EP0388908A1 - A silver halide light-sensitive photographic material - Google Patents
A silver halide light-sensitive photographic material Download PDFInfo
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- EP0388908A1 EP0388908A1 EP90105288A EP90105288A EP0388908A1 EP 0388908 A1 EP0388908 A1 EP 0388908A1 EP 90105288 A EP90105288 A EP 90105288A EP 90105288 A EP90105288 A EP 90105288A EP 0388908 A1 EP0388908 A1 EP 0388908A1
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- Prior art keywords
- photographic material
- silver
- silver halide
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- mole
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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
- G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
- G03C1/83—Organic dyestuffs therefor
- G03C1/832—Methine or polymethine dyes
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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
- G03C1/795—Photosensitive materials characterised by the base or auxiliary layers the base being of macromolecular substances
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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
- G03C11/00—Auxiliary processes in photography
- G03C11/14—Pasting; Mounting
Definitions
- the photographic material employed requires higher image density than that of ordinary color paper.
- such a material inevitably requires much increased coating amounts of silver halide and coupler than ordinary color paper, which results in requiring as double processing time as ordinary color paper and therefore, makes it necessary to process the photographic material more rapidly.
- a dye is added to a hydrophilic colloid layer in order to absorb light of a specific wavelength for controlling a sensitivity of a photographic emulsion. Also, a dye is added to inhibit halation or irradiation for improving sharpness of a photographic material.
- the dyes used for these applications are requested to have prescribed spectral absorption characteristics for the respective applications; to be thoroughly decolored, readily eluted from a photographic material and thereby prevent stain on the material after processing; to exert no adverse effects to a photographic emulsion such as sensitization, desensitization and fogging; and to have good stability in a coating solution and a photographic material.
- the photographic material for display is requested to more strictly satisfy the above requirements since it contains a larger amount of dye in order to attain higher sharpness.
- oxonol dyes having two pyrazolone skeletons have been used as a useful dye that least adversely affect a photographic emulsion since they are decolored in a processing solution and readily eluted from a photographic material.
- the sensitization to an undesirable spectral range is liable to result in worse image quality because of color imbalance in a printing process. Fog is caused most likely by an eluted or decolored dye or its decomposed product activated in a processing solution.
- the larger sensitivity fluctuation by temperature or humidity variation results in lack of stable image quality depending on storage conditions such as temperature/humidity at a laboratory.
- the object of the present invention is to provide a rapidly processable silver halide light-sensitive photographic material containing a dye that is inert in an emulsion and capable of providing an image of high sharpness.
- a backlighting type silver halide light-sensitive photographic material for photodisplay having on one side of a support at least one silver halide emulsion layer, wherein the silver halide emulsion layer contains silver halide grains of 80 mole% or more silver chloride and a compound represented by following Formula I: wherein R1 to R6 independently represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group and a heterocyclic group, provided that one of R1 and R2 and one of R3 and R4 each represent the groups other than a hydrogen atom and that at least one of R1 to R6 has a water-soluble group or a substituent having a water-soluble group; L1 to L5 independently represent a methyne group; and m and n independently represent 0 or 1.
- At least one of the silver halide emulsion layers constituting the silver halide light-sensitive photographic material of the invention contains silver halide grains having 80 mole% or more silver chloride content.
- the photographic material comprises preferably a plurality of silver halide emulsion layers of different spectral sensitivities each having a 80 mole% or more silver chloride content.
- the silver halide grains comprise silver chloride of 99.9 to 99.5 mole%, preferably 99.8 to 99.9 mole%, silver bromide of 0.1 to 1.5 mole%, preferably 0.2 to 1.0 mole%, and silver iodide of 0 to 0.02 mole, preferably 0 mole%.
- the silver halide grains may be mixed with silver halide grains of different compositions.
- the silver halide grains of the high chloride content share not less than 80 mole%, preferably not less than 90 mole% in the total silver halide grains contained in the same layer.
- the size of the silver halide grains used for the invention is preferably 0.1 to 1.5 ⁇ m, more preferably 0.3 to 1.0 ⁇ m.
- the grain size can be measured by conventional methods used in the art.
- the size distribution of the silver halide grains may be either polydispersed or monodispersed.
- the monodispersed silver halide grains are preferable, in which a variation coefficient is not more than 0.22, preferably not more than 0.15.
- the silver halide grains can be prepared by the ammonia method, and neutral or the acid method.
- the silver salts and halides solutions are added by the double-jet method, and single-jet method, the reverse-precipitation method, and the conversion method.
- the silver halide grains prepared by the neutral method or the acid method are preferable since they are highly sensitive while they have low fog and excellent pressure resistance and safelight property.
- the silver halide grains of high chloride content used for the invention may be either a surface latent image type or an internal latent image type.
- the silver halide grains contain preferably 0.1 to 1.5 mole% of silver bromide. This silver bromide may be added at any step during formation of the silver halide grains and desalination, and during or after chemical ripening.
- bromide is incorporated into the photographic material after the desalination, it may be simply added in the form of water-soluble bromide, or by adding water soluble bromide and water soluble silver salt simultaneously or separately.
- Bromide may be localized either on the surface or inside of the grains, or otherwise, uniformly distributed from the core to the surface of the grains.
- Unnecessary salts may be removed from the emulsion preferably after the formation of the grains, and the emulsion may be subjected to chemical ripening and then to conventional chemical sensitization with sulfur compounds.
- the silver halide grains may be also subjected to noble metal sensitization, sulfur sensitization with active gelatin, selenium sensitization and reduction sensitization.
- the silver halide grains may be sensitized by various sensitizing dyes in order to provide the grains with a sensitivity to a prescribed spectral range.
- the preferred sensitizing dyes are cyanine dyes, merocyanine dyes and complex cyanine dyes.
- the alkyl groups represented by R1 through R6 are methyl, ethyl, propyl, isopropyl, butyl and t-butyl, each of which may have a substituent such as a hydroxy group, a sulfo group, a carboxyl group, a halogen atom, an alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, and an aryloxycarbonyl group.
- the heterocyclic groups represented by R1 through R6 are a pyridyl group such as 2-pyridyl, 3-pyridyl, 4-pyridyl, 5-sulfo-pyridyl, 5-carboxy-2-pyridyl, 3,5-dichloro-2-pyridyl, 4,6-dimethyl-2-pyridyl, 6-hydroxy-2-pyridyl, 2,3,5,6-tetrafluoro-4-pyridyl, and 3-nitro-2-pyridyl; an oxazolyl group such as 5-sulfo-2-benzooxazolyl, 2-benzooxazolyl, and 2-oxazolyl, a thiazolyl group (e.g.
- R1, R2 and R3 independently represent an alkyl group, an alkenyl group, an aryl group and a heterocyclic group; R2 and R3 are preferably alkyl groups.
- the photographic material used in the invention may contain the dye represented by Formula I in the silver halide emulsion layers as an antiirradiation dye, or in the non-light sensitive hydrophilic colloid layers as a filter dye or an antihalation dye.
- the dye is usually incorporated into the photographic component layers by dissolving it in water or organic solvent such as alcohol, glycol, cellosolve, dimethylformaldehyde, dibutylphthalate and tricresylphosphate, if necessary, emulsifying, and then adding to a coating solution.
- organic solvent such as alcohol, glycol, cellosolve, dimethylformaldehyde, dibutylphthalate and tricresylphosphate
- An addition amount of the dye is 0.01 to 10 mg/dm2, preferably, 0.03 to 5.0 mg/dm2.
- the support used in the invention is preferably transparent or translucent.
- a translucent support containing white pigment is preferably used.
- a support of the invention is arbitrarily selected from those having an oxygen permeation rate of not more than 2.0 ml/m2.hr.atm.
- the support has preferably the oxygen permeation rate of not more than 1.0 ml/m2.hr.atm, and a plastic film can satisfy this requirement.
- the oxygen permeation rate is measured by a known method such as that specified in ASTM D-1434 Recommended Practice. This measurement method is also applicable to the present invention.
- the especially preferable is polyester since the oxygen permeation rate thereof is independent of humidity and, therefore it has the same oxygen permeation rate in a humid atmosphere as in a dry atmosphere.
- the thickness of the support is 150 to 250 ⁇ m, preferably 160 to 200 ⁇ m.
- an antihalation layer containing a material capable of absorbing light. This material has a function to prevent halation on the support by absorbing the light transmitted from the emulsion layers.
- the light-absorbing material is selected from various inorganic materials and dyes having this action.
- Example of the inorganic material is colloidal metal.
- Examples of the organic material for this purpose are dyes coupled with polymers for fixation (so-called mordant dye) so that the dye is not eluted into a color developer.
- the color developer may contain various conventional additives in addition to the above color developing agent.
- the photographic material is subjected to bleaching after color developing, and then to fixing. Bleaching and fixing may be carried out simultaneously in the same bath.
- the added amounts in the table are represented in g/m2, and the amounts of silver halide emulsion and colloidal silver are values converted to silver.
- Solutions A and B were added to 1000 ml of a 2% aqueous gelatin solution at 40°C in 30 minutes according to the double-jet method while keeping pAg at 6.5 and pH at 3.0, and then Solutions C and B were added in 180 minutes according to the double jet method while keeping pAg at 7.3 and pH at 5.5.
- DBP Dibutyl phthalate TOP : Trioctyl phosphate
- THP Trihexyl phosphate
- TCP Tricresyl phosphate
- TEHP Tri(2-ethylhexyl)phosphate
- TINP Triisononyl phosphate
- DCPP Dicresyl phenylphosphate
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- General Physics & Mathematics (AREA)
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- Spectroscopy & Molecular Physics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Description
- The present invention relates to a silver halide light-sensitive photographic material, more specifically to a silver halide light-sensitive photographic material for photodisplay application which suits rapid processing and has good sharpness.
- A typical display method with a color photograph in such locations as department stores, restaurants, hotel lobbies and subway platforms is a "transmittance system (back-light system) where an image formed on a support is displayed by light illuminated from the back of the image; this system is known to provide vivid image in a specific environment such as dark room or the outdoors at night.
- Since the image is displayed by transmitted light in this system, the photographic material employed requires higher image density than that of ordinary color paper. As a result, such a material inevitably requires much increased coating amounts of silver halide and coupler than ordinary color paper, which results in requiring as double processing time as ordinary color paper and therefore, makes it necessary to process the photographic material more rapidly.
- Configuration, size and composition of silver halide grains in a silver halide emulsion for a photographic material greatly affect a developing speed, and especially the composition of halide most significantly affects it; it is well known that silver halide of high chloride content can notably accelerate developing.
- A dye is added to a hydrophilic colloid layer in order to absorb light of a specific wavelength for controlling a sensitivity of a photographic emulsion. Also, a dye is added to inhibit halation or irradiation for improving sharpness of a photographic material.
- The dyes used for these applications are requested to have prescribed spectral absorption characteristics for the respective applications; to be thoroughly decolored, readily eluted from a photographic material and thereby prevent stain on the material after processing; to exert no adverse effects to a photographic emulsion such as sensitization, desensitization and fogging; and to have good stability in a coating solution and a photographic material.
- The photographic material for display is requested to more strictly satisfy the above requirements since it contains a larger amount of dye in order to attain higher sharpness.
- Many dyes have been so far proposed to satisfy the above requirements, such as oxonol dyes disclosed in U.S. Patent Nos. 506,385 and 3,247,127 and Japanese Patent Examined Publication 13168/1968; stylyl dyes disclosed in U.S. Patent No. 1,845,404; merocyanine dyes disclosed in U.S. Patent Nos. 2,493,747, 3,148,187 and 3,282,699; cyanine dyes disclosed in U.S. Patent No. 2,843,486; and anthraquinone dyes disclosed in U.S. Patent No. 2,865,752.
- Among these dyes, oxonol dyes having two pyrazolone skeletons have been used as a useful dye that least adversely affect a photographic emulsion since they are decolored in a processing solution and readily eluted from a photographic material.
- Many of these oxonol dyes cause no problems as far as a silver halide emulsion in a photographic material contains higher silver bromide. However, it was found that they often cause problems against a silver halide emulsion having a higher silver chloride content, such as sensitization to an undesirable spectral range, increased fog, and larger sensitivity fluctuation due to temperature or humidity change.
- The sensitization to an undesirable spectral range is liable to result in worse image quality because of color imbalance in a printing process. Fog is caused most likely by an eluted or decolored dye or its decomposed product activated in a processing solution. The larger sensitivity fluctuation by temperature or humidity variation results in lack of stable image quality depending on storage conditions such as temperature/humidity at a laboratory.
- These are the specific problems where a silver halide emulsion of higher silver chloride content is used. However, the silver halide emulsion of higher AgCℓ content is necessary for rapid processing and therefore, there is required a photographic material containing such emulsion and capable of stably providing good image quality even in a rapid processing.
- The object of the present invention is to provide a rapidly processable silver halide light-sensitive photographic material containing a dye that is inert in an emulsion and capable of providing an image of high sharpness.
- This object is attained by a backlighting type silver halide light-sensitive photographic material for photodisplay having on one side of a support at least one silver halide emulsion layer, wherein the silver halide emulsion layer contains silver halide grains of 80 mole% or more silver chloride and a compound represented by following Formula I:
- At least one of the silver halide emulsion layers constituting the silver halide light-sensitive photographic material of the invention contains silver halide grains having 80 mole% or more silver chloride content.
- The photographic material comprises preferably a plurality of silver halide emulsion layers of different spectral sensitivities each having a 80 mole% or more silver chloride content.
- In the invention, the silver halide grains comprise silver chloride of 99.9 to 99.5 mole%, preferably 99.8 to 99.9 mole%, silver bromide of 0.1 to 1.5 mole%, preferably 0.2 to 1.0 mole%, and silver iodide of 0 to 0.02 mole, preferably 0 mole%.
- The silver halide grains may be mixed with silver halide grains of different compositions.
- The silver halide grains of the high chloride content share not less than 80 mole%, preferably not less than 90 mole% in the total silver halide grains contained in the same layer.
- The size of the silver halide grains used for the invention is preferably 0.1 to 1.5 µm, more preferably 0.3 to 1.0 µm. The grain size can be measured by conventional methods used in the art.
- The size distribution of the silver halide grains may be either polydispersed or monodispersed. The monodispersed silver halide grains are preferable, in which a variation coefficient is not more than 0.22, preferably not more than 0.15.
- The silver halide grains can be prepared by the ammonia method, and neutral or the acid method. The silver salts and halides solutions are added by the double-jet method, and single-jet method, the reverse-precipitation method, and the conversion method. The silver halide grains prepared by the neutral method or the acid method are preferable since they are highly sensitive while they have low fog and excellent pressure resistance and safelight property.
- Silver salt and silver halide solutions are added preferably by the double-jet method, more preferably by the pAg-controlled double jet-method, wherein pAg is controlled in the range of 3 to 9.
- The silver halide grains of high chloride content used for the invention may be either a surface latent image type or an internal latent image type.
- The silver halide grains contain preferably 0.1 to 1.5 mole% of silver bromide. This silver bromide may be added at any step during formation of the silver halide grains and desalination, and during or after chemical ripening.
- If bromide is incorporated into the photographic material after the desalination, it may be simply added in the form of water-soluble bromide, or by adding water soluble bromide and water soluble silver salt simultaneously or separately.
- A necessary amount of silver bromide may be added in several steps; for example, in two steps, during and after the desalination. In the invention, it is added preferably during desalination.
- Bromide may be localized either on the surface or inside of the grains, or otherwise, uniformly distributed from the core to the surface of the grains.
- Unnecessary salts may be removed from the emulsion preferably after the formation of the grains, and the emulsion may be subjected to chemical ripening and then to conventional chemical sensitization with sulfur compounds.
- In addition to the above chemical sensitization, the silver halide grains may be also subjected to noble metal sensitization, sulfur sensitization with active gelatin, selenium sensitization and reduction sensitization.
- The silver halide grains may be sensitized by various sensitizing dyes in order to provide the grains with a sensitivity to a prescribed spectral range.
- The preferred sensitizing dyes are cyanine dyes, merocyanine dyes and complex cyanine dyes.
- The compound represented by Formula I may be added to the photographic component layers including other silver halide emulsion layers and non-light-sensitive layers such as an intermediate layer, a protective layer, a filter layer, and an antihalation layer as well as the emulsion layers containing the AgX grains of high AgCℓ content.
- The alkyl groups represented by R₁ through R₆ are methyl, ethyl, propyl, isopropyl, butyl and t-butyl, each of which may have a substituent such as a hydroxy group, a sulfo group, a carboxyl group, a halogen atom, an alkoxy group, an aryl group, an aryloxy group, an alkoxycarbonyl group, and an aryloxycarbonyl group.
- The aryl groups represented by R₁ through R₆ are phenyl, 2-methoxyphenyl, 4-nitrophenyl, 3-chlorophenyl, 4-cyanophenyl, 4-hydroxyphenyl, 4-methanesulfonylphenyl, 4-sulfophenyl, 3-sulfophenyl, 2-methyl-4-sulfophenyl, 2-chloro-4-sulfophenyl, 4-chloro-3-sulfophenyl, 2-chloro-5-sulfophenyl, 2-methoxy-5-sulfophenyl, 2-hydroxy-4-sulfophenyl, 2,5-dichloro-4-sulfophenyl, 2,6-diethyl-4-sufophenyl, 2,5-disulfophenyl, 3,5-disulfophenyl, 2,4-disulfophenyl, 4-phenoxy-3-sulfophenyl, 2-chloro-6-methyl-4-sulfophenyl, 3-carboxy-2-hydroxy-5-sulfophenyl, 4-carboxyphenyl, 2,5-dicarboxyphenyl, 3,5-dicarboxyphenyl, 2,4-dicarboxyphenyl, 3,6-disulfo-α-naphthyl, 8-hydroxy-3,6-disulfo-o-naphthyl, 5-hydroxy-7-sulfo-β-naphthyl, and 6,8-disulfo-β-naphthyl.
- The alkenyl groups represented by R₁ through R₆ are vinyl and allyl.
- The heterocyclic groups represented by R₁ through R₆ are a pyridyl group such as 2-pyridyl, 3-pyridyl, 4-pyridyl, 5-sulfo-pyridyl, 5-carboxy-2-pyridyl, 3,5-dichloro-2-pyridyl, 4,6-dimethyl-2-pyridyl, 6-hydroxy-2-pyridyl, 2,3,5,6-tetrafluoro-4-pyridyl, and 3-nitro-2-pyridyl; an oxazolyl group such as 5-sulfo-2-benzooxazolyl, 2-benzooxazolyl, and 2-oxazolyl, a thiazolyl group (e.g. 5-sulfo-2-benzothiazolyl, 2-benzothiazolyl, and 2-thiazolyl); an imidazolyl group such as 1-methyl-2-imidazolyl and 1-methyl-5-sulfo-2-benzoimidazolyl; furyl group such as 3-furyl; a pyrrolyl group such as 3-pyrrolyl; a thienyl group such as 2-thienyl; a pyrazinyl group such as 2-pyrazinyl); a pyrimidinyl group such as 2-pyrimidinyl and 4-chloro-2-pyrimidinyl), a pyridazinyl group such as 2-pyridazinyl; a purinyl group such as 8-purinyl; an isooxazolynyl group such as 3-isooxazolynyl; a selenazolyl group such as 5-sulfo-2-selenazolyl; a sulfolanyl group such as 3-sulfolanyl; a piperidinyl group such as 1-methyl-3-piperidinyl; a pyrazolyl group such as 3-pyrazolyl, and a tetrazolyl group such as 1-pyrazolyl. Additionally, R₁ and R₂, or R₃ and R₄ may form a ring such as piperazyl group, a piperidyl group, and a morpholyl group.
- The preferred groups represented by R₅ and R₆ are an alkyl group, an aryl group, and a heterocyclic group, more preferably, an alkyl group and an aryl or heterocyclic group that has at least one water-soluble group, and, most preferably an alkyl group.
- The water-soluble groups are a sulfo group or its salt, a carboxyl group or its salt, a hydroxy group, a sulfate ester group, a phosphynyl group, a phosphono group, and a phospholyl group.
-
- These dyes of the invention are readily synthesized by the method described in Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent 0.P.I. Publication) No. 143342/1983. A 3-carboxy-5-pyrazolone derivative, which is a starting material in this synthesis, is synthesized by the methods described in Japanese Patent O.P.I. Publication No. 185934/1988, Journal of the American Chemical Society 71, 983 (1949), and Chem. Ber. 109, 253 (1976). Typical synthesis schemes are as follows.
- In these schemes, R¹, R² and R³ independently represent an alkyl group, an alkenyl group, an aryl group and a heterocyclic group; R² and R³ are preferably alkyl groups.
- The photographic material used in the invention may contain the dye represented by Formula I in the silver halide emulsion layers as an antiirradiation dye, or in the non-light sensitive hydrophilic colloid layers as a filter dye or an antihalation dye.
- It is preferable that the compound defined by m=0 and n=0 in Formula I is present in a blue-sensitive silver halide emulsion layer; the compound defined by m=1 and n=0, in a green-sensitive silver halide emulsion layer; the compound defined by m=1 and n=1, in a red-sensitive silver halide emulsion layer.
- Two or more dyes may be used together, or in combination with other types of dyes. The dye is usually incorporated into the photographic component layers by dissolving it in water or organic solvent such as alcohol, glycol, cellosolve, dimethylformaldehyde, dibutylphthalate and tricresylphosphate, if necessary, emulsifying, and then adding to a coating solution.
- An addition amount of the dye is 0.01 to 10 mg/dm², preferably, 0.03 to 5.0 mg/dm².
- The support used in the invention is preferably transparent or translucent. A translucent support containing white pigment is preferably used.
- The useful white pigments are inorganic and organic ones, preferably an inorganic white pigment including sulfate salts of alkali earth metals such as barium sulfate; carbonate salts of alkali earth metals such as calcium carbonate; silicas such as fine powder silica and synthetic silica; calcium silicate, alumina, alumina hydrate, titanium oxide, zinc oxide, talc, and clay. Barium sulfate, calcium carbonate and titanium oxide are preferable, and barium sulfate and titanium oxide are more preferable.
- The white pigment is added in an amount of 5 to 50 wt%.
- A support of the invention is arbitrarily selected from those having an oxygen permeation rate of not more than 2.0 mℓ/m².hr.atm. The support has preferably the oxygen permeation rate of not more than 1.0 mℓ/m².hr.atm, and a plastic film can satisfy this requirement. The oxygen permeation rate is measured by a known method such as that specified in ASTM D-1434 Recommended Practice. This measurement method is also applicable to the present invention.
- Examples of polymer for the support used in the invention are polyesters such as polyethyleneterephthalate; homopolymers and copolymers of vinyl alcohol, vinyl chloride, vinyl fluoride, and vinyl acetate; and homopolymers and copolymers of cellulose acetate, acrylonitrile, methacrylonitrile, alkyl acrylate ester, alkyl methacrylate ester, alkyl vinyl ether, and polyamide.
- Among these polymers, the especially preferable is polyester since the oxygen permeation rate thereof is independent of humidity and, therefore it has the same oxygen permeation rate in a humid atmosphere as in a dry atmosphere.
- The thickness of the support is 150 to 250 µm, preferably 160 to 200 µm.
- Any support may be used as a transparent support in the invention as far as it is virtually transparent. Examples of the transparent support are cellulose acetate film, polyethylene terephthalate film, polycarbonate film, polystyrene film, and polypropyrene film. The particularly preferable is polyethylene terephthalate film.
- In the invention, there may be provided on the side opposite to the side of an emulsion layer, an antihalation layer containing a material capable of absorbing light. This material has a function to prevent halation on the support by absorbing the light transmitted from the emulsion layers.
- The light-absorbing material is selected from various inorganic materials and dyes having this action.
- Example of the inorganic material is colloidal metal. Examples of the organic material for this purpose are dyes coupled with polymers for fixation (so-called mordant dye) so that the dye is not eluted into a color developer.
- Examples of the inorganic light-absorbing materials are colloidal silver and colloidal manganese, preferably colloidal silver.
- The aromatic primary amine color developing agents used for a color developer are aminophenol derivatives and p-phenylenediamine derivatives. These compounds are used in an amount of 0.1 to 30 g, preferably 1 to 15 g per 1ℓ of a color developer.
- The color developer may contain various conventional additives in addition to the above color developing agent.
- The pH level of the color developer is usually 7 or higher, preferably 10 to 13. The color developing temperature is usually 15°C or higher, preferably 20 to 50°C. For rapid processing, the developing temperature is preferably 30°C or higher.
- Color developing time is usually 10 minutes or shorter, preferably 2 minutes 30 seconds or shorter, and more preferably 30 seconds to 2 minutes.
- The photographic material is subjected to bleaching after color developing, and then to fixing. Bleaching and fixing may be carried out simultaneously in the same bath.
- The invention is described hereunder by referring to the examples.
- Sample No. 1 was prepared by coating the respective coating solutions as shown in Table 1 on a translucent support made of 180 µm-thick transparent polyethylene terephthalate film containing barium sulfate of 10 g/m².
-
- The photographic material Sample Nos. 2 through 37 were prepared in the manner identical to Sample No. 1 except that the emulsions in Layers 1, 3 and 5 were replaced with following EM-A, EM-B and EM-C, respectively and that the dyes added to Layers 1, 3 and 6 were varied as shown in Tables 2-1 and 2-2. In Sample No. 6, there was used the same AgX emulsion of a low AgCℓ content as in Sample No. 1. The amount of the dye of the invention added to Layer 1 was 0.005 g/dm².
- Each sample was exposed by a normal method, and was subjected to developing according to processings A and B.
- Solutions A and B were added to 1000 mℓ of a 2% aqueous gelatin solution at 40°C in 30 minutes according to the double-jet method while keeping pAg at 6.5 and pH at 3.0, and then Solutions C and B were added in 180 minutes according to the double jet method while keeping pAg at 7.3 and pH at 5.5.
- pAg was controlled by the method described in Japanese Patent O.P.I. Publication No. 45437-1984, while pH was controlled with an aqueous solution of sulfuric acid or sodium hydroxide.
Solution A NaCℓ 3.42 g KBr 0.03 g Water to make 200 mℓ Solution B AgNO₃ 10 g Water to make 200 mℓ Solution C NaCℓ 102.7 g KBr 1.0 g Water to make 600 mℓ Solution D AgNO₃ 300 g Water to make 600 mℓ - After completion of addition, desalination was performed using 5% aqueous solution of Demol N (Kao Atlas) and a 20% aqueous solution of magnesium sulfate. Then, the mixture was blended with an aqueous gelatin solution to prepare monodispersed emulsion EM-1 containing AgX grains having an average grain size of 0.85 µm, a variation coefficient (σ/
r ) of 0.07, and a silver chloride content of 99.5 mole%. - EM-1 was chemically sensitized in 90 minutes at 50°C using the compounds specified below to prepare a blue-sensitive silver halide emulsion EM-A.
Sodium thiosulfate 0.8 mg/mole AgX Chloroauric acid 0.5 mg/mole AgX Stabilizer SB-5 6 x 10⁻⁴ mole/mole AgX Sensitizing dye D-1 5 x 10⁻⁴ mole/mole AgX - There was prepared in the manner identical to that of EM-1, monodispersed emulsion EM-2 containing AgX grains having an average grain size of 0.43 µm, a variation coefficient (σ/
r ) of 0.08 and a silver chloride content of 99.5 mole%, except that the time for adding Solutions A and B and Solutions C and D was changed. - EM-2 was chemically sensitized in 120 minutes at 55°C using the compounds specified below to prepare a green-sensitive silver halide emulsion EM-B.
Sodium thiosulfate 1.5 mg/mole AgX Chloroauric acid 1.0 mg/mole AgX Stabilizer SB-5 6 x 10⁻⁴ mole/mole AgX Sensitizing dye D-2 4.0 x 10⁻⁴ mole/mole AgX - There was prepared in the manner identical to that of EM-1, monodispersed emulsion EM-3 containing AgX grains having an average grain size of 0.50 µm, a variation coefficient (σ/
r ) of 0.08 and a silver chloride content of 99.5 mole%, except that the time for adding Solutions A and B and Solutions C and D was changed. - EM-3 was chemically sensitized in 90 minutes at 60°C using the compounds specified below to prepare a red-sensitive silver halide emulsion EM-C.
Sodium thiosulfate 1.8 mg/mole AgX Chloroauric acid 2.0 mg/mole AgX Stabilizer SB-5 6 x 10⁻⁴ mole/mole AgX Sensitizing dye D-3 8.0 x 10⁻⁵ mole/mole AgX Processing A Temperature Time Color developing 35.0 ± 0.3°C 45 sec. Bleach-fixing 35.0 ± 0.5°C 45 sec. Stabilizing 30 - 34°C 90 sec. Drying 60 - 80°C 60 sec. Color developer Pure water 800 mℓ Triethanolamine 10 g N,N-diethylhydroxylamine 5 g Potassium bromide 0.02 g Potassium chloride 2 g Potassium sulfite 0.3 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.0 g Ethylenediaminetetraacetic acid 1.0 g Disodium catechol-3,5-disulfonate 1.0 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-amino-aniline sulfate 4.5 g Fluorescent brightening agent (4,4′-diaminostylbene disulfonate derivative) 1.0 g Potassium carbonate 27 g - Water was added to a total of 1ℓ, and the pH was adjusted to 10.10.
Bleach-fixer Ferric ammonium ethylenediaminetetraacetate dihydrate 60 g Ethylenediaminetetraacetate 3 g Ammonium thiosulfate (70% aqueous solution) 100 mℓ Ammonium sulfite (40% aqueous solution) 27.5 mℓ - Water was added to a total of 1ℓ, and the pH was adjusted to 5.7 with potassium carbonate or glacial acetic acid.
Stabilizer 5-chloro-2-methyl-4-isothiazoline-3-one 1.0 g Ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g Ethylenediaminetetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Ammonium sulfite 3.0 g Fluorescent brightening agent (4,4′-diaminostylbene disulfonate derivative) 1.5 g - Water was added to a total of 1ℓ, and the pH was adjusted to 7.0 with sulfuric acid or potassium hydroxide.
- This processing is identical to Processing A except that processing time was varied to 90 seconds for color developing, 90 seconds for bleach-fixing, 180 seconds for stabilizing, and 120 seconds for drying.
- The samples were evaluated for the characteristic values as follows.
- Each of the processed samples was evaluated for sensitivity, gradation and maximum density (Dmax) with the PDA-65 photographic densitometer (Konica Corporation). The sensitivity is a value relative to that of Sample No. 2 processed with Processing B, which is set at 100.
- Each sample was subjected to both of the above processings, and its transmittance density was evaluated with Model 310 TR of X Right Company.
- Each sample was exposed to red light through a resolution test chart and then subjected to the above processing. The density of a cyan image was measured with a microphotometer, and the sharpness was calculated from the following equation:
- As can be understood from the results in Tables 2-1 and 2-2, Sample No. 1 (Comparison) containing the AgX emulsions of low silver chloride content exhibited insufficient sensitivity and maximum density (Dmax) even where it was treated in double processing time. In Sample No. 6 containing the same emulsion and the dyes of the invention, the sharpness was improved while the sensitivity and Dmax were not yet improved.
- Sample Nos. 2, 3, 4 and 5 (Comparison) containing the comparative dyes and the AgX emulsions of high AgCℓ content exhibited insufficient sharpness while sensitivity and Dmax were improved.
- Sample Nos. 7 through 37 (Invention) containing the AgX emulsions of high AgCℓ content and the dyes of the invention apparently exhibited improvement in all of the sensitometry, fogging and sharpness.
- Example 1 was repeated to prepare Samples No. 38 to 73 except that the support was replaced by a 180 µm-thick transparent polyethylene terephthalate film.
- Each sample was exposed, processed and evaluated in the same manners as in Example 1.
-
- It is apparent from the results in Tables 3-1 and 3-2 that the effects of the invention can be attained with the transparent polyethylene terephthalate film support.
- Examples 1 and 2 were repeated except that in Sample Nos. 7 through 37 and Sample Nos. 43 through 73, Y-1 was replaced with one of Y-2 through Y-6; M-1 with one of M-2 through M-9; C-1 and C-2 with C-3 through C-9; an antistain agent AS-1 with one of AS-2 and AS-3; high-boiling organic solvents DNP, DOP and DIDP with DBP, TOP, TCP, TINP, TEHP, DCPP and THP; a stabilizer ST-1 with one of ST-5, ST-6 and ST-7; a stabilizer ST-3 with one of ST-7, 8, 10 and 11; UV absorbers UV-1 and UV-2 with UV-3, UV-4 and UV-5.
-
- Sample Nos. 74 through 87 were prepared in the manner identical to Sample No. 2 in Example 1 except that the colloidal silver in BC Layers 1 and 2, the dyes in Layers 1, 3 and 6 were changed as shown in Table 4. The amount of colloidal silver was the same as that of Sample No. 2, and the amounts of the dyes were 0.005 g/m² in Layer 1, 0.004 g/m² in Layer 3, and 0.009 g/m² in layer 6.
- Each sample was exposed and processed in the same manner as in Example 2, and was evaluated for fogging and sharpness as well.
- The results are summarized in Table 4.
- As is apparent from the results thereof, good sharpness is attained in every sample containing colloidal silver in the BC layers. It is also apparent that colloidal silver used in combination with the dye of the invention can provide the good photographic properties while the combination of colloidal silver and the comparative dye increases fog in Processing B.
- Sample No. 88 to 107 were prepared in the same manner as in Sample No. 2 of Example 1 except that the colloidal silver was replaced with an AI dye and the dyes in Layers 1, 3 and 6 were changed as shown in Table 5. The amount of the AI dye was 0.01 g/m², and the amounts of the dyes added to Layers 1, 3 and 6 were the same as in Example 4.
- Each sample was exposed and processed in the same manner as in Example 1, and was evaluated for fog and sharpness, of which results are summarized in Table 5.
- As is apparent from the results thereof, excellent sharpness was shown in every sample containing the AI dye in the BC layers. It has been also found that the dye of the invention used in combination with the AI dye can provide the excellent photographic properties while the combination of the comparative dye and the AI dye increases fog in Processing B.
Claims (16)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP7300889 | 1989-03-24 | ||
JP73008/89 | 1989-03-24 |
Publications (2)
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EP0388908A1 true EP0388908A1 (en) | 1990-09-26 |
EP0388908B1 EP0388908B1 (en) | 1996-05-22 |
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Application Number | Title | Priority Date | Filing Date |
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EP90105288A Expired - Lifetime EP0388908B1 (en) | 1989-03-24 | 1990-03-21 | A silver halide light-sensitive photographic material |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0494121A1 (en) * | 1991-01-04 | 1992-07-08 | Konica Corporation | Silver halide photographic light sensitive material |
EP0495659A1 (en) * | 1991-01-18 | 1992-07-22 | Konica Corporation | A method for forming a dye image |
EP0568772A2 (en) * | 1992-02-07 | 1993-11-10 | Eastman Kodak Company | Translucent display paper for rear illumination |
EP0578169A1 (en) * | 1992-07-06 | 1994-01-12 | Fuji Photo Film Co., Ltd. | Color photographic material |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58143342A (en) * | 1982-02-19 | 1983-08-25 | Konishiroku Photo Ind Co Ltd | Silver halide photosensitive material containing dye |
EP0243096A2 (en) * | 1986-04-18 | 1987-10-28 | Konica Corporation | Method for processing a light-sensitive silver halide color photographic material |
DE3800130A1 (en) * | 1987-01-07 | 1988-07-28 | Fuji Photo Film Co Ltd | Colour-photographic silver-halide material |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0297940A (en) * | 1988-10-04 | 1990-04-10 | Konica Corp | Silver halide photographic sensitive material |
-
1990
- 1990-03-21 EP EP90105288A patent/EP0388908B1/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58143342A (en) * | 1982-02-19 | 1983-08-25 | Konishiroku Photo Ind Co Ltd | Silver halide photosensitive material containing dye |
EP0243096A2 (en) * | 1986-04-18 | 1987-10-28 | Konica Corporation | Method for processing a light-sensitive silver halide color photographic material |
DE3800130A1 (en) * | 1987-01-07 | 1988-07-28 | Fuji Photo Film Co Ltd | Colour-photographic silver-halide material |
Non-Patent Citations (3)
Title |
---|
PATENT ABSTRACTS OF JAPAN, vol. 10, no. 9 (P-420)[2066], 14th January 1986; & JP-A-60 166 947 (SHASHIN FILM K.K.) 30-08-1985 * |
PATENT ABSTRACTS OF JAPAN, vol. 11, no. 153 (P-577)[2600], 19th May 1987; & JP-A-61 289 346 (FUJI PHOTO FILM CO., LTD) 19-12-1986 * |
PATENT ABSTRACTS OF JAPAN, vol. 6, no. 5 (P-97)[883], 13th January 1982, page 66 P 97; & JP-A-56 130 747 (FUJI SHASHIN K.K.) 13-10-1981 * |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0494121A1 (en) * | 1991-01-04 | 1992-07-08 | Konica Corporation | Silver halide photographic light sensitive material |
EP0495659A1 (en) * | 1991-01-18 | 1992-07-22 | Konica Corporation | A method for forming a dye image |
US5238788A (en) * | 1991-01-18 | 1993-08-24 | Konica Corporation | Method for forming a dye image |
EP0568772A2 (en) * | 1992-02-07 | 1993-11-10 | Eastman Kodak Company | Translucent display paper for rear illumination |
EP0568772A3 (en) * | 1992-02-07 | 1994-10-05 | Eastman Kodak Co | Translucent display paper for rear illumination. |
EP0578169A1 (en) * | 1992-07-06 | 1994-01-12 | Fuji Photo Film Co., Ltd. | Color photographic material |
US5368996A (en) * | 1992-07-06 | 1994-11-29 | Fuji Photo Film Co., Ltd. | Color photographic material |
Also Published As
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EP0388908B1 (en) | 1996-05-22 |
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