EP0095920B1 - Matériau photographique couleur sensible à la lumière - Google Patents

Matériau photographique couleur sensible à la lumière Download PDF

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Publication number
EP0095920B1
EP0095920B1 EP19830303091 EP83303091A EP0095920B1 EP 0095920 B1 EP0095920 B1 EP 0095920B1 EP 19830303091 EP19830303091 EP 19830303091 EP 83303091 A EP83303091 A EP 83303091A EP 0095920 B1 EP0095920 B1 EP 0095920B1
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EP
European Patent Office
Prior art keywords
sensitive material
photographic light
layer
color photographic
sensitive
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
Application number
EP19830303091
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German (de)
English (en)
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EP0095920A3 (en
EP0095920A2 (fr
Inventor
Takashi Kadowaki
Kaoru Onodera
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Konica Minolta Inc
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Konica Minolta Inc
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Priority claimed from JP57093323A external-priority patent/JPS58209735A/ja
Priority claimed from JP57095145A external-priority patent/JPS58211148A/ja
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of EP0095920A2 publication Critical patent/EP0095920A2/fr
Publication of EP0095920A3 publication Critical patent/EP0095920A3/en
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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
    • G03C7/39296—Combination of additives
    • 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
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
    • 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
    • G03C2200/00—Details
    • G03C2200/20—Colour paper
    • 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
    • G03C2200/00—Details
    • G03C2200/35—Intermediate layer
    • 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
    • G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function
    • 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
    • G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor
    • G03C7/3885—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor characterised by the use of a specific solvent
    • 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
    • G03C7/39232—Organic compounds with an oxygen-containing function
    • 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
    • G03C7/39288—Organic compounds containing phosphorus or silicon

Definitions

  • the present invention relates to a color photographic light-sensitive material and, more particularly, to a color photographic light-sensitive material for use in making photographic prints.
  • multi-layered color photographic light-sensitive materials e.g.; those for use in making photographic prints have, in recent years, been produced by coating their component layers on their support in the high-speed coating process capable of coating layers very rapidly. And the coating of component layers is conducted by the simultaneous multilayer coating method in which the dew point of the drying air in the drying process is very low. For this reason, static electricity frequently occurs on the light-sensitive material during the manufacture thereof.
  • the silver halide for use in the print-making color photographic light-sensitive material consists principally of silver bromide.
  • an ultraviolet absorbing agent having an absorbency below 460 nm, the shorter wavelength end of the inherent sensitivity range of silver bromide should be contained in the topmost layer of the component-layers, that covers the silver halide layers.
  • a principal object of the present invention is to provide a color photographic light-sensitive material which is not only hardly caused to produce static marks by the static electricity brought about during the component-layer coating process or during the transport of the material through the inside of a printer but also excellent in the whiteness of its finished print.
  • the object can be attained by the use of a larger silver chloride content of the uppermost silver halide emulsion layer than that ever used, and the incorporation of an ultraviolet absorbing agent whose light-absorbency is shifted toward shorter wavelength side than that of those conventionally used into the topmost nonlight-sensitive layer coated on the emulsion layers, and, further, we have found the optimum relation between the silver chloride content and the light-absorbing characteristic of the ultraviolet absorbing agent, and thus the present invention has been completed.
  • the present invention is of a color photographic light-sensitive material comprising a reflective support having thereon a plurality of silver halide emulsions of which the silver halide emulsion layer located farthest from the support has a silver halide containing not-less-than-15% by mole of silver chloride; and a nonlight-sensitive layer on the opposite side to the support side of the silver halide emulsion layer located farthest from the support, the nonlight-sensitive layer containing an ultraviolet absorbing agent whose ratio A 1 /A 2 of the spectral absorption efficient A 1 at 350 nm to the spectral absorption efficient A 2 at 400 nm is not less than 10.
  • the respective combinations of such light-sensitive silver halide emulsion layers and couplers are, in general, the combination of a red-sensitive silver halide emulsion layer with a cyan coupler, the combination of a green-sensitive silver halide emulsion layer with a magenta coupler, and the combination of a blue-sensitive silver halide emulsion layer with a yellow couplers.
  • a yellow coupler-containing emulsion layer a magenta coupler-containing emulsion layer, and then a cyan coupler-containing emulsion layer are coated in this described order from the reflected support side.
  • any of those known couplers may be used.
  • Preferred yellow couplers are a-pivaloylacetanilide-type couplers.
  • Preferred magenta couplers are 5-pyrazolone-type, more preferably 1-phenyl-5-pyrazolone-type, and further preferably 1-phenyl-3-amino-5-pyrazolone-type couplers and pyrazolotriazole-type couplers.
  • Preferred cyan couplers are phenol-type couplers.
  • any of these couplers is used to be contained in a quantity of from 0.1 to 1 mole per mole of silver halide in a silver halide emulsion layer.
  • a silver halide in the cyan coupler-containing emulsion layer that is, the emulsion layer being located farthest from the support, of these silver halide emulsion layers, contains not less than 15 mole% of silver chloride.
  • the silver chloride content is less than 15 mole%, the end of the inherent sensitivity range largely exceeds 400 nm, so that even if such an ultraviolet absorbing agent as will be hereinafter mentioned is combinedly used, lots of static marks would be produced.
  • the end of the inherent sensitivity range shifts toward the wavelength about 400 nm or shorter.
  • the color reproducibility would become worse.
  • the silver chloride content is preferably from 15 to 70 mole%, and more preferably from 15 to 50 mole%.
  • Such a silver chloride content-having silver halide relating to the invention although it may be either silver chloroiodobromide or silver chlorobromide, is particularly desirable to be silver chloroiodobromide.
  • Such silver chloride content-having silver halide particles may be made by the normal mixing method or reverse mixing method. Otherwise, any of the double-jet method, PAg control double- ject method, acid method, ammoniacal method, conversion method, core-shell emulsion method, and the like, may be used.
  • the silver halide of the silver halide emulsion layer located farthest from the support should at least have such a silver chloride content.
  • those emulsion layers closer to the support than the emulsion layer farthest from the support may be either of such a silver chloride content-having silver halide or of any other silver halides having different contents of silver chloride.
  • a nonlight-sensitive layer adjacent this emulsion layer.
  • This nonlight-sensitive layer is composed of a hydrophilic binder such as gelatin.
  • the nonlight-sensitive layer contains an ultraviolet absorbing layer.
  • the ultraviolet absorbing agent to be used in the invention shall be such that the ratio A 1 /A 2 of the spectral absorption coefficient A 1 at 350 nm to the spectral absorption coefficient A 2 at 400 nm is not less than 10 wherein the term "spectral absorption efficient" is as defined in the "Kagaku Daijiten” (the Encyclopedia of Chemistry) Vol. 2 pp. 812-813 and Vol. 8 p. 185, published by Kyoritsu Publishing Co., Ltd. in 1962.
  • This spectral absorption coefficient is the coefficient a according to the Lambert-Beer Law: where 1 0 is the intensity of incident light of the respective wavelength, and I is the intensity of light after passage through length b of the respective medium.
  • the above A 1 and A 2 are obtained in the manner that an ultraviolet absorbing agent is dissolved into a high-boiling solvent dibutyl phthalate (ratio by weight 1:1), this solution is mixed with an aqueous gelatin solution, this mixture is emulsified to be dispersed, this dispersed liquid is then coated on a transparent base so that the coating amount of the ultraviolet absorbing agent is 2mg/dm 2 and then dried, and the spectal absorbances measured to be determined.
  • a high-boiling solvent dibutyl phthalate ratio by weight 1:1
  • the light-sensitive material becomes practically unusable because of the unsatisfactory antistatic effect, resistance to light, and whiteness.
  • a 1 is not less than 0.5, and that A 2 is not more than 0.09.
  • the ratio A 1 /A 2 is not less than 10.
  • the whiteness becomes reduced.
  • the A 1 is less than 0.5, the static mark preventive effect becomes reduced, and the resistance to light of the dye image becomes insufficient.
  • the ultraviolet absorbing agent having such a light absorbing characteristic there exists various kinds, among which those preferred in respect of being less diffusible in the nonlight-sensitive layer to contain the agent, less-vaporizable, and well-soluble in a high-boiling solvent are benzotriazole-type compounds.
  • benzotriazole-type ultraviolet absorbing agents those having the above-described ultraviolet absorbing characteristic are those compounds having the formula: wherein R 1 , R 2 and R 3 each is hydrogen, a halogen, an alkyl, an aryl, an alkoxy, an aryloxy, an alkenyl, nitro or hydroxyl radical.
  • R 1 , R 2 and R 3 each is hydrogen, a halogen, an alkyl, an aryl, an alkoxy, an aryloxy, an alkenyl, nitro or hydroxyl radical.
  • alkyl, alkoxy or alkenyl groups have up to 14 carbon atoms.
  • aryl or aryloxy groups are phenyl or phenoxy.
  • any of these ultraviolet absorbing agents may be incorporated in a quantity of from 0.001 to 2 parts by weight per part by weight of the binder of the nonlight-sensitive layer.
  • the coating amount of the binder of the nonlight-sensitive layer is normally from about 1 to about 30mg/dm 2 .
  • nonlight-sensitive layer On the opposite to the support side of the nonlight-sensitive layer is desirable to be further formed another nonlight-sensitive layer consisting substantially of a binder alone.
  • this additional nonlight-sensitive layer significantly reduces the phenomenon that the surface gloss disappears with time.
  • the coating amount of the binder of the additional nonlight-sensitive layer is also from about 1 to about 30mg/dm 2 .
  • a first interlayer be provided in between the emulsion layer closest to the support and the intermediate emulsion layer and a second interlayer be provided in between the intermediate emulsion layer and the emulsion layer farthest from the support.
  • any of the above-mentioned ultraviolet absorbing agents is desirable to be contained.
  • the adding quantity of the ultraviolet absorbing agent to the second interlayer is- generally in a proportion of from 0.1 to 50 parts by weight per part by weight of the adding quantity of the same to the nonlight-sensitive layer formed on the emulsion layer farthest from the support.
  • first and second interlayers each also has a hydrophilic binder, the coating quantity of which is desirable to be from 1 to 30mg/dm 2 .
  • these nonlight-sensitive layer, the first and second interlayers may, if necessary, contain a color-mixing preventive agent such as dioctyl hydroquinone, dibutyl hydroquinone, etc., whiteness control agent as described in Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) No. 93150/1980, coating aid, and the like.
  • a color-mixing preventive agent such as dioctyl hydroquinone, dibutyl hydroquinone, etc.
  • whiteness control agent as described in Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) No. 93150/1980, coating aid, and the like.
  • Ultraviolet absorbing agent may also be added, if necessary, to the 1st interlayer.
  • the most preferred embodiment of the layer arrangements of the invention may exemplify such a multilayered arrangement, wherein, the following component layers are coated on the support in order from the support:
  • any of those arbitrarily used in ordinary silver halide photographic emulsions such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and the like, may be used.
  • the silver halide particles of the respective emulsion layers used in the present invention may be either of the coarse-grained type or of the fine-grained type, and the particle size distribution may be either wider or narrower.
  • the crystal form of these silver halide particles may be either of the normal type or of the twin type, and those silver halide particles of crystals having any arbitrary proportion of the [100] face to the [111] face may be used.
  • these silver halide particles may be either of the structure homogeneous from the internal to the external thereof or of the structure heterogeneously stratified by the internal and the external.
  • these silver halides may be either of the type of forming a latent image principally on the surface of the particles thereof or of the type of forming the same inside the particles thereof.
  • silver halide particles may be prepared by any of those known methods which are commonly used by those skilled in the art.
  • the respective silver halide emulsions used in the light-sensitive material of the present invention although desirable to be free of soluble salts, may be used in the form of remaining undesalted.
  • the silver halide emulsion used in this invention may be a mixture of not less than two separately prepared different emulsions.
  • binder for use in the silver halide emulsion layer or in the nonlight-sensitive layer those conventionally known may be used, and those suitably usable include gelatin, gelatin derivatives such as, e.g., phenylcarbamylated gelatin, acylated gelatin, phthalated gelatin, and the like. These binder materials may be used, if necessary, in the form of a compatible mixture of not less than two kinds.
  • the silver halide photographic emulsion prepared by dispersing silver halide particles into a binder liquid may be sensitized by a chemical sensitizer.
  • chemical sensitizers advantageously usable together in the present invention are broadly classified into 4: noble-metallic sensitizers, sulfur sensitizers, selenium sensitizers and reduction sensitizers.
  • the noble-metallic sensitizers include gold compounds and those compounds of ruthenium, rhodium, palladium, iridium, platinum, and the like.
  • ammonium thiocyanate or sodium thiocyanate may be further used together.
  • the sulfur sensitizers include sulfur-compounds in addition to active gelatin.
  • the selenium sensitizers include active and inert selenium compounds.
  • the reduction sensitizers include stannous salts, polyamines, bisalkylammoniumsulfide, silane compounds, iminoaminomethanesulfinic acid, hydrazinium salts, and hydrazine derivatives.
  • an ultraviolet absorbing agent into the nonlight-sensitive layer may be made by any conventionally known method which is such that, in general, an ultraviolet absorbing agent is dissolved into a high-boiling organic solvent whose B.P. is not less than about 175°C or, if necessary, into a mixture thereof with a low-boiling solvent, and the solution is then, using a surface active agent, finely dispersed into a hydrophilic binder such as an aqueous gelatin solution, and the resulting dispersed liquid is subsequently added to the hydrophilic colloidal layer.
  • a hydrophilic binder such as an aqueous gelatin solution
  • examples of such high-boiling organic solvents are organic acid amides, carbamates, esters, ketones, urea derivatives, and the like, the esters including particularly phthalic acid esters such as, e.g., dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, di-n-octyl phthalate, diisooctyl phthalate, diamyl phthalate, dinonyl phthalate, diisodecyl phthalate, and the like; phosphoric acid esters such as tricresyl phosphate, tryphenyl phosphate, tri-(2-ethyl-hexyl)phosphate, triisononyl phosphate, and the like; sebacic acid esters such as dioctyl sebacate, di-(2-ethyl-hexyl)sebacate, diisodecyl sebacate, and
  • an ultraviolet absorbing agent is dissolved into any of these high-boiling solvents or, if necessary, into a mixture thereof with any of low-boiling solvents including methyl acetate, ethyl acetate, propyl acetate, butyl acetate, butyl propionate, cyclohexanol, cyclohexanone-tetrahydrofuran, methyl alcohol, ethyl alcohol, acetonitrile, dimethylformamide, dioxane, methyl-ethyl ketone, methyl-isobutyl ketone, diethylene-glycol monoacetate, acetyl-acetone, nitromethane, nitroethane, carbon tetrachloride, chloroform (these low-boiling solvents may be used singly or in a mixture).
  • the obtained solution is then mixed with an aqueous hydrophilic binder solution such as an aqueous gelatin solution containing an anionic surface active agent such as alkylbenzenesulfonic acid or alkylnaphthalenesulfonic acid, and/or a nonionic surface active agent such as a sorbitansesquioleic acid ester or sorbitanmonolauric acid ester, and the resulting mixture is subsequently emulsifiedly dispersed by means of a high-speed mixer, colloid mill or ultrasonic disperser. The thus produced dispersed liquid is subsequently added to a hydrophilic colloidal material.
  • an aqueous hydrophilic binder solution such as an aqueous gelatin solution containing an anionic surface active agent such as alkylbenzenesulfonic acid or alkylnaphthalenesulfonic acid, and/or a nonionic surface active agent such as a sorbitansesquioleic acid ester or sorbit
  • aqueous alkaline solution dispersion method solid dispersion method
  • latex dispersion method oil-in-water-type emulsification dispersion method
  • the latex dispersion method and the oil-in-water-type emulsification dispersion method are useful. These dispersion methods have been well known, and the latex dispersion method and the effect thereof are as described in JP-A-74538/1974, 59943/1976 and 32552/1979, and Research Disclosure No. 14850, Aug. 1976, pp. 77-79.
  • Those latexes useful in the latex dispersion method include homopolymers, copolymers and terpolymers of such monomers as, for example, styrene, ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-(methacryloyloxy)ethyl-trimethylammonium methosulfate, sodium 3-(methacroyloxy)-propane-1 -sulfate, N-isopropyl-acrylamide, N-[2-(2-methyl-4-oxo- pentyl)]acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, and the like.
  • those conventionally known methods for dispersing hydrophobic additives such as couplers are applicable which are such that the above-mentioned nondiffusible coupler is dissolved into a high-boiling solvent such as N-n-butylacetanilide, diethyllauramide, dibutyl phthalate, tricresyl phosphate, N-dodecylpyrolidone, and the like, and the solution is then finely dispersed into a hydrophilic colloid such as gelatin.
  • a high-boiling solvent such as N-n-butylacetanilide, diethyllauramide, dibutyl phthalate, tricresyl phosphate, N-dodecylpyrolidone, and the like
  • To the light-sensitive material of the present invention may be further added in addition to the above-described additives a stabilizer, development accelerator, hardening agent, surface active agent, antistain agent, lubricating agent, brightening agent, DIR material, or various other additives useful for photographic light-sensitive materials.
  • the light-sensitive material of the present invention may be arbitrarily provided with the foregoing interlayers, a protective layer, a backing layer, and the like, besides the above-described silver halide emulsion layers and the nonlight-sensitive layer.
  • those conventionally known materials such as plastic-laminated paper, baryta paper, synthetic paper or the like, may be appropriately selected according to uses, and these support materials are generally subjected to various treatments for increasing the adhesion of the photographic emulsion layer thereto.
  • the light-sensitive material of the present invention after being exposed to light through a negative material having an image composed of coupling products, is subjected to a color development.
  • the color development is carried out in the ordinary color development process.
  • the exposed light-sensitive material is first processed in a color developing agent-containing color developer solution, or alternatively, a color developing agent or the precursor thereof is in advance incorporated in a light-sensitive material, and the material is exposed and then processed in a so-called activator liquid.
  • the material generally, is bleached and fixed in the usual way.
  • the color development by use of a color developer or activator liquid, the bleaching and the fixing may be carried out independently in the separate baths provided therefor, but instead can also be carried out at a time in a monobath having the functions of these processes; for example, the processing method which uses a monobath comprising a color developer or an activator liquid containing both a bleaching agent and a fixing agent which will be hereinafter mentioned or the processing method which, after color development, uses a bleach-fixing bath containing both a bleaching agent and a fixmg agent.
  • the color development process using a color developer or activator liquid may be followed by an acid stop bath processing before the bleach-fixing process.
  • an acid stop bath there may be used an aqueous solution of acetic acid, citric acid, or the like.
  • processes as a prehardening process, a process for the neutralization thereof, washing process, stabilization process, and the like.
  • the color developing agent for use in the development of the light-sensitive material of this invention is typified by aromatic primary amine color developing agents which include aminophenol-type compounds and P-phenylenediamine-type derivatives. These compounds may be used in the free form or in the form of organic acid salts such as hydrochlorides, sulfates, P-toluenesulfonates, tetraphenyl borates, P-(t-octyl)benzenesulfonates, or the like.
  • aromatic primary amine color developing agents are O-aminophenol, P-aminophenol, 5-amino-2-oxytoluene, 2-amino-3-oxytoluene, 2-oxy-3-amino-1,4-dimethylbenzene, N,N-diethyl-P-phenylenediamine hydrochloride, N-methyl-P-phenylenediamine hydrochloride, N,N-dimethyl-P-phenylenediamine hydrochloride, N-ethyl-N-ß-methanesulfonaminoethyl-3-methyl-4-aminoaniline and the hydrochloride thereof, N-ethyl-N-ß-hydroxyethylaminoaniline, N,N-diethyl-3-(B-methanesulfonamidoethyl)-4-aminoaniline hydrochloride, 4-amino-N-(2-methoxyethyl)-N-e
  • a color developing agent precursor may be contained in the light-sensitive material of this invention.
  • the color developing agent precursor is a compound capable of producing a color developing agent under an alkaline condition, examples of which precursor are Schiff's base-type precursors with aromatic aldehyde derivatives, multivalent metallic ion complex precursors, phthalic acid imide derivative precursors, phosphoric acid imide derivative precursors, sugaramine-reactant precursors, or urethane-type precursors.
  • aromatic primary amine color developing agent precursors are as described in, e.g., U.S. Patent Nos. 3,342,599, 2,507,114, 2,695,234 and 3,719,492, British Patent No. 803,783, JP-A-135628/1978 and 79035/1979, and Research Disclosure Nos. 15159, 12146 and 13924.
  • any of these aromatic primary amine color devolping agents is contained normally in a quantity of from 1 to 20 g/liter in a color developer solution. And when contained in the precursor form in the light-sensitive material, the precursor is contained normally in a quantity of from 0.5 to 3 moles per mole of silver halide.
  • the color developer or activator solution for use in the development of the light-sensitive material of this invention contains an alkaline agent such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate or potassium tertiary phosphate; a sulfite such as sodium sulfite or potassium sulfite; a bromide such as sodium bromide, potassium bromide or ammonium bromide.
  • an alkaline agent such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate or potassium tertiary phosphate
  • a sulfite such as sodium sulfite or potassium sulfite
  • a bromide such as sodium bromide, potassium bromide or ammonium bromide.
  • a known development restrainer other than the above a thiocyanate such as sodium thiocyanate, potassium thiocyanate or ammonium thiocyanate; a chloride such as ammonium chloride, potassium chloride or sodium chloride; an organic solvent such as ethylene glycol, diethylene glycol, methanol, ethanol, n-butanol, benzyl alcohol, acetone or dimethylformamide; an amine such as hydroxylamine, ethanolamine, ethylenediamine or diethanolamine; a water softener such as sodium hexametaphosphate, sodium tripolyphosphate, ethylenediaminetetraacetate or diethylenetriamine pentaacetate; water-soluble brightening agent.
  • a thiocyanate such as sodium thiocyanate, potassium thiocyanate or ammonium thiocyanate
  • a chloride such as ammonium chloride, potassium chloride or sodium chloride
  • an organic solvent such as ethylene glycol, diethylene
  • the color developer or activator liquid used in the present invention may also contain an auxiliary developing agent.
  • auxiliary developing agents are 1-aryl-3-pyrazolidone derivatives, and may be used in a quantity of from 1 mg to 1 g, and preferably from 10 mg to 500 mg per liter of the color developer liquid or activator liquid.
  • Typical auxiliary developing agents include 1-phenyl-3-pyrazolidone, 4-methyl-1-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-3-pyrazolidone, 4-methyt-4-hydroxymethyt-1-phenyt-3-pyrazolidone, 4-methyl-4-hydroxymethyl-1-(P-tolyl)-3-pyrazolidone, and the like.
  • the color developer or activator solution used in the present invention is maintained alkaline in the usual way, and the hydrogen ion concentration of the solution, although arbitrarily selectable according to the kind, composition, purpose and uses of the negative material of the print-making light-sensitive material used in the invention, is generally from pH 9.5 to pH 13.5.
  • the color developer or activator solution used in the present invention is used generally within a certain temperature range.
  • the temperature range although arbitrarily selectable according to the kind, composition, uses and purposes of the print-making light-sensitive material of the invention, is preferably from 15°C to 70°C, and more preferably from 30°C to 50°C.
  • the bleaching agent for use in the bleaching or bleach-fixing bath may be a known compound including aminopolycarboxylic acid ferric complex salts such as, e.g., ferric-sodium ethylenediamine tetraacetate, ferric-ammonium ethylenediamine tetraacetate, and the like; and persulfates such as, e.g., ammonium persulfate, sodium persulfate, and the like.
  • aminopolycarboxylic acid ferric complex salts such as, e.g., ferric-sodium ethylenediamine tetraacetate, ferric-ammonium ethylenediamine tetraacetate, and the like
  • persulfates such as, e.g., ammonium persulfate, sodium persulfate, and the like.
  • the fixing agent for use in the bleach-fixing bath may be known compound including thiosulfates such as, e.g., sodium thiosulfate, ammonium thiosutfate, etc.; water-soluble sulfur-containing diols such as 3,6-dithia-1,8-octanediol, 3,6,9,12-tetrathia-1,14-tetradecanediol, etc.; water-soluble sulfur-containing dibasic acids such as ethylene-bis-thioglycolic acid, sodium ethylene-bis-thioglycolate, etc.; and the like.
  • thiosulfates such as, e.g., sodium thiosulfate, ammonium thiosutfate, etc.
  • water-soluble sulfur-containing diols such as 3,6-dithia-1,8-octanediol, 3,6,9,12-tetrathia-1,14-
  • the present invention enables not only to remarkably reduce possible occurrence of static marks on the light-sensitive material during the coating and drying of the component layers thereof or during the transport thereof through the inside of a photographic printer but also to increase the whiteness of the finished print as well as to form a very satisfactorily light-resistant dye image from the respective couplers contained in the light-sensitive material.
  • the following first to 6th layers were coated and dried on a polyethylene-coated paper support.
  • a second interlayer prepared by dispersing into gelatin 2,5-di-tert-octylhydroquinone and an ultraviolet absorbing agent uv-4 (4 mg.dm 2 ).
  • a protective layer composed of a gelatin layer or prepared by emulsifiedly dispersing into gelatin an ultraviolet absorbing agent uv-4, uv-7 or a comparative uv' having the formula:
  • the ultraviolet absorbing agents uv-4, uv-7 and uv' each was compatibly dissolved in dibutyl phthalate in the proportion of 1:1, and the solution was emulsifiedly dispersed into an aqueous gelatin solution.
  • the resulting dispersed liquid was then coated and dried on a transparent base support so that the coating amount of the agent is 2 mg/dm 2 , and the thus obtained sample was measured for the spectral absorbance A 1 in 350 nm and the spectral absorbance A 2 in 400 nm.
  • Table 1 The obtained results are as shown in Table 1.
  • the pieces cut from the respective samples were allowed to stand in the piled-up condition for about 24 hours in a room air-conditioned at 25°C and a relative humidity of 10%. After that, the pieces were separated, peeling apart by hand, into one by one, and each of the sample pieces was developed in the following processes:
  • composition of color developer liquid is a composition of color developer liquid
  • composition of bleach-fixing bath
  • each of the samples remaining unexposed was processed in the same manner as the above and measured for the spectral reflective density at 410 nm by means of a spectral color analyzer to thereby evaluate the whiteness.
  • the obtained results are as shown in Table 2.
  • the first to 6th layers were coated in the same manner as in Example 1, and on the 6th layer a gelatin layer was coated as the 7th layer so that the coating amount is 10 mg/dm 2 , provided ultraviolet absorbing agents uv-3, uv-7 and uv" having the following formula were used in place of the combination of the ultraviolet absorbing agents in Example 1. And samples No. 15 to No. 28 were prepared as shown in Table 4.

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Claims (11)

1. Matériau photographique couleur photosensible comprenant un support réflecteur sur lequel sont placées plusieurs couches d'émulsion d'halogénure d'argent, la couche d'émulsion d'halogénure d'argent la plus éloignée du support ayant un halogénure d'argent ne contenant pas moins de 15 moles % de chlorure d'argent et ayant du côté opposé au côté support de celle-ci une couche non photosensible, caractérisé en ce que cette couche non photosensible contient un agent d'absorption des ultraviolets dont le coefficient d'absorption spectrale (tel que défini ici) A1 à 350 nm et dont le coefficient d'absorption spectrale A2 à 400 nm sont dans un rapport A1/A2 non inférieur à 10.
2. Matériau photographique couleur photosensible suivant la revendication 1, caractérisé en ce que cette couche non photosensible comprend un liant hydrophile.
3. Matériau photographique couleur photosensible suivant la revendication 1 ou 2, caractérisé en ce que A1 n'est pas inférieur à 0,5, A2 n'est pas supérieur à 0,09, et A1/A2 n'est pas inférieur à 10.
4. Matériau photographique couleur photosensible suivant l'une quelconque des revendications précédentes, caractérisé en ce que cet agent d'absorption des ultraviolets est un composé du type benzotriazole.
5. Matériau photographique couleur photosensible suivant la revendication 4, caractérisé en ce que ce composé du type benzotriazole répond à la formule:
Figure imgb0036
dans laquelle R1, R2 et R3 sont chacun l'hydrogène, un halogène, un groupe alkyle, aryle, alcoxy, aryloxy, alcényle, nitro ou hydroxyle.
6. Matériau photographique couleur photosensible suivant la revendication 5, caractérisé en ce que ce groupe alkyle, alcoxy ou alcényle a jusqu'à 14 atomes de carbone.
7. Matériau photographique couleur photosensible suivant la revendication 5, caractérisé en ce que ce groupe aryle ou aryloxy est un groupe phényle ou phénoxy.
8. Matériau photographique couleur photosensible suivant la revendication 5, caractérisé en ce que la quantité de cet agent d'absorption des ultraviolets est de 0,001 à 2 parties en poids pour une partie en poids du liant de cette couche non photosensible.
9. Matériau photographique couleur photosensible suivant l'une quelconque des revendications précédentes, caractérisé en ce qu'une couche non photosensible ne comprenant pratiquement que du liant est prévue sur la couche non photosensible précédente.
10. Matériau photographique couleur photosensible suivant l'une quelconque des revendications précédentes, caractérisé en ce que cet halogénure d'argent est le chlorobromure d'argent ou le chloroiodobromure d'argent.
11. Matériau photographique couleur photosensible suivant l'une quelconque des revendications précédentes, caractérisé en ce qu'une seconde couche non photosensible est disposée entre cette couche d'émulsion la plus éloignée du support et la seconde couche d'émulsion la plus éloignée du support, cette seconde couche non photosensible contenant un agent d'absorption des ultraviolets dont le rapport A1/A2 n'est pas inférieur à 10.
EP19830303091 1982-06-01 1983-05-27 Matériau photographique couleur sensible à la lumière Expired EP0095920B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP93323/82 1982-06-01
JP57093323A JPS58209735A (ja) 1982-06-01 1982-06-01 カラ−写真感光材料
JP95145/82 1982-06-02
JP57095145A JPS58211148A (ja) 1982-06-02 1982-06-02 カラ−写真感光材料

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EP0095920A2 EP0095920A2 (fr) 1983-12-07
EP0095920A3 EP0095920A3 (en) 1984-04-18
EP0095920B1 true EP0095920B1 (fr) 1986-11-26

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US5731137A (en) * 1995-08-18 1998-03-24 Fuji Photo Film Co., Ltd. Emulsified dispersion and silver halide color photographic light-sensitive material containing the same

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Publication number Priority date Publication date Assignee Title
BE623419A (fr) * 1961-10-10
DE1813161A1 (de) * 1968-12-06 1970-06-25 Agfa Gevaert Ag Photographische Schichten mit einem Gehalt an ultraviolettes Licht absorbierenden Verbindungen
DE1965042A1 (de) * 1969-12-27 1971-07-15 Konishiroku Photo Ind Lichtempfindliches,farbfotographisches Aufzeichnungsmaterial
DE2036719C3 (de) * 1970-07-24 1981-10-29 Agfa-Gevaert Ag, 5090 Leverkusen Photographisches Material
JPS54119235A (en) * 1978-03-09 1979-09-17 Fuji Photo Film Co Ltd Silver halide color photographic material
IT1207929B (it) * 1979-11-09 1989-06-01 S P A 3 M Italia Composti assorbitori di u.v.ed elementi fotografici che li contengono

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EP0095920A2 (fr) 1983-12-07
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