US3794591A - Sequestering agent solutions stabilized with lithium ions - Google Patents

Sequestering agent solutions stabilized with lithium ions Download PDF

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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
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United States
Prior art keywords
lithium
solution
sequestering agent
ions
ion
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Expired - Lifetime
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US00224627A
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English (en)
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J Brown
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Eastman Kodak Co
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Eastman Kodak Co
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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
    • 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.

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  • 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)
US00224627A 1972-02-08 1972-02-08 Sequestering agent solutions stabilized with lithium ions Expired - Lifetime US3794591A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US22462772A 1972-02-08 1972-02-08

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US3794591A true US3794591A (en) 1974-02-26

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US (1) US3794591A (it)
JP (1) JPS5639359B2 (it)
AR (1) AR201425A1 (it)
AU (1) AU473440B2 (it)
BE (1) BE795156A (it)
BR (1) BR7300928D0 (it)
CA (1) CA1006736A (it)
CH (1) CH576157A5 (it)
DE (1) DE2306272C3 (it)
FR (1) FR2171220B1 (it)
GB (1) GB1420014A (it)
HK (1) HK64676A (it)
IT (1) IT978925B (it)
NL (1) NL7301760A (it)
SE (1) SE388293B (it)
ZA (1) ZA73907B (it)

Cited By (7)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
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

Cited By (7)

* Cited by examiner, † Cited by third party
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
NL7301760A (it) 1973-08-10
AU5185273A (en) 1974-08-08
DE2306272B2 (de) 1980-02-14
BE795156A (fr) 1973-08-08
JPS5639359B2 (it) 1981-09-12
AU473440B2 (en) 1976-06-24
ZA73907B (en) 1973-11-28
AR201425A1 (es) 1975-03-14
FR2171220B1 (it) 1976-11-05
IT978925B (it) 1974-09-20
DE2306272C3 (de) 1980-10-16
CH576157A5 (it) 1976-05-31
BR7300928D0 (pt) 1973-09-20
DE2306272A1 (de) 1973-08-16
GB1420014A (en) 1976-01-07
FR2171220A1 (it) 1973-09-21
HK64676A (en) 1976-10-22
SE388293B (sv) 1976-09-27
CA1006736A (en) 1977-03-15
JPS4890983A (it) 1973-11-27

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