Classifications

• • 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
  • G03C7/32—Colour coupling substances
  • G03C7/333—Coloured coupling substances, e.g. for the correction of the coloured image
  • G03C7/3335—Coloured coupling substances, e.g. for the correction of the coloured image containing an azo chromophore
• • 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
  • G03C7/32—Colour coupling substances
  • G03C7/3225—Combination of couplers of different kinds, e.g. yellow and magenta couplers in a same layer or in different layers of the photographic material

Definitions

• an Object of the present invention is to provide a color photographic light-sensitive element capable of giving image patterns of high contrast and good color saturation.
• the first compound (hereinafter coupler A") is a yellow dye that mainly absorbs light having 5 wave lengths of 400 500 m. ,u. and reacts with the ox-
• Another object of the present invention is to provide idation product of a p-phenylene diamine type color developer formed by development to provide a magenta dye that mainly absorbs light having wavelengths of 500 600 m. t. g
• the second compound (hereinafter coupler B) employed as a color coupler in this invention is converted into a cyan dye that mainly absorbs light having-wave lengths of 600 700 m. ,uby reaction with the oxidation product of a color developer.
• oETAILEDbEscRIPrION OF THE INVENTION Coupler A used in the present invention, can be selected from pyrazolone compounds, taking into consideration the requirements for spectral absorption characteristics as a yellow dye and spectral absorption characteristics as a magenta dye after thecoupling thereof with the aforesaid oxidation product.
• the compounds are represented by the following general formula:
• R man, eacifiefirsefii's'an aryl group, a substituted aryl group, a heterocylic group, or substituted heterocyclic group
• R represents an unsubstituted or substituted aryl group, and unsubstituted or substituted alkyl group, or an amino group, an acylamino group, an ureido group or a sulfonylamino group each bonded to an unsubstituted or substituted alkyl or aryl group, and at least one of R or R represents ananti-diffusion or ballast group or more than eight carbonatoms
• R is phenyl or substituted phenyl
• R is acylamino or ureido, of about eight to 30 carbon atoms
• R is aryl or substituted aryl.
• coupler A it is necessary that coupler A have an anti-diffusion group (or a ballast group having more than eight carbon atoms in the molecule at the R or R position to prevent the coupler from being crystallized in the emulsion layer, from diffusing into the other layers, and from being dissolved in a developing solution.
• anti-diffusion group or a ballast group having more than eight carbon atoms in the molecule at the R or R position
• NHC OCHCiaHar HaCOOH These compounds may be prepared by a well known process, i.e., by the coupling reaction of a pyrazolone compound and an aryldiazonium compound or a heterocyclic diazonium compound. Practical examples of the preparation of the aforesaid couplers are described in, e.g., Vittum et al.; Journal of American Chemical Society; Vol. 72, 1533-1536, Belgian Patent No. 675,259 U.S. Pat. No. 3,127,269, etc. Also, many of the 4-azopyrazolone compounds shown in these publications can be employed as coupler A in the present invention.
• Coupler 13 used in this invention may be selected from colorless compounds capable of providing cyan dyes having main absorption regions at 600 700 m. u. by the reaction thereof with the oxidation product of a color developer.
• Coupler B may be selected from compounds having wide structural ranges, since the spectral absorption of the cyan dye formed by coupler B and the oxidation product of the color developer overlaps the spectral absorption of the magenta dye formed from coupler A.
• Coupler B has a diffusion resistant or ballasting group of at least 8 carbon atoms.
• phenol derivatives or anaphthol derivatives having a ballasting group of at least 8 carbon atoms are useful.
• Compounds particularly useful in the present invention are the derivatives represented by general formula (II) and general formula (Ill) below:
• X represents an atom ora residual group capable of being split off in the coupling reaction such as a hydrogen atom, a halogen atom or a sulfone group, with at least one of R, and R and at least one of R and R having at least eight carbon atom s.
• R is hydrogen or alkyl
• R is alkyl. substituted alkyl, or substituted aryl, with at least one of R and R being a group of abouteight to 30 carbon atoms
• Ris hydrogen, R is alkyl or substituted alkyl, with at least one of R and R being a group of about eight to 30 carbon atoms
• R and R are 6-chloro and S-alkyl. wherein there are about one to live carbon atoms in the alkyl group.
• coupler B must have a ballast group for fixing the coupler in the emulsion layer.
• coupler B represented by aforesaid general formulae are as shown below.
• Coupler B ⁇ soiNa N S(i)aH l5H3l I 01 NHCONHC H
• coupler B The above compounds and other phenols and a-naphthols which can be used in this invention as coupler B are shown in W. Plez; Mit Minor aus Agfa A.G. Leverkusen”; Vol. 3, pages l56-l74 and they may be prepared by the processes illustrated in Kimura and Yoshida; Yuki Gosei Kagaku Kyokaishi (Journal of Organo Synthetic Chemistry," Vol. 23, No. lll, all herein incorporated by reference.
• a color photographic light-sensitive element having one emulsion layer containing coupler A and coupler B is, after light-exposure, processed in a usual color developer containing a p-phenylenediamine type developing agent, no coupling reaction occurs in the unexposed areas of the emulsion layer and the areas assume a yellow color due to the absorption of mainly 400 500 m. a. wave length light caused by coupler A.
• coupler A and coupler B both are subjected'to the coupling reaction in the exposed areas of the emulsion layer to provide a magneta dye and a cyan dye respectively.
• the exposed areas mainly absorb light of 500 700 m. a. in wave length and assume a blue color.
• the yellow (unexposed) areas and the blue (exposed) areas of the layer show clear and strong color contrast.
• the color photograph obtained by using the color photographic light-sensitive element of the present invention is very useful for attractively displaying figures or tables.
• the photograph can be particularly usefully employed as projection slides for education, as media for presenting technical data to the audience, or as displays for commercial purposes.
• the color photographic light-sensitive element of the present invention provides the aforesaid image having a high color contrast by a simple procedure. That is,
• black and white line patterns or continuous images may be utilized as the original.
• patterns obtained by drawing on a white paper with a black ink or an ink stick or an image obtained by printing on a white paper in a black ink maybe utilized.
• the couplers incorporated in the emulsion layer of the color photographic light-sensitive element of the present invention are substantially completely con- .11..- verted into dyes in the exposed areas by exposure and development, the blue hues obtained can be controlled, with good reproducibility, by the amount of coupler used, and clear and distinct contrast between the blue areas and the yellow areas can always be obtained.
• the color tone in blue can be delicately controlled.
• Coupler A and coupler B may be employed alone or may be used as a mixture of two or more compounds shown above.
• coupler A and B have ballast groups, for incorporating the coupler in a emulsion.
• Conventional techniques such as methods wherein the coupler is added as an aqueous solution thereof, or a solution thereof in an oil (coupler'solvent), may be employed.
• any coventional silver halide emulsion both those which are optically sensitized and those which are not, may be used in the present invention.
• blue light having wave lengths of 400 500 m. a. is absorbed by coupler A it is preferable to use a green and- /or' red sensitized emulsion to compensate for the loss of blue-sensitivity of the emulsion.
• the photographic light-sensitive element of this invention may have, on a support, besides the aforesaid silver halide emulsion layer containing the couplers, subsidiary layers such as an antihalation layer and a protective layer.
• an a-naphtholcompound having an aryl azo group or a heterocyclic azo group at the 4th carbon atom may be employed together with the colorless magenta coupler, but the yellow color of such a compound has red overtones, and thus, color contrast between the yellow color and a blue color obtained by the coupling thereof is inferior to the color contrast obtained by using coupler A according to the present invention.
• EXAMPLE 1 0.5 g. of l-(2', 4, 6', trichlorophenyl) -3-[3- (2", 4"-di-tert-amylphenoxy-acetamido benzamido)-4-(4'- metho'xy-phenyl-azo)]-5-pyrazolone and 1.0 g. of 1- hydroxy-N- n-dodecyl-Z-haphthamide were dissolved in a mixed solvent of 3 ml. of tri-o-cresyl phosphate and 2ml. of ethyl acetate. The resulting solution was dispersed in 15 ml. of an aqueous 10 percent gelatin solution containing 1 ml. of an aqueous 5 percent solution.
• the coupler dispersion thus prepared was added to 100 g. of a red-' sensitive emulsion containing 7.0 g. of gelatin and 3.3 X moles of silver chlorobromide.
• This silver halide emulsion was applied to a triacetyl cellulose film having an antihalation layer applied thereto, so that the dry thickness thereof would become 5 microns.
• the product was then dried to provide a sample film.
• the light-sensitive film thus prepared was loaded in a camera and exposed to an original drawn on a white paper with black ink and then developed for 14 minutes at 2l-C in a color developer having the following composition:
• the pH of the developer was then adjusted to 10.8 with an aqueous 10 percent sodium hydroxide solution.
• the developed photographic film was fixed in an acid fixing solution, washed with water, bleached in a bleaching solution containing a ferricyanide and potassium bromide, washed with water, fixed again, washed with water, and then dried.
• a color image having a high color contrast was obtained in which the blue areas corresponded to the white areas of the original and the yellow areas to the black figure areas.
• a black-and-white negative was prepared from the original used in the experiment a. Thereafter, the aforesaid sample film was exposed through the negative film. The sample film was then subjected to the color developement as in experiment a to provide a color photograph, from which a slide was prepared. When theslide was shown by means of a projector, a figure was obtained wherein the white areas of the original corresponded to the yellow areas of the slide and the black line or character corresponded to the blue areas.
• acidsulfonic acid-N-n-octadecyl-Z-naphthamide were dissolved in 10 ml. of water containing 0.06 g. of sodium hydroxide and the resulting solution was added to g. of a green-sensitive emulsion containing 5.0 g. of gelatin and 5.4 X 10 mole of silver iodobromide.
• the silver halide emulsion thus obtained was applied to a triacetyl cellulose film having applied thereto an antihalation layer, so that the thickness of the dry layer was 5 microns.
• Example 1 The black and white negative film obtained in experiment b of Example 1 was printed by enlarging on the sample film obtained in Example 2 by using an optical enlarger. The sample film was then subjected to the color development procedures as mentioned in experiment a of Example 1, to provide a color photograph. When the photograph was attached to glass plate and the glass plate was illuminated by fluorescent light from the back side a beautiful color figure was obtained.
• Example 2 The sample film prepared in Example 2 was inserted between a flurorescence-sensitizing plate and the chest of a human body was photographed by X rays. Then the sample film was subjected to the color development procedures as stated in experiment a of Example I to provide a color photograph in which the blue portions corresponded to the areas strongly exposed by the X-rays and the yellow portions to the areas weakly exposed by the X-rays.
• a color photographic light-sensitive element comprising a support, and a single silver halide emulsion layer containing color couplers, said couplers consisting essentially of a diffusion resisting 4-azo-pyrazolone compoundof the formula:
• R, and R each represents a member selected from the group consisting of aryl and heterocyclic, and R represents a member selected from the group consisting of alkyl, aryl, amino, acylamino, ureido, and sulfonylamino groups, wherein said amino, acylamino, ureido and sulfon'ylamino groups contain a member selected from the group consisting of alkyl, and aryl, one
• R 'or R being a ballast group of more than eight carbon atoms, and a compound selected from the group consisting of diffusion resisting colorless phenols and diffusion resisting colorless a-naphthol derivatives, said diffusion resisting colorless phenol being repre sented by the following formula:
• R is a member selected from the group consisting of hydrogen and alkyl
• R represents a member selected from the group consisting of alkyl and aryl
• R each represents a member selected from the group consisting of hydrogen, halogen, lower alkyl and lower alkoxy groups
• X represents a member selected from the group consisting of hydrogen, halogen, and sulfone groups and said a-naphthol derivative being represented by the following formula:
• R represents a member selected from the group consisting of hydrogen and alkyl
• R represents a member selected from the group consisting of alkyl and aryl
• X represents a member selected from the group consisting of hydrogen, halogen and sulfone groups, at least one of R and R having from eight to 30 carbon atoms and at least one of R5 and R7 having from eight to 30 carbon atoms.
• R is a phenyl group
• R is selected from the group consisting of acylamino and ureido groups and has from eight to 30 carbon atoms
• R is an aryl group.
• R is hydrogen
• R is an aryl' group of from eight to 30 carbon atoms
• R is 6-chloro
• R is a S-alkyl group of one to five carbon atoms.
• a process for preparing a photographic image having high blue to yellow contrast comprising imagewise exposing to light a photographic light-sensitive element comprising a support and a single silver halide emulsion layer containing color couplers, said couplers consisting essentially of:
• R is a member selected from the group consisting of hydrogen and alkyl
• R represents a member selected from the group consisting of alkyl and aryl
• R is a member selected from the group consisting of alkyl and aryl
• R each represents a member selected from the .group consisting of hydrogen, halogen, lower alkyl and lower alkoxy groups
• X represents a member selected from the group consisting of hydrogen, halogen
• R represents a member selected from the group consisting of hydrogen and alkyl
• R represents a member selected from the group consisting of alkyl and aryl
• X represents a member selected from the from eight to 30 carbon atoms
• R is a phenyl group
• R is a member selected from the group consisting of an acylamino group and ureido group having from eight to 30 carbon atoms
• R is an aryl group.
• R is hydrogen
• R is an aryl group
• R is 6-chloro
• R is a 5- alkyl group having from one to five carbon atoms.

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Cited By (6)

Citations (4)

• 1969
  • 1969-05-09 FR FR6914896A patent/FR2009879A1/fr not_active Withdrawn
  • 1969-05-09 DE DE19691923849 patent/DE1923849A1/de active Pending
  • 1969-05-13 GB GB24386/69A patent/GB1236690A/en not_active Expired
• 1972
  • 1972-03-07 US US00232518A patent/US3790379A/en not_active Expired - Lifetime

Patent Citations (4)

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