JP2006227255A - Color image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide color photosensitive material excellent in depiction of a high density portion, ensuring little blur of the thin lines of a character, etc., and capable of obtaining a print with a high contrast ratio in a short period of time, and to provide an image forming method. <P>SOLUTION: In the method for forming a color image by digital-exposing and subsequently, developing the silver halide photographic sensitive material having a yellow developing layer, a magenta developing layer and a cyan developing layer, AgX contained in the yellow developing layer has an average grain diameter of 0.40-0.60 μm, gamma between the logarithm of exposure giving a density of 1.0 of the color image and that of exposure giving a density of 2.0 is 4.0-6.0, and a relationship of 0.0≤Y/X≤0.6 (1.0≤X≤2.0) is established between the density X of a maximumly exposed area at the time of exposure at 400 dpi and development and the minimum density Y of unexposed thin lines of one-pixel width drawn in the maximumly exposed area. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention belongs to the field of digital photo printing in which an image is formed by digital exposure and development from digital image data, and in particular, the reproducibility of character image data has been improved by achieving both high-density area descriptiveness and a clear white background. The present invention relates to a color photographic light-sensitive material capable of providing high-quality photographic prints and an image forming method using the same.

  The flow of obtaining photo prints from image data edited and processed by a personal computer (PC) by improving the image quality of digital still cameras (DSC) such as single-lens digital cameras (D-SLR) and flood bed scanners is common. As a result, the user can select a printing method according to various uses such as the purpose of use, the required level of image quality, and the delivery date. There are various types of digital photo prints, such as inkjet, dye thermal transfer (sublimation), and toner transfer methods. Among them, the gradation is rich and high-definition, and prints can be created in a relatively short time. In many cases, the silver halide photography method is selected as the method.

  In the silver salt photography system, photographic prints can be obtained continuously in a short time by the development processing following the high illumination exposure. The exposure method used in the high-illuminance exposure process is generally laser scanning exposure or a line-type light source array head. The exposure control values (exposure amounts) of RGB are obtained based on the gradation values of the image data. Then, exposure is performed by conveying a color photosensitive material (photographic paper) through the exposure unit. In order to obtain a desired print density, this exposure control value is controlled so that, for example, exposure with higher illuminance is performed if a high density is required.

  However, in general, an exposure method used for high-illuminance exposure causes an image blur due to the influence of light scattering when passing through a beam imaging surface or a lens system when the exposure amount is increased to obtain a high density. It is easy to visually recognize this exposure blur as a significant difference in images with high contrast ratios such as letters. Especially in photographic prints for commercial use via DTP (desktop publishing), high descriptiveness up to high density There is a need for a technology that achieves conflicting characteristics such as the reproducibility of thin lines such as text and characters.

As a technique for achieving this, for example, Patent Document 1 controls the average value of point gamma and its fluctuation range in a constant density range, and Patent Document 2 defines the relationship between instantaneous contrast and exposure amount. Patent Document 3 discloses a photosensitive material having a high γ, such as a method of setting the maximum gamma within a certain exposure range and the fill-in Dmax density to a certain value or more. Further, Patent Document 4 discloses a method for defining an effective gradation area in each color image forming layer. Although these methods can achieve both high density and reduction of blurring, they achieve high descriptiveness in the high density area and excellent character reproduction, which are required for actual photographic printing, and print in a short time. There is a need for an image forming method capable of producing the image.
Japanese Patent Laid-Open No. 3-158847 JP-A-8-36247 JP-A-9-171237 JP 2003-202647 A

  An object of the present invention relates to a silver halide photographic printing system, which is excellent in descriptiveness at a high density portion, has little blur of fine lines such as letters, and can obtain a high contrast ratio print in a short time. It is to provide a photosensitive material and an image forming method.

  The above object of the present invention is achieved by the following means.

(Claim 1)
In a method of forming a color image by a development processing step following a digital exposure step using a silver halide photographic light-sensitive material having at least three color development layers of a yellow color development layer, a magenta color development layer, and a cyan color development layer,
(1) The average grain size of the silver halide emulsion contained in the yellow color developing layer of the silver halide photographic light-sensitive material is 0.40 μm or more and 0.60 μm or less,
(2) The sensitometric gamma between the logarithm of the exposure amount giving the density of 1.0 and the logarithm of the exposure amount giving the density of 2.0 is 4.0 or more and 6.0 or less. ,
(3) When X is the density of the maximum exposure area when exposure is performed at a resolution of 400 dpi and development processing is performed, and Y is the minimum density of an unexposed fine line of 1 pixel width drawn in the maximum exposure area,
A color image forming method, wherein a relationship of 0.0 ≦ Y / X ≦ 0.6 is established in a range satisfying at least 1.0 ≦ X ≦ 2.0.

(Claim 2)
2. The color image forming method according to claim 1, wherein the digital exposure step is performed using an exposure head including a PLZT array element and R, G, and B LED light sources.

(Claim 3)
The maximum exposure area of the color image is 0.0 ≦ L ^* ≦ 5.0 in the CIE 1976-L ^* a ^* b ^* color system, and the developed silver halide photographic light-sensitive material is subjected to development processing. The unexposed portion is 91.0 ≦ L ^* ≦ 96.0, 0.5 ≦ a ^* ≦ 1.5, −6.0 ≦ b ^* ≦ −3.0, or 3. A color image forming method according to 2.

(Claim 4)
The development processing step comprises at least a color development step, a bleach-fixing step, and a water washing (stabilization) step, and the water washing (stabilization) step comprises at least four steps, and the water washing (stabilization). The color image forming method according to any one of claims 1 to 3, wherein a fluorescent brightening agent is contained in at least the final tank of the process.

(Claim 5)
5. The color image forming method according to claim 4, wherein the color development step has a processing time in liquid of 10 seconds to 30 seconds.

  According to the present invention, it is possible to provide a high-quality color photographic print having excellent character quality and good depiction of a shadow portion.

  Next, the best mode for carrying out the present invention will be described, but the present invention is not limited thereto.

The color image forming method of the present invention uses a silver halide photographic material having at least three color developing layers of a yellow color developing layer, a magenta color developing layer, and a cyan color developing layer, and a color image by a development processing step following a digital exposure step. When forming
(1) The average grain size of the silver halide emulsion contained in the yellow color developing layer of the silver halide photographic light-sensitive material is 0.40 μm or more and 0.60 μm or less,
(2) The sensitometric gamma between the logarithm of the exposure amount giving the density of 1.0 and the logarithm of the exposure amount giving the density of 2.0 is 4.0 or more and 6.0 or less. ,
(3) When X is the density of the maximum exposure area when exposure is performed at a resolution of 400 dpi and development processing is performed, and Y is the minimum density of an unexposed fine line of 1 pixel width drawn in the maximum exposure area,
This is achieved by using a silver halide photographic light-sensitive material that satisfies the relationship of 0.0 ≦ Y / X ≦ 0.6 in a range satisfying at least 1.0 ≦ X ≦ 2.0.

  Each component of the silver halide color photographic light-sensitive material according to the present invention will be described.

  The silver halide grains in the silver halide emulsion according to the present invention preferably have a silver chloride content of 90 mol% or more, more preferably a silver chloride content of 93 mol% or more, and 95 mol%. More preferably, the above is true. The silver bromide content is preferably 0.1 to 10 mol%, more preferably 0.5 to 8 mol%, and still more preferably 2 to 8 mol%. The silver iodide content is preferably 0.05 to 2 mol%, more preferably 0.05 to 1 mol%.

  In the present invention, a silver halide emulsion having a portion containing silver bromide at a high concentration is also preferably used. In this case, the portion containing silver bromide at a high concentration is epitaxially bonded to the silver halide emulsion grains. Or a so-called core-shell emulsion, or a complete layer may not be formed and only regions having different compositions may exist. Further, although the composition may change continuously or discontinuously, it is preferable that the silver halide grains have a silver bromide localized phase in at least a part of the outermost shell, in the vicinity of the vertex. It is more preferable to have a silver bromide localized phase.

  In the present invention, the silver bromide localized phase is a silver halide phase containing silver bromide having a silver bromide content of at least twice the average silver bromide content of the silver halide grains according to the present invention, It preferably contains silver bromide having a silver bromide content of 3 times or more of the average silver bromide content of the silver halide grains, and preferably contains silver bromide having a silver bromide content of 5 times or more.

  The silver bromide localized phase preferably contains a group 8 metal compound described later. In this case, the Group 8 metal compound used is preferably an iridium complex.

  In the present invention, silver halide grains having at least one silver iodide localized phase inside the grains can also be preferably used. In the present invention, the term “grain interior” refers to a silver halide phase excluding the grain surface in silver halide grains. In the present invention, the silver iodide localized phase is a silver halide phase containing silver iodide having a silver iodide content of at least twice the average silver iodide content of the silver halide grains according to the present invention, It preferably contains silver iodide having a silver iodide content of at least 3 times the average silver iodide content of the silver halide grains, and preferably contains silver iodide having a silver iodide content of 5 times or more. In the present invention, the position of the silver iodide localized phase is preferably 60% or more outside the silver halide volume from the grain center, more preferably 70% or more, and more preferably 80% or more outside. Is most preferred.

  One of the preferred forms of the silver iodide localized phase is that the silver iodide localized phase is present in a layered form inside the silver halide grains (hereinafter also referred to as a silver iodide localized layer). It is also preferable to introduce two or more silver halide localized layers. In that case, at least one layer (hereinafter referred to as sublayer) having a main layer introduced under the above conditions and having a concentration lower than the maximum iodide concentration is more than the main layer. Further, it is preferably introduced near the particle surface. The I concentration of the main layer and sublayer can be arbitrarily selected according to the purpose. From the viewpoint of latent image stability, the main layer preferably has a high density as much as possible, and the sublayer preferably has a lower density than the main layer. In the present invention, another preferred form of the silver iodide localized phase is that the silver iodide localized phase is present in the vicinity of the apex or the ridge line of the silver halide grain, and is used in combination with the above-mentioned silver iodide localized layer. It is also preferable to do.

  When the silver halide emulsion in the present invention contains silver bromide and / or silver iodide, the silver bromide content of silver halide grains and / or the inter-grain variation coefficient of silver iodide content are respectively It is preferably less than 30%, more preferably less than 20%. The lower limit of the coefficient of variation between grains of the silver bromide content is 0.01%.

  The silver bromide content and silver iodide content of the silver halide grains can be determined by the EPMA method (Electron Probe Micro Analyzer method). Specifically, a sample in which silver halide grains are well dispersed so as not to contact each other is prepared, and irradiated with an electron beam while being cooled to −100 ° C. or lower with liquid nitrogen, and emitted from individual silver halide grains. By determining the characteristic X-ray intensities of silver, bromine and iodine, the silver bromide content and silver iodide content of the individual silver halide grains can be determined.

  By the above method, the silver bromide content and silver iodide content of the silver halide grains determined for each silver halide grain were determined for 300 or more silver halide grains, and the averages were average silver bromide, respectively. The content ratio and the silver iodide content, and the grain-to-grain variation coefficient of the silver bromide content and the silver iodide content of the silver halide grains according to the present invention are determined by the following formula.

Coefficient of variation between grains of silver bromide content = (standard deviation of silver bromide content of silver halide grains) / (average silver bromide content) × 100 (%)
Coefficient of variation between grains of silver iodide content = (standard deviation of silver iodide content of silver halide grains) / (average silver iodide content) × 100 (%)
In the present invention, it is also preferable to use silver halide grains having dislocation lines inside the grains.

  In the present invention, various bromides or iodides can be used to contain silver bromide or silver iodide in the silver halide grains. For example, silver halide fine particles containing silver bromide or silver iodide disclosed in JP-A-2-68538, etc., a method using an aqueous solution of bromide salt or iodide salt such as potassium bromide aqueous solution or potassium iodide Alternatively, a method using a halide ion releasing agent can be arbitrarily used. In the present invention, the silver iodide content, silver bromide content, silver iodide localized phase, silver bromide localized layer, or dislocation line introduction in the silver halide grains, the concentration and amount of these additives, etc. Can be adjusted arbitrarily.

  In order to obtain a silver halide emulsion according to the present invention, it is advantageous to contain heavy metal ions. Heavy metal ions that can be used for such purposes include Group 8-10 metals such as iron, iridium, platinum, palladium, nickel, rhodium, osmium, ruthenium, cobalt, and twelfth metals such as cadmium, zinc, and mercury. Group transition metals and ions of lead, rhenium, molybdenum, tungsten, gallium, and chromium can be given.

  In the present invention, the silver halide grains preferably contain one or more group 8 metal complexes, and include one or more group 8 metal complex complexes having one or more water ligands and / or organic ligands. It is more preferable to contain.

  The group 8 metal complex used in the present invention is preferably a metal complex of iron, iridium, rhodium, osmium, ruthenium, cobalt and platinum. As the metal complex, a six-coordinate complex, a five-coordinate complex, a four-coordinate complex, a two-coordinate complex, and the like can be used, and a six-coordinate complex and a four-coordinate complex are preferable. The group 8 metal complex having one or more water ligands and / or organic ligands is more preferably an iridium metal complex.

  In the present invention, the ligand constituting the Group 8 metal complex is a carbonyl ligand, a fullinate ligand, a thiocyanate ligand, a nitrosyl ligand, a thionitrosyl ligand, a cyano ligand, or water coordination. Arbitrary, halogen ligands, ammonia, hydroxide, nitrous acid, sulfurous acid, peroxide ligands and organic ligands can be used, but nitrosyl ligands, thionitrosyls. It is preferable to contain one or more ligands selected from a ligand, a cyano ligand, a water ligand, a halogen ligand, and an organic ligand.

  In the present invention, an organic ligand refers to a compound that contains one or more H—C, C—C, or C—N—H bonds and can be coordinated to a metal ion. The organic ligand used in the present invention is selected from pyridine, pyrazine, pyrimidine, pyran, pyridazine, imidazole, thiazole, isothiazole, triazole, pyrazole, furan, furazane, oxazole, isoxazole, thiophene, phenanthroline, bipyridine, and ethylenediamine. It is preferable that the compound is a compound, an ion, or a compound obtained by introducing a substituent into these compounds.

  In the silver halide emulsion according to the present invention, a group 8 metal complex represented by the following general formula (A) can also be preferably used.

Formula (A)
R _n [MX _m Y _6-m ]
In the formula, M represents a metal selected from Group 8 elements of the periodic table, and is iron, cobalt, ruthenium, iridium, rhodium, osmium, or platinum, and more preferably iron, ruthenium, rhodium, iridium, or osmium. R represents an alkali metal, preferably cesium, sodium or potassium. m represents an integer of 0 to 6, and n represents an integer of 0 to 4. X and Y represent ligands, such as a carbonyl ligand, a fullinate ligand, a thiocyanate ligand, a nitrosyl ligand, a thionitrosyl ligand, a cyano ligand, a halogen ligand, ammonia, water Represents oxide, nitrous acid, sulfurous acid, and peroxide ligands.

  These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt. When metal ions form a complex, any counter cation such as potassium ions, calcium ions, sodium ions, ammonium ions, etc. can be used. Moreover, when a metal complex is a cation, what is known in this industry, such as a nitrate ion, a halogen ion, a perchlorate ion, can be used as a counter anion.

  In order to contain heavy metal ions in the silver halide emulsion according to the present invention, the heavy metal compound is added before the formation of silver halide grains, during the formation of silver halide grains, during physical ripening after the formation of silver halide grains. What is necessary is just to add in the arbitrary places of each process. In order to obtain a silver halide emulsion satisfying the above-mentioned conditions, the heavy metal compound can be dissolved together with the halide salt and continuously added throughout the grain forming process or a part thereof.

The amount of the heavy metal ion added to the silver halide emulsion is preferably 1 × 10 ⁻⁹ mol to 1 × 10 ⁻² mol per mol of silver halide, and 1 × 10 ⁻⁸ mol to 5 × 10 ⁻⁵ mol. Mole is more preferred.

  Any shape can be used for the silver halide grains according to the present invention, but a preferred example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat. Nos. 4,183,756, 4,225,666, JP-A-55-26589, and JP-B-55-42737, The Journal of Photographic Science (J. Photogr. Sci.) Volumes of 21, 39 (1973) etc. are used to make particles having shapes such as octahedron, tetrahedron, twenty-fourhedron, dodecahedron, etc. Can also be used. Further, grains having a twin plane other than normal crystals or tabular grains may be used.

  The silver halide grains according to the present invention are preferably grains having a single shape, but two or more monodispersed silver halide emulsions can be added to the same layer.

  The grain size of the silver halide grains according to the present invention is not particularly limited, but is preferably 0.1 to 5.0 μm, more preferably 0.8 μm in consideration of other photographic performances such as rapid processability and sensitivity. It is in the range of 2 to 3.0 μm. In particular, when cubic particles are used, it is preferably in the range of 0.1 to 1.2 μm, more preferably 0.15 to 1.0 μm.

  In particular, the average grain size of the silver halide emulsion contained in the yellow coloring layer of the silver halide photographic light-sensitive material is required to be in the range of 0.40 μm or more and 0.60 μm or less in order to achieve the effects of the present invention. is there.

  The grain size distribution of the silver halide grains of the present invention is preferably monodispersed silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, more preferably 0.10 or less. Here, the variation coefficient is a coefficient representing the breadth of the particle size distribution, and is defined by the following equation.

Coefficient of variation = S / R
(Here, S represents the standard deviation of the particle size distribution, and R represents the average particle size.)
The average grain diameter here is the diameter in the case of spherical silver halide grains, and in the case of grains of shapes other than cubes or spheres, the projected image observed with the electron microscope is converted into a circular image of the same area. Represents the average diameter when converted. 1,000 or more particles are selected indiscriminately.

  As a silver halide emulsion preparation apparatus and method, various methods known in the art can be used.

  The silver halide emulsion according to the present invention may be obtained by any of acidic method, neutral method and ammonia method. The particles may be grown at one time, or may be grown after the seed particles are made. The method for making seed particles and the method for growing them may be the same or different.

  Further, the form of reacting the soluble silver salt and the soluble halide salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method, a combination thereof, and the like, but those obtained by the simultaneous mixing method are preferred. Furthermore, the pAg controlled double jet method described in JP-A No. 54-48521 can be used as one type of the simultaneous mixing method.

  Further, an apparatus for supplying a water-soluble silver salt solution and a water-soluble halide salt aqueous solution from an addition device arranged in a reaction mother liquor described in JP-A-57-92523 and JP-A-57-92524, German Published Patent No. 2921164 An apparatus for continuously adding a water-soluble silver salt solution and a water-soluble halide salt aqueous solution described in JP-A No. 56-501776, etc. An apparatus that forms grains while maintaining the distance between silver halide grains constant by concentration by a method may be used.

  Further, if necessary, a silver halide solvent such as thioether may be used. Further, 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.

  The silver halide photographic emulsion according to the present invention is preferably desalted after grain formation. Desalting can be performed, for example, by the method of RD17643, Item II. More specifically, in order to remove unnecessary soluble salts from the precipitated product or the emulsion after physical ripening, a noodle water washing method in which gelatin is gelled may be used, and inorganic salts and anionic surfactants may be used. An anionic polymer (eg, polystyrene sulfonic acid) can be used, but a precipitation method using gelatin derivatives and chemically modified gelatin (eg, acylated gelatin, carbamoylated gelatin) or ultrafiltration using membrane separation. Desalting is preferred.

  As the dispersion medium used in the production of the silver halide emulsion according to the present invention, a compound having a protective colloid property for silver halide grains can be arbitrarily used. Examples of the dispersion medium that can be preferably used in the present invention include gelatin and hydrophilic colloid. Examples of gelatin include alkali-treated gelatin and acid-treated gelatin having a molecular weight of about 100,000, or oxidized gelatin and enzyme-treated gelatin. Can be preferably used. The average molecular weight of gelatin at the time of nucleation of silver halide grains is preferably 10,000 to 70,000, and more preferably 10,000 to 50,000. It is also preferable to use gelatin having a low methionine content during nucleation, and the methionine content per unit mass (gram) of the dispersion medium is preferably 50 μmol or less, more preferably 20 μmol or less. Examples of hydrophilic colloids include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sodium alginate, starch derivatives Sugar derivatives such as: polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl imidazole, various kinds such as copolymers such as polyvinyl pyrazole A synthetic hydrophilic polymer substance or the like can be used.

  The silver halide emulsion according to the present invention can be used in combination of a sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer.

  As a chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, and the like can be used, and a sulfur sensitizer and / or a selenium sensitizer are usable. Agents are preferred.

  Sulfur sensitizers include 1,3-diphenylthiourea, triethylthiourea, thiourea derivatives such as 1-ethyl-3- (2-thiazolyl) thiourea, rhodanine derivatives, dithiacarbamic acids, polysulfide organic compounds, thiosulfuric acid Salt, sulfur alone and the like are preferable. In addition, as sulfur simple substance, the alpha-sulfur which belongs to an orthorhombic system is preferable. In addition, U.S. Pat. Nos. 1,574,944, 2,410,689, 2,278,947, 2,728,668, 3,501,313, No. 3,656,955, etc., West German Published Application (OLS) 1,422,869, JP-A-56-24937, 55-45016, etc. are used. be able to.

  As the selenium sensitizer, an unstable selenium compound capable of reacting with silver nitrate in an aqueous solution to form a silver selenide precipitate is preferably used. For example, U.S. Pat. Nos. 1,574,944, 1,602,592, 1,623,499, JP-A-60-150046, JP-A-4-25832, and 4-109240. 4-147250 and the like. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (such as allyl isoselenocyanate), selenoureas (such as N, N-dimethylselenourea, N, N, N'-triethylseleno). Urea, N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'- 4-nitrophenylcarbonylselenourea etc.), selenoketones (eg selenoacetone, selenoacetophenone etc.), selenoamide (eg selenoacetamido, N, N-dimethylselenobenzamide etc.), selenocarboxylic acids and selenoesters (eg 2-selenopropionic acid, methyl-3-selenobutyrate, etc.) Phosphates (eg, tri-p-triselenophosphate, etc.), selenides (eg, dimethyl selenide, triphenylphosphine selenide, pentafluorophenyl-diphenylphosphine selenide, trifurylphosphine selenide, Trypyridylphosphine selenide). Particularly preferred selenium sensitizers are selenourea, selenoamides, and selenides.

  In the present invention, noble metal salts such as gold, platinum, palladium, iridium and the like described in RD magazine 307, 307105 are preferably used, and in particular, a gold sensitizer is preferably used in combination. Useful gold sensitizers include U.S. Pat. Nos. 2,597,856, 5,049,485, and Japanese Patent Publication No. 44-15748 in addition to chloroauric acid, gold thiosulfate, gold thiocyanate and the like. And organic gold compounds disclosed in JP-A-1-147537 and 4-70650, gold sulfide, and gold sulfide silver. Further, when performing a sensitization method using a gold complex salt, it is preferable to use a gold ligand such as thiosulfate, thiocyanate, and thioether as an auxiliary agent, and in particular, it is preferable to use thiocyanate. .

  In the above-mentioned various chemical sensitizers, postscript inhibitors, oxidizing agents and the like according to the present invention, JP 2001-318443, JP 2003-29472, JP 2004-37554, 2004-4144, 2004-4446, 2004-4442, 2004-4456, 2004-4458, 2004-4656, 2004-4672, 2003-307803, 2003-287841, 2003 287842, 2003-233146, 2003-172990, 2003-172991, 2003-113193, 2003-113194, 2003-114489, 2002-372765, 2002-296721 No. 2002-278011, No. 2002 No. 268169, No. 2002-244241, No. 2002-259882, No. 2002-258427, No. 2002-268168, No. 2002-268170, No. 2000-193942, No. 2001-75214, No. 2001-75215 2001-75216, 2001-75217, 2001-75218, 2001-100352, 2004-70363, 2004-67695, 2002-131858, 2001-166612, etc. The compounds described in the gazette, European Patent Nos. 1094360, 13888752, U.S. Pat. Nos. 6,686,143 and 6,322,961, and the techniques for using them can also be preferably used.

The addition amount of the chalcogen sensitizer and gold sensitizer is not uniform depending on the type of silver halide emulsion, the type of compound used, and the ripening conditions, but usually 1 × 10 ⁻⁹ per mole of silver halide. It is preferably ˜1 × 10 ⁻⁵ mol. More preferably, it is 1 × 10 ⁻⁸ mol to 1 × 10 ⁻⁴ mol. Depending on the nature of the sensitizer used, the above-mentioned various sensitizers may be added by dissolving them in water or an organic solvent such as methanol alone or in a mixed solvent, or by premixing with a gelatin solution. The method of addition may be the method disclosed in JP-A-4-140739, that is, the method of adding in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer.

  In the present invention, reduction sensitization may be used, and reducing compounds described in RD magazine 307, 307105, JP-A-7-78685, and the like may also be used.

  The silver halide emulsion according to the present invention is known for the purpose of preventing fogging that occurs during the preparation process of a silver halide photographic light-sensitive material, reducing fluctuations in performance during storage, and preventing fogging that occurs during development. Antifoggants, oxidizing agents, inhibitors, stabilizers and the like can be used. Examples of preferred compounds that can be used for such purposes include compounds represented by the general formula (II) described in JP-A-2-14636, page 7, lower column, and more preferred specific compounds. As the compounds (IIa-1) to (IIa-8) and (IIb-1) to (IIb-7) described on page 8 of the same publication, and 1- (3-methoxyphenyl) -5-mercapto Preferred are compounds such as tetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole, general formula (S) compounds described in JP-A-8-6201, thiosulfonic acid compounds, disulfide compounds, polysulfide compounds, and the like. The compounds described in Nos. 29472, 2003-10482, 2002-31557 and the like can be preferably used.

Depending on the purpose, these compounds are added in steps such as a silver halide emulsion grain preparation step, a chemical sensitization step, a chemical sensitization step, and a coating solution preparation step. A preferable addition amount of these compounds is 1 × 10 ⁻⁸ to 1 × 10 ⁻¹ mol / mol Ag ×, more preferably 1 × 10 ⁻⁷ to 1 × 10 ⁻² mol per mol of silver halide. For the addition of these compounds, methods commonly used in the art when additives are added to photographic emulsions, coating solutions, preparation solutions and the like can be applied. For example, in the case of a water-soluble compound, an aqueous solution having an appropriate concentration is used. In the case of a compound that is insoluble or sparingly soluble in water, any organic solvent that can be mixed with water, for example, alcohols, glycols, ketones It can be dissolved in a solvent that does not adversely affect photographic properties such as esters and amides, and added as a solution.

  In the silver halide color photographic light-sensitive material according to the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any known compound can be used. In particular, as dyes having absorption in the visible region, the dyes AI-1 to 11 described in JP-A-3-252840, page 30 and The dyes described in JP-A-6-37706 are preferably used, and the infrared absorbing dyes are represented by the general formulas (I), (II), and (III) described in JP-A-1-280750, page 2, lower left column. The compounds have preferred spectral properties and are preferred without affecting the photographic properties of the silver halide photographic emulsion and without contamination by residual colors. Specific examples of preferred compounds include the exemplified compounds (1) to (45) listed in the same publication, page 3, lower left column to page 5, lower left column.

  For the purpose of improving sharpness, the amount of these dyes added is preferably such that the spectral reflection density at 680 nm of the unprocessed sample of the photosensitive material is 0.7 to 3.0. More preferably 0.

  It is preferable to add a fluorescent brightening agent to the silver halide color photographic light-sensitive material according to the present invention, since the white background can be improved. Preferred examples of the compound include compounds represented by the general formula (II) described in JP-A-2-232652.

  The silver halide color photographic light-sensitive material according to the present invention has a layer containing a silver halide emulsion spectrally sensitized in a specific region of a wavelength region of 400 to 900 nm in combination with a yellow coupler, a magenta coupler, and a cyan coupler. The silver halide emulsion contains one or a combination of two or more sensitizing dyes.

  As the spectral sensitizing dye used in the silver halide emulsion according to the present invention, any known compound can be used. As the blue-sensitive sensitizing dye, it is described in JP-A-3-251840, page 28. BS-1 to BS-8 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the same publication are preferably used. As the red photosensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used. In addition, when performing image exposure with infrared light using a semiconductor laser or the like, it is necessary to use an infrared photosensitive sensitizing dye. As the infrared photosensitive sensitizing dye, JP-A-4-285950 is disclosed. The pigments IRS-1 to IRS11 described in JP-A No. 6-8 are preferably used. Further, these infrared, red, green and blue photosensitive sensitizing dyes are supersensitizers SS-1 to SS-9 described in JP-A-4-285950, pages 8 to 9 and JP-A-5-66515. It is preferable to use a combination of compounds S-1 to S-17 described in JP-A No. 15-17.

  These sensitizing dyes may be added at any time from silver halide grain formation to coating solution preparation.

  As a method for adding a sensitizing dye, it may be added as a solution by dissolving it in water-miscible organic solvent such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide or water, or as a solid dispersion. Also good.

  As a coupler used in the silver halide color photographic light-sensitive material according to the present invention, a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm can be formed by a coupling reaction with an oxidized form of a color developing agent. Any compound can be used, but particularly representative couplers include yellow dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 350 to 500 nm, and magenta dye formation having a spectral absorption maximum wavelength in the wavelength range of 500 to 600 nm. Examples of couplers include those known as cyan dye-forming couplers having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

  As a cyan dye-forming coupler that can be preferably used in the silver halide color photographic light-sensitive material according to the present invention, general formulas (CI) and (C-II) described in JP-A-4-114154, page 5, lower left column. ) Can be mentioned. Specific compounds include those described as CC-1 to CC-9 in page 5, lower right column to page 6, lower left column.

  As a magenta dye-forming coupler which can be preferably used in the silver halide color photographic light-sensitive material according to the present invention, general formulas (M-I) and (M-II) described in JP-A-4-114154, page 4, right upper column. ) Can be mentioned. Specific compounds include those described as MC-1 to MC-11 in page 4, lower left column to page 5, upper right column. Among the magenta dye-forming couplers, a coupler represented by the general formula (M-I) described in the upper right column on page 4 of the same publication is preferred. Among them, the RM of the general formula (M-I) is used. A coupler in which is a tertiary alkyl group is particularly preferred because of excellent light resistance. MC-8 to MC-11 described in the upper column of page 5 of the same publication are preferable because they are excellent in color reproduction from blue to purple and red, and are excellent in detail descriptive power.

  Examples of preferred couplers represented by the above general formula (M-I) are exemplified compounds 1 to 64 described on pages 5 to 9 of JP-A No. 63-253934 and JP-A No. 2-100048. Exemplified compounds M-1 to M-29 described on pages 5 to 6, Exemplified compounds (1) to (36) described on pages 5 to 12 of JP-A-7-175186, JP-A-7-219170 Exemplified compounds M-1 to M-33 described on pages 14 to 22 of the publication, Exemplified compounds M-1 to M-16 described on pages 5 to 9 of JP-A-8-304972, and JP-A-10- Exemplified compounds M-1 to M-26 described on pages 5 to 10 of 207024, Exemplified compounds M-1 to M-36 described on pages 5 to 22 of JP-A-10-207025, US Patent Exemplified compounds described on pages 3 to 6 of No. 5,576,150 -1 to M-24, Exemplified compounds M-1 to M-48 described on pages 3 to 9 of US Pat. No. 5,609,996, 3 of US Pat. No. 5,667,952 Exemplified compounds M-1 to M-23 described on pages 5 to 5, Exemplified compounds M-1 to M-26 described on pages 3 to 6 of US Pat. No. 5,698,386, etc. Can do.

Examples of yellow dye-forming couplers that can be preferably used include couplers represented by general formula (Y-I) described in JP-A-4-114154, page 3, upper right column. Specific compounds include those described as YC-1 to YC-9 in the lower left column on page 3 of the publication. Among them, a coupler in which RY _{1 in the} general formula [Y-1] is an alkoxy group, or a coupler represented by the general formula [I] described in JP-A-6-67388 is preferable because it can reproduce a yellow color having a preferable color tone. Among these, as particularly preferred compound examples, YC-8, YC-9 described in JP-A-4-114154, page 4, upper left column, and No. described in JP-A-6-67388, pages 13-14 The compound shown by 1)-(47) can be mentioned. The most preferred compounds are those represented by the general formula [Y-1] described in JP-A-4-81847, pages 1 and 11-17.

  In the case of using an oil-in-water emulsion dispersion method to add a coupler or other organic compound used in the silver halide color photographic light-sensitive material according to the present invention, a water-insoluble high-boiling organic compound having a boiling point of 150 ° C. or higher is usually used. If necessary, the solvent is dissolved in combination with a low boiling point or water-soluble organic solvent, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As the dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. A step of removing the low boiling point organic solvent may be added after the dispersion or simultaneously with the dispersion.

  Examples of the high-boiling organic solvent that can be used to dissolve and disperse the coupler include phthalic acid esters such as dioctyl phthalate, di-i-decyl phthalate, and dibutyl phthalate, and phosphoric acid such as tricresyl phosphate and trioctyl phosphate. Esters are preferably used. Further, the dielectric constant of the high boiling point organic solvent is preferably 3.5 to 7.0. Two or more high boiling point organic solvents can be used in combination.

  Further, instead of using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound is dissolved in a low-boiling and / or water-soluble organic solvent as necessary. In addition, a method of emulsifying and dispersing by various dispersing means using a surfactant in a hydrophilic binder such as an aqueous gelatin solution can also be used. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

  Compounds containing a hydrophobic group having 8 to 30 carbon atoms and a sulfonic acid group or a salt thereof as one of the surfactants used for dispersing the photographic additive and adjusting the surface tension during coating. Is mentioned. Specific examples include A-1 to A-11 described in JP-A No. 64-26854. A surfactant in which a fluorine atom is substituted on the alkyl group is also preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, but it is better that the time until dispersion is added to the coating solution after dispersion and the time from addition to coating after coating is shorter. It is preferably within 10 hours, more preferably within 3 hours and within 20 minutes.

  Each of the above couplers is preferably used in combination with an anti-fading agent in order to prevent fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by the general formulas [I] and [II] described on page 3 of JP-A-2-66541, and a general formula [IIIB] described in JP-A-3-1741503. A phenol compound represented by formula (A), an amine compound represented by formula [A] described in JP-A No. 64-90445, a general formula [XII], [XIII], [XIV described in JP-A No. 62-182741 ] And [XV] are particularly preferable for magenta dyes. Further, the compound represented by the general formula [I] described in JP-A-1-196049 and the compound represented by the general formula [II] described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

  For the purpose of shifting the absorption wavelength of the coloring dye, compounds such as compound (d-11) described in JP-A-4-114154, page 9, lower left column, compound (A'-1) described in page 10, lower left column, etc. Can be used. In addition, fluorescent dye releasing compounds described in US Pat. No. 4,774,187 can also be used.

  In the silver halide color photographic light-sensitive material according to the present invention, a compound that reacts with an oxidized developing agent is added to the layer between the photosensitive layer to prevent color turbidity or added to the silver halide emulsion layer. Thus, it is preferable to improve fog and the like. The compound for this purpose is preferably a hydroquinone derivative, more preferably a dialkyl hydroquinone such as 2,5-di-t-octyl hydroquinone. Particularly preferred compounds are compounds represented by the general formula [II] described in JP-A-4-133056, compounds II-1 to II-14 described on pages 13 to 14 and compound-1 described on page 17 Is mentioned.

  In the silver halide color photographic light-sensitive material according to the present invention, it is preferable to add an ultraviolet absorber to prevent static fogging or to improve the light resistance of a dye image. Preferred ultraviolet absorbers include benzotriazoles, and particularly preferred compounds are those represented by general formula [III-3] described in JP-A-1-250944, and general formulas described in JP-A-64-66646. Compounds represented by [III], UV-1L to UV-27L described in JP-A-63-187240, compounds represented by general formula [I] described in JP-A-4-16333, JP-A-5-165144 And compounds represented by the general formulas (I) and (II) described in Japanese Patent Publication.

  In the silver halide color photographic light-sensitive material according to the present invention, it is advantageous to use gelatin as a binder, but if necessary, other gelatin, gelatin derivatives, gelatin and other polymer graft polymers, other than gelatin. Hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, synthetic hydrophilic polymer materials such as mono- or copolymers can also be used. The calcium content in gelatin is preferably 100 ppm or less, more preferably 50 ppm or less, and even more preferably 30 ppm or less. Further, the content of heavy metals such as zinc, copper, manganese, and iron in gelatin is preferably 10 ppm or less, more preferably 5 ppm or less, and still more preferably 3 ppm or less.

  As these binder hardeners, vinylsulfone type hardeners, chlorotriazine type hardeners, and carboxyl group active hardeners are preferably used alone or in combination. It is preferable to use compounds described in JP-A Nos. 61-249054 and 61-245153. Further, in order to prevent the growth of soot and bacteria that adversely affect photographic performance and image storage stability, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 in the colloid layer. In order to improve the physical properties of the surface of the photosensitive material or processed sample, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 and JP-A-2-73250 to the protective layer.

In the silver halide color photographic light-sensitive material according to the present invention, the total Coating amount of gelatin structure layer is 3 g / m ² or more, preferably 6 g / m ² or less, 3 g / m ² or more, 5 g / m More preferably, it is ² or less. Further, even in the case of ultra-rapid processing, in order to satisfy development progress, fixing bleachability, and residual color, the total thickness of the constituent layers is preferably 3 μm to 7.5 μm, and more preferably 3 μm to 6.5 μm. It is preferable that The dry film thickness can be measured by measuring the change in film thickness before and after peeling the dry film, or by observing the cross section with an optical microscope or an electron microscope. In the present invention, the swelling film thickness is preferably 8 μm to 19 μm, and more preferably 9 μm to 18 μm, in order to achieve both development progress and increase in the drying speed. The swollen film thickness can be measured by the dot method in a state where the dried photosensitive material is immersed in an aqueous solution at 35 ° C. and swelled to reach a sufficient equilibrium. Coated silver amount in the present invention is ^{0.3g / m 2 ~0.6g / m 2} .

  Further, it is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 in the colloid layer in order to prevent the growth of soot and bacteria that adversely affect photographic performance and image storage stability. In order to improve the physical properties of the surface of the photosensitive material or the processed sample, it is preferable to add a slipping agent or a matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer. The film pH of the photosensitive material is preferably from 4.0 to 7.0, more preferably from 4.0 to 6.5.

  The silver halide color photographic light-sensitive material according to the present invention may have at least one yellow image forming layer, magenta image forming layer, and cyan image forming layer, but may form a plurality of color images as necessary. Units may be formed of layers.

  As the support used in the silver halide color photographic light-sensitive material according to the present invention, any material may be used, such as paper coated with polyethylene or polyethylene terephthalate, paper support made of natural pulp or synthetic pulp, vinyl chloride. Sheets, polypropylene that may contain a white pigment, polyethylene terephthalate support, baryta paper, and the like can be used. Especially, the support body which has a water-resistant resin coating layer on both surfaces of a base paper is preferable. As the water resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferable.

  As the white pigment used for the support, inorganic and / or organic white pigments can be used, and inorganic white pigments are preferably used. For example, alkaline earth metal sulfate such as barium sulfate, alkaline earth metal carbonate such as calcium carbonate, silica such as fine silicate, synthetic silicate, calcium silicate, alumina, alumina hydrate, oxidation Examples thereof include titanium, zinc oxide, talc, and clay. The white pigment is preferably barium sulfate or titanium oxide.

  The amount of the white pigment contained in the water-resistant resin layer on the surface of the support is preferably 13% by mass or more, and more preferably 15% by mass for improving sharpness.

  The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, and more preferably 0.15 or less, as the coefficient of variation described in the above publication.

  Further, the value of the center plane average roughness (SRa) of the support is preferably 0.15 μm or less, and more preferably 0.12 μm or less, because the effect of good gloss is obtained. Also, in order to improve the whiteness by adjusting the spectral reflection density balance of the white background after treatment in the white pigment-containing water-resistant resin of the reflective support or in the coated hydrophilic colloid layer, a trace amount of ultramarine, oil-soluble dyes, etc. It is preferable to add a blue tinting agent or a red tinting agent.

  The silver halide color photographic light-sensitive material according to the present invention is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface as necessary, and then directly or undercoat layer (adhesion of the support surface, antistatic property). One or more subbing layers for improving the properties, dimensional stability, rub resistance, hardness, antihalation properties, frictional properties and / or other properties.

  When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used to improve the coating property. As the coating method, extrusion coating and curtain coating capable of simultaneously coating two or more layers are particularly useful. As the coating device, a slide coater, a curtain coater, an extrusion coater, or the like can be used.

  In order to form a photographic image using the silver halide color photographic light-sensitive material according to the present invention, the image recorded on the negative is optically imaged on the silver halide photographic light-sensitive material to be printed. Alternatively, after the image is converted into digital information, the image is formed on a CRT (cathode ray tube), and the image is formed on the silver halide photographic material to be printed and printed. Alternatively, printing may be performed by changing the intensity of laser light based on digital information and scanning.

  The silver halide color photographic light-sensitive material according to the present invention is preferably applied to a silver halide color photographic light-sensitive material that does not contain a developing agent, and in particular, a silver halide color photographic light-sensitive material that forms an image for direct viewing. A material is preferred. Examples thereof include color paper, color reversal paper, photosensitive material for forming a positive image, photosensitive material for display, and photosensitive material for color proof, and among them, a silver halide color photographic photosensitive material having a reflective support. It is preferable to apply to.

  In the present invention, the average grain size of the silver halide emulsion contained in the yellow coloring layer of the silver halide photographic light-sensitive material is 0.40 μm or more and 0.60 μm or less as described above. When a color image is formed by the subsequent development processing step, sensitometric gamma between the logarithm of the exposure amount giving a density of 1.0 and the logarithm of the exposure amount giving a density of 2.0 of the obtained color image is 4 0.0 or more and 6.0 or less, and X is the density of the maximum exposure area when digital exposure is performed at a resolution of 400 dpi and development processing is performed, and an unexposed fine line of 1 pixel width drawn in the maximum exposure area When the minimum density is Y, a relationship of 0.0 ≦ Y / X ≦ 0.6 is established in a range satisfying at least 1.0 ≦ X ≦ 2.0.

The digital exposure process is preferably performed using an exposure head composed of a PLZT array element and LED light sources of R, G, and B, and the maximum exposure area of a color image obtained by performing development processing is In the CIE1976-L ^* a ^* b ^* color system, the lightness index represented by L ^* is 0.0 ≦ L ^* ≦ 5.0, and the silver halide photographic light-sensitive material subjected to development processing The unexposed portions of 91.0 ≦ L ^* ≦ 96.0, 0.5 ≦ a ^* ≦ 1.5, and −6.0 ≦ b ^* ≦ −3.0.

  If the unexposed portion is out of this range, the color is observed on a white background, which is not preferable.

  In addition, since the brightness area of the maximum density portion is within this range, an image having a high contrast such as a character has a high contrast ratio, and sharpness is remarkably improved.

Brightness index in the present invention L ^*, the perceptual chromaticity indices a ^*, b ^* The, CIELAB (Commission Internationale de 1 "Echairage" encouragement of L ^*, a *, b * color system abbreviations) in accordance with lightness L ^* Yes, details are described in the item “CIEL ^* a ^* b ^* ” in “New Color Science Handbook (Edited by Japan Society of Color Science), page 267”.

The details of the CIE 1976 L ^* a ^* b ^* color space according to the present invention are also described in detail in “Fine Imaging and Color Hard Copy” on page 354 (1999, published by Corona) edited by the Japanese Society of Photography and Imaging Society of Japan. ing. The trichromatic stimulus value when using this color space is a value obtained according to the method described in JIS Z 8717 which defines the tristimulus value measuring method of the X, Y, and Z coordinates of the fluorescent reflecting object. CIE1976L ^* a ^* b ^* Color space is measured using the standard white color system, CIED65 (6504K), which is the international standard for standard daylight, using the color matching function of the standard color system. To do. As a measuring instrument, any chromaticity measuring device capable of measuring chromaticity in the CIE 1976 L ^* a ^* b ^* color space can be used. For example, it can be measured using a C-2000 color analyzer manufactured by Hitachi, Ltd. and CIE D65 (6504K) as a reference light source.

  In the present invention, specifically, CIE whiteness Wa measured by irradiating a tungsten light source directly to a sample using a C-2000 color analyzer manufactured by Hitachi, Ltd. is defined as CIE whiteness Wa obtained by white light illumination. To do. In this case, the white light illumination includes ultraviolet light and infrared light in addition to the three primary colors of blue, green, and red.

  Further, the sensitometric gamma between the logarithm of the exposure amount giving the density of 1.0 and the logarithm of the exposure amount giving the density of 2.0 of the obtained color image is 4.0 or more and 6.0 or less. That is, after the development process following the digital exposure process (for example, the digital exposure processes (1) and (2) in the embodiment), the status A density at one point on the step chart for each sample is 1 for each of B, G, and R. When exposure is performed so as to be reproduced at 0.0, and development processing (for example, development processing step (2) in the embodiment) is performed, estimation is performed from the status A density, and the average value of each of B, G, and R is obtained.

  As a result, in digital photographic prints, in which images are formed by digital exposure and development from digital image data, the depiction of high-density areas is particularly good, and the white background is good, the reproduction of character image data is improved, and the image quality is high. Photo prints can be provided.

  Hereinafter, exposure by an exposure head composed of a PLZT array element and R, G, and B LED light sources, which is a digital exposure process preferably used in the present invention, will be described.

  FIG. 1 is a schematic configuration diagram of a 400 dpi photographic digital printer (hereinafter referred to as “printer”) 1 used in a digital exposure process in the image forming method of the present invention. The printer 1 has a conveyance mechanism 2 for conveying a silver halide photographic light-sensitive material (hereinafter referred to as photographic paper) 3 as a recording material in the X direction as a conveyance direction (sub-scanning direction), and is orthogonal to the X direction. Of an exposure mechanism 4 as a recording head, a light source color switching unit 5, a driver IC 6, and a transport mechanism 2 for forming an image on the photographic paper 3 in a line shape along the Y direction which is the direction (main scanning direction). A light source color switching unit 5, a driver IC 6, and a transport drive unit based on the transport drive unit 7 that performs driving and image data (hereinafter referred to as “image data”) of input RGB exposure colors (light source colors). 7 and an exposure control unit 8 for controlling the image forming apparatus 7 and a support member 9 for supporting the photographic paper 3 from below at an exposure portion exposed in a line by the exposure mechanism 4.

  The conveyance mechanism 2 includes driving rollers 21 and 21 that rotate around an axis perpendicular to the X direction by power of a motor or the like, and press-contact rollers 22 that are in parallel with the driving roller 21 and press-contact with the driving rollers 21. 22, one drive roller 21 and the pressure roller 22 are arranged on the upstream side in the X direction, and the other drive roller 21 and the pressure roller 22 are provided on the downstream side in the X direction. The photographic paper 3 carried out from the supply position (not shown) is sandwiched between the drive roller 21 and the pressure roller 22 and is conveyed in the X direction by the rotation of the drive rollers 21 and 21.

  The photographic paper 3 is a silver halide light-sensitive material, and a color developing layer for forming each color forms a layer structure. A layer that develops cyan when exposed to red light (R) from the side closest to the surface, a layer that develops magenta when exposed to green light (G), and a blue light (B) are exposed. In this way, a yellow color layer is formed. The photographic paper 3 is wound in a roll shape at a supply position (not shown).

The exposure mechanism 4 includes an LED light source 41 that is a light source composed of R (red), G (green), and B (blue) light source colors, and an exposure head 42 that is disposed opposite to the photographic paper 3 between two drive rollers 21. A SELFOC lens array 43 provided between the exposure head 42 and the photographic paper 3, an optical fiber array 44 for guiding light from the LED light source 41 to the exposure head 42, and one end of the optical fiber array 44. And an integrator 45 interposed between the LED light source 41 and the like.

The photographic paper 3 is transported by the transport mechanism 2 and moved relative to the exposure mechanism 4 to record an image corresponding to the image data.

  The exposure head 42 is, for example, a PLZT shutter array head in which PLZT (Plumb Lanthanum Zirconate Titanate) elements as a plurality of recording elements are arranged in an array along the Y direction as pixels of light emission points.

  Specifically, the exposure head 42 forms an array by arranging a plurality of PLZT chips 421 composed of a plurality of PLZT elements 425 on a ceramic or glass substrate (not shown) having a slit-shaped opening, and A plurality of driver ICs 6 as drive units are arranged on both sides of a plurality of PLZT chips 421.

  As shown in FIG. 2, the PLZT chip 421 has a three-dimensional shape, and is provided with a PLZT element 425, individual electrodes 422, a common electrode 423, and the like.

  Specifically, a large number of PLZT elements 425 corresponding to one pixel are arranged in two columns, and each PLZT element 425 is formed in a staggered pattern by one pixel, so that two columns (Odd column, Even column) are main. An image of one line is formed in the scanning direction Y.

  The common electrode 423 is provided in common for the Odd row and the even row, and the individual electrode 422 is provided separately for the odd row and the even row, and is provided individually for each PLZT element 425. Further, both electrodes 422 and 423 are provided on both sides of the PLZT element 425 in parallel to the optical path, and have a structure capable of realizing a large light transmission amount even with a low applied voltage.

  The voltage applied to the exposure head (individual electrode 422 and common electrode 423) is changed by the driver IC 6 to drive the PLZT element 425. That is, the PLZT element 425 in the odd column and the PLZT element 425 in the even column are individually driven. To do.

  As is well known, PLZT is a translucent ceramic having an electro-optic effect with a large Kerr constant. Light that has been linearly changed by a polarizer (not shown) is applied by applying a voltage to the PLZT element 425. The polarization plane is rotated, and is emitted from an analyzer (not shown). When the voltage is turned off, the plane of polarization of the transmitted light does not rotate, such transmitted light is cut by an analyzer (not shown), and the light emitted from the analyzer (not shown) passes through the Selfoc lens array 43. An image is formed on the photographic paper 3 and functions as an optical shutter.

  The PLZT element 425 is ON / OFF controlled (main scanning) line by line based on the image data, and two-dimensional on the photographic paper 3 by this main scanning and movement of the photographic paper 3 in the X direction (sub scanning). The image is exposed.

  Actually, as shown in the schematic diagram of FIG. 3, the exposure head 42 includes twelve PLZT chips 421a, 421b,..., 421l, and eight driver ICs 6a provided for each of the plurality of PLZT chips. 6b,..., 6h, etc.

  On / off control of the PLZT chip 421 is performed for each driver IC 6. Therefore, when the driver IC 6a applies the applied voltage, the PLZT elements 425 on the Odd column side of the PLZT chips 421a, 421b, 421c and simultaneously the driver IC 6e applies the applied voltage, so that the PLZT chips 421a, 421b, The PLZT element 425 on the Even column side of 421c is also in a driving state.

  By performing exposure while the PLZT element 425 transmits light, the exposure time is controlled according to the image data, and gradation is expressed.

  The SELFOC lens array 43 is formed by integrating a plurality of optically equivalent SELFOC lenses in parallel with each other, and forms an image of light transmitted through the exposure head 42 on the photographic paper 3. Further, the exposure location is in a line shape along the scanning direction Y on the imaging surface formed by the SELFOC lens array 43, and the length of the exposure location along the scanning direction Y is arranged at the exit point of the exposure head 42. It is substantially the same as the length.

  One end of the plurality of optical fibers is bundled at one end of the optical fiber array 44, and the end of the optical fiber array 44 is directed to the LED light source 41. At the other end of the optical fiber array 44, each end of the optical fiber is connected to a PLZT element 425, which is an optical shutter element.

  The integrator 45 is provided to efficiently guide the light from the LED light source 41 to the optical fiber array 44, disperse the luminance unevenness of the light source, and obtain a uniform illuminance distribution. Not composed of input lens, fly-eye lens, output lens, filter, aperture, etc.

  The light source color switching unit 5 switches the RGB light source colors (exposure colors) constituting the LED light source 41 by, for example, an ON / OFF instruction from the exposure control unit 8, and sequentially switches the color of the light to be exposed.

  The conveyance driving unit 7 drives the driving roller 21 to control the conveyance of the photographic paper 3.

  The exposure control unit 8 controls the light source color switching unit 5, the driver IC 6, and the transport driving unit 7 in synchronization, and includes a CPU (Central Processing Unit) 81, a RAM (Random Access Memory), and a ROM (Read Only). Memory) and the like.

  The CPU performs various calculations, instructions to each functional unit, data transfer, and the like based on various programs stored in the ROM according to a predetermined timing or the like.

  The RAM is used for storing data processed by the CPU under the control of the CPU and outputting the stored data to the CPU.

  The ROM mainly stores programs, data, and the like for performing various operations executed by the transport mechanism 2 and the exposure mechanism 4. Specifically, for example, as shown in FIG. Stores programs, drive control programs, photographic paper transport control programs, and the like.

  The light source color switching program is a program for switching the RGB light source colors a multiple of the number of light source colors (3), that is, six times while the recording head 42 moves by one pixel in the sub-scanning direction. The CPU executes the light source color switching program to control the light source color switching unit 5 and functions as a light source color switching unit.

  Specifically, for example, one line is recorded by switching the light source colors R, G, and B six times, that is, by switching the light source colors RGB twice.

  Here, in the 400 dpi printer 1, for example, if the output value of the output data per pixel (depth of the output signal value) is 11 bits (2048 gradations), recording with the light source color RGB is 10 bits (1024 gradations). ) Can be executed in the time required to reproduce the output value, and the control part sequence can be simplified.

  The drive control program is a program for driving the exposure head, and the CPU controls the driver IC 6 by executing the drive control program and functions as a drive control unit.

  Specifically, the CPU as the drive control means performs control to shift the drive start timing of each driver IC 6 by a predetermined interval.

  Further, the CPU performs control to switch the applied voltage applied to the driver IC 6 that drives each PLZT chip 421 in accordance with the RGB light source color, and functions as a drive control unit.

  FIG. 5 shows the transmittance distribution of the PLZT shutter for each light source color with respect to the applied voltage. (X), (y), and (z) respectively indicate transmittance distributions of 450 nm wavelength light, 530 nm wavelength light, and 700 nm wavelength light. That is, the transmittance distribution depends on the emission wavelength of each light source color, and the voltage indicating the maximum transmittance is different. Therefore, different applied voltages are applied according to the respective light source colors. At this time, if the applied voltages corresponding to the RGB light source colors are V (R), V (G), and V (B), as shown in FIG. 5, V (R)> V (G)> V (B ) Is preferable.

  Also, assuming that the voltage application time for each RGB light source color is t (R), t (G), and t (B), t (R), t (G), and t (B) are each 500 (μs). The following is preferable. This is because if it exceeds 500 (μs), it cannot be used for high-speed printing.

  More specifically, the layer of photographic paper 3 that develops yellow when B is exposed has the highest sensitivity, and then the layer that develops magenta when G is exposed has the highest sensitivity, and R is exposed. As a result, the layer that develops cyan has the lowest sensitivity. Therefore, it is preferable to set the exposure time longer in the order of RGB.

  In general, as a capability required for a photographic exposure device, a spec of L size 700 sheets / hour or more is required. Assuming an L-size feed length of 89 mm and a paper interval of 20 mm, a writing time of one line of 400 dpi is about 3.0 ms. In order to make the sub-scanning direction 800 dpi, 500 μs or less is essential.

  Further, the CPU performs control to start driving each PLZT chip 421 after elapse of 10 (μs) since the switching of the applied voltage, and functions as a drive control unit.

  The photographic paper transport control program is a program for transporting the photographic paper 3, and the CPU 81 controls the transport controller 7 by executing the photographic paper transport control program 833.

  In the present invention, since the printer 1 is a photographic digital printer of 400 dpi or more, pixel displacement caused by driving each PLZT chip 421 at a different timing by setting the substantial image density to 800 dpi or more. Can be made 0.0065 mm or less, so that the deviation is below the level at which it can be visually recognized, and deterioration of image quality can be prevented.

  Further, by using an LED as the light source, the light source color can be switched at high speed, and the speed can be increased.

  Furthermore, in each RGB light source color, the time during which the applied voltage is applied is 500 (μs) or less, so that the writing time for one line is suppressed to 3.0 (ms) or less, and the conveyance speed of the photographic paper 3 is 22 Since it can be (mms) or more, it can be applied to high-speed printing.

  Note that the CPU (light source color switching means) may switch the light source color a plurality of times for only one of the RGB light source colors. In this case, the recording element is driven a plurality of times for at least one of the light source colors. Therefore, as in the case where the light source color is switched multiple times the number of the light source colors, the recording for one pixel is finely performed in a plurality of times, and the drive start timing of the recording element chip is shifted. The resulting image shift in the sub-scanning direction can be reduced and image quality deterioration can be prevented.

  Next, a method for processing a silver halide photographic material according to the present invention will be described.

  The method for processing a silver halide color photographic light-sensitive material according to the present invention comprises subjecting an exposed silver halide color photographic light-sensitive material to a color developing step (color developer), followed by a bleaching step (bleaching solution) and a fixing step. (Fixing solution) or bleach-fixing step (bleaching fixing solution) and stabilization step (stabilizing solution), followed by drying. Further, development processing can be continuously performed while replenishing a replenishing color developer, a replenishing bleaching solution, a replenishing fixing solution, a replenishing bleach-fixing solution, a replenishing stabilizing solution, or the like. The color developer, bleaching solution, bleach-fixing solution, fixing solution, stabilizing solution, and rinsing solution used in the present invention will be described below.

  Preferred examples of the color developing agent used in the color developing solution according to the present invention are known aromatic primary amine color developing agents, particularly p-phenylenediamine derivatives. Representative examples are shown below, but are not limited thereto. It is not something.

1) N, N-diethyl-p-phenylenediamine 2) 4-amino-3-methyl-N, N-diethylaniline 3) 4-amino-N- (β-hydroxyethyl) -N-methylaniline 4) 4 -Amino-N-ethyl-N- (β-hydroxyethyl) aniline 5) 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline 6) 4-amino-3-methyl-N -Ethyl-N- (3-hydroxypropyl) aniline 7) 4-Amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline 8) 4-Amino-3-methyl-N-ethyl-N -(Β-Methanesulfonamidoethyl) aniline 9) 4-Amino-N, N-diethyl-3- (β-hydroxyethyl) aniline 10) 4-Amino-3-methyl-N-ethyl-N- (β- Me Xylethyl) aniline 11) 4-Amino-3-methyl-N- (β-ethoxyethyl) -N-ethylaniline 12) 4-Amino-3-methyl-N- (3-carbamoylpropyl) -Nn-propyl -Aniline 13) 4-amino-N- (4-carbamoylbutyl) -Nn-propyl-3-methylaniline 14) N- (4-amino-3-methylphenyl) -3-hydroxypyrrolidine 15) N- (4-Amino-3-methylphenyl) -3- (hydroquinmethyl) pyrrolidine 16) N- (4-amino-3-methylphenyl) -3-pyrrolidinecarboxamide Among the p-phenylenediamine derivatives, particularly preferred Illustrative compounds 5), 6), 7), 8) and 12), among which exemplary compounds 5) and 8) are preferred. These p-phenylenediamine derivatives are in the form of salts such as sulfates, hydrochlorides, sulfites, naphthalene disulfonates, p-toluenesulfonates, or free base types (also referred to as free forms). The concentration of the aromatic primary amine developing agent in the working solution is preferably 2 mmol to 200 mmol, more preferably 6 mmol to 100 mmol, and particularly preferably 10 mmol to 40 mmol per liter of the developing solution.

  The color developer used in the present invention preferably contains a preservative to reduce the disappearance of the color developing agent due to oxidation. Representative preservatives include hydroxylamine derivatives. Examples of the hydroxylamine derivatives that can be used in the present invention include hydroxylamine salts such as hydroxylamine sulfate and hydroxylamine hydrochloride, as well as JP-A-1-97953, 1-186939, 1-186940, Although the hydroxylamine derivative described in 1-187557 etc. can be used, the hydroxylamine derivative represented with the following general formula [A] is especially preferable.

  In the above general formula [A], L represents an alkylene group which may be substituted, and A represents a carboxyl group, a sulfo group, a phosphono group, a phosphine group, a hydroxyl group, an amino group which may be alkyl-substituted, or an alkyl-substituted group. Represents an ammonio group which may be substituted, a carbamoyl group which may be substituted with alkyl, a sulfamoyl group which may be substituted with alkyl, an alkylsulfonyl group, a hydrogen atom, an alkoxyl group, or —O— (B—O) n—R ′; , R ′ each represents a hydrogen atom or an optionally substituted alkyl group. B represents an alkylene group which may be substituted, and n represents an integer of 1 to 4.

  In the general formula [A], L is preferably a linear or branched alkylene group having 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms. Specifically, groups such as methylene, ethylene, trimethylene and propylene are preferred examples. Examples of the substituent include a carboxyl group, a sulfo group, a phosphono group, a phosphine group, a hydroxyl group, and an ammonio group that may be alkyl-substituted, and preferred examples include a carboxyl group, a sulfo group, a phosphine group, and a hydroxyl group. A represents a carboxyl group, a sulfo group, a phosphono group, a phosphine group, a hydroxyl group, or an amino group, an ammonio group, a carbamoyl group, or a sulfamoyl group, each of which may be alkyl-substituted. Preferred examples include a carbamoyl group which may be substituted with a group or an alkyl group. As examples of -LA, carboxymethyl group, carboxyethyl group, carboxypropyl group, sulfoethyl group, sulfopropyl group, sulfobutyl group, phosphonomethyl group, phosphonoethyl group, and hydroxyethyl group can be mentioned as preferred examples. The group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group, phosphonoethyl group can be mentioned as particularly preferred examples. R is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, particularly preferably having 1 to 5 carbon atoms. Examples of the substituent include a carboxyl group, a sulfo group, a phosphono group, a phosphinic acid group, a hydroxyl group, or an amino group, an ammonio group, a carbamoyl group, a sulfamoyl group, an alkoxyl group, -O- (B -O) n-R 'and the like. B and R ′ are synonymous with those described in the description of A. There may be two or more substituents. Preferred examples of R include a hydrogen atom, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a phosphonomethyl group, a phosphonoethyl group, and a hydroxyethyl group. The group, carboxyethyl group, sulfoethyl group, sulfopropyl group, phosphonomethyl group, phosphonoethyl group can be mentioned as particularly preferred examples. L and R may be linked to form a ring.

  Although the typical compound example is shown below among the compounds represented by general formula [A], this invention is not limited to these compounds.

  Further, it is also preferable to use sulfite as a preservative, and the concentration thereof is preferably 0.005 to 1.0 mol / L in the color developer for color negative film, and in the color developer for color paper, 0 to 0.1 mol / L is preferable. Examples of sulfites that can be used in the present invention include sodium sulfite, potassium sulfite, and ammonium sulfite.

  In the color developer, in addition to the preservative according to the present invention described above, use of the preservative shown below is not limited. Hydroxamic acids, hydrazides, phenols, α-hydroxy ketones, α-amino ketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds And condensed amines. These are disclosed in JP-A 63-4235, 63-30845, 63-21647, 63-44655, 63-53551, 63-43140, 63-56654, 63- 58346, 63-43138, 63-146041, 63-44657, 63-44656, U.S. Pat.Nos. 3,615,503, 2,494,903, JP-A 52- No. 143,020, Japanese Patent Publication No. 4,830,496 and the like.

  In addition, various metals described in JP-A-57-44148 and JP-A-57-53749, salicylic acids described in JP-A-59-180588, triethanolamine, and triisopananolamine The alkanolamines described in US Pat. No. 54-3532, aromatic polyhydroxy compounds described in US Pat. No. 3,746,544 and the like may be contained as necessary.

  The color developer used in the present invention is preferably 9.0 or more and 13.5 or less, more preferably 9.5 or more and 12.0 or less, and an alkaline agent and a buffer so that the pH value can be maintained. Agents and optionally acids can be included.

  From the viewpoint of maintaining the pH when the color developing solution is prepared, it is preferable to use the buffer shown below. Examples of the buffer include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4- Dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroquinaminomethane salt, lysine salt, and the like can be used. Carbonate, phosphate, tetraborate, and hydroxybenzoate are particularly excellent in buffering ability in a high pH range of pH 10.0 or higher, and even when added to a color developer, they adversely affect photographic performance (capriformation). Etc.) and a preferable buffer from the viewpoint of being inexpensive.

  Exemplary compounds of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate , Sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) And potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the present invention is not limited to these compounds.

  These buffers are preferably 0.01 to 2 mol, more preferably 0.1 to 0.5 mol, per liter of color developer.

  As the other components, for example, calcium and magnesium precipitation inhibitors and various chelating agents that are also stability improvers can be added to the color developer used in the present invention. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ′, N′-tetramethylenesulfonic acid, transsirohexasidiaminetetraacetic acid, 1,2-diaminopropan tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, ethylenediamine disuccinic acid (SS form), N- (2-carboxylateethyl) -L-aspartic acid, β-alanine diacetic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N′-bis (2-hydroxybenzyl) ethylenediamine-N, N′-diacetic acid, 1,2 -Dihydroxybenzene-4,6-disulfonic acid and the like It is. These chelating agents may be used in combination of two or more as required. Further, the amount of these chelating agents may be an amount sufficient to sequester metal ions during color developer processing. For example, 0. 1 per liter. It is added so as to be about 1 to 10 g.

  If necessary, an arbitrary development accelerator can be added to the color developer used in the present invention. Examples of the development accelerator include JP-B-37-16088, JP-A-37-5987, JP-A-38-7826, JP-A-44-12380, JP-A-45-9019, and U.S. Pat. No. 3,813,247. Or neo ether compounds represented in the specification, p-phenylenediamine compounds represented in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B 44-30074 Quaternary ammonium salts, U.S. Pat. Nos. 2,494,903, 3,128,182, and 4,230,796, which are described in JP-A-56-156826 and JP-A-52-43429. No. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Pat. Nos. 2,482,546, 2,596,926, and 3,582,346, etc. Amine compounds described in the report or specification, Japanese Patent Publication No. 37-16088, Japanese Patent Publication No. 42-25201, US Pat. No. 3,128,183, Japanese Patent Publication No. 41-11431, Japanese Patent Publication No. 42-23883, and US Pat. Polyalkylene oxide, other 1-phenyl-3-virazolitones or imidazoles represented in each publication or specification such as 3,532,501 can be added as necessary. Their concentration is preferably 0.001 to 0.2 mol, more preferably 0.01 to 0.05 mol, per liter of the color developer.

  In addition to halogen ions, an optional antifoggant can be added to the color developer as required. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 -Representative examples include nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

  In addition, a fluorescent whitening agent can be used in the color developer used in the present invention, if necessary. As the optical brightener, a bis (triazinylamino) stilbene sulfonic acid compound is preferred. As the bis (triazinylamino) stilbene sulfonic acid compound, a known or commercially available diaminostilbene-based auto-enhancing agent can be used. As the known bis (triazinylamino) stilbene sulfonic acid compound, for example, compounds described in JP-A-6-329936, JP-A-7-140625, JP-A-10-14049 and the like are preferable. Commercially available compounds are described, for example, in “Dyeing Note”, 9th edition (Colored Dyeing), pages 165 to 168, and among the compounds described therein, Blankophor BSU liq. And Hakkol BRK.

  As other bis (triazinylamino) stilbene sulfonic acid compounds, compounds I-1 to I-48 and JP-A-2001-2001 described in paragraphs [0038] to [0049] of JP-A No. 2001-281823 are disclosed. The compounds II-1 to II-16 described in paragraph Nos. [0050] to [0052] of JP-A-281823 can also be mentioned. The addition amount of the above-described optical brightener is preferably 0.1 to 0.1 mol per liter of color developer.

When bromine ions are contained in the color developing solution for color paper, it is preferably 1.0 × 10 ⁻³ mol / liter or less. The color developing solution for color paper preferably contains chlorine ions of 3.5 × 10 ^{−2 to} 1.5 × 10 ⁻¹ mol / liter, but chlorine ions are usually developed as a by-product of development. Since it is released into the liquid, it may not be necessary to add to the replenisher.

In the present invention, the processing temperature of color development that can be applied by the processing method is preferably 30 to 55 ° C., more preferably 35 to 35 ° C., when the silver halide color photographic light-sensitive material to be developed is color paper. It is 55 degreeC, More preferably, it is 38-45 degreeC. The color development processing time is preferably from 5 to 90 seconds, more preferably from 15 to 60 seconds. The replenishment amount is preferably small, but 15 to 600 ml per 1 m ^{2 of} the light-sensitive material is suitable, preferably 15 to 120 ml, particularly preferably 30 to 60 ml. In the present invention, the color development time refers to the time from when the photosensitive material enters the color developer to the next processing step (for example, bleach-fixing solution). When processed by an automatic developing machine or the like, the time during which the photosensitive material is immersed in the color developer (so-called submerged time) and the photosensitive material leave the color developer, and the solution is prepared for the next processing step. The total of both the time for transporting outside (so-called crossover time) is called color development time. The crossover time is preferably 10 seconds or less, more preferably 5 seconds or less.

  In the present invention, any bleaching agent may be used as the bleaching agent used in the bleaching solution or the bleach-fixing solution. Particularly, an organic complex salt of iron (III) (for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid). Aminopolycarboxylic acids such as cyclohexanediaminetetraacetic acid and ethylenediaminedisuccinic acid, complex salts such as aminopolyphosphonic acid, phosphonocarboxylic acid and organic phosphonic acid) or organic acids such as citric acid, tartaric acid and malic acid; persulfates Hydrogen peroxide is preferred.

  Of these, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, ethylenediaminedisuccinic acid, and iron (III) complex salt of methyliminodiacetic acid are preferred because of their high bleaching power. These ferric ion complex salts may be used in the form of complex salts or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, and phosphonocarboxylic acid may be used to form a ferric ion complex salt in a solution. Moreover, you may use a chelating agent in excess rather than forming a ferric ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferable, and the addition amount is preferably 0.01 to 1.0 mol / liter, more preferably 0.05 to 0.50 mol / liter.

  In the bleaching solution or the bleach-fixing solution, various compounds can be used as a bleaching accelerator. For example, a compound having a mercapto group or disulfide bond described in Research Disclosure No. 17129 (July 1978), a thiourea compound, or a halide such as iodine or bromine ion is preferable in terms of excellent bleaching power. .

  In addition, the bleaching solution or the bleach-fixing solution may contain a rehalogenating agent such as bromide (for example, potassium bromide), chloride (for example, potassium chloride) or iodide (for example, ammonium iodide). One or more inorganic acids with pH buffering capacity such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, citric acid, sodium citrate, tartaric acid, succinic acid, maleic acid, glycolic acid Organic acids and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

  Fixing agents used in the fixing solution or the bleach-fixing solution are known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene bisthioglycolic acid Water-soluble silver halide solubilizers such as thioether compounds such as 3,6-dithia-1,8-octanediol and thioureas can be used singly or in combination of two or more. In the present invention, it is preferable to use thiosulfuric acid, particularly ammonium thiosulfate. The amount of the fixing agent per liter is preferably 0.1 to 5.0 mol, more preferably 0.3 to 2.0 mol. The pH range of the bleach-fixing solution or the fixing solution is preferably from 3 to 10, more preferably from 5 to 9.

  In addition, the bleaching solution, the fixing solution, and the bleach-fixing solution may contain various other kinds of fluorescent whitening agents, antifoaming agents or surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

  Bleaching solutions, fixing solutions, bleach-fixing solutions are sulphites as preservatives, for example, sodium sulfite, potassium sulfite, ammonium sulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, metabisulfite. Addition of ammonium sulfate or the like is common, but in addition, ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, or the like may be added.

  Furthermore, you may add a buffering agent, a fluorescent whitening agent, a chelating agent, an antifoamer, an antifungal agent, etc. as needed. The ammonium cation concentration in the bleaching solution, the fixing solution, and the bleach-fixing solution is preferably 50 mol% or less with respect to the total cations from the viewpoint of workability, but from the viewpoint of processability, the ammonium cation concentration is 50 mol% or more. It is preferable that there is.

In the present invention, the time required for the bleach-fixing step that can be applied to the method for processing a silver halide color photographic light-sensitive material is preferably 90 seconds or less, more preferably 45 seconds or less. The time required for the bleach-fixing step here refers to the time from when the photosensitive material is immersed in the first tank until it leaves the final tank when the process has a plurality of tanks. It refers to the time until the photosensitive material is immersed in the subsequent rinsing or stabilizing solution, and includes the crossover time therebetween. The crossover time is preferably 10 seconds or less, more preferably 5 seconds or less. Also. The temperature of the bleach-fixing solution is preferably 20 to 70 ° C, and desirably 25 to 50 ° C. Further, the replenishment rate of the bleach-fixing solution is preferably 200 ml / m ² or less, and more preferably ^{20ml / m 2 ~100ml / m 2} .

The replenishment rate of the bleaching treatment solution is preferably 200 ml / m ² or less, and more preferably ^{50ml / m 2 ~200ml / m 2} . The total processing time of the bleaching step is preferably 15 seconds to 90 seconds. The time required for the bleaching step here refers to the time from when the photosensitive material is immersed in the first tank until it leaves the final tank when the process has a plurality of tanks. It refers to the time until the photosensitive material is immersed in the rinse or stabilizing solution, and includes the crossover time between them. The crossover time is preferably 10 seconds or less, more preferably 5 seconds or less. Moreover, it is preferable that processing temperature is 25 degreeC-50 degreeC. The replenishment rate of the fixing treatment solution is preferably 600 ml / m ² or less, and more preferably ^{20ml / m 2 ~500ml / m 2} . The total processing time of the fixing process is preferably 15 seconds to 90 seconds. The time required for the fixing process here refers to the time from when the photosensitive material is immersed in the first tank until it exits the final tank when the process has a plurality of tanks. It refers to the time until the photosensitive material is immersed in the rinse or stabilizing solution, and includes the crossover time between them. The crossover time is preferably 10 seconds or less, more preferably 5 seconds or less. Moreover, it is preferable that processing temperature is 25 degreeC-50 degreeC.

  Next, the rinsing or stabilizing process and the treatment liquid used therein will be described.

  Rinsing or stabilizing solution used in the stabilization step includes chelating agents (ethylenediamine tetraacetic acid, diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, etc.), buffering agents (potassium carbonate, borate, acetate, Phosphates, etc.), antifungal agents (Dearside 702 (made by Dearborn, USA), p-chloro-m-cresol, benzoisothiazolin-3-one, etc.), fluorescent brighteners (triazinyl stilbene compounds, etc.) ), Antioxidants (ascorbate, etc.), water-soluble metal salts (zinc salt, magnesium salt, etc.), and the like, which are usually contained in a stable solution, can be used as appropriate.

Further, the rinse or stabilizing solution may contain arylsulfinic acid such as p-toluenesulfinic acid and m-carboxybenzenesulfinic acid from the viewpoint of liquid storage stability, and may contain sulfite, bisulfite or metabisulfite. It is preferable to contain a salt. Any organic or inorganic substance may be used as long as it releases sulfite ions, but inorganic salts are preferred. Preferred specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and the like. These salts are preferably added in an amount of at least 1 × 10 ⁻³ mol / L or more, more preferably 5 × 10 ⁻³ mol / L to 5 × 10 ⁻² mol / L in the stabilizing solution. It is added to become L.

  4-10 are preferable and, as for the preferable pH of a stabilization process, More preferably, it is 5-8.

  The temperature of the stabilization step can be variously set depending on the use and characteristics of the silver halide color photographic light-sensitive material to be processed, but is generally preferably 15 to 45 ° C, more preferably 20 to 40 ° C. Although the time can be set arbitrarily, a shorter time is desirable from the viewpoint of reducing the processing time. The time is preferably 5 seconds to 1 minute 45 seconds, more preferably 10 seconds to 1 minute. However, when the silver halide color photographic light-sensitive material is color paper, the time required for the stabilization processing step is 8 to 26 seconds. In addition, when the silver halide color photographic light-sensitive material is a color negative film, the time required for the stabilization process is preferably 10 to 40 seconds.

  A smaller replenishment amount is preferable from the viewpoint of running cost, reduction of discharge amount, handling property, and the like.

A specific preferable replenishing amount is preferably 0.5 to 50 times, more preferably 3 to 40 times the amount of silver halide color photographic light-sensitive material, which is brought from the previous bath per unit area. Alternatively, the amount is preferably 1 liter or less per 1 m ^{2 of} silver halide color photographic light-sensitive material, more preferably 500 ml or less. The replenishment may be performed continuously or intermittently.

  In the treatment method according to the present invention, the structure of the stabilization process using the stabilizing liquid may be composed of one tank or may be composed of two or more layers, preferably two or more tanks. It is preferable to use a multistage countercurrent system constituted by:

  Multi-stage counter-current system is a method of conveying silver halide photographic light-sensitive materials in a stabilizing tank divided into a plurality of stages, while the stabilizing solution overflows into each multi-stage divided stabilizing tank from the downstream to the upstream in the conveying direction of the photosensitive material. It is a system that flows along the road and performs a stabilization process.

The development processing apparatus used for processing the silver halide color photographic light-sensitive material of the present invention fixes the light-sensitive material to the belt even if it is a roller transport type that conveys the light-sensitive material sandwiched between rollers arranged in a processing tank. It may be an endless belt system that conveys
From the viewpoint of exhibiting the objective effects of the present invention, it is preferable to use a roller transport type in which the silver halide color photographic light-sensitive material cut into a sheet is conveyed by being sandwiched between rollers.

  In addition, as the processing tank, the processing tank is formed in a slit shape, and the processing liquid is supplied to the processing tank and the photosensitive material is transported, the spraying method of spraying the processing liquid, and the processing liquid is impregnated. A web system using contact with a carrier, a system using a viscous treatment liquid, or the like can also be used. In the case of processing in large quantities, it is normal that the running processing is performed using an automatic processor. In this case, the replenishing amount of the replenisher is preferably as small as possible, and the most preferable processing form in view of environmental suitability is the tablet as a replenishing method. The method described in the published technique 94-16935 is most preferable.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, it is not limited to this.
<Production of photosensitive material>
<< Preparation of silver halide emulsion >>
[Preparation of silver halide emulsion (B-1)]
While stirring vigorously using a mixing and stirring apparatus described in JP-A-62-160128, a double ion exchange treated ossein gelatin (calcium content 10 ppm) 2% gelatin aqueous solution kept at 40 ° C. Using the jet method, the following (A1 liquid) and (B1 liquid) were simultaneously added over 17 minutes while controlling pAg = 7.3 and pH = 3.0. Subsequently, the following (A2 solution) and (B2 solution) were simultaneously added over 90 minutes while controlling pAg = 8.0 and pH = 5.5. Furthermore, the following (A3 liquid) and (B3 liquid) were simultaneously added over 15 minutes, controlling pAg = 8.0 and pH = 5.5. At this time, the pAg was controlled by the method described in JP-A-59-45437, and the pH was controlled and adjusted using sulfuric acid or an aqueous sodium hydroxide solution.

(A1 solution)
Sodium chloride 3.42g
Potassium bromide 0.021g
Water was added to make up to 200 ml.

(A2 liquid)
Sodium chloride 72.0g
K ₂ [IrCl ₆ ] 4.8 × 10 ⁻⁹ mol / mol AgX
K ₂ [IrBr ₆ ] 3.2 × 10 ⁻⁹ mol / mol AgX
K ₂ [IrCl ₅ (H ₂ O)] 2.9 × 10 ⁻⁷ mol / mol AgX
K ₂ [IrCl ₅ (thiazole)] 1.6 × 10 ⁻⁸ mol / mol AgX
K ₄ Fe (CN) ₆ 8.0 × 10 ⁻⁶ mol / mol AgX
Potassium bromide 0.44g
Water was added to make 420 ml.

(A3 liquid)
Sodium chloride 30.7g
Potassium bromide 0.63g
Water was added to make 180 ml.

(B1 solution)
Silver nitrate 10g
Water was added to make up to 200 ml.

(B2 liquid)
210g silver nitrate
Water was added to make 420 ml.

(B3 liquid)
90g silver nitrate
Water was added to make 180 ml.

  After completion of the addition, a 15% aqueous solution containing 30 g of chemically modified gelatin (modified rate of 95%) in which the amino group is phenylcarbamoylated is added using the method described in JP-A-5-72658, and then desalted. A silver halide emulsion (B-1) having an average grain size of 0.70 μm was prepared by mixing with an aqueous solution.

[Preparation of silver halide emulsion (G-1)]
In the preparation of the silver halide emulsion (B-1), K ₂ [IrCl ₆ ], K ₂ [IrBr ₆ ], K ₂ [IrCl ₅ (H ₂ O)], K ₂ [IrCl] in (A2 liquid) ₅ (thiazole)] and the amount of K ₄ Fe (CN) ₆ were each changed to 2.0 times, and (A1 solution), (A2 solution), (A2a solution), (A3 solution), (B1 solution) ), (B2 solution), and (B3 solution), except that the addition time was appropriately changed, to prepare a silver halide emulsion (G-1) having an average grain size of 0.55 μm.

[Preparation of silver halide emulsion (GG-1)]
In the preparation of the silver halide emulsion (B-1), K ₂ [IrCl ₆ ], K ₂ [IrBr ₆ ], K ₂ [IrCl ₅ (H ₂ O)], K ₂ [IrCl] in (A2 liquid) ₅ (thiazole)] and the amount of K ₄ Fe (CN) ₆ were each changed to 3.8 times, and (A1 solution), (A2 solution), (A2a solution), (A3 solution), (B1 solution) ), (B2 solution), and (B3 solution), except that the addition time was appropriately changed, to prepare a silver halide emulsion (GG-1) having an average grain size of 0.43 μm.

[Preparation of silver halide emulsion (R-1)]
In the preparation of the silver halide emulsion (B-1), K ₂ [IrCl ₆ ], K ₂ [IrBr ₆ ], K ₂ [IrCl ₅ (H ₂ O)], K ₂ [IrCl] in (A2 liquid) ₅ (thiazole)] and K ₄ Fe (CN) ₆ are each changed to 4.5 times, and (A1 solution), (A2 solution), (A2a solution), (A3 solution), (B1 solution) ), (B2 solution), and (B3 solution), except that the addition time was appropriately changed, to prepare a silver halide emulsion (R-1) having an average grain size of 0.43 μm.

[Preparation of silver halide emulsion (RR-1)]
In the preparation of the silver halide emulsion (B-1), K ₂ [IrCl ₆ ], K ₂ [IrBr ₆ ], K ₂ [IrCl ₅ (H ₂ O)], K ₂ [IrCl] in (A2 liquid) ₅ (thiazole)] and K ₄ Fe (CN) ₆ were changed to 8.0 times each, and (A1 solution), (A2 solution), (A2a solution), (A3 solution), (B1 solution) ), (B2 solution), and (B3 solution), except that the addition time was appropriately changed, to prepare a silver halide emulsion (RR-1) having an average grain size of 0.40 μm.

  In each silver halide emulsion prepared as described above, cubic silver halide grains accounted for 99% or more of the number of silver halide grains.

<Preparation of blue-sensitive silver halide emulsion>
[Preparation of blue-sensitive silver halide emulsion (B-1a)]
To the silver halide emulsion (B-1) prepared above, the following sensitizing dyes BS-1 and BS-2 were added at 60 ° C., pH 5.8, and pAg 7.5, followed by sodium thiosulfate and trifurylphosphine. Selenide and chloroauric acid were sequentially added to perform spectral and chemical sensitization. After the chemical sensitizer is added and optimally ripened, the compounds (S-1), (S-2), and (S-3) are sequentially added to stop the ripening, and the blue-sensitive silver halide emulsion (B -1a) was obtained.

Sodium thiosulfate 3.9 × 10 ⁻⁶ mol / mol AgX
Trifurylphosphine selenide 2.6 × 10 ⁻⁶ mol / mol AgX
Chloroauric acid 1.9 × 10 ⁻⁵ mol / mol AgX
Compound (S-1) 2.0 × 10 ⁻⁴ mol / mol AgX
Compound (S-2) 2.0 × 10 ⁻⁴ mol / mol AgX
Compound (S-3) 2.0 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: BS-1 5.2 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: BS-2 1.3 × 10 ⁻⁴ mol / mol AgX
<< Preparation of green sensitive silver halide emulsion >>
[Preparation of green-sensitive silver halide emulsion (G-1a)]
The following sensitizing dye (GS-1) is added to the silver halide emulsion (G-1) at 60 ° C., pH 5.8, and pAg 7.5, and then sodium thiosulfate, trifurylphosphine selenide and chloride. Gold acid was sequentially added to perform spectral sensitization and chemical sensitization. After the chemical sensitizer was added and optimally ripened, the compound (S-1) was added to stop the ripening to obtain a green sensitive silver halide emulsion (G-1a).

Sensitizing dye: GS-1 5.3 × 10 ⁻⁴ mol / mol AgX
Sodium thiosulfate 3.3 × 10 ⁻⁶ mol / mol AgX
Trifurylphosphine selenide 2.2 × 10 ⁻⁶ mol / mol AgX
Chloroauric acid 1.5 × 10 ⁻⁵ mol / mol AgX
Compound (S-1) 1.5 × 10 ⁻⁴ mol / mol AgX
[Preparation of green-sensitive silver halide emulsion (GG-1a)]
In the preparation of the green-sensitive silver halide emulsion (G-1a), the silver halide emulsion (GG-1) was replaced with the silver halide emulsion (GG-1) prepared above, and sodium thiosulfate, Silver halide accompanying the addition of trifurylphosphine selenide, chloroauric acid, and sensitizing dye (GS-1) when the average grain size of silver halide grains is changed from 0.55 μm to 0.43 μm A green-sensitive silver halide emulsion (GG-1a) was prepared in the same manner except that the addition amount per unit surface area was changed in consideration of the increase in grain surface area.

<< Preparation of red-sensitive silver halide emulsion >>
[Preparation of red-sensitive silver halide emulsion (R-1a)]
The following sensitizing dyes (RS-1) and (RS-2) were added to the silver halide emulsion (R-1) at 60 ° C., pH 5.0, and pAg 7.1, followed by sodium thiosulfate, Furylphosphine selenide and chloroauric acid were sequentially added to give spectral and chemical sensitization. After the chemical sensitizer was added and optimally ripened, compound (S-1) was added to stop ripening, and a red-sensitive silver halide emulsion (R-1a) was prepared.

Sodium thiosulfate 7.2 × 10 ⁻⁶ mol / mol AgX
Trifurylphosphine selenide 4.8 × 10 ⁻⁶ mol / mol AgX
Chloroauric acid 1.5 × 10 ⁻⁵ mol / mol AgX
Compound (S-1) 1.2 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-1 1.0 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye: RS-2 1.0 × 10 ⁻⁴ mol / mol AgX
[Preparation of red-sensitive silver halide emulsion (RR-1a)]
In the preparation of the red-sensitive silver halide emulsion (R-1a), the silver halide emulsion (RR-1) prepared above was used instead of the silver halide emulsion (R-1), and sodium thiosulfate, The addition amount of furylphosphine selenide, chloroauric acid, sensitizing dye (RS-1) and sensitizing dye (RS-2) was changed from 0.43 μm to 0.40 μm in the average grain size of silver halide grains. In consideration of the increase in the surface area of the silver halide grains accompanying the formation of the red-sensitive silver halide emulsion (RR-1a), except that each addition amount was changed so that the addition amount per unit surface area was the same. ) Was prepared.

In the preparation of each red-sensitive silver halide emulsion, 2.0 × 10 ⁻³ mol / mol AgX of SS-1 was added at the end of the preparation.

<< Preparation of silver halide color photographic material >>
[Preparation of Sample 101]
High-density molten polyethylene containing anatase-type titanium oxide dispersed in a content of 15% by mass is laminated on the photosensitive layer coated surface of paper pulp having a basis weight of 180 g / m ² , and the back surface has a high density. A silver halide color photographic light-sensitive material is formed by subjecting a reflective support laminated with polyethylene to corona discharge treatment, and then providing a gelatin subbing layer and further coating each photographic constituent layer having the constitution shown in Tables 1 and 2. Sample 101 was prepared. In addition, the silver halide emulsion described in the table is represented by a value converted to silver.

In addition, a surfactant (SU-2) is used for preparing a coupler dispersion of each layer, and surfactants (SU-1) and (SU-3) are used as coating aids for adjusting the surface tension of each constituent layer. Was added. Moreover, the antifungal agent (F-1) was added to each layer so that the whole quantity might be set to 0.04 g / m < ² >. In addition, hardening agents (H-1), (H-2), dyes (AI-1), (AI-2), (AI-3) and additive-1 were added as appropriate.

  Details of each additive used for preparation of the sample 101 are as follows.

Sol-1: tricresyl phosphate Matting agent 1: SiO ₂ (average particle diameter: 3.0 μm)

[Production of Sample 102]
In the preparation of the silver halide emulsion (B-1), the addition conditions of (A1 liquid) and (B1 liquid) were adjusted to prepare a silver halide emulsion having an average grain diameter of 0.60 μm,
Spectral sensitization and chemical sensitization were performed in the same manner as the blue-sensitive silver halide emulsion (B-1a), and after addition of chemical sensitizers and optimal ripening, compounds (S-1) and (S-2) , (S-3) are sequentially added to stop ripening, and the blue-sensitive silver halide emulsion (B-2a) prepared in the same manner is used instead of the blue-sensitive silver halide emulsion (B-1a). A sample 102 was produced.

[Production of Sample 103]
In preparing the silver halide emulsion (B-1), after adjusting the addition conditions of (A1 solution) and (B1 solution) to prepare a silver halide emulsion having an average grain size of 0.50 μm,
Spectral sensitization and chemical sensitization were performed in the same manner as the blue-sensitive silver halide emulsion (B-1a), and after addition of chemical sensitizers and optimal ripening, compounds (S-1) and (S-2) , (S-3) are sequentially added to stop ripening, and the blue-sensitive silver halide emulsion (B-3a) prepared in the same manner is used instead of the blue-sensitive silver halide emulsion (B-1a). Thus, a sample 103 was manufactured.

  Following the average particle diameter (μm) of silver halide grains contained in the Y coloring layer of each of the samples 101 to 103 used in Table 3 and digital exposure to each sample (digital exposure steps (1) and (2)) After the development processing, when exposure is given so that the status A density at one point on each step chart in each sample is reproduced to be 1.0 for each BGR, after the development processing (development processing step (2)), the status A The gamma value estimated from the density and obtained by the average value of each of gamma values of B, G, and R is shown.

  Using the produced photosensitive material samples 101 to 103, digital exposure and development processing were combined in the following manners (Examples 1 to 7).

Digital exposure process (1):
Digital exposure with a resolution of 400 dpi was performed by using Lambda 76 manufactured by Durst and scanning and exposing each laser beam of RGB light with a polygon mirror. In the exposure with Lambda 76, the exposure amount of the machine is obtained using a photosensitive material whose exposure amount is known, a sensitometric density curve with respect to the exposure amount is drawn from the step chart, and the unexposed one pixel width drawn in the step chart The minimum density of the fine line was obtained, and the exposure amount of +0.1 LogE was determined as the maximum exposure amount from the exposure amount at which the difference between the step chart density and the minimum density of the fine line was the largest (see FIG. 4).

Digital exposure process (2):
LED light was guided to the PLZT array element with an optical fiber and exposed to a resolution of 400 dpi on one line. The exposure was performed by sequentially switching the LED light of RGB for one pixel (the apparatus described in FIGS. 1 to 3 was used). Similarly to the digital exposure step (1), the minimum density of the unexposed fine line having a width of one pixel drawn in the step chart is obtained, and the difference between the step chart density and the minimum density of the fine line is made the same. The maximum exposure value was determined.

Development processing step (1): (processing time is 45 seconds in liquid)
Using an RA-4RT type treatment kit manufactured by Eastman Kodack, the treatment was performed in a normal continuous treatment state (a state in which a prescribed treatment level was maintained by the RA-4 control strip).

<Processing process>
Processing temperature Processing time Tank capacity color development 35.0 ° C 45 seconds 50.0L
Bleach fixing 33.0 ° C 45 seconds 50.0L
Water washing-(1) 33.0 ° C 45 seconds 50.0L
Water washing-(2) 33.0 ° C 45 seconds 50.0L
Development processing step (2): (Processing time is the time of in-liquid + transit rack, 26 seconds in liquid)
The automatic developing machine manufactured by Konica Minolta Co., Ltd. was remodeled so that the processing conditions were as follows, and the photosensitive materials (101 to 103) prepared above were each subjected to imagewise exposure to perform continuous processing (running processing). In the processing, the automatic developing machine was operated for 12 hours a day, and the running amount was 0.1R in increments of 2R. 2R means that the color developer replenisher of twice the color developer tank capacity is replenished.

<Processing process>
Processing temperature Processing time Tank capacity Replenishment amount Color development 38.0 ° C 30 seconds 10.2L 50ml / m ²
Bleach fixing 38.0 ° C. 30 seconds 10.0 L 37 ml / m ²
Stabilization-(1) 38.0 ° C 24 seconds 8.0L
Stabilization-(2) 38.0 ° C 24 seconds 8.3L
Stabilization-(3) 38.0 ° C 24 seconds 8.6L
Stabilization- (4) 38.0 ° C. 24 seconds 9.0 L 150 ml / m ²
Drying 60 to 80 ° C. Stabilization for 30 seconds is a countercurrent system from (4) → (3) → (2) → (1).

  The tank liquid and replenisher are shown below.

(Color developer: per liter)
Tank liquid Replenisher diethylene glycol 10.0 g 10.0 g
Polyethylene glycol (average molecular weight 4000) 6.0 g 6.0 g
p-Toluenesulfonic acid 10.0 g 10.0 g
Potassium chloride 4.0 g −
Diethylenetriaminepentaacetic acid 6.0 g 6.0 g
Bis (triazinylamino) stilbene fluorescent whitening agent
1.0g 1.0g
N, N-bis (sulfoethyl) hydroxylamine 5.0 g 11.0 g
Lithium hydroxide-3.5g
Potassium carbonate 14.0g 14.0g
Sodium carbonate 10.0g 10.0g
4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline 2/3 sulfate 6.0 g 12.0 g
1-octane sodium sulfonate 1.0 g 1.0 g
pH 10.00 12.10
Water was added to 1 L, and the pH was adjusted with potassium hydroxide solution, sodium hydroxide solution or sulfuric acid.

(Bleaning fixer per liter)
Tank liquid Replenisher Ammonium ferric ammonium tetraacetate 0.20 mol 0.37 mol
Ammonium thiosulfate 0.54 mol 1.0 mol
Ammonium sulfite 0.15 mol 0.25 mol
Succinic acid 10.0g 18.0g
N-lauroyl sarcosine sodium 1.5g 1.5g
Nitric acid (67%) 10.0 g 16.0 g
pH 6.0 4.8
Water was added to 1 L, and the pH was adjusted with aqueous ammonia or sulfuric acid.

(Stabilizing liquid: per liter)
Tank liquid = replenisher 1-hydroxyethylidene-1,1-diphosphonic acid tetrasodium 2.0 g
Ethylenediaminetetraacetic acid disodium 2.0g
o-Phenylphenol 0.1g
Bis (triazinylamino) stilbene fluorescent whitening agent 1.0 g
Sodium sulfite 0.2g
Sodium benzenesulfinate (exemplary compound) 0.8g
1-octane sodium sulfonate 0.2g
pH 7.5
Water was added to 1 L, and the pH was adjusted using an aqueous ammonia solution or sulfuric acid.

Development processing step (3): (Processing time is the time of in-liquid + crossing rack, 26 seconds in liquid)
The development was carried out in the same manner as in the development processing step (2) except that the automatic processing machine manufactured by Konica Minolta Co., Ltd. was modified so that the processing conditions were as follows.

<Processing process>
Processing temperature Processing time Tank capacity Replenishment amount Color development 38.0 ° C 30 seconds 10.2L 50ml / m ²
Bleach fixing 38.0 ° C. 30 seconds 10.0 L 37 ml / m ²
Stabilization-(1) 38.0 ° C 24 seconds 8.3L
Stabilization-(2) 38.0 ° C 24 seconds 8.6L
Stabilization- (3) 38.0 ° C. 24 seconds 9.0 L 150 ml / m ²
Drying 60 to 80 ° C. Stabilization for 30 seconds is a countercurrent system from (3) → (2) → (1).

Development processing step (4): (Processing time is the time of in-liquid + transit rack, 19 seconds in liquid)
The development was carried out in the same manner as in the development processing step (2) except that the automatic processing machine manufactured by Konica Minolta Co., Ltd. was modified so that the processing conditions were as follows.

<Processing process>
Processing temperature Processing time Tank capacity Replenishment amount Color development 39.8 ° C 22 seconds 10.2L 50ml / m ²
Bleach fixing 38.0 ° C. 22 seconds 10.0 L 37 ml / m ²
Stabilization-(1) 38.0 ° C 18 seconds 8.0L
Stabilization-(2) 38.0 ° C 18 seconds 8.3L
Stabilization-(3) 38.0 ° C 18 seconds 8.6L
Stabilization- (4) 38.0 ° C. 18 seconds 9.0 L 150 ml / m ²
Drying 60 to 80 ° C. Stabilization for 22 seconds is a countercurrent system from (4) → (3) → (2) → (1).

  Samples 1 to 3 were processed by the exposure process and the development process shown in Table 2 to prepare development samples.

<< Evaluation Method 1 >>
From each image exposed and developed at the resolution of the step chart 400 dpi, the density of the maximum exposure area is X, and the minimum density of the unexposed fine line of one pixel width drawn in the maximum exposure area is 1.0. The maximum value of Y / X in the range of ≦ X ≦ 2.0 was determined.

  The minimum density of unexposed fine lines was measured as follows.

  About the obtained print, using a microdensitometer (PDM-5AR: manufactured by Konica Corporation), B, G, and R filters for status A concentration measurement (for example, blue B: Latten No. 98 + No. 98 + No. 2E, By replacing green G: Latten No. 74, red R: No. 29 + No. 25), the total magnification is 50 times, the aperture size is 400 × 4 μm, and the density is measured while scanning in the direction perpendicular to the fine line at 4 μm intervals. Concentration profiles of B, G and R components were obtained. The lowest density was obtained from this density profile, and the lowest density Y of the unexposed fine line having a width of one pixel drawn in the maximum exposure area was obtained.

Further, the black background and white background CIE and L ^* of each image were measured using a Minolta color meter CM-2022.

<< Evaluation Method 2 >>
Separately, prints of landscape images, portraits, character images, etc. were created, and the 20 items were given a relative evaluation of the three items “character reproducibility”, “shadow part description” and “highlight description”. I was asked to score and averaged. Also, the average value of the above three items was added to obtain the total image quality.

  According to the present invention, it can be seen that a print having a high overall image quality, which is excellent in the depiction of the high density portion and the highlight portion, has a high contrast ratio, and is excellent in character reproducibility can be obtained in a short time.

1 is a schematic configuration diagram of a digital printer according to the present invention. It is a perspective view of a PLZT chip. It is a schematic block diagram of an exposure head. A sensitometric curve of unexposed fine line density and chart density is shown.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Printer 2 Conveyance mechanism 3 Printing paper 4 Exposure mechanism 42 Exposure head 421 PLZT chip 422 Individual electrode 423 Common electrode 425 PLZT element 5 Light source color switching part 6 Driver IC
7 Transport drive unit 8 Exposure control unit

Claims (5)

In a method of forming a color image by a development processing step following a digital exposure step using a silver halide photographic light-sensitive material having at least three color development layers of a yellow color development layer, a magenta color development layer, and a cyan color development layer,
(1) The average grain size of the silver halide emulsion contained in the yellow color developing layer of the silver halide photographic light-sensitive material is 0.40 μm or more and 0.60 μm or less,
(2) The sensitometric gamma between the logarithm of the exposure amount giving the density of 1.0 and the logarithm of the exposure amount giving the density of 2.0 is 4.0 or more and 6.0 or less. ,
(3) When X is the density of the maximum exposure area when exposure is performed at a resolution of 400 dpi and development processing is performed, and Y is the minimum density of an unexposed fine line of 1 pixel width drawn in the maximum exposure area,
A color image forming method, wherein a relationship of 0.0 ≦ Y / X ≦ 0.6 is established in a range satisfying at least 1.0 ≦ X ≦ 2.0. 2. The color image forming method according to claim 1, wherein the digital exposure step is performed using an exposure head including a PLZT array element and R, G, and B LED light sources. The maximum exposure area of the color image is 0.0 ≦ L ^* ≦ 5.0 in the CIE 1976-L ^* a ^* b ^* color system, and the developed silver halide photographic light-sensitive material is subjected to development processing. The unexposed portion is 91.0 ≦ L ^* ≦ 96.0, 0.5 ≦ a ^* ≦ 1.5, −6.0 ≦ b ^* ≦ −3.0, or 3. A color image forming method according to 2. The development processing step comprises at least a color development step, a bleach-fixing step, and a water washing (stabilization) step, and the water washing (stabilization) step comprises at least four steps, and the water washing (stabilization). The color image forming method according to any one of claims 1 to 3, wherein a fluorescent brightening agent is contained in at least the final tank of the process. 5. The color image forming method according to claim 4, wherein the color development step has a processing time in liquid of 10 seconds to 30 seconds.

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