US3770446A - Color photographic silver halide material containing acetanilide couplers - Google Patents

Color photographic silver halide material containing acetanilide couplers Download PDF

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Publication number
US3770446A
US3770446A US00203882A US3770446DA US3770446A US 3770446 A US3770446 A US 3770446A US 00203882 A US00203882 A US 00203882A US 3770446D A US3770446D A US 3770446DA US 3770446 A US3770446 A US 3770446A
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US
United States
Prior art keywords
alpha
acetanilide
chloro
isobutyryl
coupler
Prior art date
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Expired - Lifetime
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US00203882A
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English (en)
Inventor
M Furuya
T Endo
S Sato
T Hanzawa
I Inoue
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Konica Minolta Inc
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Konica Minolta Inc
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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
    • G03C7/32—Colour coupling substances
    • G03C7/36—Couplers containing compounds with active methylene groups

Definitions

  • Ar and Ar are an aryl group and X is hydrogen or a group capable of being released at the time of color development, is produced which is high in coupling reactivity, have spectral absorption characteristics suitable for the color reproduction principle of the tricolor substractive color photography and form dye images which are stable to heat, light and humidity.
  • Couplers used for forming color photographic images should satisfy the following fundamental requirements:
  • the couplers are required to be such that they are easily dispersible in photographic emulsions and do not fog photographic emulsions or deteriorate the photographic speeds thereof.
  • Ar which is aryl group used in a yellow dye imagefonning acylacetoanilidetype coupler of the prior art
  • the coupler of the aforesaid general'forinula displays excellent effects which cannot be expected from the conventional couplers, as mentioned previously. These excellent effects are considered ascribable to the aryloxy group introduced into the a-position of the isobutyryl group shown in the aforesaid formula. That is, a color photographic material containing a coupler of the aforesaid general formula, in which an alkyl, aryl or alkoxy group has been introduced into the a-position of said isobutyryl group, is poor in linearity of the characteristic curve thereof and hence gives a dye image low in gradation.
  • the thus formed ester is treated with sodium acetonitrile to prepare an aryloxyisobutyryl acetonitrile, which is then imino-etherified and hydrolyzed to obtain an aryloxy-isobutyrylacetic acid es- 35 ter.
  • This ester may alternatively be synthesized by condensing an acetoacetic acid ester with an aryloxyisobutyric acid chloride, and hydrolyzing the condensation product.
  • the thus obtained acetic acid ester is condensed with a correspondingarylamine to obtain a coupler of the aforesaid general formula in which X is hydrogen.
  • the couplers of the type exemplified by the numbers (l2), (l3) and (14) are those which have been called two-equivalent couplers by those skilled in the art.
  • an ordinary coupler requires 4 moles of silver halide
  • the two-equivalent coupler requires only 2 moles of silver halide.
  • the coupler of the two-equivalent type requires a smaller amount of silver halide in forming a definite amount of dye, and hence brings about many such advantages in preparing a color photographic material as saving of silver, thinning of emulsion film, improvement in sharpness, etc.
  • the coupler of the type exemplified by the number is a coupler for use in a light-sensitive material to be developed according to dye image transfer method, i.e., a coupler suitable for use in a lightsensitive material to be color-developed according to a method in which the diffusibility of a dye formed in the light-sensitive layer of the photographic material is utilized, and the dye'is diffused and transferred to the image-receiving layer adjacent to the light-sensitive layer, thereby forming a dye image in the image-receiving lay- Concrete procedures for synthesizing the exemplified couplers are set forth below with reference to synthesis examples.
  • Synthesis Example 1 a A solution of 23 g. of metallic sodium in 1 liter of distilled alcohol was charged with 94 g. of phenol and then boiled for 30 minutes. Thereafter, 195 g. of
  • Typical examples of the nitrile compounds are set forth in Table 2.
  • This acid was treated with phosphorus pentachloride in chloroform to form an acid chloride, which was then reacted with an ethoxymagnesium salt of acetoacetic acid ethyl ester to synthesize a-(3-nitrophenoxy) isobutyrylacetic acid ethyl ester (n,, 1.5150).
  • This ester was condensed with anilinein xylene to a-[a-3- nitrophenoxy) isobutyryl1acetanilide (m.p. l 15C.), which was then converted into a-[a-(S-aminophenoxy) isobutyry1]acetanilide (m.p. 103104C.) and thereafter condensed with lauric acid chloride in acetonitrile to synthesize the exemplified coupler (9), m.p. 95-97C.
  • a color photographic material may be prepared accordingto the socalled protect type dispersion procedure carried out by dissolving the coupler in a high boiling solvent such as dibutyl phthalate or tricresyl phosphate or a low boiling solvent such as ethyl acetate or butyl acetate, or in a mixture thereof, mixing the resulting solution with an aqueous gelatin solution containing a surface active agent, dispersing the mixed solution by means of a col loid mill or a high speed rotary mixer to form a coupler dispersion, adding the coupler dispersion directly to a silver halide photographic emulsion, coating the emulsion on a suitable support such as a glass plate
  • a color photographic material may be prepared according to the so-called Fischers method carried out by dissolving the coupler in an aqeuous caustic alkali oralkali carbonate solution, either alone or in combination with a hydrophilic organic solvent, adding the resulting solution directly to a silver halide photographic emulsion, coating the emulsion to such a support as mentioned above, and then drying the emulsion.
  • the amount of the coupler to be incorporated into the emulsion is preferably in' the range from to 100 g. per mole of silver halide, but is not always limited to said range and is variable according to the kind of the coupler and the application purpose of the resulting color photographic material.
  • the coupler may be used in combination with a coupler of same or different kind in order to improve the dispersibility thereof into the photographic emulsion and to satisfy such conditions as the variation and control of hue which are necessary for preparation and properties of color photographic material.
  • the silver halide photographic silver halide emulsions used in the present invention may be prepared by use of various silver halides such as silver chloride, silver iodobromide and silver chlorobromide. These emulsions may contain chemical sensitizers, e.g., sulfur sensitizers, such natural sensitizer as present in gelatin, reduction sensitizers and noble metal salts. Further, the emulsions may have been incorporated with ordinary photographic additives such as, for example, antifoggants, stabilizers, anti-stain agents, anti-irradiation agents, physical property-improving high polymer additives, hardeners and coating aids, and may contain known carbocyanine dye, merocyanine dye, etc. as optical sensitizers therefor.
  • chemical sensitizers e.g., sulfur sensitizers, such natural sensitizer as present in gelatin, reduction sensitizers and noble metal salts.
  • the emulsions may have been incorporated with ordinary photographic
  • color photographic materials are exposed to a-rays, B-rays or the like radiations, visible rays or infrared rays, developed with a developer containing a p-phenylenediamine type developing agent, and then bleached, desilvered and fixed, whereby high density dye images excellent in spectral absorption characteristics, light fastness and moisture fastness and high in gradation can be obtained.
  • an ultraviolet absorber of the benzophenone type e.g., 2-hydroxy-4-dodecyloxybenzophenone
  • the triazole type e.g. 2-(2-hydroxy-3', 5-di-tert-butylphenyl)benzotriazole
  • the light fastness of the resulting color image canfurther be enhanced. It is also possible to further enhance the light fastness by use of said ultraviolet absorber in combination with an alkyl-substituted phenol.
  • Typical developing agents used for development of the color photographic materials according to the present invention are sulfates sulfites and hydrochlorides of:
  • colordevelopers may contain development-controlling agents, e.g. citrazinic acid, in addition to the above-mentioned developing agents.
  • development-controlling agents e.g. citrazinic acid
  • Example 1 20 Grams of each of the exemplified couplers l and (8) was dissolved at 60C. in a mixed solvent comprising 20 ml. of dibutyl phthalate and 60 ml. of butyl acetate. The resulting solution was mixed with 10 m1. of a 10 percent aqueous solution of alkanol B (alkyl-naphthalenesulfonate produced by Du Font) and 200 ml. of a 5 percent aqueous gelatin solution, and the mixed so solution was dispersed by means of a colloid mill to form a coupler dispersion. This coupler dispersion was added to 1 kg.
  • alkanol B alkyl-naphthalenesulfonate produced by Du Font
  • the bleached photographic materials were further washed with water for 5 minutes, and then treated at 25C. for 5 minutes in a fixing bath of the following composition:
  • the latitude is the difference between the optical density 1.4 on the characteristic curve of the color photographic material and the amount of exposure corresponding to 0.3, and is represented by a relative value based on the difference in the case of the known coupler (II);
  • the AA is the value (unit mg.) of difference between the absorption wavelength corresponding to the optical density 0.2 on the characteristic curve of the photographic material and the absorption maximum wavelength ()tmax), when the optical density of the absorption maximum wavelength is deemed as 1.0;
  • the light fastness is the ratio of residual density to initial density when a sample having an initial density of 1.0 was exposed to an arc lamp for 16 hours; and the moisture fastness is the ratio of residual density to initial density when a sample having an initial density was allowed to stand for 14 days in an atmosphere at 50C. and 80 percent relative humidity.
  • the color photographic material according to the present invention is more improved than the photographicmaterial containingthe known coupler (II) in photographic speed and maximum color density of dye image and is higher in gradation to bring about marked advantages in the reproduction of color, and that the color photographic material of the present invention gives a dye image far more excellent in spectral characteristics and fastnessesthan that formed by the photographic material containing the known coupler (1).
  • Example 2 Using 20 g. of eachof the exemplified couplers (l) and (5) and the known coupler (II), a coupler dispersion was prepared in the same manner as in Example 1. This dispersion was added to 1 kg. of a silver chlorobromide emulsion, which was then coated on a baryta paper and dried to obtain a'color photographic material.
  • tetraacetic acid 40 g.
  • Ferric chloride 30 g.
  • Sodium thios'ulfate (pentahydrate) 200 g. Water to make 1,000 ml.
  • the thus treated photographic materials were washed with water for 10 minutes, immersed for 2 minutes in a stabilization bath and then dried.
  • Example 3 A solution of the exemplified coupler (15) in an aqueous lN-caustic potash solution was added to a gelatin silver iodobromide emulsion. After adjusting to pH 6.5, the emulsion was coated on a film base and then dried to prepare a color photographic material. After exposure, the photographic material was contacted with a mordant-incorporated image-receiving sheet, which had previously been impregnated with a develaqueous sodium hydroxide solution.
  • the film was peeled off from the image-receiving sheet, whereby'a mordant-loaded yellow dye image was transferred onto said sheet.
  • This dye image was not only excellent in light fastness and moisture fastness, like the images obtained in other examples, but also had a sufficient density and was high in gradation.
  • a light-sensitive silver halide color photographic material which comprises a support and coated thereon a light-sensitive silver halide emulsion layer, characterized in that a yellow coupler of the general formula 3 Ar O CC-O -CH CONH-Ar' CH X wherein Ar and A1" are individually an aryl group; and X is hydrogen, chlorine, bromine, acetoxy, lauryloxy, stearoxy, phenylthio, 4-carboxy phenoxy, methylsulfonyloxy or benzotriazole is located in said material.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00203882A 1970-12-18 1971-12-01 Color photographic silver halide material containing acetanilide couplers Expired - Lifetime US3770446A (en)

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Application Number Priority Date Filing Date Title
JP45113101A JPS4917734B1 (ja) 1970-12-18 1970-12-18

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JP (1) JPS4917734B1 (ja)
DE (1) DE2162899C3 (ja)
GB (1) GB1346952A (ja)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3929484A (en) * 1974-03-08 1975-12-30 Eastman Kodak Co Color developer compositions containing improved yellow dye-forming coupler
US3933501A (en) * 1973-11-28 1976-01-20 Eastman Kodak Company Photographic elements containing color-forming couplers having and inhibiting effect upon the reactivity of competing couplers
US4072525A (en) * 1975-08-08 1978-02-07 Fuji Photo Film Co., Ltd. Silver halide photographic material containing two-equivalent color coupler
US4106942A (en) * 1974-04-02 1978-08-15 Fuji Photo Film Co., Ltd. Silver halide emulsion containing yellow color couplers
USRE30211E (en) * 1973-11-28 1980-02-12 Eastman Kodak Company Photographic elements containing color-forming couplers having an inhibiting effect upon the reactivity of competing couplers
EP0200502A2 (en) 1985-04-30 1986-11-05 Konica Corporation Light-sensitive silver halide color photographic material
EP0452984A1 (en) 1985-09-25 1991-10-23 Fuji Photo Film Co., Ltd. Process for processing silver halide color photographic material for photographing use
US5196298A (en) * 1991-02-14 1993-03-23 Agfa-Gevaert, N.V. Photographic developing solution containing an ascorbic acid derivative
WO1998022822A1 (en) * 1996-11-21 1998-05-28 Applied Imaging Corporation Photographic color couplers used as cytochemical contrast markers

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3277155A (en) * 1960-08-24 1966-10-04 Eastman Kodak Co Monofluoro-beta-ketoacetanilide couplers for color photography
US3384657A (en) * 1960-04-28 1968-05-21 Eastman Kodak Co Acetoacetamide couplers in which the non-oxo carbon atom of the aceto group is a tertiary carbon atom
US3664841A (en) * 1969-11-28 1972-05-23 Konishiroku Photo Ind Light-sensitive silver halide color photographic emulsion containing yellow-forming coupler

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3384657A (en) * 1960-04-28 1968-05-21 Eastman Kodak Co Acetoacetamide couplers in which the non-oxo carbon atom of the aceto group is a tertiary carbon atom
US3277155A (en) * 1960-08-24 1966-10-04 Eastman Kodak Co Monofluoro-beta-ketoacetanilide couplers for color photography
US3664841A (en) * 1969-11-28 1972-05-23 Konishiroku Photo Ind Light-sensitive silver halide color photographic emulsion containing yellow-forming coupler

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3933501A (en) * 1973-11-28 1976-01-20 Eastman Kodak Company Photographic elements containing color-forming couplers having and inhibiting effect upon the reactivity of competing couplers
USRE30211E (en) * 1973-11-28 1980-02-12 Eastman Kodak Company Photographic elements containing color-forming couplers having an inhibiting effect upon the reactivity of competing couplers
US3929484A (en) * 1974-03-08 1975-12-30 Eastman Kodak Co Color developer compositions containing improved yellow dye-forming coupler
US4106942A (en) * 1974-04-02 1978-08-15 Fuji Photo Film Co., Ltd. Silver halide emulsion containing yellow color couplers
US4072525A (en) * 1975-08-08 1978-02-07 Fuji Photo Film Co., Ltd. Silver halide photographic material containing two-equivalent color coupler
EP0200502A2 (en) 1985-04-30 1986-11-05 Konica Corporation Light-sensitive silver halide color photographic material
EP0452984A1 (en) 1985-09-25 1991-10-23 Fuji Photo Film Co., Ltd. Process for processing silver halide color photographic material for photographing use
US5196298A (en) * 1991-02-14 1993-03-23 Agfa-Gevaert, N.V. Photographic developing solution containing an ascorbic acid derivative
WO1998022822A1 (en) * 1996-11-21 1998-05-28 Applied Imaging Corporation Photographic color couplers used as cytochemical contrast markers

Also Published As

Publication number Publication date
JPS4917734B1 (ja) 1974-05-02
GB1346952A (en) 1974-02-13
DE2162899C3 (de) 1979-03-15
DE2162899A1 (de) 1972-07-13
DE2162899B2 (de) 1978-07-06

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