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
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
  • G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
  • Y10S430/1055—Radiation sensitive composition or product or process of making
  • Y10S430/106—Binder containing
  • Y10S430/11—Vinyl alcohol polymer or derivative

Definitions

• a multilayered color photographic material having increased viscosity and coagulation temperature at application and having excellent permeability of treating solution at development and providing good hard film after fixing can be obtained by incorporating a styrene/maleic anhydride copolymer and/ or a condensation reaction product of said copolymer and polyvinyl alcohol in gelatin.
• the present invention relates to a multilayered color photographic material obtained according to a process in which is used an emulsion prepared by dissolving a waterinsoluble or slightly water-soluble coupler in a high boiling solvent, dispersing the solution by means of a colloid mill or the like in gelatine in the presence of a surface active agent and redispersing the resulting dispersion in a silver halide emulsion.
• the development of such a multilayered color photographic material involves not only the step for reduction of the silver halide but also the step for coupling of the coupler with an oxidation product of developing agent which is formed at the time of reduction of the silver halide, and as disclosed in British Pat.
• a film formed by use of a gelatine-silver halide emulsion containing a styrene-maleic anhydride copolymer or a condensation reaction product thereof with polyvinyl alcohol is excellent, as compared with the case of gelatine alone, in permeability for such developer components as alkali, developing agent and solvent, e.g.
• the film is successfully hardened particularly when treated with such an inorganic hardener as chromium alum or potassium alum at the hardening-fixing step, and even a film low in hardness at the development step becomes successfully applicable to a dry glazing plate, with the 3,723,127 Patented Mar. 27, 1973 result that the color development conditions can be made advantageous.
• a multilayered color photographic material in which the gelatine used has been partly substituted by the styrene-maleic anhydride copolymer in accordance with the present invention, is markedly improved in film hardness after the hardening-fixing step, even when the film hardness is relatively low at the development step, whereby an image favorable in the applicability to dryglazing plate can be obtained.
• the substitution ratio of the styrene-maleic anhydride copolymer is preferably in the range of 2% to 40%. If the ratio becomes more than 40%, there is brought about such disadvantage that the White background of the photographic material is yellowed due to deposition of the developing agent.
• the condensation ratio of the former to the latter is desirably in the range of 1:5 or less by weight. If the proportion of polyvinyl alcohol is made greater than that indicated above, there are caused such drawbacks that the condensate is lowered in compatibility with gelatine, and the hardening elfect on the film at the hardening treatment step is decreased.
• the above-mentioned condensed polymer is desirably substituted in an amount of 2 to 40% based on the amount of the gelatine. If the amount of the condensed polymer is less than 2%, the effect is low, while if the amount thereof is more than 40%, the hardening effect at the hardening step becomes excessive, whereby the film becomes brittle and tends to form cracks.
• the present invention not only display excellent features in permeability for developer components and in hardening effect at the fixing treatment, as mentioned above, but also solves various problems of the prior art in the steps for production of multilayered color photographic materials, particularly in the coating treatment of light-sensitive emulsions, as mentioned below.
• a so-called protective (oil-soluble) coupler is water-insoluble or slightly water-soluble and, in order to disperse said coupler in a gelatine-silver halide photographic emulsion, there is adopted such a process that the coupler is dissolved in a high boiling solvent, e.g. dibutyl phthalate or tricresyl phosphate, the resulting solution is dispersed by means of a colloid mill or the like in an aqueous gelatine solution in the presence of a surface active agent, and then the thus formed dispersion is redispersed in the silver halide emulsion.
• a high boiling solvent e.g. dibutyl phthalate or tricresyl phosphate
• the coupler dispersion when added to the silver halide emulsion, the gelatine is deteriorated in physical properties and the coagulation temperature of the emulsion is greatly lowered. Further, depending on the kind and amount of the oil used, the emulsion is lowered in viscosity to bring about such difliculties in the production of photographic material that the flow of the emulsion is caused at the time of the coating or the swelling of the resulting film is caused at the drying step.
• the viscosity of a photographic emulsion containing an oil soluble coupler is increased by substituting a part of the gelatine by a styrene-maleic anhydride copolymer or a condensation reaction product thereof with polyvinyl alcohol; that when the thus treated emulsion is coated on a support and then dried, the emulsion is greatly increased in viscosity and becomes difiicultly fiowable to bring about such effect that the coagulation temperature thereof has substantially been increased, and thus the emulsion can be uniformly coated on a support without increasing the thickness of the resulting film; and that the emulsion film containing the aforesaid polymer is more excellent in permeability for developer components and is more increased in photographic speed than an emulsion containing only gelatine.
• preferably 2% to 40%, more preferably to 15% of the gelatine is substituted when the styrene-maleic anhydride copolymer is used alone.
• substitution ratio increases, the viscosity-increasing effect becomes greater, but when the substitution ratio becomes more than 40%, the photographic properties of the resulting color photographic material are deteriorated, conversely.
• the condensation reaction product of styrenemaleic anhydride copolymer and polyvinyl alcohol is prepared by using each component at a purity as high as possible.
• the polymerization degree of the polyvinyl alcohol is preferably 500 to 1,000.
• the reaction conditions should be controlled depending on the blending ratio and molecular weights of the two components and the pH and temperature of the liquid.
• the blending ratio of styrene-maleic anhydride to polyvinyl alcohol is preferably from 1:05 to 1:4. If the proportion of the polyvinyl alcohol becomes great, the condensate is deteriorated in compatibility with the gelatine.
• the substitution ratio of the gelatine is preferably 2 to 40%, more preferably 5 to 15%, whereby more favorable results can be obtained.
• the amount of sum of them is also preferably 2 to 40%.
• EXAMPLE 1 1 this case, Formalin was used as a hardener in an amount of 2% based on the amount of the gelatin.
• the emulsion was charged with a stabilizer and saponin, and then coated on the layer formed in the preceding step (2) so that the amount of the coupler in the resulting layer became 0.5 g./m.
• the emulsion contained no hardener. (Magenta layer.)
• a 3% gelatin solution (incorporated with formalin in an amount of 1% based on the amount of the gelatin) was further coated so as to form a layer of about 1.5, in thickness.
• the emulsion was charged with a stabilizer and saponin and then coated on the layer formed in the preceding step (4) so that the amount of the coupler became 0.4 g./m.
• the emulsion contained no hardener. (Cyan layer.)
• a 4% gelatin solution was coated so as to form a layer of 2.0g in thickness.
• formalin was used in an amount of 2% based on the amount of the gelatin.
• a multilayered color photographic printing paper (sample A) was prepared as a control.
• Yellow layer 3% of the gelatin was substituted.
• Magenta layer 5% of the gelatin was substituted.
• Cyan layer 10% of the gelatin was substituted.
• each sample was bleached and fixed by use of a bleaching solution and a hardening-fixin solution of the compositions set forth below to remove undeveloped silver halide and reduced silver formed.
• the samples after treatments were individually passed to a dry-glazing plate-As the result, the sample A was dissolved on the surface and adhered to the dry-glazing plate.
• the sample B was low in film hardness, like the sample A, when it was in the development and bleaching steps.
• the sample B became extremely high in film hardness and, even when passed to a dry-glazing plate kept at 80 C., it did not adhere to the plate and gave a printed image excellent in applicability to the dry-glazing plate.
• Polyvinyl alcohol (polymerizationdegree 500) g 50 Styrene-maleic anhydride copolymer g 50 Water ml 700 The above-mentioned components were dissolved together at an elevated temperature, and the resulting solution was adjusted to pH 4.0 and heated with stirring at 95 C. for 5 hours. After cooling the solution to room temperature, the total amount was made 800 g. and the pH was controlled.
• Example 1 Using the thus prepared condensed polymer, the gelatin in the yellow, magenta and cyan layers of Example 1 was substituted in such proportions as set forth below.
• Yellow layer 5% of the gelatin was substituted.
• Magenta layer 3% of the gelatin was substituted.
• Cyan layer 20% of the gelatin was substituted.
• the thus obtained multilayered color photographic printing paper was low in film hardness during the color development treatment, whereby the color development conditions were made advantageous. After the hardening treatment, the printing paper became extremely high in hardness and was favorable in applicability to dry-glazing plate. Thus, the color photographic printing paper obtained in the above manner was markedly excellent from the practical standpoint.
• EXAMPLE 3 A multilayered color photographic printing paper was prepared in the same manner as in Example 1, except that the gelatine in the yellow, magenta and cyan layers was partly substituted by the polymers set forth below.
• Polyvinyl alcohol (polymerization degree 500) g 20 Polyvinyl alcohol (polymerization degree 1,000) g 10 Styrene-maleic anhydride copolymer g 20 Water ml 700
• the above-mentioned components were dissolved together at an elevated temperature, and the resulting solution was adjusted to pH 4.5 and heated with stirring at 98 C. for 4 hours. After cooling the solution to room temperature, the total amount was made 800 g.
• the thus obtained multi-layered color photographic printing paper was low in film hardness at the time of color development, but became extremely high in film hardness by the subsequent hardening treatment and gave an excellent color image favorable in applicability to dry-glazing plate.
• EXAMPLE 4 3 g. of the cyan coupler 1-hydroxy-Z-naphthoyloctylamide was dissolved in 4.5 g. of dibutyl phthalate, and the resulting solution was dispersed by means of a colloid mill in ml. of 2% gelatin in the presence of saponin. The resulting dispersion was added to a chlorobromidegelatin emulsion containing 4 g. of silver halide. The thus treated emulsion was charged according to an ordinary procedure with sensitizing dye, stabilizer and activator, and the total amount was made 590 g. to prepare a control emulsion. The gelatin concentration of the control emulsion was 2.57%.
• the two emulsions thus prepared were individually coated according to dipping method on a baryta paper having a basis weight of g. so that the amount of each emulsion coated became 80 g./m.
• the viscosities at 40 C. of the two emulsions and the coagulation temperatures thereof according to the PAGI method were as set forth in the following table:
• control emulsion flowed even though the coating was effected in cold air at 10 C., whereas the present emulsion sufficiently set at a rate of 2.5 m./min. and did not flow at all.
• an emulsion of the present invention was prepared in the same manner as above, except that 28 g. of the aforesaid dope of the condensation reaction product of styrene-maleic anhydride copolymer and polyvinyl alcohol was used to reduce the amount of gelatine.
• the two emulsions thus prepared were individually coated according to dipping method on a baryta paper having a basis weight of 210 g.
• the emulsions were so coated that the amounts of the coupler coated became identical.
• the photographic properties of the individual photographic materials were as shown in the table below, and, as is clear from the table, the emulsion of the present invention was more increased in speed.
• EXAMPLE 6 o-omoonn-Qoo CHzCONH- 10 g. of a yellow coupler of the above Formula 1 was dispersed in gelatine according to an ordinary procedure. The resulting dispersion was added to a silver iodobromide emulsion containing 10 g. of silver halide, and the total amount was made 540 g. to prepare a control emulsion.
• an emulsion of the present invention was prepared in the same manner as above, except that 8% of the gelatin in the yellow emulsion was substituted by the copolymer of Example 2.
• Control emulsion 540 4. 32 70 3. 02 Present emulsion 640 1. 89 70 1. 56
• a photographic silver halide emulsion having dispersed therein an oil-soluble coupler, said silver halide emulsion containing gelatin, the improvement in which said silver halide emulsion contains a condensation reaction product of a styrene/maleic anhydride copolymer and polyvinyl alcohol.
• polymerization degree of said polyvinyl alcohol is 500 to 1,000.
• a layer of a color photographic material which comprises a silver halide emulsion having dispersed therein an oil-soluble coupler, said silver halide emulsion containing gelatin and a condensation reaction product of styrene/maleic anhydride copolymer and polyvinyl alcohol.
• a multilayered color photographic material comprising at least one layer of a silver halide emulsion having an oil-soluble coupler dispersed therein, said silver halide emulsion containing gelatin and a condensation reaction product of styrene/maleic anhydride copolymer and polyvinyl alcohol.
• each layer comprises a silver halide emulsion having dispersed therein an oilsoluble coupler, said silver halide emulsion containing gelatin and a condensation reaction product of styrene/ maleic anhydride copolymer.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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ID=13191950

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Cited By (7)

Families Citing this family (2)

• 1969
  • 1969-08-06 JP JP44062156A patent/JPS4843135B1/ja active Pending
• 1970
  • 1970-07-30 US US00059688A patent/US3723127A/en not_active Expired - Lifetime

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