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
  • G03C7/392—Additives
  • G03C7/39208—Organic compounds
  • G03C7/3924—Heterocyclic
  • G03C7/39244—Heterocyclic the nucleus containing only nitrogen as hetero atoms
  • G03C7/39252—Heterocyclic the nucleus containing only nitrogen as hetero atoms two nitrogen atoms

Definitions

• This invention rerates to silver halide color photographic materials, more particularly to silver halide color photographic materials that are protected against deterioration in photographic performance during storage that would otherwise occur on account of deleterious substances such as formaldehyde.
• JP-B as used hereunder means an "examined Japanese patent publication”
• JP-B-46-34675 JP-B-63-32378
• JP-A-59-19945 the term “JP-A” as used hereunder means an "unexamined published Japanese patent application”
• JP-A-48-39029 JP-A-57-133450
• JP-A-58-150950 U.S. Patent Nos. 4,411,987, 3,811,891, 4,003,748, 4,414,309
• Research Disclosure Vol. 101, No. 10133.
• the ability of these compounds to trap aldehyde gases is insufficient to guarantee that the deterioration in photographic performance which plagues silver halide color light-sensitive materials in commercial use today can be prevented in a satisfactory way merely by adding those compounds.
• aldehyde scavengers are used in large amounts, the film characteristics of light-sensitive materials will deteriorate as typically evidenced by photographic coatings becoming vulnenerable. Since excessive use of aldehyde scavengers also causeadverse effects on the photographic performance of light-sensitive materials, there has been as inherent limit on the amount in which they can be added.
• the present invention has been achieved under these circumstances and has as an object providing a silver halide color photographic material that will not experience any deterioration in its photographic performance such as reduced color density or gamma, color contamiuation or increased fog even if it is exposed to formaldehyde and other deleterious gases for a long time of storage before it is subjected to color development and subsegvent photographic processing.
• a silver halide color photographic material comprising: a support and provided thereon a photographic constituent layer unit having a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer, and a non-light-sensitive hydrophilic colloidal layer, wherein one of said layers contains a compound represented by the following formula (I): (where R1 is a hydrogen atom or a monovalent substituent; and R2 is a group having a Hammett's value ⁇ p of at least 0.2).
• Examples of the substituent represented by R1 in the general formula (I) include an alkyl group, an aryl group, a cycloalkyl group, an acyl group, a carbamoyl group, a sulfamoyl group, and an alkoxycarbonyl group. These groups may gave substituents such as carboxyl, sulfo, hydroxyl and amino groups.
• the substituent represented by R2 has a Hammett's value ⁇ p of at least 0.2.
• the Hammett's value ⁇ p of the substituent represented by R2 is preferably 0.2 - 1.0, more preferably 0.3 - 0.7. If the Hammett's value ⁇ p of R2 is lower than 0.2, the compound (I) will enter into a coupling reaction with quinonedimine which is the oxidation product of a color developing agent and the consumption of quinonediimine in the light-sensitive material will lead to a lower color density.
• the dye produced as a result of coupling between the compound (I) and quinonedimine will remain in the light-sensitive material to cause color contamination or staining. Furthermore, if the dye dissolves out into the color developing solution, its accumulation can cause staining, particularly in a processing line that is adapted for low pollution by using reduced amounts of replenishers.
• the Hammett's value ⁇ p of R2 is extremely higher than 1.0, it is not highly reactive with quinonediimine and the color density is low enough to cause little effect on the photographic performance of the light-sensitive material.
• the reactivity of R2 with deleterious substances substances such as formaldehyde is also low and is not capable of achieving the object of the present invention in an effective way.
• Examples of the substituent represented by R2 which has a Hammett's value ⁇ p of at least 0.2 include cyano, carbamoyl, carboxyl, alkoxycarbonyl, acyl, haloalkyl, nitro, sulfamoyl and alkylsulfonyl groups.
• the aldehyde acavengers to be used in the present invention are preferably incorporated in a layer that contains a magenta coupler and/or in an overlying photographic constituent layer of the silver halide color photographic material. It is effective and most preferred for the scavengers to be incorporated in the layer that is the remotest from the support, for example, in a protective layer.
• aldehyde scavengers may be used either singly or in combination with themselves or with other aldehyde scavengers than the compounds (I).
• photographic constituent layer unit includes not only light-sensitive silver halide emulsion layers that are optically or chemically sensitized but also other layers that comprise a light-sensitive material and that have no light sensitivity such as intermediate layers, uv absorbing layers, yellow filter layers, protective layers and any other auxiliary layers.
• aldehyde scavengers or compounds (I), in the photographic layers, they may be dissolved in respective coating solutions with the aid of suitable solvents such as water and methanol.
• suitable solvents such as water and methanol.
• the aldehyde scavengers may be added at any stage of the process of manufacture.
• the aldehyde scavengers are desirably added just before application of coating solutions if they are to be incorporated in silver halide emulsion layers.
• the aldehyde scavengers are preferably added in amounts of 0.01 - 5.0 g per square meter of the color photographic material and the most preferred results can be attained by adding them in amounts of 0.1 - 2.0 g.
• the silver halide emulsion to be used in the present invention may incorporate any types of silver halides such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide and silver chloride that are commonly employed in silver halide emulsions.
• the silver halide grains to be used in silver halide emulsions may have a homogeneous silver halide composition in their interior, or they may have a core/shell structure in which the interior of grains has a different silver halide composition than the surface layers.
• the silver halide grains may be of a type that forms a latent image predominantly on the surface or of a type that forms a latent image predominantly in the interior.
• the silver halide emulsions may have any grain size distribution. Emulsions having a broad grain size distribution (called “polydispersed emulsions”) may be used or, alternatively, emulsions having a narrow grain size distribution (named “monodispersed emulsions”) may be used either singly or as admixtures. If desired, a polydispersed emulsion may be used in combination with a monodispersed emulsion.
• the emulsions may be chemically sensitized in the usual manner or they may be optically sensitized with spectral sensitizers to have sensitivity in a desired wavelength region.
• Antifoggants, stabilizers and other additives may be added to silver halide emulsions.
• Gelatin is advantageously used as a binder for the emulsions.
• Emulsion layers and other hydrophilic colloidal layers can be hardened. If desired, plasticizers or dispersions (latices) of water-insoluble or slightly water-soluble synthetic polymers may be incorporated in those layers.
• Couplers are used in the emulsion layers of the color photographic material of the present invention. Further, competitive couplers that are capable of color correction, as well as compounds that couple with the oxidation product of developing agents to release photographically useful fragments such as a development accelerator, a bleach accelerator, a developing agent, a silver halide solvent, a toning agent, a hardener, a foggant, an antifoggant, a chemical sensitizer, a spectral sensitizer and a desensitizer may be employed.
• a development accelerator a bleach accelerator, a developing agent, a silver halide solvent, a toning agent, a hardener, a foggant, an antifoggant, a chemical sensitizer, a spectral sensitizer and a desensitizer.
• acylacetanilide compounds are preferably used as yellow-dye forming couplers and among them benzoylacetanilide and pivaloylacetanilide compounds are particularly advantageous.
• magenta-dye forming couplers include 5-pyrazolone, pyrazoloazole, pyrazolobenzimidazole, open-chain acylacetonitrile and indazole compounds. Particularly significant results are attained in the present invention by using four-equivalent 5-pyrazolone compounds.
• Phenolic or naphtholic compounds are generally used as cyan-dye forming couplers.
• the light-sensitive material of the present invention may be provided with auxiliary layers such as a filter layer, an anti-halo layer and an anti-irradiation layer. Dyes that dissolve out of the light-sensitive material during development or that are bleached may be incorporated in those auxiliary layers and/or emulsion layers.
• the light-sensitive material of the present invention may also contain a matting agent, a lubricant, an image stabilizer, a uv absorber, an optical brightening agent, a surfactant, a development accelerator, a development retarder or a bleach accelerator.
• Supports that can be used in the present invention include polyethylene-laminated paper, a polyethylene terephthalate film, baryta paper, triacetyl cellulose, etc
• the color photographic material of the present invention is first exposed imagewise and then subjected to known procedures of color photographic processing.
• the amounts of all components in the prepared samples of silver halide photographic material are in grams per square meter unless otherwise noted.
• the amounts of silver halide and colloidal silver are calculated for silver, and the amounts of spectral sensitizers are in moles per mole of silver.
• Example 1 Layers having the compositions set forth below were coated onto a triacetyl cellulose film base, with the first layer being formed the closest to the base, whereby a sample of multi-layered color photographic material (Sample 1) was prepared.
• a coating aid (SU-2), a dispersion aid (SU-1), a hardener (H-1), and dyes (AI-1) and (AI-2) were added as appropriate to the respective layers.
• the emulsions used in sample 1 had the following characteristics. Each of them was a monodispersed emulsion with high iodine content in the interior.
• Additional samples 2 - 24 were prepared in the same manner as in sample 1 in Example 1 except that aldehyde scavengers (see Table 1 below) were added to the eleventh layer (PRO-1) each in an amount of 3 x 10 ⁇ 3 moles/m2.
• a 35% aqueous solution of glycerin (300 cc) was charge into a gas-tight container and each of the sample was held in air equilibrated with glycerin in the container at 30°C for 3 days.
• a 35% aqueous solution of glycerin (300 cc) containing 6 cc of a 35% aqueous formaldehyde solution was charged into a gastight container and each of the samples was held in air equilibrated with glycerin + formaldehyde in the container at 30°C for 3 days.
• the developing, bleaching, fixing and stabilizing solutions were prepared according to the following formulas.
• sample 2 which used HS-1 as a comparative aldehyde scavenger experienced a marked drop in the maximum density of magenta color as a result of treatment 2.
• the compounds of the present invention used in samples 5 - 24 were in no way deleterious to color formation and these samples experienced only a small decrease in the maximum density of magenta color as a result of treatment 2.
• samples 5 - 24 the present invention experienced no deterioration in photographic performance such as lower gamma, color contamination or increased fog.
• Example 1 Additional samples were prepared as in Example 1 except that magenta coupler M-1 used in the sixth and seventh layers was replaced by M-2 or M-3 identified below. When those samples were subjected to the same tests as in Example 1, the effectiveness of the present invention was verified.
• the silver halide color photographic material of the present invention will not experience any deterioration in its photographic performance such as reduced color density or gamma, color contamination or increased fog even if it is exposed to formaldehyde and other deleterious gases for a long time of storage before it is subjected to color development and subsegvent photographic processing.

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• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

Applications Claiming Priority (2)

Publications (1)

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ID=14062156

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Cited By (3)

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Citations (2)

• 1990
  • 1990-04-06 JP JP2092715A patent/JP2852685B2/ja not_active Expired - Lifetime
• 1991
  • 1991-04-04 EP EP91302994A patent/EP0450965A1/en not_active Withdrawn

Patent Citations (2)

Non-Patent Citations (1)

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