CH442002A (en) | 1967-08-15 |
| BE642789A (en) | 1964-05-15 |
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