US3839045A - Photographic color developer solution stabilized with lithium ions - Google Patents
Photographic color developer solution stabilized with lithium ions Download PDFInfo
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- US3839045A US3839045A US00368167A US36816773A US3839045A US 3839045 A US3839045 A US 3839045A US 00368167 A US00368167 A US 00368167A US 36816773 A US36816773 A US 36816773A US 3839045 A US3839045 A US 3839045A
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- 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
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- 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
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- ABSTRACT The incorporation of small amounts of lithium ion into a solution of a heavy metal sequestering agent of the formula:
- R is a lower alkyl radical having from one to five 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, propane] and butane] 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 one to five carbon atoms and the use of these materials as complex formers (sequestering agents) for metal ions and particularly polyvalent metal ions.
- acylation products can be produced, e.g., by reacting phosphorous acid with acid anhydrides and/or acid chlorides, especially those of acetic, propionic, butyric, valeric and caproic acid.
- acid anhydrides and/or 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 and 200C.
- 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 ppm. 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:
- the lithium ion can be supplied to the solution of sequestering agent in any suitable form.
- a soluble salt of lithium for example as lith ium sulfate, lithium sulfite. lithium hydroxide, etc.
- photographic developer compositions which have very sensitive balances of a variety of ions for example, sulfite, sulfate, buffer (i.e. borate, carbonate, etc.) and halogen ion it is generally advisable to add the lithium as a salt whose anion is common to the system and compatible therewith.
- 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.
- lithium ions in a concentration sufficient to substantlally prevent formation in said solution of a precipitate of said sequestering agent.
- Table IV gives the time (in days) until 0n the total polyvalent metal ion concentration and the i bl precipitate f -m d i an aqueous 025 M concentration of lithium ions in said solution is at least K CO solution containing 1 ml/l of a 60 percent aqueabout pmous solution of l-hydroxyethylidene-l ,l-diphosphonic 3.
- W V valent metal ions are calcium ions.
- a solution as claimed in claim 1 wherein the conpamcularly Photographlc developer composltlonscentration of said lithium ions is from about lOO ppm
- the invention has been described in detail with parto about 450 ppm ticular reference to the preferred embodiments 40
- An aqueous alkaline photographic color developer i at least about (105 to 1 sohmon compnsmg, 10.
- Polyvalent fnetal 1on5 is in the rangefrom about 0.5:1 to about
- a solution as claimed in claim 1 additionally con- Sald q f agent bemg Selected from the taining hydroxylamine sulfate, sulfite ion and benzyl group consisting of i i V V I Phosphorus. Compounds Ofthe l 12.
- a solution as claimed in claim 1 wherein said color developing agent is 4-amino-N-ethyl-N-(B- 0 R methanesulfonamidoethyl)-m-toluidine sesquisulfate o i monohydrate.
- An aqueous alkaline photographic color developer solution comprising l. a color developing agent, lltlgerrltsa R 15 an alkyl group of from one to five carbon 2.
- Calcium ions 0 3. a sufficient amount of l-hydroxyethylidene-l,lb. alkali metal, ammonium and ethanolamme salts diphosphonic acid to sequester Said calcium ions of said phosphorus compounds, and 4 S dium r otasshm ion t bl f c.
- alkali metal ions selected from the group consistmm 10mm an amount suffic'em to Substama y ing of sodium ions and potassium ions in a concentration capable of resulting in the formation of a precipitate of said sequestering agent, and
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Abstract
WHEREIN R is a lower alkyl radical having from one to five 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 incorporation of small amounts of lithium ion into a solution of a heavy metal sequestering agent of the formula:
The incorporation of small amounts of lithium ion into a solution of a heavy metal sequestering agent of the formula:
Description
United States Patent [191 Brown Oct. 1, 1974 IONS [75] Inventor: Jesse L. Brown, Rochester, NY. [73] Assignee: Eastman Kodak Company, 4 Rochester, NY. [22] Filed: June 8, 1973 [211 App]. No.: 368,167
Related US. Application Data [62] Division of Ser. No. 224,627, Feb. 8, 1972, Pat. No.
[52] US. Cl. 96/66.4, 96/66 R [51] Int. Cl G03c 5/30 [58] Field of Search 96/66, 66.4
[56] References Cited UNITED STATES PATENTS 2,541,470 2/1951 Henn 96/66.4 3,201,246 8/1965 Allen et al. 96/66.4 3,647,449 3/1972 Malloy 96/66 R 3,746,544 7/1973 Heilmann 96/66.4
Primary Examiner-Mary F. Kelley Attorney, Agent, or Firm-A. P. Lorenzo [57] ABSTRACT The incorporation of small amounts of lithium ion into a solution of a heavy metal sequestering agent of the formula:
wherein R is a lower alkyl radical having from one to five 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, propane] and butane] also provide useful sequestering agents.
13 Claims, No Drawings PHOTOGRAPHIC COLOR DEVELOPER SOLUTION STABILIZED WITH LITHIUM IONS This is a division of application Ser. No. 224,627 filed Feb. 8, 1972, and issued Feb. 26, 1974, as U.S. Pat. No. 3,794,591.
FIELD OF THE INVENTION 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.
BACKGROUND OF THE INVENTION U.S. Pat. No. 3,214,454 to Blaser et al., issued Oct. 26, 1965 describes the preparation of organic acylation products of phosphorous acid and particularly compounds of the formula:
.SBE.. ...I ...-.E...
wherein R is a lower alkyl group having from one to five carbon atoms and the use of these materials as complex formers (sequestering agents) for metal ions and particularly polyvalent metal ions.
The utility of these compounds as sequestering agents and their exceptional abilities as complex formers of heavy metal ions is well known by those skilled in this art. However, these materials do have at least one relatively major shortcoming. This shortcoming is clearly manifested when compounds of the class described are used to sequester, for example, calcium from an alkaline solution which also contains, for example, sodium or potassium ion. In such a sytem a characteristic white precipitate, which is readily recognized by the skilled artisans in this field, forms after a very short period of time.
Im many usages, and in particular in photographic development, this precipitate can produce deleterious effects some of which are similar to those which prompted addition of the sequestrant initially.
OBJECTS OF THE INVENTION It is therefore an object of the present invention to provide a method of sequestering, for example, calcium ion from a solution using the aforementioned acylation.
SUMMARY OF THE INVENTION According to the present invention, the formation of a white precipitate when an organic acylation product of phosphorus acid and in particular compounds of the formula n o lIOI 4JI 0H dn II on wherein R is a lower alkyl group having from one to five carbon atoms, is used to sequester heavy metal ions, especially calcium, is inhibited by the addition of small amounts of lithium ion to the sequestering agent solution.
DETAILED DESCRIPTION OF THE INVENTION In a solution containing alkali metal ions other than lithium, for example, sodium and potassium ions as well as polyvalent metal ions, attempts to sequester the polyvalent metal ions with organic acylation products of the type described above and in U.S. Pat. No. 3,214,454 have resulted in the formation of a white precipitate. It has now been discovered that the incorporation of at least about ppm of lithium ion in such a solution inhibits the formation of such a white precipitate. I
These acylation products can be produced, e.g., by reacting phosphorous acid with acid anhydrides and/or acid chlorides, especially those of acetic, propionic, butyric, valeric and caproic acid. When both 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. In lieu of phosphorous acid and one of the acid chlorides named above, 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 and 200C.
As described in the aforementioned U.S. Pat. No. I
3,214,454 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.
According to a preferred embodiment of the present invention wherein the organic acylation product of phosphorous acid is used as a sequestering agent in a photographic developer the concentration of lithium ion ranges between about 100 and 450 ppm. 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.
In solutions of sequestering agents of the type described above, which solutions are used in an environment other than that of a photographic developer, 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 lith ium sulfate, lithium sulfite. lithium hydroxide, etc. In photographic developer compositions which have very sensitive balances of a variety of ions for example, sulfite, sulfate, buffer (i.e. borate, carbonate, etc.) and halogen ion it is generally advisable to add the lithium as a salt whose anion is common to the system and compatible therewith. For example, when a carbonate buffer is used in such a system, the lithium is advantageously added as lithium carbonate. 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.
Although 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.
Similarly, although the improved results of the instant invention are achieved when almost any polyvalent metal ion is being sequestered (for example, Mg Ca Cu Zn +2 and Fe the most obvious improvement is obtained in solutions used to sequester calcium in (Ca since it is in this medium that the most aggravated precipitation occurs, particularly in the photographic field where sequestering agents of this type are used as anti-calcium agents.
Although applicant does not wish to be bound by any particular theory for the mechanism of his invention it is believed that in solutions containing polyvalent metal ions, (Ca Cu etc.) a sequestering agent of the type described and alkali metal ions other than lithium, for example, sodium and/or potassium the dialkali, monopolyvalent ion salt of the sequestering agent is formed and it is this species which precipitates. Thus, where the solution contains sodium and calcium ion, the disodium, monocalcium salt of the sequestering agent would form the precipitate. In the case where both sodium and potassium were present in the solution the precipitate formed could be the disodium, dipotassium or monosodium, monopotassium, monocalcium salt of the sequestering agent, etc.
From this, or any other theory for the formation of the precipitate, it seems very surprising that the addition of further amounts of an alkali metal ion, namely lithium, would provide any beneficial effect let alone the elimination of the precipitate which presumably includes alkali metal ion.
The following examples will serve to demonstrate the invention described herein.
EXAMPLE 1 A photographic developer solution having the following composition Hydroxylamine sulfate I 4.5 gm
Sodium Hydroxide (50 80 gm Benzyl alcohol 15.7 ml
-Continued Potassium hydroxide 51 gm sodium sulfite 1.9 gm Boric acid 19.0 gm 4-amino-N-ethyl-N[B-methanesulfonamidoethyll-m-toluidine (sequisulfate monohydrate) 5.3 gm Sufficient water to make 1 liter was prepared and utilized to develop imagewise exposed, silver coupler color print material. To this seasoned solution were added the amounts of calcium ion, and organic phosphorous acid sequestering agent, indicated in Table 1 below.
TABLE I Cad-l- 60% aqueous solution Results after 38 days of sequestering Agent 350 ppm 2 mill Precipitate 300 ppm 2 ml/l Precipitate 250 ppm 2 ml/l Precipitatc 200 ppm 2 ml/l Precipitate 150 ppm 2 ml/l Precipitate Thus, precipitate formed at all of these levels of Ca-l-iwhen the organic phosphorous acid derivative was used as sequestrant.
EXAMPLE 2 The method of Example 1 was repeated except that the addition to the seasoned developer comprised:
0.25 M K CO l ml/l 60 percent aqueous solution of sequestering agent* and ppm Ca-H- In addition to the foregoing the additions shown in Table II were incorporated into the seasoned developer and the results indicated.
TABLE II Additive Result Standard (no further additive) Precipitate (3 days) 1 g/l potassium hexametaphosphate Precipitate (3 days) 0.05 M Li+ No precipitate 0.05 M Rb+ Precipitate (3 days) 0.05 M Cs+ Precipitate (3 days) EXAMPLE 3 An aqueous solution comprising 0.25 M K CO l ml/l of a 60 percent aqueous solution of organic phosphorous acid sequestering agent* and 100 ppm of Ca-H- was prepared. To this solution the additions indicated in Table III were made. The approximate weight of precipitate formed after 10 and 17 days is shown in Table 111.
5. lithium ions in a concentration sufficient to substantlally prevent formation in said solution of a precipitate of said sequestering agent.
2. A solution as claimed in claim 1 wherein said seused as sequestering agent 5 questering agent is present in said solution in an amount of from about 1 mole per 5000 moles of poly- EXAMPLE 4 valent metal ion up to stoichiometric quantities based The following Table IV gives the time (in days) until 0n the total polyvalent metal ion concentration and the i bl precipitate f -m d i an aqueous 025 M concentration of lithium ions in said solution is at least K CO solution containing 1 ml/l of a 60 percent aqueabout pmous solution of l-hydroxyethylidene-l ,l-diphosphonic 3. A solution as claimed in claim 1 wherein said polyacid. W V valent metal ions are calcium ions.
TABLE IV Na Concentration 0.2 M 0.1 M 0.04 M 0.02 M
Ca Cone. (ppm) 100 200 100 200 100 200 I00 200 Li Conc.
0.l M 48 days 0.04 M 13 days days 48 days 48 days 0.02 M 13 days 20 days 20 days 48 days 0.00 M 1 day 7 days 68 days From the foregoing Example 4, it should be clear that 4. A solution as claimed in claim 1 wherein said alkali highest stability (ie., resistance to precipitation) for sometal 1008 a SOdlutn Ions. lutions containing calcium is achieved when the weight Asolutlon as clalfned l" 1 Where!" Said alkali ratio of lithium ion to other alkali metal ions is at least metal lons f POtaSSIPm F about 0.02:1. Further improved results are achieved A ,Solutlon dammed g l l when this ratio is at least about 0.05:1 and optimum reqpestermg a e cqmpoun o t m? sults are achieved at the level where this ratio is at least about 0.1:1 The upper limit of this ratio will depend to i a large extent upon the concentration and solution tol- HOP --POH erance factors described above. Thus, no absolute OH 6 upper limit can be described, however, as a practical 3 5 matter, lithium to other alkali metal ion ratios above m 1031 would appear Serve no useful P f 7. A solution as claimed in claim 1 wherein the conpamcularly Photographlc developer composltlonscentration of said lithium ions is from about lOO ppm The invention has been described in detail with parto about 450 ppm ticular reference to the preferred embodiments 40 A Solution as claimed in claim 1 wherein the b be understood h 9' and weight ratio of said lithium ions to said alkali metal ions modifications can be effected within the spirit and is at least about 0 02 to 1 Scope 9 the mvemlon- 9. A solution as claimed in claim 1 wherein the I clam: weight ratio of said lithium ions to said alkali metal ions 1. An aqueous alkaline photographic color developer i at least about (105 to 1 sohmon compnsmg, 10. A solution as claimed in claim 1 wherein the a Color developmg agent weight ratio of said lithium ions to said alkali metal ions Polyvalent fnetal 1on5 is in the rangefrom about 0.5:1 to about l 5:l.
a ,sequestefmgagem for sald, polyvalem metal lens 11. A solution as claimed in claim 1 additionally con- Sald q f agent bemg Selected from the taining hydroxylamine sulfate, sulfite ion and benzyl group consisting of i i V V I Phosphorus. Compounds Ofthe l 12. A solution as claimed in claim 1 wherein said color developing agent is 4-amino-N-ethyl-N-(B- 0 R methanesulfonamidoethyl)-m-toluidine sesquisulfate o i monohydrate.
6 H 13. An aqueous alkaline photographic color developer solution comprising l. a color developing agent, lltlgerrltsa R 15 an alkyl group of from one to five carbon 2. Calcium ions 0 3. a sufficient amount of l-hydroxyethylidene-l,lb. alkali metal, ammonium and ethanolamme salts diphosphonic acid to sequester Said calcium ions of said phosphorus compounds, and 4 S dium r otasshm ion t bl f c. monoalkyl and dialkyl esters of said phosphorus o f S m g q i compounds with methanol, ethanol, propanol or mg m h orma a 'P' o e butanol, -h) 'droxyet y1dene-l, l-diphosphonic acid, a ntlll 4. alkali metal ions selected from the group consistmm 10mm an amount suffic'em to Substama y ing of sodium ions and potassium ions in a concentration capable of resulting in the formation of a precipitate of said sequestering agent, and
prevent the formation of a precipitate of the l-hydroxyethylidene-l l-diphosphonic acid.
Claims (26)
1. A COLOR DEVELOPING AGENT,
1. AN AQUEOUS ALKALINE PHOTOGRAPHIC COLOR DEVELOPER SOLUTION COMPRISING
2. polyvalent metal ions,
2. POLYVALENT METAL IONS,
2. calcium ions,
2. A solution as claimed in claim 1 wherein said sequestering agent is present in said solution in an amount of from about 1 mole per 5000 moles of polyvalent metal ion up to stoichiometric quantIties based on the total polyvalent metal ion concentration and the concentration of lithium ions in said solution is at least about 100 ppm.
3. a sufficient amount of 1-hydroxyethylidene-1,1-diphosphonic acid to sequester said calcium ions,
3. A SEQUESTERING AGENT FOR SAID POLYVALENT METAL IONS, SAID SEQUESTERING AGENT BEING SELECTED FROM THE GROUP CONSISTING OF A. PHOSPHORUS COMPOUNDS OF THE FORMULA
3. A solution as claimed in claim 1 wherein said polyvalent metal ions are calcium ions.
3. a sequestering agent for said polyvalent metal ions, said sequestering agent being selected from the group consisting of a. phosphorus compounds of the formula
4. 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, AND
4. sodium or potassium ions in an amount capable of resulting in the formation of a precipitate of the 1-hydroxyethylidene-1, 1-diphosphonic acid, and
4. 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, and
4. A solution as claimed in claim 1 wherein said alkali metal ions are sodium ions.
5. A solution as claimed in claim 1 wherein said alkali metal ions are potassium ions.
5. lithium ions in a concentration sufficient to substantially prevent formation in said solution of a precipitate of said sequestering agent.
5. lithium ions in an amount sufficient to substantially prevent the formation of a precipitate of the 1-hydroxyethylidene-1, 1-diphosphonic acid.
5. LITHIUM IONS IN A CONCENTRATION SUFFICIENT TO SUBSTANTIALLY PREVENT FORMATION IN SAID SOLUTION OF A PRECIPITATE OF SAID SEQUESTERING AGENT.
6. A solution as claimed in claim 1 wherein said sequestering agent is the compound of the formula:
7. A solution as claimed in claim 1 wherein the concentration of said lithium ions is from about 100 ppm to about 450 ppm.
8. A solution as claimed in claim 1 wherein the weight ratio of said lithium ions to said alkali metal ions is at least about 0.02 to 1.
9. A solution as claimed in claim 1 wherein the weight ratio of said lithium ions to said alkali metal ions is at least about 0.05 to 1.
10. A solution as claimed in claim 1 wherein the weight ratio of said lithium ions to said alkali metal ions is in the range from about 0.5:1 to about 1.5:1.
11. A solution as claimed in claim 1 additionally containing hydroxylamine sulfate, sulfite ion and benzyl alcohol.
12. A solution as claimed in claim 1 wherein said color developing agent is 4-amino-N-ethyl-N-( Beta -methanesulfonamidoethyl)-m-toluidine sesquisulfate monohydrate.
13. An aqueous alkaline photographic color developer solution comprising
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US00368167A US3839045A (en) | 1972-02-08 | 1973-06-08 | Photographic color developer solution stabilized with lithium ions |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US22462772A | 1972-02-08 | 1972-02-08 | |
| US00368167A US3839045A (en) | 1972-02-08 | 1973-06-08 | Photographic color developer solution stabilized with lithium ions |
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| US3839045A true US3839045A (en) | 1974-10-01 |
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| US00368167A Expired - Lifetime US3839045A (en) | 1972-02-08 | 1973-06-08 | Photographic color developer solution stabilized with lithium ions |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3912645A (en) * | 1974-02-11 | 1975-10-14 | Addressograph Multigraph | Liquid developer for latent electrostatic images |
| US4046570A (en) * | 1975-06-13 | 1977-09-06 | Agfa-Gevaert N.V. | Hardening fixer for photographic silver halide material |
| US4330616A (en) * | 1980-07-31 | 1982-05-18 | Konishiroku Photo Industry Co., Ltd. | Method for processing silver halide color photographic material |
| US4546068A (en) * | 1983-06-09 | 1985-10-08 | Konishiroku Photo Industry Co., Ltd. | Method for processing of light-sensitive silver halide color photographic material |
| US4596765A (en) * | 1983-12-05 | 1986-06-24 | Konishiroku Photo Industry Co., Ltd. | Composition of a photographic color forming agent |
| US4837139A (en) * | 1986-07-26 | 1989-06-06 | Konishiroku Photo Industry Co., Ltd. | Method for processing a light-sensitive silver halide color photographic material using at least one silver halide emulsion layer and at least one of a cyan coupler and magneta coupler |
| US4892804A (en) * | 1986-01-24 | 1990-01-09 | Eastman Kodak Company | Photographic color developing compositions which are especially useful with high chloride photographic elements |
| US5273865A (en) * | 1990-04-24 | 1993-12-28 | Minnesota Mining And Manufacturing Company | Photographic color developing composition and method for processing a silver halide color photographic element |
| US5763147A (en) * | 1995-02-21 | 1998-06-09 | Eastman Kodak Company | Method for processing high silver bromide color negative photographic films using a peroxide bleaching composition |
| US5773202A (en) * | 1995-02-21 | 1998-06-30 | Haye; Shirleyanne Elizabeth | Method for processing color photographic films using a peroxide bleaching composition |
| US6037111A (en) * | 1998-11-06 | 2000-03-14 | Eastman Kodak Company | Lithium and magnesium ion free color developing composition and method of photoprocessing |
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| US3746544A (en) * | 1970-04-01 | 1973-07-17 | Agfa Gevaert Ag | Photographic color developer |
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| US2541470A (en) * | 1947-05-28 | 1951-02-13 | Eastman Kodak Co | Photographic silver halide developing solutions containing calcium precipitation inhibitors |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3912645A (en) * | 1974-02-11 | 1975-10-14 | Addressograph Multigraph | Liquid developer for latent electrostatic images |
| US4046570A (en) * | 1975-06-13 | 1977-09-06 | Agfa-Gevaert N.V. | Hardening fixer for photographic silver halide material |
| US4330616A (en) * | 1980-07-31 | 1982-05-18 | Konishiroku Photo Industry Co., Ltd. | Method for processing silver halide color photographic material |
| US4546068A (en) * | 1983-06-09 | 1985-10-08 | Konishiroku Photo Industry Co., Ltd. | Method for processing of light-sensitive silver halide color photographic material |
| US4596765A (en) * | 1983-12-05 | 1986-06-24 | Konishiroku Photo Industry Co., Ltd. | Composition of a photographic color forming agent |
| US4892804A (en) * | 1986-01-24 | 1990-01-09 | Eastman Kodak Company | Photographic color developing compositions which are especially useful with high chloride photographic elements |
| US4837139A (en) * | 1986-07-26 | 1989-06-06 | Konishiroku Photo Industry Co., Ltd. | Method for processing a light-sensitive silver halide color photographic material using at least one silver halide emulsion layer and at least one of a cyan coupler and magneta coupler |
| US4948713A (en) * | 1986-07-26 | 1990-08-14 | Konishiroku Photo Industry Co., Ltd. | Processing solution for a light-sensitive silver halide color photographic material |
| US5273865A (en) * | 1990-04-24 | 1993-12-28 | Minnesota Mining And Manufacturing Company | Photographic color developing composition and method for processing a silver halide color photographic element |
| US5763147A (en) * | 1995-02-21 | 1998-06-09 | Eastman Kodak Company | Method for processing high silver bromide color negative photographic films using a peroxide bleaching composition |
| US5773202A (en) * | 1995-02-21 | 1998-06-30 | Haye; Shirleyanne Elizabeth | Method for processing color photographic films using a peroxide bleaching composition |
| US6037111A (en) * | 1998-11-06 | 2000-03-14 | Eastman Kodak Company | Lithium and magnesium ion free color developing composition and method of photoprocessing |
| EP0999471A1 (en) * | 1998-11-06 | 2000-05-10 | Eastman Kodak Company | Lithium and magnesium ion free color developing composition and method of photoprocessing |
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