EP0490302B1 - Photographische Silberhalogenidmaterialien - Google Patents

Photographische Silberhalogenidmaterialien Download PDF

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Publication number
EP0490302B1
EP0490302B1 EP19910121005 EP91121005A EP0490302B1 EP 0490302 B1 EP0490302 B1 EP 0490302B1 EP 19910121005 EP19910121005 EP 19910121005 EP 91121005 A EP91121005 A EP 91121005A EP 0490302 B1 EP0490302 B1 EP 0490302B1
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Prior art keywords
silver halide
groups
present
layer
group
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EP19910121005
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French (fr)
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EP0490302A3 (en
EP0490302A2 (de
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Kunio Ishigaki
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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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
    • G03C1/7614—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 concerns silver halide photographic materials, and in particular it concerns silver halide photographic materials whose pressure resistance properties are improved.
  • Silver halide photographic materials are in general materials which have a light-sensitive emulsion layer and, as required, various combinations of structural layers such as intermediate layers, protective layers, backing layers, antihalation layers and anti-static layers, for example, coated onto a support such as a synthetic resin film, paper or a paper which has been covered with a synthetic resin, or glass, for example.
  • Silver halide photographic materials frequently exhibit pressure fogging as a result of contact between the photosensitive material and various types of apparatus used in the manufacturing of the material such as processes of coating, drying and finishing, for example, and during transport through a camera, during development processing, during printing or during projection, for example; as a result of contact friction between the photosensitive material and other materials; or as a result of contact friction between photographic materials themselves, e.g., which occurs between a photosensitive material surface and the reverse surface of a photographic material.
  • Patent 3,121,060 a method in which paraffins and carboxylic acid salts are used is disclosed in JP-A-49-5017 and a method in which alkyl acrylates and organic acids are used is disclosed in JP-B-53-28086 (the terms "JP-A”and “JP-B” as used herein refer to a "published unexamined Japanese patent application” and an “examined Japanese patent publication”, respectively).
  • plasticizers are added reduce the mechanical strength of the emulsion layer and so the amount of plasticizer which may be used is limited, and when the silver halide/gelatin ratio is reduced, development is retarded and there is the disadvantage in that the suitability for rapid processing is lost.
  • polyhydroxybenzene compounds have been introduced for various purposes into silver halide photographic materials which contain hydrazine derivatives, as is disclosed, for example, in U.S. Patents 4,332,108, 4,385,108 and 4,377,634, and a technique for the prevention of pressure sensitization is disclosed in JP-A-62-21143.
  • rapid development processing signifies processing in which the time elapsing from the entry of the leading edge of the film into an automatic processor through the development tank, the crossover part, the fixing tank, the crossover part, the water washing tank and the drying part until the leading edge of the film emerges from the drying part is from 15 to 60 seconds.
  • An object of the present invention is to provide silver halide photographic materials with an improvement in pressure fogging which is caused by contact friction with various materials and which can be subjected to rapid processing.
  • a silver halide photographic material comprising a support having thereon at least one silver halide emulsion layer and at least one protective layer above the emulsion layer, wherein colloidal silica having an average particle size of from 5 to 1000 m ⁇ is present in at least one of the silver halide emulsion layers and the dynamic friction coefficient of the surface of the outermost layer of the protective layer is 0.35 or less, wherein the outermost layer of the protective layer contains a lubricant.
  • the colloidal silica which is used in the present invention has an average particle size of
  • the colloidal silica is Si0 2 , but for example, alumina or sodium aluminate may be included as minor components (i.e., stabilizers) of the colloidal silica (an amount of the components: 3.0 wt% or less based on the colloidal silica), together with the colloidal silica.
  • inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia, and organic bases such as tetramethylammonium ions, may be included as stabilizers (preferably in an amount of 1.0 wt% or less based on the colloidal silica) in this colloidal silica.
  • colloidal silica of this type is disclosed in JP-A-53-112732, JP-B-57-009051 and JP-B-57-051653.
  • colloidal silica examples are available commercially from Nissan Chemicals (Tokyo, Japan) under the trade names Snowtex 20 (SiO 2 /Na 2 O ⁇ 57), Snowtex 30 (SiO 2 /Na 2 O) - 50), Snowtex C (SiO 2 /Na 2 O ⁇ 100) and Snowtex O (SiO 2 /Na 2 O) ⁇ 500), for example.
  • the ratio Si0 2 /Na 2 0 represents the ratio by weight of the amount of silicon dioxide (Si0 2 ) and sodium hydroxide present, the sodium hydroxide being calculated as Na 2 0, and the values given are those listed in the trade literature (i.e., the catalog).
  • the amount of colloidal silica used in the silver halide emulsion layer of the present invention in terms of the dry weight ratio based on the gelatin which is used as the binder in the layer in which the colloidal silica is present is preferably from 0.05 to 1.0, and most desirably from 0.1 to 0.6.
  • the dynamic friction coefficient (pk) in the present invention can be obtained using the same principle as the friction coefficient test method described in JIS K7125.
  • a sapphire needle for example, having a diameter of from 0.5 to 5 mm
  • the contact force, Fp for example, Fp: from 50 to 200 g
  • the surface of the silver halide photographic materials is moved at constant speed (for example, from 20 to 100 cm/min)
  • the tangential force (Fk) at this time is measured and the dynamic friction coefficient is determined using the equation shown below.
  • measurements can be made using a device for measuring surface properties (model HEI-DON-14) made by Shinto Science (Co.).
  • Lubricants are preferably used to set the dynamic friction coefficient of the outermost layer to 0.35 or less in the present invention.
  • Typical lubricants which can be used in the present invention include silicone based lubricants disclosed, for example, in U.S. Patent 3,042,522, British Patent 955,061, U.S. Patents 3,080,317, 4,004,927, 4,047,958 and 3,489,567, and British Patent 1,143,118; higher fatty acid based, alcohol based and acid amide based lubricants disclosed, for example, in U.S. Patents 2,454,043, 2,732,305, 2,976,148 and 3,206,311, and German Patents 1,284,295 and 1,284,294; metal soaps disclosed, for example, in British Patent 1,263,722 and U.S.
  • Patent 3,933,516 ester based and ether based lubricants disclosed in U.S. Patents 2,588,765 and 3,121,060, and British Patent 1,198,387; taurine based lubricants disclosed in U.S. Patents 3,502,473 and 3,042,222, and the above described colloidal silica.
  • the alkylpolysiloxanes which can be represented by formula (I), formula (II) or formula (III) shown below and liquid paraffins which are in a liquid state at room temperature (e.g., about 20 to 30°C) is preferably used as the lubricant in the present invention. Moreover, the use of the alkylpolysiloxanes which have a polyoxyalkylene chain as a side chain represented by formula (I) and the alkylpolysiloxanes represented by formula (II) is especially desirable.
  • R represents an aliphatic group (for example, an alkyl group (which preferably has from 1 to 8 carbon atoms), a substituted alkyl group (such as aralkyl, alkoxyalkyl or aryloxyalkyl, for example)) or an aryl group (for example, phenyl).
  • R' represents a hydrogen atom, an aliphatic group (for example, an alkyl group (which preferably has from 1 to 12 carbon atoms) or a substituted alkyl group), or an aryl group (for example, phenyl).
  • R" represents an alkyl group (for example, methyl) or an alkoxyalkyl group (for example, methoxymethyl).
  • A represents a divalent residual group of an aliphatic hydrocarbon.
  • f represents 0 or an integer of from 1 to 12
  • p is a number of from 0 to 50
  • q is a number of from 2 to 50 (and preferably from 2 to 30)
  • x is a number of from 0 to 100
  • y is a number of from 1 to 50
  • z is a number of from 0 to 100
  • x+y+z is a number of from 5 to 250 (and preferably of from 10 to 50).
  • R examples include methyl, ethyl, propyl, pentyl, cyclopentyl, cyclohexyl, dimethylpentyl, heptyl, methylhexyl, octyl, dodecyl, octadecyl, phenylethyl, methylphenylethyl, phenylpropyl, cyclohexylpropyl, benzyloxypropyl, phenoxypropyl, ethyloxypropyl, butyloxyethyl, and phenyl.
  • alkyl groups represented by R' include methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl and dodecyl.
  • Formula (II) includes cyclic siloxanes which have siloxane units which can be represented by formula (II-1) and linear siloxanes which have terminal groups which can be represented by formula (11-2).
  • R represents an alkyl group which has from 5 to 20 carbon atoms, a cycloalkyl group, an alkoxyalkyl group, an arylalkyl group, an aryloxyalkyl group or a glycidyloxyalkyl group.
  • R 2 represents an alkyl group which has from 1 to 20 carbon atoms, or a cycloalkyl group, an alkoxyalkyl group, an arylalkyl group, an aryloxyalkyl group or a glycidyloxyalkyl group which has from 5 to 20 carbon atoms.
  • n is 0 or has a numerical value of at least 1
  • m has a numerical value of at least 1
  • n+m has a numerical value of from 1 to 1,000.
  • n+m is preferably from 2 to 500.
  • R in compounds represented by formula (II) include pentyl, methylpentyl, cyclopentyl, cyclohexyl, dimethylpentyl, heptyl, methylheptyl, octyl, eicosyl, phenylethyl, methylphenylethyl, phenylpropyl, cyclohexylpropyl, benzyloxypropyl, phenoxypropyl, tolyloxypropyl, naphthylpropyl, ethyloxypropyl, buty- loxypropyl, octadecyloxypropyl, glycidyloxypropyl and glycidyloxybutyl.
  • R 3 represents an alkyl group which has from 1 to 3 carbon atoms and R 4 represents an alkyl group which has from 1 to 3 carbon atoms or an alkoxy group which has 1 or carbon atoms.
  • m' is an integer of from 0 to 2,000.
  • anionic surfactants represented by formula (IV) shown below is also desirable in the present invention.
  • R represents a substituted or unsubstituted alkyl group which has from 3 to 30 carbon atoms, an unsubstituted or substituted alkenyl group which has from 3 to 30 carbon atoms or an unsubstituted or substituted aryl group which has from 6 to 30 carbon atoms
  • R' represents a hydrogen atom, a substituted or unsubstituted alkyl group which has from 1 to 10 carbon atoms, an unsubstituted or substituted alkenyl group or an unsubstituted or substituted aryl group.
  • n represents a number of from 2 to 6
  • M represents a hydrogen atom or an inorganic or organic cation.
  • anionic surfactants which can be used in the present invention are shown below.
  • the amount of lubricant coated in terms of the ratio by weight based on the amount of binder in the outermost layer is preferably from 0.01 to 1.0, more preferably from 0.05 to 0.5, and most preferably from 0.01 to 0.1.
  • the amount of anionic surfactant used is preferably from 0.001 to 0.5 g/m 2 and more preferably from 0.01 to 0.2 g/ m 2.
  • the dynamic friction coefficient ( ⁇ k) is generally 0.35 or less, and preferably is from 0.35 to 0.10.
  • polyhydroxybenzene compounds to increase pressure resistance and improve shelf life without loss of sensitivity is also desirable in the present invention.
  • Compounds which have any of the structures shown below are preferred as polyhydroxybenzene compounds.
  • X and Y each represents -H, -OH, a halogen atom, -OM (where M is an alkali metal atom), an alkyl group, a phenyl group, an amino group, a carbonyl group, a sulfo group, a sulfonphenyl group, a sulfonalkyl group, a sulfonamino group, a sulfoncarbonyl group, a carboxyphenyl group, a carboxyalkyl group, a carbox- yamino group, a hydroxyphenyl group, a hydroxyalkyl group, an alkylether group, an alkylphenyl group, an al- kylthioether group or a phenylthio
  • X and Y each represents, for example, -H, -OH, -Cl, -Br, -COOH, -CH 2 CH 2 COOH, -CH 3 , -CH 2 CH 3 , -CH(CH 3 ) 2 , -C(CH 3 ) 3 , -OCH 3 , -CHO, -S0 3 Na, -S0 3 H, -SCH 3 ,
  • the polyhydroxybenzene compounds may be present in an emulsion layer of the sensitive material or to a layer other than an emulsion layer.
  • An amount of the polyhydroxybenzene compound used is preferably from 1 x 10 -5 to 1 mol per mol of silver and more preferably from 1 x 10- 3 to 1 x 10- 1 mol per mol of silver.
  • the protective layer preferably comprises at least two layers .
  • the hydrophilic colloid layers become brittle when a silver halide photographic material is stored under low humidity conditions.
  • the inclusion of a polymer latex which has a glass transition point (referred to hereinafter as Tg) of 20°C or less in the emulsion layer and/or protective layer is desirable to improve this situation.
  • Tg glass transition point
  • the protective layer comprises two or more layers, the inclusion of the polymer latex in an intermediate layer between the emulsion layer and the outermost layer is desirable because brittleness is improved without loss of film strength in development processing solutions or adhesion of sensitive materials under the conditions of high humidity.
  • the dry film strength is improved at the same time as the slipping properties are improved and this is desirable from the viewpoint of further improving scratch resistance.
  • the amount of colloidal silica which is present in the outermost layer of the protective layer is, in terms of the ratio by weight with respect to the amount of binder in the outermost layer, generally from 0.01 to 1.0, and most desirably from 0.1 to 0.5.
  • Hydrates of vinyl polymers such as acrylic acid esters, methacrylic acid esters or styrene, for example, as disclosed, for example, in U.S. Patents 2,772,166, 3,325,286, 3,411,911, 3,311,912 and 3,525,620 and Research Disclosure, No. 195, 19551 (July, 1980) can be used as polymer latexes contained in the protective layer in the present invention.
  • Preferred polymer latexes of which the Tg is 20°C or less include homopolymers of alkyl acrylates, such as methyl acrylate, ethyl acrylate and butyl acrylate, copolymers such as alkyl acrylates with acrylic acid and N-methylolacrylamide, for example (which preferably have an acrylic acid, etc., copolymer component of up to 30 wt%), butadiene homopolymers or copolymers of butadiene and one or more of styrene, butoxymethylacrylamide and acrylic acid, and vinylidene chloridemethyl acrylate-acrylic acid terpolymers.
  • alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate
  • copolymers such as alkyl acrylates with acrylic acid and N-methylolacrylamide, for example (which preferably have an acrylic acid, etc., copolymer component of up to 30 wt%)
  • the Tg of a polymer latex can be obtained using differential scanning calorimetry (DSC).
  • a preferred range for the average particle size of a polymer latex which is used in the present invention is from 0.005 to 1 ⁇ m, and most desirably from 0.02 to 0.1 ⁇ m.
  • the amount of polymer latex employed is generally from 5 to 200%, and preferably from 10 to 100%, based on the amount of hydrophilic colloid in the layer in which it is present.
  • polymer latexes having Tg of 20°C or less which can be used in the present invention are shown below, but the polymer latex is not limited to these examples.
  • Dyes for example, can be included in the photosensitive material of the present invention for antihalation purposes, to improve safe-light safety and for improving reverse side recognition.
  • Tetrazolium compounds or hydrazine derivatives may also be present in the emulsion layer or in a layer adjacent thereto in the photosensitive material of the present invention.
  • JP-A-53-17719, JP-A-53-17720, JP-A-53-95618, JP-A-58-186740 or JP-A-61-117535 is desirable, and the compounds listed below are especially desirable.
  • the tetrazolium compounds used in the present invention are preferably employed in an amount of from 1 x 10- 3 to 5 x 10- 2 mol, and particularly from 5 x 10- 3 to 3 x 10- 2 mol, per mol of silver halide.
  • the hydrazine derivatives which can be used in the present invention are preferably compounds represented by formula (V) indicated below.
  • R 5 represents an aliphatic group or an aromatic group
  • R 6 represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group or a hydrazino group
  • V represents a group, an -S0 2 - group, an -SO- group, a group, a group, a thiocarbonyl group or an iminomethylene group
  • B 1 and B 2 are both hydrogen atoms or one represents a hydrogen atom and the other represents a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group.
  • Aliphatic groups represented by R 5 in formula (V) preferably have from 1 to 30 carbon atoms, and they are most desirably linear, branched or cyclic alkyl groups which have from 1 to 20 carbon atoms which may be substituted.
  • Aromatic groups represented by R 5 in formula (V) are monocyclic or bicyclic aryl groups or unsaturated heterocyclic groups.
  • an unsaturated heterocyclic group may be condensed with an aryl group.
  • Aryl groups are preferred for R 5 , and those which contain a benzene ring are especially preferred.
  • the aliphatic groups or aromatic groups for R 5 may have substituents, and typical examples of substituents include alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryl groups, substituted amino groups, ureido groups, urethane groups, aryloxy groups, sulfamoyl groups, carbamoyl groups, alkyl- or arylthio groups, alkyl- or arylsulfonyl groups, alkyl- or arylsulfinyl groups, hydroxy groups, halogen atoms, cyano groups, sulfo groups, aryloxycarbonyl groups, acyl groups, alkoxycarbonyl groups, acyloxy groups, carboxamide groups, sulfonamide groups, carboxyl groups, phosphonamide groups, diacylamino groups, imide groups and R s -NHCON(R s )CO- groups, and the preferred substituent
  • Alkyl groups represented by R 6 in formula (V) are preferably alkyl groups which have from 1 to 4 carbon atoms, and monocyclic or bicyclic aryl groups (for example those containing a benzene ring) are preferred as aryl groups.
  • R 6 is preferably a hydrogen atom, an alkyl group (for example, methyl, trifluoromethyl, 3-hydroxypropyl, 3-methane-sulfonamidopropyl, phenylsulfonylmethyl), an aralkyl group (for example, o-hydroxybenzyl) or an aryl group (for example, phenyl, 3,5-dichlorophenyl, o-methanesulfonamidophenyl, 4-methanesulfonylphenyl, 2-hydroxymethylphenyl), and among these, a hydrogen atom is most preferred.
  • an alkyl group for example, methyl, trifluoromethyl, 3-hydroxypropyl, 3-methane-sulfonamidopropyl, phenylsulfonylmethyl
  • an aralkyl group for example, o-hydroxybenzyl
  • an aryl group for example, phenyl, 3,5-dichlorophenyl,
  • R 6 may be substituted, and substituents cited as examples of substituents for R 5 can be used here as substituents.
  • the -CO- group is the most desirable group for V in formula (V).
  • R 6 may be a group such that the V-R s moiety is cleaved from the remainder of the molecule and a cyclization reaction occurs in which a ring structure which contains the atoms of the -V-R 6 moiety is formed, and that disclosed, for example, in JP-A-63-29751 can be cited as an example.
  • B 1 and B 2 are most desirably hydrogen atoms.
  • R 5 or R 6 in formula (V) may include a ballast group or a polymer which has been introduced in the normal way to render immobile photographically useful additives such as couplers, for example.
  • a ballast group is a group which has at least 8 carbon atoms which is comparatively inert with respect to photographic properties, and is selected from alkyl groups, alkoxy groups, phenyl groups, alkylphenyl groups, phenoxy groups and al- kylphenoxy groups, for example.
  • those disclosed, for example, in JP-A-1-100530 can be cited as polymers.
  • R 5 or R 6 in formula (V) may incorporate a group which is strongly adsorbed on a silver halide grain surface.
  • Thiourea groups, heterocyclic thioamide groups, mercapto heterocyclic groups and triazole groups for example, as disclosed in U.S.
  • the amount of hydrazine derivative employed in the present invention is preferably from 1 x 10- s mol to 5 x 10- 2 mol, and most desirably from 1 x 10- s mol to 2 x 10- 2 mol, per mol of silver halide.
  • the photosensitive silver halide emulsions in the present invention may be spectrally sensitized to comparatively long wavelength blue light, green light, red light or infrared light using sensitizing dyes.
  • Cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, styryl dyes, hemicyanine dyes, oxonol dyes and hemioxonol dyes for example, can be used as sensitizing dyes.
  • Sensitizing dyes which have spectral sensitivities corresponding to the spectral characteristics of various scanner light sources can be selected appropriately.
  • A) the simple merocyanine dyes disclosed in JP-A-60-162247, JP-A-2-48653, U.S. Patent 2,161,331 and West German Patent 936,071 can be selected for an argon laser light source
  • B) the trinuclear cyanine dyes disclosed in JP-A-50-62425, JP-A-54-18726 and JP-A-59-102229 can be selected for a helium neon laser light source
  • C) the thiacarbocyanines disclosed in JP-B-48-42172, JP-B-51-9609, JP-B-55-39818 and JP-A-62-284343 can be selected for an LED light source
  • D) the tricarbocyanines disclosed in JP-A-59-191032, JP-A-60-80841 and the 4-quinoline nucleus containing dicarbocyanines disclosed in JP-A-59-192242 can be selected for a semiconductor laser light source.
  • Y 1 and Y 2 each represents a group of nonmetal atoms required to form a heterocyclic ring such as a benzothiazole ring, a benzoselenazole ring, a naphthothiazole ring, a naphthoselenazole ring ora quinoline ring, and these heterocyclic rings may be substituted with lower alkyl groups (having 1 to 6 carbon atoms), alkoxy groups, hydroxy groups, aryl groups, alkoxycarbonyl groups and halogen atoms.
  • R 1 and R 2 each represents a lower alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms which has a sulfo group or a carboxy group as a substituent.
  • R 3 represents a lower alkyl group, and X 1 represents an anion.
  • n 1 and n 2 each represents 1 or 2.
  • sensitizing dyes may be used individually, or combinations of these dyes may be used. Combinations of sensitizing dyes are often used to achieve supersensitization. Substances which exhibit supersensitization, which are dyes themselves which have no spectral sensitizing action or substances which have essentially no absorption in the visible range, may also be present in the emulsion together with the sensitizing dyes.
  • sensitizing dyes Useful sensitizing dyes, combinations of dyes which exhibit supersensitization and substances which exhibit supersensitization are disclosed in Research Disclosure, Volume 176,17643 (published December, 1978), page 23, Section IV-J.
  • the amount of sensitizing dye included in the present invention is preferably selected optimally in accordance with the grain size, halogen composition and the method and extent of chemical sensitization of the silver halide emulsion, the relationship between the layer in which the compounds are included and the silver halide emulsion layer, and the type of antifogging compounds which are used. Test methods for making such a selection are well known to those in the art.
  • the amount used is preferably within the range of from 1 x 10- 7 mol to 1 x 10- 2 mol, and most desirably within the range of from 1 x 10- 6 mol to 5 x 10- 3 mol, per mol of silver halide.
  • the silver halide which is used in the present invention may be, for example, silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide or silver chloroiodobromide.
  • the use of silver chloroiodobromides, silver chlorobromides and silver iodobromides of the above silver halides is preferred in the present invention.
  • the use of silver chlorobromides or silver chloroiodobromides having a silver iodide content of from 0 to 1 mol% is especially desirable.
  • a monodispersion is one comprising grains such that at least 95% of the grains in terms of the number of grains or by weight are of a size within ⁇ 40% of the average grain size.
  • the silver halide grains in a photographic emulsion may have a regular crystalline form such as a cubic or octahedral form, an irregular crystalline form such as a spherical or plate-like form or a form which is a composite of these crystalline forms.
  • the silver halide grains may have a structure in which the interior and surface layer are a uniform phase or they may comprise a single phase. Mixtures of two or more types of silver halide emulsions which have different forms can also be used.
  • the silver halide emulsion layer may be a single layer or it may comprise multiple layers (of two or three layers, for example), and in the case of multiple layers the silver halide emulsions which are used may be the same or different.
  • Cadmium salts, lead salts, thallium salts, rhodium salts or complex salts thereof or iridium salts or complex salts thereof may be present during the processes of silver halide grain formation or physical ripening of a silver halide emulsion used in the present invention.
  • water soluble rhodium salts typically rhodium chloride, rhodium trichloride and rhodium ammonium chloride, for example, is preferred in the present invention.
  • complex salts of the water soluble rhodium salts can also be used.
  • the time of the addition of these rhodium salts is before the completion of the first ripening during the manufacture of the emulsion, and addition during grain formation is particularly desirable.
  • the amount added is preferably in the range of at least 1 x 10- 8 mol but not more than 1 x 10- s mol per mol of silver.
  • Silver halides prepared in the presence of from 1 x 10- 8 to 1 x 10- 5 mol per mol of silver of an iridium salt or complex salt are especially suitable for use in the present invention.
  • the addition of the iridium salt in the amount indicated above before the end of physical ripening and especially during the formation of the grains in the preparation of the silver halide emulsion is desirable.
  • the iridium salts used are water soluble iridium salts or iridium complex salts, and examples include iridium trichloride, iridium tetrachloride, potassium salt of hexachloroiridium(III) acid, potassium salt of hexachloroiri- dium(IV) acid, and ammonium salt of hexachloroiridium(III) acid.
  • Gelatin is useful as the binding agent or protective colloid for photographic emulsion, but other hydrophilic colloids may also be used.
  • gelatin derivatives such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfate esters; sodium alginate; sugar derivatives such as starch derivatives; and various synthetic water soluble polymeric materials such as homopolymer or copolymers of poly(vinyl alcohol), partially acetalated poly(vinyl alcohol, poly(N-vinylpyrrolidone), poly(acrylic acid), poly(methacrylic acid), polyacrylamide, polyvinylimidazole and polyvinylpyrazole can be used.
  • the silver halide emulsions used in the present invention may or may not be chemically sensitized.
  • Sulfur sensitization, reduction sensitization and noble metal sensitization methods are known for chemical sensitization of silver halide emulsions, and these methods may be used independently or in combination.
  • Gold sensitization is typical of noble metal sensitization methods and gold compounds, and principally gold complex salts, are used in this case.
  • sulfur compounds such as thiosulfates, thioureas, thiazoles and rhodanines, for example, can be used as sulfur sensitizing agents as well as the sulfur compounds which are present in gelatin.
  • JP-A-60-140340 and JP-A-61-167939 can be present in the photosensitive material of the present invention to increase photographic speed and promote high contrast. These compounds may be used individually, or two or more compounds can be used in combination.
  • Various compounds can be present in a photosensitive material of the present invention to prevent fogging during the manufacture, storage or photographic processing of the photosensitive material, or to stabilize photographic performance.
  • antifogging agents or stabilizers including azoles, for example, benzothiazolium salts, nitroimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles and nitro- benzotriazoles; mercaptopyrimidines; mercaptotriazines; thioketo compounds, such as oxazolinethione, for example; azaindenes, for example, triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,3,3a,7)tetraazaindenes) and pentaazaindenes; benzenethiosulfonic acid
  • Inorganic or organic gelatin hardening agents can be present in the photographic emulsions and the light- insensitive hydrophilic colloids in the present invention.
  • active vinyl compounds for example, 1,3,5-triacryloyl-hexahydro-s-triazine, bis(vinylsulfonyl)methyl ether, N,N-methylenebis[ ⁇ 3-(vinylsulfonyl)propionamide]
  • active halogen compounds for example, 2,4-dichloro-6-hydroxy-s-triazine
  • mucohalogen acids for example, mucochloric acid
  • N-carbamoylpyridinium salts for example, (1-morpholylcarbonyl-3-pyridinio)methanesulfonate
  • haloammidinium salts for example, 1-(1-chloro-1-pyridinomethylene)pyrrolidinium, 2-naphthalenesulfonate
  • Various surfactants may be present for various purposes in the photographic emulsion layers or other hydrophilic layers of the photosensitive material of the present invention. They are used, for example, as coating aids or as antistatic agents, for emulsification and dispersion purposes, for the prevention of adhesion and for improving photographic performance (for example, accelerating development, increasing contrast or increasing photographic speed).
  • nonionic surfactants such as saponin (steroid based), alkylene oxide derivatives (for example, polyethylene glycol, polyethylene glycol/polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol aryl alkyl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides and poly(ethylene oxide) adducts of silicones), glycidol derivatives (for example, alkenylsuccinic acid polyglyceride, alkylphenol polyglyceride), fatty acid esters of polyhydric alcohols and the alkyl esters of sugars; anionic surfactants which include acidic groups, such as carboxy groups, sulfo groups, phospho groups, sulfate groups and phosphate groups, for example, alkylcarboxylates, alkylsulfonates, alkylbenzenesulf
  • Matting agents such as silica, magnesium oxide and poly(methyl methacrylate), for example, can be present in the photographic emulsion layers or other hydrophilic colloid layers in a photosensitive material of the present invention to prevent adhesion.
  • Dispersions of water insoluble or sparingly soluble synthetic polymers can be included in the photosensitive material of the present invention to improve dimensional stability.
  • Cellulose acetate, cellulose diacetate, nitrocellulose, polystyrene and poly(ethylene terephthalate), for example, can be used for the support of the photosensitive material of the present invention, but the use of poly(ethylene terephthalate) films is most desirable.
  • These supports may be subjected to a corona treatment using known methods, and subbing layer processing may be completed using known methods, if desired.
  • waterproofing layers which contain poly(vinylidene chloride) based polymers may be employed to increase dimensional stability which relates to the changes in dimensions which arise as a result of changes in temperature and humidity.
  • Compounds which have acid groups are preferably present in the silver halide emulsion layers and other layers of the photosensitive materials of the present invention.
  • Organic acids such as salicylic acid, acetic acid and ascorbic acid, for example, and polymers or copolymers including acid monomers such as acrylic acid, maleic acid or phthalic acid as repeating units can be cited as compounds which have acid groups.
  • Ascorbic acid as a low molecular weight compound and water dispersible latexes of copolymers of acid monomers such as acrylic acid and crosslinking monomers which have two or more unsaturated groups, such as divinylbenzene, as polymeric compounds are especially desirable of these compounds.
  • the silver halide photographic materials of the present invention can provide negative images of satisfactory super-high contrast using developers which contain at least 0.15 mol/liter of sulfite as a preservative and which have a pH of from 10.5 to 12.3, and especially a pH of from 11.0 to 12.0.
  • Hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone and 2,5-dimethylhydroquinone, for example, are preferred as the dihydroxybenzene developing agent which is used in the present invention.
  • 1-Phenyl-3-pyrazolidone and developing agents derived therefrom which can be used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-p-aminophenyl-4,4-dimethyl-3-pyrazolidone and 1-p-tolyl-4,4-dimethyl-3-pyrazolidone.
  • N-Methyl-p-aminophenol, p-aminophenol, N-(p-hydroxyethyi)-p-aminophenoi, N-(4-hydroxyphenyl)glycine, 2-methyl-p-aminophenol and p-benzylaminophenol can be cited, for example, as p-aminophenol based developing agents which can be used in the present invention, and of these the use of N-methyl-p-aminophenol is preferred.
  • the developing agent in an amount of from 0.05 moi/iiter to 0.8 mol/liter is generally desirable.
  • the dihydroxybenzenes are preferably used in amounts of from 0.05 mol/liter to 0.5 mol/liter and the 1-phenyl-3pyrazolidones or p-aminophenols are preferably used in amounts of 0.06 mol/liter or less.
  • amino compounds disclosed in JP-A-2-208652 can also be used as developers in the present invention.
  • Sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabi- sulfite and formaldehyde/sodium bisulfite can be used as sulfite preservatives in the present invention.
  • the sulfite is preferably present in an amount of at least 0.4 mol/liter, and more desirably in an amount of at least 0.5 mol/liter. Furthermore, an upper limit of up to 2.5 mol/liter is desirable.
  • pH controlling agents and buffers such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate and potassium triphosphate, are included among alkali agents which can be used to set the pH.
  • the pH of the developer is generally 10.5 to 12.3.
  • the compounds disclosed in JP-A-56-24347 can be used in the developers of the present invention as agents for preventing silver contamination.
  • the compounds disclosed in JP-A-61-267759 can be used as dissolution aids and can be added to the developer.
  • the compounds disclosed in JP-A-60-93433 or the compounds disclosed in JP-A-62-186259 can be used as pH buffers which are used in the developer.
  • Aqueous solutions which contain hardening agents (for example, water soluble aluminum compounds) and acetic acid and dibasic acids (for example, tartaric acid, citric acid and their salts), as required, in addition to a fixing agent can be used as a fixer, and the pH is preferably at least 3.8, and most desirably from 4.0 to 5.6.
  • Sodium thiosulfate and ammonium thiosulfate can be used as fixing agents and the use of ammonium thiosulfate is preferred from the standpoint of fixing rate.
  • the amount of fixing agent used can be varied appropriately, but it is generally from about 0.1 to about 0.5 mol/liter.
  • Water soluble aluminum salts which are used principally as film hardening agents in fixers are compounds which are generally known as film hardening agents for acid film hardening fixers, and examples of the film hardening agents include aluminum chloride, aluminum sulfate and potassium alum.
  • Tartaric acid or derivatives thereof, or citric acid or derivatives thereof can be used individually or as combinations of two or more thereof as the dibasic acid referred to above. These compounds are effective when used in amounts of at least 0.005 mol per liter of fixer, and they are especially effective when used in amounts of from 0.01 mol/liter to 0.03 mol/liter.
  • Actual examples include tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, ammonium tartrate and ammonium potassium tartrate.
  • citric acid and derivatives thereof which are effective in the present invention include citric acid, sodium citrate and potassium citrate.
  • Preservatives for example, sulfite, bisulfite
  • pH buffers for example, acetic acid, boric acid
  • pH controlling agents for example, ammonia, sulfuric acid
  • agents for improving image storage for example, potassium iodide
  • chelating agents can be present if desired in a fixer.
  • the pH buffers are used in amounts of from 10 to 100 g/liter and preferably in amounts of from 18 to 25 g/liter, since the pH of the developer is high.
  • the photosensitive material of the present invention exhibits excellent rapid processing performance with a total processing time in an automatic processor of from 15 seconds to 60 seconds.
  • the times and temperatures of the development and fixing in the rapid development processing in the present invention are generally not more than 25 seconds at a temperature of from about 25°C to 50°C, and preferably from 4 to 15 seconds at a temperature of from 30°C to 40°C.
  • a water washing or stabilization process is preferably carried out after the development and fixation of the photosensitive material in the present invention.
  • the water washing process can be carried out using a two or three stage countercurrent washing system in order to economize on water usage.
  • the establishment of squeegee rollerwashing tanks is desirable when washing with a small amount of water in order to reduce the amount of washing water.
  • part or all of the overflow from the water washing bath or stabilizing bath can be used in the fixer as disclosed in JP-A-60-235133. The amount of liquid effluent is reduced when this is done and this is desirable.
  • fungicides for example, the compounds disclosed in Horiguchi, The Chemistry of Biocides and Fungicides, and in JP-A-62-115154
  • washing accelerators sulfites, for example
  • chelating agents may be present in the water washing water.
  • the time and temperature in the washing or stabilizing bath using the method described above is from 5 seconds to 30 seconds at a temperature of from 0°C to 50°C, and preferably from 4 seconds to 20 seconds at a temperature of from 15°C to 40°C.
  • the developed, fixed and washed photosensitive material is dried through a squeegee roller.
  • the drying is carried out for from 4 seconds to 30 seconds at a temperature of from 40°C to 80°C.
  • the total processing time in the present invention is the total time elapsed from the entry of the leading edge of the film into the inlet port of the automatic processor, through the development tank, the carry-over part (i.e., traveling part), the fixing tank, the carry-over part, the water washing tank, the carry-over part and the drying part until the leading edge of the film emerges from the drier.
  • the carry-over part i.e., traveling part
  • the fixing tank the carry-over part
  • the water washing tank the carry-over part and the drying part until the leading edge of the film emerges from the drier.
  • the amount of gelatin which is used for the binder in the emulsion layers and protective layers can be reduced in the silver halide photographic material of the present invention without the disadvantage of pressure fogging and so development processing can be carried out without loss of developing speed, fixing speed or drying speed even with rapid processing with a total processing time of from 15 to 60 seconds.
  • the second and third liquids were added simultaneously over a period of 10 minutes, with stirring, to the first liquid which was maintained at 38°C, pH 4.5 and nuclei grains having a diameter of 0.16 ⁇ m were formed. Then, the fourth and fifth liquids shown below were added over a period of 10 minutes. Moreover, 0.15 g of potassium iodide was added and grain formation was completed.
  • the mixture was subsequently washed using the flocculation method and 30 g of gelatin was added.
  • the emulsion so obtained was divided into four equal parts, the pH was adjusted to 5.1, the pAg was adjusted to 7.5 and 2 mg of sodium thiosulfate and 3 mg of chloroauric acid were added and optimal chemical sensitization was carried out at 60°C. Moreover, 50 mg of 2-methyl-4-hydroxy-1,3,3a,7-tetraazaindene was added as a stabilizer and 100 mg/mol-Ag of C-1 and C-4 were added as spectral sensitizing dyes.
  • Phenoxyethanol was added at a concentration of 100 ppm as a fungicide, and finally a cubic silver iodochlorobromide emulsions having average grain size of 0.20 ⁇ m which contained 80 mol% of silver chloride was obtained (variation coefficient: 9%).
  • Hydroquinone and 1-phenyl-5-mercaptotetrazole were added to the emulsion as antifoggants in amounts of 2.5 g and 50 mg respectively per mol of silver, poly(ethyl acrylate) latex was added in an amount of 25% with respect to the gelatin binder as a plasticizer, and 2-bis(vinylsulfonylacetamido)ethane was added as a film hardening agent and, moreover, colloidal silica was added as shown in Table 1 below.
  • the emulsions were then coated on polyester supports as to provide a coated silver weight of 3.0 g/m 2 and a coated gelatin weight of 1.0 g/ m2 .
  • the support used in this example had a backing layer and a backing protective layer of the compositions indicated below.
  • the samples obtained were exposed with a xenon flash light of 1 x 10- s sec through an interference filter which had a peak at 670 nm and a continuous wedge, processed at the times and temperatures indicated below using an automatic processor FG-710NH made by the Fuji Photo Film Co., Ltd. and subjected to sensitometry.
  • LD835 and FL308 made by the Fuji Photo Film Co., Ltd. were used as the developer and fixer, respectively.
  • the surface of the samples was rubbed with a sapphire needle of a diameter of 1 mm under a load of from 0 to 200 g under conditions of 25°C, 60% RH and then the samples were developed and processed under the same conditions as in 1) above and the load under which pressure fogging occurred was measured.
  • the dynamic friction coefficient was measured under conditions of 25°C, 60% RH using a sapphire needle of a diameter of 1 mm with a load of 100 g after the sample was left to stand for 1 hour as the speed in 60 cm/min.
  • An aqueous silver nitrate solution and an aqueous solution of a solution which contained 3 x 10- 7 mol of K 3 1rC1 6 and 3 x 10- 7 mol of (NH 4 ) 3 RhCl 6 per mol of silver and sodium bromide corresponding to 30 mol% per mol of silver were added simultaneously over a period of 30 minutes to an aqueous gelatin solution which was maintained at 48°C and a monodisperse silver chlorobromide emulsion of an average grain size of 0.28 ⁇ m was prepared by maintaining the potential during this time at 70 mV.
  • a 1% aqueous solution of potassium iodide was added to the obtained emulsion in an amount of 0.2 mol% per mol of silver and, after conversion, the emulsion was desalted using the flocculation method.
  • Sodium thiosulfate and chloroauric acid were added to the emulsion and chemical sensitization was carried out while maintaining a temperature of 60°C, after which a 1 % aqueous solution of4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene was added in an amount of 30 ml per mol of silver.
  • This emulsion was sensitized to the infrared region by adding 60 ml of a 0.05% solution of the infra-red sensitizing dye represented by D-2 to 1 kg of the emulsion.
  • a 0.5% methanol solution (70 ml) of 4,4'-bis-(4,6- dinaphthoxypyrimidin-2-ylamino)stilbene disulfonic acid, disodium salt and 90 ml of a 0.5% methanol solution of2,5-dimethyl-3-allylbenzothiazole iodide were added to the emulsion for supersensitization and stabilization.
  • colloidal silica as shown in Table 3 below, 100 mg/m 2 of hydroquinone, 25% with respect to the gelatin binder of poly(ethyl acrylate) latex as a plasticizer and 160 mg/m 2 of 2-bis(vinylsulfonylacetamido)ethane as a film hardening agent were added and the obtained emulsions were coated on a polyester support in a coated weight of silver of 3.4 g/m 2 .
  • the coated weight of gelatin was 2.0 g/m 2 .
  • Samples 21 to 29 obtained in this way were evaluated with respect to 1) relative photographic speed (using an interference filter which had a peak at 780 nm), 2) pressure fogging and 3) dynamic friction coefficient in the same way as described in Example 1.
  • aqueous silver nitrate solution and an aqueous potassium iodide, potassium bromide solution were added simultaneously over a period of 60 minutes in the presence of 4 x 10- 7 mol per mol of silver of potassium salt of hexachloroiridium(III) acid, and ammonia to an aqueous gelatin solution which was maintained at 50°C, and, by maintaining the pAg at 7.8 during this period, a cubic monodisperse emulsion having an average silver iodide content of 1 mol% and an average grain size of 0.28 ⁇ m was obtained.
  • This emulsion was washed in the usual way and the soluble salts were removed, after which gelatin was added. Then 0.1 mol% per mol of silver of an aqueous potassium iodide solution was added and the grain surfaces were subjected to conversion and Emulsion A was obtained.
  • Illustrative Compounds C-1 and C-4 of formula (VI) (4.0 x 10- s mol/mol-Ag of each) as sensitizing dyes, and 1.2 x 10- 3 mol/mol-Ag of Compound V-7 of formula (V) and 5.0 x 10- 5 mol/mol-Ag of Compound V-19 as hydrazine derivatives were added sequentially to Emulsion A, and 8 mg/m 2 of 4-hydroxy-6-methyI-1,3,3a,7-tetraazaindene as stabilizer, 600 mg/m 2 of poly(ethyl acrylate) latex (particle size: 0.05 ⁇ m), 20 mg/m 2 of 5-methylbenzotriazole, 10 mg/m 2 of 1,4-bis[3-(4-acetylaminopyridinio)-propionyloxy]tetramethylenedibromide, the amounts shown in Table 4 below of colloidal silica and 145 mg/m 2 of 2-bis(vinylsulf
  • Samples 30 to 38 obtained in this way were evaluated as to 1) relative photographic speed (using an interference filter which had a peak at 633 nm), 2) pressure fogging and 3) dynamic friction coefficient in the same way as described in Example 1.
  • the development processing was carried out using GR-D1 (developer) and GR-F1 (fixer) made by Fuji Photo Film Co., Ltd. using an FG-660F automatic processor (Fuji Photo Film Co., Ltd.) under development conditions of 34°C, 30".
  • the results obtained are shown in Table 4 below.
  • Emulsion layers and lower and upper protective layers of the formulations shown below were coated simultaneously on one side of a biaxially stretched poly(ethylene terephthalate) film support having a subbing layer on both sides of a thickness of 100 ⁇ m.
  • Solution II and Solution III were added simultaneously at a constant rate to Solution I which was maintained at 50°C.
  • Gelatin was added after removing the soluble salts from the emulsion.
  • the average grain size of this monodisperse emulsion was 0.28 ⁇ m, and the gelatin content was 56 g per kg of emulsion.
  • the backing layer and the protective layer of the formulations shown below were coated simultaneously onto the reverse side.
  • Samples 39 to 47 obtained in this way were evaluated in the same way as in Example 3.
  • the exposure conditions for the relative speed involved the use of a tungsten light source of a color temperature of 3,200°K and an exposure of 300 lux.
  • the results obtained are shown in Table 5 below.
  • a silver chloroiodobromide emulsion (cubic, 2 mol% silver iodide, 33 mol% silver chloride) of average grain size 0.35 ⁇ m was prepared using the double jet method and, after desalting, the emulsion was subjected to gold and sulfur sensitization and 6-methyl-4-hydroxy-1,3,3a,7-tetraazaindene was added as a stabilizer and 150 mg per mol of silver halide in the emulsion of 1-( ⁇ -hydroxyethyl)-3-phenyl-5-[(3- ⁇ -sulfopropyl- ⁇ -benzox- azolidine)ethylidene]thiohydantoin was added as a sensitizing dye.
  • the present invention provides sensitive materials which had improved pressure fogging resistance which arises as a result of contact friction of the sensitive material with other substances and which are suitable for rapid processing, by including colloidal silica in the silver halide emulsion layer and setting the dynamic friction coefficient of the outermost surface layer on the side of the emulsion layer to 0.35 or less.

Claims (5)

1. Photographisches Silberhalogenidmaterial, umfassend einen Träger, der darauf zumindest eine Silberhalogenid-Emulsionsschicht und zumindest eine Schutzschicht oberhalb der Emulsionsschicht aufweist, worin colloidales Silica mit einer durchschnittlichen Teilchengröße von 5 bis 1000 mµ in zumindest einer der Silberhalogenid-Emulsionsschichten vorhanden ist, und wobei der dynamische Friktionskoeffizient der Oberfläche der äußersten Schicht der Schutzschicht 0,35 oder weniger ist, worin die äußerste Schicht der Schutzschicht ein Schmiermittel umfaßt.
2. Photographisches Silberhalogenidmaterial nach Anspruch 1, worin die Silberhalogenid-Emulsionsschicht oder andere hydrophile colloidale Schichten zumindest eine Polyhydroxybenzolverbindung umfassen.
3. Photographisches Silberhalogenidmaterial nach Anspruch 1 oder 2, worin die Schutzschicht 2 oder mehr Schichten umfaßt, worin die äußerste dieser Schichten ein Schmiermittel und colloidales Silica umfaßt, und worin die Schutzschicht, die zwischen der äußersten Schutzschicht und der Emulsionsschicht ist, ein Polymerlatex mit einem Glasübergangspunkt von 20°C oder weniger umfaßt.
4. Photographisches Silberhalogenidmaterial nach einem derAnsprüche 1 bis 3, worin ein Trockengewichtsverhältnis des colloidalen Silicas, basierend auf der Gelatine in der Schicht, worin das colloidale Silica vorhanden ist, von 0,05 bis 1,0 ist.
5. Photographisches Silberhalogenidmaterial nach einem der Ansprüche 1 bis 4, worin ein Gewichtsverhältnis des Schmiermittels, bezogen auf die Menge an Bindemittel in der äußersten Schicht, von 0,01 bis 1,0 ist.
EP19910121005 1990-12-11 1991-12-06 Photographische Silberhalogenidmaterialien Expired - Lifetime EP0490302B1 (de)

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JPH05188528A (ja) * 1991-06-25 1993-07-30 Eastman Kodak Co 圧力吸収保護層含有写真要素
JPH05188527A (ja) * 1991-06-25 1993-07-30 Eastman Kodak Co 圧力吸収中間層含有写真要素
US5288602A (en) * 1992-08-24 1994-02-22 Agfa-Gevaert Aktiengesellschaft Photographic silver halide element containing silicone oil
US5550003A (en) * 1992-12-24 1996-08-27 Fuji Photo Film Co., Ltd. Silver halide photographic photosensitive materials and a method of image formation in which they are used
DE69419949T2 (de) * 1993-02-22 2000-01-20 Mitsubishi Paper Mills Ltd Photographisches lichtempfindliches Silberhalogenidmaterial
DE4311888A1 (de) * 1993-04-10 1994-10-13 Du Pont Deutschland Lichtempfindliches Silberhalogenid-Aufzeichnungsmaterial mit verminderter Druckempfindlichkeit
JPH07104428A (ja) * 1993-09-30 1995-04-21 Fuji Photo Film Co Ltd ハロゲン化銀感光材料およびその処理方法
WO1995022786A1 (fr) * 1994-02-21 1995-08-24 Soken Chemical & Engineering Co., Ltd. Materiau photosensible a base d'halogenure d'argent
DE4442876A1 (de) * 1994-12-02 1996-06-13 Du Pont Deutschland Spektral sensibilisiertes photographisches Silberhalogenid-Aufzeichnungsmaterial und Verfahren zu dessen Herstellung
US5876908A (en) * 1997-04-22 1999-03-02 Eastman Kodak Company Photographic element containing improved interlayer
JP3646285B2 (ja) * 1998-12-14 2005-05-11 コニカミノルタホールディングス株式会社 ハロゲン化銀写真感光材料の画像形成方法
US6387112B1 (en) 1999-06-18 2002-05-14 Novare Surgical Systems, Inc. Surgical clamp having replaceable pad

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JPS53100226A (en) * 1977-02-14 1978-09-01 Fuji Photo Film Co Ltd Photosensitive material with film physical property improved
JPS6023848A (ja) * 1983-07-20 1985-02-06 Fuji Photo Film Co Ltd 帯電防止をしたハロゲン化銀写真感光材料
JPS60238841A (ja) * 1984-05-11 1985-11-27 Fuji Photo Film Co Ltd 透光性感光記録材料
JPS61140939A (ja) * 1984-12-12 1986-06-28 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
JPH07101289B2 (ja) * 1987-03-11 1995-11-01 コニカ株式会社 高速処理可能なハロゲン化銀写真感光材料
JPS6461748A (en) * 1987-09-01 1989-03-08 Fuji Photo Film Co Ltd Silver halide photographic sensitive material
JPH0820693B2 (ja) * 1987-09-11 1996-03-04 富士写真フイルム株式会社 ハロゲン化銀写真感光材料
JPH02153344A (ja) * 1988-12-05 1990-06-13 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
JPH02161425A (ja) * 1988-12-15 1990-06-21 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
JPH02285346A (ja) * 1989-04-26 1990-11-22 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料及びその処理方法
JPH02298938A (ja) * 1989-05-12 1990-12-11 Konica Corp ハロゲン化銀写真感光材料

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DE69107971D1 (de) 1995-04-13
JPH04214551A (ja) 1992-08-05
EP0490302A3 (en) 1993-03-17
EP0490302A2 (de) 1992-06-17
JP2802684B2 (ja) 1998-09-24

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