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
  • G03C1/74—Applying photosensitive compositions to the base; Drying processes therefor
• • 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
  • G03C1/74—Applying photosensitive compositions to the base; Drying processes therefor
  • G03C2001/7451—Drying conditions
• • 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
  • G03C1/74—Applying photosensitive compositions to the base; Drying processes therefor
  • G03C2001/7481—Coating simultaneously multiple layers

Definitions

• the present invention relates to a process for producing a light-sensitive silver halide photographic material. More particularly it relates to a process for producing a light-sensitive silver halide photographic material having a superior dimensional stability during its processing.
• Gelatin is commonly much used as a binder in light-sensitive silver halide photographic materials.
• Gelatin is highly swellable and capable of gelling, and can be readily cross-linked using various hardening agents.
• gelatin is a binder having very good properties for carrying out uniform coating over a wide area when a coating solution of materials that are easily affected by high temperatures, as light-sensitive silver halides are, is coated while controlling its physical properties.
• Japanese Patent O.P.I. Publication No. 123044/1992 discloses a method in which a polymer latex is incorporated in silver halide emulsion layers. This method makes it possible to achieve a dimensional stability before and after processing at the level of no practical problem in an environment of a humidity ranging from 20% to 60%, which, however, is still at unsatisfactory level under conditions of a lower humidity, e.g., a humidity ranging from 5% to 10%RH.
• U.S. Patent No. 4,645,731 discloses a light-sensitive silver halide photographic material having a subbing layer comprised of a highly crystalline vinylidene chloride, which, however, still can not perfectly improve the dimensional stability in an environment of an ultra-low humidity.
• Japanese Patent O.P.I. Publication No. 230035/1989 also discloses a means by which the difference in dimensions before and after processing at a low humidity is lessened, employing special coating-drying conditions. This means, however, tends to enlarge the difference in the direction in which the difference in dimensions before and after processing at a high humidity is further reduced.
• an object of the present invention is to provide a process for producing a light-sensitive silver halide photographic material having a superior dimensional stability, in particular, causing less dimensional elongation after processing at a low humidity, and promising smaller variations or difference in dimensions before and after processing even when changes occur in environmental humidity.
• the above object of the present invention can be achieved by a process for producing a light-sensitive silver halide photographic material.
• the process comprises the steps of (1) coating one or more layers including at least one silver halide emulsion layer on a support, (2) drying the one or more layers, and (3) winding up the support with the dried coating layers.
• the total amount of gelatin provided on the emulsion coated side of the support is not more than 2.9 g per square meter, and the surface of the coating layers is contacted to air having an absolute humidity not higher than 0.5% or a relative humidity not lower than 5% for a time not shorter than 5 seconds at a time after completion of drying and before start of winding-up.
• the completion of drying is defined as a time of point at which the average surface temperature of coating layer has become lower by 1°C than the temperature of air for drying.
• the gelatin on the side having the silver halide emulsion layer is in an amount of from 0.5 g/m2 to 2.7 g/m2, and at least one hydrophilic colloid layer on the side having at least one light-sensitive silver halide emulsion layer, opposite to the support, contains a latex stabilized with gelatin.
• the coating solution may particularly preferably be brought into contact with the dry air having the stated condition, for a period of at least 5 seconds within 5 minutes from the time of completion of drying the coating layer.
• the completion of drying is defined by the point at which the average surface temperature of the coating solution has become lower by 1°C than the temperature of the dry air.
• the light-sensitive material according to the present invention is, after brought into contact with the dry air having the condition of the present invention and before completely wound up, handled substantially under conditions of a relative humidity of not lower than 50%.
• the condition the dry air to be contacted to the coating layer after the completion of drying thereof has in the present invention may particularly preferably be an absolute humidity of not lower than 0.5% and a relative humidity of not lower than 3%.
• the light-sensitive material may be brought into contact with at least the dry air satisfying the condition of the present invention, and a period may be present for which the light-sensitive material is brought into contact with air having a condition other than the condition of the present invention.
• the conditions as disclosed in Japanese Patent O.P.I. Publications No. 127049/1991 and No. 288843/1991 may be used in combination.
• the gelatin on the emulsion layer side of the light-sensitive material according to the present invention must be in an amount not more than 2.9 g/m2, and preferably 0.5 g/m2 to 2.9 g/m2. It may particularly preferably be in an amount of from 0.5 g/m2 to 2.7 g/m2.
• Usual latexes are in the form of aqueous dispersions making use of surface active agents.
• the latex polymerized in the presence of gelatin that can be preferably used in the present invention is one in which at least part of the polymerization reaction for the polymer is carried out in a solvent containing the gelatin.
• the polymer and gelatin that constitutes the latex may have any bond. In such an instance, the polymer and the gelatin may be directly bonded, or may be bonded through a cross-linking agent.
• the monomer constituting the latex should preferably contain a monomer having a reactive group such as a carboxyl group, an amino group, an amido group, an epoxy group, a hydroxyl group, an aldehydo group, an oxazoline group, an ether group, an ester group, a methylol group, a cyano group, an acetyl group and an unsaturated carbon bond.
• a reactive group such as a carboxyl group, an amino group, an amido group, an epoxy group, a hydroxyl group, an aldehydo group, an oxazoline group, an ether group, an ester group, a methylol group, a cyano group, an acetyl group and an unsaturated carbon bond.
• a cross-linking agent those used as usual crosslinking agents for gelatin can be used.
• cross-linking agents of an aldehyde type a glycol type, a triazine type, an epoxy type, a vinylsulfone type, an oxazoline type, a methacrylic type and an acrylic type.
• the weight ratio of the gelatin to the polymer is preferably from 1/100 to 2/1, and particularly preferably from 1/50 to 1/2.
• the present invention can be effective when the amount of the polymer component added in the latex is 20% to 200% based on the amount of the gelatin in a layer to which the latex has been added.
• the polymer may be added in an amount of from 0.05 to 5 g/m2, and particularly preferably from 0.1 to 2.5 g/m2.
• the gelatin used for stabilizing the latex of the present invention may include gelatin, gelatin derivatives and graft polymers of gelatin with other macromolecule, and other hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives homo- or copolymer synthetic hydrophobic macromolecules can also be used in combination.
• Lime-treated gelatin as well as acid treated gelatin including the acid treated gelatin as disclosed in Bull. Soc. Sic. Phot. Japan, No. 16, page 30 (1966), may also be used as the gelatin. It is also possible to use hydrolysates or enzymolysates of gelatin.
• gelatin derivatives products obtained by reacting gelatin with various compounds as exemplified by acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleimide compounds, polyalkyleneoxides and epoxy compounds can be used. Examples thereof are disclosed in U.S. Patents No. 2,614,928, No. 3,132,945, No. 3,186,846 and No. 3,312,553, British Patents No. 861,414, No. 1,033,189 and No. 1,005,784, and Japanese Patent Examined Publication No. 26845/1967.
• the proteins may include albumin and casein, the cellulose derivatives, hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfate, and the sugar derivatives, sodium alginate and starch derivatives, which may be used in combination with the gelatin.
• graft polymers of gelatin with other macromolecule it is possible to use polymers obtained by grafting on the gelatin, acrylic acid, methacrylic acid, a derivative such as an ester or amide of any of these or a homo- or copolymer of vinyl monomers such as acrylonitrile or styrene.
• polymers having a compatibility with the gelatin to a certain extent as exemplified by graft polymers with acrylic acid, acrylamide, methacrylamide or a hydroxyalkyl methacrylate are preferred. Examples of these are disclosed in U.S. Patents No. 2,763,625, No. 2,831,767 and No. 2,956,884.
• the polymer component of the latex that may be incorporated in the light-sensitive photographic material of the present invention may include hydrates of vinyl polymers such as acrylates, methacrylates or styrene, as disclosed, for example, in U.S. Patents No. 2,772,166, No. 3,325,286, No. 3,411,911, No. 3,312,912 and No. 3,525,620 and Research Disclosure No. 19519551 (September, 1980).
• any compounds having a double bond such as acrylic acid, methacrylic acid or a salt thereof, maleic acid or a salt thereof, fumaric acid or a salt thereof, alkyl acrylic acid esters such as methyl acrylate and ethyl acrylate, alkyl methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, styrene, styrene sulfonic acid or a salt thereof, N-substituted or unsubstituted acrylamide, vinyl alcohols, hydroxyalkyl methacrylates and butadiene can be selected as copolymer components.
• the latex of the present invention may be comprised of any combination (kinds, compositional ratio) of these monomers.
• the support may have at least one antistatic layer on its backing side and/or emulsion layer side.
• the surface specific resistivity on the side provided with the antistatic layer may preferably be not higher than 1.0 x 1012 ⁇ , and particularly preferably not higher than 8 x 1011 ⁇ , in an environment of 25°C and 50%RH.
• the antistatic layer may preferably be an antistatic layer containing a water-soluble conductive polymer, hydrophobic polymer particles and a reaction product of a hardening agent, or a antistatic layer containing a metal oxide.
• the water-soluble conductive polymer may include polymers having at least one conductive group selected from a sulfonic group, a sulfate group, a quaternary ammonium salt, a tertiary ammonium salt, a carboxyl group and a polyethylene oxide group. Of these groups, a sulfonic acid group, a sulfonate group and a quaternary ammonium group are preferred.
• the conductive group must be in an amount of not less than 5% by weight per mole of the water-soluble conductive polymer.
• a carboxyl group, a hydroxyl group, an amino group, an epoxy group, an aziridine group, an active methylene group, a sulfinic acid group, an aldehyde group, a vinylsulfone group or the like is contained.
• a carboxyl group, a hydroxyl group, an amino group, an epoxy group, an aziridine group or an aldehyde group may preferably be contained. Any of these groups must be contained in an amount not less than 5% by weight per mole of the polymer.
• the water-soluble conductive polymer may have a number average molecular weight of from 3,000 to 100,000, and preferably from 3,500 to 50,000.
• metal oxide tin oxide, indium oxide, vanadium oxide, antimony oxide, zinc oxide, or any of these metal oxides doped with metallic phosphorus, metallic silver or metallic indium may preferably be used. These metal oxides may preferably have an average particle diameter of from 1 ⁇ to 0.01 ⁇ .
• a subbing layer may be used in the present invention, which may include subbing layers using an organic solvent containing polyhydroxybenzenes, as disclosed in Japanese Patent O.P.I. Publication No. 3972/1974, aqueous latex type subbin layers as disclosed in Japanese Patent O.P.I. Publications No. 11118/1974, No. 104913/1977, No. 19941/1984, No. 19940/1984, No. 18945/1984, No. 112326/1976, No. 117617/1976, No. 58469/1976, No. 114120/1976, No. 121323/1976, No. 123139/1976, No. 114121/1976, No. 139320/1977, No. 65422/1977, No.
• the subbing layer may usually be subjected to chemical or physical treatment on its surface.
• the treatment may include surface activating treatment such as treatment with chemicals, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high-frequency treatment, glow discharge treatment, active-plasma treatment, laser beam treatment, mixed acid treatment and ozone oxidation treatment.
• the subbing layer is distinguished from the coating layers according to the present invention, and there are no limitations on the time at which and conditions under which the subbing layer is provided by coating.
• a solid-dispersed dye may be contained in any hydrophilic colloid layer.
• the layer to which it is added may be the outermost layer on the emulsion layer side, and, for the purpose of anti-halation, may also be a layer lower than emulsion layers and/or a layer on the backing side. It may also be added in an appropriate amount in an emulsion layer formed for the controlling of irradiation.
• plural kinds of solid-dispersed dyes may be added to plural layers.
• the solid-dispersed dye may preferably be added in an amount of from 5 mg/m2 to 1 g/m2, and particularly preferably from 10 mg/m2 to 800 mg/m2, for each kind.
• Fine particles of the solid-dispersed dye used can be obtained by pulverizing the dye by means of a dispersion machine such as a ball mill or a sand mill, followed by dispersion together with water, a hydrophilic colloid such as gelatin, or a surface active agent such as sodium dodecylbenzenesulfonate, sodium fluorinated octylbenzenesulfonate, saponin or nonylphenoxypolyethylene glycol.
• a dispersion machine such as a ball mill or a sand mill
• a hydrophilic colloid such as gelatin
• a surface active agent such as sodium dodecylbenzenesulfonate, sodium fluorinated octylbenzenesulfonate, saponin or nonylphenoxypolyethylene glycol.
• the solid-dispersed dye may include those represented by the formulas described in U.S. Patent No. 4,857,446, etc.
• those represented by Formulas I to V may preferably be used.
• the present invention can be applied to various types of light-sensitive materials for graphic arts, X-ray photography, general-purpose negatives, general-purpose reversals, general-purpose positives and direct positives, and can be particularly remarkably effective when applied to graphic arts light-sensitive materials for which a very high dimensional stability is required.
• the light-sensitive silver halide photographic material according to the present invention may preferably be developed at a temperature of 50°C or below, and particularly preferably from about 25°C to about 40°C. It is common for its photographic processing to be completed within 2 minutes. In particular, it is preferable to carry out 5 to 60 second rapid processing.
• This emulsion was subjected to sulfur sensitization by a conventional method, and 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene was added as a stabilizer. Thereafter, gelatin was added so as to be in an amount of 1.2 g/m2 when the coat amount of the emulsion was 3.5 g/m2 in terms of silver, followed by addition of additives shown below.
• An emulsion coating solution E-O was thus prepared.
• an emulsion protective layer coating solution P-O, a backing layer coating solution B-O and a backing protective layer coating solution BP-O were prepared to have the composition shown below.
• emulsion coating solution E-0 Compound (a) 1 mg/m2 NaOH (0.5N) adjusted to pH 5.6 Compound (b) 40 mg/m2 Compound (c) 30 mg/m2 Saponin (20%) 0.5 cc/m2 Sodium dodecylbenzene sulfonate 20 mg/m2 5-Methylbenzotriazole 10 mg/m2 Compound (d) 2 mg/m2 Compound (e) 10 mg/m2 Compound (f) 6 mg/m2 Latex La 1.0 g/m2 Styrene/maleic acid copolymer 90 mg/m2 (thickening agent) A 50:46:4 mixture of (A):(B):(C)
• Emulsion protective layer coating solution P-O Emulsion protective layer coating solution P-O:
• Backing layer coating solution B-O Gelatin 1.0 g/m2 Compound (j) 100 mg/m2 Compound (k) 18 mg/m2 Compound (l) 100 mg/m2 Saponin (20%) 0.6 ml/m2 Latex (m) 300 mg/m2 5-Nitroindazole 20 mg/m2 Styrene/maleic acid copolymer 45 mg/m2 (thickening agent) Glyoxal 4 mg/m2 Compound (n) 10 mg/m2 Compound (p) 10 mg/m2 5-Methylbenzotriazole 20 mg/m2
• Backing protective layer coating solution BP-O Gelatin 0.5 g/m2 Compound (g) (1%) 2 ml/m2 Spherical polymethyl methacrylate (4 ⁇ ) 25 mg/m2 Sodium chloride 70 mg/m2 Glyoxal 22 mg/m2 Compound (o) 100 mg/m2
• an emulsion layer and an emulsion protective layer as layers on the emulsion layer side were provided in this order from the side close to the support, by simultaneous multi-layer coating by a slide hopper system while maintaining the temperature at 35°C and while adding formalin as a hardening agent in an amount of 30 mg per gram of gelatin, and the material thus coated was passed through a cold-air set zone (5°C). Thereafter, to form a backing layer and a backing coating layer, the backing layer coating solution and the backing protective layer coating solution were coated also by a slide hopper system while adding a hardening agent, followed by cold-air setting (5°C).
• the coatings were satisfactorily set. Subsequently, in a drying zone, the coated material was dried simultaneously on its both sides under drying conditions shown below. After the coating on the backing layer side, the coated material was transported completely without contact with rollers and other members until it was wound up. In this instance, the coating was carried out at a speed of 150 m/min.
• the coatings were dried with 30°C air until the weight ratio of H20 to gelatin came to be 800%, and dried with 35°C and 30%RH dry air until it came to be more than 800% to 200%. Keeping them subjected to that air until they came to have a surface temperature of 34°C (regarded as "drying completed"), and 30 seconds after this time of point the coatings were further contacted for 1 minute with air under conditions shown in Table 1 later.
• drying from its initiation until the H20/gelatin ratio came to be 800% was carried out for 50 seconds; until more than 800% to 200%, for 35 seconds; and from 200% until "drying completed", for 5 seconds.
• the light-sensitive material thus obtained was wound up in an environment of 23°C and 40%RH, subsequently cut in the same environment, and then sealed in a barrier bag having been moisture-conditioned for 3 hours in the same environment, together with thick paper having been moisture-conditioned for 8 hours in an environment of 40°C and 10%RH and thereafter moisture-conditioned for 2 hours in an environment of 23°C and 40%RH.
• the light-sensitive material thus produced had a coated silver weight of 3.5 g/m2.
• the sample was cut in a size of 30 cm ⁇ 60 cm, imagewise exposed so as to form two thin lines at an interval of 56 cm using a light-room printer P-627M (manufactured by Dainippon Screen Mfg. Co., Ltd.), and then photographically processed.
• the resulting sample was used as an original.
• This original, an unexposed sample having the same size as the original, the printer and an automatic processor were moisture-conditioned for 2 hours in an environment of 23°C and 5%RH. Thereafter the original and the unexposed sample ware subjected to contact (face-to-face) exposure, and then photographically processed using the automatic processor.
• the sample having been processed was moisture-conditioned for 2 hours, and thereafter superposed on the initial original to measure any difference in configuration of the thin lines from the original ones, using a magnifier with scale.
• composition A Ammonium thiosulfate (aqueous 72.5 w/v solution) 230 ml Sodium sulfite 5.6 g Sodium acetate trihydrate 27.8 g Boric acid 9.8 g Sodium citrate dihydrate 2.0 g Acetic acid (aqueous 90% w/v solution) 6.4 ml
• Composition B Pure water (ion-exchanged water) 28 ml Sulfuric acid (aqueous 50% w/v solution) 6.7 g
• Aluminum sulfate 25.31 g (aqueous solution with a content of 8.1% w/v in terms of Al2O3)
• the composition A and the composition B were dissolved in this order in 500 ml of water, and made up to 1 liter for its use.
• This fixing solution had a pH of about 4.4.
• Example 1 Experiments were made in the same manner as in Example 1 except that the light-sensitive material as used in Example 1 was made to have a gelatin weight on the emulsion layer side as shown in Table 2. Flow rate of air for drying each sample was controlled so that the drying was carried out under the conditions corresponding to those for No. 13 in Table 1.
• Table 2 Amount of gelatin (g/m2) Difference in dimensions before and after processing Invention No. Protective layer/emulsion layer Total (a) (b) (c) 20 0.25/0.25 0.5 +10 +5 5 Yes 21 0.5/0.5 1.0 +11 +4 7 Yes 22 0.6/0.6 1.2 +9 +1 8 Yes 23 1.0/1.0 2.0 +9 ⁇ 0 9 Yes 24 1.1/1.2 2.3 +7 -5 12 Yes 25 1.2/1.3 2.5 +5 -10 15 Yes 26 1.3/1.4 2.7 +6 -14 20 Yes 27 1.4/1.5 2.9 +6 -19 25 Yes 28 1.5/1.5 3.0 -3 -27 30 No 29 1.6/1.6 3.2 -5 -40 45 No 30 2.0/2.0 4.0 -10 -45 55 No
• the difference in dimensions before and after processing is not more than ⁇ 20 ⁇ m over the range of 5 to 60%RH when the amount of gelatin is not more than 2.9 g/m2, showing good results.
• the value (c) in the difference in dimensions before and after processing is within 20 ⁇ m over the range of 5 to 60%RH when the amount of gelatin is not more than 2.7 g/m2, showing very good results.
• Lb was prepared in the manner shown below. With regard to sample No. 24 used in Example 2, La was removed and Lb was added as shown in Table 3 below to prepare samples. The dimensional stability was evaluated in the same manner as in Example 2.
• the comparison of No. 24 in Table 2 with No. 31 in Table 3 proves that the use of the latex polymerized in the presence of gelatin brings about a more improvement in the dimensional stability.
• the latex polymerized in the presence of gelatin may be added in an mount of 0.1 g/m2 at least in the emulsion layer and may also be added in a non-sensitive hydrophilic colloid layer.

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

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Citations (3)

• 1992
  • 1992-04-02 JP JP8095292A patent/JPH05281655A/ja active Pending
• 1993
  • 1993-04-02 EP EP93302626A patent/EP0564304A1/en not_active Withdrawn

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