EP0504838A2 - Bilderzeugungsverfahren - Google Patents

Bilderzeugungsverfahren Download PDF

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Publication number
EP0504838A2
EP0504838A2 EP92104682A EP92104682A EP0504838A2 EP 0504838 A2 EP0504838 A2 EP 0504838A2 EP 92104682 A EP92104682 A EP 92104682A EP 92104682 A EP92104682 A EP 92104682A EP 0504838 A2 EP0504838 A2 EP 0504838A2
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EP
European Patent Office
Prior art keywords
group
wavelength
layer
silver halide
light
Prior art date
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EP92104682A
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English (en)
French (fr)
Inventor
Junichi C/O Konica Corporation Fukawa
Akira c/o Konica Corporation Kobayashi
Kenji C/O Konica Corporation Goto
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Konica Minolta Inc
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Konica Minolta Inc
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Publication of EP0504838A2 publication Critical patent/EP0504838A2/de
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    • 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
    • G03C1/067—Additives for high contrast images, other than hydrazine compounds
    • 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
    • G03C1/061—Hydrazine compounds
    • 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
    • G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion

Definitions

  • the present invention relates to a method of image formation with excellent antistatic property using a silver halide photographic light-sensitive material, more specifically a method of image formation which is suitable for electrostatic adsorption cameras and offers good reproduction for dot to dot enlargement and dot to dot curtailment.
  • plastic films are very liable to charge, and this nature often poses many limitations on their use.
  • polyethylene terephthalate is commonly used as a support for silver halide photographic light-sensitive materials, but it is liable to charge at low humidity such as in winter.
  • high-sensitivity photographic emulsions to be coated at high speed or for high-sensitivity light-sensitive materials to be exposed in automatic printer. In these situations, much weight should be placed on antistatic measures.
  • antistatic agents are usually used in light-sensitive materials.
  • fluorine-containing surfactants cationic surfactants, amphoteric surfactants, surfactants or polymeric compounds containing a polyethylene oxide group, and polymers having a sulfonic acid group or phosphoric acid group in their molecular structure.
  • this antistatic layer is usually provided on the backing coat layer side.
  • the conventional lithographic developing methods have been replaced by new developing processes which use a contrast improver such as a hydrazine compound or tetrazolium compound to ensure highly preservable, stable and very high contrast.
  • a contrast improver such as a hydrazine compound or tetrazolium compound
  • cameras such as C-880, produced by Dainippon Screen Manufacturing Co., Ltd., are effective in this situation.
  • the film backing coat layer is electrostatically adsorbed to the drum and rolled around the drum before exposure, and they, have a drawback that the film fails to be rolled around the drum (jamming) upon exposure when an antistatic layer is present on the backing coat layer side.
  • the object of the present invention is to provide a method of image formation using a silver halide photographic light-sensitive material which offers excellent reproduction for dot to dot enlargement and dot to dot curtailment, makes it possible to carry out exposure free of transportation failure even with electrostatic adsorption camera, and has excellent antistatic property.
  • the object described above is accomplished by a method of forming an image,comprising the step of, providing a silver halide photographic light-sensitive material on a drum in a camera, imagewise exposing the material to light which has the wavelength of 460 to 600 nm and has not substantially the wavelength of 360 nm or less, and developing the exposed material, said material comprising a support and provided thereon, a silver halide emulsion layer containing a sensitizing dye having an absorption maximum within the wavelength range of 450 to 580 nm and provided on the surface of the support opposite to the emulsion layer, a backing coat layer comprising a hydrophilic colloid layer and having a specific resistance of from 1 ⁇ 109 to 1 ⁇ 1012 ⁇ at 25°C and 20% RH, said material containing a hydrazine derivative or tetrazolium derivative and oriented to curve to the backing coat layer side to be capable of being wound round said drum easily with the backing coat layer cantacting said drum.
  • curling of the light-sensitive material in the backing coat layer side means that the light-sensitive material curls with the backing coat layer face sunk, including curls resulting from film rolling.
  • curling can be adjusted by changing the amount of gelatin coated on each of the faces sandwiching the support; the film can be curled toward the backing coat side by increasing the amount of gelatin coated on the backing coat side relative to the amount of gelatin coated on the opposite side with respect to the support (silver halide emulsion layer side in the present invention).
  • the gelatin amount ratio (total amount of gelatin on the silver halide emulsion layer side)/(total amount of gelatin on the backing coat side), is preferably less than 1.0. More preferably, the amount of gelatin coated on the backing coat side is 2.5 to 3.5 g/m2.
  • the film can be curled toward the backing coat side by changing the amount of polymer latex or matting agent added to the film.
  • the film can be curled by keeping the film rolled with its backing coat side by a heat treatment at over 30°C while keeping the film rolled with its backing coat surface facing indide.
  • imagewise exposure with 460 to 600 nm light which is substantially free from light whose wavelength is under 360 nm can be achieved by the use of a UV-cutting optical filter or by the use of the light-sensitive material containing a UV absorbent.
  • an optical filter which does not substantially transmit light having a wavelength of not more than 360 nm, like Refilter, produced by Konica Corporation. More specifically, the transmittance of the optical filter is preferably not more than 30%, more preferably not more than 10% of light having the wavelength of not more than 360 nm.
  • the optical filter's transmittance is preferably not less than 50%, more preferably not less than 80%.
  • Examples of light sources used for the method of image formation of the present invention include halogen lamps, xenon lamps and fluorescent lamps, with the effect of the invention enhanced when using a xenon light source.
  • the hydrazine derivative for the present invention preferably has a structure represented by the following Formula H.
  • A represents an aryl group or a heterocyclic group having at least one of a sulfur atom and an oxygen atom
  • G represents a group, a sulfonyl group, a sulfoxy group, a group or a iminomethylene group
  • n represents an integer of 1 or 2
  • A1 and A2 independently represent a hydrogen atom or a substituted or unsubstituted alkylsulfonyl group or substituted or unsubstituted acyl group and at least one of them is a hydrogen group
  • R represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, a carbamoyl group, an oxycarbonyl group or -O-R3 group (R3 represents an alkyl group, an alkenyl group or a saturated heterocyclic group.
  • the compound is represented by the following Formula A or B.
  • A represents an aryl group or a heterocyclic group having at least one of a sulfur atom and an oxygen atom
  • n represents an integer of 1 or 2.
  • R1 and R2 independently represent a a hydrogen atom, an alkyl group, an alkenyl group, an alkinyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkinyloxy group, an aryloxy group or a heterocyclic oxy group; R1 and R2 may cooperate with the nitrogen atom to form a ring.
  • R1 and R2 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkinyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkinyloxy group, an aryloxy group or a heterocyclic oxy group.
  • at least one of R1 and R2 represents an alkenyl group, an alkinyl group, a saturated heterocyclic group, a hydroxy group, an alkoxy group, an alkenyloxy group, an alkinyloxy group, an aryloxy group or a heterocyclic oxy group.
  • R3 represents an alkinyl group or a saturated heterocyclic group.
  • the compound represented by Formula A or B includes those wherein at least one of the H atoms in -NHNH- has been substituted by a substituent.
  • the H atoms in -NHNH- in Formulas A and B i.e., the hydrogen atoms of hydrazine may be substituted by a substituent such as a sulfonyl group (e.g., methanesulfonyl, toluenesulfonyl), an acyl group (e.g., acetyl, trifluoroacetyl, ethoxycarbonyl) or an oxalyl group (e.g., ethoxalyl, pyruvoyl); the compounds represented by Formulas A and B include such substituted compounds.
  • a substituent such as a sulfonyl group (e.g., methanesulfonyl, toluenesulfonyl), an acyl group (e.g., acetyl, trifluoroacetyl, ethoxycarbonyl) or an oxalyl group (e.
  • R1 and R2 independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkinyl group, an aryl group, a saturated or unsaturated heterocyclic group, a hydroxy group or an alkoxy group and at least one of R1 and R2 represent an alkenyl group, an alkinyl group, a saturated heterocyclic group, a hydroxy group or an alkoxy group.
  • Typical examples of the compounds represented by Formulas A and B include Compounds H-1 through H-187 described in Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) No. 327402/1990, pp. 20-58, Compounds I-1 through I-45 described in Japanese Patent O.P.I. Publication No. 17054/1990, pp. 23-32, and the following compounds.
  • the tetrazolium compound used for the present invention is described below.
  • nucleustion-promoting compounds described on line 1 in page 68 to line 12 in page 144 of Japanese Patent Application 234203/1990 is contained in a silver halide emulsion layer and/or non-light-sensitive layer on the side of silver halide emulsion layer on the support.
  • nucleustion-promoting compounds are as follows: In addition to the above mentioned compounds, compounds I-1 - I-26 described in pp. 69 - 72 of Japanese Patent Application 234203/1990, compounds II-1 - II-29 described in pp. 73 - 78 of said Application, compounds III-1 - III-25 described in PP.
  • the tetrazolium compound can be represented by the following formula T:
  • the substituents R1, R2 and R3 for the phenyl group of the triphenyltetrazolium compound represented by Formula T are preferably hydrogen atoms or groups whose Hammett's ⁇ value ( ⁇ P), which indicates the tendency toward electron attraction, has a negative or positive sign, with preference given to those having a negative value.
  • ⁇ P Hammett's ⁇ value
  • Specific figures for Hammett's ⁇ value in phenyl substitution are given in a large number of papers, including the report by C. Hansch et al. cited in the Journal of Medical Chemistry, 20 , 304 (1977).
  • the tetrazolium compound for the present invention can easily be synthesized in accordance with the method described in Chemical Review, 55 , 335-483, for instance.
  • the tetrazolium compound for the present invention is used preferably in the content range from about 1 mg to 10g, more preferably from about 10 mg to 2 g per mol of silver halide contained in the silver halide photographic light-sensitive material of the invention.
  • tetrazolium compound for the present invention gives good results when used singly, one or more kinds thereof can be used in any ratio without deterioration of the desired properties.
  • the tetrazolium compound relating to the invention may be contained in the silver halide photographic light-sensitive material by dissolving it in an appropriate organic solvent such as methanol, ethanol or another alcohol, ether or ester and coating the solution directly on the outermost layer on the silver halide emulsion layer side of the silver halide photographic light-sensitive material by the overcoat method, for instance.
  • an appropriate organic solvent such as methanol, ethanol or another alcohol, ether or ester
  • the light-sensitive material of the present invention preferably incorporates a sensitizing dye represented by the following Formula 1, 2, 3 or 4.
  • a cyanin dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holo polar cyanine dye, a hemicyanine dye, a styryl dye and a hemioxonol dye are included.
  • Especially preferable dyes are a cyanine dye, a merocyanine dye and a dye belonging to a complex merocyanine dye.
  • any nuclel conventionally used for cyanine dyes as basic heterocyclic ring nuclei can be used.
  • heterocyclic ring nuclei having 5 to 6 members such as a pyrasoline-5-on nucleus, a thiohydantoin nucleus, a 2-thio-oxazolidine-2,4-dion nucleus, a thiazoline-2,4-dion nucleus, a rhodanine nucleus and a thiobarbituric acid nucleus can be used.
  • R1, R2 and R3 independently represent a substituted or unsubstituted alkyl group.
  • U, V, W and Y independently represent a hydrogen atom, a halogen atom, a trifluoromethyl group, a cyano group, a carboxyl group, an alkoxy group, an alkoxycarbonyl group, a hydroxyl group, an acyloxy group, a hydroxyalkyl group, a hydroxyalkoxy group or a phenyl group.
  • X ⁇ represents an acid anion.
  • m represents 1 or 2; when an intramolecular salt is formed, m is 1.
  • R1, R2, R3 and R4 independently represent a substituted or unsubstituted alkyl group (see Table 2)
  • U, V, W and Y independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkoxycarbonyl group, a carboxyl group, a hydroxyl group, a cyano group or a substituted or unsubstituted acyloxy group, and l represents 1 or 2, provided that when an intramolecular salt is formed, l is 1.
  • the anion represented by X ⁇ has the same definition as X ⁇ in Formula 1.
  • the sensitizing dyes represented by Formulas 1 through 3 for the present invention are known compounds which can easily be synthesized by known methods, including the method described in a reference cited in "The Cyanine Dyes and Related Compounds", written by F. M. Homes, published by Interscience Publishers, New York (1964).
  • Formula 4 is described below. wherein Z represents a group of atoms necessary to form an oxazole nucleus, benzoxazole nucleus or naphthoxazole nucleus.
  • R2 represents an alkoxycarbonylalkyl group, a hydroxyalkyl group, a hydroxyalkoxyalkyl group, a carbamoylalkyl group, a hydroxyphenyl group, a hydroxyalkylphenyl group, a phenyl group, an alkoxyalkyl group or the substituent (CH2) n -A or (CH2) n -O-(CH2) n -A, wherein A represents a nitrile group, an alkylsulfonyl group, a sulfonamide group, an alkylsulfonylamino group or a lower alkoxy group; n represents an integer of 1 to 4.
  • R3 and R4 whether identical or not, independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkylsulfonyl group, a sulfo group, a chlorine atom, a fluorine atom or a carboxyl group.
  • R1 preferably represents a sulfo group or a linear or a branched C1 ⁇ 4 alkyl group substituted by a carboxyl group and/or a hydroxyl group.
  • groups for R1 include a sulfoethyl group, a sulfopropyl group, a 3-sulfobutyl group, a 4-sulfobutyl group, a carboxymethyl group, a carboxyethyl group, a hydroxyethyl group and a 3-sulfo-2-hydroxypropyl group.
  • Typical examples of the compound of Formula 4 for the present invention include Compounds I-1 through I-37 described in Japanese Patent O.P.I. Publication No. 151504/1989, pp. 14-26, except for the following compounds. Typical examples are given below.
  • the compound of Formula 4 for the present invention can be synthesized in accordance with the methods of synthesis of dimethinemerocyanine described in Japanese Patent Examined Publication Nos. 549/1971, 18105/1971, 18106/1971, 18108/1971, 4085/1972 and 52574/1983 and US Patent Nos.2,839,403, 3,384,486, 3,625,698, 3,480,439 and 3,567,458.
  • Addition and dispersion of the merocyanine dyes represented by Formulas 1 through 4 for the present invention into silver halide emulsion can be achieved by known conventional methods, including the method described in Japanese Patent Examined Publication No. 44895/1974 and Japanese Patent O.P.I. Publication No. 11419/1975, wherein the dye is added in dispersion along with surfactant, the method described in Japanese Patent O.P.I. Publication Nos. 16624/1978, 102732/1978 and 102733/1978 and US Patent Nos. 3,469,987 and 3,676,147, wherein the dye is added in dispersion along with hydrophilic medium, and the method described in East German Patent No. 143,324, wherein the dye is added in solid solution.
  • the merocyanine dye may be added to the emulsion in dispersion in a water-soluble solvent, such as water, ethanol, methanol, acetone, n-propanol, fluorinated alcohol or pyridine or mixture thereof.
  • a water-soluble solvent such as water, ethanol, methanol, acetone, n-propanol, fluorinated alcohol or pyridine or mixture thereof.
  • addition may be at any time during the emulsion processing process, it is preferable to add the dye during or after chemical ripening.
  • the amount of merocyanine dye added for the present invention is such that the silver halide emulsion is spectrally sensitized, for example, 1 mg t 2 g, preferably 10 mg to 1 g per mol of silver halide.
  • the merocyanine dye for the present invention may be used in combination in any ratio with other dyes disclosed in Japanese Patent Examined Publication Nos. 4933/1968, 4936/1968, 18107/1971, 1999/1971, 11114/1972, 1762/1973, 38408/1973, 38937/1981 and 52574/1983 and US Patent Nos. 2,519,001 and 3,745,014.
  • the ionic inorganic compound is preferably an alkali metal salt or alkaline earth metal salt, such as LiCl, NaCl, KNO3, KBr or CaCl.
  • the amount of its addition is preferably 10 to 1000 mg/m2.
  • the electroconductive layer preferably comprises a metal oxide or a reaction product or a metal oxide reaction product a water-soluble electroconductive polymer, a hydrophobic latex, and or epoxy hardener.
  • the water-soluble electroconductive polymer has at least one electroconductive group selected from a sulfonic acid group, a sulfate group, a quaternary ammonium salt, a tertiary ammonium salt and a carboxyl group.
  • the electroconductive group should be present at not less than 5% by weight per polymer molecule.
  • the water-soluble electroconductive polymer may contain a hydroxyl group, an amino group, an epoxy group, an aziridine group, an active methine group, a sulfinic acid group, an aldehyde group and a vinylsulfone group.
  • the number-average molecular weight of the polymer is 3000 to 100000, preferably 3500 to 50000.
  • Mn ⁇ represents average molecular weight (average molecular weight means number-average molecular weight in the present specification) as determined by GPC and expressed as polyethylene glycol.
  • the hydrophobic polymer grains contained in the water-soluble electroconductive polymer layer comprise a latex which is substantially insoluble in water.
  • the hydrophobic polymer is obtained by polymerizing any combination of monomers selected from styrene, styrene derivatives, alkyl acrylates, alkyl methacrylates, olefin derivatives, halogenated ethylene derivatives, vinyl ester derivatives and acrylonitrile, with preference given to those containing at least 30 mol%, more preferably not less than 50 mol% of styrene derivative, alkyl acrylate or alkyl methacrylate.
  • Any epoxy hardener can be used with no limitation, as long as it has an epoxy group. It can be used in combination with one or more other hardeners such as aldehyde hardeners and vinylsulfone hardeners.
  • the epoxy compound preferably contains a hydroxyl group or ether condensation linkage.
  • epoxy equivalence is obtained by the following equation.
  • Epoxy equivalence molecular weight/number of epoxy groups in one molecule. This value can also be obtained colorimetrically by the method described in "Shin Jikken Kagaku Koza, Vol. 13 (1), Yuki Kozo", p. 58, published by Maruzen.
  • the epoxy equivalence is preferably 50 to 300, more preferably 80 to 210. Epoxy equivalence values exceeding 300 result in insufficient hardening; coatability decreases as the amount increases. Insufficient hardening tends to lead to scratches. Epoxy equivalence values under 50 offer strong hardening but result in haze and residual color deterioration; no improvement is obtained even when the amount is reducing.
  • the amount of epoxy hardener added is preferably 5 mg/m2 to 1 g/m2.
  • the epoxy hardener may be also added to any of an antistatic layer, subbing layer, emulsion layer, backing coat layer and protective layer. It is preferably added to the antistatic layer or the hydrophilic colloid layer on the antistatic layer side.
  • electroconductive layer described above which comprises a reaction product of a water-soluble electroconductive polymer, a hydrophobic latex and an epoxy hardener
  • the metal oxide for the electroconductive layer may be indium oxide, tin oxide or a metal oxide doped with antimony atom, or any combination thereof.
  • indium oxide Two types of indium oxide, namely indous oxide In2O and indic oxide In2O3 are known, but it is preferable to use indic oxide for the present invention.
  • stannous oxide SnO stannous oxide SnO2
  • stannic oxide SnO2 Two types of tin oxide, namely stannous oxide SnO and stannic oxide SnO2 are known, but it is preferable to use stannic oxide for the present invention.
  • metal oxides doped with antimony atom examples include tin oxide and iridium oxide. To dope these metal oxides with antimony, a halide, alkoxy derivative or nitrate of tin or indium and a halide or nitrate of antimony and a halide, alkoxy derivative or nitrate of antimony are mixed, oxidized and burnt. These metal compounds are easily available from metal compound manufacturers such as Nippon Yttrium Co., Ltd.
  • the doping antimony content is preferably 0.5 to 10% by weight of the weight of tin or indium.
  • These inorganic compounds are added preferably in dispersion in a hydrophilic colloid such as gelatin or in a polymeric compound such as acrylic acid or maleic acid. The amount of their addition per binder is preferably 1 to 100% by weight.
  • the film surface pH of the electroconductive layer for the present invention is preferably not more than 8.0, more preferably 3.0 to 7.5. Too low film surface pH values are undesirable from the viewpoint of film stability.
  • electroconductive layer for the present invention may be on the support side with respect to the light-sensitive layer or the opposite side or on both sides, preference is given to the opposite side.
  • the electroconductive layer is coated on a transparent support.
  • a transparent support any photographic transparent support can be used, it is preferable to use polyethylene terephthalate or cellulose triacetate as prepared to have a visible light transmittance of over 90%.
  • the silver halide emulsion for the present invention may comprise any silver halide in common use in silver halide emulsions, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide and silver chloride.
  • the silver halide emulsion for the present invention permits the use of sensitizing methods and other various techniques and additives known to those skilled in the art.
  • the silver halide photographic emulsion and backing coat layer for the present invention may contain various chemical sensitizers, toning agents, hardeners, surfactants, thickeners, plasticizers, lubricants, developing inhibitors, UV absorbents, anti-irradiation dyes, heavy metals and matting agents, by various methods. They may also contain a polymer latex.
  • supports which can be used for the silver halide photographic light-sensitive material of the present invention include cellulose acetate, cellulose nitrate, polyesters such as polyethylene terephthalate, polyolefins such as polyethylene, polystyrene, baryta paper, polyolefin-coated paper, glass and metals. These supports are undercoated as necessary.
  • the silver halide photographic light-sensitive material of the present invention can be developed by various known methods such as those in common use after exposure.
  • the black-and-white developer is an alkaline solution containing a developing agent such as hydroxybenzene, aminophenol or amino benzene, and may contain other sulfites, carbonates, bisulfites, bromides and iodides of alkali metal salts.
  • a developing agent such as hydroxybenzene, aminophenol or amino benzene
  • Polyethylene terephthalate which was subbed with styrene-containing hydrophobic latex after corona discharge at an energy level of 10W/(m2 ⁇ min), was again subjected to corona discharge at an energy level of 10W/(m2 ⁇ min).
  • an epoxy hardener (E) was added to an antistatic solution with the following composition, and after adjusting to a pH of 5.0 with sulfuric acid, it was coated using an air knife coater at a rate of 50 m/min to obtain the solution coating amount of 10 cc/m2.
  • Water-soluble electroconductive polymer P-3 60 g/l Hydrophobic polymer grains L-3 40 g/l Ammonium sulfate 0.5 g/l Polyethylene oxide compound (molecular weight 600) 6 g/l Hardener E-1 6 g/l Hardener E-6 6 g/l Water was added to make a total quantity of 1 liter. E was added while coating.
  • a polyethylene terephthalate support which was subbed with styrene-containing hydrophobic latex after corona discharge at an energy level of 10 W/(m2 ⁇ min), was again subjected to corona discharge at an energy level of 10 W/(m2 ⁇ min). Then, an antistatic solution with the following composition was coated.
  • Solution A Ossein gelatin 17 g Sodium polyisopropylene-polyethyleneoxydisuccinate in 10% aqueous solution of ethanol 5 ml Distilled water 1280 ml Solution B Silver nitrate 170 g Distilled water 410 ml Solution C Sodium chloride 45.0 g Potassium bromide 27.4 g Rhodium trichloride trihydrate 28 ⁇ g Sodium polyisopropyleneoxydisuccinate in 10% ethanol solution 3 ml Ossein gelatin 11 g Distilled water 407 ml
  • EAg value was changed from 160 mV to 120 mV using a 3 ml/l aqueous solution of sodium chloride 5 minutes after initiation of addition, and whereafter this level was maintained until completion of mixing.
  • Solutions B and C After completion of addition of Solutions B and C, the emulsion was subjected to Ostwald ripening for 10 minutes, after which it was desalted and washed with water by a conventional method. Then, 1 g of a mixture of the following compounds (Components A, B and C) and 600 ml of an aqueous solution of ossein gelatin (containing 30 g of ossein gelatin) were added and dispersed at 55°C for 30 minutes with stirring, followed by addition of water to make a total quantity of 750 ml.
  • Components A, B and C 600 ml of an aqueous solution of ossein gelatin (containing 30 g of ossein gelatin) were added and dispersed at 55°C for 30 minutes with stirring, followed by addition of water to make a total quantity of 750 ml.
  • the tetrazolium compound of Formula T was added at 700 mg per mol of silver halide as shown in Table 4, and 300 mg of sodium p-dodecylbenzenesulfonate, 2 g of styrene-maleic acid copolymer and 1.25 g/m2 of styrenebutyl acrylate-acrylic acid copolymer latex (average grain size about 0.25 ⁇ m) were added.
  • This mixture was coated on the supports 1 and 2 on the side having no electroconductive layer to obtain an Ag amount of 4.0 g/m2 and a gelatin amount of 2.0 g/m2.
  • a backing coat layer and a backing protective layer were coated to be in the amount described above of the component.
  • the surface specific resistance on the backing coat layer side was 1 ⁇ 1011 ⁇ for support 1, 4 ⁇ 1011 ⁇ for support 2 and 4 ⁇ 1012 ⁇ for support 3.
  • Exposure time was obtained so that 95% portion of the dot to dot enlargement original step wedge became 5% on the sample, and was expressed as percent value relative to 100 of the sensitivity obtained in Test No.1.
  • a 10 mm ⁇ 50 cm film sample was cut out from a 508 mm ⁇ 61 m roll after each sample was kept for 4 hours under the condition of 25°C and 20% RH, it was suspended so that its longer side was in the vertical direction, and the distance between the lowermost end of the sample and the vertical line was measured. When this distance is zero, the sample has no curling.
  • a shift to the emulsion side means emulsion side curling
  • a shift to the backing side means BC side curling.
  • emulsion side curling is represented by + and BC side curling by -.
  • a roll of film with a size of 508 mm width ⁇ 61 m length was loaded on C880F, Fine Zoom produced by Dainippon Screen Manufacturing Co., Ltd., and transportability was evaluated for a distance of 30 cm.
  • the evaluation criteria are as follows.
  • each obtained sample was charged using a rubber roller and brought into cantact with the emulsion face side charged with cigarette ash. Then, after the cigarette ash was gently brushed down, exposure was conducted using the Fine Zoom C-880F, produced by Dainippon Screen Manufacturing Co., Ltd., and a 10% dot original, under such conditions that a 90% dot area was obtained.
  • the exposed samples were processed with the following developer and fixer in an automatic developing machine.
  • Composition B Pure water (ion exchange water) 3 ml Diethylene glycol 50 g Disodium ethylenediaminetetraacetate 25 mg Acetic acid (90% aqueous solution) 0.3 ml 5-nitroindazole 110 mg 1-phenyl-3-pyrazolidone 700 mg Compositions A and B were dissolved in 500 ml of water in this order and was diluted to 1 liter for use as a developer.
  • Composition A Ammonium thiosulfate (72.5% W/V aqueous solution) 240 ml Sodium sulfite 17 g Sodium acetate trihydrate 6.5 g Boric acid 6 g Sodium citrate dihydrate 2 g Acetic acid (90% W/W aqueous solution) 13.6 ml Composition B Pure water (ion exchange water) 17 ml Sulfuric acid (50% W/W aqueous solution) 4.7 g Aluminum sulfate (8.1% Al2O3 W/W aqueous solution) 26.5 g Compositions A and B were dissolved in 500 ml of water in this order and were diluted to 1 liter for use as a fixer.
  • Composition A Ammonium thiosulfate 240 ml Sodium sulfate 17 g Sodium acetate trihydrate 6.5 g Boric acid 6.0 g Sodium citrate dihydrate 2.0 g Composition B Pure water (ion-exchange water) 17 ml Sulfuric acid (an aqueous solution with 50%w/v) 4.7 g Aluminum sulfate (an aqueous solution having 8.1 %w/v in terms of Al2O3) 26.5 g
  • the above-mentioned components A and B were dissolved into water of 500 ml to make 1 l in all to be used.
  • the pH of this fixer was adjusted to 4.8 with acetic acid.
  • An aqueous solution of silver nitrate and an aqueous solution of potassium bromide and potassium iodide were mixed by the double jet method while keeping a pAg of 7.9 under the presence of ammonia to yield a monodispersed silver iodobromide emulsion B comprising cubic grains with an average grain size of 0.2 ⁇ m (silver iodide content of 1 mol%, silver bromide content of 99 mol%).
  • an aqueous solution of silver nitrate and an aqueous solution of potassium bromide were mixed by the double jet method while keeping a pAg of 7.9 under the presence of ammonia to yield a monodispersed silver iodobromide emulsion C comprising cubic grains with an average grain size of 0.35 ⁇ m.
  • Emulsion B was subjected to sulfur sensitization with sodium thiosulfate.
  • Emulsions B and C were each spectrally sensitized by the addition of the sensitizing dye 1-4 of 6 ⁇ 10 ⁇ 4 mol and 4.5 ⁇ 10 ⁇ 4 mol, respectively, per mol of silver along with 0.4 mol% of potassium iodide per mol of silver.
  • Emulsions B and C thus treated were mixed to have a silver halide ratio of 6 to 4 by weight.
  • To the resulting emulsion was added 1200 g of the hydrazine compound [H] shown in Table 6 per mol of silver.
  • each emulsion was coated on the support so that the amount of silver coated was 3.6 g/m2 and the amount of gelatin coated was 2 g/m2. Also, a protective layer was formed thereon so that the amount of gelatin coated was 0.75 g/m2.
  • Figure 1 is a graph showing the absorption spectra of the filters for the present invention, in which the symbols F1, F2, F3 and F4 each denote a filter.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP92104682A 1991-03-19 1992-03-18 Bilderzeugungsverfahren Withdrawn EP0504838A2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP54678/91 1991-03-19
JP5467891 1991-03-19

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EP0504838A2 true EP0504838A2 (de) 1992-09-23

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0647880A1 (de) * 1993-10-06 1995-04-12 Konica Corporation Verfahren zur Behandlung von lichtempfindlichem, photographischem Silberhalogenidmaterial

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0647880A1 (de) * 1993-10-06 1995-04-12 Konica Corporation Verfahren zur Behandlung von lichtempfindlichem, photographischem Silberhalogenidmaterial
USH1608H (en) * 1993-10-06 1996-11-05 Konica Corp. Method of processing silver halide photographic light-sensitive material

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