US3794591A - Sequestering agent solutions stabilized with lithium ions - Google Patents
Sequestering agent solutions stabilized with lithium ions Download PDFInfo
- Publication number
- US3794591A US3794591A US00224627A US3794591DA US3794591A US 3794591 A US3794591 A US 3794591A US 00224627 A US00224627 A US 00224627A US 3794591D A US3794591D A US 3794591DA US 3794591 A US3794591 A US 3794591A
- Authority
- US
- United States
- Prior art keywords
- lithium
- solution
- sequestering agent
- ions
- ion
- 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
Images
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
- G03C5/3053—Tensio-active agents or sequestering agents, e.g. water-softening or wetting agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
- C02F5/145—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus combined with inorganic substances
Definitions
- R is a lower alkyl radical having from 1 to 5 carbon atoms, inhibits the formation of the white precipitate characteristically produced when sequestrants of this type are used to sequester ions of heavy metals such as calcium.
- Alkali metal, ammonium and ethanolamine salts of compounds of the above formula and mono and dialkyl esters thereof with methanol, ethanol, propanol and butanol also provide useful sequestering agents.
- the present invention relates to improved methods for sequestering heavy metal ions and in particular to photographic developer solutions which contain such heavy metal ion sequestering agents and small amounts of lithium.
- R is a lower alkyl group having from 1 to 5 carbon atoms and the use of these materials as complex formers (sequestering agents) for metal ions and particularly polyvalent metal ions.
- Yet another object of the present invention is the provision of sequestering solutions of the aforementioned organic acylation products of phosphorous acid (and in particular color photographic developer solutions) which when used to sequester, for example, calcium ion, do not produce the aforementioned white precipitate.
- acylation products can be produced, e.g. by reacting phosphorous acid with acid anhydrides and/0r acid chlorides, especially those of acetic, propionic, butyric, valeric and caproic acid.
- acid anhydrides and/0r acid chlorides especially those of acetic, propionic, butyric, valeric and caproic acid.
- the anhydride and the chloride are used simultaneously, they must be derived from the same acid, e.g. the anhydride and the chloride of acetic acid can be used simultaneously, but not acetic anhydride together with propionic chloride.
- phosphorus trichloride can be reacted with one of the carboxylic acids themselves.
- Particularly readily available are the reaction products of phosphorous acid with acetic anhydride, with acetyl chloride or with a mixture thereof.
- the reactions opportunely are carried out at elevated temperatures, preferably between 50 and 200 C.
- the concentration of sequestering agent may range from 1 mol per 5000 mols of metal up to stoichiometric quantities of sequestering agent and polyvalent metal ion.
- the concentration of lithium ion ranges between about 100 and 450 p.p.m. Below this range insufficient lithium is present to inhibit precipitate formation while at concentrations substantially above this range undesirable sensitometric effects occur which make use of such levels of lithium in a photographic environment practically impossible.
- the effective upper limit of lithium ion concentration can be governed by one or more of the following factors: (1) tolerance of the solution for lithium ion; (2) the upper limit of solubility of the source of lithium ion in the particular solution; and (3) perhaps in some cases toxicity levels of lithium compounds which might to some degree limit their use.
- the lithium ion can be supplied to the solution of sequestering agent in any suitable form.
- This generally will be as a soluble salt of lithium, for example as lithium sulfate, lithium sulfite, lithium hydroxide, etc.
- a soluble salt of lithium for example as lithium sulfate, lithium sulfite, lithium hydroxide, etc.
- ions for example, sulfite, sulfate, buffer (i.e. borate, carbonate, etc.) and halogen ion
- the lithium is advantageously added as lithium carbonate.
- lithium hydroxide In a developer which contains a sequestering agent of the type described and a borate buffer the lithium is advantageously added as lithium hydroxide. Similarly lithium sulfate is preferred when the developer contains hydroxylamine sulfate. Since it is generally advisable to maintain a low halogen ion concentration in photographic developers, the addition of lithium as lithium chloride, bromide or iodide generally produces undesirable sensitometric effects, however, in other sequestering mediums where halogen ion content produces no adverse effect lithium ion can be provided in the form of a halogen salt.
- the concentration of lithium in the sequestering bath may vary broadly within the limits described above, superior results are achieved when the ratio of lithium ion to other alkali metal ions in the solution ranges from about 0.5 to 1.5: 1. At this level of lithium ion substantially complete freedom from undesirable precipitate is noted.
- Example 1 A photographic developer solution having the following composition Hydroxylamine sulfate gm 4.5 Sodium hydroxide (50%) gm 80 Benzyl alcohol ml 15.7 Potassium hydroxide gm 51 Sodium sulfite gm 1.9 Boric acid gm 19.0 4-amino N ethyl-N[fi-methanesulfonamidoethyl]- m-toluidine (sesquisulfate monohydrate) gm 5.3
- Example 2 The method of Example 1 was repeated except that the addition to the seasoned developer comprised: 0.25 M K 00 1 ml./l., 60% aqueous solution of sequestering agent 1 and p.p.m. Ca'
- Example 4 The following Table IV gives the time (in days) until noticeable precipitate formed in an aqueous 0.25 M K CO solution containing 1 ml./l. of a 60% aqueous solution of l-hydroxyethylidene-l,l-diphosphortic acid.
- Ca++ concentration (p.p.m.). 100 200 100 200 100 200 100 200 Li+ concentration:
- a sequestering agent for said polyvalent metal ions said sequestering agent being selected from the group consisting of (a) phosphorus compounds of the formula R HO 1' E 1'LOH where R is an alkyl group of from 1 to carbon atoms,
- alkali metal ions selected from the group consisting of sodium ions and potassium ions in a concentration capable of resulting in the formation of a precipitate of said sequestering agent
- a solution as claimed in claim 1 wherein said polyvalent metal ions are calcium ions.
- a solution as claimed in claim 1 wherein the concentration of said lithium ions is from about 100 p.p.m. to about 450 p.p.m.
- lithium ions in an amount sufiicient to substantially prevent the formation of a precipitate of the l-hydroxyethylidene-l, l-diphosphonic acid.
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (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)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US22462772A | 1972-02-08 | 1972-02-08 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3794591A true US3794591A (en) | 1974-02-26 |
Family
ID=22841479
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00224627A Expired - Lifetime US3794591A (en) | 1972-02-08 | 1972-02-08 | Sequestering agent solutions stabilized with lithium ions |
Country Status (16)
Country | Link |
---|---|
US (1) | US3794591A (xx) |
JP (1) | JPS5639359B2 (xx) |
AR (1) | AR201425A1 (xx) |
AU (1) | AU473440B2 (xx) |
BE (1) | BE795156A (xx) |
BR (1) | BR7300928D0 (xx) |
CA (1) | CA1006736A (xx) |
CH (1) | CH576157A5 (xx) |
DE (1) | DE2306272C3 (xx) |
FR (1) | FR2171220B1 (xx) |
GB (1) | GB1420014A (xx) |
HK (1) | HK64676A (xx) |
IT (1) | IT978925B (xx) |
NL (1) | NL7301760A (xx) |
SE (1) | SE388293B (xx) |
ZA (1) | ZA73907B (xx) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3994730A (en) * | 1972-09-22 | 1976-11-30 | Agfa-Gevaert, A.G. | Photographic color developer mixture |
US4046570A (en) * | 1975-06-13 | 1977-09-06 | Agfa-Gevaert N.V. | Hardening fixer for photographic silver halide material |
US4666481A (en) * | 1986-03-10 | 1987-05-19 | Union Carbide Corporation | Process for producing liquid helium |
EP0782042A2 (en) | 1995-12-27 | 1997-07-02 | Fuji Photo Film Co., Ltd. | Hydrazine compound and silver halide photographic photosensitive material comprising the same |
EP0789272A1 (en) | 1996-02-07 | 1997-08-13 | Fuji Photo Film Co., Ltd. | Developer for silver halide photographic photosensitive material |
EP1975698A1 (en) | 2007-03-23 | 2008-10-01 | FUJIFILM Corporation | Method and apparatus for producing conductive material |
EP2009977A2 (en) | 2007-05-09 | 2008-12-31 | FUJIFILM Corporation | Electromagnetic shielding film and optical filter |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07111571B2 (ja) * | 1987-09-03 | 1995-11-29 | 富士写真フイルム株式会社 | ハロゲン化銀カラー写真感光材料の処理方法 |
-
0
- BE BE795156D patent/BE795156A/xx not_active IP Right Cessation
-
1972
- 1972-02-08 US US00224627A patent/US3794591A/en not_active Expired - Lifetime
-
1973
- 1973-01-22 CA CA161,782A patent/CA1006736A/en not_active Expired
- 1973-02-06 AU AU51852/73A patent/AU473440B2/en not_active Expired
- 1973-02-07 CH CH175173A patent/CH576157A5/xx not_active IP Right Cessation
- 1973-02-07 FR FR7304244A patent/FR2171220B1/fr not_active Expired
- 1973-02-07 BR BR73928A patent/BR7300928D0/pt unknown
- 1973-02-08 AR AR246481A patent/AR201425A1/es active
- 1973-02-08 GB GB626073A patent/GB1420014A/en not_active Expired
- 1973-02-08 NL NL7301760A patent/NL7301760A/xx unknown
- 1973-02-08 ZA ZA730907A patent/ZA73907B/xx unknown
- 1973-02-08 IT IT20166/73A patent/IT978925B/it active
- 1973-02-08 JP JP1522773A patent/JPS5639359B2/ja not_active Expired
- 1973-02-08 DE DE2306272A patent/DE2306272C3/de not_active Expired
- 1973-02-08 SE SE7301730A patent/SE388293B/xx unknown
-
1976
- 1976-10-14 HK HK646/76*UA patent/HK64676A/xx unknown
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3994730A (en) * | 1972-09-22 | 1976-11-30 | Agfa-Gevaert, A.G. | Photographic color developer mixture |
US4046570A (en) * | 1975-06-13 | 1977-09-06 | Agfa-Gevaert N.V. | Hardening fixer for photographic silver halide material |
US4666481A (en) * | 1986-03-10 | 1987-05-19 | Union Carbide Corporation | Process for producing liquid helium |
EP0782042A2 (en) | 1995-12-27 | 1997-07-02 | Fuji Photo Film Co., Ltd. | Hydrazine compound and silver halide photographic photosensitive material comprising the same |
EP0789272A1 (en) | 1996-02-07 | 1997-08-13 | Fuji Photo Film Co., Ltd. | Developer for silver halide photographic photosensitive material |
EP1975698A1 (en) | 2007-03-23 | 2008-10-01 | FUJIFILM Corporation | Method and apparatus for producing conductive material |
EP2009977A2 (en) | 2007-05-09 | 2008-12-31 | FUJIFILM Corporation | Electromagnetic shielding film and optical filter |
Also Published As
Publication number | Publication date |
---|---|
JPS4890983A (xx) | 1973-11-27 |
AU5185273A (en) | 1974-08-08 |
DE2306272C3 (de) | 1980-10-16 |
DE2306272A1 (de) | 1973-08-16 |
DE2306272B2 (de) | 1980-02-14 |
GB1420014A (en) | 1976-01-07 |
ZA73907B (en) | 1973-11-28 |
AU473440B2 (en) | 1976-06-24 |
JPS5639359B2 (xx) | 1981-09-12 |
NL7301760A (xx) | 1973-08-10 |
FR2171220A1 (xx) | 1973-09-21 |
FR2171220B1 (xx) | 1976-11-05 |
BE795156A (fr) | 1973-08-08 |
CA1006736A (en) | 1977-03-15 |
AR201425A1 (es) | 1975-03-14 |
IT978925B (it) | 1974-09-20 |
CH576157A5 (xx) | 1976-05-31 |
HK64676A (en) | 1976-10-22 |
BR7300928D0 (pt) | 1973-09-20 |
SE388293B (sv) | 1976-09-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3994730A (en) | Photographic color developer mixture | |
EP0158369B1 (en) | A method of stabilizing a light-sensitive silver halide color photographic material | |
US3201246A (en) | Photographic developers containing calcium precipitation inhibitors | |
US3839045A (en) | Photographic color developer solution stabilized with lithium ions | |
US3794591A (en) | Sequestering agent solutions stabilized with lithium ions | |
GB496252A (en) | Improvements relating to photographic treating solutions | |
JPH06222517A (ja) | 写真現像溶液 | |
US4987060A (en) | Concentrated photographic developer composition and method of making it | |
US2656273A (en) | Photographic developers containing diamino-propanol tetracetic acid | |
JPS54121127A (en) | Photographic processing composition | |
GB1251558A (xx) | ||
US3811888A (en) | Composition for processing silver halide photographic light-sensitive elements | |
US3467521A (en) | Developer compositions containing sequestering agents | |
US2541470A (en) | Photographic silver halide developing solutions containing calcium precipitation inhibitors | |
JPS554024A (en) | Developing solution for silver halide color photographic material | |
GB1386718A (en) | Use of phosphorus compounds in controlling corrosion of metal parts | |
US2184053A (en) | Stable compositions useful in the compounding of photographic developers | |
US2625476A (en) | Photographic silver halide developing solutions containing calcium precipitation inhibitors | |
US3751251A (en) | Method for preparing bleach-fix regenerator concentrate | |
US5693456A (en) | Photographic bleaching compositions and method of photographic processing using mixture of ferric complexes | |
US2256390A (en) | Method of preventing precipitation of alkaline-earth metal salts in gelatin | |
US3432298A (en) | Silver salt diffusion process | |
JPH06167788A (ja) | 写真材料用漂白浴 | |
JPS57179843A (en) | Color developer composition for color photographic sensitive silver halide material | |
GB1471554A (en) | X-ray recording development process |