US2685513A - Method of stabilizing hydrates of sodium metaborate and single powder photographic developers containing same - Google Patents

Method of stabilizing hydrates of sodium metaborate and single powder photographic developers containing same Download PDF

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Publication number
US2685513A
US2685513A US295804A US29580452A US2685513A US 2685513 A US2685513 A US 2685513A US 295804 A US295804 A US 295804A US 29580452 A US29580452 A US 29580452A US 2685513 A US2685513 A US 2685513A
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Prior art keywords
sodium metaborate
stabilizing
hydrates
sodium
single powder
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US295804A
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Richard W Henn
Arthur A Rasch
John I Crabtree
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to BE521001D priority Critical patent/BE521001A/xx
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Priority to US295804A priority patent/US2685513A/en
Priority to GB17747/53A priority patent/GB732945A/en
Priority to FR1098529D priority patent/FR1098529A/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/06—Boron halogen compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/10—Compounds containing boron and oxygen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
    • C01B35/10—Compounds containing boron and oxygen
    • C01B35/12—Borates
    • 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
    • G03C5/264—Supplying of photographic processing chemicals; Preparation or packaging thereof
    • G03C5/265—Supplying of photographic processing chemicals; Preparation or packaging thereof of powders, granulates, tablets

Definitions

  • This invention relates to single-powder photographic developers and more particularly to a method of stabilizing hydrates of sodium metaborate, and to single-powder photographic develolJer compositions containing such stabilized salt.
  • Various single-powder photographic developers have been known heretofore. They may contain an organic silver halide developer component or mixtures of such components, including monomethyl p-aminophenol sulfate (Elon or metol), hydroquinone, p-aminophenol hydrochloride, p-aminophenol sulfate, pyrogallol, phydroxy phenyl glycine, catechol, diaminophenol hydrochloride, and others, with an alkali component, a stabilizing component,an oxidation inhibitor, a sequestering agent, and an antifogging component.
  • an organic silver halide developer component or mixtures of such components, including monomethyl p-aminophenol sulfate (Elon or metol), hydroquinone, p-aminophenol hydrochloride, p-aminophenol sulfate, pyrogallol, phydroxy phenyl glycine, catechol, diamin
  • the alkali component may be the stable hydrate of an alkali carbonate, a desiccated alkali carbonate, an alkalimetaborate, or an alkali sulfite. Generally the stable alkali carbonate monohydrate is preferred.
  • the oxidation-preventing component may be an alkali sulfite, and the antifoggant may be potassium bromide, potassium iodide, or an organic compound.
  • Stabilizing components for such a single-powder developer are disclosed in Patent 2,384,592 of September 11, 1945, and include maleic anhydride, salicyclic acid, alkali metabisulfite, benzoic anhydride, orthobenzoic sulfimide, p-hthal- 1 imide, and phthalic anhydride.
  • the latter has outstanding stabilizing properties in the presence of either sodium carbonate or borax and has been employed considerably more than the other stabilizers mentioned in the patent.
  • the stabilizing efiect of the phthalic anhydride is very good, it has been employed most successfully in developer compositions having as the alkali component either sodium carbonate or sodium sulfite, or mixtures thereof; less success has been attained in the case of the important class of developers containing sodium metaborate as the alkali ingredient.
  • boric anhydride is disclosed as an improved stabilizer for such sin- .gle powders as described above. In certain respects boric anhydride is superior to phthalic anhydride in stabilizing such powders.
  • Another object of the invention is to prepare 7 more stable hydrates of sodium metaborate than is possible by other methods.
  • Still another object is to stabilize hydrates of sodium metaborate by a method which does not substantially lessen their alkalinity.
  • Example 4 'KTheheatdtreatment be accomplished at a low temperature for a long period of time (Example 4) or by treatment at a higher temperature for a shorter time (Examples 1, 2, and 3). In the extreme case (Example this heat treatment is accompanied by appreciable dehydra tion which further improves the stability of the mixture.
  • Suitable stabilizing compounds include those mentioned previously in this specification and of these, boric anhydride, metaboric acid and phthalic anhydride have been found to be most successful although the other stabilizing compounds are satisfactory.
  • boron oxide hydrated to any degree intermediate to boric anhydride and metaboric acid is suitable.
  • Sodium metaborate tetrahydrate so treated can be advantageously incorporated in singlepowder formulas which do not show any indication that a reaction has taken place between the components of the mixture even after prolonged exposure to relatively high temperatures.
  • the total amount of protectant used is generally less than that used in cases where treatment is by another method.
  • Example 1 Boric anhydride was added to sodium metaborate tetrahydrate in a concentration of per cent and the mixture heated for 4 hours at 70 C. This mixture was packed in a formula consisting of:
  • This single powder did not discolor or otherwise deteriorate when stored.
  • Example 2 Phthalic anhydride was added to sodium metaborate tetrahydrate in a concentration of 2.5 per cent and the mixture heated for 4 hours at 70 C. This mixture was packed in a formula consisting of:
  • Example 3 4 Sodium sulfite 22.5 Sodium metaborate tetrahydrate 10 per 7 cent metaboric acid 39.6 Potassium bromide 2.0
  • This single powder d d not discolor or otherwise deteriorate on storage.
  • Example 4 Phthalic anhydride was added to sodium metaborate tetrahydrate in a concentration of 10 per 'cent and the mixture was heated at 40 C. for 30 days. The mixture was packed in a formula consisting of:
  • This single powder did not discolor or otherwise deteriorate when stored for three weeks at F.
  • the method of stabilizing hydrates of sodium metaborate which comprises mixing powder like particles thereof with 2.5 to 10% by weight of a finely divided stabilizer selected from the group consisting of phthalic anhydride, boric anhydride, and metaboric acid and heating the mixture for approximately 4 hours at 70 C.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Processing Of Solid Wastes (AREA)

Description

Patented Aug. 3, 1954 METHOD OF STABILIZING HYDRATES OF SODIUM METABORATE AND SINGLE POW- DER PHOTOGRAPHIC DEVELOPERS CON- TAINING SAME Richard W. Henn, Arthur A. Rasch, and John I.
Crabtree, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application June 26, 1952, Serial No. 295,804
This invention relates to single-powder photographic developers and more particularly to a method of stabilizing hydrates of sodium metaborate, and to single-powder photographic develolJer compositions containing such stabilized salt.
Various single-powder photographic developers have been known heretofore. They may contain an organic silver halide developer component or mixtures of such components, including monomethyl p-aminophenol sulfate (Elon or metol), hydroquinone, p-aminophenol hydrochloride, p-aminophenol sulfate, pyrogallol, phydroxy phenyl glycine, catechol, diaminophenol hydrochloride, and others, with an alkali component, a stabilizing component,an oxidation inhibitor, a sequestering agent, and an antifogging component. The alkali component may be the stable hydrate of an alkali carbonate, a desiccated alkali carbonate, an alkalimetaborate, or an alkali sulfite. Generally the stable alkali carbonate monohydrate is preferred. The oxidation-preventing component may be an alkali sulfite, and the antifoggant may be potassium bromide, potassium iodide, or an organic compound.
Stabilizing components for such a single-powder developer are disclosed in Patent 2,384,592 of September 11, 1945, and include maleic anhydride, salicyclic acid, alkali metabisulfite, benzoic anhydride, orthobenzoic sulfimide, p-hthal- 1 imide, and phthalic anhydride. The latter has outstanding stabilizing properties in the presence of either sodium carbonate or borax and has been employed considerably more than the other stabilizers mentioned in the patent.
While the stabilizing efiect of the phthalic anhydride is very good, it has been employed most successfully in developer compositions having as the alkali component either sodium carbonate or sodium sulfite, or mixtures thereof; less success has been attained in the case of the important class of developers containing sodium metaborate as the alkali ingredient.
In the copending application by William J. Rogers, S. N. 210,284, filed February 9, 1951, entitled Stabilizing Agent for Single Powder Photographic Developers, now S. Patent No. 2,606,118 of August 5, 1952, boric anhydride is disclosed as an improved stabilizer for such sin- .gle powders as described above. In certain respects boric anhydride is superior to phthalic anhydride in stabilizing such powders.
However, we have found that the addition of these protectants to single-powder formulas in which the alkali ingredient is a hydrate of so- 3 Claims. (Cl. 95-88) dium metaborate such as sodium metaborate tetrahydrate does not protect the powders as fully as may be desired when exposed to certain conditions and some discoloration may be caused by the reaction between the developing agents and the alkali.
One method which has been proposed to overcome this disadvantageous situation is to sta-' bilize the sodium metaborate tetrahydrate with a gas such as carbon dioxide. Another method of stabilization specifically for sodium metaborate tetrahydrate in which part of the water of crystallization is removed by drying has also been suggested. In applying these two methods in treating sodium metaborate tetrahydrate, considerable equipment and handling is neces: sary including chemical analysis of the product and single powder developer mixtures prepared therefrom, require in most instances the further addition of the usual protectants. A much simplermethod is, therefore, desired.
It is an object of the invention to provide a method whereby hydrates of sodium metaborate' can be stabilized suitably for use in single-powder developer formulas by a more facile method than those known in the prior art.
Another object of the invention is to prepare 7 more stable hydrates of sodium metaborate than is possible by other methods.
Still another object is to stabilize hydrates of sodium metaborate by a method which does not substantially lessen their alkalinity.
, Other objects will appear hereinafter.
In accordance with the present invention we stabilize hydrates of sodium metaborate by sepafree alkali, either by volatilizing and coating them or by simple contact, and (3) heatin moves loose water and some water of crystallizationi,
'KTheheatdtreatment be accomplished at a low temperature for a long period of time (Example 4) or by treatment at a higher temperature for a shorter time (Examples 1, 2, and 3). In the extreme case (Example this heat treatment is accompanied by appreciable dehydra tion which further improves the stability of the mixture.
Suitable stabilizing compounds include those mentioned previously in this specification and of these, boric anhydride, metaboric acid and phthalic anhydride have been found to be most successful although the other stabilizing compounds are satisfactory.
Specifically, boron oxide hydrated to any degree intermediate to boric anhydride and metaboric acid is suitable.
Sodium metaborate tetrahydrate so treated can be advantageously incorporated in singlepowder formulas which do not show any indication that a reaction has taken place between the components of the mixture even after prolonged exposure to relatively high temperatures. At the same time the total amount of protectant used is generally less than that used in cases where treatment is by another method.
The following examples illustrate the method of the present invention and will also indicate the proportionate quantities in which the respective components can be mixed together in a dry form to make up single-powder developer mixtures.
Example 1 Boric anhydride was added to sodium metaborate tetrahydrate in a concentration of per cent and the mixture heated for 4 hours at 70 C. This mixture was packed in a formula consisting of:
Grams Elon 2.0 Hydroquinone 4.0 Sodium sulfite 22.5 Sodium metaborate tetrahydrate 10 per 1 cent boric anhydride 39.6 Potassium bromide 2.0
This single powder did not discolor or otherwise deteriorate when stored.
Example 2 Phthalic anhydride was added to sodium metaborate tetrahydrate in a concentration of 2.5 per cent and the mixture heated for 4 hours at 70 C. This mixture was packed in a formula consisting of:
Grams Elon 2.0
Hydroquinone 4.0
Sodium sulfite 22.5 Sodium metaborate tetrahydrate 2.5 per cent phthalic anhydride 37.8
Potassium bromide 2.0
This single powder discolored slightly after one month storage at 110 F. The addition of one gram of boric anhydride to the formula prevented discoloration altogether.
Example 3 4 Sodium sulfite 22.5 Sodium metaborate tetrahydrate 10 per 7 cent metaboric acid 39.6 Potassium bromide 2.0
This single powder d d not discolor or otherwise deteriorate on storage.
Example 4 Phthalic anhydride was added to sodium metaborate tetrahydrate in a concentration of 10 per 'cent and the mixture was heated at 40 C. for 30 days. The mixture was packed in a formula consisting of:
Grams Elon' 2.0
Hydroquinone 4.0
Sodium sulfite 22.5 Sodium metaborate tetrahydrate 10 per cent phthalic anhydride 36.9
Potassium bromide 2.0
This single powder did not discolor or otherwise deteriorate when stored for three weeks at F.
Example 5 Grams Elon 2.5 Hydroquinone 2.5 Sodium sulfite 50.0 Treated sodium metaborate-boric anhydride mixture 11.0 Potassium bromide 0.5
This single powder did not discolor or otherwise deteriorate when stored for 2 months at 110 F. However a formula using a similarly dehydrated metaborate, but one from which the boric anhydride was omitted was found to have inferior stability on storage.
We claim:
1. The method of stabilizing hydrates of sodium metaborate which comprises mixing powder like particles thereof with 2.5 to 10% by weight of a finely divided stabilizer selected from the group consisting of phthalic anhydride, boric anhydride, and metaboric acid and heating the mixture for approximately 4 hours at 70 C.
2. The product of the method of claim 1.
3. A single-powder photographic developer composition containing an organic silver halide developer and the product of the method of claim 1.
References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,847,836 Kelly Mar. 1, 1932 1,976, 99 Russell Oct. 9, 1934 2,095,836 Russell Oct. 12, 1937 2,384,592 Bean Sept 11, 1945 2,606,118 Rogers Aug. 5, 1952

Claims (1)

1. THE METHOD OF STABILIZING HYDRATES OF SODIUM METABORATE WHICH COMPRISES MIXING POWDER LIKE PARTICLES THEREOF WITH 2.5 TO 10% BY WEIGHT OF A FINELY DIVIDED STABLIZER SELECTED FROM THE GROUP CONSISTING OF PHTHALIC ANHYDRIDE, BORIC ANHYDRIDE, AND METABORIC ACID AND HEATING THE MIXTURE FOR APPROXIMATELY 4 HOURS AT 70* C.
US295804A 1952-06-26 1952-06-26 Method of stabilizing hydrates of sodium metaborate and single powder photographic developers containing same Expired - Lifetime US2685513A (en)

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BE521001D BE521001A (en) 1952-06-26
US295804A US2685513A (en) 1952-06-26 1952-06-26 Method of stabilizing hydrates of sodium metaborate and single powder photographic developers containing same
GB17747/53A GB732945A (en) 1952-06-26 1953-06-26 Improved method of stabilizing hydrates of sodium metaborate
FR1098529D FR1098529A (en) 1952-06-26 1953-06-26 Process for stabilizing hydrated sodium metaborates and photographic developers containing these stabilized products

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2816026A (en) * 1954-11-26 1957-12-10 Eastman Kodak Co Stabilizing agents for single powder photographic developers
US3130036A (en) * 1961-02-01 1964-04-21 United States Borax Chem Process for preparing flakes of sodium metaborate and mixtures thereof
US5780211A (en) * 1991-05-01 1998-07-14 Konica Corporation Processing composition in the tablet form for silver halide photographic light-sensitive material
CN104386705A (en) * 2014-10-31 2015-03-04 辽宁首钢硼铁有限责任公司 Method for preparing sodium metaborate with coproduct of light magnesium carbonate from low-grade ores containing magnesium and boron

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995002491A1 (en) * 1993-07-15 1995-01-26 Lee Steere Christopher Ian Preservative

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1847836A (en) * 1929-04-09 1932-03-01 Borax Cons Ltd Production of sodium metaborate
US1976299A (en) * 1934-01-26 1934-10-09 Eastman Kodak Co Photographic developer
US2095836A (en) * 1936-05-06 1937-10-12 Eastman Kodak Co Photographic developer
US2384592A (en) * 1943-04-22 1945-09-11 Eastman Kodak Co Single-powder photographic developers
US2606118A (en) * 1951-02-09 1952-08-05 Eastman Kodak Co Stabilizing agent for single powder photographic developers

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1847836A (en) * 1929-04-09 1932-03-01 Borax Cons Ltd Production of sodium metaborate
US1976299A (en) * 1934-01-26 1934-10-09 Eastman Kodak Co Photographic developer
US2095836A (en) * 1936-05-06 1937-10-12 Eastman Kodak Co Photographic developer
US2384592A (en) * 1943-04-22 1945-09-11 Eastman Kodak Co Single-powder photographic developers
US2606118A (en) * 1951-02-09 1952-08-05 Eastman Kodak Co Stabilizing agent for single powder photographic developers

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2816026A (en) * 1954-11-26 1957-12-10 Eastman Kodak Co Stabilizing agents for single powder photographic developers
US3130036A (en) * 1961-02-01 1964-04-21 United States Borax Chem Process for preparing flakes of sodium metaborate and mixtures thereof
US5780211A (en) * 1991-05-01 1998-07-14 Konica Corporation Processing composition in the tablet form for silver halide photographic light-sensitive material
CN104386705A (en) * 2014-10-31 2015-03-04 辽宁首钢硼铁有限责任公司 Method for preparing sodium metaborate with coproduct of light magnesium carbonate from low-grade ores containing magnesium and boron

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GB732945A (en) 1955-06-29
BE521001A (en)

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