US1930140A - Acid hardening fixing bath - Google Patents
Acid hardening fixing bath Download PDFInfo
- Publication number
- US1930140A US1930140A US588502A US58850232A US1930140A US 1930140 A US1930140 A US 1930140A US 588502 A US588502 A US 588502A US 58850232 A US58850232 A US 58850232A US 1930140 A US1930140 A US 1930140A
- Authority
- US
- United States
- Prior art keywords
- acid
- hardening
- fixing bath
- acetic acid
- fixing
- 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
- 239000002253 acid Substances 0.000 title description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 51
- 235000011054 acetic acid Nutrition 0.000 description 17
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 14
- 239000004327 boric acid Substances 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 8
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 7
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 6
- 239000004848 polyfunctional curative Substances 0.000 description 6
- 229940050271 potassium alum Drugs 0.000 description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910021538 borax Inorganic materials 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 239000004328 sodium tetraborate Substances 0.000 description 4
- 235000010339 sodium tetraborate Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 3
- 229940001474 sodium thiosulfate Drugs 0.000 description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical class [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 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 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 108010025899 gelatin film Proteins 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011975 tartaric acid 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
- G03C5/38—Fixing; Developing-fixing; Hardening-fixing
- G03C5/386—Hardening-fixing
Definitions
- ком ⁇ онент in addition to fixing out the unexposed silver salts.
- the acid in them neutralizes the developer carried over by films or prints and prevents the fixing bath from becoming alkaline.
- ing agent often included in such formulas also serves to harden the emulsion and protect it from mechanical injury or from slightly elevated temperatures used in drying.
- a hardening agent the most commonly used substance is ordinary alum or potassium aluminum sulphate.
- Many fixing baths of the acid hardening type contain, in addition to hypo, potassium alum, acetic acid and sodium sulphite.
- a fixing bath of this type represents a very complex chemical system and one in which certain factors must be accurately adjusted to give satisfactory results.
- Qualities of such a fixing bath such as degree of hardening, hardening life, sludging, rate of sulphurization, etc., are all interdependent and are influenced by the amounts of the various ingredients and the ratio of these amounts to each other. It is usually true that if one attempts to adjust the bath for the optimum of one property, one or more of the other properties is sacrificed to some extent.
- hardening life I, of course, mean the amount of fixing which can be done, the fixing bath still maintaining a satisfactory degree of hardening.
- the hardening life may be measured, for example, by plotting the temperature at which the gelatin film begins to melt against the amount of a given developer which has been added to the fixing bath. This test is closely parallel to the practical conditions under which the bath is used. The type of curve obtained with the usual fixing bath is one that quickly rises to a maximum and then rapidly falls as more developer is added. When a moderate amount of developer has been 55 added, the fixing bath will no longer harden satis- A harden-.
- Fixing baths made in accordance with my invention will maintain satisfactory hardening over a much wider range, that is, they will still harden satisfactorily when a large amount of developer has been added to them.
- Acid fixing baths made according to my invention include a substance capable of furnishing acetate ions (that is, the ion--OOC.CH3) and boric acid. Satisfactory substances which fur- 55 nish the acetate ion are acetic acid and sodium acetate, though other acetates may be used.
- the boric acid is added either as such or is supplied by borax and acetic acid in solution. At any rate, a small amount of bric acid is present in the fixing bath simultaneously with the acetate ion.
- acetic acid may be replaced by equivalent amounts of citric or tartaric acids. .They are not, however, as satisfactory as acetic acid. If all citric or all tartaric acid is used, the fixing bathsshow a marked improvement over the older acid hardening baths, in that the hardening life is somewhat increased and sludging is less. The improvement is, however, not so great as when acetic acid alone is used.
- the boric acid will be present in the fixing bath through interaction of the borax with the weak acid, acetic acid.
- boric acid itself is added. All of these fixing baths will give a greatly increased hardening life. They will still harden satisfactorily when from three to four times as much developer is carried over as will render an ordinary bath unfit for further use.
- the usual range of concentration of the acetate ions is from 10 grams per liter to 40 grams per liter and the concentration of boric acid is at least half that of the acetate ions, but can be more, and the amount of hardeners is not less than 5 grams and is preferably less than 30 grams per liter.
- An acid hardening fixing bath comprising an aqueous solution of sodium thin-sulfate, a sulfite, a hardening agent, boric acid and a compound capable of furnishing acetate ions, the concentration of acetate ions being greater than 10 grams per liter and the concentration of boric acid being at least half that of the acetate ions.
- An acid hardening fixing bath comprising an aqueous solution of sodium thiosulfate, a sulfite, acetic acid, boric acid and a hardener, the acetic acid being present in a concentration greater than 10 grams per liter and the concentration of the boric acid being at least half that of the acetic acid.
- An acid hardening fixing bath comprising an aqueous solution of sodium thio-sulfate, a sulfite, acetic acid, boric acid and potassium alum, the acetic acid concentration being greater than 10 grams per liter, the boric acid concentration being substantially half that of the acetic acid.
- An acid hardening fixing bath comprising an aqueous solution of sodium thio-sulfate, a sulfite, acetic acid, boric acid and potassium alum, the acetic acid concentration being greater than 10 grams per liter, the boric acid concentration being substantially half that of the acetic acid and the potassium alum concentration being not over 30 grams per liter.
Description
Patented Oct. 10, 1933 UNITED STATES PATENT OFFICE ACID HARDENING FIXING BATH Reinhold S. Becker, Scottsville, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New York No Drawing. Application January 23, 1932 i Serial'No. 588,502
4 Claims.
tions in addition to fixing out the unexposed silver salts. The acid in them neutralizes the developer carried over by films or prints and prevents the fixing bath from becoming alkaline. ing agent often included in such formulas also serves to harden the emulsion and protect it from mechanical injury or from slightly elevated temperatures used in drying. As a hardening agent, the most commonly used substance is ordinary alum or potassium aluminum sulphate. Many fixing baths of the acid hardening type contain, in addition to hypo, potassium alum, acetic acid and sodium sulphite.
A fixing bath of this type represents a very complex chemical system and one in which certain factors must be accurately adjusted to give satisfactory results. Qualities of such a fixing bath such as degree of hardening, hardening life, sludging, rate of sulphurization, etc., are all interdependent and are influenced by the amounts of the various ingredients and the ratio of these amounts to each other. It is usually true that if one attempts to adjust the bath for the optimum of one property, one or more of the other properties is sacrificed to some extent. Thus, for example,
it is possible that if one attempts to secure the maximum degree of hardening, the rate of sul- 35 phurization or of sludging may be adversely affected. Accordingly, nearly every fixing bath of the acid hardening type represents a compromise of some kind.
I have found a successful method of increasing the hardening life of a fixing bath without adversely affecting any of its other qualities. By hardening life, I, of course, mean the amount of fixing which can be done, the fixing bath still maintaining a satisfactory degree of hardening. The hardening life may be measured, for example, by plotting the temperature at which the gelatin film begins to melt against the amount of a given developer which has been added to the fixing bath. This test is closely parallel to the practical conditions under which the bath is used. The type of curve obtained with the usual fixing bath is one that quickly rises to a maximum and then rapidly falls as more developer is added. When a moderate amount of developer has been 55 added, the fixing bath will no longer harden satis- A harden-.
factorily. Fixing baths made in accordance with my invention, on the other hand, will maintain satisfactory hardening over a much wider range, that is, they will still harden satisfactorily when a large amount of developer has been added to them.
Acid fixing baths made according to my invention include a substance capable of furnishing acetate ions (that is, the ion--OOC.CH3) and boric acid. Satisfactory substances which fur- 55 nish the acetate ion are acetic acid and sodium acetate, though other acetates may be used. The boric acid is added either as such or is supplied by borax and acetic acid in solution. At any rate, a small amount of bric acid is present in the fixing bath simultaneously with the acetate ion.
The following examples will serve to illustrate the invention:
Example 1 Water 1 liter Hypo 320 grams Add to this the following hardener:
Water 240 0. c. 30 Sodium sulphite 20 grams Acetic acid 28% 60 c. 0. Potassium alum 40 grams When dissolved, add to this hardener 10 grams of borax dissolved in 1'70 c. c. of hot water. After dissolving the borax in the hardener, the entire hardener is added to the hypo solution.
Sodium bi-sulphite 12.5 grams 10 Potassium alum 15 grams Sodium acetate crystals l 30 grams Boric acid 5 grams Water to 1 liter In these formulas a portion or all of the acetic acid may be replaced by equivalent amounts of citric or tartaric acids. .They are not, however, as satisfactory as acetic acid. If all citric or all tartaric acid is used, the fixing bathsshow a marked improvement over the older acid hardening baths, in that the hardening life is somewhat increased and sludging is less. The improvement is, however, not so great as when acetic acid alone is used.
In the first of these examples, the boric acid will be present in the fixing bath through interaction of the borax with the weak acid, acetic acid. In the second and third examples, boric acid itself is added. All of these fixing baths will give a greatly increased hardening life. They will still harden satisfactorily when from three to four times as much developer is carried over as will render an ordinary bath unfit for further use. In any case the usual range of concentration of the acetate ions is from 10 grams per liter to 40 grams per liter and the concentration of boric acid is at least half that of the acetate ions, but can be more, and the amount of hardeners is not less than 5 grams and is preferably less than 30 grams per liter.
I consider as included in my invention, all equivalents and modifications coming within the scope of the appended claims.
What I claim is:
1. An acid hardening fixing bath comprising an aqueous solution of sodium thin-sulfate, a sulfite, a hardening agent, boric acid and a compound capable of furnishing acetate ions, the concentration of acetate ions being greater than 10 grams per liter and the concentration of boric acid being at least half that of the acetate ions.
2. An acid hardening fixing bath comprising an aqueous solution of sodium thiosulfate, a sulfite, acetic acid, boric acid and a hardener, the acetic acid being present in a concentration greater than 10 grams per liter and the concentration of the boric acid being at least half that of the acetic acid.
3. An acid hardening fixing bath comprising an aqueous solution of sodium thio-sulfate, a sulfite, acetic acid, boric acid and potassium alum, the acetic acid concentration being greater than 10 grams per liter, the boric acid concentration being substantially half that of the acetic acid.
4. An acid hardening fixing bath comprising an aqueous solution of sodium thio-sulfate, a sulfite, acetic acid, boric acid and potassium alum, the acetic acid concentration being greater than 10 grams per liter, the boric acid concentration being substantially half that of the acetic acid and the potassium alum concentration being not over 30 grams per liter.
REINHOLD s. BECKER.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US588502A US1930140A (en) | 1932-01-23 | 1932-01-23 | Acid hardening fixing bath |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US588502A US1930140A (en) | 1932-01-23 | 1932-01-23 | Acid hardening fixing bath |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US1930140A true US1930140A (en) | 1933-10-10 |
Family
ID=24354101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US588502A Expired - Lifetime US1930140A (en) | 1932-01-23 | 1932-01-23 | Acid hardening fixing bath |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US1930140A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2475134A (en) * | 1945-11-08 | 1949-07-05 | Gen Aniline & Film Corp | Sulfite antistain bath for multilayer color film |
| US2483971A (en) * | 1947-11-18 | 1949-10-04 | Gen Aniline & Film Corp | Antistain baths for sensitive color photographic material |
| US2515121A (en) * | 1945-11-08 | 1950-07-11 | Gen Aniline & Film Corp | Process for preventing stains in photographic color material by treatment with basic acids immediately prior to drying |
| US2584030A (en) * | 1947-02-07 | 1952-01-29 | Polaroid Corp | Light sensitive silver halide photographic product for image transfer and process utilizing the same |
| US2635048A (en) * | 1948-07-06 | 1953-04-14 | Polaroid Corp | Photographic transfer product and process |
| US2663641A (en) * | 1946-10-07 | 1953-12-22 | Gevaert Photo Prod Nv | Production of reversal images |
| US3061433A (en) * | 1958-08-04 | 1962-10-30 | Ilford Ltd | Process and solution for bleaching photographic images |
-
1932
- 1932-01-23 US US588502A patent/US1930140A/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2475134A (en) * | 1945-11-08 | 1949-07-05 | Gen Aniline & Film Corp | Sulfite antistain bath for multilayer color film |
| US2515121A (en) * | 1945-11-08 | 1950-07-11 | Gen Aniline & Film Corp | Process for preventing stains in photographic color material by treatment with basic acids immediately prior to drying |
| US2663641A (en) * | 1946-10-07 | 1953-12-22 | Gevaert Photo Prod Nv | Production of reversal images |
| US2584030A (en) * | 1947-02-07 | 1952-01-29 | Polaroid Corp | Light sensitive silver halide photographic product for image transfer and process utilizing the same |
| US2483971A (en) * | 1947-11-18 | 1949-10-04 | Gen Aniline & Film Corp | Antistain baths for sensitive color photographic material |
| US2635048A (en) * | 1948-07-06 | 1953-04-14 | Polaroid Corp | Photographic transfer product and process |
| US3061433A (en) * | 1958-08-04 | 1962-10-30 | Ilford Ltd | Process and solution for bleaching photographic images |
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