EP0107817B2 - Multilayer silver halide reversal color photographic material - Google Patents
Multilayer silver halide reversal color photographic material Download PDFInfo
- Publication number
- EP0107817B2 EP0107817B2 EP19830109961 EP83109961A EP0107817B2 EP 0107817 B2 EP0107817 B2 EP 0107817B2 EP 19830109961 EP19830109961 EP 19830109961 EP 83109961 A EP83109961 A EP 83109961A EP 0107817 B2 EP0107817 B2 EP 0107817B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- emulsion
- emulsion layer
- silver halide
- photographic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229910052709 silver Inorganic materials 0.000 title claims description 66
- 239000004332 silver Substances 0.000 title claims description 66
- -1 silver halide Chemical class 0.000 title claims description 54
- 239000000463 material Substances 0.000 title claims description 27
- 239000000839 emulsion Substances 0.000 claims description 165
- 230000035945 sensitivity Effects 0.000 claims description 88
- 238000009826 distribution Methods 0.000 claims description 43
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 6
- 239000010410 layer Substances 0.000 description 153
- 235000013339 cereals Nutrition 0.000 description 89
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 35
- 229910021612 Silver iodide Inorganic materials 0.000 description 35
- 229940045105 silver iodide Drugs 0.000 description 35
- 235000019580 granularity Nutrition 0.000 description 28
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 24
- 108010010803 Gelatin Proteins 0.000 description 23
- 239000000975 dye Substances 0.000 description 23
- 229920000159 gelatin Polymers 0.000 description 23
- 239000008273 gelatin Substances 0.000 description 23
- 235000019322 gelatine Nutrition 0.000 description 23
- 235000011852 gelatine desserts Nutrition 0.000 description 23
- 238000000034 method Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 13
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- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 12
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- 238000012545 processing Methods 0.000 description 6
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- 206010070834 Sensitisation Diseases 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 230000008313 sensitization Effects 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
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- 239000002356 single layer Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
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- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
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- UDATXMIGEVPXTR-UHFFFAOYSA-N 1,2,4-triazolidine-3,5-dione Chemical compound O=C1NNC(=O)N1 UDATXMIGEVPXTR-UHFFFAOYSA-N 0.000 description 1
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical class C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 1
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- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
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- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- ZAKLKBFCSHJIRI-UHFFFAOYSA-N mucochloric acid Natural products OC1OC(=O)C(Cl)=C1Cl ZAKLKBFCSHJIRI-UHFFFAOYSA-N 0.000 description 1
- JRNGUTKWMSBIBF-UHFFFAOYSA-N naphthalene-2,3-diol Chemical compound C1=CC=C2C=C(O)C(O)=CC2=C1 JRNGUTKWMSBIBF-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- QUBQYFYWUJJAAK-UHFFFAOYSA-N oxymethurea Chemical compound OCNC(=O)NCO QUBQYFYWUJJAAK-UHFFFAOYSA-N 0.000 description 1
- 229950005308 oxymethurea Drugs 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- ZFLIKDUSUDBGCD-UHFFFAOYSA-N parabanic acid Chemical compound O=C1NC(=O)C(=O)N1 ZFLIKDUSUDBGCD-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
- 229960001553 phloroglucinol Drugs 0.000 description 1
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical compound O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- HBCQSNAFLVXVAY-UHFFFAOYSA-N pyrimidine-2-thiol Chemical class SC1=NC=CC=N1 HBCQSNAFLVXVAY-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 150000003455 sulfinic acids Chemical class 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003475 thallium Chemical class 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 125000005323 thioketone group Chemical group 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229920003170 water-soluble synthetic polymer Polymers 0.000 description 1
- 235000020985 whole grains Nutrition 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/3022—Materials with specific emulsion characteristics, e.g. thickness of the layers, silver content, shape of AgX grains
Definitions
- This invention relates to a color photographic light-sensitive material of a multilayer construction.
- the present invention achieves an improvement in granularity of dye image grains which are produced by processing a sensitive material, which contains silver halides and nondiffusible couplers as main components, with a first developing solution containing a black-and-white developing agent of pyrazolidone type and subsequent processing of the resulting material with a reversal color developing solution containing a color developing agent of paraphenylenediamine type.
- a coupler incorporated color photographic light-sensitive material comprises a support coated generally with a nondiffusible cyan-forming coupler incorporated red-sensitive silver halide emulsion layer, a nondiffusible magenta-forming coupler incorporated green-sensitive emulsion layer and a nondiffusible yellow-forming coupler incorporated blue-sensitive emulsion layer.
- most color photographic light-sensitive materials for taking photographs are constructed of a support, e.g., a cellulose triacetate film, a polyethylene terephtalate film or the like which is provided with a subbing layer in advance and has provided thereon, a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer in that order. Further a yellow filter layer is put in between the green-sensitive layer and the blue-sensitive layer and further, a gelatin protective layer is provided as the topmost layer of the sensitive material.
- a support e.g., a cellulose triacetate film, a polyethylene terephtalate film or the like which is provided with a subbing layer in advance and has provided thereon, a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer in that order.
- a yellow filter layer is put in between the green-sensitive layer and the blue-sensitive layer and further, a gelatin protective layer is provided as the topmost layer of the sensitive material.
- the so-called mixed emulsion e.g., the combination of a high sensitivity emulsion containing relatively coarse grains and a low sensitivity emulsion containing fine grains, is employed as the silver halide emulsion for the purpose of attaining desired gradation.
- German Patent 1,121,470 and British Patent 923,045 disclose another method of improving granularity of a dye image in which-as described in their respective examples-an emulsion which has been conventionally coated in a single layer is separated into two layers, a high sensitivity emulsion layer and a low sensitivity emulsion layer, which have their sensitivities in the same visible region and which contain their respective nondiffusible couplers which form colors of substantially the same hue, and which are coated in a double layer.
- Such a method makes it possible to increase the sensitivity of a multilayer color photographic light-sensitive material without deteriorating the granularity in a practically important density range of the granulation curve, and in proportion to this gain in the sensitivity the grain size of the silver halide emulsion can be decreased resulting in the improvement of the granularity.
- a method can exhibit its effect on improvement of the granularity in a negative-type film which contains a small amount of coupler in its high sensitivity emulsion layer, it is not effective for reversal-type films, because it is necessary for reversal type film to contain a large amount of coupler in its high sensitivity emulsion layer in order to render the gradation hard in a high density range.
- an emulsion contains grains among which there exists a distribution of sizes, and deterioration of granularity due to coarse grains present in a specific proportion is unavoidable. Accordingly, the improvement in granularity attained by the above-described method is far from being sufficient.
- a high sensitivity emulsion layer If one intends to achieve an improvement of the granularity by narrowing a distribution of grain sizes of an emulsion, one must separate the emulsion into three layers, that is, a high sensitivity emulsion layer, an intermediate sensitivity emulsion layer and a low sensitivity emulsion layer.
- An object of this invention is to improve the granularity of a multilayer reversal color photographic material.
- a multilayer silver halide reversal colour photographic material comprising a support bearing three silver halide emulsion layers having the same colour sensitivity but different photographic sensitivities, among the emulsion layers at least both the emulsion layer having the highest photographic sensitivity and the emulsion layer having the second highest photographic sensitivity satisfying the following conditions:
- a grain size and a grain size distribution can be determined according to methods described in T.H. James, The Theory of Photographic Process, the 4th Ed., pp. 100-102 (1977).
- Reducing iodide contents in the highest sensitivity emulsion layer and the second highest sensitivity emulsion layer to 4.5 mole % or less results in accelerating the progress of development and consequently, such layers become contrasty and an influence of their granularities upon emulsions having lower sensitivities can be diminished.
- This invention makes it possible to improve the granularity without making the gradation contrasty. Namely, in the density range near 1.0 based on the reversal density which has the greatest influence on qualities of reversal image, the highest sensitivity emulsion layer and the second highest sensitivity emulsion layer both exert a slight influence on the granularity and therefore, this invention can provide reversal images excellent in the granularity.
- the preferable iodide content in the highest sensitivity emulsion layer and/or the second highest sensitivity emulsion layer is within the range of 0.5 mole % to 3.0 mole %.
- This invention can produce satisfactory results in any of the sensitive emulsion layers, such as a red-sensitive emulsion layer, a green-sensitive emulsion layer or a blue-sensitive emulsion layer.
- a red-sensitive emulsion layer such as a red-sensitive emulsion layer, a green-sensitive emulsion layer or a blue-sensitive emulsion layer.
- it has a great effect in a red-sensitive emulsion layer and a green-sensitive emulsion layer in which difference in granularity is more liable to be perceived.
- an emulsion layer having one kind of color sensitivity has three constituent layers differing in photographic sensitivity, and the constituent layers are arranged nearer to the support in order of decreasing sensitivity.
- a difference in photographic sensitivity between the highest sensitivity emulsion layer and the second highest sensitivity emulsion layer ranges from 0.2 to 1.0, preferably from 0.3 to 0.8, expressed in terms of logarithmic units.
- the preferable difference in photographic sensitivity between the second highest sensitivity emulsion layer and the lowest sensitivity emulsion layer is from 0.3 to 1.5, expressed in terms of logarithmic units.
- a mole ratio of silver to coupler in the highest sensitivity emulsion layer is smaller than that in the second highest emulsion layer. It is especially preferable to control the radio of silver to coupler in the higher sensitivity emulsion layer to a lower value than that in the lower sensitivity emulsion layer.
- both silver iodobromide and silver iodochlorobromide can be incorporated.
- a photographic emulsion of this invention no particular regard need be paid to the mean grain size of silver halide grains to be contained therein (the mean grain size being determined by averaging grain sizes based on the projection area wherein a grain diameter in case of spherical or nearly spherical grains and an edge length in case of cubic grains are taken as the grain sizes).
- the mean grain size being determined by averaging grain sizes based on the projection area wherein a grain diameter in case of spherical or nearly spherical grains and an edge length in case of cubic grains are taken as the grain sizes.
- a silver halide emulsion having a mean grain size of 3 ⁇ m or less is preferred.
- the silver halide grains in the photographic emulsions of this invention may have a regular crystal form, such as that of a cube or an octahedron; an irregular crystal form, such as that of a sphere, a plate or so on; or a composite form thereof.
- a mixture of various crystal forms of silver halide grains may be also present.
- the interior and the surface of the silver halide grains may differ, or the silver halide grains may be uniform throughout. Further, either silver halide grains of the kind which form latent image predominantly at the surface of the grains, or grains of the kind which mainly form latent image inside the grains can be used.
- the photographic emulsion to be employed in this invention can be prepared using various methods as described in, for example, P. Glafkides, Chimie et Physique Photographique , Paul Montel, Paris (1967), G.F. Duffin, Photographic Emulsion Chemistry , The Focal Press, London (1966), and V.L. Zelikman et al, Making and Coating Photographic Emulsion .
- Such methods include the acid process, the neutral process, the ammonia process and so on.
- Suitable methods for reacting a water-soluble silver salt with a water-soluble halide include a single jet method, a double jet method, a combination thereof and so on.
- a method in which silver halide grains are produced in the presence of excess silver ions can be employed in this invention.
- the so-called controlled double jet method in which the pAg of the liquid phase in which silver halide grains are to be precipitated is maintained constant, may also be employed therein.
- a silver halide emulsion having a regular crystal form and almost uniform grain size that is to say, a monodisperse silver halide emulsion can be obtained.
- a mixture of two or more silver halide emulsions prepared separately may be employed.
- cadmium salts zinc salts, lead salts, thallium salts, iridium salts or complexes, rhodium salts or complexes, iron salts or complexes and/or the like may be present.
- Removal of the soluble salts from the silver halide emulsion is, in general, carried out after the formation of the silver halide or after physical ripening.
- the removal can be effected using the well-known noodle washing method which comprises gelling the gelatin, or using a sedimentation process (thereby causing flocculation in the emulsion) taking advantage of a sedimenting agent such as a polyvalent anion-containing inorganic salt (e.g., sodium sulfate), an anionic surface active agent or an anionic polymer (e.g., polystyrene sulfonic acid), or a gelatin derivative (e.g., an aliphatic acylated gelatin, an aromatic acylated gelatin, an aromatic carbamoylated gelatin or the like).
- a sedimenting agent such as a polyvalent anion-containing inorganic salt (e.g., sodium sulfate), an anionic surface active agent or an anionic polymer (e.g.
- the silver halide emulsion of this invention can be a so-called un-after-ripened emulsion (e.g., a primitive emulsion), that is to say, a chemically unsensitized emulsion.
- a chemically unsensitized emulsion e.g., a chemically unsensitized emulsion.
- the emulsion of this invention it is usual for the emulsion of this invention to be chemically sensitized. Chemical sensitization can be carried out using processes described in P. Glafkides, supra , V. L. Zelikman et al, supra , or H Frieser, Die Grundlagen der Photographischenificate mit Siberhalogeniden , Akademische Verlagsgesellschaft (1968).
- sulfur sensitization using compounds containing sulfur capable of reacting with silver or active gelatin, reduction sensitization using reducing materials, sensitization with gold or other noble metal compounds and so on can be employed individually or as a combination thereof.
- suitable sulfur sensitizers which can be used include thiosulfates, thioureas, thiazoles, rhodanines and other sulfur-containing compounds.
- Specific examples of sulfur sensitizers are disclosed in U.S. Patents 1,574,944; 2,410,689; 2,278,947; 2,728,668; 3,656,955; 4,032,928 and 4,067,740.
- Suitable reducing sensitizers include stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds and the like, and specific examples of these sensitizers are described in U.S. Patents 2,487,850; 2,419,974; 2,518,698; 2,983,609; 2,983,610; 2,694,637; 3,930,867 and 4,054,458.
- Complex salts of the metals of Group VIII of the Periodic Table such as those of platinum, iridium, palladium, etc.
- Specific examples of these metal complexes are disclosed in U.S. Patents 2,399,083 and 2,448,060; British Patent 618,061; and so on.
- the photographic emulsion to be employed in this invention can contain a wide variety of compounds for purposes of preventing fogging or stabilizing photographic functions during production, storage or processing of the sensitive material.
- azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro- or halogen-substituted ones) etc.
- heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazones, mercaptotrazoles (especially 1 - phenyl - 5 - mercaptotetrazole), mercaptopyrimidines, etc.
- the above-described heterocyclic mercapto compounds containing water soluble groups such as carboxyl group, sulfonyl group or the like
- thioketo compounds such as oxazolinethiones; azain
- the photographic emulsion layers and other hydrophilic colloidal layers of the photographic material prepared in accordance with an embodiment of this invention can contain dispersions of water insoluble or slightly water soluble synthetic polymers for purposes of improvement in dimensional stability and so on.
- Suitable examples of such polymers include those which contain as monomer components alkyl(metha)acrylate, alkoxyalkyl(metha)acrylate, glycidyl(metha)acrylate, (metha)acrylamide, vinyl ester (e.g., vinyl acetate, etc.), acrylonitrile, olefins, styrene and so on individually or in combination of two or more thereof, or in combination with one or two of the above-described monomers with acrylic acid, methacrylic acid, ⁇ , ⁇ -unsaturated dicarboxylic acid, hydroxyalkyl(metha)acrylate, sulfoalkyl(metha)acrylate, styrenesulfonic acid or so on.
- the photographic emulsion layers and other hydrophilic colloidal layers of the photographic material prepared in accordance with an embodiment of this invention can contain inorganic or organic hardeners.
- inorganic or organic hardeners for example, chromium salts (e.g., chrome alum, chromium acetate, etc.), aldehydes (e.g., formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (e.g., dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (e.g., 2,3-dihydroxydioxane, etc.), active vinyl-containing compounds (e.g., 1,3,5-triacryloyl-hexahydroxy-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen-containing compounds (e.g., 2,4 - dichlor
- the sensitive material prepared in accordance with an embodiment of this invention may contain as a color fog-preventing agent hydroquinone derivative, aminophenol derivatives, gallic acid derivatives, ascorbic acid derivatives and the like.
- color fog-preventing agents are described in U.S. Patent 2,360,290; 2,336,327; 2,403,721; 2,418,613; 2,675,314; 2,701,197; 2,704,713; 2,728,659; 2,732,300 and 2,735,365, published unexamined Japanese Patent Applications 92988/′75, 92989/′75, 93928/′75, 110,337/′75 and 146235/′77, published examined Japanese Patent Application 23813/′75, and so on.
- the sensitive material prepared in accordance with an embodiment of this invention may contain an ultraviolet ray-absorbing agent in its hydrophilic colloidal layer.
- an ultraviolet ray-absorbing agent for example, benzotriazole compounds substituted with aryl groups, 4-thiazolidone compounds, benzophenone compounds, cinnamic acid esters, butadiene compounds, benzoxazole compounds and further, such polymers as to absorb ultraviolet rays can be employed as such an agent.
- These ultraviolet absorbing agents may be fixed in the hydrophilic colloidal layer to which they are added.
- UV absorbing agents are described in U.S. Patents 3,533,794; 3,314,794 and 3,352,681, published unexamined Japanese Patent Application 2784/′71, U.S. Patents 3,705,805; 3,707,375; 4,045,229; 3,700,455 and 3,499,762, West German Published Application (OLS) 1,547,863; and so on.
- Hydrophilic colloidal layers of the sensitive material prepared in accordance with an embodiment of this invention may contain water soluble dyes as a filter dye, or for other various purposes, e.g., antiirradiation and so on.
- water soluble dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes.
- oxonol dyes, hemioxonol dyes and merocyanine dyes are used to greater advantage.
- Suitable couplers to be incorporated in hydrophilic colloidal layers of the sensitive material prepared in accordance with an embodiment of this invention are oil soluble couplers.
- Such couplers may be polymeric ones.
- magenta couplers include 5-pyrazolone type couplers.
- magenta couplers which can be used in this invention are those described in U.S. Patents 2,600,788; 2,983,608; 3,062,653; 3,127,269; 3,311,476; 3,419,391; 3,519,429; 3,558,319; 3,582,322; 3,615,506; 3,834,980 and 3,891,445 German Patent 1,810,464, West Germany Patent Applications (OLS) 2,408,665; 2,417,945; 2,418,959 and 2,424,467, published examined Japanese Patent Application 6031/′65, published unexamined Japanese Patent Applications 20826/′76, 58922/′77, 129538/′74 74027/′74, 159336/′75, 42121/′77, 74028/′74, 60233/′75, 26541/′76, 55122/′78, 94752/′82 and 35858/′82
- Preferred yellow couplers include benzoylacetonilide type and pivaloylacetoanilide type compounds.
- Specific examples of yellow couplers which can be used in this invention are those which are described in U.S. Patents 2,875,057; 3,265,506; 3,408,194; 3,551,155; 3,582,322; 3,725,072 and 3,891,445, West German Patent 1,547,868, West German Patent Applications (OLS) 2,219,917; 2,261,361 and 2,414,006, British Patent 1,425,020, published examined Japanese Patent Application 10783/′76, published unexamined Japanese Patent Applications 26133/′72, 73147/′73, 102636/′76, 6341/′75, 123342/′75, 130442/′75, 21827/′76, 87650/′75, 82424/′77 and 115219/′77, U.S. Patents 3,211,552; 3,370,952; 3,451,820; 3,926,4
- Useful cyan couplers include phenolic compounds and naphtholic compounds. Specific examples of such compounds include those which described in U.S. Patents 2,369,929; 2,434,272; 2,474,293; 2,521,908; 2,895,826; 3,034,892; 3,311,476; 3,458,315; 3,476,563; 3,583,971; 3,591,383; 3,767,411; and 4,004,929, West German Patent Applications (OLS) 2,414,830 and 2,454,329, published unexamined Japanese Patent Applications 59838/′73, 26034/′76, 5055/′73, 146828/′76, 69624/′77 and 90932/′77, U.S. Patents 3,211,552; 3,370,952; 3,451,820; 3,926,436; 4,080,211 and 4,128,427 and Research Disclosure , No. 21728.
- the photographic emulsions to be used in this invention may be spectrally sensitized using methine dyes or other dyes.
- Useful sensitizing dyes include those described in German Patent 929,080, U.S. Patents 2,493,748; 2,503,776; 2,519,001; 2,912,329; 3,656,959; 3,672,897 and 4,025,349, British Patent 1,242,588; and published examined Japanese Patent Application 14030/′69.
- sensitizing dyes may be employed individually or in combination. Combinations of sensitizing dyes are often employed for the purpose of supersensitization. Typical examples of supersensitizing combinations are described in U.S. Patents 2,688,545; 2,977,229; 3,397,060; 3,522,052; 3,527,641; 3,617,293; 3,628,964; 3,666,480; 3,672,898; 3,679,428; 3,814,609; and 4,026,707; British Patent 1,344,281, published examined Japanese Patent Applications 4936/′68 and 12375/′78; and published unexamined Japanese Patent Applications 110618/′77 and 109925/′77.
- the sensitive material prepared in accordance with an embodiment of this invention can contain in its hydrophilic colloidal layers a so-called gas fog preventing agent which can prevent deterioration of photographic properties, e.g., decrease in developed color density, increase in color stain and fog, etc., from occuring upon contact with harmful gases such as formaldehyde and the like.
- gas fog preventing agent which can prevent deterioration of photographic properties, e.g., decrease in developed color density, increase in color stain and fog, etc., from occuring upon contact with harmful gases such as formaldehyde and the like.
- gas fog preventing agent which can prevent deterioration of photographic properties, e.g., decrease in developed color density, increase in color stain and fog, etc., from occuring upon contact with harmful gases such as formaldehyde and the like.
- amines including alkylamine, arylamines and heterocyclic amines
- amides amides
- cyclic or acyclic ureas sul
- gas fog preventing agents are described in published examined Japanese Patent Applications 34675/′71, 38418/′73 and 23908/′76, published unexamined Japanese Patent Applications 47335/′73, 43923/′75 and 87028/′75.
- gas fog preventing agents which can be used in this invention include urea, ethylene diurea, ethylene urea, melamine, hydantoin, allantoin, urazol, parabanic acid, biuret, glycoluril, 1-methylglycoluril, phthalimide, succinimide, benzenesulfunic acid, styrenesulfinic acid polymer, malonic acid, cyanoacetic acid, dimedone barbituric acid, semicarbazie, 5-pyrazolone type magenta couplers, acylacetoanilide type yellow couplers, resorcinol, phloroglucinol, 2,3-dihydroxynaphthalene, sodium sulfite and so on.
- the first layer Low sensitivity red-sensitive emulsion layer
- a 500 g portion of the thus obtained emulsion was mixed with 1 kg of a red-sensitive low sensitivity silver iodobromide emulsion (containing silver iodobromide grains having such a grain size distribution that 81% by number of the whole grains have sizes which are within ⁇ 40% of its mean grain size, 70 g of silver, 60 g of gelatin and 6 mole % of silver iodide), and coated in a layer having a dry thickness of 2 ⁇ m (containing 0.5 g/m2 of silver).
- the second layer Intermediate sensitivity red-sensitive emulsion layer
- a 1,000 g portion of the thus obtained emulsion was mixed with 1 kg of a red-sensitive intermediate sensitivity silver iodobromide emulsion (having such a grain size distribution that the percentage of grains as described in the first layer was 76% and containing 70 g of silver, 60 g of gelatin and 6 mole % of silver iodide), and coated in a layer having a dry thickness of 1 ⁇ m (containing 0.4 g/m2 of silver).
- the third layer High sensitivity red-sensitive emulsion layer
- a 1,000 g portion of the thus obtained emulsion was mixed with 1 kg of a red-sensitive high sensitivity silver iodobromide emulsion (having such a grain size distribution that the percentage of grains as described in the first layer was 78%, and containing 70 g of silver, 60 g of gelatin and 6 mole % of silver iodide), and coated in a layer having a dry thickness of 1 ⁇ m (containing 0.4 g/m2 of silver).
- the fourth layer Interlayer
- 2,5-di-t-octylhydroquinone was dissolved in a mixture of 100 ml of dibutyl phthalate and 100 ml of ethyl acetate, and the resulting solution was stirred at a high speed together with 1 kg of 10% gelatin water solution.
- a 1 kg portion of the thus obtained emulsion was mixed with 1 kg of a 10% aqueous gelating solution, and coated in a layer having a dry thickness of 1 ⁇ m.
- the fifth layer Low sensitivity green-sensitive emulsion layer
- the sixth layer Intermediate sensitivity green-sensitive emulsion layer
- the seventh layer High sensitivity green-sensitive emulsion layer
- the eighth layer Interlayer
- a 1 kg portion of the same emulsion as employed in the fourth layer was mixed with 1 kg of a 10% aqueous gelatin solution, and coated in a layer having a dry thickness of 1 ⁇ m.
- the ninth layer Yellow filter layer
- An emulsion containing yellow colloidal silver was coated in a layer having a dry thickness of 1 ⁇ m.
- the tenth layer Low sensitivity blue-sensitive emulsion layer
- the eleventh layer Intermediate sensitivity blue-sensitive emulsion layer
- the twelfth layer High sensitivity blue-sensitive emulsion layer
- the thirteenth layer Second protective layer
- a 1 kg portion of the same emulsion as used in the fourth layer was mixed with 1 kg of a 10% aqueous gelatin solution, and coated in a layer having a dry thickness of 2 ⁇ m.
- the fourteenth layer First protective layer
- a 10% gelatin aqueous solution containing a chemically unsensitized fine grain emulsion (having a grain size of 0.15 ⁇ m, and containing 1 mole % of silver iodobromide) was coated in a layer having a dry thickness of 1 ⁇ m at a silver coverage of 0.3 g/m2.
- Sample B was prepared in the same manner as in Sampe A except that in the emulsion used in the second layer the silver iodide content and the percentage in the grain size distribution were changed to 2.5 mole % and 87%, respectively, and in the emulsion used in the third layer the silver iodide content and the percentage in the grain size distribution were changed to 2.5 mole % and 87%, respectively.
- Sample C was prepared in the same manner as in Sample A except that in the emulsion used in the second layer the silver iodide content and the percentage in the grain size distribution were changed to 6 mole % and 88%, respectively, and in the emulsion used in the third layer the silver iodide content and the percentage in the grain size distribution were 6 mol % and 88%, respectively.
- Sample D was prepared in the same manner as in Sample A except that in the emulsion used in the second layer the silver iodide content and the percentage in the grain size distribution were changed to 2.5 mole % and 80%, respectively, and in the emulsion used in the third layer the silver iodide content and the percentage in the grain size distribution were changed to 2.5 mole % and 80%, respectively.
- Sample E was prepared in the same manner as in Sample A except that in the emulsion used in the second layer the silver iodide content and the percentage in the grain size distribution were changed to 3 mol % and 91%, respectively, and in the emulsion used in the third layer the silver iodide content and the percentage in the grain size distribution were changed to 3 mole % and 91% respectively.
- Each of these sample films was exposed to light through a step wedge for RMS measurement (root mean square measurement) and then, subjected to the following reversal processings.
- Sample F was prepared in the same manner as in Sample A of Example 1 except that in the emulsion used in the sixth layer the silver iodide content and the percentage in the grain size distribution were changed to 5.2 mole % and 88% respectively, and in the emulsion used in the seventh layer the silver iodide content and the percentage in the grain size distribution were changed to 5.2 mole % and 90% respectively.
- Sample G was prepared in the same manner as in Sample A of Example 1 except that in the emulsion used in the sixth layer the silver iodide content and the percentage in the grain size distribution were changed to 3.2 mole % and 90 % respectively, and in the emulsion used in the seventh layer the silver iodide content and the percentage in the grain size distribution were changed to 3.2 mole % and 90% respectively.
- Sample H was prepared in the same manner as in Sample A of Example 1 except that in the emulsion used in the sixth layer the silver iodide content and the percentage in the grain size distribution were changed to 4.5 mole % and 77% respectively, and in the emulsion used in the seventh layer the silver iodide content and the percentage in the grain size distribution were changed to 4.5 mole % and 80% respectively.
- Sample I was prepared in the same manner as in Sample A of Example 1 except that in the emulsion used in the sixth layer the silver iodide content and the percentage in the grain size distribution were changed to 4.3 mole % and 90% respectively, and in the emulsion used in the seventh layer the silver iodide content and the percentage in the grain size distribution were changed to 4.3 mole % and 92% respectively.
- Sample J was prepared in the same manner as in Sample A of Example 1 except that in the emulsion used in the eleventh layer the silver iodide content and the percentage in the grain size distribution were changed to 6 mole % and 92% respectively, and in the emulsion used in the twelfth layer the silver iodide content and the percentage in the grain size distribution were changed to 6 mole % and 90% respectively.
- Sample K was prepared in the same manner as in Sample A except that in the emulsion used in the eleventh layer the silver iodide content and the percentage in the grain size distribution were changed to 4.2 mole % and 88% respectively, and in the emulsion used in the twelfth layer the silver iodide content and the percentage in the grain size distribution were changed to 4.2 mole % and 88% respectively.
- Sample L was prepared in the same manner as in Sample A except that in the emulsion used in the eleventh layer the silver iodide content and the percentage in the grain size distribution were changed to 3.5 mole % and 91% respectively, and in the emulsion used in the twelfth layer the silver iodide content and the percentage in the grain size distribution were changed to 3.5 mole % and 91% respectively.
- Sample M was prepared in the same manner as in Sample A except that in the emulsion used in the eleventh layer the silver iodide content and the percentage in the grain size distribution were changed to 3.5 mole % and 77% respectively, and in the emulsion used in the twelfth layer the silver iodide content and the percentage in the grain size distribution were changed to 3.5 mole % and 75% respectively.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17519982A JPS5964842A (ja) | 1982-10-05 | 1982-10-05 | 多層ハロゲン化銀カラ−反転感光材料 |
JP175199/82 | 1982-10-05 |
Publications (4)
Publication Number | Publication Date |
---|---|
EP0107817A2 EP0107817A2 (en) | 1984-05-09 |
EP0107817A3 EP0107817A3 (en) | 1984-06-06 |
EP0107817B1 EP0107817B1 (en) | 1986-12-30 |
EP0107817B2 true EP0107817B2 (en) | 1992-03-04 |
Family
ID=15992021
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19830109961 Expired EP0107817B2 (en) | 1982-10-05 | 1983-10-05 | Multilayer silver halide reversal color photographic material |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0107817B2 (enrdf_load_stackoverflow) |
JP (1) | JPS5964842A (enrdf_load_stackoverflow) |
DE (1) | DE3368776D1 (enrdf_load_stackoverflow) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6175347A (ja) * | 1984-09-20 | 1986-04-17 | Konishiroku Photo Ind Co Ltd | ハロゲン化銀カラ−写真感光材料 |
EP0296784A3 (en) * | 1987-06-21 | 1990-01-31 | Konica Corporation | Silver halide reversal photographic light-sensitive material |
JP2519946B2 (ja) * | 1987-08-24 | 1996-07-31 | 富士写真フイルム株式会社 | ハロゲン化銀カラ−反転写真感光材料 |
DE4109075A1 (de) * | 1991-03-20 | 1992-09-24 | Agfa Gevaert Ag | Farbfotografischer umkehrfilm |
EP1070988A3 (en) * | 1999-07-23 | 2003-03-19 | Konica Corporation | Silver halide light sensitive color reversal photographic material |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3505068A (en) * | 1967-06-23 | 1970-04-07 | Eastman Kodak Co | Photographic element |
JPS5267325A (en) * | 1975-12-01 | 1977-06-03 | Mitsubishi Paper Mills Ltd | Direct reversal color photosensitive material and method of treating same |
DE2708466A1 (de) * | 1977-02-26 | 1978-08-31 | Agfa Gevaert Ag | Emulsionsabmischungen fuer colorumkehr-(aufsichts-)material |
DE2718437A1 (de) * | 1977-04-26 | 1978-11-09 | Agfa Gevaert Ag | Photographisches aufzeichnungsmaterial mit verstaerktem zwischenbildeffekt |
JPS57112751A (en) * | 1980-12-29 | 1982-07-13 | Fuji Photo Film Co Ltd | Multilayered photosnsitive color reversal material |
WO1983000234A1 (en) * | 1981-07-10 | 1983-01-20 | Yamashita, Kiyoshi | Silver halide color photographic sensitive material |
-
1982
- 1982-10-05 JP JP17519982A patent/JPS5964842A/ja active Granted
-
1983
- 1983-10-05 DE DE8383109961T patent/DE3368776D1/de not_active Expired
- 1983-10-05 EP EP19830109961 patent/EP0107817B2/en not_active Expired
Also Published As
Publication number | Publication date |
---|---|
EP0107817B1 (en) | 1986-12-30 |
JPS5964842A (ja) | 1984-04-12 |
EP0107817A3 (en) | 1984-06-06 |
JPH0324659B2 (enrdf_load_stackoverflow) | 1991-04-03 |
EP0107817A2 (en) | 1984-05-09 |
DE3368776D1 (en) | 1987-02-05 |
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