US3068097A - Developers for color photography containing sulfite ester polymers - Google Patents

Developers for color photography containing sulfite ester polymers Download PDF

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Publication number
US3068097A
US3068097A US97446A US9744661A US3068097A US 3068097 A US3068097 A US 3068097A US 97446 A US97446 A US 97446A US 9744661 A US9744661 A US 9744661A US 3068097 A US3068097 A US 3068097A
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United States
Prior art keywords
photographic
color
developer
tert
cyan
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Expired - Lifetime
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US97446A
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English (en)
Inventor
Judith A Schwan
Peter P Chiesa
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Eastman Kodak Co
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Eastman Kodak Co
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Publication date
Priority to BE615409D priority Critical patent/BE615409A/xx
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Priority to US97446A priority patent/US3068097A/en
Priority to FR891757A priority patent/FR1320315A/fr
Priority to GB11025/62A priority patent/GB978624A/en
Application granted granted Critical
Publication of US3068097A publication Critical patent/US3068097A/en
Anticipated expiration legal-status Critical
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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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/407—Development processes or agents therefor
    • G03C7/413—Developers

Definitions

  • Multilayer photographic elements used for color photography usually have at least three selectively sensitive emulsion layers coated on one side of a support.
  • the uppermost layer is generally blue-sensitive
  • the next layer is generally green-sensitive
  • the layer adjacent to the support is generally red-sensitive.
  • Between the blueand green-sensitive emulsion layers typically is a filter layer for absorbing blue radiation which may be transmitted through the uppermost blue-sensitive layer.
  • Such multilayer photographic elements can also, of course, have other interlayers for specialized purposes.
  • Such multilayer materials have previously been described in the art, reference being made to Mannes US. Patent No. 2,252,718, issued August 19, 1941.
  • the exposed material In processing exposed reversal color systems the exposed material is given a conventional black-and white development to produce a black-and-White image and a second exposure or exposures through separation filters followed by at least one additional development in a color developer for producing a colored image, the colored image bearing a complementary relationship to the the region of the spectrum to which the photographic emulsion layer has been differentially sensitized.
  • One of the problems in the color development of such systems is connected with the first color development, namely, the cyan development of the red-sensitized layer.
  • the desired maximum cyan dye density must be obtained in the exposed regions With a minimum of cyan fog in the unexposed areas such as cyan development in the greenand blue-sensitive layers which have not been re-exposed.
  • the developer compositions of the invention are alkaline aqueous compositions comprising a typical arylene amine color developing agent and a sulfite ester polymer, such sulfite ester polymers being novel addenda to color developing compositions.
  • the sulfite ester polymers of the invention consist essentially of the recurring structural unit OSOX- wherein the substituent X is a polyoxyethylene radical having the structure wherein the substituent X is a polyoxyalkylene radical as described above.
  • this reaction is carried out by slowly adding substantially equal molar proportions of thionyl chloride to a polyalkylene glycol in a suitable inert organic solvent such as benzene and thereafter refluxing the resulting reaction mixture for a few minutes.
  • resulting polymeric sensitizer can then be readily separated from the reaction mixture by distilling off the solvent. Further purification of the polymer can be effected, if desired, by conventional methods.
  • Polyalkylene glycols are well-known compositions of commerce and can be prepared from alkylene oxides such as ethylene oxide, 1,2-propylene oxide, 1,3-butylene oxide and the like which have in turn been prepared from the corresponding unsaturated hydrocarbon.
  • Typical polyalkylene glycols that can be employed to prepare the present sulfite ester polymers include:
  • Typical color developers useful in combination with the sulfite ester polymer addenda of the invention are the well-known color-forming developers that have previously been described in the art.
  • the color-forming developers that have been found especially useful in our invention comprise aromatic primary amines containing an amino (substituted or unsubstituted) or hydroxyl radicals. Excellent results are obtained with p-phenylenediamines and substituted derivatives thereof containing a primary amino radical.
  • Typical of such color-forming developers that can be suitably employed in combination with the sulfite ester polymers of the invention are the -August 28, 1951.
  • phenylenediarnine color-forming developers can be employed to like advantage in the developing process of the invention.
  • novel developer compositions of the invention are alkaline aqueous compositions.
  • the developer compositions of the invention also include such usual addenda as alkali metal sulfites and the like.
  • Our invention is primarily directed to the development of ordinarily employed gelatino-silver-halide developingout emulsions such as gelatino-silver-chloride, gelatinochlorobromide, gelatino-chloroiodide, gelatino-chlorobromiodide, gelatino-bromide and gelatino-bromiodide developing-out emulsions.
  • gelatino-silver-chloride, gelatinochlorobromide, gelatino-chloroiodide, gelatino-chlorobromiodide, gelatino-bromide and gelatino-bromiodide developing-out emulsions The photographic silver halide emulsions that can be developed with the subject novel developer compositions can be prepared according to known methods, such as those described in Hewitson et al. US. Patent 2,618,556, issued November 18, 1952, for example. Of course, emulsions prepared by other methods can
  • Photographic silver halide emulsions that can be developed with the subject developer compositions can contain common emulsion addenda as chemical sensitizers such as sulfur sensitizers, gold compounds, azaindene compounds and others such as are disclosed in US. Patents 2,540,085, 2,597,856, 2,597,915, 2,716,062, 2,937,089 and in others.
  • chemical sensitizers such as sulfur sensitizers, gold compounds, azaindene compounds and others such as are disclosed in US. Patents 2,540,085, 2,597,856, 2,597,915, 2,716,062, 2,937,089 and in others.
  • the subject sulfite ester polymers can be employed in' color-developing compositions containing color couplers.
  • Such compounds usually belong to one of three widely known types, i.e. pyrazolone couplers, phenol coupers and open chain ketomethylene couplers which combine with developer oxidation products to produce magenta, cyan and yellow images respectively.
  • Our invention is particularly useful in reversal color photographic processes wherein the color-forming compound or coupler is incorporated in one of the developing baths.
  • Colorforming compounds or couplers which are soluble in the strongly alkaline developing aqueous compositions are well-known to those skilled in the art.
  • the developer compositions of the invention can also be utilized to process photographic emulsions having couplers incorporated therein.
  • Typical color-forming compounds or couplers which are useful in color photography, according to our invention include the following:
  • amylbenzoylarnino)-5-pyrazolone 1phenyl-3-diamylbenzoylamino-5-pyrazolone l-phenyl-3-5-naphthoylamino5'-pyrazolone l-phenyl-3-phenylcarbamylamino-5-pyrazolone 1-phenyl-3-palmitylarnino-5 -pyrazolone l-phenyl-3 -benzenesulfonylamino-S-pyrazolone 1- (p-phenoxyphenyl) -3- (p-tert.
  • amyloxybenzoyl) amino- 5-pyrazolone 1- (2,4',6'-tribromophenyl) -3-benzamido-5-pyrazolone l- 2',4,6'-trichlorophenyl) -3-benzamido-5-pyrazolone 1-
  • emulsions can be coated in the usual manner on any suitable support including cellulose nitrate, cellulose acetate, polyesters, polyvinyl acetal, polyethylene terephathalate, polystyrene and related film-forming resins, as well as, paper, glass, metal and the like.
  • the developer compositions of the invention are particularly useful as color developers for improving cyan D-max./fog ratio in multilayer color films of the reversal color type such as illustrated by the well-known Kodachrome film.
  • a maximum dye density is obtained in the exposed regions with a minimum of cyan fog in the unexposed areas. Cyan development in the greenand blue-sensitive layers is diminished in accordance with the invention.
  • Example 1 A solution of g. (1.0 mole) of triethylene glycol in 250 ml. of benzene was heated to boiling on a steam bath. The heat was then shut oif and 119 g. (1.0 mole) of thionyl chloride was added dropwise at a rate sufficient to keep the benzene solution refluxing. After completion of the addition of the thionyl chloride, the resulting solution was refluxed for about 5 more minutes, after which the volatile constitutents were stripped off with a water aspirator. The remaining syrupy residue was dissolved in ethyl acetate, boiled with charcoal, filtered, and the solvent evaporated in vacuo.
  • the remaining sulfite ester polymer was a light amber syrup having an average molecular weight of about 1540.
  • other polymeric compositions of the invention were prepared by substituting other polyalkylene glycols or by employing other proportions of benzene solvent to reactants.
  • Carbowox 200 a polyethylene glycol having an average molecular weight of about 200.
  • polybutylene derivatives can be prepared by substituting a polybutylene glycol such as dibutylene or tributylene glycol for the described alkylene glycols.
  • Example 2 A color film comprising a cellulose acetate support containing superimposed gelatino-bromoiodide emulsion layers sensitized to red, green and blue with the redsensitive layer next to the support and the blue-sensitive layer furthest from the support was prepared.
  • the bluesensitive and green-sensitive layers were separated by a yellow colloidal silver interlayetr. Reference is made to Mannes et al. US. Patent 2,252,718, issued August 19, 1941, for the details of preparation for such films.
  • the color film was then exposed for second to a 500 watt, 3000" K. light source through a Wratten #29 filter plus a 0.6 neutral density filter On an Eastman Type Ib sensitoi'neter.
  • the exposed film was then developed for 8 minutes at 80 F. in an MQ photographic developer having the formula below:
  • the resulting film containing a black-and-white silver negative image was washed in water for 2 minutes, then given a 2 minute antifoggant bath and then washed again in water for 2 minutes, the antifoggant bath having the formula:
  • ANTIFOGGANT BATH 3 (2 benzothiazolyl methyl) benzothiazolium -ptoluene sulfonate g 0.5 Methanol cc 100 Water cc 900
  • the resulting film was then given a reversal exposure through the support for 15 seconds through a Wratten #92 filter with a No. 2 Photofiood light set at a distance of one meter. Samples of the resulting film were then developed for 10 and minute intervals in a cyan developer having the formula:
  • CYAN DEVELOPER 8 CYAN DEVELOPERContinued H-acid --g-.. Water to make 1 liter.
  • Example 3 The color film having the emulsion layers described in Example 2 was exposed in an Eastman Type Ib sensitometer as described in Example 2 and then developed for 3 minutes and 30 seconds at F. in an MQ photographic developer having the formula:
  • the resulting film containing a blackand-white silver negative image was washed in water for 2 minutes and then re-exposed through a Wratten #92 filter as described in Example 2. Samples of the resulting film were then developed for 5 and 8 minute intervals in a cyan developer having the following formula and containing various sulfite ester polymeric addenda of the invention:
  • Example 2 The resulting cyan-developed film was then washed for minutes in water, bleached for 3 minutes, fixed for 2 minutes and washed again for 5 minutes, the bleach and fix employed being described in Example 2.
  • Table C summarizes the color density to fog ratios for cyan development times of 5 and 8 minutes in the cyan developer containing 3 grams per liter of developer of the various sulfite ester polymers described in Table A of Example 1.
  • polymeric addenda correspond in number to the sulfite ester polymers identified in Table A of Example 1.
  • Example 4 Samples of a single layer gelatino-bromoiodide emulsion optically sensitized to the green portion of the spectrum and coated on a cellulose acetate support were exposed for ,4 second to a 500 watt, 3000 K. light source through a Wratten No. 61 filter plus a No. 16 filter on an Eastman Type II) sensitometer. The exposed film samples were then developed to form a black-and-white silver negative image as described in Example 2, and washed in water for 3 minutes. One-half of the samples were given a reversal exposure through the support for 10 seconds with a No. 2 Photoflood lamp set at a distance of one meter.
  • Example 2 The remaining strips were not given this reexposure so that the fog level of the strip could be determined. All of the film samples were then developed for 10, and minute intervals in the cyan developer described in Example 2. Thereafter the cyan-developed film samples were washed, bleached and fixed as described in Example 2. The ratio of maximum densities of the strips which were re-exposed to that of the strips which were not re-eXposed is similar to the D-max/fog ratio of a multilayer coating. Table D below summarizes the color D-max./fog ratios obtained for the various development times, the cyan developer containing one gram per liter of several of the sulfite ester polymeric addenda of the invention as described in Example 1.
  • the polymeric addenda correspond in number to the snlflte ester polymers identified in Table A of Example 1.
  • the Wratten filters referred to herein are well-known in the art and are described in Handbook of Chemistry and Physics, 30th Ed. 1947, pages 2269-2279, Chemical Rubber Publishing 00., Cleveland, Ohio.
  • the molecular weights referred to herein were determined by the conventional boiling point elevation method.
  • An alkaline aqueous developer composition for color photography comprising: (1) an aromatic primary amine developing agent containing, in addition to the primary amine radical, a substituent selected from the group consisting of hydroxyl radicals and amino radicals, and; (2) .1 to 10 grams per liter of said developer composition of a sulfite ester polymer consisting essentially of the recurring structural unit 0 1 0soX- wherein X is a polyoxyalkylene radical'having alkylene moieties with 2v to 4 carbon atoms and an average molecular weight of less than about 300.
  • a photographic developer composition for color photography comprising an aqueous alkaline solution of an arylene-diamine photographic developing agent and .1 to 10 grams per liter of said developer composition of a sulfite ester polymer having an average molecular weight in the range of about 400 to 3000 and consisting essentially of the recurring structural unit OSOX wherein X is a polyoxyalkylene radical having alkylene moieties with 2 to 4 carbon atoms and an average molecular weight of less than about 300.
  • a photographic developer composition for color photography comprising an aqueous alkaline solution of a p-phenylenediamine color developer, a color-forming compound capable of coupling with the oxidation products of said p-phenylenediamine color developer and .1 to 10 grams per liter of said developer composition of a sulfite ester polymer having an average molecular weight in the range of about 400 to 3000 and consisting essentially of the recurring structural unit 0 T OSOX wherein X is a polyoxyalkylene radical having alkylene moieties with 2 to 4 carbon atoms and an average molecular weight of less than about 300.
  • a photographic developer composition for color photography comprising an aqueous alkaline solution of a p-phenylenediamine color developer, a phenolic cyan coupler compound capable of coupling with the oxidation products of said p-phenylenediamine color developer and .1 to 10 grams per liter of said developer composition of a sulfite ester polymer having an average molecular weight in the range of about 400 to 2000 and consisting essentially of the recurring structural unit wherein X is a polyoxyalkylene radical having alkylene moieties with 2 to 4 carbon atoms and an average molecular weight of less than about 300.
  • a multilayer photographic element containing a plurality of differentially sensitized photographic silver halide emulsion layers is given a first exposure, followed by development in a photographic developer for producing a black-and-white negative image and a second exposure, followed by at least one additional development in a photographic developer for producing a colored image, said colored image bearing a complementary relationship to the region of the spectrum to which said photographic silver halide emulsion has been differentially sensitized
  • the improvement which comprises producing said colored image bydeveloping in an aqueous alkaline color developer composition comprising an alkali metal sulfite, a p-phenylenediamine color developer, a phenolic cyan coupler compound capable of coupling with the oxidation products of said p-phenylenediamine color developer and .1 to 10 grams per liter of said developer composition of a sulfite ester polymer having an average molecular weight in the range of about 400 to 2000 and consisting essentially

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optical Filters (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US97446A 1961-03-22 1961-03-22 Developers for color photography containing sulfite ester polymers Expired - Lifetime US3068097A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BE615409D BE615409A (d) 1961-03-22
US97446A US3068097A (en) 1961-03-22 1961-03-22 Developers for color photography containing sulfite ester polymers
FR891757A FR1320315A (fr) 1961-03-22 1962-03-21 Nouveau révélateur pour la photographie en couleurs, contenant des polymères d'esters sulfitiques
GB11025/62A GB978624A (en) 1961-03-22 1962-03-22 Photographic colour developers and processes of colour development therewith

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
WO2012035314A1 (en) 2010-09-17 2012-03-22 Fujifilm Manufacturing Europe Bv Photographic paper
WO2021213762A1 (en) 2020-04-24 2021-10-28 Fujifilm Manufacturing Europe Bv Photographic paper
US11549975B2 (en) 2007-07-03 2023-01-10 Cypress Semiconductor Corporation Capacitive field sensor with sigma-delta modulator

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US11549975B2 (en) 2007-07-03 2023-01-10 Cypress Semiconductor Corporation Capacitive field sensor with sigma-delta modulator
WO2012035314A1 (en) 2010-09-17 2012-03-22 Fujifilm Manufacturing Europe Bv Photographic paper
WO2021213762A1 (en) 2020-04-24 2021-10-28 Fujifilm Manufacturing Europe Bv Photographic paper

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GB978624A (en) 1964-12-23

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