US3801322A - Improved process for preventing the discoloration of a color image and improving image stability - Google Patents

Improved process for preventing the discoloration of a color image and improving image stability Download PDF

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Publication number
US3801322A
US3801322A US00313917A US3801322DA US3801322A US 3801322 A US3801322 A US 3801322A US 00313917 A US00313917 A US 00313917A US 3801322D A US3801322D A US 3801322DA US 3801322 A US3801322 A US 3801322A
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group
compound
general formula
processing
color
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US00313917A
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English (en)
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K Shirasu
H Amano
R Ohi
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • G03C7/3046—Processing baths not provided for elsewhere, e.g. final or intermediate washings

Definitions

  • ABSTRACT In a process for preventing the discoloration of a color image by developing an exposed silver halide color photographic material, removing the silver image thus formed together with the residual silver halide and stabilizing the thus formed color image with a stabilizing solution, the improvement which comprises employing a stabilizing solution containing:
  • R represents a member selected from the group consisting of a hydrogen atom, an alkyl group, an ally] group, an aryl group and NHR
  • R and R represent a member selected from the group consisting of a hydrogen atom, an alkyl group, a carboxyalkyl group, a sulfoalkyl group, an ally] group and an aryl group; said R and R may combine with each other to fonn a S-membered or 6-membered heterocyclic ring
  • k, m, and n are 0 or 1
  • the present invention relates to an improvement in the stability of images of color photographic materials. More particularly, the present invention relates to an improvement in the stability of images of color photographic materials by processing the color photographic materials in a bath containing a urea compound, a guanidine compound, or a derivative of each of them, together with a dior tri-hydroxy benzene derivative.
  • a material absorbing ultraviolet light is incorporated in color photographic materials (see, e.g., specifications of U.S. Pat. Nos. 2,632,701 and 2,747,996).
  • a reducing agent or an antioxidant is incorporated in color photographic materials (see, e.g., specifications of U.S. Pat. Nos. 2,384,658 and 3,095,302).
  • Color photographic light sensitive material is ordinarily subjected to the following processing steps after exposure: For instance, the color photographic material is subjected to the steps of color development, stopfixing, washing, bleaching, washing, hardener fixing, washing and stabilization as described in The British Journal of Photography, Sept. 27, 838 (1968') or the steps of pre-bathing, rinsing, color development, rinsing, fixing, washing, bleaching, washing, fixing, washing, and stabilization as described in Journal of the SMPTE Vol. 61, No. 12,667 (1963).
  • gallic acid improves the stability of the images (see the specification of U.S. Pat. No. 3,069,262).
  • gallic acid not only weakly improves the light fastness of the magenta dye as compared with the compounds described in U.S. Pat. No. 2,384,658 mentioned above, but also produces severe brown stains as well.
  • Urea, guanidine or a derivative thereof is also known as a light-fading preventing agent (see the specification of U.S. Pat. No. 3,095,302).
  • the effect of urea, guanidine and the derivatives thereof are insufficient in effectively preventing light fading.
  • carbohydrazide improves the light fastness of a magenta dye (see the specification of U.S. Pat. No. 3,201,244).
  • the light fastness of the magenta dye is improved by processing a color photographic material with a bath containing this compound, when the color photograph thus processed is preserved at a high temperature, e.g., at 76.7 C, the magenta dye is extremely faded.
  • polyhydroxy compounds see the specification of U.S. Pat. No. 3,095,302
  • cystein see the specification of U.S. Pat. No. 3,201,243
  • an object of this invention is to provide a processing bath which will prevent the fading of color images by light and heat as well as preventing the formation'of stains.
  • Another object of the present invention is to provide color photographic materials, such as color films, transparency, color prints, etc., stable against light and heat by processing the color photographic materials with a specific stabilizing bath.
  • the urea compound and guanidine compound applicable to the present invention include the compounds represented by the general formula (1):
  • R represents a hydrogen atom, an alkyl group, an allyl group, an aryl group or NHR
  • R and R represent a hydrogen atom, an alkyl group, a carboxyalkyl group, a sulfoalkyl group, an allyl group, or an aryl group, said R and R may combine with each other to form a S-membered or 6-membered heterocyclic ring
  • k, m and n are 0 or 1.
  • the dihydroxybenzene compound and the trihydroxybenzene compound applicable to the present invention include the compounds represented by the general formula (2):
  • the compound represented by the general formula l or the compund represented by the general formula (2) has hitherto been used individually as a light-fading preventing agent.
  • the effect thereof is not always sufficient and also is accompanied with undesirable phenomena.
  • both compounds are used together according to the present invention, totally unexpected results are obtained. That is to say, a combination of the compound represented by the general formula (2) with the compound represented by the general formula (1) inhibits stain formation and also effectively prevents light-fading.
  • the compound represented by the general formula l may be used in the form of an addition salt thereof, such as a carbonate, a hydrochloride, a sulfate, etc., for increasing the water-solubility thereof.
  • the light sensitive materials to be processed by the processing bath of this invention may be colored photographic light sensitive materials containing acetanilide type yellow couplers as disclosed in the specifications of British Patent No. 1,113,038 and U.S. Pat. No. 3,409,439; the pyrazolone type magenta couplers described in the specifications of British Patent No. 1,142,553 and U.S. Pat. No. 3,337,344; and the phenolic couplers described in the specifications of U.S. Pat. Nos. 2,423,730, 2,474,493, and 2,801,171.
  • the present invention is not limited to these light sensitive materials alone.
  • the processing bath of this invention may be more profitably applied to light-sensitive materials containing ultraviolet absorbers (see, e.g., specifications of U.S. Pat. No. 3,352,681 and British Patent No. 1,026,142). Also, it is effective to add the compound represented by the general formulas (1) and 2) to the stabilizing bath as described in The British Journal of Photography, Sept. 27, 838 (1968) or Journal 65 of the SMPTE, Vol. 61, No. 12, 667 (1963).
  • Ammonium thiosulfate 120 Sodium sulfite 5 Boric acid 2, Formalin (-40%) 30 Water to make A color photographic light-sensitive paper produced by coating a baryta-coated paper with a blue-sensitive silver iodobromide emulsion layer containing benzoylaceto-2-chloro-5-dodecyloxycarbonyl anilide as a yellow coupler, an intermediate gelatin layer, a greensensitive silver chlorobromide emulsion layer containing l-phenyl-3-[3-(N-butylcaprylamidopropionamido)]-5-pyrazolone as a magenta coupler, an intermediate gelatin layer, a red-sensitive silver chlorobromide emulsion layer containing l-hydroxy-2'[3- (2,4-t-amylphenoxy)propyl]-naphthamide as a cyan coupler, and a protective gelatin layer in the successive order was exposed and subjecte
  • the addition amount of the additive is the gram number of the additive per 1 liter of the processing bath.
  • the fading ratio is the ratio of the color density reduced during the test ofthe portion having an initial density of 10 "ADV is the value 01' the density increase of the non-exposed portion shown by the density of the yellow component.
  • the processing baths 58 of this invention gave remarkable light-fading prevention eHect of magenta dye, which has never been obtained by using the known Compound 1 or 16 individually.
  • the processing baths 5-8 of this invention gave excellent light-fading prevention effect of the yellow dye as well as preventing the formation of stains upon light exposure.
  • Fluorescent Lamp (10,000 Lux) heat and also formed fewer stains upon heating.
  • the fading ratio is the ratio ofthc color density reduced during the test of the portion having an initial dcsnity of L0.
  • ADY is the value of the density increase of the nonexposcd portion shown by the density of yellow component.
  • the processing baths of this invention exhibited remarkable lightfading prevention on magenta dyes, light-fading prevention effect on yellow dyes, as well as preventing the formation of stains. Moreover, when the samples processed by the processing baths of this invention were stored at 76.7 C under a low humidity condition, the fading of the cyan dye and the formation of stains were less asillustrated in Example 1.
  • EXAMPLE 3 A color photographic positive film produced by coating an acetate film with a blue-sensitive silver iodobromide emulsion layer containing benzoylaceto-Z-chloro- 5-dodecyloxycarbonyl anilide as a yellow coupler, an intermediate gelatin layer, a red-sensitive silver chlorobromide emulsion layer containing l-hydroxy-2-[3- (2,4-t-amylphenoxy)propyllnaphthamide as a cyan coupler, an intermediate gelatin layer, a green-sensitive chiorobromide emulsion layer containing l-phenyl-3- [3-(N-butyl-caprylamidopropionamide)]-5-pyrazolone as a magenta coupler, and a protective gelatin layer in successive order was exposed and subjected to the following processings at2l C; i.e. to the steps of prebathing for ten seconds, rinsing for fifteen seconds
  • the photographic film thus processed was processed -for two minutes with each of the following processing
  • the samples processed in each of the above processing baths were tested for stability of the images thus obtained under the conditions shown in the following table, the results of which are shown in the same table.
  • Processing bath 2 i770 35% 10% 40.04 17% 34% l37( 4004 Processing bath 4 20% 29% 11% -10. 10 20% 30% 13% +0.1 1
  • *Th'e fading ratio is the ratio of the color density reduced during the test of the portion having an initial density of 1.0.
  • *ADY is the value of the density increase of the non-exposed portion shown by the density of the yellow component.
  • the processing baths of this invention give remarkable light-fading prevention of magenta dyes, light-fading prevention of yellow dyes, and effectively prevent the formation of stains. Also, when the samples processed by the processing baths of this invention were preserved at 76.6 C under conditions oflow humidity, the fading of the cyan dye and the formation of stain was less as seen in Example 1.
  • a stabilizing solution consisting essentially of:
  • R represents a member selected from the group consisting of a hydrogen atom, an alkyl group, an ally] group, an aryl group and NHR
  • R and R represent a member selected from the group consisting of a hydrogen atom, an alkyl group, a carboxyalkyl group, a sulfoalkyl group, an ally] group and an aryl group; said R and R may combine with each other to form a S-membered or 6- membered heterocyclic ring
  • k, m, and n are 0 or 1

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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)
US00313917A 1970-01-27 1972-12-11 Improved process for preventing the discoloration of a color image and improving image stability Expired - Lifetime US3801322A (en)

Applications Claiming Priority (1)

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JP45007201A JPS4926140B1 (enrdf_load_stackoverflow) 1970-01-27 1970-01-27

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US3801322A true US3801322A (en) 1974-04-02

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JP (1) JPS4926140B1 (enrdf_load_stackoverflow)
GB (1) GB1293715A (enrdf_load_stackoverflow)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4113488A (en) * 1975-05-13 1978-09-12 Fuji Photo Film Co., Ltd. Method for improving the light fastness of color photographic dye images
US4277553A (en) * 1978-09-20 1981-07-07 Konishiroku Photo Industry Co., Ltd. Light-sensitive color photographic material
US4286042A (en) * 1978-06-06 1981-08-25 Fuji Photo Film Co., Ltd. Light reflecting layer for color diffusion transfer photographic system
US4797352A (en) * 1984-06-08 1989-01-10 Konishiroku Photo Industry Co., Ltd. Method of processing a silver halide photographic light-sensitive material
US4859574A (en) * 1988-03-15 1989-08-22 Eastman Kodak Company Process for stabilizing photographic elements using a solution comprising a water-soluble N-methylol compound and a buffering agent
US5217852A (en) * 1990-12-07 1993-06-08 Fuji Photo Film Co., Ltd. Color image-stabilization processing solution used for processing a silver halide color photographic material and a processing method using the same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52142241U (enrdf_load_stackoverflow) * 1976-04-23 1977-10-28

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4113488A (en) * 1975-05-13 1978-09-12 Fuji Photo Film Co., Ltd. Method for improving the light fastness of color photographic dye images
US4286042A (en) * 1978-06-06 1981-08-25 Fuji Photo Film Co., Ltd. Light reflecting layer for color diffusion transfer photographic system
US4277553A (en) * 1978-09-20 1981-07-07 Konishiroku Photo Industry Co., Ltd. Light-sensitive color photographic material
US4797352A (en) * 1984-06-08 1989-01-10 Konishiroku Photo Industry Co., Ltd. Method of processing a silver halide photographic light-sensitive material
US4859574A (en) * 1988-03-15 1989-08-22 Eastman Kodak Company Process for stabilizing photographic elements using a solution comprising a water-soluble N-methylol compound and a buffering agent
US5217852A (en) * 1990-12-07 1993-06-08 Fuji Photo Film Co., Ltd. Color image-stabilization processing solution used for processing a silver halide color photographic material and a processing method using the same
US5348845A (en) * 1990-12-07 1994-09-20 Fuji Photo Film Co., Ltd. Color image-stabilization processing solution used for processing a silver halide color photographic material and a processing method using the same

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Publication number Publication date
GB1293715A (en) 1972-10-25
DE2103806B2 (de) 1976-04-29
JPS4926140B1 (enrdf_load_stackoverflow) 1974-07-06
DE2103806A1 (de) 1971-08-26

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