US3928042A - Preservatives for photographic developers - Google Patents
Preservatives for photographic developers Download PDFInfo
- Publication number
- US3928042A US3928042A US490361A US49036174A US3928042A US 3928042 A US3928042 A US 3928042A US 490361 A US490361 A US 490361A US 49036174 A US49036174 A US 49036174A US 3928042 A US3928042 A US 3928042A
- Authority
- US
- United States
- Prior art keywords
- solution
- plicatic acid
- plicatic
- plicatate
- developer
- 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
- 239000003755 preservative agent Substances 0.000 title claims description 17
- PGFBYAIGHPJFFJ-UHFFFAOYSA-N Plicatic acid Natural products C1=2C=C(O)C(OC)=CC=2CC(O)(CO)C(O)(C(O)=O)C1C1=CC(O)=C(O)C(OC)=C1 PGFBYAIGHPJFFJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- PGFBYAIGHPJFFJ-PWIZWCRZSA-N Plicatic acid Chemical compound C1([C@@H]2[C@](O)([C@](O)(CO)CC=3C=C(C(=CC=32)O)OC)C(O)=O)=CC(O)=C(O)C(OC)=C1 PGFBYAIGHPJFFJ-PWIZWCRZSA-N 0.000 claims abstract description 19
- -1 silver halide Chemical class 0.000 claims abstract description 19
- 150000001408 amides Chemical class 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 150000002148 esters Chemical class 0.000 claims abstract description 12
- 229910052709 silver Inorganic materials 0.000 claims abstract description 9
- 239000004332 silver Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 63
- 238000000034 method Methods 0.000 claims description 15
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 229910052700 potassium Inorganic materials 0.000 claims description 12
- 239000011591 potassium Substances 0.000 claims description 12
- 230000002335 preservative effect Effects 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 7
- 239000011550 stock solution Substances 0.000 claims description 5
- 108010082075 plicatamide Proteins 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 10
- 238000005273 aeration Methods 0.000 description 9
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 8
- 239000003490 Thiodipropionic acid Substances 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 235000019303 thiodipropionic acid Nutrition 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000003078 antioxidant effect Effects 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-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
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 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
- 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
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 241000218638 Thuja plicata Species 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000006286 aqueous extract Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000019282 butylated hydroxyanisole Nutrition 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002023 wood 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
- G03C5/305—Additives other than developers
Definitions
- ABSTRACT The storage life of silver halide developer solutions is extended by the addition to the solutions of salts, esters and amides of plicatic acid.
- salts, esters and amides of plicatic acid act as preservatives when added to solutions for developing silver halide photographic material.
- the plicatic acid compounds produce no loss in film speed when addedto'such solutions and have no significant effect on the fog level of the developed film.
- Plicatic acid is a polyphenolic compound obtained from aqueous extracts of western red cedar wood. Processes for its separation and recovery are described in US. Pat. No. 3,716,574, assigned to the present assignee.
- the salts and esters of plicatic acid are disclosed in US. Pat. Nos. 3,754,937 and 3,644,481, both assigned to the present assignee.
- the amides of plicatic acid are disclosed in copending US. application Ser. No. 316,056, filed 12-18-72, now US. Pat. No. 3,810,941 also assigned to the present assignee.
- plicatic acid esters and salts which are useful in the invention are sodium and potassium plicatate and lower alkly plicatates such as methyl, ethyl, n-propyl, iso-propyl and Z-butyl plicatate.
- useful amides are ethyl and n-propyl plicatamide.
- Plicatic acid itself has been found to be too highly'acidic to be useful it tends to neutralize and thus impair the effectiveness of the normally alkaline developer solution.
- the amount of plicatic acid derivative used may, at the lower end, be any amount which is effective to extend the life of the developer. As little as 0.01% (0.1 grams/liter) has been found to be effective to extend the storage life of the solutions.
- the maximum amount of plicatic acid derivative is that which is soluble in the developer solution, normally about 0.5% (5 grams/liter).
- a preferred amount of the preservative is from 0.02 to 0.3% (.2 to 3 grams/liter). (Percentages of preservative, as used herein, are weight by volume, being 1000 grams/liter).
- the normally somewhat acidic plicatic acid derivative be neutralized or made slightly alkaline prior to addition to the alkaline developer solution. This may conveniently be done, for example, by adding sodium carbonate or other mild alkali to a water solution of the plicatic acid derivative to raise its pH to 7 or above, preferably about 7.5. Neutralization avoids alteration of the alkalinity of the developer and hence prevents degradation of the quality of the developed film. Developers (such as Eastman Kodak D-76) are commercially available as. premixed powders which the user dissolves in water to obtain the final developer solution. It is possible to obtain at least some of the plicatic acid derivatives in either neutral or slightly alkaline crystalline form which can be incorporated directly into such preparations.
- Photographic developer solutions with which the preservatives of the invention are useful are well known in the art. They are chemical solutions widely used in developing exposed silver halide photographic materials and are described in detail, for example, in Photo- Lab-lndex, Henry M. Lester, published by Morgan and Morgan, Dobbs Ferry, N.Y., 1973 (published annually with quarterly supplements).
- a typical composition consists of aqueous solutions of a reducer which is the developing agent, an accelerator (an alkali), a stabilizer to inhibit aerial oxidation and a retardant to limit development of unexposed silver grain.
- Commonly used developing agents are hydroquinone, p-aminophenol or p-methylaminophenol sulfate.
- Useful accelerators are alkalis such as borax or sodium carbonate.
- a commonly used stabilizer is sodium ,sulflte.
- Potassium bromide is a frequencly used retardant. It should be understood that the foregoing compositions are merely illustrative.
- Catechol 274 126 calibrated to give equal flow in the lines to the tank Samoqui 403 185 distribution tUbCS. Aeration was carried out at ambient Number of hours of aeration to reduce the maximum negative density to 70% of room temperatures. The color and height of the developers in the tank were checked daily, the latter being maintained at 9.0 inches above the gas distribution The results show that all of the plicatic acid derivatives tubes by the addition of distilled water to insure a conextended the aging life of the developer. It also shows stant hydrostatic pressure. that, at the 0.10% level, the other commercial antioxi- Negative film optical densities were measured with a dants also extended developer life.
- Catechol will afthe density of the unexposed portion of each film to feet the kinetics of the developer solution because of its obtain their fog densities.
- Fog, or negative density produced by factors other The following six commercially available antioxithan image exposure, is also an important factor in dants were also investigated for their comparative evaluating developers. High fog levels are undesirable value in extending the life of photographic developer because they reduce negative contrast and increase solutions. The last three of the antioxidants were found printing exposure time.
- Butylated hydroxy toluene (BHT) solubility in Groups 1 and 2 containing 0.1% additive were aerated water (0.0575 gm./1.) was too low for comparative at a rate of 2.5 liters per minute.
- the tests of Group 3 tests. were aerated at 3.5 liters per minute in an attempt to S.
- Butylated hydroxy anisole (BHA) dissolved but reduce the time required to inactivate the solutions.
- the invention thus offers a relatively simple and economical method of increasing the working life of developer solutions.
- the invention is particularly significant where batches of films are processed at intervals and stored for prolonged periods between batches. It is accordingly applicable, not only to amateur photographic practice, but also to experimental laboratories, photographic studios and other processors using manual batch development as opposed to continuous machine processing.
- An aqueous solution for developing photographic material comprising a silver halide developing agent and as a preservative therefor a compound selected from the group consisting of salts, esters and amides of plicatic acid in an amount effective to extend the storage life of said solution, said amount being at least 0.01% on a weight/volume basis.
- a process for extending the storage life of aqueous solutions for developing photographic materials comprising adding to said solution containing a silver halide developing agent a preservative compound selected from the group consisting of salts, esters and amides of plicatic acid in an amount effective to extend the storage life of said solution, said amount being at least 0.01% on a weight/volume basis.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US490361A US3928042A (en) | 1974-07-22 | 1974-07-22 | Preservatives for photographic developers |
| CA231,546A CA1069746A (fr) | 1974-07-22 | 1975-07-15 | Derive d'acide plicatique pour la conservation du revelateur agx |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US490361A US3928042A (en) | 1974-07-22 | 1974-07-22 | Preservatives for photographic developers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3928042A true US3928042A (en) | 1975-12-23 |
Family
ID=23947719
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US490361A Expired - Lifetime US3928042A (en) | 1974-07-22 | 1974-07-22 | Preservatives for photographic developers |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US3928042A (fr) |
| CA (1) | CA1069746A (fr) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4014699A (en) * | 1973-05-17 | 1977-03-29 | Ciba-Geigy Ag | Preparation for the processing of photographic materials |
| US5863713A (en) * | 1997-04-07 | 1999-01-26 | Aviles; John Jay | Process repeatedly regenerates developers |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3515556A (en) * | 1967-08-01 | 1970-06-02 | Eastman Kodak Co | Photographic developing process utilizing hemlock tannin polymer |
| US3644481A (en) * | 1968-03-06 | 1972-02-22 | Itt Rayonier Inc | Plicatic acid esters |
| US3716574A (en) * | 1967-12-01 | 1973-02-13 | Rayonier Inc | Pure crystalline plicatic acid tetrahydrate and the methyl ester thereof |
| US3754937A (en) * | 1972-08-13 | 1973-08-28 | Rayonier Inc | Plicatic acid esters |
| US3810941A (en) * | 1972-12-18 | 1974-05-14 | Itt | Plicatamides |
-
1974
- 1974-07-22 US US490361A patent/US3928042A/en not_active Expired - Lifetime
-
1975
- 1975-07-15 CA CA231,546A patent/CA1069746A/fr not_active Expired
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3515556A (en) * | 1967-08-01 | 1970-06-02 | Eastman Kodak Co | Photographic developing process utilizing hemlock tannin polymer |
| US3716574A (en) * | 1967-12-01 | 1973-02-13 | Rayonier Inc | Pure crystalline plicatic acid tetrahydrate and the methyl ester thereof |
| US3644481A (en) * | 1968-03-06 | 1972-02-22 | Itt Rayonier Inc | Plicatic acid esters |
| US3754937A (en) * | 1972-08-13 | 1973-08-28 | Rayonier Inc | Plicatic acid esters |
| US3810941A (en) * | 1972-12-18 | 1974-05-14 | Itt | Plicatamides |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4014699A (en) * | 1973-05-17 | 1977-03-29 | Ciba-Geigy Ag | Preparation for the processing of photographic materials |
| US5863713A (en) * | 1997-04-07 | 1999-01-26 | Aviles; John Jay | Process repeatedly regenerates developers |
Also Published As
| Publication number | Publication date |
|---|---|
| CA1069746A (fr) | 1980-01-15 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: ITT CORPORATION Free format text: CHANGE OF NAME;ASSIGNOR:INTERNATIONAL TELEPHONE AND TELEGRAPH CORPORATION;REEL/FRAME:004389/0606 Effective date: 19831122 |