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
  • G03C1/047—Proteins, e.g. gelatine derivatives; Hydrolysis or extraction products of proteins
• • 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
• • 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
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/95—Photosensitive materials characterised by the base or auxiliary layers rendered opaque or writable, e.g. with inert particulate additives

Definitions

• the present invention relates to a silver halide photographic light-sensitive material, more specifically a silver halide photographic light-sensitive material with excellent dryability.
• the object of the present invention is to provide a silver halide photographic light-sensitive material with improved dryability which undergoes no silver sludge formation or density reduction even when subjected to rapid processing.
• a silver halide photographic light-sensitive material comprising a support having thereon a silver halide emulsion layer and a non-light-sensitive hydrophilic colloid layer arranged at a position farther from said support than the position of said silver halide emulsion layer, wherein said non-light-sensitive layer contains a polymer latex comprising polymer particles which are formed by polymerization reaction in a medium-containing gelatin.
• a latex is used in a non-light-sensitive hydrophilic colloid layer such as a protective layer to accomplish the object Gelatin is used at the time of synthesis of latex.
• the latices which can be used for the present invention are characterized in that the plymer latex has been stably dispersed by the presence of gelatin at the surface and/or inside of the polymer particles.
• the gelatin-stabilized latex of the present invention is characterized in that at least a part of the polymerizing reaction of the latex-constituting polymer is carried out in a gelatin-containing medium.
• US Patent No. 5,026,632 discloses a method in which pressure resistance is improved by adding to the layer polymer particles which are prepared by forming a solid shell of gelatin hardened with a crosslinking agent on the surfaces of previously polymerized polymer particles having a Tg of mat more than 25°C.
• US Patent Nos. 4, 920,004 and 4,855,219 disclose a method in which adhesion is improved by using previously-polymerized polymer particles forming a covalent bond with gelatin as a matting agent. However, these particles do not offer a silver sludge preventive effect, the object of the present invention.
• US Patent No. 2,852,382 describes polymer synthesis in the presence of gelatin, but it is directed to the use for containment in a silver halide emulsion layer of color photographic light-sensitive material, offering no silver sludge preventive effect as with the present invention.
• US Patent No. 2,787,545 discloses a method of desalting a silver halide emulsion using a graft polymer of gelatin and acrylic acid, but even the use of such an emulsion does not offer a silver sludge preventive effect as with the present invention.
• Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) Nos. 121327/1984 and 115152/1987 describe the addition of latex to an upper non-light-sensitive layer or protective layer, but they do not offer an effect like the that obtained with the latex of the present invention.
• the weight ratio of gelatin and polymer, Gel/Poly, upon completion of synthesis, finished latex is preferably 1/100 to 2/1, more preferably 1/50 to 1/2.
• the effect of the present invention is enhanced when the amount of polymer component of latex is not less than 20% in weight of the gelatin in the layer to which said latex has been added.
• the amount of polymer added is preferably 0.05 to 5 g/m2, more preferably 0.1 to 2.5 g/m2.
• the latex of the present invention permits changing its MFT (minimum filming temperature) according to the monomer composition, its effect is enhanced when the MFT is not more than 60°C, more preferably not more than 50°C.
• MFT of the latex can be measured by an ordinary method such as 'Test Method of Synthetic Latex-1988' of Japanese Emulsion Industrial Standard.
• the grain size of the latex of the invention is not more than 0.3 ⁇ m. Greater grain sizes result in a reduced silver sludge preventive effect; this is attributable to a decline in packing density as a result of increase in grain size.
• the particularly preferable range of grain size is from 0.01 to.0.27.
• Examples of the polymer component of the latex added to the photographic light-sensitive material of the present invention include vinyl polymers such as acrylates, methacrylates and styrene described in US Patent Nos. 2,772,166, 3,325,286, 3,411,911, 3,311,912 and 3,525,620, Research Disclosure No. 19551 (July, 1980) and other publications.
• polymer components include compounds having a double bond, including acrylic acid or salts thereof, methacrylic acid or salts thereof, maleic acid or salts thereof, fumaric acid or salts thereof, alkyl acrylates such as methyl acrylate and ethyl acrylate, alkyl methacrylates such as methyl methacrylate and ethyl methacrylate, styrene, styrenesulfonic acid or salts thereof, N-substituted or non-substituted acrylamides, vinyl alcohols, hydroxyalkyl methacrylates and butadiene, which can be optionally selected as homopolymer or copolymer components.
• acrylic acid or salts thereof methacrylic acid or salts thereof, maleic acid or salts thereof, fumaric acid or salts thereof
• alkyl acrylates such as methyl acrylate and ethyl acrylate
• alkyl methacrylates such as methyl methacrylate and ethy
• the latex-constituting polymer and gelatin may have formed a bond.
• the polymer and gelatin may have bound directly or via a crosslinking agent.
• the latex-constituting monomer preferably has a reactive group such as a carboxyl group, amino group, amido group, epoxy group, hydroxyl group, aldehyde group, oxazoline group, ether group, ester group, methylol group, cyano group, acetyl group or unsaturated carbon bond.
• a crosslinking agent it may be one in common use for gelatin. Examples of such crosslinking agents include those based on aldehyde, glycol, triazine, epoxy, vinyl sulfone, oxazoline, methacrylic acid or acrylic acid.
• the latex of the present invention can be prepared with any combination, kind and composition, of these monomers.
• gelatin gelatin derivatives, cellulose derivatives, graft polymers of gelatin and another polymer and other hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives and synthetic hydrophilic polymer substances in the form of homo- or copolymer.
• gelatin derivatives which can be used include those prepared by reacting gelatin with various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimides, polyalkylene oxides and epoxy compounds. Specific examples are given in US Patent Nos. 2,614,928, 3,132,945, 3,186,846 and 3,312,553, British Patent Nos. 861,414, 1,033,189 and 1,005,784 and Japanese Patent Examined Publication No. 26845/1967.
• Preferable proteins are albumin and casein; preferable cellulose derivatives are hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfate; a preferable sugar derivative is sodium alginate; starch derivatives may be used in combination with gelatin.
• graft polymer of gelatin and another polymer there can be used those prepared by grafting gelatin with a homopolymer or copolymer of a vinyl monomer such as acrylic acid, methacrylic acid, ester or amide derivative thereof, acrylonitrile or styrene.
• graft polymers of gelatin with a polymer which is somewhat compatible with gelatin such as acrylic acid, acrylamide, methacrylamide or hydroxyalkyl methacrylate. Examples thereof are given in US Patent Nos. 2,763,625, 2,831,767 and 2,956,884.
• the polymer latex for the present invention should have been added to at least one non-light-sensitive hydrophilic colloid layer. It may be added to any other optionally selected layer, a number of non-light-sensitive hydrophilic colloid layers and/or silver halide emulsion layers. It is most preferable that the latex is contained in both of the silver halide emulsion layer and the non-light-sensitive layer provided on the silver halide emulsion layer. It may also be added to one face alone of the support or both faces. A known conventional latex may be added to any of the latex-containing layers and latex-free layers of the present invention. When it is added to both faces of the support, the kind and/or amount of polymer latex added may be the same or not in the two faces.
• the present invention is particularly effective when the total amount of hydrophilic binders on the support's side having the light-sensitive silver halide emulsion layer is 0.5 to 2.7 g/m2. This is because the present invention aims at prevention of silver sludge when the amount of hydrophilic colloids such as gelatin is reduced to improve the dryability of the light-sensitive material, though the latex of the invention offers an effect even when the total amount of hydrophilic binders exceeds 2.7 g/m2. More preferably, the total amount of hydrophilic binders on the support's side having the light-sensitive silver halide emulsion layer is not more than 2.5 g/m2.
• one or more antistatic layers may be formed on the backing and/or emulsion layer side of the support.
• the surface resistivity of the antistatic layer side is preferably not more than 1.0 x 1012 ⁇ , more preferably not more than 8 x 1011 ⁇ at a temperature of 25°C and a humidity of 50%.
• the antistatic layer preferably contains an electro-conductive substance such as a water-soluble electro-conductive polymer, a hydrophobic polymer particles, a reaction product of hardener or a metal oxide.
• an electro-conductive substance such as a water-soluble electro-conductive polymer, a hydrophobic polymer particles, a reaction product of hardener or a metal oxide.
• water-soluble electro-conductive polymer examples include polymers having at least one electro-conductive group, such as sulfonic acid group, sulfate group, quaternary ammonium salt group, tertiary ammonium salt group, carboxyl group and polyethylene oxide group. Of these groups, sulfonic acid group, sulfate group and quaternary ammonium salt group are preferred.
• the electro-conductive group content must be not less than 5% by weight per molecule of the water-soluble electro-conductive polymer.
• the water-soluble electro-conductive polymer contains a carboxyl group, hydroxyl group, amino group, epoxy group, aziridine group, active methylene group, sulfinic acid group, aldehyde group, vinyl sulfone group or another group, of which the carboxyl group, hydroxyl group, amino group, epoxy group, aziridine group and aldehyde group are preferred.
• the content of these groups must be not less than 5% by weight per molecule of the polymer.
• the number-average molecular weight of the water-soluble electro-conductive polymer is normally 3000 to 100000, preferably 3500 to 50000.
• Examples of substances which are preferably used as the metal oxide described above include tin oxide, indium oxide, vanadium oxide, antimony oxide, zinc oxide and those prepared by doping these metal oxides with metallic phosphorus, metallic silver or metallic indium.
• the average grain size of these metal oxides is preferably 0.01 to 1 ⁇ .
• subbing layer for the present invention examples include the subbing layers prepared using an organic solvent system containing polyhydroxybenzene, described in Japanese Patent O.P.I. Publication No. 3972/1974, and the aqueous latex subbing layers described in Japanese Patent O.P.I. Publication Nos.. 11118/1974, 104913/1977, 19941/19840, 19940/1984, 18945/1984, 112326/1976, 117617/1976, 58469/1976, 114120/1976, 121323/1976, 123139/1976, 114121/1976, 139320/1977, 65422/1977, 109923/1977, 119919/1977, 65949/1980, 128332/1982 and 19941/1984 and other publications.
• the vinylidene chloride subbing layers described in US Patent Nos. 2,698,235, 2,779,684, 425,421 and 4,645,731 and other publications may also be used.
• the subbing layer may be subjected to a chemical or physical surface treatment.
• Such treatments are performed for the purpose of surface activation, including chemical treatment, mechanical treatment, corona discharge, flaming, ultraviolet irradiation, high frequency wave treatment, glow discharge, active plasma treatment, laser treatment, mixed acid treatment and ozonization.
• the subbing layer unlike the coating layer for the present invention, is not subject to any limitation with respect to the timing or conditions of coating.
• a solid-dispersed dye in addition to ordinary water-soluble dyes, may have been added to a hydrophilic colloidal layer, which layer may be the outermost layer on the emulsion face side.
• the dye may be added to a layer below the emulsion layer and/or the backing coat side for the prevention of halation and for other purposes.
• An appropriate amount of the dye may be added also to the emulsion layer to obtain controlled irradiation. It is of course possible that a number of solid-dispersed dyes may be contained in a number of layers.
• the amount of solid-dispersed dye added is preferably 5 mg/m2 to 1 g/m2, more preferably 10 to 800 mg/m2 for each kind.
• the fine particles of solid dispersion used can be prepared by milling the dye using a dispersing machine such as a ball mill or sand mill and dispersing it together with water or a hydrophilic colloid such as gelatin and a surfactant such as sodium dodecylbenzenesulfonate, fluorinated sodium octylbenzenesulfonate, saponin or nonylphenoxypolyethylene glycol.
• a dispersing machine such as a ball mill or sand mill and dispersing it together with water or a hydrophilic colloid such as gelatin and a surfactant such as sodium dodecylbenzenesulfonate, fluorinated sodium octylbenzenesulfonate, saponin or nonylphenoxypolyethylene glycol.
• the present invention is applicable to various light-sensitive materials such as those for printing, X-ray photography, ordinary negative films, ordinary reversal films, ordinary positive films and direct positive films, a marked effect is obtained when it is applied to light-sensitive materials for printing, which are required to have very high dimensional stability.
• the developing temperature for the silver halide photographic light-sensitive material of the present invention is preferably under 50°C, more preferably around 25 to 40°C.
• the developing time is normally within 2 minutes, but rapid processing for 5 to 60 seconds may be carried out.
• a monodispersed latex having an average grain size of 0.25 ⁇ m and a Tg of about 0°C was thus obtained.
• Latices Lx-2 through Lx-5 relating to the present invention were synthesized in the same manner as with Lx-1 except that the monomer composition was changed as follows. The figures for amount are expressed in kg unit.
• a latex Lx-6 was synthesized in the same manner as with Lx-1 except that 0.25 kg of KMDS (sodium salt of dextran sulfate, produced by Meito Sangyo Co., Ltd.), in place of gelatin, was added to the system before polymerization and gelatin was not added after adding the monomer.
• KMDS sodium salt of dextran sulfate, produced by Meito Sangyo Co., Ltd.
• a solution of silver nitrate and a solution prepared by adding rhodium hexachloride complex to an aqueous solution of sodium chloride and potassium bromide to have a final concentration of 8 x 10 ⁇ 5 mol/Ag mol were simultaneously added to a gelatin solution while controlling the flow rate.
• the resulting mixture was desalted to yield a monodispersed silver chlorobromide emulsion comprising cubic crystal grains having an average grain size of 0.13 ⁇ and a silver bromide content of 1 mol%.
• This emulsion was sulfur-sensitized by an ordinary method. After adding 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene as a stabilizer, the following additives were added to yield emulsion coating liquids E-1 through E-14. Then, an emulsion protective layer coating liquid P-0, a backing layer coating solution B-0 and a backing protective layer coating liquid BP-0 were prepared with the following compositions.
• Emulsion protective layer coating liquid P-0 Emulsion protective layer coating liquid
• the emulsion coating face of a polyethylene terephthalate base of 100 ⁇ m in thickness was subbed as described in Japanese Patent O.P.I. Publication No. 19941/1984 and the opposite face was subjected to corona discharge at 10 W/(m2 ⁇ min)
• the following composition was coated using a roll fit coating pan and an air knife. Drying was carried out in a parallel stream of hot blow at 90°C for 30 minutes and subsequently at 140°C for 90 seconds with an overall coefficient of heat transfer of 25 kcal(m2 ⁇ hr ⁇ °C) . After drying, the layer had a thickness of 1 ⁇ m and a surface resistivity of 1 x 108 ⁇ at a temperature of 23°C and a humidity of 55%.
• an emulsion layer and an emulsion protective layer were double coated in this order from the support side for the emulsion face side while keeping a temperature of 35°C by a slide hopper method while adding a formalin solution as a hardener to have a formalin concentration of 30 mg per gram of gelatin.
• a backing layer and a backing protective layer were similarly coated using a slide hopper while adding a hardener, and were then set with cold air blow at 5°C.
• Each coating liquid showed satisfactory setting upon passing each set zone.
• both faces were simultaneously dried in a drying zone under the following drying conditions. After coating the backing coat side, the light-sensitive material was transported with no contact with the rollers or other devices until winding. The coating speed was 100 m/min.
• the light-sensitive material was dried with dry air blow at 30°C until the weight ratio of H2O/gelatin reached 800%, followed by drying with dry air blow at 35°C (30%) until the weight ratio decreased from 800% to 200%.
• Hot air blow was further supplied, and 30 seconds after the surface temperature reached 34°C, regarded as completion of drying at this time, the light-sensitive material was dried with air having a temperature of 48°C and a humidity of 2% for 1 minute.
• the drying time was 50 seconds from initiation of drying to obtainment of an H2O/Gel ratio of 800%, 35 seconds from 800% to 200% and 5 seconds from 200% to completion of drying.
• This light-sensitive material was wound up at a temperature of 23°C and a humidity of 40%, cut under the same conditions and then tightly packed in an airtight bag subjected to humidity conditioning under the same conditions for 3 hours, together with thick paper subjected to humidity conditioning at a temperature of 40°C and a humidity of 10% for 8 hours and then at a temperature of 23°C and a humidity of 40% for 2 hours.
• the amount of silver coated was 4.0 g/m2 and the amount of gelatin coated on the emulsion layer was 2.0 g/m2.
• Sample Nos. 1 through 27 were prepared by adding Lx-6, a conventional latex, to the emulsion layer at 1.0 g/m2 as described above, and Lx-1 through Lx-5 with the foregoing compositions to the emulsion protective layer as shown in Table 1. Also, sample No. 28 was prepared without adding the latex to the protective layer, and sample No. 29 was prepared by tripling the amount of hardener added to sample No. 28.
• a total of 500 sheet samples with a size of 610 x 508 mm were continuously processed at 5-second intervals using the Konica automatic processing machine GR-27 (developer tank capacity 40 liters), and the developer was analyzed for silver concentration. One per 5 sheet samples was totally blackened and the others were kept unexposed.
• the amount of replenisher added was 20 cc per sheet sample for both the developer and fixer.
• the drying condition immediately after discharge from the automatic developing machine was evaluated by finger touch feeling.
• the evaluation criteria were as follows.
• the maximum density provided by changing the amount of exposure is the maximum density provided by changing the amount of exposure.
• composition A Composition A
• compositions A and B were dissolved in 500 ml of water in this order, and the solution was filled to make a total quantity of 1 l.
• composition A Composition A
• the samples prepared in accordance with the present invention have improved dryability with no silver sludge deterioration or density reduction.
• Sample Nos. 30 through 34 were prepared using latices Lx-1 through Lx-5 of the present invention to add to the emulsion layer as well as the protective layer, with the same latex added to the protective and emulsion layers.
• the amount of latex added was 1 g/m2 in the protective layer and 1 g/m2 in the emulsion layer.
• the amount of gelatin added was 0.7 g/m2 in the protective layer and 0.8 g/m2 in the emulsion layer, including the gelatin in the latex.
• Sample No. 35 was prepared in the absence of latex in any layer. The obtained samples were evaluated in the same manner as in Example 1. The results are shown in Table 2.
• Latices Lx-8 through Lx-11 were synthesized under the same conditions as above using the following monomer mixture compositions 8 through 11.
• the latices thus obtained had the following values for MFT.
• a comparative latex Lx-12 was synthesized in the same manner as with Lx-7 except that 1.25 kg of gelatin was replaced with 0.75 kg of dodecylbenzenesulfonic acid.
• a dispersion GP of a graftpolymer of gelatin and styrene/butyl acrylate/methacrylic acid copolymer was prepared as directed in Examples 13 through 15 of us Patent No. 5,026,632.
• sample Nos. 36 through 42 were prepared in accordance with the method of Example 1, wherein the same latex was added to the emulsion layer and the emulsion protective layer at 0.5 g/m2.
• the amounts of gelatin added were 1.29 g/m2 and 1.1 g/m2 in the emulsion layer and the emulsion protective layer, respectively.
• Each sample was evaluated in the same manner as in Example 1, but fixers with the following compositions were used in addition to the fixer used in Example 1. The evaluation results are shown in Table 3.
• composition A Composition A
• the above compositions A and B were dissolved in 500 ml of water in this order, and the solution was filled to make a total quantity of 1 l.
• This fixer had a pH of about 4.3.
• composition A Composition A
• the above compositions A and B were dissolved in 500 ml of water in this order, and the solution was filled to make a total quantity of 1 l.
• This fixer had a pH of about 4.4.
• composition A Composition A
• the above composition A was dissolved in water to make a total quantity of 1 l.
• This fixer had a pH of about 4.7.
• Example 43 through 63 were prepared in the same manner as with the samples obtained in Example 3 except that these latices or gelatin graft polymer dispersions were used. Each sample was evaluated in the same manner as in Example 3 except that fixer No. 2 was used. The evaluation results are shown in Table 4.
• Sample Nos. 64, 65 and 66 were prepared in the same manner as with sample No. 38 in Example 3 except that the total amount of gelatin added was 3.3 g/m2, 2.7 g/m2 or 1.9 g/m2, respectively, with a constant ratio of the emulsion layer and the protective layer. Also, sample Nos. 67 through 70 were prepared in the same manner as with sample Nos. 64, 65, 38 and 66, respectively, except that Lx was not added. Each sample was tested in the same manner as in Example 4. The results are shown in Table 5.
• the latices of the present invention underwent much reduced silver sludge when compared with the case where Lx was replaced with the same amount of gelatin.
• Sample No. 71 was prepared in the same manner as in Sample No. 65 of Example 5 except that the latex was eliminated from the protective layer of the sample so that the latex was contained only in the emulsion layer.
• the sample was evaluated in the same manner as in Example 5. The results listed in Table 6 were obtained.

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Citations (5)

• 1992
  • 1992-04-22 CA CA 2066832 patent/CA2066832A1/en not_active Abandoned
  • 1992-04-23 EP EP92303643A patent/EP0510961A1/de not_active Withdrawn

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