EP0566374A2 - Matériau photographique sensible à la lumière à base d'halogénure d'argent et procédé pour l'obtention d'une image - Google Patents

Matériau photographique sensible à la lumière à base d'halogénure d'argent et procédé pour l'obtention d'une image Download PDF

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Publication number
EP0566374A2
EP0566374A2 EP93302877A EP93302877A EP0566374A2 EP 0566374 A2 EP0566374 A2 EP 0566374A2 EP 93302877 A EP93302877 A EP 93302877A EP 93302877 A EP93302877 A EP 93302877A EP 0566374 A2 EP0566374 A2 EP 0566374A2
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EP
European Patent Office
Prior art keywords
group
hydrogen atom
silver halide
formula
alkyl group
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Granted
Application number
EP93302877A
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German (de)
English (en)
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EP0566374B1 (fr
EP0566374A3 (fr
Inventor
Nobuaki Tsuji
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Konica Minolta Inc
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Konica Minolta Inc
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Publication date
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Publication of EP0566374A3 publication Critical patent/EP0566374A3/fr
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Publication of EP0566374B1 publication Critical patent/EP0566374B1/fr
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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
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/85—Photosensitive materials characterised by the base or auxiliary layers characterised by antistatic additives or coatings
    • G03C1/89—Macromolecular substances therefor

Definitions

  • the present invention relates to a silver halide photographic light-sensitive material and an image forming method, more specifically a silver halide photographic light-sensitive material excellent in antistatic property and development uniformity in processing using an automatic processing machine, and a rapid image forming method thereof.
  • the object of the present invention is to provide a silver halide photographic light-sensitive material excellent in antistatic property and development evenness in processing using an automatic processing machine, and a rapid image forming method thereof.
  • the object of the present invention has been accomplished by:
  • the present inventors found that uneven development occurred in a photographic light-sensitive material containing a nonionic surfactant can be reduced significantly by incorporating at least one kind of the hydrophilic polymerofformula I or oft he hydrophilic polymer comprising a repeating unit represented by formula II into the hydrophylic colloidal layer on the silver halide emulsion layer side.
  • the inventors also found that the effect of the containment of the above compound increases as the degree of surface matting on the silver halide emulsion layer side decreases (not higher than 50 mmHg).
  • the inventors also found that the effect of the containment of the above compounds increases as the total processing time decreases (not longer than 50 seconds).
  • R 1 represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, an alkenyl group or an aryl groups
  • A represents an -O- group, an -S- group, a -COO- group, an -N-R 10 group, a -CO-N-R 10 group or an -S0 2 N-R group
  • R 10 represents a hydrogen atom or a substituted or unsubstituted alkyl group).
  • Water-soluble polymers represented by formula I used for the present invention are described below.
  • the number-average molecular weight (M n ) of the water-soluble polymer ranges normally from 500 to 5,000,000, preferably 1,000 to 500,000.
  • Water-soluble polymers of the present invention comprising at least one kind of a repeat unit represented by formula II, are described below.
  • R 1 through R 6 independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms or -SO 3 X, where X represents a hydrogen atom, an atom of alkali metal, an atom of alkaline earth metal, an ammonium group or an organic ammonium group, and at least one of R 1 through R 6 is -SO 3 X.
  • a compound having a repeat unit of the above formula II, used for the present invention can be obtained by sulfonating and then polymerizing a diene monomer or by polymerizing a diene monomer and then sulfonating.
  • the content of the repeat unit represented by formula II is not less than 10 mol%, preferably not less than 20 mol%.
  • diene monomers used for the present invention include 1,3-butadiene, 1,2-butadiene, 1,2-pentadiene, 1,3-pentadiene, 2,3-pentadiene, isoprene, 1,2-hexadiene, 1,3-hexadiene, 1,4-hexadiene, 1,5-hexadiene, 2,3-hexadiene, 2,4-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,2-heptadiene, 1,3-heptadiene, 1,4-heptadiene, 1,5-heptadiene, 1,6-heptadiene, 2,3-heptadiene, 2,5-heptadiene, 3,4- heptadiene, 3,5-heptadiene and 2-phenylbutadiene, and also various branched diene monomers.
  • diene monomers may be used singly or in combination.
  • the sulfonate can be produced by, for example, sulfonating the diene monomer as described below while retaining the double bond thereof.
  • a diene monomer can be sulfonated under conventional conditions such as those described in Jikken Kagaku Koza, edited by the Chemical Society of Japan, and Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) No. 26310/1989.
  • the sulfonate thus obtained is not subject to limitation as to cationic moiety, the cation is preferably hydrogen, alkali metal, alkaline earth metal, ammonium, amine or the like from the viewpoint of water solubility.
  • Such alkali metals include sodium and potassium.
  • Such amines include alkylamines such as methylamine, ethylamine, propylamine, dimethylamine, diethylamine, triethylamine, butylamine, dibutylamine and tributylamine, polyamines such as ethylenediamine, diethylenetriamine and triethylenetetramine, morpholine and piperidine.
  • Such alkaline earth metals include calcium and magnesium.
  • cations may be exchanged with other cations by various ion exchanging techniques.
  • a compound of the present invention having a repeat unit represented by the above formula II, may be copolymerized with other monomer copolymerizable with the diene monomer (hereinafter referred to as "other monomers") in not less than 99% by weight, preferably 1 to 98% by weight, and more preferably about 10 to 90% by weight.
  • Such other copolymerizable monomers include aromatic compounds such as styrene, u-methylstyrene, vinyltoluene and p-methylstyrene, alkyl esters of acrylic or methacrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, anhydrides of mono-or dicarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid, aliphatic conjugated dienes such as butadiene, isoprene, 2-chloro-1,3-butadiene and 1-chloro-1,3-butadiene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl methyl
  • a sulfonate of the above diene monomer and, where necessary, one or more other monomers copolymerizable therewith are subjected to radical polymerization in the presence of a solvent for polymerization such as water or an organic solvent using a radical polymerization initiator, chain transferring agent and other additives.
  • a solvent for polymerization such as water or an organic solvent using a radical polymerization initiator, chain transferring agent and other additives.
  • the sulfonated polymer thus obtained can have repeat units represented by formulas II' and/or II", as well as a repeat unit represented by formula II.
  • the unit represented by formula II' and/or II" is contained in an amount of 0 to 70 mol%, preferably 0 to 50 mol%. This content can be controlled according to polymerizing conditions.
  • R 1 through R 6 are identical to those defined in the above formula II.
  • the weight-average molecular weight (Mw) of the sulfonated polymer thus obtained varies depending on the use thereof, it is normally 500 to 5,000,000, preferably 1,000 to 500,000.
  • the sulfonated polymer of the present invention may be converted to acid forms or salts of alkali metal, alkaline earth metal, ammonium, amine, etc. by ion exchanging or neutralization.
  • the sulfonated polymer thus obtained is neutralized in an aqueous alkali solution such as aqueous sodium hydroxide, potassium hydroxide or ammonia to yield a water-soluble or hydrophilic polymer salt wherein at least some of the sulfone groups have formed salt.
  • an aqueous alkali solution such as aqueous sodium hydroxide, potassium hydroxide or ammonia
  • the sulfonate is not subject to limitation as to cation for forming a salt in the sulfone group thereof, the cation is preferably hydrogen atom, alkali metal, alkaline earth metal, ammonium, amine or the like from the viewpoint of water solubility as described above.
  • cations may be exchanged mutually with other cations by various ion exchanging techniques.
  • the degree of sulfone group neutralization can be chosen as appropriate, as long as the (co)polymer salt is soluble or dispersible in water, and sulfone groups may form different salts.
  • a (co)polymer of the present invention can be obtained from a sulfonated diene monomer, but alternatively, it can also be obtained by polymerizing and then sulfonating a diene monomer.
  • the (co)polymer may be produced by any of these methods, which are carried out by known procedures.
  • JSR water-soluble polymers from Japan Synthetic Rubber Co., Ltd.
  • the water-soluble polymer represented by formula I or formula II is contained in an amount of 5 mg to 5 g, preferably 10 mg to 2 g per m 2 of the photographic material.
  • Nonionic surfactants of the present invention represented by formula III, III' or III", are described below.
  • R 1 represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, an alkenyl group or an aryl groups
  • A represents -O-, -S-, -COO-, or -SO 2 N-R 10 , wherein R 10 represents a hydrogen atom or a substituted or unsubstituted alkyl group.
  • R 2 , R 3 , R 7 and Rg independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group, a halogen atom, an acyl group, an amide group, a sulfonamide group, a carbamoyl group or a sulfamoyl group.
  • R 6 and R 8 independently represent a substituted or unsubstituted alkyl group, an aryl group, an alkoxy group, a halogen atom, an acyl group, an amide group, a sulfonamide group, a carbamoyl group or a sulfamoyl group. With respect to formula III".
  • R 4 and R 5 independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or an aryl group.
  • R 4 and R 5 , R 6 and R 7 , and R 8 and Rg, may bind together to form a substituted or unsubstituted ring.
  • n 1 , n 2 , n 3 and n 4 independently represent the degree of polymerization of ethylene oxide, ranging from 2 to 50, and m represents the degree of polymerization, ranging from 2 to 50.
  • the above compounds can easily be synthesized by adding ethylene oxide to respective corresponding fatty acid monoethanolamides and carrying out a reaction therebetween.
  • Amizet 5C and Amizet 10C both produced by Nikko Chemical
  • other commercial products are categorized under this compound 4 and can be used in the present invention.
  • the amount of the surfactant used varies depending on the shape, kind and coating method of the photographic light-sensitive material used, it is preferable to use the surfactant in an amount of 1 to 1000 mg, particularly 5 to 200 mg per m 2 of photographic light-sensitive material.
  • the surfactant For introducing the surfactant to a layer of the photographic light-sensitive material, it is dissolved in water, an organic solvent such as methanol, ethanol or acetone, or a mixed solvent of water and an organic solvent as above, after which the solution is added to a light-sensitive emulsion layer or non-light-sensitive auxiliary layer (e.g., anti-halation layer, interlayer, protective layer) on the support, or is sprayed or coated on the surface of the support, or the photographic light-sensitive material is immersed in said solution, followed by drying.
  • a light-sensitive emulsion layer or non-light-sensitive auxiliary layer e.g., anti-halation layer, interlayer, protective layer
  • two or more kinds of nonionic and anionic surfactants may be used in combination.
  • a matting agent and/or lubricant may be added to the emulsion layer or protective layer of the silver halide photographic material of the present invention.
  • a silver halide photographic material contains a matting agent and the surface of the photographic material has a mattness of not more than 50 mmHg.
  • the term "mattness" is expressed in smoothness of the surface, which is determined under a specific condition by measuring a suction force on an unprocessed photographic material.which has been stored for three hours under 23°C and 48 %R.H. The larger the value is, the greater the mattness.
  • the measurement of the suction force is carried out using a SMOOSTER (produced by Toei Denshi Kogyo K.K.), as described later.
  • the silver halide photographic light-sensitive material of the present invention is subjected to exposure and processing by using an automatic processing machine.
  • a conventional developing solution can be used, as exemplified by that containing hydroquinone, 1-phenyl-3-pyrazolidone, N-methyl-paminophenol or p-phenylenediamine, which can be used alone or in combination thereof.
  • Adeveloping solution containing an aldehyde hardening agent can be used in the silver halide photographic light-sensitive material of the invention.
  • a conventional developing solution containing dialdehyde such as maleic dialdehyde, or glutaraldehyde, and sodium bisulfites thereof can be used.
  • an overall processing time refers to the period of time through which the photographic material of the present invention is inserted to the first roller, which constitute the inlet of an automatic processing machine, and thereafter it passes through a developing tank, a fixing tank, and a drying tank until it reaches the last roller at a drying section outlet.
  • the overall processing time is 50 seconds or less, and preferably from 20 to 50 seconds.
  • a processing time of less than 20 seconds may give rise to insufficient sensitivity, or bring about a dye residue or an image poor in uniformity.
  • the processing is carried out at a temperature of 60°C or less, and preferably from 20 to 45°C.
  • the present invention is by no means limited by these examples.
  • This emulsion comprised grains having an average grain size of 0.27 ⁇ m wherein 90% of the total number of grains fell in the grain size range of 0.1 to 0.70 ⁇ m.
  • an aqueous solution of ammoniacal AgN0 3 and an aqueous solution of potassium bromide were added by the double jet method, and a monodispersed emulsion comprising cubic AgBrl grains having an average grain size of 0.25 ⁇ and an average Agl content of 0.4 mol% was grown.
  • the coefficient of variation (a/r) was 0.17.
  • a backing-coated support was prepared as follows: First, a backing layer coating solution, comprising a dye emulsion dispersion comprising 400 g of gelatin, 2 g of polymethyl methacrylate having an average grain size of 6 ⁇ m, 24 g of KN0 3 , 6 g of sodium dodecylbenzenesulfonate and 20 g of the following anti-halation dye 1, in an amount equivalent to 2 g/m 2 , and glyoxal, was prepared.
  • a backing layer coating solution comprising a dye emulsion dispersion comprising 400 g of gelatin, 2 g of polymethyl methacrylate having an average grain size of 6 ⁇ m, 24 g of KN0 3 , 6 g of sodium dodecylbenzenesulfonate and 20 g of the following anti-halation dye 1, in an amount equivalent to 2 g/m 2 , and glyoxal, was prepared.
  • an aqueous terpolymer dispersion was prepared by diluting to a 10% by weight of a terpolymer comprising 50% by weight glycidyl methacrylate, 10% by weight methyl acrylate and 40% by weight butyl methacrylate, and this dispersion, as a subbing solution, was coated on a polyethylene terephthalate base.
  • the above backing layer coating solution along with a protective layer coating solution comprising gelatin, a matting agent, glyoxal, and sodium dodecylbenzenesulfonate, was coated, to yield a support having a backing layer.
  • the coating weight was 2.0 g/m 2 , based on the amount of gelatin applied, for each of the backing and protective layers.
  • Emulsion-side protective layer coating solution Emulsion-side protective layer coating solution
  • composition is as follows: Figures for the amount of addition are per liter of coating solution.
  • Polymethyl methacrylate grains having an average size of 4 ⁇ m were added to provide a degree of matting shown in Table 1.
  • the silver halide emulsion layer coating solution and protective layer coating solution were simultaneously coated in this sequence from the support by the slide hopper method at a coating speed of 80 m/min, to yield a red-sensitive photographic sample.
  • the coating weight of silver was 2.5 g/m 2
  • the coating weight of gelatin was 2.2 g/m 2 for the emulsion layer and 1.2 g/m 2 for the protective layer.
  • the resulting reaction mixture was desalinized using an aqueous solution of Demol-Na (produced by Kao Atlas) and an aqueous solution of magnesium sulfate, after which it was re-dispersed in an aqueous gelatin solution, to yield a seed emulsion comprising spherical grains having an average grain size of 0.23 f..lm and a coefficient of variation of 0.28.
  • Demol-Na produced by Kao Atlas
  • grains were grown as follows: To an aqueous solution containing ossein gelatin and disodium salt of propyleneoxy-polyethyleneoxy disuccinate being stirred vigorously at 75°C, an aqueous solution of potassium bromide and potassium iodide and an aqueous solution of silver nitrate were added by the double jet method, while maintaining a pH of 5.8 and a pAg of 9.0. Aftercompletion of the addition, pH was adjusted to 6.0, and 400 mg/mol AgX of an anhydride of sodium salt of 5,5'-dichloro-9-ethyl-3,3'-di-(3-sulfopropyl )oxacarbocyanine was added.
  • This mixture was further desalinized at 40°C, using an aqueous solution of Demol-Na (produced by Kao Atlas) and an aqueous solution of magnesium sulfate, after which it was re-dispersed in an aqueous gelatin solution.
  • the additives used in the protective layer on the emulsion surface side are as follows: The amount of addition are per liter of coating solution.
  • a 175 ⁇ m polyethylene terephthalate film base coated with an aqueous dispersion of a terpolymer comprising 50% by weight glycidyl methacrylate, 10% by weight methyl acrylate and 40% by weight butyl methacrylate, diluted to a concentration of 10% by weight, was coated with an emulsion layer and protective layer on one face and with upper and lower backing layers on the opposite face simultaneously at a coating speed of 90 m/min and dried in 2 minutes and 15 seconds, to yield green-sensitive sample Nos. 15, 16 and 44, wherein the coating weight of silver was 2.9 g/m 2 for the emulsion layer and that of gelatin was 1.1 g/m2 for the protective layer.
  • compositions of the backing layer solutions are given below.
  • a water-soluble polymer was added as shown in Table 1.
  • Backing layer coating solution compositions are given below.
  • Two backing layers i.e., the upper and lower backing layers, were coated, in a coating weight of gelatin of 1.2 g/m 2 for the upper layer and 3.0 g/m 2 for the lower layer.
  • the backing layer coating solutions were prepared as follows:
  • the mattness is evaluated with the aid of SMOOSTER(produced by Toei Denshi Kogyo K.K.).
  • SMOOSTER produced by Toei Denshi Kogyo K.K.
  • an inflow rate of air variable depending upon smoothness of the surface is measured as a change of pressure.
  • the mattness is defined as a pressure value expressed in mmHg. The larger is the value, the greater the mattness.
  • Sample Nos. 1 through 45 were subjected to uniform exposure to tungsten light to a density of 1.1 ⁇ 0.1 and then subjected to the following developing and other processes, after which they were macroscopically evaluated for uneven development. The results are given in Table 2.
  • Developing was achieved using the following developers and fixer, using the automatic processing machine SRX-501 (produced by Konica Corporation) at a developing temperature of 35°C and a fixing temperature of 33°C. Washing water at 18°C was supplied at a flow rate of 3.5 I per minute. Drying temperature was 45°C. The whole processing was performed over a period of time of 45 seconds in total, as shown in Table 1,

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
EP19930302877 1992-04-15 1993-04-14 Matériau photographique sensible à la lumière à base d'halogénure d'argent et procédé pour l'obtention d'une image Expired - Lifetime EP0566374B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP95539/92 1992-04-15
JP9553992 1992-04-15
JP9553992A JPH05289243A (ja) 1992-04-15 1992-04-15 ハロゲン化銀写真感光材料及び画像形成方法

Publications (3)

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EP0566374A2 true EP0566374A2 (fr) 1993-10-20
EP0566374A3 EP0566374A3 (fr) 1994-10-26
EP0566374B1 EP0566374B1 (fr) 1999-12-08

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EP19930302877 Expired - Lifetime EP0566374B1 (fr) 1992-04-15 1993-04-14 Matériau photographique sensible à la lumière à base d'halogénure d'argent et procédé pour l'obtention d'une image

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EP (1) EP0566374B1 (fr)
JP (1) JPH05289243A (fr)
DE (1) DE69327190T2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1227366A1 (fr) * 2001-01-24 2002-07-31 Eastman Kodak Company Compositions de développement noir-et-blanc et procédé pour leur utilisation

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3436622A1 (de) * 1983-10-07 1985-04-25 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Photographisches silberhalogenidmaterial
EP0242853A2 (fr) * 1986-04-21 1987-10-28 Konica Corporation Matériau photographique à l'halogénure d'argent à propriétés antistatiques
EP0267019A2 (fr) * 1986-11-04 1988-05-11 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière capable d'un traitement ultrarapide
EP0398223A2 (fr) * 1989-05-16 1990-11-22 Konica Corporation Couche anti-statique
EP0409665A1 (fr) * 1989-07-21 1991-01-23 Konica Corporation Matériel photographique à halogénure d'argent avec revêtement antistatique
EP0410820A2 (fr) * 1989-07-28 1991-01-30 Konica Corporation Matériel photographique à l'halogénure d'argent

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3436622A1 (de) * 1983-10-07 1985-04-25 Fuji Photo Film Co., Ltd., Minami-Ashigara, Kanagawa Photographisches silberhalogenidmaterial
EP0242853A2 (fr) * 1986-04-21 1987-10-28 Konica Corporation Matériau photographique à l'halogénure d'argent à propriétés antistatiques
EP0267019A2 (fr) * 1986-11-04 1988-05-11 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière capable d'un traitement ultrarapide
EP0398223A2 (fr) * 1989-05-16 1990-11-22 Konica Corporation Couche anti-statique
EP0409665A1 (fr) * 1989-07-21 1991-01-23 Konica Corporation Matériel photographique à halogénure d'argent avec revêtement antistatique
EP0410820A2 (fr) * 1989-07-28 1991-01-30 Konica Corporation Matériel photographique à l'halogénure d'argent

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1227366A1 (fr) * 2001-01-24 2002-07-31 Eastman Kodak Company Compositions de développement noir-et-blanc et procédé pour leur utilisation
US6602655B2 (en) 2001-01-24 2003-08-05 Eastman Kodak Company Black-and-white developing compositions and methods of use

Also Published As

Publication number Publication date
EP0566374B1 (fr) 1999-12-08
EP0566374A3 (fr) 1994-10-26
DE69327190T2 (de) 2000-05-11
JPH05289243A (ja) 1993-11-05
DE69327190D1 (de) 2000-01-13

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