US3619189A - Color photographic developing process - Google Patents

Color photographic developing process Download PDF

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Publication number
US3619189A
US3619189A US4660A US3619189DA US3619189A US 3619189 A US3619189 A US 3619189A US 4660 A US4660 A US 4660A US 3619189D A US3619189D A US 3619189DA US 3619189 A US3619189 A US 3619189A
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US
United States
Prior art keywords
anilide
methoxy
coupler
methoxybenzoylaceto
ethoxybenzoylaceto
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US4660A
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English (en)
Inventor
Makoto Yoshida
Momotoshi Tsuda
Isao Shimamura
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
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Publication of US3619189A publication Critical patent/US3619189A/en
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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
    • 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
    • G03C7/362—Benzoyl-acetanilide couplers

Definitions

  • the present invention relates to color photography and, more particularly, to a color photographic developing process using a color developer containing an improved yellow coupler.
  • couplers react with the oxidation products of aromatic primary amines to form dyes which are insoluble in water or ordinary processing solutions, whereby. colored images are formed which remain in the photographic emulsion layers.
  • Such couplers may be incorporated in a developing solution or in a photographic emulsion layer prior to exposure.
  • the improved coupler of the present invention is of a type which is incorporated in a developing solution.
  • Couplers are incorporated into the developer is usually conducted by a subtractive color process and the couplers form cyan, magenta, and yellow dyes in the process.
  • the coupler useful for color photography form a dye having particular desired spectral absorption characteristics.
  • the yellow coupler is theoretically required which would form a dye which completely absorbs blue light and completely transmits green and red light.
  • many yellow couplers which have hitherto been used are not sufficiently effective with regard to these characteristics.
  • the yellow dye or color image is formed by subjecting the blue-sensitive layer, after black and white development, to a reversal blue exposure and then subjecting the layer to a yellow color development, bleaching and fixing. It frequently occurs that the oxidation of developed silver is delayed by the bleaching process, thus leaving reduced silver. Further, the silver is often not completely removed by the fixing process, thus leaving the silver in the yellow (this phenomenon is called weak silver removing property). The occurrence of a weak silver removing property severely degrades the transparency of the yellow image.
  • An object of the present invention is to provide a color photographic developing process resulting in an ideal yellow image.
  • Another object of the present invention is to provide a color photographic developing process for forming a yellow dye having excellent spectral absorption characteristics and possessing a good silver removing property.
  • benzoylacetanilide is useful as a yellow coupler, but the dye image obtained by using such a yellow coupler is low in silver removing property and is inferior in spectral absorption characteristics.
  • the substitution of the benzoyl nucleus of benzoylacetanilide can be considered.
  • the absorption maximum (Amax) shifts to a shorter wavelength to provide a desired color hue, but the coupling property of the coupler is reduced and the water solubility of the coupler is severely lowered.
  • the coupling property of the coupler may be improved, but the silver removing property is diminished and the water solubility of the coupler is also severely reduced.
  • a coupler formed by introducing a chlorine atom to the ortho-position of the anilide nucleus of the latter, i.e., 2-methoxybenzoylaceto[2-chloro-4(4-toluenesulfonamide)lanilide also gives a reddish yellow image.
  • l the spectral absorption curve A of color image (A) formed by the coupling of a typical coupler used in the present invention, 4- ethoyxbenzoylacetol24-(4-toluenesulfonamido)]- anilide, and the oxidation product of a color developer, 4- N ,N-diethylaminoaniline, (2) the spectral absorption curve B of color image (B) formed by the coupling of a control coupler, benzoylacetanilide, and the oxidation product of the aforesaid color developer, and (3) the spectral absorption curve C of color image (C) formed by the coupling of another control coupler, benzoylaceto-(Z-methoxy) anilide and the oxidation product of the aforesaid color developer.
  • the coupler of the present invention has preferable silver removing properties.
  • the silver removing property is shown by the ratio of the silver image density measured by using a red filter to the sum of the densities of dye image and silver image measured by using a blue filter; thus, it is shown by lied dvu ii v l)r Blue density (Db Nurm-ricul value 0,, 0.5 L 2.0 Color Image E 0.l l 0.06 0.04
  • couplers of the present invention are excellent in silver removing properties. It is also clear that the excellent silver removing properties gives a color image having good transparency and is very profitable for the reproduction of color photography.
  • the reason that the color images obtained from the couplers of the present invention have excellent spectral absorption characteristics and that the coupler provides excellent silver removing properties is believed to be found in the specific chemical structure, that is, the presence of an alkoxy group at the 2- or 4- position of the benzoyl nucleus as well as an alkoxy group at the 2-position of the anilide'nucleus and a sulfonamido group at the 4- or position of the anilide nucleus of the benzoylacetonanilide.
  • the coupler of the present invention is used not only for natural color photography, but also may be employed in monochromatic or dichromatic photography.
  • yellow couplers which may be employed in the process of the present invention are shown below:
  • Coupler 1 OCH
  • Coupler ti Coupler 7 OCH
  • Coupler 8 O CzHs Coupler 10 1TH S 0 2C H; CEHtlOQC o c1120 OHN l O CH;
  • Coupler 11 OCH
  • Coupler 12 cum-Q-o 0 01120 OHN lTlHS O2CH3 OCH:
  • the above compound was prepared by repeating the procedure of preparation l-a) using 236 g. of ethyl-4-ethoxybenzoyl acetate instead of the ethyl-4-methoxybenzoyl acetate used in (l-a) and using 168 g. of 2-methoxy-4- nitroaniline and 250 ml. of xylol to provide 304 g. of the above compound having a melting point of 175 C. with a yield of (4-b): Preparation of 4-ethoxybenzoylaceto)2-methoxy-4- amino)anilide hydrochloride:
  • the white crystals thus formed were recovered by filtration, washed with water acidified with hydrochloric acid and then washed with acetonitrile to provide 100 g. of the above compound having a decomposition point of 202 C. with a yield of 64%.
  • EXAMPLE 1 A gelatlno silver iodobromlde emulsion which had not been subjected to color sensitization (a blue-sensitive emulsion for By repeating the procedure of example 1. but using 2- color photographic elements of [he [ype developed in methoxybenzoylaceto(2-methoxy-4-benzenesulfonamtdo )amdevelopers containing couplers) was applied to a cellulose (Yellow F p l4) l ofthe Coupler used exam" acetate film.
  • Black 6 White Developer Yellow color developer N-Methyl-p-aminophenol sulfite 20 g. ig g s s i ur fiii mide I. Sodium sulfite 90 g. Sodium sum 5 Potassium iodide (0.1% aq, 50in.) 16 ml. Sodium carbonate monohydrar: 52.5 g. sodium hydroxidc 0% q min.) 28 ml. Potassium bromide 5.0 g.
  • orrc cl g. I Water to make 1.000 ml. What Is clalmed Fixing Solution l.
  • a color photographic developer comprising an aromattc primary amino developing agent and a coupler having the for- Sodium thiosulfate 150 g. Sodium sulfitc 10 g. Water to make 1.000 ml. R0 NHS 02X @cocmc 0HN By this procedure, a positive image of yellow dye having an absorption maximum at 438 my and very good transparency was obtained.
  • the color photographic developer of claim 1 wherein the fonamido)anilide (Yellow coupler 5) was used instead of the coupler has the formula: coupler used in example 1, a positive yellow dye image having an absorption maximum at 441 my and very good trans- O R parency was obtained. l
  • R, R and X are as set forth in claim 1 6.
  • the color photographic developer of claim 1 wherein the coupler is selected from the group consisting of 4-methoxybenzoylaceto-(2-methoxy-4-methanesulfonamido)anilide, 4 methoxy-benzoylaceto-(2-methoxy-4-benzenesulfonamido)anilide, 4-methoxy-benzoylaceto [2-methoxy-4-(4- toluenesulfonamido)lanilide, 4-methoxybenzoylaceto- [2 methoxy-5-( 4-toluenesulfonamido lanilide, 4-ethoxybenzoylaceto(2-methoxy-4-methanesulfonamido)anilide, 4- ethoxybenzoylaceto(2-methoxy-40benzenesulfonamido)anilide, 4-ethoxybenzoylaceto [2-methoxy-4( 4-to
  • a color developing process which comprises developing an exposed silver halide photographic emulsion layer with an aromatic primary amino developing agent in the presence of a coupler having the formula:
  • R and R may be the same or different and each is an alkyl group having one and three carbon atoms and X is a C C alkyl group, a phenyl group, a methylphenylene group, a dimethyl phenylene group or an ethylphenylene group, wherein the -OR group is in the 2- or 4-position and the NH- SQ X group is in the 4- or 5-position.
  • coupler is selected from the group consisting of 4-methoxybenzoylaceto(2-methoxy-4-methanesulfonamido)anilide, 4-benzoylacet0-(2-methoxy-4-benzenesulfonamido)anilide.

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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)
US4660A 1969-01-22 1970-01-21 Color photographic developing process Expired - Lifetime US3619189A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP44004579A JPS4815873B1 (de) 1969-01-22 1969-01-22

Publications (1)

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US3619189A true US3619189A (en) 1971-11-09

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US4660A Expired - Lifetime US3619189A (en) 1969-01-22 1970-01-21 Color photographic developing process

Country Status (6)

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US (1) US3619189A (de)
JP (1) JPS4815873B1 (de)
CA (1) CA925749A (de)
CH (1) CH530657A (de)
DE (1) DE2002378A1 (de)
GB (1) GB1288733A (de)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2350138A (en) * 1940-08-22 1944-05-30 Eastman Kodak Co Nondiffusing acylacetyl sulphonamide coupler
US2407210A (en) * 1944-04-14 1946-09-03 Eastman Kodak Co Color couplers
GB595314A (en) * 1944-11-02 1947-12-02 Kodak Ltd Improvements in photographic colour forming developers and process of colour development

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2350138A (en) * 1940-08-22 1944-05-30 Eastman Kodak Co Nondiffusing acylacetyl sulphonamide coupler
US2407210A (en) * 1944-04-14 1946-09-03 Eastman Kodak Co Color couplers
GB595314A (en) * 1944-11-02 1947-12-02 Kodak Ltd Improvements in photographic colour forming developers and process of colour development

Also Published As

Publication number Publication date
GB1288733A (de) 1972-09-13
CA925749A (en) 1973-05-08
CH530657A (de) 1972-11-15
DE2002378A1 (de) 1970-08-13
JPS4815873B1 (de) 1973-05-17

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