WO2004068239A1 - Procede de formation d'images - Google Patents

Procede de formation d'images Download PDF

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Publication number
WO2004068239A1
WO2004068239A1 PCT/JP2003/000988 JP0300988W WO2004068239A1 WO 2004068239 A1 WO2004068239 A1 WO 2004068239A1 JP 0300988 W JP0300988 W JP 0300988W WO 2004068239 A1 WO2004068239 A1 WO 2004068239A1
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WO
WIPO (PCT)
Prior art keywords
exposure
silver halide
color
image
image forming
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PCT/JP2003/000988
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English (en)
Japanese (ja)
Inventor
Toyoki Nishijima
Original Assignee
Konica Corporation
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Publication date
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Priority to PCT/JP2003/000988 priority Critical patent/WO2004068239A1/fr
Publication of WO2004068239A1 publication Critical patent/WO2004068239A1/fr

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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
    • G03C7/3041—Materials with specific sensitometric characteristics, e.g. gamma, density
    • 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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • 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
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • G03C2001/097—Selenium
    • 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
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/04—Photo-taking processes

Definitions

  • the present invention relates to an image forming method using a silver halide color photographic light-sensitive material, in which the density fluctuation in a high-speed digital print and the gradation fluctuation in a multiple exposure are improved and excellent in sharpness.
  • Image information captured by a digital camera or image information that has been converted into digital data from a film or print using a scanner, etc. can be edited and processed on a computer, and data such as character first can be added. Can be done relatively easily.
  • Hard copy materials for producing hard copies based on such digitized image information include, for example, sublimation type thermal transfer prints, fusion type thermal transfer prints, ink jet prints, electrostatic transfer type prints, Photochromic materials and silver halide color photographic light-sensitive materials can be mentioned.
  • silver halide color photographic light-sensitive materials (hereinafter, also referred to as color prints or light-sensitive materials) are high. It has excellent properties compared to other print materials, such as sensitivity, excellent gradation, excellent image preservation, and low cost. Especially today for creating high quality hard copy It has been.
  • Image information that has been converted into digital data using a scanner or the like can be edited and processed on a computer, or data such as character diasts can be added relatively easily.For example, people, landscapes, still life, etc.
  • image output based on digital data it is necessary to simultaneously satisfy the two requirements of reproducing scene images more naturally and character images without blurring.
  • gradation degradation due to reciprocity failure characteristics in short-time exposure of a silver halide color photographic light-sensitive material is likely to occur.
  • a high illuminance such as a laser can be obtained by adjusting the amount of a doped metal, for example, iridium, in a silver halide emulsion. It is known that high gradation can be obtained by short-time exposure.
  • the output is due to differences in the exposure model and changes in the light source suitability of the laser exposure unit when printing large amounts. Fluctuates in the printed print (concentration variation) The problem that g) occurs has been identified, and urgent improvement is required.
  • An image forming method in which a silver halide color photographic light-sensitive material is subjected to scanning exposure with a light beam such that the exposure time per pixel is 10 to 3 seconds or less and then color development processing is performed. adjusts the maximum exposure amount at the time more image formed on the output of the patch (E max), and said silver halide color - photographic light-sensitive material, a pair of exposure amount giving a reflection density 0. 3 (E ..
  • the difference ⁇ L 0 g E between the numerical value and the logarithmic value of E max is as follows in the blue-sensitive yellow-color image forming layer, the green-sensitive magenta image forming layer, and the red-sensitive cyan image forming layer, respectively. 0.35 or more, 0.6 or less and the number of color image forming layers is small. Both one layer, the image forming how, characterized in that it contains a silver halide that has been subjected to by Ri chemical sensitization selenium compound.
  • the horizontal axis is obtained by performing exposure and color development processing in (2) 10 6 seconds or less exposure time: exposure (L o g E), vertical axis: on the characteristic curve consisting of color density, density 0.
  • exposure (L o g E) exposure (L o g E)
  • vertical axis on the characteristic curve consisting of color density, density 0.
  • the exposure time is obtained by performing exposure and color development processing at 90 seconds and 10 one 6 seconds, the yellow color image (B), magenta color image (G ) And the density ratio (D maxB / D maxG , D raaxR D raaxG ) of each maximum density D ma on the characteristic curves of the cyan image (R) are in the range of 0.7 to 1.3 , respectively.
  • the present inventors have conducted intensive studies in view of the above problems, and as a result, have found that a blue-sensitive yellow image forming layer containing a photosensitive silver halide, a green photosensitive magenta image forming layer, After subjecting a silver halide color photographic material having at least one photosensitive cyan image forming layer to scanning exposure with a light beam such that the exposure time per pixel is 10 to 3 seconds or less,
  • the maximum exposure amount (E max ) during image formation is adjusted by the output of a calibration patch, and the silver halide color photographic material has a reflection density of 0.3. and the logarithm of the exposure amount (E ..
  • the output of the calibration patch is adjusted according to, and the logarithm of the exposure (Eo. 3 ) which gives the silver halide color photographic light-sensitive material a reflection density of 0.3,
  • the difference ⁇ LogE from the logarithmic value of max is 0.35 or more for the blue-sensitive yellow one-color image forming layer, the green-sensitive magenta color image-forming layer, and the red-sensitive cyan color image-forming layer.
  • One feature is that it is less than 6.
  • the logarithmic value in the present invention is a common logarithmic value with a base of 10.
  • image information is digitized and handled, it is common to divide the original image into small squares and digitize and handle the density information for each square.
  • the minimum unit in the case where the original image is divided into squares and handled is one pixel. Therefore, the exposure time per pixel can be considered as the time during which the intensity or the irradiation time of the light beam is controlled based on the digital data for one pixel.
  • Scanning exposure with a light beam is usually performed by linear exposure with a light beam (raster exposure: main scanning) and relative movement (sub-scanning) of the photosensitive material in a direction perpendicular to the linear exposure direction.
  • a photosensitive material is fixed to the outer or inner circumference of a cylindrical drum, and the drum is rotated while irradiating a light beam to perform main scanning, and at the same time, the light source is moved perpendicular to the rotation direction of the drum.
  • a sub-scanning method drum method
  • the drum method is performed by irradiating a rotated polygon mirror with a light beam, and the reflected beam is scanned (horizontal scanning) horizontally with the rotation direction of the polygon mirror.
  • a method of performing sub-scanning by transporting the polygon perpendicular to the rotation direction of the polygon (polygon method) is often used.
  • a portion corresponding to main scanning is substituted by an array light source. Can be considered.
  • Era ax refers to data representing the maximum density on image data when exposing based on digitized image data (for example, processed on Adobe's P hot 0 Sh 0 p
  • digitized image data for example, processed on Adobe's P hot 0 Sh 0 p
  • the exposure amount when exposure is performed based on (R, G, B) (0, 0, 0) is the image data representing the maximum density).
  • E o. 3 stearyl one task A reflection density (R, G, B) and outputs the gray patches of the secondary (0.3 0, 0.3 0, 0.3 0) It is defined as the amount of exposure necessary for each color image forming layer.
  • the horizontal axis is obtained by performing exposure ⁇ beauty color development following the exposure time 10- 6 seconds: exposure (L 0 g E), vertical axis: or color density It is preferable that the variation of the average gradient of a straight line passing through the point giving the density of 0.5 and the point giving the density of 1.5 on the characteristic curve be within 10% in multiple exposure.
  • the characteristic curve referred to in the present invention is that, after performing high illuminance exposure for 10 to 16 seconds or less, and performing an image obtained by performing a standard color development process, the horizontal axis represents Log E (E is the exposure amount), The vertical axis is the curve plotted with D (color density).
  • the multiple exposure the time of the high intensity exposure below 10- 6 seconds, exposed to the same pixel more than once which means that pressurized Erareru.
  • the variation of the average gradient at that time means that after performing one and two exposures, the characteristic curve obtained by color development passes through the points where density 0.5 and density 1.5 are given. It means the difference gradient (ta n) when a straight line is drawn.
  • the fluctuation of the density gradient due to multiple exposure is a state where there is no fluctuation of the average gradient.
  • a silver halide color one photographic light-sensitive material the exposure time is obtained by performing exposure and color development processing at 90 seconds and 10 6 seconds, the yellow color image (B) , Magenta color image (G) and cyan color image (R) on each characteristic curve, the density ratio of each maximum density Dmax ( DmaxB / DmaxG , D / D power, each in the range of 0.7 to 1.3) Is preferred.
  • the maximum exposure amount (E max ) during image formation is adjusted by the output of the calibration patch, and each of the yellow, magenta, and cyan image forming layers is exposed at the exposure amount E max.
  • Cyan image reflection density of black image area The ratio of (D maxR ) to the magenta color image reflection density (D maxG ) (Dma ZD xG) and the ratio of the yellow one-color image reflection density (D maxB ) to (D raaxG ) (D maxB / D raaxG ) are: Each is preferably from 0.7 to 1.3, more preferably from 0.8 to 1.2, and still more preferably from 0.9 to 1.2.
  • the reflection density here indicates the status A reflection density.
  • the types of light sources that can be used in the image forming method of the present invention include a light emitting diode (LED), a gas laser, a semiconductor laser (LD), a solid laser using an LD or an LD as an excitation light source, and a second laser.
  • LED light emitting diode
  • LD semiconductor laser
  • a solid laser using an LD or an LD as an excitation light source and a second laser.
  • Well-known such as a combination with a harmonic change element (so-called SHG element), a combination of a tungsten light and a bandpass filter, a combination of a halogen lamp, a PLZT element and a color filter, a combination of a VF PH element and a color filter, etc. Any light source can be used.
  • blue light sources with a wavelength of 400 to 450 nm are currently being vigorously researched and developed, mainly for high-density recording on optical discs such as digital video discs (DVDs).
  • a semiconductor laser with an oscillation wavelength of 800 to 900 nm - e.g., G a A s system
  • the second harmonic generation (S HG) element e.g., L i N b 0 3 system, L Inorganic crystals such as iTa03 series, organic crystals such as 2-methyl-14-nitroaniline
  • oscillation wavelengths of 380 to 380 nm using InGaN-based materials for example, a semiconductor laser with an oscillation wavelength of 800 to 900 nm - (e.g., G a A s system) and the second harmonic generation (S HG) element (e.g., L i N b 0 3 system, L Inorganic crystals such as iTa03 series, organic crystals such as 2-methyl-14-nitroaniline), and
  • a blue semiconductor laser with a wavelength of 430 nm and a dye laser using a scintillator dye or a coumarin dye are known.
  • the overlap with the spectral sensitivity distribution of the green photosensitive layer is slightly smaller for solid-state lasers in combination with SHG and for semiconductor lasers whose oscillation wavelength is 380 to 430 nm compared to 431 to 480 nm.
  • the green photosensitive layer This is a particularly preferable exposure light source in the present invention, because unnecessary color development can be reduced, and bleeding of a yellow image, which is considered to be caused by a decrease in light scattering in the support, can be reduced.
  • the characteristics of the photosensitive silver halide contained in the photosensitive material are appropriately controlled, Reproduction density on data that represents maximum density on digitized image data, by appropriately controlling the amount of neutral silver halide, coupler, or anti-irradiation dye, or by setting calibration
  • the methods for appropriately controlling the target values can be used alone or in combination.
  • the composition of the silver halide emulsion used in the light-sensitive material according to the present invention may be any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and silver chloroiodide.
  • halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and silver chloroiodide.
  • silver chlorobromide containing 95 mol% or more of silver chloride and containing substantially no silver iodide the effect of the present invention is remarkable, which is preferable.
  • a silver halide emulsion containing preferably 97 mol% or more, more preferably 98 to 99.9 mol% of silver chloride is preferable.
  • silver halide having a high-concentration portion of silver bromide is used.
  • Emulsions can also be preferably used.
  • the portion containing a high concentration of silver bromide may be formed by epitaxy bonding to silver halide grains, a so-called core-shell emulsion, or simply a partial formation without forming a complete layer.
  • the composition may be changed continuously or discontinuously.
  • the part where silver bromide is present in high concentration It is particularly preferred that the surface be the surface of silver gemide grains or the apex of crystal grains.
  • silver halide grains containing heavy metal ions from the viewpoint of reducing softening caused by high-illuminance short-time scanning exposure.
  • Heavy metal ions that can be used for such purposes include irons, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, cobalt and other Group 8-10 metals, cadmium, zinc, mercury, etc.
  • metal ions of iron, iridium, platinum, ruthenium, gallium, and osmium are preferred. These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt.
  • its ligand or ion may be a cyanide ion, a thiocyanate ion, a cyanate ion, an isothiocyanate ion, a chloride ion, a bromide ion, an iodide ion, or nitric acid. Ions, carbonyl, ammonia and the like. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.
  • the heavy metal compound is physically added before forming silver halide grains, during silver halide grains, after forming silver halide grains, or the like. What is necessary is just to add in arbitrary places in each process during ripening.
  • the solution of the heavy metal compound can be continuously added over the whole or a part of the particle forming step.
  • the amount is more preferably 1 ⁇ 10 to 9 mol or more and 1 ⁇ 10 to 2 mol or less, more preferably 1 ⁇ 10 to 2 mol per mol of silver halide.
  • X 10- 8 mol 5 X 10_ 5 moles or less is preferable.
  • any shape can be used for the silver halide grains.
  • One preferable example is a cube having a (100) plane as a crystal surface.
  • Particles having shapes such as octahedron, tetrahedron, and dodecahedron can be prepared and used by methods described in documents such as 21, 39 (1973). Further, particles having twin planes may be used.
  • silver halide grains having a single shape are preferably used, but it is particularly preferable to add two or more monodispersed silver halide emulsions to the same layer. .
  • the grain size of the silver halide grains according to the invention is not particularly limited, but is preferably 0.1 to 1.2 ⁇ m, more preferably 0.1 to 1.2 ⁇ m, in consideration of other photographic properties such as rapid processing and sensitivity. , 0.2-1.0 m.
  • This particle size can be measured using the projected area of the particle or its approximate diameter. If the particles are substantially uniform, the size distribution can represent this fairly accurately as a diameter or projected area o
  • the particle size distribution of the silver halide grains used in the light-sensitive material according to the present invention is preferably a monodispersed silver halide grain having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and particularly preferably. Is to add two or more monodisperse emulsions having a coefficient of variation of 0.15 or less to the same layer.
  • the particle size referred to here is the diameter of a spherical silver halide particle, or the diameter of a cubic or non-spherical particle when the projected image is converted into a circular image of the same area. Represent.
  • the silver halide emulsion used in the light-sensitive material according to the present invention may be obtained by any of an acid method, a neutral method, and an ammonium method.
  • the particles may be grown at one time or may be grown after seed particles have been made.
  • the method for producing the seed particles and the method for growing them may be the same or different.
  • the form of reacting the soluble silver salt with the soluble halide salt may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like, but a method obtained by a simultaneous mixing method is preferable. Further, as one form of the simultaneous mixing method, a pAg control single-jet method described in JP-A-54-48521 can be used.
  • a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble haeganide salt from an addition device disposed in a reaction mother liquor described in JP-A Nos. 57-92523 and 57-92524, published in Germany Apparatus for continuously changing the concentration of water-soluble silver salt and water-soluble halide salt aqueous solution described in Patent No. 2,921,164, etc., and reaction outside the reactor described in JP-B-56-501776, etc.
  • An apparatus may be used in which the mother liquor is taken out and concentrated by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant.
  • a silver halide solvent such as polyester may be used.
  • a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.
  • At least one of the color image forming layers contains silver halide chemically sensitized with a selenium compound (hereinafter, also referred to as a selenium sensitizer). Containing is one feature.
  • a selenium compound hereinafter, also referred to as a selenium sensitizer
  • an unstable selenium compound that can react with silver nitrate in an aqueous solution to form a silver selenide precipitate is preferably used.
  • Useful selenium sensitizers include colloid selenium metal, isoselenosocyanates (eg, aryliselenosinate), selenoureas (eg, N, N-dimethylselenourea, N, N, N ′).
  • a preferable addition amount of the selenium sensitizer according to the present invention 1 X 1 0- 9 ⁇ 1 X 1 0- 1 molar Z moles A g X, more preferably 1 X 1 0- 8 ⁇ 1 X 1 0 mol / Mol A g X
  • a method generally used in the art for adding an additive to a photographic emulsion can be applied.
  • the compound is a water-soluble compound
  • an aqueous solution having an appropriate concentration is used.
  • any organic solvent that can be mixed with water for example, alcohols, glycols, and ketones.
  • Can be added as a solution by dissolving in a solvent that does not adversely affect the photographic properties such as alcohols, esters and amides.
  • a known chemical sensitization method for example, a sensitization method using a gold compound, or a sensitization method using a chalcogen sensitizer is used together with the selenium sensitizer. Sensitization can be used.
  • a chalcogen sensitizer applied to the silver halide emulsion an io sensitizer, a tellurium sensitizer and the like can be used, and an io sensitizer is preferable.
  • zeosensitizer examples include thiosulfate, trithiothiolbamidothiourea, T-lylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, and inorganic zeolite.
  • the addition amount of the sensitizer is preferably changed depending on the type of the silver halide emulsion to be applied and the size of the expected effect, but is preferably from 5 ⁇ 10 to 10 ⁇ 5 to 1 ⁇ 10 per mol of silver halide. ID- 5 mols, preferably 5 X 1 0 one 8 ⁇ 3 X 1 0- 5 mole range is preferred.
  • gold sensitizer various gold complexes such as chloroauric acid and gold sulfide can be added.
  • the ligand compound to be used include dimethyl rhodanine, thiocyanate, mercaptotetrazol, and mercaptotriazole.
  • the amount of the gold compound, the kind of silver halide emulsion, the type of compound used, but are not and ripening conditions, is usually 1 mol of silver halide per 1 X 1 0 one 4 mol ⁇ 1 X 1 It is preferably 0-1 s mole. More preferably, it is from 1 ⁇ 10 to 5 mol to 1 ⁇ 10 to 8 mol.
  • a silver halide emulsion can be optically spectrally sensitized to a desired wavelength region by adding a dye (spectral sensitizing dye) that absorbs light in a wavelength region corresponding to a target spectral sensitivity.
  • a dye spectral sensitizing dye
  • the spectral sensitizing dye used at this time is, for example, FM Hamer Hetercycling—IC co mp ounds—C vaninedesandrelatedco mp ounds (John Wileyand Sons; New York, 1964).
  • Examples of the spectral sensitizing dye used in the present invention include a cyanine dye, a merocyanine dye, and a complex merocyanine dye.
  • cyanine dyes there are complex cyanine dyes, horopora-cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes.
  • cyanine dye simple cyanine dye, carbocyanine dye, and dicarbocyanine dye are preferably used.
  • the support that can be used in the present invention is preferably a paper support in which a resin coating layer is applied to both surfaces of a substrate.
  • a paper support obtained by laminating both sides of the base paper with a polyolefin is preferable, and a paper support laminated with polyethylene is particularly preferable. is there.
  • the base paper used for the paper support is made of wood pulp as the main raw material, and if necessary, is made using synthetic pulp such as polypropylene or synthetic fibers such as Nyopen® polyester in addition to wood pulp. .
  • synthetic pulp such as polypropylene or synthetic fibers such as Nyopen® polyester in addition to wood pulp.
  • any of LBKP, LB SP, NBKP, NB SP, LDP, NDP, LUKP, NUKP can be used, but L BKP, NB SP, LB SP, NDP, L It is preferred to use more DP.
  • the ratio of LBSP and / or LDP is preferably from 10% by mass to 70% by mass.
  • the pulp a chemical pulp (sulfate / pulp or sulfite pulp) containing a small amount of impurities is preferably used, and a pulp having improved whiteness by a bleaching treatment is also useful.
  • the base paper contains sizing agents such as higher fatty acids and alkyl ketene dimers, white pigments such as calcium carbonate, talc, and titanium oxide; paper strength agents such as starch, polyacrylamide, and polyvinyl alcohol; and polyethylene glycol.
  • a water-retaining agent such as water, a dispersant, a softening agent such as quaternary ammonium, and the like can be appropriately added.
  • the oil-soluble fluorescent whitening agent according to the present invention can also be used.
  • the freeness of the pulp used in papermaking is preferably 200 to 50 Om1 according to the CSF regulations, and the fiber length after beating is specified in JIS-P-8207. It is preferable that the sum of the mass and the mass% of the remaining 42 mesh is 30 to 70%. Preferably, the mass% of the four-mesh flower is 20% by mass or less.
  • the basis weight of the base paper is preferably 30 to 250 g / m 2 , particularly preferably 50 to 200 g / m 2 .
  • the thickness of the base paper is preferably from 40 to 250 m.
  • the base paper can be calendered at the papermaking stage or after papermaking to provide high smoothness.
  • the density of the base paper is generally 0.7 to 1.2 gZcm 3 (JIS-P-811).
  • the rigidity of the base paper is preferably 20 to 200 g under the conditions specified in JIS-P-8143.
  • a surface sizing agent may be applied to the surface of the base paper.
  • the surface sizing agent the same sizing agent as that which can be added to the base paper can be used.
  • the pH of the base paper is preferably 5 to 9 when measured by the hot water extraction method specified in JIS-P-8113.
  • the polyethylene that covers the front and back surfaces of the base paper is mainly low-density polyethylene (LDPE) and / or high-density polyethylene (HDPE), but some are also LLDPE (linear low-density-polyethylene) ⁇ polypropylene, etc. Can be used.
  • the polyethylene layer on the side of the photosensitive layer has improved opacity and whiteness by adding rutile or anatase type titanium oxide to polyethylene, as is widely practiced in photographic printing paper. preferable.
  • the content of titanium oxide is usually 3 to 20% by mass relative to polyethylene, preferably 4 to 13% by mass.
  • Polyethylene-coated paper can be used as glossy paper, or when polyethylene is melted and extruded onto the surface of a base paper to perform coating, a so-called molding process is performed to obtain a pine paper that can be obtained with ordinary photographic printing paper.
  • a material having a textured surface-silk surface can also be used in the present invention.
  • the amount of each polyethylene used on the front and back of the base paper is usually in the range of 20 to 40 m for the polyethylene layer on the side where the photosensitive layer is provided and 10 to 30 m for the back layer side.
  • polyethylene-coated paper support preferably has the following properties.
  • Tensile strength "The strength specified by IS-P-8113, preferably 20 to 300 N in the vertical direction and 10 to 200 N in the horizontal direction.
  • Tear strength According to the method specified in JIS-P-8116, it is preferable that the vertical direction is 0.1 to 20N and the horizontal direction is 2 to 2 ON.
  • Opacity 80% or more, particularly preferably 85 to 98%, as measured by the method specified in JIS_P-8138
  • Clark stiffness a support having a Clark stiffness of 50 to 300 cm10 in the recording medium transport direction is preferable.
  • Moisture content of middle paper usually 2 to 100% by mass, preferably 2 to 6% by mass based on the middle paper
  • constituent elements other than those described above for example, other silver halide photographic emulsions, emulsion additives, sensitization methods, anti-fog agents, stabilizers, Anti-syllable dyes, yellow couplers, magenta couplers, cyan couplers, spectral dyes, emulsification dispersion method, surfactants, anti-turbidity agents, binders, hardeners, slip agents and matting agents, supports , Bluing agents and reddish agents, coating methods, color developing agents, processing methods, development processing equipment, processing agents, etc. are described in JP-A-1113-147615, p. No.
  • the above-described configuration according to the present invention can improve sensitivity fluctuation, density fluctuation, and gradation fluctuation in multiple exposure even when a large amount of printing is performed by a high-speed printer.
  • a high-speed printer capable of outputting 1000 or more L-hour equivalent prints or more can exert the effects of the present invention, and more preferably a high-speed printer capable of printing 1500 L-hour prints or more.
  • Particularly preferred is a high-speed printer of 2000 sheets / L plate or more.
  • Each silver halide emulsion was prepared by the following method.
  • Emulsion EMP-1 was obtained as a monodisperse cubic emulsion having an average particle size of 0.40 m, a coefficient of variation of the particle size distribution of 0.07, and a silver chloride content of 99.5 mol% by mixing with an aqueous gelatin solution.
  • the average particle size was 0.38 in the same manner as in Emulsion EMP-1 except that the addition time of (A) and (B) and the addition time of (C) and (D) were changed.
  • the emulsion EMP-1B was obtained as a monodisperse cubic emulsion having a m of 0.07, a coefficient of variation of the particle size distribution of 0.07, and a silver chloride content of 99.5 mol%.
  • the above emulsion EMP-1 was optimally chemically sensitized at 60 ° C using the following compounds. Similarly, after optimally chemical sensitizing the emulsion EMP-1B, the sensitized emulsion EMP-1 and the emulsion EMP_1B were mixed at a silver ratio of 1: 1. A red-sensitive silver halide emulsion (101R) was obtained.
  • the average particle size was 0.40 m in the same manner except that the addition time of (solution A) and (solution B) and the addition time of (solution C) and (solution D) were changed.
  • the emulsion EMP-2 was obtained as a monodisperse cubic emulsion having a coefficient of variation of 0.08 and a silver chloride content of 99.5%.
  • the average particle size was adjusted in the same manner except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed.
  • Emulsion EMP-2B was obtained as a monodisperse cubic emulsion having a particle size of 50 m, a coefficient of variation of 0.08 and a silver chloride content of 99.5%.
  • the emulsion EMP-2 prepared above was optimally chemically sensitized at 55 ° C using the following compounds. Similarly, after optimally chemical sensitizing the emulsion EMP-2B, the sensitized emulsion EMP-2 and emulsion EMP-2B were mixed at a silver ratio of 1: 1. To obtain a green photosensitive silver halide emulsion (101G).
  • the average particle size was 0.71 in the same manner except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed.
  • the emulsion EMP-3 was obtained as a monodisperse cubic emulsion having a size of ⁇ m, a coefficient of variation of 0.08 and a silver chloride content of 99.5%.
  • the average particle size was adjusted in the same manner except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed.
  • Emulsion EMP-3B was obtained as a monodisperse cubic emulsion having a length of 64 m, a coefficient of variation of 0.08 and a silver chloride content of 99.5%.
  • Sample 101 As a silver halide color photographic light-sensitive material.
  • the coating solution was prepared as described below.
  • DBP high-boiling organic solvent
  • DNP high-boiling organic solvent
  • SU-1 surfactant
  • the coating liquids for the second layer to the second layer were prepared using the following additives in the same manner as in the preparation method of the first layer coating liquid.
  • UV absorber UV-1) 0.12 UV absorber (UV-2) 0.04 UV absorber (UV-3) 0.16 Sting inhibitor (HQ-5) 0.04 PVP ( Polyvinylpyrrolidone) 0.03.
  • Anti-irradiation dye AI-1) 0.011 (5th layer: red-sensitive layer)
  • Gelatin 1 30 Red light-sensitive silver halide emulsion (10 1 R) 0 21 Cyan coupler (C-1) 0 25 Cyan coupler (C-2) 0 08 Dye image stabilizer (ST-1) 0 10 Sting inhibitor (HQ -1) 0 004 D 0 P 0 34 4th layer: UV absorbing layer>
  • UV absorber UV-1) 0.28 UV absorber (UV-2) 0.09 UV absorber (UV-3) 0.38 Sting inhibitor (HQ-3) 0.10 Anti-irradiation dye (AI-1) 0.02
  • Second layer Green photosensitive layer>
  • H-1 Tetrakis (vinylsulfonylmethyl) methane
  • HQ—1 2,5—G-t-octyl high droquinone
  • HQ—2 2,5-di-sec—dodecylhydroquinone
  • Image stabilizer A P-t one-year-old octylphenol
  • sample 101 In the preparation of Sample 101, the silver halide amount and the coupler addition amount of the first layer (blue-sensitive layer), the third layer (green-sensitive layer), and the fifth layer (red-sensitive layer) were appropriately increased.
  • a sample 102 was prepared in the same manner except that AL og E was 0.39 for the first layer, 0.40 for the third layer, and 0.37 for the fifth layer.
  • Sample 103 In the preparation of Sample 103, the amounts of silver halide and couplers in the first layer (blue-sensitive layer), the third layer (green-sensitive layer), and the fifth layer (red-sensitive layer) were appropriately changed. Samples 104 to 109 having ⁇ L 0 gE shown in the following table were prepared in the same manner except for the above.
  • each photosensitive silver halide emulsion in the preparation of each photosensitive silver halide emulsion, a chemical sensitizer (sodium thiosulfate, trifrinylphosphine serenide, chloroauric acid) and a stabilizer (ST By changing the amount of AB_1 to STAB-3) and the chemical sensitization conditions (temperature and time) as appropriate, each photosensitive silver halide emulsion with different suitability for multiple exposure was prepared and used.
  • a sample 110 was prepared in the same manner except for the above.
  • Sample 11 was prepared in the same manner except that the amounts of couplers of the first layer, the third layer, and the fifth layer were appropriately changed and the Dma X balance was changed. . * 1 ⁇ L 0 g E Remarks
  • the present invention * 1 The chalcogen sensitizer of each of the first, third and fifth layers of the photosensitive silver halide emulsions Constituent ratio (molar ratio): sodium thiosulfate / triphenylphosphine resin
  • each sample is subjected to scanning exposure based on the image data created on PhotoShop 5.0, and the Processing was performed.
  • dpi refers to the number of dots per 2.54 cm.
  • a helium-power laser beam (about 422 nm) was used as the blue light source, a purple neon laser (about 544 nm) as the green light source, and a red light source (about 544 nm).
  • An optical system using a gallium aluminum arsenic semiconductor laser (approximately 780 nm) as the light source.
  • a beam diameter of approximately 80 m, a polygon mirror is used, and a scanning speed of 16 Om / s, 1 pixel
  • the following three types of exposure were performed under the conditions of an exposure time of 5 ⁇ 10 17 seconds.
  • Time replenishment rate color developing 38 0 ⁇ 0. 3 ° C 45 seconds 80 m 1 / m 2 blix 3 5. 0 ⁇ 0. 5 ° C 45 sec 1 20 m 1 / m 2 depreciation in the constant I inhibit 3 0-34 6 0 seconds 1 50 m 1 / m 2 drying 6 0 to 80 ° C 3 0 seconds
  • composition of each developing solution used in the developing step is shown below.
  • Diethylene triammonium pentaacetate diammonium dihydrate 65 g Getilent rimamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4-thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml water was added to make up the whole volume to 1 liter, and the pH was adjusted to 5.0 with potassium carbonate or glacial acetic acid.
  • Stabilizing solution tank solution and replenisher>
  • 1-Hydroxyshethylidene_1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate / 7 hydrate 0.2 g PVP l. O g Ammonia water (ammonium hydroxide 2.5 g Trisodium triacetate trisodium salt 1.5 g Water was added to make up to 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or aqueous ammonia. I adjusted it.
  • the obtained gradation image was measured with a reflection densitometer (X-Rite 938 manufactured by X-Rite), and the horizontal axis was the exposure amount (L 0 g E), vertical axis: After creating a characteristic curve consisting of the color density (D), the gradient ry of the density change with respect to the exposure amount between each density 0.5 and 1.5 of yellow, magenta, and cyan images. For rm, rc, tilt at l exposures? The absolute value of the rate of change of the slope r2 in the two exposures to ⁇ was determined as the gradation variation rates ⁇ ry, Arm, and Arc according to the following equation, and this was used as a measure of the suitability for multiple exposure.
  • the sharpness chart image of each sample prepared above was visually observed by 10 people. If there were ⁇ , 7 or 8 ⁇ , 5 or 6 ⁇ , and 4 or less X.
  • the present invention * 1 The image density area after printing for 1 hour continuously with a high-speed digital printer.
  • samples 106 to 111 using the selenium compound and having a structure defined by the present invention in which ⁇ .Log E is in the range of 0.35 to 0.6 in all three layers are: Compared to the comparative example, even after continuous printing with a high-speed digital printer, a stable image was obtained with less variation in the image density portion. In addition, an image having excellent image clarity was obtained. Also, it can be seen that the effects of the present invention are greater in the samples 109 to 111 in which the gradation variation in the multiple exposure is less than 10%. In addition, it can be seen that the sample 110 in which each Dmax concentration ratio is in the range of 0.7 to 1.3 has a greater effect of the present invention.
  • the sample having the configuration specified by the present invention has less variation in the image density portion and excellent sharpness even after continuous printing with a high-speed digital printer compared to the comparative example. It was confirmed that a stable image could be obtained.
  • an image forming apparatus that can provide a stable image with less variation in the image density portion and excellent sharpness can be obtained.
  • a method can be provided.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Abstract

Cette invention concerne un procédé de formation d'images permettant de former une image stable qui présente une excellente netteté et aucune variation de densité dans la partie image, même après une impression continue effectuée à l'aide d'une imprimante numérique à grande vitesse. Selon ce procédé, un matériau photosensible aux couleurs à base d'halogénure d'argent comprenant des couches photosensibles au bleu, au vert et au rouge contenant de l'halogénure d'argent et formées sur un support, est balayé par un faisceau de lumière pendant une durée de rayonnement inférieure ou égale à 1x10-3 secondes par pixel puis soumis à un développement couleur. Ce procédé se caractérise en ce que l'exposition maximale (Emax) pour la formation d'images est définie par le produit d'une tâche d'étalonnage, la différence ΔlogE entre le logarithme de l'exposition (E0.3) à laquelle la densité de réflexion du matériau photosensible aux couleurs à base d'halogénure d'argent est de 0,3 et le logarithme de Emax est comprise entre 0,35 et 0,6 pour les couches photosensibles au bleu, au vert et au rouge. Au moins une des couches de formation d'images en couleurs contient de l'halogénure d'argent sensibilisé chimiquement par un composé sélénium.
PCT/JP2003/000988 2003-01-31 2003-01-31 Procede de formation d'images WO2004068239A1 (fr)

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Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0816918A1 (fr) * 1996-06-28 1998-01-07 Fuji Photo Film Co., Ltd. Produit photographique couleur à l'halogénure d'argent
EP0967518A2 (fr) * 1998-06-26 1999-12-29 Konica Corporation Produits photographiques à l'halogénure d'argent sensible à la lumière et procédé pour la formation d'une image avec ces produits
JP2000214559A (ja) * 1999-01-27 2000-08-04 Konica Corp ハロゲン化銀写真感光材料
JP2000227638A (ja) * 1999-02-05 2000-08-15 Konica Corp 画像形成方法
EP1048976A2 (fr) * 1999-04-26 2000-11-02 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensible à la lumière et méthode de formation d'images utilisant ce matériau
US6221569B1 (en) * 1997-08-05 2001-04-24 Fuji Photo Film Co., Ltd. Method of forming color images and picture-taking color photographic material used therein
EP1098221A2 (fr) * 1999-11-04 2001-05-09 Konica Corporation Méthode de formation d'images
JP2001133922A (ja) * 1999-11-04 2001-05-18 Konica Corp ハロゲン化銀カラー写真感光材料及び画像形成方法
JP2001356433A (ja) * 2000-06-14 2001-12-26 Konica Corp 画像形成方法
US20020001783A1 (en) * 1999-12-28 2002-01-03 Akito Yokozawa Silver halide color photographic light-sensitive material
US6348302B1 (en) * 1999-07-13 2002-02-19 Fuji Photo Film Co., Ltd. Image forming method
JP2002296737A (ja) * 2001-03-30 2002-10-09 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料、処理方法およびカラープルーフの画像形成方法
JP2002351022A (ja) * 2001-05-23 2002-12-04 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0816918A1 (fr) * 1996-06-28 1998-01-07 Fuji Photo Film Co., Ltd. Produit photographique couleur à l'halogénure d'argent
US6221569B1 (en) * 1997-08-05 2001-04-24 Fuji Photo Film Co., Ltd. Method of forming color images and picture-taking color photographic material used therein
EP0967518A2 (fr) * 1998-06-26 1999-12-29 Konica Corporation Produits photographiques à l'halogénure d'argent sensible à la lumière et procédé pour la formation d'une image avec ces produits
JP2000214559A (ja) * 1999-01-27 2000-08-04 Konica Corp ハロゲン化銀写真感光材料
JP2000227638A (ja) * 1999-02-05 2000-08-15 Konica Corp 画像形成方法
EP1048976A2 (fr) * 1999-04-26 2000-11-02 Konica Corporation Matériau photographique couleur à l'halogénure d'argent sensible à la lumière et méthode de formation d'images utilisant ce matériau
US6348302B1 (en) * 1999-07-13 2002-02-19 Fuji Photo Film Co., Ltd. Image forming method
EP1098221A2 (fr) * 1999-11-04 2001-05-09 Konica Corporation Méthode de formation d'images
JP2001133922A (ja) * 1999-11-04 2001-05-18 Konica Corp ハロゲン化銀カラー写真感光材料及び画像形成方法
US20020001783A1 (en) * 1999-12-28 2002-01-03 Akito Yokozawa Silver halide color photographic light-sensitive material
JP2001356433A (ja) * 2000-06-14 2001-12-26 Konica Corp 画像形成方法
JP2002296737A (ja) * 2001-03-30 2002-10-09 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料、処理方法およびカラープルーフの画像形成方法
JP2002351022A (ja) * 2001-05-23 2002-12-04 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料

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