US2756151A - Reduction of dye stain in processed photographic papers containing dyes - Google Patents

Reduction of dye stain in processed photographic papers containing dyes Download PDF

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Publication number
US2756151A
US2756151A US302237A US30223752A US2756151A US 2756151 A US2756151 A US 2756151A US 302237 A US302237 A US 302237A US 30223752 A US30223752 A US 30223752A US 2756151 A US2756151 A US 2756151A
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paper
processing
washed
dye stain
processed
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US302237A
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Walter J Weyerts
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Eastman Kodak Co
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Eastman Kodak Co
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/38Fixing; Developing-fixing; Hardening-fixing

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  • This invention relates to the reduction of dye stain in processed photographic papers containing sensitizing dyes by the addition of aryl or alkaryl sulfonic acids or their water-soluble salts to the stop bath or the fixing bath which are employed in processing those papers.
  • the emulsions employed for photographic papers often contain sensitizing dyes and many of the dyes of this nature have a tendency to introduce stain into the paper upon the processing of those papers. This effect has been noted, for instance, in the case of papers for producing direct positive photographs, for example, of the type described in U. S. Patent No. 2,497,875 of George E. Falleson. Also, in cases where dyes have been used in higher than normal concentration, or in some cases of special processing, my invention finds application.
  • Types of sensitizing dyes which, when used in photographic paper emulsions, have a tendency to stain the paper upon its processing are acid type dyes such as the merocyanines, the eosins, the oxonols and the acid azo dyes, such as Congo red and Glycine red.
  • acid type dyes such as the merocyanines, the eosins, the oxonols and the acid azo dyes, such as Congo red and Glycine red.
  • One object of my invention is to provide a procedure for processing photographic paper in which staining of the paper by the sensitizing dye in the photographic emulsion used is substantially eliminated.
  • Another object of my invention is to provide a method for processing photographic papers in which an aryl or alkaryl sulfonic acid or its soluble salt is employed in the stop bath or the fixing bath in which the paper is processed.
  • a further object of my invention is to prevent staining of photographic paper in the machine processing of photographic paper in which the washing time is relatively short (such as less than 4 minutes). Where a relatively long time of washingis employed, such as on the order of minutes, staining of the paper is negligible. Other objects of my invention will appear herein.
  • the paper In the use of photographic papers, the paper is exposed, thereby producing a latent image in the emulsion thereof.
  • the paper ordinarily is then put through a development bath to bring out the image, followed by immersion in an acid stop bath to end the development and then in a fixing bath to fix the print so obtained.
  • a short washing time as used in machine processing, contributes to staining of the paper by those dyes, and, to prevent or minimize such staining, an aryl sulfonic acid, an alkaryl sulfonic acid or a soluble salt of one of these is added to the acid stop bath or to the fixing bath in accordance with my invention.
  • sulfonates which have been found to be especially useful in accordance with my invention are sodium anthraquinone-beta-sulfonate, sodium anthraquinone-alpha-sulfonate and sodium m terephenyl-4-sulfonate.
  • sodium anthraquinonebeta-sulfonate in an acid stop bath in a concentration of 0.5% almost completely eliminated dye stain in processed paper, and the other sulfonates mentioned were substantially equally eflective.
  • naphthalene sulfonic acids naphthol sulfonic acids, napthyl amine sulfonic acids, alkyl naphthalene sulfonic acids, diphenyl disulfonic acids, p-toluen'e sulfonic acids and salts thereof.
  • sulfonates or sulfonic acids are generally effective in concentrations within the range of 0.l-l but higher concentrations than the range given can be employed in stop baths or fixing baths in accordance with my invention, and in some cases the use of higher conproximately 1 minutes.
  • centrations than 1% are even preferred, such as where dye staining is especially pronounced.
  • a photographic paper such as of the type described in Patent No. 2,497,875 of Falleson, may be carried out by developing that emulsion layer, after its exposure, in a developer of the type disclosed and claimed in application Serial No. 218,071 of Russell and Haist, now U. S. Patent 2,625,475, such as for ap- After this development the paper is placed in an acid stop bath, suchas a 3% aqueous solution of citric acid or acetic acid, such as for approximately A minute. The paper is then placed in a fixing bath, such as for approximately 2 minutes, which bath may have a formula as follows:
  • Example 1 A photographic paper was processed as described above, however, a stop bath consisting of an aqueous solution of citric acid, 3% concentration and 0.5% of sodium rn-diphenylbenzene sulfonate was employed. After fixing, washing and drying, a paper was obtained substantially free from dye stain.
  • Example 3 A photographic paper, after exposure, was processed as described above using as the stop bath therein an aqueous solution containing 3% of citric acid and 1% of dibutyl phenyl phenol sodium disulfonate. The paper obtained had little or no noticeable dye stain therein.
  • Example 4 An exposed photographic paper was processed as described above, but a fixing bath having the Water to make 1.0 liter After fixing, the paper was then washed and dried, and was found to be free of any appreciable stain from the sensitizing dye employed inthe photographic emulsion.
  • the method of reducing .dye stain in the processed, washed and dried paper which comprises treating'the paper in the processing operation between the developing and final washing steps with a fixing bath containing in solution therein a compound selected from the aryl and alkaryl sulfonic acids and their water soluble salts.
  • the method of reducing dye stain in the processed, washed and dried paper which comprises treating the paper in the processing operation between the developing and final washing steps with a fixing bath containing sodium anthraquinone-psulfonate.
  • the method of reducing dye stain in the processed, washed and dried paper which comprises treating the paper in the processing operation between the developing and final washing steps with a fixing bath containing sodium m-terephenyl-4'- sulfonate.
  • the method of reducing dye stain in the processed, washed and dried paper which comprises treating the paper in the processing operation between the developing and final washing steps with a fixing bath containing monobutyl diphenyl sodium sulfonate.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Description

United States Patent REDUCTION OF DYE STAIN IN PROCESSED ggggoomruc PAPERS CONTAINING Walter J. Weyerts, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application August 1, 1952, Serial No. 302,237
5 Claims. (Cl. 95-88) y This invention relates to the reduction of dye stain in processed photographic papers containing sensitizing dyes by the addition of aryl or alkaryl sulfonic acids or their water-soluble salts to the stop bath or the fixing bath which are employed in processing those papers.
The emulsions employed for photographic papers often contain sensitizing dyes and many of the dyes of this nature have a tendency to introduce stain into the paper upon the processing of those papers. This effect has been noted, for instance, in the case of papers for producing direct positive photographs, for example, of the type described in U. S. Patent No. 2,497,875 of George E. Falleson. Also, in cases where dyes have been used in higher than normal concentration, or in some cases of special processing, my invention finds application. Types of sensitizing dyes which, when used in photographic paper emulsions, have a tendency to stain the paper upon its processing are acid type dyes such as the merocyanines, the eosins, the oxonols and the acid azo dyes, such as Congo red and Glycine red.
One object of my invention is to provide a procedure for processing photographic paper in which staining of the paper by the sensitizing dye in the photographic emulsion used is substantially eliminated. Another object of my invention is to provide a method for processing photographic papers in which an aryl or alkaryl sulfonic acid or its soluble salt is employed in the stop bath or the fixing bath in which the paper is processed. A further object of my invention is to prevent staining of photographic paper in the machine processing of photographic paper in which the washing time is relatively short (such as less than 4 minutes). Where a relatively long time of washingis employed, such as on the order of minutes, staining of the paper is negligible. Other objects of my invention will appear herein.
In the use of photographic papers, the paper is exposed, thereby producing a latent image in the emulsion thereof. The paper ordinarily is then put through a development bath to bring out the image, followed by immersion in an acid stop bath to end the development and then in a fixing bath to fix the print so obtained. It has been found that, with certain types of dyes, a short washing time, as used in machine processing, contributes to staining of the paper by those dyes, and, to prevent or minimize such staining, an aryl sulfonic acid, an alkaryl sulfonic acid or a soluble salt of one of these is added to the acid stop bath or to the fixing bath in accordance with my invention.
Some of the sulfonates which have been found to be especially useful in accordance with my invention are sodium anthraquinone-beta-sulfonate, sodium anthraquinone-alpha-sulfonate and sodium m terephenyl-4-sulfonate. For instance, the use of sodium anthraquinonebeta-sulfonate in an acid stop bath in a concentration of 0.5% almost completely eliminated dye stain in processed paper, and the other sulfonates mentioned were substantially equally eflective. Other compounds which exhibited a stain-reducing effect when used in the acid stop ice bath or in the fixing bath in addition to those mentioned above were naphthalene sulfonic acids, naphthol sulfonic acids, napthyl amine sulfonic acids, alkyl naphthalene sulfonic acids, diphenyl disulfonic acids, p-toluen'e sulfonic acids and salts thereof. Another material which is effective is Tamol, which is the sodium salft of naph= thalene sulfonic acid condensed with formaldehyde.
These sulfonates or sulfonic acids are generally effective in concentrations within the range of 0.l-l but higher concentrations than the range given can be employed in stop baths or fixing baths in accordance with my invention, and in some cases the use of higher conproximately 1 minutes.
centrations than 1% are even preferred, such as where dye staining is especially pronounced.
The processing of a photographic paper, such as of the type described in Patent No. 2,497,875 of Falleson, may be carried out by developing that emulsion layer, after its exposure, in a developer of the type disclosed and claimed in application Serial No. 218,071 of Russell and Haist, now U. S. Patent 2,625,475, such as for ap- After this development the paper is placed in an acid stop bath, suchas a 3% aqueous solution of citric acid or acetic acid, such as for approximately A minute. The paper is then placed in a fixing bath, such as for approximately 2 minutes, which bath may have a formula as follows:
FIXING BATH Grains Sodium thiosulfate (hypo) a r rr; r 300.0 Sodium bisulfite a- 7.5 Sodium sulfite (desiccated) 7.5 Sodium citrate 2.0 Ammonium sulfate 30.0
Water to make 1 liter The paper is then washed, such as in running water, forapproximately 2 /2 minutes and dried. Without the benefit of my invention (unless long-time washing is used), the final prints ordinarily exhibit an objectionable amount of dye stain. The following examples of stop or fixing baths which can be employed in accordance with my invention to prevent the dye staining in the processing described are illustrative:
Example 1 Example 2 A photographic paper was processed as described above, however, a stop bath consisting of an aqueous solution of citric acid, 3% concentration and 0.5% of sodium rn-diphenylbenzene sulfonate was employed. After fixing, washing and drying, a paper was obtained substantially free from dye stain.
Example 3 A photographic paper, after exposure, was processed as described above using as the stop bath therein an aqueous solution containing 3% of citric acid and 1% of dibutyl phenyl phenol sodium disulfonate. The paper obtained had little or no noticeable dye stain therein.
Example 4 An exposed photographic paper was processed as described above, but a fixing bath having the Water to make 1.0 liter After fixing, the paper was then washed and dried, and was found to be free of any appreciable stain from the sensitizing dye employed inthe photographic emulsion.
I claim:
1. In the processing of silver halide sensitized papers containing sensitizing dyes in which the paper after exposure is developed, fixed and washed, the method of reducing .dye stain in the processed, washed and dried paper which comprises treating'the paper in the processing operation between the developing and final washing steps with a fixing bath containing in solution therein a compound selected from the aryl and alkaryl sulfonic acids and their water soluble salts.
2. In the processing of silver halide sensitized papers containing sensitizing dyes in which the paper after exposure is developed, fixed and washed, the method of reducing dye stain in the processed, washed and dried paper which comprises treating the paper in the processing operation between the developing and final washing steps with a fixing bath containing sodium anthraquinone-psulfonate.
3. In the processing of silver halide sensitized papers containing sensitizing dyes in which the paper after exposure is developed, fixed and washed, the method of reducing dye stain in the processed, washed and dried paper which comprises treating the paper in the processing operation between the developing and final washing steps with a fixing bath containing sodium m-terephenyl-4'- sulfonate.
4. In the'processing of silver halide sensitized papers containing sensitizing dyes in which the paper after exposure is developed, fixed and washed, the method of reducing dye stain in the processed, washed and dried paper which comprises treating the paper in the processing operation between the developing and final washing steps with a fixing bath containing sodium m-diphenyl benzene snlfonate.
5. In the processing of silver halide sensitized papers containing sensitizing dyes in which the paper after exposure is developed, fixed and washed, the method of reducing dye stain in the processed, washed and dried paper which comprises treating the paper in the processing operation between the developing and final washing steps with a fixing bath containing monobutyl diphenyl sodium sulfonate.
References Cited in the file of this patent UNITED STATES PATENTS 2,322,084 Young et a1. June 15, 1943 2,367,516 Muehler et a1. Jan. 16, 1945 2,428,208 Edgerton Sept. 30, 1947 2,440,954 Jennings May 4, 1948 2,453,347 Russell Nov. 9, 194-8 2,578,075 Kienast Dec. 11, 1951 2,615,807 Umberger Oct. 28, 1952

Claims (1)

1. IN THE PROCESSING OF SILVER HALIDE SENSITIZED PAPERS CONTAINING SENSITIZING DYES IN WHICH THE PAPER AFTER EXPOSURE IS DEVELOPED, FIXED AND WASHED, THE METHOD OF REDUCING DYE STAIN IN THE PROCESSED, WASHED AND DRIED PAPER WHICH COMPRISES TREATING THE PAPER IN THE PROCESSING OPERATION BETWEEN THE DEVELOPING AND FINAL WASHING STEPS WITH A FIXING BATH CONTAINING IN SOLUTION THEREIN A COMPOUND SELECTED FROM THE ARYL AND ALKARYL SULFONIC ACIDS AND THEIR WATER SOLUBLE SALTS.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3467519A (en) * 1965-04-28 1969-09-16 Agfa Gevaert Ag Swelling reduction treatment for the accelerated processing of gelatin photographic materials

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2322084A (en) * 1940-01-11 1943-06-15 Eastman Kodak Co Simultaneous bleaching and fixing bath
US2367516A (en) * 1941-11-29 1945-01-16 Eastman Kodak Co Water spot prevention in photographic film
US2428208A (en) * 1945-06-20 1947-09-30 Eastman Kodak Co Dichromate bleach bath containing a wetting agent and method of bleaching therewith
US2440954A (en) * 1945-08-23 1948-05-04 Du Pont Process for eliminating stain from color-yielding elements by treatment with aromatic aldehydes containing an acyl group
US2453347A (en) * 1946-11-30 1948-11-09 Eastman Kodak Co Stabilization of photographic prints with thiophenols
US2578075A (en) * 1949-06-18 1951-12-11 Keuffel & Esser Co Brownprint fixing composition containing alkali thiosulfate, alkali oxalate, and a surface active wetting agent
US2615807A (en) * 1949-02-11 1952-10-28 Du Pont Stripping film and method of stripping

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2322084A (en) * 1940-01-11 1943-06-15 Eastman Kodak Co Simultaneous bleaching and fixing bath
US2367516A (en) * 1941-11-29 1945-01-16 Eastman Kodak Co Water spot prevention in photographic film
US2428208A (en) * 1945-06-20 1947-09-30 Eastman Kodak Co Dichromate bleach bath containing a wetting agent and method of bleaching therewith
US2440954A (en) * 1945-08-23 1948-05-04 Du Pont Process for eliminating stain from color-yielding elements by treatment with aromatic aldehydes containing an acyl group
US2453347A (en) * 1946-11-30 1948-11-09 Eastman Kodak Co Stabilization of photographic prints with thiophenols
US2615807A (en) * 1949-02-11 1952-10-28 Du Pont Stripping film and method of stripping
US2578075A (en) * 1949-06-18 1951-12-11 Keuffel & Esser Co Brownprint fixing composition containing alkali thiosulfate, alkali oxalate, and a surface active wetting agent

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3467519A (en) * 1965-04-28 1969-09-16 Agfa Gevaert Ag Swelling reduction treatment for the accelerated processing of gelatin photographic materials

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