US2967772A - Photographic tanning developer - Google Patents
Photographic tanning developer Download PDFInfo
- Publication number
- US2967772A US2967772A US758576A US75857658A US2967772A US 2967772 A US2967772 A US 2967772A US 758576 A US758576 A US 758576A US 75857658 A US75857658 A US 75857658A US 2967772 A US2967772 A US 2967772A
- Authority
- US
- United States
- Prior art keywords
- ascorbic acid
- developer
- tanning
- tanning developer
- 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
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 60
- 235000010323 ascorbic acid Nutrition 0.000 claims description 32
- 239000011668 ascorbic acid Substances 0.000 claims description 32
- 229960005070 ascorbic acid Drugs 0.000 claims description 32
- -1 SILVER HALIDE Chemical class 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 11
- 239000004332 silver Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000000839 emulsion Substances 0.000 claims description 9
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 229940079877 pyrogallol Drugs 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000000126 substance Substances 0.000 description 10
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 8
- 108010010803 Gelatin Proteins 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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000003064 anti-oxidating effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000004679 hydroxides Chemical class 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-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
- 229930003268 Vitamin C Natural products 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000003863 ammonium salts Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 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
- 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
- G03C5/315—Tanning development
Definitions
- the present invention relates to a process for inhibiting the aerial oxidation of a tanning developer, and more particularly to a process whereby this oxidation is inhibited by the use of a stable anti-oxidizing agent which does not compete with the tanning developing substance.
- polyhydroxybenzenes especially pyrocatechol and pyrogallol, both in alkaline medium
- the drawbacks of such developers are their instability and their quite rapid darkening and uselessness by aerial oxidation.
- Sodium sulphite generally known as a very fiective agent against aerial oxidation of developers cannot be used or at least not in the necessary amount in a tanning developer since the formed oxidation products of the developing substance react with the sodium sulphite and not with the gelatin, so that the latter is not hardened anymore on the exposed areas, with the consequence that no relief image can be obtained anymore; in most cases, the tanning developers are prepared just before use and discarded after use.
- vitamin C vitamin C
- tanning developers U.S.P. 2,415,666
- ascorbic acid vitamin C
- ascorbic acid is unstable in alkaline medium which results in a strong decrease of the anti-oxidizing action.
- the relief image on removing the non-developed unhardened gelatin, is insufliciently hardened and is either completely or partially washed away by the warm water. This occurs in particular when relatively large quantities of ascorbic acidwhich owing to the instability of ascorbic acid in alkaline medium are necessary to keep useful the tanning developer for a sufliciently long periodare added to the developer,
- .It is an object of the present invention to provide a photographic tanning developerwhich is stable to aerial tilling the water under reduced pressure.
- a further object is to provide a novel antioxidizing agent which does not compete with the tanning developer substance used.
- a silver halide tanning developer solution comprising an alkaline solution of a polyhydroxybenzene, of a water soluble salt of an ascorbic acid borate. It was stated, indeed, that the as.- corbic acid borates contrary to the free ascorbic acid, are very stable in alkaline medium where they act as their corresponding salts, and moreover that theydo not compete with the tanning developer substance used.
- Ascorbic acid borate is prepared by esterifying ascorbic acid with boric acid. When the esterification is carried out in the presence of a base, salts of ascorbic acid borate are obtained. In this way, potassium ascorbic acid borate can be obtained by heating'to 70 C. 2 mol eq. of ascorbic acid with 1 mol eq. of boric acid and 1 mol eq.
- hydroxides of alkali, metals such as sodium hydroxide, or hydroxides of alkalineearth'metals, such as barium hydroxide, or still other hydroxides, such as ammonium hydroxide, the corresponding salts of ascorbic acid borate can be prepared.
- a further great advantage of the ascorbic acid borates in respect of ascorbic acid is. the very strongly reduced competition with the present tanning developer substance duringdevelopment.
- a photographic paper provided with a light-sensitive silver halide emulsion is exposed to an image and divided into three strips. Each strip is immersed for one minute at 20 C. in developers C/D, and E resp. On washing in warm Water, the developed areas obtained with the rel nted Jan. 10, 1,9 1
- the developers which stability to aerial oxidation is increased by the application of the process according to the present invention can possess besides the tanning developer substance and the ascorbic acid borate, still other usual bath ingredients such as for instance wetting agents and sequestering compounds.
- Example I A contrasty light-sensitive silver halide emulsion on a paper support is exposed to an image and developed for 1 minute at 20 C. in the following bath:
- Example 2 A contrasty light-sensitive silver halide emulsion on a paper support is exposed to an image and developed for 1 minute at 20 C. in the following bath:
- Example 3 A contrasty light-sensitive silver halide emulsion on a 4 paper support is exposed to an image and developed for 1 minute at 20 C. in the following bath:
- Example 4 A contrasty light-sensitive silver halide emulsion on a paper support is exposed to an image and developed for 1 minute at 20 C. in the following bath:
- a photographic tanning developer solution having reduced tendency to aerial oxidation and capable of forming relief images upon development of an exposed silver halide emulsion comprising an alkaline solution of a polyhydroxybenzene selected from the group consisting of pyrogallol and pyrocatechol and a water-soluble salt of a boron ascorbic acid compound which is the reaction product of boric acid and ascorbic acid.
- a developer as defined in claim 1 wherein the salt is an alkali-metal salt.
- a developer as defined in claim 1 wherein the salt is an alkali-earth metal salt.
- a developer as defined in claim 1 wherein the salt is an ammonium salt.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL220541A NL96063C (en。) | 1957-09-05 | 1957-09-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2967772A true US2967772A (en) | 1961-01-10 |
Family
ID=19750970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US758576A Expired - Lifetime US2967772A (en) | 1957-09-05 | 1958-09-02 | Photographic tanning developer |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US2967772A (en。) |
| BE (1) | BE570926A (en。) |
| DE (1) | DE1060715B (en。) |
| FR (1) | FR1202502A (en。) |
| GB (1) | GB862615A (en。) |
| NL (1) | NL96063C (en。) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3250790A (en) * | 1962-11-14 | 1966-05-10 | Hoffmann La Roche | 6-o-higher alkenoyl-ascorbic acid esters and their preparation |
| US4699868A (en) * | 1984-03-02 | 1987-10-13 | Minnesota Mining And Manufacturing Company | Photographic tanning developer formulation |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2635102A (en) * | 1945-03-12 | 1953-04-14 | Simon L Ruskin | Boron derivatives of ascorbic acid |
| US2816026A (en) * | 1954-11-26 | 1957-12-10 | Eastman Kodak Co | Stabilizing agents for single powder photographic developers |
-
1957
- 1957-09-05 NL NL220541A patent/NL96063C/xx active
-
1958
- 1958-09-02 US US758576A patent/US2967772A/en not_active Expired - Lifetime
- 1958-09-04 BE BE570926A patent/BE570926A/xx unknown
- 1958-09-04 GB GB28424/58A patent/GB862615A/en not_active Expired
- 1958-09-04 FR FR1202502D patent/FR1202502A/fr not_active Expired
- 1958-09-04 DE DEG25246A patent/DE1060715B/de active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2635102A (en) * | 1945-03-12 | 1953-04-14 | Simon L Ruskin | Boron derivatives of ascorbic acid |
| US2816026A (en) * | 1954-11-26 | 1957-12-10 | Eastman Kodak Co | Stabilizing agents for single powder photographic developers |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3250790A (en) * | 1962-11-14 | 1966-05-10 | Hoffmann La Roche | 6-o-higher alkenoyl-ascorbic acid esters and their preparation |
| US4699868A (en) * | 1984-03-02 | 1987-10-13 | Minnesota Mining And Manufacturing Company | Photographic tanning developer formulation |
Also Published As
| Publication number | Publication date |
|---|---|
| GB862615A (en) | 1961-03-15 |
| DE1060715B (de) | 1959-07-02 |
| FR1202502A (fr) | 1960-01-11 |
| NL96063C (en。) | 1960-11-15 |
| BE570926A (en。) | 1958-09-30 |
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