EP0675404B1 - Procédé de formation d'image - Google Patents
Procédé de formation d'image Download PDFInfo
- Publication number
- EP0675404B1 EP0675404B1 EP95302141A EP95302141A EP0675404B1 EP 0675404 B1 EP0675404 B1 EP 0675404B1 EP 95302141 A EP95302141 A EP 95302141A EP 95302141 A EP95302141 A EP 95302141A EP 0675404 B1 EP0675404 B1 EP 0675404B1
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- EP
- European Patent Office
- Prior art keywords
- light
- silver halide
- layer
- given
- image forming
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- 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.)
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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
- G03C1/95—Photosensitive materials characterised by the base or auxiliary layers rendered opaque or writable, e.g. with inert particulate additives
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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
- G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper
- G03C1/79—Macromolecular coatings or impregnations therefor, e.g. varnishes
Definitions
- This invention relates to a silver halide color light-sensitive material and a color image forming process in which the above-mentioned color light-sensitive material is used and, particularly, to a silver halide color light-sensitive material suitable for forming a color image for proofing use (that is so-called a color proof) in such a manner that a transmission type black-and-white half tone dot information color separated from a color original document.
- an over-lay method and a surprint method have been used as a method for obtaining a color proof from a plurality of black-and-white half tone dot images obtained by carrying out a color separation and a half tone dot conversion.
- a method of improving the defects of the above-mentioned over-lay method and a surprint method a method using a silver halide color light-sensitive material is disclosed in Japanese Patent Publication Open to Public Inspection (hereinafter referred to as JP OPI Publication) Nos. 62-280747/1987 through 62-280750/1987 and 62-280849/1987.
- the silver halide emulsions used therein are silver chlorobromide emulsions having a high silver bromide content, and there is no description of a high silver chloride containing emulsion having a rapid developability and an environmental aptitude, which may be put into practical use.
- a light-sensitive material For a light-sensitive material, it has been required to practically use a silver chloride rich emulsion capable of realising the improvements of working environment and environmental aptitude. And, a light-sensitive material has recently been used not only for layout proof to confirm the positions of letters and drawings, but also for tone proof to confirm a colour tone, as the fields of utilising the light-sensitive materials, so that the quality thereof required by the market has been increased.
- Japanese Patent Open to Public Inspection Publication No. 197069/1993 discloses an image forming process in which a silver halide colour photographic light-sensitive material is exposed to light in a scanning-exposure system to form a proof. In this disclosure, however, there is no suggestive description of an amount of a white pigment to be filled.
- EP-A-0578248 and EP-A-0578249 relate to silver halide colour photographic light-sensitive materials each comprising a support and provided thereon photographic layers comprising at least one light-sensitive silver halide emulsion containing a yellow dye-forming coupler, at least one light-sensitive emulsion layer containing a magenta dye-forming coupler and at least one light-sensitive emulsion layer containing a cyan dye-forming coupler together with at least one non-light-sensitive hydrophilic colloid layer.
- at least one of the hydrophilic colloid layers is provided between the support and the silver halide emulsion layer closest thereto and contains a white pigment.
- the object of the invention is to provide an image forming method in which a proof is rapidly prepared by making a scanning-exposure when a colour-separation and a half tone dot image conversion are made by using a silver halide colour photographic light-sensitive material and a colour proof is so prepared as to be based on the resulting half tone dot image information.
- a preferable embodiment of the invention is that the above-mentioned silver halide color photographic light-sensitive material is to contain a white pigment in an amount of not less than 20% by weight in the above-mentioned white pigment layer and that at least one of the above-mentioned silver halide emulsion layers is to contain an silver halide emulsion having a silver chloride content of not less than 80 mol%.
- the white pigments employed preferably in the invention include, for example, a rutile type titanium dioxide, an anatase type titanium dioxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide and kaolin. Among them, titanium dioxide is more preferable.
- a white pigment can be dispersed in a water-soluble binder of a hydrophilic colloid such as gelatin that can make a processing solution permeable thereto so that the white pigment can be coated to form a white pigment layer.
- a coated amount of the white pigment is preferably within the range of 0.5 g/m 2 to 50 g/m 2 and, more preferably, 1 g/m 2 to 20 g/m 2 .
- the layer is provided under the lowermost layer of the light-sensitive layers.
- a support and the lowermost layer of the light-sensitive layers it is allowed, if required, to provide, besides the layer containing a white pigment, a sublayer on the support, or a light-insensitive hydrophilic colloidal layer such as an intermediate layer to any preferable position.
- a layer containing a white pigment other than light-sensitive layers is to have a percentage of voids within the range of from 5 to 35 % by weight.
- a percentage of void (%) (a measured layer thickness - a theoretical layer thickness)/(a measured layer thickness) * 100.
- the theoretical layer thickness is calculated based upon each of addition amounts and each of density values of compositions contained in a layer.
- a hollow polymer grain means that a grain has a hollow inside, but has no polymer inside.
- a polymer having a hollow inside is preferable, because a fine bubble grain can stably be made present and a light reflectance can also be improved.
- the hollow polymers applicable thereto include, for example, a hollow polymer of styrene-acrylic resin produced by Japan Synthetic Rubber Co.
- the methods for providing a white pigment layer on a support include, for example, a method of making use of a paper sheet laminated with plastic film containing a white pigment as described in JP OPI Publication No. 1-177536/1989, another method of making use of a polyester film containing a white pigment as described in JP OPI Publication No. 2-235045/1990, and a further method of making use of a paper sheet prepared in such a manner that a polyethylene layer containing a white pigment is hardened by making use of an electron beam as described in JP OPI Publication No. 2-176648/1990. It is particularly preferable to use a method of using a paper sheet laminated with a plastic film, and another method of using a paper sheet prepared in such a manner that a polyethylene layer is hardened by using an electron beam.
- an electron beam hardening coatable coating solution is comprised of at least one kind of an organic compound capable of producing a hardened resin by applying electron beam, and a pigment including preferably an inorganic pigment each as the principal components thereof and, if required, other additives.
- the organic compounds polymerized and hardened by irradiating with an electron beam include an unsaturated compound having not less than two carbon-carbon double bonds in one molecule thereof, such as an acrylic or methacrylic type oligomer and a multifunctional acrylic or methacrylic type monomers.
- Unsaturated compounds having at least one carbon-carbon double bond in one molecule thereof such as a monofunctional acrylic monomer; and a vinyl monomer may be additionally present.
- These unsaturated organic compounds are polymerized by the radicals produced by irradiating with an electron beam and then hardened by a crosslinkage produced in an intermolecular or intramolecular crosslinking reaction, so that a hardened resin can be produced.
- the acryl and methacryl types oligomers include, for example, a polyurethane acrylic or methacrylic acid ester, a polyether alcohol acrylic or methacrylic acid ester, an acrylic or methacrylic acid ester of bisphenol A and maleic or fumaric acid ester type polyester.
- the multifunctional acrylic or methacrylic monomers include, for example, 1,6-hexanediol diacrylic monomer, neopentyl diacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, glycerol trimethacrylate, stearyl acrylate, polyethylene glycol diacrylate, butoxyethyl acrylate, 1,4-butanediol diacrylate, ethylene glycol dimethacrylate, glycidyl methacrylate, trimethylolpropane triacrylate, pentaerythritol acrylate and pentaerythritol pentacrylate.
- the monofunctional acrylic or methacrylic monomers and the vinyl monomers include, for example, styrene, N-vinylpyrrolidone, a polyoxyethylene phenyl alcohol acrylic acid ester and 2-ethylhexyl acrylate.
- a coating solution useful in the method of the invention contains a pigment uniformly mixed with an electron-hardenable organic compound including, commonly, a white inorganic pigment.
- the white inorganic pigments applicable thereto include, for example, titanium dioxide (of the anatase or rutile type), barium sulfate, calcium carbonate, aluminium oxide and magnesium oxide. It is also allowed that the surface of a titanium dioxide grain is processed with a metal oxide such as moisture-containing alumina oxide so that the dispersibility thereof can be improved.
- an amount of a white pigment to be contained in a coating solution so as to be within the range of 20 to 80% by weight of the whole weight of the solids contained in a layer other than light-sensitive layers or a resin layer.
- the amount thereof is less than 20% by weight, the resulting photographic image sharpness on a print leaves something to be desired.
- exceeding 80% by weight the plasticity of the resulting hardened resin-coated layer is lowered, so that a layer fracture may be produced.
- a white inorganic pigment can be dispersed in an electron-hardenable unsaturated organic compound by making use of a three-roll mill, a two-roll mill, a homomixer, a sand grinder, a supersonic dispersing machine and so forth.
- the organic solvents applicable thereto include, for example, acetone, methylethyl ketone, ethyl acetate, butyl acetate, ether, glycol monoethyl ether, dioxane, benzene, toluene, xylene, ethylene chloride, carbon tetrachloride, chloroform and dichlorobenzene.
- a roller coating method may be used.
- it is also allowed to use any one of commonly known sheet-coating methods such as a bar coating method, an air-doctor coating method, a blade coating method, a squeeze coating method, an air-knife coating method, a reverse-roll coating method and a transfer coating method. It is further allowed to use a fountain coater system or a slit-orifice coater system.
- an electron-beam irradiator there is no special limitation to an electron-beam irradiator applicable to a process of the invention.
- the electron-beam accelerators for irradiating an electron beam generally, those of the curtain-beam system may effectively be used, because they are comparatively inexpensive and have a high power output.
- the acceleration voltage is, preferably, within the range of 100 to 300kv.
- the suitable thickness of a coated layer is to be within the range of 3 to 100 ⁇ m and, preferably, 5 to 50 ⁇ m. When the thickness thereof is out of the above-given range, it is not preferable from the viewpoint of quality, because a coating unevenness is produced or a plenty of energy is required for hardening a layer, so that the hardening result may leave something to be desired.
- After a layer is coated or hardened it is also allowed, if required, to apply a surface smoothing treatment with the use of a mirror-finished roll or a surface matting treatment with the use of a mat-finished roll such as a silk-finished roll.
- the base members applicable to the invention every one of them can be used for, provided that they may be used generally to a support for photographic use.
- a support base member as mentioned above is commonly made of paper.
- the paper sheets applicable to a sheet-shaped base member include, for example, a natural pulp paper, a synthetic pulp paper, a paper mixedly made of natural pulp and, besides, various combination paper boards.
- an additive having generally been used for making paper such as a sizing agent, a paper-strength reinforcing agent, a fixer, an antistatic agent, a pH controller, a pigment and a dyestuff. It is further allowed to apply a surface-coating with a surface sizing agent, a paper surface reinforcing agent and an antistatic agent.
- the well-known light sources thereof include, for example, a combination of a filter and a lamp serving as a white light-source, such as a glow lamp, a xenon lamp, a mercury lamp and a tungsten lamp; a light emitting diode, a gas-laser, a solid-laser, a conductive-laser and so forth.
- a laser beam having a substantially narrow light-output intensity distribution is particularly preferred.
- a combination of various laser beams and a wavelength conversion element may also be used. From the viewpoint of compactness, a combination of an infra-red semiconductive laser and an SHG element is preferred.
- blue-light sources include, for example, a He-Cd gas-laser (with 441.6nm), an Ar + laser (with 488.0nm), and a He-Ne gas-laser (with 442.0nm);
- green-light sources include, for example, a He-Ne gas-laser (with 543.5nm), an Ar + gas-laser (with 514.5nm), a Kr + gas-laser (with 520.8nm), a YAG laser, and a combination of an infra-red semiconductive laser and an SHG element;
- red-light sources include, for example, a He-Ne gas-laser (with 632.8nm), a Kr + gas-laser (with 647.1nm) and a semiconductive laser (with 678nm, 750nm or 780nm).
- a He-Ne gas-laser When a He-Ne gas-laser is used particularly as a light-source, a stable, inexpensive and compact apparatus may be provided. It is also advisable that a plurality of oscillations are obtained from a single He-Ne gas-laser and may then be used upon separating the oscillations each other by making use of a dichroic mirror. For example, from a single He-Ne gas-laser, four lines of oscillations (442nm, 543.5nm, 594.1nm and 632.8nm) may be obtained.
- Silver halide applicable to a light-sensitive material useful in the method of the invention include any one of silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloride and so forth which may be ordinarily applied to a silver halide emulsion. From the viewpoint of a rapid processing, it is advisable to use a highly silver chloride containing emulsion having a silver chloride content of, preferably, not less than 80 mol% and, more preferably, not less than 95 mol%.
- the couplers applicable to a silver halide lightsensitive material useful in the method of the invention also include any compound capable of producing a coupling product having a maximum spectral absorption wavelength in a long wavelength region longer than 340nm, upon making a coupling reaction with a color developing agent.
- the particularly typical couplers include, for example, those having been known as a yellow coupler having a spectral absorption maximum in a wavelength region within the range of from 350 to 500nm, a magenta coupler having a spectral absorption maximum in a wavelength region within the range of from 500 to 600nm and a cyan coupler having a spectral absorption maximum in a wavelength region within the range of from 600 to 750nm.
- Particular cyan couplers include, for example, a coupler represented by Formulae (C-I) or (C-II) given in JP OPI Publication No. 4-114154/1992, p. 5 in the lower left column.
- the typical compounds thereof include, for example, those given in the above-given JP OPI Publication, in the lower right column of p. 5 to the upper left column of p. 6.
- Suitable Magenta couplers preferably include, for example, a coupler represented by Formula (M-I) given in JP OPI Publication No. 4-114154/1992, p. 4, in the upper right column.
- the typical compounds thereof include, for example, those denoted by MC-1 to MC-7 given on p. 5 in the upper left column to the upper right column.
- Suitable yellow couplers of a yellow color developable blue light-sensitive layer include, for example, a coupler represented by Formula (Y-1) given in JP OPI Publication No. 4-114154/1992, p.3 in the upper right column.
- Typical compounds thereof include, for example, those denoted YC-1 to YC-9 given in p. 3 in the lower left column to p. 4 in the upper left column.
- YC-8 and YC-9 given on, ibid., p. 4 in the upper left column are preferable, because they can reproduce a desirable yellow tone.
- an oil-drop-in-water type emulsification-dispersion method for adding a coupler the following procedures are usually taken.
- the coupler is dissolved in a water-insoluble high boiling organic solvent having a boiling point of not lower than 150°C and, if required, with a low boiling and/or a water-soluble organic solvent in combination, and the resulting solution is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution by making use of a surfactant.
- the dispersion means applicable thereto include, for example, a stirrer, a homogenizer, a colloid mill, a flow-jet mixer and a supersonic disperser. It is also allowed to add a step of removing the low boiling organic solvent, after or at the same time when completing the dispersion,
- a high boiling organic solvent applicable to dissolve and disperse a coupler (and a photographically useful organic compound such as a UV absorbent and a color stain preventive of which will be detailed later), such a solvent as mentioned above include, preferably, a high boiling organic solvent having a vapor pressure of not higher than 0.5 mmHg at 100°C.
- Typical compounds thereof include, for example, the the compounds, II-1 to II-9 and III-1 to III-6, given in JP OPI Publication No. 63-103245/1988, the compounds H-1 to H-22, given in JP OPI Publication No. 1-196048/1989, the compounds II-1 to II-38, given in JP OPI Publication No. 64-66646/1989, or such a phosphine oxide as given below.
- a phosphoric acid ester and a phosphine oxide are preferably used for.
- a coupler and a water-insoluble and organic solvent-soluble polymer compound are dissolved, if required, in a low boiling and/or water-soluble organic solvent, and the resulting solution is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution by making use of a surfactant.
- the water-insoluble and organic solvent-soluble polymers include, for example, poly(N-t-butyl acrylamide).
- Ethyl acetate is preferably used as a low boiling organic solvent.
- a surfactant preferably applicable when making a dispersion include, for example, a compound having collectively a hydrophobic group having 8 to 30 carbon atoms and either -SO 3 M group or a -OSO 3 M group (in which M represents a hydrogen atom or a cation) in a molecule thereof.
- the typical examples of the surfactant compounds preferably applicable thereto include the anionic surfactants, A-1 through A-11 and, more preferably, A-1 and A-8, given in JP OPI Publication No. 64-26854/1989, p. 15, in the upper left column to the upper right column. It is also preferable to use a surfactant in which a fluorine atom is substituted to an alkyl chain.
- the above-mentioned surfactant is added to a coating solution.
- the resulting dispersed solution thereof is usually added to a coating solution containing a silver halide emulsion or the like and the resulting solution is then coated.
- the dispersed solution is to be added to a coating solution, preferably within 10 hours, more preferably, within 3 hours and, most preferably, within 20 minutes after completing the dispersion.
- the amounts of the couplers to be added there is no special limitation to the amounts of the couplers to be added, provided that a satisfactorily high density can be obtained. However, they may be used within the range of from 1x10 -3 to 5 mols per mol of silver halide used and, preferably from 1x10 -2 to 1 mol.
- the magenta couplers useful in the invention may also be used in combination with a color-fading preventive.
- Suitable examples of the color-fading preventive include a phenylethyl ether represented by Formulas I and II given in JP OPI Publication No. 2-66541/1990, p. 3, in the upper left column to the upper right column.
- Typical compounds thereof include, for example, the compounds, I-1 to I-32 and II-1 to I-18, given in, ibid., p. 3, in the lower right column to p. 5, in the upper right column.
- the preferable compounds are those respectively denoted by I-13 and II-9.
- the second example of the color-fading preventives preferably used in combination include a phenol compound represented by Formula IIIB given in JP OPI Publication No. 3-174150/1991.
- compounds III-1, III-12, III-13 and III-14 given therein are more preferable and compound denoted by III-14 is particularly preferable.
- the third example of the color-fading preventives preferably used in combination include an amine type compound represented by Formula A given in JP OPI Publication No. 64-90445/1989.
- the typical examples of the compounds include A-1 to A-15 given in, ibid., p. , in the upper right column. Among them, a further preferable compound is denoted by A-3.
- the yellow couplers and cyan couplers each useful in the invention are preferably used in combination with a color-fading preventive.
- the preferable compounds include, for example, the compounds represented by Formula I' given in JP OPI Publication No. 1-196049/1989, p. 8, in the upper left column, and the compounds given in JP Application No. 3-185113/1991.
- the further preferable compounds include, for example, those denoted by I-10 to I-13 each given on p. 9, in the upper left column to the upper right column.
- a color-fading preventive used with the above-mentioned magenta, yellow or cyan coupler in combination is to be added, together with a coupler, in a proportion within the range of, preferably from 0.1 to 3 mols per mol of the coupler in one and the same oil drop and, more preferably from 0.5 to 1.5 mols. It is preferable that a color-fading preventive is used with a different kind of compound in combination.
- the preferable examples thereof include a combination use of a phenol type compound represented by Formula IIIB given in JP OPI Publication No. 3-17450/1991 and a phenyl ether type compound represented by Formula I or II given in JP OPI Publication No. 2-66541/1990, p. 3, in the upper right column.
- the preferable examples thereof also include a combination use of a phenol type compound represented by Formula IIIB given in JP OPI Publication No. 3-17450/1991 and an amine type compound represented by Formula A given in JP OPI Publication No. 64-90445/1989.
- a UV absorbent useful in the invention include, for example, a compound having the maximum spectral absorption wavelength in the ultra-violet region (of not higher than 400nm) and a spectral absorption coefficient of not less than 5000.
- Preferable compounds include, for example, a compound represented by Formula III-3 given in JP OPI Publication No. 1-250944/1989 and a compound represented by Formula I given in JP OPI Publication No. 4-1633/1992.
- Typical examples of the compounds include IIIc-1 to IIIc-17 given in JP OPI Publication No. 1-250944/1989, III-1 to III-24 given in JP OPI Publication No. 64-66646/1989, UV-1L to UV-22L given in JP OPI Publication No.
- the particularly preferable compounds include, for example, IIIc-7 and IIIc-12 given in JP OPI Publication No. 1-250944/1989, in the upper left column of p. 15. and a liquid phase UV absorbent UV-23L given in JP OPI Publication No. 63-187240/1988. It is preferable to add the above-given UV absorbents in the foregoing dispersion method.
- a high boiling organic solvent applicable to a UV absorbent-containing layer is to be added in a proportion by weight within the range of from 0.3 to 0, preferably from 0.1 to 0 and, most preferably from 0 to an amount of a UV absorbent added.
- a high boiling organic solvent preferably applicable thereto include, for example, a compound to be used for dispersing the foregoing couplers.
- a UV absorbent is preferably contained in a light-insensitive layer.
- the light-insensitive layer is a light-insensitive intermediate layer positioned farther apart from a silver halide emulsion layer positioned farthest from a support, and a light-insensitive layer interposed between an emulsion layer farthest positioned from the support and another emulsion layer second farthest positioned from the support.
- the matting agents include, preferably, a compound given in JP OPI Publication No. 2-73250/1990, p. 2, in the upper right column, the 9th line to the 20th line and, most preferably, crystallized or non-crystallized silica.
- the matting agents may be used independently or in combination.
- the average particle size of the above-mentioned matting agent is to be within the range of, preferably from 1 to 10 ⁇ m and, more preferably from 2 to 7 ⁇ m.
- the matting agents may be coated in an amount within the range of, preferably from 0.021 to 0.1 g/m 2 and, more preferably from 0.025 to 0.08 g/m 2 .
- the high boiling organic solvents preferably added to the surface layer include, preferably, a high boiling organic solvent having a vapor pressure of not higher than 0.5 mmHg at 100°C and, more preferably, a compound having a dielectric constant of not higher than 6.0.
- Typical examples of the compounds include the same as those given in the foregoing description of the coupler dispersion as they are.
- the amount thereof to be added is within the range of from 1 to 100 mg/m 2 and, preferably from 10 to 50 mg/m 2 .
- a fluorine-containing surfactant or organopolysiloxane may also be added to a light-sensitive material useful in the invention.
- the preferable fluorine-containing surfactants include, for example, a compound represented by Formulas (I), (II) and (III) each given in JP Application No. 4-270425/1992.
- the particularly preferable compounds include, for example, those denoted by FI-55, FI-81, FK-5, FK-13 and FK-23.
- the preferable organopolysiloxane include, for example, a compound represented by Formulas (S1), (S2), (I), (II) and (III) each given in JP Application No. 4-270425/1992.
- the particularly preferable compounds include, for example, those denoted by S-7 and S-19.
- an oil-soluble dyestuff is preferably used.
- An oil-soluble dyestuff means an organic dyestuff having a water-solubility of not higher than 0.01 at 20°C. It is preferably a compound having a molecular absorptivity coefficient of not less than 20000 in the maximum absorption wavelength in a wavelength of not shorter than 400nm.
- Preferable compounds include, for example, a compound represented by Formula II or III given in JP OPI Publication No. 2-842/1990, p. 7, the lower right column to p. 8, the upper left column.
- Preferable compounds include, typically, compounds 1 to 27 given in the same JP OPI Publication, p. 8, the lower left column to p. 9, the upper right column. Among them, compounds 4 and 9 are particularly preferable.
- An oil-soluble dyestuff is preferable to be added in an amount within the range of from 0.05 to 5 mg/m 2 , to a light-insensitive layer.
- fluorescent whitening agents as mentioned above include, preferably, a compound represented by Formula II given in JP OPI Publication No. 2-232652/1990.
- the examples of those compounds include, typically, compounds 1 to 6 given in the same JP OPI Publication, p. 6, the lower right column to p. 7, the upper right column.
- compound Nos. 3, 1 and 5 are particularly preferable.
- These fluorescent whitening agents are preferably added in an amount within the range of, preferably from 0.001 to 0.3 mg/m 2 and, more preferably from 0.1 to 0.2 mg/m 2 , to a light-insensitive layer.
- a water-soluble polymer compound so as to assist the above-mentioned fluorescent whitening agent to enhance the fluorescent whitening effect.
- Preferable compounds include, for example, a polymer containing polyvinyl pyrrolidone or vinyl pyrrolidone as a repetition unit. These compounds are preferably contained in a UV absorbent-containing layer positioned farthest from a support and/or a layer further apart from the above-mentioned UV absorbent-containing layer.
- the preferable anti-irradiation dyestuffs include the following compounds, for example. Namely, the compounds represented by Formulas II given in JP OPI Publication No. 62-253146/1987 (including, typically, compounds II-1 to II-19 given in the same JP OPI Publication, pp. 12-13), the compounds represented by Formula I given in JP OPI Publication No. 64-26850/1989 (including, typically, compounds 1 to 85 given in the same JP OPI Publication, p. 7, the upper left column to p.
- the preferable compounds include, for example, compound No. 47 represented by Formula I given in JP OPI Publication No. 64-26850/1989, compound No. 54 represented by Formula I given in JP OPI Publication No. 2-97940/1990, and compounds 1, 4, 6, 7 and 9 each given in JP Application No. 4-182885/1992.
- an anti-irradiation dyestuff and a dyestuff having a different maximum absorption wavelength It is also preferable to make combination use of a dyestuff having the maximum absorption within the range of from 600 to 700nm, a dyestuff having the maximum absorption within the range of from 500 to 600nm, and a dyestuff having the maximum absorption within the range of from 400 to 500nm.
- These dyestuffs may be added to any layers, however, they are preferred to be added to a light-insensitive layer.
- Each of the compounds may be added in an amount preferably within the range of from 1 to 100 mg/m 2 .
- a suitable silver halide emulsion may be those prepared in any one of an acidic process, a neutral process and an ammoniacial process.
- the grains thereof may be those grown up at the same time or may also be grown up after seed grains are prepared.
- the process for preparing the seed grains and the process for growing them up may be the same with or may also be different from each other.
- any one of a normal precipitation process, a reverse precipitation process, a simultaneous precipitation process, and the combination thereof may be used.
- a reactant thereof is preferably obtained in a simultaneous precipitation process. It is also allowed that a pAg-controlled ⁇ double-jet process detailed in JP OPI Publication No. 54-48521/1979 and so forth may be used as one of the systems of the simultaneous precipitation process.
- an apparatus for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide from an adding device arranged inside a mother liquid for making reaction as detailed in JP OPI Publication Nos. 57-92523/1982 and 57-92524/1982; an apparatus for adding an aqueous solution of a water-soluble silver salt and a water-soluble halide with continuously changing the concentration of the solution, as detailed in German Patent (OLS) No.
- a silver halide solvent such as thioether may also be used, if required.
- a silver halide solvent such as thioether may also be used, if required.
- An unnecessary soluble salt may be removed from an emulsion containing silver halide grains after completing the growth of the silver halide grains, or such a salt as mentioned above may also be contained therein as they are. When removing the salts, it can be performed in the procedures described in Research Disclosure No. 17643.
- any desired configuration of a silver halide grain relating to the invention can be used.
- One of the preferable examples thereof is a cube having ⁇ 100 ⁇ faces as the crystal faces thereof.
- grains having such a configuration as an octahedron, a tetradecahedron and a dodecahedron are prepared and are then used for. Further, grains having twinned crystal faces may also be used.
- the silver halide grains may be those having one and the same configuration or those formed of a mixture of grains having various configuration.
- the grain size of any silver halide grain there is no special limitation to the grain size of any silver halide grain. However, taking other photographic characteristics such as rapid processability and photosensitivity into consideration, it is to be within the range of, preferably from 0.1 to 1.6 ⁇ m and, more preferably from 0.2 to 1.2 ⁇ m.
- the above-mentioned grain can be measured in various procedures having commonly been used in the technical field of the art.
- a grain size can be obtained by making use of the projected area or approximate diameter thereof. When grains have a substantially uniform configuration, a fairly accurate grain size distribution thereof can be obtained by making use of the diameters or projected areas thereof.
- the grain size distribution of silver halide grains may be of the polydisperse type or of the monodisperse type.
- a variation coefficient of the silver halide grain distribution is, preferably, not more than 0.22 and, more preferably, not more than 0.15.
- a grain size herein stated means a diameter.
- a silver halide grain is cubic shaped or other shaped than the spherical shaped, it means the diameter of a circle having the same area with the projected image area of the grain.
- a suitable silver halide grain comprises silver iodobromide, silver chloroiodobromide, silver chlorobromide, silver bromide or silver chloride.
- a preferable grain is a silver chlorobromide grain comprising silver chloride in a proportion of not less than 90 mol% and without substantially containing any silver iodide, or it is a silver chloride grain.
- the expression, without substantially containing any silver iodide means that a silver iodide content is not more than 0.5 mol%, preferably, not more than 0.1 mol% and, more preferably, not contained at all.
- the silver halide grain comprises silver chlorobromide containing silver bromide
- it is allowed, without limitation, to be a core/shell type grain having the different compositions inside the silver halide grains, or a grain having a silver bromide-localized phase made present on the surface or inside thereof.
- the metals introducible thereinto include, for example, those belonging to Groups VIB, VIIB, VIII, IIB, IIIA and IVA of the periodic table.
- the preferable metals include, for example, the salts or complex salts of Mn, Fe, Co, Ni, Zn, Ga, Ge, Mo, Ru, Pd, Cd, In, Sn, W, Re, Os, Ir, Pt, Tl and Au. They may be used independently or in combination.
- the preferable metal salts or the complex salts thereof are given in, for example, JP Application Nos. 2-162332/1990, 2-253667/1990, 3-109173/1991, 4-251468/1992 and 4-82250/1992, and JP OPI Publication Nos. 4-125629/1992, 4-251469/1992 and 4-253081/1992.
- These compounds may be added in an amount preferably within the range of 10 -11 to 10 -3 mols per mol of silver halide used, provided, however, that the amount thereof to be added is so widely varied as to meet the kinds and application purposes of the compounds.
- a silver halide grain emulsion can be treated by making combination use of a gold sensitization process using a gold compound and a (sulfur) sensitization process using a chalcogen sensitizing agent.
- a gold sensitizer may be added in the form of chloroauric acid, gold chloride, gold thiosulfate or the like and, besides, a variety of gold complex.
- the oxide compounds applicable thereto include, for example, dimethyl rhodanine, thiocyanic acid, mercaptotetrazole and mercaptotriazole.
- a gold sensitizer may usually be used in an amount within the range of, preferably, 1x10 -9 to 1x10 -4 mols per mol of silver halide used and, more preferably, 1x10 -8 to 1x10 -5 mols.
- the chalcogen sensitizers applicable thereto include, for example, a sulfur sensitizer, a selenium sensitizer and a tellurium sensitizer. Among them, a sulfur sensitizer is preferred.
- the sulfur compounds include, for example, a thiosulfate, allylthiocarbamide, thiourea, allylthiocyanate, cystine, p-toluene sulfonate, rhodanine and inorganic sulfur.
- the light-sensitive material may be treated in a reduction sensitization.
- reduction sensitization processes There are well-known reduction sensitization processes. For example, it is allowed to use a process of adding various kinds of reducing agents, another process of carrying out a ripening treatment under the conditions of a high silver ion concentration, and a further process of carrying out a ripening treatment under the conditions of a high pH.
- the reducing agents applicable to a reduction sensitization treatment include, for example, a stannous salt such as stannous chloride, a borane such as tri-t-butylamine borane, a sulfite such as sodium sulfite and potassium sulfite, a reductone such as ascorbic acid, and thiourea dioxide.
- the preferable compounds include, for example, thiourea dioxide, ascorbic acid and the derivatives thereof, and a sulfite.
- a process of using such a reducing agent as mentioned above is preferred, because the resulting reduction characteristics can be excellent.
- These reducing agents may be dissolved in water or a solvent such as alcohol and the resulting solution is then added to a silver halide emulsion, so that a ripening treatment can be carried out, or they may also be added when forming silver halide grains and then a reduction sensitization is carried out at the same time when forming the grains.
- These reducing agents may usually be added preferably in an amount within the range of from 10 -7 to 10 -2 mols per mol of a silver halide used.
- an oxidizing agent For modifying a reduction sensitization nucleus after completing a reduction sensitization or for deactivating a remaining reducing agent, small amount of an oxidizing agent may be used.
- the compounds applicable for the above-mentioned purposes include, for example, iron (III) potassium hexacyanate, bromosuccinimide, p-quinone, potassium perchlorate, thiosulfinic acid. and aqueous hydrogen peroxide.
- the silver halide emulsion may also be added by a silver halide solvent in the course of carrying out a sensitization treatment.
- the silver halide solvents preferably applicable thereto include, for example, a thiocyan compound such as potassium thiocyanate, sodium thiocyanate, calcium thiocyanate, magnesium thiocyanate, silver thiocyanate and ammonium thiocyanate,
- a pH and a pAg in the course of carrying out a sensitization treatment.
- a pH and a pAg are usually kept within the range of from 4.0 to 11.0 and from 4.5 to 8.5, respectively.
- an antifoggant and a stabilizer each having been well known may be applied to the silver halide emulsion.
- the compounds applicable to meet the above-mentioned purposes include, for example, the compounds represented by the following formula [S]. wherein Q represents a group consisting of non-metal atoms necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring; and M represents a hydrogen atom or an alkali metal atom.
- the 5-membered heterocyclic rings represented by Q include, for example, an imidazole ring, a tetrazole ring, a thiazole ring, an oxazole ring, a selenazole ring, a benzoimidazole ring, a naphthoimidazole ring, a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring, a naphthoselenazole ring and a benzoxazole ring.
- the 6-membered heterocyclic rings represented by Q include, for example, a pyridine ring, a pyrimidine ring and a quinoline ring.
- These 5- or 6-membered heterocyclic rings include those having a substituent.
- the alkali metal atoms represented by M include, for example, a sodium atom and a potassium atom.
- the preferable structures of a mercapto compounds represented by Formula [S] are given in JP Application No. 4-330655/1992, paragraphs 0016 to 0032.
- the concrete compounds thereof include, for example, S-1-1 to S-4-8 given in ibid., paragraphs 0034 to 0039.
- the compounds represented by Formula [I] given in JP Application No. 4-80948/1992 are also preferred, and the concrete examples thereof include 1 to 49 given in ibid., paragraphs 0026 to 0028.
- the spectrally sensitizing dyes applicable to the silver halide emulsion include any one of well-known compounds.
- the blue light-sensitive sensitizing dyes those denoted by BS-1 to BS-8 given in JP Application No. 2-51124/1990, pp. 108-109 can preferably be used independently or in combination.
- the green light-sensitive sensitizing dyes those denoted by GS-1 to GS-5 given in ibid., p. 110, can preferably be used.
- the dyes IRS-1 to IRS-11 given in JP Application No. 3-73619/1991, pp. 12-14 can preferably be used. It is also preferable to make combination use of the above-given dyes and supersensitizers SS-1 to SS-9 given in ibid., pp. 14-15.
- an exposure means equipped with a semiconductive laser When exposing the light-sensitive material to laser beam, it is advantageous to use an exposure means equipped with a semiconductive laser, because the exposure means can be made smaller in size.
- an exposure time per pixel corresponds to an exposure time for actually exposing a silver halide emulsion to light.
- an exposure time per pixel may be considered as (A luminous flux diameter) / (a scanning speed), provided that, in a spatial variation of a luminous flux intensity, a point where the laser beam intensity becomes one half of the maximum intensity thereof is regarded as the outer edge of the laser luminous flux, and that the luminous flux diameter is regarded as a distance between two points at one of which intersecting a line parallel to the scanning line and at the same time passing through a point maximizing the light intensity and at the other of which intersecting the outer edge line of the luminous flux.
- the invention is particularly advantageous when making use of a means having a shorter exposure time per pixel.
- the laser printers include, for example, those described in JP OPI Publication Nos. 55-4071/1980, 59-11062/1984, 63-197947/1988, 2-74942/1990 and 2-236538/1990, JP Examined Publication Nos. 56-14963/1981 and 56-40822/1981, European Regional Patent No. 77410, "The Institute of Electronics & Communication Engineers' Study Reports", Vol. 80, No. 244, "The Magazine of Cinematography and Television", 1984/6 (382), pp. 34-36, and so forth.
- the red-sensitive sensitizing dyes applicable thereto include, for example, a cyan dye represented by the following Formulas [2] and [3].
- R 1 , R 2 , R 3 and R 4 represent each an alkyl group, an alkenyl group or an aryl group;
- L 1 , L 2 , L 3 , L 4 and L 5 represent each a methyl group;
- Z 1 , Z 2 , Z 3 and Z 4 represent each an atom necessary to form a 5- or 6-membered heterocyclic ring or the group consisting of the same atoms;
- m 1 , m 2 , m 3 and m 4 are each an integer of 0 or 1;
- n is an integer of 0 or 1;
- X - represents an acid anion; and
- Y 1 and Y 2 are each an integer of 0 or 1, provided that Y 1 and Y 2 are each an integer of 0 when the subject compound produces an intramolecular salt.
- Supersensitizers applicable to the silver halide emulsion include, for example, a compound such as stilbene, azaindene, a mercapto-heterocyclic compound, and a condensate of thiourea or a phenol and hexamethylene tetramine. Among them, a heterocyclic ring-containing cyclic compound having a 9-membered or more membered ring is preferred.
- the cyclic compounds include, preferably, those having an aliphatic ring and/or an aromatic ring and an ether bond, more preferably, those having not more than four aliphatic rings capable of producing a cyclic compound and, further preferably, a macrocyclic compound having an aromatic ring.
- Typical compounds include, for example, a crown ether.
- Specific examples of these cyclic compounds include S-1 to S-39 given in JP Application No. 4-330655/1992, paragraphs 0049-0055.
- the light-sensitive material prefferably includes gelatin as a binder for making a dispersion and a coating solution.
- Gelatin is prepared in, for example, the process described in T.H. James, The Theory of The Photographic Process, 4th ed., (1977), p. 55, and The Fundamentals of Photographic Engineering ⁇ A volume on Silver Salts, pp. 119-124.
- the raw materials thereof ossein, cowhide, and pig skin are used.
- the raw materials made of ossein are preferred, and two or more kinds of the above-mentioned raw materials may be mixed up.
- an alkali treatment, an acid treatment, an oxygen treatment and so forth may be applied.
- an alkali-treated gelatin is preferred.
- the isoelectric point of an alkali-treated gelatin is preferably not lower than 4.5 and, more preferably, not lower than 5.
- Gelatin may usually be ion-exchange treated.
- amphoteric ion-exchange-treated gelatin is preferred, provided that, among cation ion-exchange-treated gelatin, anion-exchange-treated gelatin, and amphoteric ion-exchange-treated gelatin, any of the gelatin can suitably be so selected as to meet an application purpose.
- hydrogen peroxide-treated gelatin may also preferably be used.
- the hydrogen peroxide treatment may be applied in any steps of a gelatin preparation process. For example, it can be applied directly to ossein, or may also applied in the midst of or after carrying out an alkali treatment, or after extracting a gelatin solution. It is preferable to use gelatin prepared by adding aqueous oxygen peroxide in the course of carrying out an alkali treatment. Hydrogen peroxide may be added in an amount within the range of from 1 to 100 g in terms of pure H 2 O 2 per kg of ossein used. And, it is also preferable to make an ossein reaction with hydrogen peroxide at a pH of not lower than 9.0.
- the low molecular weight component thereof is the less, the better, that is, the high molecular weight component thereof is the more, the better.
- a high and low molecular weight thereof can be measured in the procedures described in JP OPI Publication No. 1-265247/1989, p. 2, the 15th line in the lower left column to p. 3, the 8th line in the upper left column.
- the high and low molecular weight components thereof are preferably not lower than 30% for the former and/or not higher than 40% for the latter, according to the expressions given in the procedures.
- Gelatin suitably has a molecular weight within the range of from 10,000 to 200,000.
- Gelatin preferably has a higher jelly strength that is, preferably, not lower than 250 and, more preferably, not lower than 270.
- An ion content of gelatin is preferable to be lower.
- the calcium content thereof is to be not more than 5000 ppm and, preferably, not more than 2000 ppm. However, in some emulsion, it may sometimes be preferable that calcium may be made present in a proportion within the range of from 4000 to 5000 ppm.
- the content of a heavy metal ion such as iron ion and copper ion is to be not more than 500 ppm in total and not more than 10 ppm in each component.
- an iron content of gelatin is to be not more than 5 ppm and, preferably, not more than 3 ppm.
- a specific optical rotation angle of gelatin is preferably higher and, particularly, not narrower than 150. When gelatin is used in the uppermost layer, the specific optical rotation angle thereof is preferably not narrower than 210.
- the tinctorial power of gelatin is the less, the better.
- the transmittance of gelatin at 420nm is advantageous for the transmittance of gelatin at 420nm to be not less than 50%, preferably not less than 60% and, more preferably not less than 70%.
- a raw material selection, a hydrogen peroxide treatment, an ion-exchange treatment, an adsorption treatment with a chelating resin and so forth are suitably carried out.
- a total amount of gelatin to be contained in the light-sensitive material is to be not more than 10.0 g/m 2 and, preferably, not more than 7.0 g/m 2 .
- a gelatin amount can be obtained in the moisture measurement procedures described in PAGI method in which a gelatin amount is obtained by converting it into an amount by weight of gelatin containing 11.0% of moisture.
- a layer hardener may be used as binder.
- the layer hardeners preferably applicable thereto include, for example, a vinyl sulfone type layer hardener and a chlorotriazine type layer hardener.
- a vinylsulfone type layer hardener preferably applicable thereto include, for example, the compounds given in JP OPI Publication No. 61-249054/1986, p. 25, the 13th line in the upper right column to p. 27, the 2nd line in the upper right column. Besides the above, compound H-12 given in ibid., p. 26 can more preferably be used.
- the chlorotriazine type layer hardeners preferably applicable thereto include, for example, the compounds given in JP OPI Publication No.
- the compound denoted by XII-1 given in ibid., p. 4 is more preferable.
- These layer hardeners are preferably used with other kinds of compounds in combination. They may also be added to any layers. The layer hardeners are preferably used in a proportion within the range of from 0.1 to 10% by weight to a binder used.
- Preferable antimolds include, for example, the compounds represented by Formula II given in JP Application No. 1-298092/1989, p. 9.
- Specitic examples of the compounds include, typically, compound examples No. 9 to No. 22 each given in ibid., pp. 69-70.
- the particularly preferable one is compound No. 9.
- a preservative and an antimold can be used.
- Preferable examples thereof include the compounds given in JP OPI Publication No. 3-157646/1991, p. 17, the 16th line in the lower right column to p. 19, the lower left column.
- the base paper applicable to the support can be selected from any materials having been commonly used.
- the base paper for a support use include, for example, a natural wood pulp such as a sulfuric acid-bleached needle-leafed wood pulp (or NBKP), a sulfuric acid-bleached broad-leafed wood pulp (or LBKP), a sulfurous acid-bleached needle-leaved wood pulp (or NBSP) and a sulfurous acid-bleached broad-leaved wood pulp (or LBSP).
- a natural wood pulp such as a sulfuric acid-bleached needle-leafed wood pulp (or NBKP), a sulfuric acid-bleached broad-leafed wood pulp (or LBKP), a sulfurous acid-bleached needle-leaved wood pulp (or NBSP) and a sulfurous acid-bleached broad-leaved wood pulp (or LBSP).
- sizing agents applicable thereto include, for example, an alkylketene dimer fatty acid salt, rosin, maleic rosin, an alkenyl succinic acid salt, an alkyl succinic acid salt and a polysaccharide.
- an alkylketene dimer fatty acid salt can preferably be used. They are preferably used in a proportion within the range of from 0.2 to 2% per an amount of pulp used.
- Dry paper strength reinforcing agents applicable thereto include, for example, a cationic polyacrylamide, an anionic polyacrylamide and a carboxy-denatured polyvinyl alcohol.
- a cationic starch and an anionic polyacrylamide are preferred.
- Wet paper strength reinforcing agents applicable thereto include, for example, a melamine resin, a urea resin and an epoxidated polyamido resin. Among them, an epoxidated polyamido resin is preferred.
- the surface of pulp is tub-sized or size-pressed with a solution containing a water-soluble macromolecular additive.
- the macromolecular additives applicable thereto include, for example, cationic starch, polyvinyl alcohol, carboxy-denatured polyvinyl alcohol, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxyethyl cellulose, polyacrylamide and gelatin. Among them, cationic starch and polyvinyl alcohol are preferred.
- the antifoggants applicable thereto include, for example, the water-soluble iodine compounds given in JP OPI Publication No. 55-103549/1980, the weak acid salts or oxides of magnesium, calcium or zinc each given in JP OPI Publication No. 56-43637/1981, the urea compounds having a molecular weight of not more than 150 such as described in JP OPI Publication No. 56-97343/1981 and the magnesium compounds given in JP OPI Publication No. 5-19405/1993.
- magnesium hydroxide, magnesium oxide, calcium oxide and zinc oxide are preferred, and they are used in a proportion within the range of 0.1 to 10% by weight of the weight of a pulp used.
- the inorganic electrolytes applicable thereto include, for example, edible salt and Glauber's salt and, among them, edible salt is preferred.
- the hygroscopic substances applicable thereto include, for example, glycerol and polyethylene glycol.
- the pH controllers applicable thereto include, for example, hydrochloric acid, sodium hydroxide and sodium carbonate.
- the additives such as a dyestuff (including, preferably, a blue dyestuff and a ultramarine blue dye), a fluorescent whitening agent, an antistatic agent and a defoamer may be used in combination.
- a pulp is processed in the following treatments. After it is suitably pulverized to prepare a pulp slurry containing the above-given additives if required.
- the resulting slurry is formed into paper by a paper-making machine such as a Fourdrinier paper making machine, and the resulting paper is dried up and then super-calendered. Before or after drying the paper, it is surface-sized.
- a support is coated with a polyolefin resin on both sides of the resulting base paper of the support.
- the polyolefin resins include, for example, a single polymer of ⁇ -polyolefin such as polyethylene and polypropylene and the mixtures of each of the polymers.
- the particularly preferable polyolefins include, for example, a high-density polyethylene, a low-density polyethylene, or the mixtures thereof.
- the molecular weights of the above-mentioned polyolefins is no special limitation to the molecular weights of the above-mentioned polyolefins. However, a polyolefin having a molecular weight within the range of from 20,000 to 200,000 is commonly used.
- the layer thickness of a polyolefin resin-coated layer is usually within the range of from about 15 to 50 ⁇ m.
- a support is made of paper
- any supports having various types can be used.
- it is also allowed to use a thin type base paper having a thickness within the range of from 80 to 180 ⁇ m, a delaminable and adhesive type support described in Japanese Utility Model Application No. 64-29550/1989, and a thick type base paper.
- a support made of polypropylene or polyethylene terephthalate it is also allowed to prepare them in such a manner that a white pigment is coated in a controlled amount over each of transparent, translucent or opaque type base paper.
- the oxygen permeability of a support is preferably not more than 2.0 cc/m 2 ⁇ hr ⁇ atm.
- the light-sensitive material is, if required, corona-discharged, UV-irradiated, flame-treated and so forth, it is also allowed to be coated directly or through a sublayer (that is one or not less than two under-coat layers for improving the adhesiveness, antistatic property, dimensional stability, frictional resistance, hardness, antihalation property, frictional property and/or other characteristics each of the surface of a support).
- a sublayer that is one or not less than two under-coat layers for improving the adhesiveness, antistatic property, dimensional stability, frictional resistance, hardness, antihalation property, frictional property and/or other characteristics each of the surface of a support.
- a thickening agent may be used when coating a light-sensitive material applied with a silver halide emulsion.
- an extrusion coating method capable of coating two or more layers at the same time, or a curtain coating method are particularly useful.
- the above-given color developing agents may be used independently or in combination with any well-known p-phenylenediamine derivatives.
- the color developing agents are each used commonly in an amount within the range of 1 ⁇ 10 -2 to 2 ⁇ 10 -1 mols per liter of a developer used. From the viewpoint of a rapid process, they are preferably used in an amount within the range of 1.5 ⁇ 10 -2 to 2 ⁇ 10 -1 mols per liter of a color developer used.
- color developing agents CD-5, CD-6 and CD-9 are preferred. Among them CD-5 is particularly preferred so as to make it closer to a printing ink tone.
- p-phenylenediamine derivatives are commonly used in the salt forms such as a sulfate, a hydrochloride, a sulfite, a nitrate and a p-toluene sulfonate.
- any benzyl alcohol is not substantially contained therein.
- the expression, "--- be not substantially contained ---", herein means that benzyl alcohol is contained in an amount of 2cc per liter of the subject developer. In the invention, it is most preferable when none of benzyl alcohol is contained at all.
- a color developer the following developer components, besides the above-mentioned components, may be contained.
- an alkalizer for example, sodium hydroxide, potassium hydroxide, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax and a silicate may be used independently or in combination, provided that they are used without producing any precipitation and a pH stabilizing effect can be maintained.
- salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate and a borate.
- a color developer contains chloride ions in an amount within the range of from 2.5 ⁇ 10 -2 to 5 ⁇ 10 -1 mols per liter of the color developer.
- chloride ions and bromide ions may be added directly to a developer, or it may be dissolved out of a light-sensitive material into the developer in the course of carrying out the development.
- the substances for supplying chloride ions include, for example, sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride and cadmium chloride.
- sodium chloride and potassium chloride are preferred. They may also be supplied from a fluorescent whitening agent contained in a developer.
- the substances for supplying bromide ions include, for example, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, nickel bromide, magnesium bromide, manganese bromide, calcium bromide, cadmium bromide, cerium bromide and thallium bromide.
- the preferable substances include, for example, sodium bromide and potassium bromide.
- organic preservatives can preferably be used in place of hydroxyl amine having so far been used as a preservative; namely, organic preservatives including, for example, a hydroxyl amine derivative such as those given in JP OPI Publication Nos.
- a hydroxamic acid a hydrazine, a phenol, an ⁇ -hydroxyketone, ⁇ -aminoketone, a sugar, a monoamine, a diamine, a quaternary ammonium salt, a nitroxy radical, an alcohol, an oxime, a diamido compound, and a condensed-ring type amine.
- a development accelerator may also be used, if required.
- the development accelerators include, for example, various kinds of pyridinium compounds typified by those given in, for example, US Patent Nos. 2,648,604 and 3,671,247 and JP Examined Publication No. 44-9503/1969, cationic dyes such as other cationic compounds and phenosafranine, neutral salts such as thallium nitrate, a polyethylene glycol and the derivatives thereof such as those given in, for example, US Patent Nos. 2,533,990, 2,531,832, 2,950,970 and 2,577,127 and JP Examined Publication No.
- nonionic compounds such as a polythioether, organic solvents given in, for example, JP Examined Publication No. 44-9509/1969, an organic amine, ethanolamine, ethylenediamine, diethanolamine and triethanolamine.
- organic solvents given in, for example, JP Examined Publication No. 44-9509/1969
- an organic amine ethanolamine, ethylenediamine, diethanolamine and triethanolamine.
- phenethyl alcohol given in, for example, US Patent No. 2,304,925 and, besides, acetylene glycol, methylethyl ketone, cyclohexanone, pyridine, ammonia, hydrazine, a thioether, an amine, and so forth may also be included.
- a dissolving aid such as ethylene glycol, methyl cellosolve, methanol, acetone, dimethyl formamide, ⁇ -cyclodextrin, p-toluene sulfonic acid and, besides, the compounds given in, for example, JP Examined Publication Nos. 47-33378/1972 and 44-9509/0969.
- auxiliary developer can also be used together with a developing agent.
- the auxiliary developers having been known include, for example, a N-methyl-p-aminophenol sulfate, phenidone, an N,N-diethyl-p-aminophenol chloride and an N,N,N',N'-tetramethyl-p-phenylene diamine chloride. They may be added usually in an amount within the range of 0.01 to 1.0 g per liter of a developer used.
- auxiliary developers Besides the above-mentioned auxiliary developers, a competing coupler, a foggant, a development-inhibitor-releasing type coupler (or a DIR coupler), a development-inhibitor-releasing type compound and so forth may also be added. Further, a variety of additives such as other antistaining agent, an antisludging agent, an interlayer effect accelerator and so forth may be added.
- Each component of the above-mentioned color developers can be prepared by adding and stirring it in a specific amount of water.
- a component having a relatively lower solubility to water may be added upon mixing it with the foregoing organic solvents such as triethanol amine.
- a color developer can also be prepared in the following manner. A plurality of components thereof which can stably coexist together are prepared in the form of an aqueous concentrated solution or in the solid state. The resulting conc.-solution is put into a small vessel in advance and is added to and then stirred in water, so that the color developer can be prepared.
- the sulfite concentration of a color developer is preferably not more than 1x10 -2 mols per liter of the developer. It becomes excellent when the concentration thereof is not more than 7x10 -3 mols per liter, including 0 and, particularly, it is preferable when the concentration thereof is not more than 5x10 -3 mols per liter, including 0.
- a color developer can be used in any pH regions. However, it is preferably within the range of pH9.5 to 13.0 and, more preferably, 9.8 to 12.0, from the viewpoint of a rapid processing.
- a processing temperature is preferably within the range of 25 to 70°C. It is preferable when a processing temperature is higher, because a processing time can be shortened. However, the processing temperature is preferable to be rather lower, from the viewpoint of the stability of a processing solution, and it is, therefore, preferable to process with a color developer at a temperature within the range of 25 to 50°C.
- a color development time is to be within the range of 70 to 240 seconds. When it is shorter than 70 seconds, the maximum density will come out instable when carrying out a continuous processing. When it is longer than 240 seconds, there will come out such a defect that a sludge is liable to produce in a color developer. It is, therefore, preferably within the range of 90 to 220 seconds.
- An amount of a color developer to be replenished is preferably not more than 700cc per liter, more preferably, not more than 500cc and, further preferably, within the range of 20 to 280cc.
- the processing steps comprise substantially a color developing step, a bleach-fixing step and a washing step (including a stabilizing step in place of the washing step). It is allowed to add the other processing steps or to replace the above-mentioned steps by any steps having the functions equivalent to those of the above-mentioned steps.
- the above-mentioned bleach-fixing step may be separated into a bleaching step and a fixing step and, further, another bleaching step may be added before the bleach-fixing step.
- the metal complex salts of an organic acid are preferred.
- the complex salts thereof include, for example, polycarboxylic acid, aminopolycarboxylic acid or an organic acid such as oxalic acid and citric acid is coordinated with a metal ion such as that of iron, cobalt or copper.
- polycarboxylic acid and aminopolycarboxylic acid may be given.
- the above-mentioned polycarboxylic acid or aminopolycarboxylic acid is allowed to be an alkali-metal salt, an ammonium salt or a water-soluble amine salt.
- the concrete compounds thereof include, for example, compounds 2 through 20 given in JP OPI Publication No. 1-205262/1989, pp. 58-59.
- the above-mentioned bleachers are each used in an amount within the range of 5 to 450 g per liter of a bleach-fixer used and, more preferably, 20 to 250 g.
- a bleach-fixer contains a silver halide fixing agent, as well as the above-mentioned bleaching agent. If required, a solution having a composition containing a sulfite is also applied as a preservative. It is also allowed to use a bleach-fixer comprising a composition added with a relatively large amount of a halide such as ammonium bromide, and a specialty bleach-fixer having a composition comprising a combination of an iron(III) ethylenediamine tetraacetate bleaching agent and a relatively large amount of a halide such as ammonium bromide, besides an iron(III) ethylenediamine tetraacetate bleaching agent and a silver halide fixing agent.
- a bleach-fixer comprising a composition added with a relatively large amount of a halide such as ammonium bromide
- a specialty bleach-fixer having a composition comprising a combination of an iron(III) ethylenediamine tetraa
- halides also applicable thereto include, for example, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide and ammonium iodide, besides ammonium bromide.
- halide fixing agents contained in a bleach-fixer include, for example, a compound capable of producing a water-soluble complex salt upon making a reaction with such a silver halide as is commonly applicable to a fixing treatment. They include, typically, a thiosulfate such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate, a thiocyanate such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate, thiourea and thioether.
- a thiosulfate such as potassium thiosulfate, sodium thiosulfate and ammonium thiosulfate
- a thiocyanate such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate
- These fixing agents may be used in an amount of not less than 5g per liter of a bleach-fixer used, provided that it can be dissolved. It is commonly used in an amount within the range of 70 to 250g.
- a bleach-fixer is allowed to contain a variety of pH buffer, independently or in combination, such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide. It can also contain a variety of fluorescent whitening agents, defoamers and surfactants.
- It can further suitably contain a preservative such as hydroxyl amine, hydrazine and the bisulfurous acid adducts of an aldehyde compound, an organic chelating agent such as aminopolycarboxylic acid, a stabilizer such as nitroalcohol and a nitrate, and an organic solvent such as methanol, dimethyl formamide and dimethyl sulfoxide.
- a preservative such as hydroxyl amine, hydrazine and the bisulfurous acid adducts of an aldehyde compound
- an organic chelating agent such as aminopolycarboxylic acid
- a stabilizer such as nitroalcohol and a nitrate
- an organic solvent such as methanol, dimethyl formamide and dimethyl sulfoxide.
- the bleach-fixers are allowed to be added by a variety of such a bleaching accelerator as given in JP OPI Publication No. 46-280/1971, JP Examined Publication Nos. 45-8506/1970 and 46-556/1971, Belgian Patent No. 770,910, JP Examined Publication Nos. 45-8836/1970 and 53-9854/1978, JP OPI Publication Nos. 54-71634/1979 and 49-42349/1974, and so forth.
- a bleach-fixer is used at a pH of not lower than 4.0, commonly, within the range of 4.0 to 9.5, preferably, 4.5 to 8.5 and, most preferably, 5.0 to 8.5. It is also used at a temperature of not higher than 80°C and, preferably, not higher than 55°C so as to inhibit it from producing an evaporation.
- a bleach-fixing time thereof is preferably not longer than 240 seconds.
- washing treatment is carried out after a color development and then a bleach-fixing process.
- a preferable embodiment of the washing treatment will now be detailed.
- the compounds preferably applicable to a washing liquid include, for example, a chelating agent having a chelation-stabilization constant to an iron ion of not less than 8.
- a chelation-stabilization constant herein means a constant having generally been known in L.G. Sillen & A.E. Martell, "Stability Constant of Metal Ion Complexes", The Chemical Society, London, (1964); S. Chaberek & A.E. Martell, "Organic Sequestering Agents", Wiley, (1959); and so forth.
- the chelating agents each having a chelation-stabilization constant to iron ion of not less than 8 include, for example, an organic carboxylic acid chelating agent, an organic phosphoric acid chelating agent, an inorganic phosphoric acid chelating agent and a polyhydroxy compound.
- the above-mentioned iron ion means ferric ion.
- the concrete compounds for a chelating agent having a chelation-stabilization constant to ferric ion of not less than 8 include, for example, the compounds given in JP OPI Publication No. 1-205162/1989, p. 63, the 15th line to p. 64, the 17th line.
- the above-mentioned chelating agent may be used in an amount within the range of, preferably, 0.01 to 50g and, more preferably, 0.05 to 20g per liter of a washing liquid used.
- an ammonium compound is particularly preferred. They are supplied from an ammonium salt of various kinds of inorganic compounds. They include, concretely, the compounds given in JP OPI Publication No. 1-205162/1989, p. 65, the 5th line to p. 66, the 11th line. Such an ammonium compounds as mentioned above may be added in an amount of, preferably, not less than 1.0x10 -5 mols per liter of a washing liquid used, more preferably, within the range of 0.001 to 5.0 mols and, particularly, within the range of 0.002 to 1.0 mols.
- an aqueous solution contains a sulfite in such an amount that no bacteria can be produced.
- the sulfites to be contained in an aqueous solution may be any one of organic or inorganic matters, provided that the sulfites can release sulfite ions.
- the preferable sulfites are of the inorganic salts.
- the concrete compounds thereof include, for example, sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite, sodium hydrosulfite, sodium glutaraldehyde bisbisulfite and sodium succinaldehyde bisbisulfite.
- Support A was prepared by laminating a high density polyethylene on the both sides of a pulp paper having a balance weight of 130 g/m 2 , wherein a surface-treated anatase type titanium dioxide is contained in an amount of 15 % by weight in a polyethylene laminated layer of emulsion layer side.
- Support B was prepared in the same manner as in Support A, except that 90 parts by weight of polyethylene terephathalate and 10 parts by weight of anatase type titanium dioxide white pigment were each added and kneaded together, and then, a water-proof resin layer containing 30 g/m 2 was coated on the surface of emulsion side of a pulp paper.
- an electron beam-hardenable coating solution having the following composition was prepared.
- Epoxyacrylate oligomer with the trade name of FS-3118, produced by Mitsubishi Rayon Co.
- 70 wt% Titanium oxide with the trade name of A-220, produced by Ishihara Sangyo Co.
- compositions were well mixedly dispersed for 20 minutes by making use of a cowl-less dissolver.
- the resulting coating solution was coated at a line-speed of 30 m/min. on the circumferential surface of a rotary drum being rotated having a high-glossy, mirror-finished circumferential surface, by making use of a slit-orifice coater so that the amount coated (of the solid parts) could be 6 g/m 2 .
- a base paper for photographic print paper support having a balance weight of 180 g/m 2 and being run by coupling to the drum rotation speed was pressed down and laminated on the resulting coating solution layer, and an electron beam was irradiated from the back side of the base paper so that the beam absorption could be 1 Mrad at an acceleration voltage.
- the coating solution layer was hardened thereby and the resulting multilayered member was peeled off, so that a support (Support C) could be obtained.
- Supports D and E were prepared each by making use of the following compositions, respectively.
- Composition of the coating solution for Support D Polyester acrylate (having four double-bonds per about 1000 molecules) 25 wt% Trimethylolpropane triacrylate 25 wt% Titanium dioxide (of the rutile type) 50 wt%
- Composition of the coating solution for Support E Urethane acrylate 25 wt% Epoxy acrylate 25 wt% Titanium dioxide (anatase type) 50 wt%
- a color photographic light-sensitive material was prepared by coating the following Layer 1 through Layer 7 on Support A and then by coating a backing layer on the back side of Support A.
- the amounts of the silver halide emulsions added are indicated in terms of the silver contents of the emulsions, respectively.
- Samples 102, 103, 105 to 107 and 109 to 111 were each prepared in the same manner as in Sample 101, except that the materials were changed as shown in Table 1 and added to the samples.
- Layers HC-1, HC-2 and S-2 each, (H-2) was added as a gelatin layer hardener so as to be in a proportion of 5 mg/m 2 ; and to Layer S-2, it was so added as to be in a proportion of 20 mg/m 2 .
- Em-B, Em-C and Em-R were each prepared in the following manners.
- a silver chlorobromide emulsion having an average grain size of 0.7 ⁇ m and a silver bromide content of 80% was subjected to the optimum sensitization at 57°C by making use of sodium thiosulfate, and sensitizing dye (BS-1) and a stabilizer STB-1 were then added thereto.
- sensitizing dye (BS-1) and a stabilizer STB-1 were then added thereto.
- a silver chlorobromide emulsion having an average grain size of 0.5 ⁇ m and a silver bromide content of 70% was subjected to the optimum sensitization at 59°C by making use of sodium thiosulfate, and sensitizing dye (GS-1) and a stabilizer STB-1 were then added thereto.
- a silver chlorobromide emulsion having an average grain size of 0.4 ⁇ m and a silver bromide content of 60% was subjected to the optimum sensitization at 59°C by making use of sodium thiosulfate, sensitizing dye (RS-1) and phenol resin, and a stabilizer STB-1 was then added thereto.
- an apparatus was assembled so as to be capable of exposing scanningwise a luminous flux having a 100 ⁇ m-pitch and a 80 ⁇ m-flux size to samples being moved toward the direction vertical to the scanning direction, at a scanning speed of 1.6m/second.
- Processing step Processing temp. Processing time Color developing 38.0 ⁇ 0.3°C 120 sec. Bleach-fixing 35.0 ⁇ 0.5°C 45 sec. Stabilizing 30-34°C 90 sec. Drying 60-80°C 30 sec.
- the stabilizing was carried out in a counter-current system comprising a double-tank structure.
- the white background and halftone-dot quality can be compatible in the invention.
- Em-B2, Em-G2 and Em-R2 were prepared, respectively.
- the following solutions A and B were added at the same time to 1000 ml of an aqueous 2% gelatin solution being kept at 40°C by taking 30 minutes while controlling the pAg and pH to be 6.5 and 3.0, respectively. Further, the following solutions C and D were also added at the same time thereto by taking 180 minutes while controlling the pAg and pH to be 7.3 and 5.5, respectively.
- the pAg was controlled in the method described in JP OPI Publication No. 59-45437/1984 and the pH was controlled by making use of an aqueous sulfuric acid or sodium sulfate solution.
- the desalting treatment was carried out by making use of an aqueous solution of 5% Demol N produced by Kao-Atlas Corp. and an aqueous 2% magnesium sulfate solution, and the resulting desalted solution and an aqueous gelatin solution were mixed together, so that a monodisperse type cubic-grained emulsion EMP-1 having an average grain size of 0.85 ⁇ m, the variation coefficient of the grain-size distribution of 0.07 and a silver chloride content of 99.5 mol% could be prepared.
- EMP-1 was subjected to the optimum chemical sensitization at 50°C by making use of the following compounds, so that a blue-sensitive silver halide emulsion (Em-B2) could be prepared.
- Sodium thiosulfate 0.8 mg/mol of AgX Chloroauric acid 0.5 mg/mol of AgX Stabilizer STAB-1 6x10 -4 mols/mol of AgX Sensitizing dye BS-1 4x10 -4 mols/mol of AgX Sensitizing dye BS-3 1x10 -4 mols/mol of AgX
- Em-G2 and Em-R2 were each prepared. And, the chemical structures of the stabilizer and sensitizing dyes will be given later.
- a monodisperse type cubic-grained emulsion EMP-2 having an average grain size of 0.43 ⁇ m, a variation coefficient of 0.08 and a silver chloride content of 99.5% could be prepared in the same manner as in EMP-1, except that the time of adding Solutions A and B and the time of adding Solutions C and D were each changed.
- EMP-2 was subjected to the optimum chemical sensitization at 55°C by making use of the following compounds, so that a green-sensitive silver chloride emulsion (Em-G2) could be prepared.
- Em-G2 green-sensitive silver chloride emulsion
- Sodium thiosulfate 1.5 mg/mol of AgX Chloroauric acid 1.0 mg/mol of AgX Stabilizer STAB-1 6x10 -4 mols/mol of AgX Sensitizing dye GS-1 4x10 -4 mols/mol of AgX
- a monodisperse type cubic-grained emulsion EMP-3 having an average grain size of 0.50 ⁇ m, a variation coefficient of 0.08 and a silver chloride content of 99.5% could be prepared in the same manner as in EMP-1, except that the time of adding Solutions A and B and the time of adding Solutions C and D were each changed.
- EMP-3 was subjected to the optimum chemical sensitization at 60'C by making use of the following compounds, so that a green-sensitive silver chloride emulsion (Em-R2) could be prepared.
- Em-R2 green-sensitive silver chloride emulsion
- Sodium thiosulfate 1.8 mg/mol of AgX Chloroauric acid 2.0 mg/mol of AgX Stabilizer STAB-1 6x10 -4 mols/mol of AgX Sensitizing dye RS-1 1x10 -4 mols/mol of AgX
- Processing step Processing temperature Processing time Amount replenished Color developing 37.0 ⁇ 0.3°C 120 sec. 300cc Bleach-fixing 35.0 ⁇ 0.5°C 45 sec. 300cc Stabilizing 30 to 35°C 90 sec. 600cc Drying 50 to 80°C 40 sec.
- compositions of the development processing solutions will be given below.
- O-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazoline-3-one 0.02 g 2-methyl-4-isothiazoline-3-one 0.02 g
- Diethylene glycol 1.0 g
- Fluorescent whitening agent (Cinopar SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g
- Sodium ethylenediaminetetraacetate 1.5
- Potassium sulfite 5.0 g
- Add water to make in total 1 liter Adjust pH with aqueous ammonia to be pH 8.0 Sample No.
- the result of the color-stain was evaluated in the following manner.
- a red-color exposure was made by making a red-color-separation exposure with a coating solution obtained by two-cycle-running a fresh solution
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- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Claims (9)
- Méthode de formation d'image, comprenant les étapes consistant :(1) à exposer un matériau photosensible photographique couleur à l'halogénure d'argent avec une lumière laser à balayage ; et(2) à développer le matériau photosensible photographique couleur à l'halogénure d'argent exposé comprenant un support ayant une couche de résine qui comprend un composé organique durci en appliquant un faisceau d'électrons, et le composé organique n'a pas moins de deux doubles liaisons carbone-carbone dans une molécule de celui-ci, étant disposées sur le support au moins une couche photosensible incluant des grains d'halogénure d'argent et au moins une couche autre que les couches photosensibles, disposée sous la couche la plus basse des couches photosensibles, dans laquelle au moins l'une des couches autres que les couches photosensibles ou la couche de résine comprend un pigment blanc en une quantité non inférieure à 20 % en poids.
- Méthode de formation d'image selon la revendication 1, dans laquelle au moins l'une des couches autres que les couches photosensibles ou la couche de résine comprend un pigment blanc en une quantité de 20 à 80 % en poids.
- Méthode de formation d'image selon la revendication 1 ou 2, dans laquelle au moins l'une des couches autres que les couches photosensibles a un pourcentage de vides dans la gamme de 5 à 35 % en poids.
- Méthode de formation d'image selon l'une quelconque des revendications précédentes, dans laquelle la teneur en chlorure d'argent des grains d'halogénure d'argent n'est pas inférieure à 80 % en moles.
- Méthode de formation d'image selon la revendication 4, dans laquelle la teneur en chlorure d'argent des grains d'halogénure d'argent n'est pas inférieure à 95 % en moles.
- Méthode de formation d'image selon l'une quelconque des revendications précédentes, dans laquelle le pigment blanc est choisi parmi un dioxyde de titane rutile, un dioxyde de titane anatase, un sulfate de baryum, un stéarate de baryum, une silice, une alumine, un oxyde de zirconium et un kaolin.
- Méthode de formation d'image selon la revendication 6, dans laquelle le pigment blanc est choisi parmi un dioxyde de titane rutile et un dioxyde de titane anatase.
- Méthode de formation d'image selon l'une quelconque des revendications précédentes, dans laquelle le composé organique est choisi parmi un oligomère acrylique, un oligomère méthacrylique, un monomère acrylique, un monomère méthacrylique, un monomère acrylique multifonctionnel et un monomère méthacrylique multifonctionnel.
- Méthode de formation d'image selon l'une quelconque des revendications précédentes, dans laquelle le matériau photosensible photographique couleur à l'halogénure d'argent est exposé avec une lumière laser à balayage selon une information d'image par points de simili séparée en couleurs en une information d'image jaune, magenta, cyan et noire.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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JP65131/94 | 1994-04-01 | ||
JP6513194A JPH07270967A (ja) | 1994-04-01 | 1994-04-01 | 画像形成方法 |
JP6513194 | 1994-04-01 |
Publications (2)
Publication Number | Publication Date |
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EP0675404A1 EP0675404A1 (fr) | 1995-10-04 |
EP0675404B1 true EP0675404B1 (fr) | 2001-09-26 |
Family
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Application Number | Title | Priority Date | Filing Date |
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EP95302141A Expired - Lifetime EP0675404B1 (fr) | 1994-04-01 | 1995-03-30 | Procédé de formation d'image |
Country Status (3)
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EP (1) | EP0675404B1 (fr) |
JP (1) | JPH07270967A (fr) |
DE (1) | DE69522845T2 (fr) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH11184043A (ja) * | 1997-12-17 | 1999-07-09 | Konica Corp | ハロゲン化銀カラー写真感光材料及びカラープルーフの作製方法 |
DE69924543T2 (de) * | 1998-01-23 | 2006-02-09 | Fuji Photo Film Co. Ltd., Minamiashigara | Photographisches lichtempfindliches Silberhalogenidfarbmaterial und Verfahren zur Bilderzeugung, das dieses verwendet |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0578248A2 (fr) * | 1992-07-09 | 1994-01-12 | Fuji Photo Film Co., Ltd. | Produit photographique couleur à l'halogénure d'argent sensible à la lumière |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH04306647A (ja) * | 1991-04-03 | 1992-10-29 | Fuji Photo Film Co Ltd | 白色のポリマー組成物、それを用いた写真用反射支持 体及び写真印画紙用支持体 |
JPH0675348A (ja) * | 1992-07-09 | 1994-03-18 | Fuji Photo Film Co Ltd | ハロゲン化銀カラー写真感光材料 |
-
1994
- 1994-04-01 JP JP6513194A patent/JPH07270967A/ja active Pending
-
1995
- 1995-03-30 DE DE1995622845 patent/DE69522845T2/de not_active Expired - Fee Related
- 1995-03-30 EP EP95302141A patent/EP0675404B1/fr not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0578248A2 (fr) * | 1992-07-09 | 1994-01-12 | Fuji Photo Film Co., Ltd. | Produit photographique couleur à l'halogénure d'argent sensible à la lumière |
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JPH07270967A (ja) | 1995-10-20 |
DE69522845D1 (de) | 2001-10-31 |
DE69522845T2 (de) | 2002-04-04 |
EP0675404A1 (fr) | 1995-10-04 |
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