JP2005070576A - Silver halide color photosensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide color photosensitive material which ensures little coating trouble and improved temperature dependency in exposure of the sample after storage. <P>SOLUTION: In the silver halide color photosensitive material having on a reflective support at least one yellow developing photosensitive silver halide emulsion layer, at least one magenta developing photosensitive silver halide emulsion layer and at least one cyan developing photosensitive silver halide emulsion layer, a dye forming coupler contained in at least the yellow developing photosensitive silver halide emulsion layer is at least one represented by formula (a), the dye forming coupler is added as a coupler dispersion prepared by dissolving the dye forming coupler in a high-boiling-point solvent and a low-boiling-point solvent and dispersing the resulting solution in a hydrophilic colloidal aqueous solution, and a low-boiling-point solvent content of the coupler dispersion is set at 2-10 mass%. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a silver halide color light-sensitive material, and more particularly to a silver halide color light-sensitive material with less coating failure and improved temperature dependence upon exposure of a sample after storage.

  Silver halide color light-sensitive materials are frequently used today because of their high sensitivity (hereinafter also simply referred to as light-sensitive materials), excellent color reproducibility, and suitability for continuous processing. Because of these characteristics, silver halide color photosensitive materials are widely used not only in the field of photography but also in the field of printing, in the field of so-called color proofing for checking the state of the finished printed matter in the middle of printing. It has become to.

  In the field of color proofing, yellow (Y), magenta (M), and cyan (C) are output by outputting an image edited on a computer to a printing film and separating and exposing the developed film as appropriate. Each image is formed, and an image of the final printed matter is formed on color photographic paper, thereby determining the suitability of the layout and color of the final printed matter.

  On the other hand, plate making methods that convert an image into a digital signal and edit the image on a computer without using a black and white film of halftone dots have come to be widely used. By digitizing the image information, it is possible to quickly send an image to image processing, a remote place, or to quickly edit an image whose layout or color tone has been changed.

  In recent years, this proof has been used not only for plate inspection for confirming characters and patterns but also for inspection for confirming subtle shadows and hues. In the proof field, various printing conditions, printing machines, and the like are used, and it has been required to be usable in a wide range due to differences in the pattern of printed matter.

  For this purpose, various methods such as a sublimation type / melting heat transfer method, an electrophotographic method, and an ink jet method have been tried. However, a method capable of obtaining a high-quality image is expensive and inferior in productivity. On the other hand, the method with low cost and excellent productivity has the disadvantage that the image quality is inferior. A system using a silver halide color light-sensitive material enables high-quality image formation such as the formation of an accurate halftone dot image due to excellent sharpness and the like, and further enables continuous processing as described above. In addition, it has become possible to realize high productivity because of features such as simultaneous writing of images on a plurality of color image forming units.

  In recent years, so-called digitization has progressed in the field of printing, and the demand for obtaining images directly from data in computers has increased. For the reasons described above, silver halide photosensitive materials have begun to be used advantageously in this field.

  The most commonly used color image forming method in silver halide color light-sensitive materials is to react an oxidized aromatic primary amine color developing agent with a coupler using exposed silver halide as an oxidizing agent. To form indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine and similar dyes. In such a method, a method of reproducing a color image by a subtractive color method is used. In general, a color image is formed by changing the generation amounts of three colors of yellow, magenta, and cyan. Of these, acylacetanilide couplers are widely used as color developing couplers used for forming yellow dye images. A benzoylacetanilide type compound with good color development is favorably used as a photographic sensitive material, and a pivaloylacetanilide type compound with excellent color tone is favorably used as an ornamental sensitive material. The basic properties required for these couplers are not only to form a dye, but also to have excellent spectral absorption characteristics of the formed dye, a high dye forming speed, a high color density, and formation. It is desired that the dyes have various properties such as high fastness to light, heat and moisture. In particular, in recent years when high sensitivity and high image quality are required for photosensitive materials, development of couplers having high color density and high fastness to light of the formed dye is strongly demanded.

  Examples of yellow couplers with improved color reproducibility, high color development and light resistance include an alkoxy group at the 2-position of the anilide moiety as described in JP-A-63-123047, for example. And yellow couplers having an acylamino group at the position. However, these couplers inherently have high pKa, and improvements are desired in terms of color development.

  In conventional yellow dye-forming couplers, the color reproducibility and absorption coefficient of the dyes formed are small, and a large amount of couplers and silver halide are required to obtain the required color density, which increases the cost of the photosensitive material. However, there have been problems such as an increase in the film thickness of the photosensitive material and a decrease in the sharpness of the resulting color image.

  Also, light resistance is not sufficient, and an acetanilide type coupler in which pyrimidin-4-one in which an alkyl group having 1 to 6 carbon atoms is substituted with a nitrogen atom is bonded is disclosed as a coupler for solving this problem (Patent Document 1). ). As the leaving group of the coupler described in the patent, 1,2,3-triazole or 1,2,4-triazole is considered particularly preferable. In the light-sensitive material, it has been clarified that the preservation of the dark portion of the white background where the coupler remains, that is, the stain occurs.

  Furthermore, an acetanilide type coupler to which pyrimidin-4-one substituted with a substituted alkyl group is bonded (Patent Document 2), an acetanilide type coupler to which pyrimidin-4-one substituted with an aryl group or a heterocyclic group is bonded (Patent Document 3) , An acetanilide coupler to which a pyrimidin-4-one introduced with a divalent linking group such as a hetero atom is bonded (Patent Document 4), an acetanilide to which a pyrimidin-4-one substituted with an alkyl group having 7 or more carbon atoms is bonded A type coupler (Patent Document 5) has been proposed, and color reproducibility and light resistance are further improved.

  Further, the silver halide photographic light-sensitive material usually has a plurality of layers, and each coating solution is prepared and applied in multiple layers to coat each layer. Coupled with these coating solutions are water-insoluble organic compounds such as couplers useful for photography, UV absorbers, anti-turbidity agents, and anti-fading agents. These organic compounds are usually finely dispersed in the form of an oil-in-water dispersion and mixed with the coating solution. Upon fine dispersion, these organic compounds are dissolved in a high-boiling organic solvent or water-insoluble polymer in an oil form, and then added to an aqueous solution containing a hydrophilic colloid (protective colloid) such as gelatin. Is finely dispersed.

  On the other hand, in the production of photosensitive materials, the occurrence of coating failure leads to a decrease in yield, and therefore reduction of failures such as dots and streaks is required. When the above organic compound is dissolved in an oil form, an organic solvent having a low boiling point is usually added as an auxiliary solvent in order to assist the dissolution. However, if the auxiliary solvent is large, the coating failure such as streaks tends to occur due to this, and the low boiling organic solvent is often distilled off.

  In Patent Document 6, it is proposed to use an oil-in-water dispersion containing a specific compound and having a specific low-boiling organic solvent content for the purpose of improving coating failure. However, as a result of examining oil-in-water dispersions for photographic use containing such specific compounds and having a low low-boiling organic solvent, the coating failure can be reduced. There was a problem that the color density varied depending on the temperature.

Accordingly, as a result of various studies, the present inventor has used a specific dye-forming coupler and has a low boiling point solvent content in the dye-forming coupler dispersion of 2 to 10% by mass, so that the coating property and the exposure temperature are increased. As a result, the present inventors have found that the color density stability of the toner is improved.
US Pat. No. 5,455,149 JP 2002-296740 A JP 2002-296671 A JP 2002-318442 A JP 2002-318443 A Japanese Patent Laid-Open No. 10-90822

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a silver halide color light-sensitive material with less coating failure and improved temperature dependency upon exposure of a sample after storage.

The above object of the present invention has been achieved by the following constitution.
(Claim 1)
In a silver halide color light-sensitive material having at least one each of a yellow color-sensitive silver halide emulsion layer, a magenta color-sensitive silver halide emulsion layer, and a cyan color-sensitive silver halide emulsion layer on a reflective support. The dye-forming coupler contained in at least the yellow color-forming photosensitive silver halide emulsion layer is at least one represented by the following general formula (a), and the dye-forming coupler is used as a high-boiling solvent or a low-boiling solvent. It is added as a coupler dispersion dispersed in an aqueous hydrophilic colloid solution after being dissolved, and the low boiling point solvent content in the coupler dispersion is 2 to 10% by mass. Silver halide color light-sensitive material.

(In the general formula (a), R represents a substituent, and Z represents an atomic group necessary for forming a nitrogen-containing 6-membered ring or 7-membered ring together with the —N—C═N part. R ′ represents a substituent. N represents an integer of 0 to 4, X represents a hydrogen atom or a substituent, and A represents a hydrogen atom or a group that can be eliminated by coupling with an oxidized form of a color developing agent.
(Claim 2)
The silver halide color photographic material according to claim 1, wherein, in the general formula (a), Z is a 3H-pyrimidin-4-one ring or a 1H-pyrimidin-4-one ring residue.
(Claim 3)
In the general formula (a), Z is a 2H- [1,2,4] thiadiazine-1,1-dioxide ring or a 4H- [1,2,4] thiadiazine-1,1-dioxide ring residue. The silver halide color light-sensitive material according to claim 1.

  According to the present invention, it was possible to provide a silver halide color light-sensitive material having both coatability and temperature dependency upon exposure when storing a raw sample.

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

First, the dye-forming coupler represented by the general formula (a) will be described.
R in the general formula (a) represents a substituent, and the substituent represented by R is not particularly limited, but an alkyl group (for example, methyl group, isopropyl group, (t) butyl group, cyclohexyl group, dodecyl group) Etc.), alkenyl group (eg vinyl group, allyl group etc.), alkynyl group (eg propargyl group etc.), aryl group (eg phenyl group, naphthyl group etc.), heterocyclic group (eg pyridyl group, thiazolyl group etc.) Oxazolyl group, imidazolyl group, furyl group, pyrrolyl group, pyrazinyl group, selenazolyl group, sulfolanyl group, piperidinyl group, tetrazolyl group, etc.), halogen atom (eg, chlorine atom, fluorine atom etc.), alkoxy group (eg, methoxy group) Propyloxy group, pentyloxy group, cyclohexyloxy group, etc.), aryloxy group (for example, Phenoxy group, naphthyloxy group, etc.), heterocyclic oxy group (eg, pyridyloxy group, tetrahydropyranyloxy group, etc.), alkoxycarbonyl group (eg, ethyloxycarbonyl group, octyloxycarbonyl group, etc.), aryloxycarbonyl group (Eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfonamide group (eg, methylsulfonylamino group, ethylsulfonylamino group, cyclohexylsulfonylamino group, dodecylsulfonylamino group, phenylsulfonylamino group, etc.), sulfamoyl group (For example, aminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, octylaminosulfonyl group, phenylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), Raid groups (eg, methylureido group, ethylureido group, cyclohexylureido group, octylureido group, phenylureido group, naphthylureido group, etc.), acyl groups (eg, acetyl group, propylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group) 2-ethylhexylcarbonyl group, phenylcarbonyl group, pyridylcarbonyl group etc.), acyloxy group (eg acetyloxy group, ethylcarbonyloxy group, octylcarbonyloxy group, phenylcarbonyloxy group etc.), carbamoyl group (eg aminocarbonyl) Group, dimethylaminocarbonyl group, cyclohexylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group), Ruamino group (for example, methylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, 2-ethylhexylcarbonylamino group, dodecylcarbonylamino group, naphthylcarbonylamino group, etc.), alkylsulfonyl group or arylsulfonyl group (for example, ethyl Sulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, phenylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, 2-ethylhexylamino group, dodecyl) Amino group, anilino group, 2-pyridylamino group, etc.), cyano group, nitro group, sulfo group, carboxyl group, hydroxyl group, etc., and these groups are further substituted by the above substituents. It can have.

  The group represented by R is preferably an alkyl group or an aryl group, more preferably an alkyl group having 2 to 24 carbon atoms in total including a substituent further substituted on R, or similarly a total carbon number of 6 to 24 aryl groups. The group represented by R is more preferably an alkyl group having 2 to 18 carbon atoms in total including a substituent further substituted on R, or an aryl group having 6 to 18 carbon atoms in the same manner. Here, the group substituted for R may include a hetero atom, and the total number of carbon atoms does not include the number of hetero atoms.

  In general formula (a), the group represented by R ′ represents a substituent, and n represents an integer of 0 to 4. n is preferably 0-2.

  There is no restriction | limiting in particular as a substituent represented by R ', The group synonymous with the group quoted by R in General formula (a) can be mentioned. R ′ is preferably an acylamino group, a sulfonylamino group, an oxycarbonyl group and the like.

  X represents a hydrogen atom or a substituent. Examples of the substituent represented by X include the same groups as the substituent represented by R ′. X is preferably an alkoxy group, an aryloxy group, a halogen atom, an amino group, an acylamino group, a ureido group or a sulfonamide group, more preferably an alkoxy group, an aryloxy group, a halogen atom or an acylamino group.

  Z represents an atomic group necessary for forming a nitrogen-containing 6-membered ring or 7-membered ring together with the —N—C═N part.

  Examples of the nitrogen-containing 6-membered ring formed by Z include pyrimidin-4-one, 1,3-diazine-4,6-dione, [1,3,5] triazin-2-one, [1,2, 4) Triazin-5-one, [1,2,4] thiadiazine-1,1-dioxide and the like.

  Examples of the nitrogen-containing 7-membered ring formed by Z include 1,3-diazepin-4-one, 1,3-diazepin-5-one, [1,2,4] thiadiazepine-1,1-dioxide, [ 1,3,5] thiadiazepine-1,1-dioxide and the like.

Z is preferably a 6-membered ring, and a 6-membered ring is preferably a residue that forms a pyrimidin-4-one ring or a [1,2,4] thiadiazine-1,1-dioxide ring. That Z is _{-C (-R 2) = C (} -R 3) -CO-, or _{-C (-R 2) = C (} -R 3) -SO 2 - represented by. R ₂ and R ₃ are bonded to each other to form a 5- to 7-membered ring together with the —C═C— moiety, or each independently represents a hydrogen atom or a substituent. The ring formed by combining R ₂ and R ₃ together with the —C═C— moiety is preferably a 5- to 7-membered alicyclic, aromatic, or heterocyclic ring, such as a benzene ring, a pyrazole ring, a furan A ring, a thiophene ring, a cyclopentene ring, and a cyclohexene ring. More preferably, the ring is a 6-membered aromatic ring, most preferably a benzene ring. When R ₂ and R ₃ represent a substituent, these may be the same or different, and examples of the substituent include those listed as examples of the substituent represented by the aforementioned R ′. .

  In the general formula (a), A represents a hydrogen atom or a group that can be removed upon coupling with an oxidized form of a developing agent. Examples of the group capable of leaving upon coupling with the oxidized developer of the developing agent represented by A in the general formula (a) include, for example, a phenoxy group, an alkoxy group, an acyloxy group, a carbamoyl group, a sulfonyl group, or a nitrogen-containing complex. Examples thereof include a ring group (for example, imidazolyl group, pyrazolyl group, or hydantoinyl group). These groups represented by A can also have a substituent, and examples of the substituent include the same groups as those exemplified for the group represented by R in the general formula (a). More specifically, examples thereof include those having the same meaning as the group represented by W described in paragraphs (0033) to (0043) of JP-A-8-29932.

  Specific examples of the coupler represented by the general formula (a) of the present invention are shown below, but the present invention is not limited thereto.

  The coupler represented by the general formula (a) according to the present invention can be synthesized according to a method described in, for example, US Pat. No. 5,455,149, US Patent Publication No. 2003-64332, and the like.

The yellow coupler used in the light-sensitive material of the present invention can usually be used in the range of 1 × 10 ⁻³ mol to 1 mol, preferably 1 × 10 ⁻² mol to 8 × 10 ⁻¹ mol, per mol of silver halide. . The coupler of the present invention can be used in combination with other types of couplers. For the coupler used in the light-sensitive material of the present invention, the methods and techniques used in ordinary dye-forming couplers are similarly applied.

  As the magenta coupler used in the light-sensitive material according to the present invention, a compound represented by the general formula M-I or M-II described in JP-A-8-328210, page 2 is preferable. Specific examples of preferred compounds include MCP-1 to MCP-41 described on pages 6 to 16 of the same. As other specific examples, compounds M-1 to M-61 described in European Patent No. 0273712, pages 6 to 21 and compounds 1 to 223 described in JP 0235913, pages 36 to 92 are described above. There are other than the typical examples.

The magenta coupler can also be used in combination with other types of magenta couplers and is usually 1 × 10 ⁻³ mol to 1 mol, preferably 1 × 10 ⁻² mol to 8 × 10 ⁻¹ mol, per mol of silver halide. Can be used in a range.

The λmax of the spectral absorption of the magenta image formed in the photosensitive material according to the present invention is preferably ₅₃₀ to 560 nm, and λL0.2 is preferably 580 to 635 nm. λ _L0.2 is a wavelength at which the absorbance is 0.2 when the maximum absorbance is 1.0 in the spectral absorbance curve of the image dye, which is longer than the wavelength indicating the maximum absorbance. This amount is a measure indicating the magnitude of unnecessary absorption on the long wave side of the image dye, and indicates that the closer to λmax, the smaller the unnecessary absorption and the better.

  The magenta image forming layer of the silver halide light-sensitive material according to the present invention preferably contains a yellow coupler in addition to the magenta coupler. Preferred yellow couplers to be contained in the magenta image-forming layer of the light-sensitive material of the present invention include known pivaloyl acetanilide type or benzoylacetanilide type couplers. Specific examples of preferable yellow couplers to be contained in the magenta image-forming layer of the light-sensitive material of the present invention include couplers represented by YCP-1 to YCP-39 described in the right column on pages 6 to 15 of JP-A-8-314079. Of course, it is not limited to these.

  As the cyan coupler contained in the cyan image forming layer in the light-sensitive material according to the present invention, known phenol-based, naphthol-based or imidazole-based, and azole-based couplers can be used. For example, phenol couplers substituted with alkyl groups, acylamino groups, or ureido groups, naphthol couplers formed from a 5-aminonaphthol skeleton, and 2-equivalent naphthol couplers introduced with an oxygen atom as a leaving group are representative. The Among these, preferred compounds include general formulas [CI] and [C-II] described on page 13 of JP-A-6-95283.

  As the azole coupler, a pyrazoloazole coupler represented by the general formula [I] or [II] described on page 2 of JP-A-8-171185, or a general formula (I) described in JP-A-11-282138 The pyrroloazole coupler represented by these can be mentioned.

The cyan coupler can usually be used in the silver halide emulsion layer in the range of 1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻¹ mol, per mol of silver halide.

  In order to adjust the spectral absorption characteristics of the magenta color image, cyan color image, and yellow color image, it is preferable to add a compound having a color tone adjusting action. As the compound for this purpose, a phosphoric acid ester compound represented by the general formula [HBS-I] described in JP-A-6-95283, page 22 and a phosphine oxide compound represented by [HBS-II] are more preferable. A compound represented by the general formula [HBS-II] described on page 22 of the same number is preferred.

  Each of the magenta, cyan, and yellow couplers can be used in combination with an anti-fading agent for preventing fading of the formed dye image due to light, heat, humidity, and the like. Preferred compounds include phenyl ether compounds represented by general formulas I and II described on page 3 of JP-A-2-66541, phenolic compounds represented by general formula IIIB described in JP-A-3-174150, Particularly preferred for magenta dyes are amine compounds represented by the general formula A described in No. 90445 and metal complexes represented by the general formulas XII, XIII, XIV and XV described in JP-A No. 62-182741. Further, a compound represented by the general formula I ′ described in JP-A-1-196049 and a compound represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

  An oil-in-water emulsion dispersion method is used to add other organic compounds such as a dye-forming coupler and stain inhibitor used in the silver halide photosensitive material according to the present invention. In the oil-in-water emulsion dispersion method, the coupler or other organic compound is usually combined with a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher and, if necessary, a low-boiling and / or water-soluble organic solvent. Dissolve and emulsify and disperse using a surfactant in a hydrophilic colloid binder such as an aqueous gelatin solution. As the dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used.

  The content of the low boiling point organic solvent in these oil-in-water dispersions used in the silver halide photosensitive material according to the present invention is preferably 2 to 10% by mass or less. For adjusting the content of the low-boiling organic solvent, a step of removing the low-boiling organic solvent by distillation under reduced pressure or the like after dispersion or simultaneously with dispersion is used.

  In particular, as the yellow color-developing photosensitive silver halide emulsion layer, an oil-in-water type dispersion having a low boiling point organic solvent content in the above range is used, using a dye-forming coupler represented by the general formula (a). Thus, a coating failure is reduced, and there is no variation in color density due to temperature during exposure, and a silver halide color photographic light-sensitive material having improved color density stability can be obtained.

  The low boiling point organic solvent according to the present invention is an organic solvent having a boiling point of 200 ° C. or lower (101.3 kPa) and preferably has a boiling point of 100 ° C. or lower. A typical low boiling point organic solvent is ethyl acetate.

  Examples of high-boiling organic solvents that can be used to dissolve and disperse the dye-forming coupler and stain inhibitor according to the present invention include phosphate esters such as tricresyl phosphate and trioctyl phosphate, and trioctylphosphine. Preference is given to phosphine oxides such as oxides, higher alcohol compounds represented by (ai) to (ax) described on page 5 of JP-A-4-265975. The dielectric constant of the high boiling point organic solvent is preferably 3.5 to 7.0. Two or more high-boiling organic solvents can be used in combination.

  The silver halide emulsion used in the present invention is preferably a silver halide emulsion comprising 95 mol% or more of silver chloride, and any halogen such as silver chloride, silver chlorobromide, silver chloroiodobromide, silver chloroiodide, etc. What has a composition is used. Among them, a silver chlorobromide containing 95 mol% or more of silver chloride, a silver halide emulsion having a portion containing a high concentration of silver bromide is particularly preferably used, and 0.05% of silver iodide is present in the vicinity of the surface. Silver chloroiodide containing ˜0.5 mol% is also preferably used. Of the silver halide emulsion having a silver bromide-rich portion, the silver bromide-containing portion may be a so-called core-shell emulsion, or simply forming a complete layer without forming a complete layer. A so-called epitaxy-bonded region in which only a region having a partially different composition exists may be formed. The portion where silver bromide is present at a high concentration is particularly preferably formed at the apex of the crystal grain on the surface of the silver halide grain. Further, the composition may change continuously or discontinuously.

  It is advantageous that the negative silver halide emulsion used in the present invention contains heavy metal ions. This is expected to improve so-called reciprocity failure and prevent desensitization in high-illuminance exposure and prevent softening on the shadow side. 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. Of these, metal ions of iron, iridium, platinum, ruthenium, gallium and osmium are preferable. These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt. When the heavy metal ion forms a complex, as its ligand, cyanide ion, thiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, carbonyl, nitrosyl, ammonia, 1, 2, 4-triazole, thiazole, etc. can be mentioned. Of these, chloride ion, bromide ion and the like are preferable. These ligands may be used alone or in combination with a plurality of ligands.

  These metal compounds can also be characterized as the depth of electron traps when incorporated in silver halide emulsion grains. Examples of the compound that gives a shallow electron trap having a depth of 0.2 eV or less include a compound having a second lead ion or a cyano ligand, which is effective in improving a reciprocity failure, particularly a low illumination failure. . In addition, examples of the compound that provides a deep electron trap having a depth of 0.35 eV or more include Ir, Rh, and Ru compounds having halide ions and nitrosyl ligands. These can be preferably used for improving high-illuminance reciprocity failure. It is also preferable to use a compound that provides a shallow electron trap having a depth of 0.2 eV or less and a compound that provides a deep electron trap having a depth of 0.35 eV or more in combination. These compounds are described in detail in JP-A No. 2000-214561, pages 4-5.

  In order to contain a heavy metal ion in a silver halide emulsion, the heavy metal compound may be added to any step during physical ripening before formation of silver halide grains, during formation of silver halide grains, and after formation of silver halide grains. It may be added at the place.

The heavy metal compound can be dissolved together with the halide salt and added continuously throughout the grain formation process. It can also be prepared by previously forming silver halide fine particles containing these heavy metal compounds and adding them. The amount of the heavy metal ion added to the silver halide emulsion is more preferably 1 × 10 ⁻⁹ mol or more and 1 × 10 ⁻² mol or less, and especially 1 × 10 ⁻⁸ mol or more and 5 or less per mol of silver halide. × 10 ⁻⁵ mol or less is preferable.

  Any particle shape can be used in the present invention. One preferable example is a cube having a (100) plane as a crystal surface. U.S. Pat. Nos. 4,183,756, 4,225,666, JP-A-55-26589, JP-B-55-42737, and The Journal of Photographic Science (J. Photogr. Sci.) 21, 39 (1973), etc., particles having an octahedron, tetrahedron, dodecahedron, etc. can be produced and used. Furthermore, particles having twin planes may be used.

  The grains used in the present invention are preferably grains having a single shape, but it is particularly preferred to add two or more monodispersed silver halide emulsions in the same layer.

  The particle size of the particles used in the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably 0.2 when considering other photographic performances such as rapid processability and sensitivity. It is the range of -1.0 micrometer.

  This particle size can be measured using the projected area or diameter approximation of the particle. If the particles are substantially uniform in shape, the particle size distribution can be expressed fairly accurately as a diameter or projected area.

  The grain size distribution of the silver halide grains used in 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, and particularly preferably a coefficient of variation of 0. Two or more monodispersed emulsions of 15 or less are added to the same layer. 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 is the standard deviation of the particle size distribution and R is the average particle size.)
As a silver halide emulsion preparation apparatus and method, various methods known in the art can be used.

  The emulsion used in the present invention may be obtained by any of the 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. 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 negative silver halide emulsion used in 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 the chalcogen sensitizer, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, and a sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, triethylthiourea, allylthiocarbamide thiourea, allyl isothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, inorganic sulfur and the like.

The amount of the sulfur sensitizer, it is preferred to vary the size, etc. of the effect of the type of silver halide emulsions applied or expectations, per mol of silver halide 5 × 10 ^-10 ~5 × 10 ^- A range of ⁵ mol, preferably 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol is preferable.

As the gold sensitizer, various gold complexes such as chloroauric acid and gold sulfide can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, mercaptotriazole and the like. The amount of gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but usually 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ per mol of silver halide. Mole is preferred. More preferably, it is 1 * 10 <^-5> mol-1 * 10 <^-8> mol. These compounds can be added for various purposes not as a sensitizer but at the stage of preparing a coating solution.

  As a chemical sensitization method for the negative silver halide emulsion used in the present invention, a reduction sensitization method may be used.

The silver halide emulsion used in the present invention is known for the purpose of preventing fogging during the preparation process of the silver halide light-sensitive material, reducing performance fluctuation during storage, and preventing fogging during development. Antifoggants and stabilizers can be used. Examples of preferable compounds that can be used for such purposes include nitrogen-containing heterocyclic mercapto compounds represented by the general formula (II) described in JP-A-2-14636, page 7, lower column. Specific examples of the compound include compounds (IIa-1) to (IIa-8) and (IIb-1) to (IIb-7) described on page 8 of the same publication, and page 8 of JP-A-2000-267235. The compounds described in the right column, lines 32-36 can be mentioned. 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. When chemical sensitization is carried out in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ⁻⁵ mol to 5 × 10 ⁻⁴ mol per mol of silver halide. When added at the end of chemical sensitization, the amount is preferably about 1 × 10 ⁻⁶ mol to 1 × 10 ⁻² mol per mol of silver halide, preferably 1 × 10 ⁻⁵ mol to 5 × 10 ⁻³ mol. More preferred. In the coating solution preparation step, when added to the silver halide emulsion layer, the amount of 1 × 10 ^-6 mol to 1 × 10 ^-1 mol per mol of silver halide is preferred, 1 × 10 ^-5 mol to 1 × 10 ⁻² mol is more preferred. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is preferably about 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol per 1 m ² .

  Other additives can be added to the silver halide emulsion used in the present invention for various purposes. For example, disulfides and polysulfides such as A-20, C-1, C-9, C-14, C-15, C-16, C-40 and the like specifically described in JP-A-2-146036 It is preferable to use compounds, thiosulfonic acid compounds such as D-1, D-3, D-6, and D-8, inorganic sulfur, and the like.

  In the photographic light-sensitive material used in the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and preventing 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-3-251840, page 308 and JP-A-6 A dye described in No. 3770 is preferably used.

  The silver halide light-sensitive material according to the present invention is a hydrophilic colloid colored with at least one layer of a diffusion-resistant compound on the side closer to the support than the silver halide emulsion layer closest to the support in the silver halide emulsion layer. It is preferable to have a layer. As the coloring substance, a dye or other organic or inorganic coloring substance can be used.

The silver halide light-sensitive material used in the present invention has at least one colored hydrophilic colloid layer on the side closer to the support than the silver halide emulsion layer closest to the support among the silver halide emulsion layers. Is preferable, and the layer may contain a white pigment. For example, rutile type titanium dioxide, anatase type titanium dioxide, barium sulfate, barium stearate, silica, alumina, zirconium oxide, kaolin and the like can be used, and titanium dioxide is particularly preferable for various reasons. The white pigment is dispersed in an aqueous binder of hydrophilic colloid such as gelatin so that the treatment liquid can penetrate. The coating with the amount of the white pigment is preferably in the range of ^{0.1g / m 2 ~50g / m 2} , more preferably in the range of ^{0.2g / m 2 ~5g / m 2} .

  Between the support and the silver halide emulsion layer closest to the support, in addition to the white pigment-containing layer, an undercoat layer as required, or a non-photosensitive hydrophilic colloid layer such as an intermediate layer at an arbitrary position Can be provided.

  Addition of a fluorescent brightening agent to the silver halide light-sensitive material according to the present invention is preferred because the white background can be further improved. The optical brightener is not particularly limited as long as it is a compound that can absorb ultraviolet rays and emit visible light fluorescence, but is a diaminostilbene compound having at least one sulfonic acid group in the molecule, These compounds are preferable because they have an effect of promoting the elution of the sensitizing dye to the outside of the sensitive material. Another preferred form is a solid particulate compound having a fluorescent whitening effect.

  The silver halide 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. 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 used in 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 8 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to 5 described on page 28 of the same publication are preferably used. As the red photosensitive sensitizing dye, RS-1 to 8 described in page 29 of the same publication are preferably used.

  These sensitizing dyes may be added at any time from the formation of silver halide grains to the end of chemical sensitization. In addition, these dyes may be added as a solution by dissolving in water or an organic solvent miscible with water such as methanol, ethanol, fluorinated alcohol, acetone, dimethylformamide, or a sensitizing dye. May be added as a water miscible solvent solution, emulsion or suspension having a density greater than 1.0 g / ml.

As a method for dispersing the sensitizing dye, in addition to a method of mechanically pulverizing and dispersing fine particles having a size of 1 μm or less in an aqueous system using a high-speed stirring type disperser, a pH of 6 to 5 as described in JP-A No. 58-105141 can be used. 8. A method of mechanically pulverizing and dispersing fine particles having a size of 1 μm or less in an aqueous system under conditions of 60 to 80 ° C., and a surface tension described in JP-B-60-6496 of 3.8 × 10 ⁻² N / m or less A method of dispersing in the presence of a surfactant that suppresses to a low level, as disclosed in JP-A-50-80826, is dissolved in an acid that is substantially free of water and does not exceed pKa of 5, and is added to the aqueous liquid A method of dispersing and adding this dispersion to a silver halide emulsion can be used.

  The dispersion medium used for dispersion is preferably water, but a small amount of an organic solvent can be added to adjust the solubility, or a hydrophilic colloid such as gelatin can be added to improve the stability of the dispersion.

  Examples of the dispersion apparatus that can be used to prepare the dispersion include a high speed stirring type disperser described in FIG. 1 of JP-A-4-125561, a ball mill, a sand mill, an ultrasonic disperser, and the like. be able to.

  Further, when using these dispersing apparatuses, as described in JP-A-4-125632, a pre-treatment such as dry pulverization is performed in advance, followed by wet dispersion.

  The silver halide emulsion used in the present invention may contain one or a combination of two or more sensitizing dyes.

  As a preferable compound as a surfactant used for dispersion of photographic additives used in the light-sensitive material according to the present invention and adjustment of surface tension during coating, a hydrophobic group having 8 to 30 carbon atoms and sulfone in one molecule. The thing containing an acid group or its salt 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 for an alkyl group is also preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, but the time until the addition to the coating solution after dispersion and the time until the coating after addition to the coating solution should be short, and 10 hours each. Is preferably within 3 hours, and more preferably within 20 minutes.

  In the silver halide light-sensitive material according to the present invention, a compound that reacts with an oxidized developing agent is added to the layer between the light-sensitive layer to prevent color turbidity, or it is 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, and examples thereof include compounds II-1 to II-14 described on pages 13 to 14 and compound 1 described on page 17.

  In the 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. Particularly preferred compounds are compounds represented by general formula III-3 described in JP-A-1-250944, and compounds represented by general formula III described in JP-A 64-66646. Compounds represented by general formula I described in JP-A No. 63-187240, UV-1L to UV-27L described in JP-A No. 63-187240, general formula I described in JP-A No. 4-1633, general formula (I) described in JP-A No. 5-165144, The compound shown by (II) is mentioned.

  The light-sensitive material according to the present invention preferably contains an oil-soluble dye or pigment, since the white background is improved. Representative examples of oil-soluble dyes include compounds 1-27 described in JP-A-2-842, pages 8-9.

  In the silver halide light-sensitive material according to the present invention, it is advantageous to use gelatin as a binder. If necessary, other gelatins, hydrophilic colloids such as gelatin derivatives, gelatin and other polymer graft polymers, Hydrophilic colloids such as proteins other than gelatin, sugar derivatives, cellulose derivatives, synthetic hydrophilic polymer materials such as mono- or copolymers can also be used.

  It is preferable to use a vinylsulfone type hardener or a chlorotriazine type hardener alone or in combination as a hardener for these binders. It is preferable to use compounds described in JP-A-61-249054 and JP-A-61-245153. It is preferable to add a preservative and an antifungal agent as described in JP-A-3-157646 to the colloid layer in order to prevent the growth of mold and bacteria that adversely affect photographic performance and image storage stability. In order to improve the physical properties of the surface of the light-sensitive 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.

  As the support used for the photosensitive 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 sheet, white pigment. Polypropylene, polyethylene terephthalate support, baryta paper and the like which may be contained 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 support having a water-resistant resin coating layer on the surface of paper, a smooth surface having a mass of 50 to 300 g / m ² is usually used, but for the purpose of obtaining a proof image, a feeling of handling to approximate the printing paper, 130 g / m ² or less of the base paper is preferably used, it is preferably used further 70~120g / m ² base paper.

  The support used in the present invention can be preferably used even if it has random irregularities or is smooth.

  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.

  The resin layer of the paper support having water-resistant resin layers on both sides used in the present invention may be a single layer or a plurality of layers. When a plurality of layers are used and a white pigment is contained at a high concentration in the contact with the emulsion layer, sharpness is greatly improved, which is preferable for forming a proof image.

  Further, it is more preferable that the average surface roughness (SRa) of the support is 0.15 μm or less, and further 0.12 μm or less, because the effect that the gloss is good is obtained.

  The photographic light-sensitive material used in 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 properties, dimensions). One or more subbing layers for improving the degree of stability, rub resistance, hardness, antihalation, friction properties and / or other properties.

  In the light-sensitive material according to the present invention, the silver halide emulsion layer is laminated and coated on a support, but the order from the support may be any order. In addition to this, an intermediate layer, a filter layer, a protective layer, and the like can be disposed as necessary.

  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 width of the photosensitive material, a material having an arbitrary width can be used according to the use, but a width of 400 mm or more is preferably used for the proof use. A photosensitive material having a width of 800 mm or more is also preferably used.

  As the exposure light source of the exposure apparatus used in the present invention, any known light source can be preferably used, but a laser or a light emitting diode (hereinafter referred to as LED) is more preferably used.

  As the laser, a semiconductor laser (hereinafter referred to as LD) is preferably used because it is compact and has a long light source life. LDs are used for applications such as DVDs, optical pickups for music CDs, barcode scanners for POS systems, optical communications, etc., and they are inexpensive and can provide relatively high output. have. Specific examples of the LD include aluminum, gallium, indium, arsenic (650 nm), indium, gallium, phosphorus (up to 700 nm), gallium, arsenic, phosphorus (610-900 nm), gallium, aluminum, arsenic (760-850 nm). And the like. Recently, a laser that oscillates blue light has been developed. However, at present, it is advantageous to use an LD as a light source having a wavelength longer than 610 nm.

  As a laser light source having an SHG element, light emitted from an LD or YAG laser is converted to a half-wavelength light by an SHG element and emitted, and since visible light is obtained, there is no green light source. ~ Used as a light source in the blue region. An example of this type of light source is a YAG laser combined with an SHG element (532 nm).

  Examples of the gas laser include a helium / cadmium laser (about 442 nm), an argon ion laser (about 514 nm), a helium neon laser (about 544 nm and 633 nm), and the like.

  LEDs having the same composition as LD are known, but various LEDs from blue to infrared have been put into practical use.

  As the exposure light source used in the present invention, each laser may be used alone, or may be used in combination as a multi-beam. In the case of an LD, for example, a beam composed of 10 luminous fluxes can be obtained by arranging 10 LDs. On the other hand, in the case of a helium neon laser, light emitted from the laser is divided into, for example, 10 light beams by a beam separator.

  The intensity change of the exposure light source can be directly modulated to change the value of the current flowing through each element in the case of an LD or LED. In the case of an LD, the intensity may be changed using an element such as an AOM (acousto-optic modulator). In the case of a gas laser, devices such as AOM and EOM (electro-optic modulator) are generally used.

  When an LED is used as the light source, a method of exposing the same pixel with a plurality of elements may be used if the amount of light is weak.

  Moreover, you may use an organic light emitting element as a light source which replaces these, These are described in Unexamined-Japanese-Patent No. 2000-258846 etc., for example.

  In the present invention, the term area gradation image is used, but this is not expressed by the shading of the color of each pixel, but by the size of the area of the color developed at a specific density. It can be considered synonymous with halftone dots.

  In the case of normal area gradation exposure, the purpose can be achieved by causing Y, M, C, and black to be colored. More preferably, in order to identify that a single color such as M or C has developed in addition to black, it is preferable to perform exposure using different exposure amounts of three or more. In printing, a specially colored plate may be used, but in order to reproduce this, it is preferable to use an exposure amount of 4 or more for different exposures.

  In the case of a laser light source, the beam diameter is preferably 25 μm or less, more preferably 6 to 22 μm. If it is smaller than 6 μm, it is preferable in terms of image quality, but adjustment is difficult or the processing speed decreases. On the other hand, if it is larger than 25 μm, unevenness increases and the sharpness of the image also deteriorates. By optimizing the beam diameter, high-definition images without unevenness can be written at high speed.

  In order to draw an image with such light, it is necessary to scan the light flux on the silver halide photosensitive material. The photosensitive material is wound around a cylindrical drum and rotated at a high speed in a direction perpendicular to the rotational direction. A cylindrical outer surface scanning method for moving a light beam may be used, and a cylindrical inner surface scanning method in which a silver halide photosensitive material is brought into close contact with a cylindrical depression for exposure can also be preferably used. A planar scanning method may be employed in which the polyhedron mirror is rotated at a high speed to expose the silver halide photosensitive material conveyed by moving the light beam at right angles to the conveying direction. In order to obtain a high image quality and a large image, the cylindrical outer surface scanning method is more preferably used.

  In order to perform exposure by the cylindrical outer surface scanning method, the silver halide photosensitive material must be brought into close contact with the cylindrical drum accurately. For this to be done accurately, it needs to be accurately aligned and transported. The silver halide photographic material used in the present invention can be preferably used because the surface on the side to be exposed is wound outward so that it can be aligned more accurately. From the same viewpoint, the support used for the silver halide photosensitive material used in the present invention has an appropriate rigidity, and the Taber rigidity is preferably 0.8 to 4.0.

  The drum diameter can be arbitrarily set according to the size of the silver halide photosensitive material to be exposed. The number of revolutions of the drum can also be set arbitrarily, but an appropriate number of revolutions can be selected according to the beam diameter of the laser beam, the energy intensity, the writing pattern and the sensitivity of the photosensitive material. From the viewpoint of productivity, it is preferable that scanning exposure can be performed at a higher rotation speed. Specifically, 200 to 3000 rotations per minute is preferably used.

  The silver halide photosensitive material can be fixed to the drum by mechanical means, or a large number of fine holes that can be sucked on the drum surface are provided according to the size of the photosensitive material. It can also be adhered by suction. In order to prevent troubles such as image unevenness, it is important to make the photosensitive material as close as possible to the drum.

  In the present invention, the color developer can be used in any pH range, but it is preferably pH 9.5 to 13.0, more preferably pH 9.8 to 12.0, from the viewpoint of rapid processing. Used in

  The processing temperature for color development according to the present invention is preferably 35 ° C. or higher and 70 ° C. or lower. The higher the temperature, the shorter the treatment possible and the better. However, it is preferable that the temperature is not so high from the stability of the treatment liquid, and the treatment is preferably performed at 37 ° C. or more and 60 ° C. or less.

  The color development time is generally about 3 minutes 30 seconds, but in the present invention, it is preferably within 45 seconds, and more preferably within 25 seconds.

  In addition to the color developing agent, a known developer component compound can be added to the color developer. Usually, an alkali agent having a pH buffering action, a development inhibitor such as chloride ions and benzotriazoles, a preservative and a chelating agent are used.

  The silver halide light-sensitive material of the present invention is subjected to bleaching and fixing after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed. Moreover, you may perform a stabilization process as an alternative to a washing process. The development processing apparatus used for the development processing of the silver halide photosensitive material of the present invention fixes the photosensitive material to the belt even if it is a roller transport type that conveys the photosensitive material between rollers arranged in a processing tank. The endless belt method may be used, but the processing tank is formed in a slit shape, the processing liquid is supplied to the processing tank, and the photosensitive material is transported and the processing liquid is sprayed. Also, a web system by contact with a carrier impregnated with a treatment liquid, a system by a viscous treatment liquid, or the like can be used. In the case of processing in large quantities, it is usual that the running processing is performed using an automatic processor. At this time, the replenishment amount of the replenisher is preferably as small as possible. And the method described in the published technical report 94-16935 is most preferable.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, the aspect of this invention is not limited to this.

Example 1
A polyethylene laminated paper reflective support (Taber stiffness) with a mass per square meter of 115 g of laminated high-density polyethylene on one side and molten polyethylene containing 15% by mass of anatase-type titanium oxide dispersed on the other side. = 3.5, PY value = 2.7 μm), each layer having the layer constitution shown in the following Table 1 was coated on the polyethylene layer side containing titanium oxide, and further on the back side, gelatin 6.00 g / m. ² and multilayer silver halide photosensitive material sample No. ² coated with 0.65 g / m ² of silica matting agent. 101 was produced.

The coupler and each additive were dissolved in a high boiling point solvent and ultrasonically dispersed by the preparation method shown below, and added as an oil-in-water dispersion. At this time, as a surfactant (SU-1) Was used. Moreover, (H-1) and (H-2) were added as a hardening agent. Further, (F-1) was added to each layer so that the total amount was 0.04 g / m ² .

As coating aids, 20 mg / m ² to surfactant (SU-2) Eighth layer, surfactant (SU-3) were 15 mg / m ² added to the first layer, to adjust the surface tension. Further, (F-1) was added to each layer so that the total amount was 0.04 g / m ² .

  In addition, in the layers other than the photosensitive layers (second layer, fourth layer, sixth layer, eighth layer, etc.), the additive is dissolved together with the high boiling point organic solvent, and basically the coupler dispersion liquid and It was added as a similar oil-in-water dispersion.

SU-1: Sodium tri-i-propylnaphthalene sulfonate SU-2: Sulfosuccinic acid di (2-ethylhexyl) sodium salt SU-3: Sulfosuccinic acid di (2,2,3,3,4,4,4) 5,5-octafluoropentyl) sodium salt H-1: Tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-1: 2,5-di -T-octylhydroquinone HQ-2: 2,5-di ((1,1-dimethyl-4-hexyloxycarbonyl) butyl) hydroquinone HQ-3: 2,5-di-sec-dodecylhydroquinone and 2,5- A mixture of di-sec tetradecyl hydroquinone and 2-sec-dodecyl-5-sec-tetradecyl hydroquinone in a mass ratio of 1: 1: 2. HQ-4: 2,5-di-t-butylhydroquinone SO-1: trioctylphosphine oxide SO-2: di (i-decyl) phthalate SO-3: oleyl alcohol SO-4: tricresyl phosphate PVP: polyvinyl Pyrrolidone A method for preparing a coupler dispersion used for each photosensitive layer is shown below.

(Yellow coupler dispersion for blue photosensitive layer)
The yellow coupler (Y-1, Y-2, Y-3) was 64 g at a mass ratio of 16:13:35, and 2 g of the stain inhibitor (HQ-1) was added to a high boiling point organic solvent (SO-1). ) 43 g, (SO-2) 15 g and ethyl acetate 240 ml were dissolved and this solution was dissolved in 740 ml of 10% gelatin aqueous solution containing 24 ml of 20% surfactant (SU-1) using an ultrasonic homogenizer. The mixture was emulsified and dispersed to prepare an oil-in-water dispersion type yellow coupler dispersion. The amount of ethyl acetate in the yellow coupler dispersion was adjusted by distilling off ethyl acetate by distillation under reduced pressure so that the content was 2.2% by mass.

  This yellow coupler dispersion was mixed with the blue-sensitive silver halide emulsion prepared as follows to prepare a coating solution for a blue-sensitive layer. The amount of gelatin was adjusted by adding gelatin so as to be the amount shown in Table 1.

(Cyan coupler dispersion for green photosensitive layer)
The types and amounts of couplers, stain inhibitors and high-boiling organic solvents are as shown in Table 1. Cyan couplers (13 g each for C-1 and C-2), 5 g stain inhibitor (HQ-4), high boiling point In place of the organic solvent (27 g each for SO-2 and SO-3), ethyl acetate was distilled off to prepare a cyan coupler dispersion basically in the same manner as the yellow coupler dispersion. This cyan coupler dispersion was mixed with the green-sensitive silver halide emulsion prepared in the following manner in the amount shown in Table 1 to prepare a green-sensitive layer coating solution. The amount of gelatin was adjusted by adding gelatin so as to be the amount shown in Table 1.

(Magenta coupler dispersion for red photosensitive layer)
As shown in Table 1, magenta couplers (M-1, M-2, 15 g, 30 g), yellow couplers (Y-1, Y-2, respectively) 4g, 5g), 1g of stain inhibitor (HQ-1), and 18g of compound cpd-1 were added and changed to a high boiling point organic solvent (SO-1 and SO-4 respectively 27g, 50g). In the same manner as the coupler dispersion, ethyl acetate was distilled off to prepare a coupler dispersion.

  This coupler dispersion was mixed with the amount shown in Table 1 of the red-sensitive silver halide emulsion prepared as follows to prepare a coating solution for a red-sensitive layer. The amount of gelatin was adjusted by adding gelatin so as to be the amount shown in Table 1.

  In addition, preparation methods of blue-sensitive silver halide emulsion, green-sensitive silver halide emulsion and red-sensitive silver halide emulsion were shown.

(Preparation of blue-sensitive silver halide emulsion)
The following (A solution) and (B solution) were simultaneously added to 1 liter of 2% gelatin aqueous solution kept at 40 ° C. while controlling pAg = 7.3 and pH = 3.0, and the following (C solution) and (D liquid) was simultaneously added while controlling pAg = 8.0 and pH = 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled using sulfuric acid or an aqueous sodium hydroxide solution.
(Liquid A)
Sodium chloride 3.42g
Potassium bromide 0.03g
200ml with water
(Liquid B)
Silver nitrate 10g
200ml with water
(C liquid)
Sodium chloride 102.7g
Potassium hexachloroiridium (IV) 4 × 10 ⁻⁸ mol Potassium hexacyanoferrate (II) 2 × 10 ⁻⁵ mol Potassium bromide 1.0 g
600ml with water
(Liquid D)
300 g of silver nitrate
600ml with water
After completion of addition, desalting was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd. and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to obtain an average particle size of 0.71 μm and a coefficient of variation in particle size distribution. A monodispersed cubic emulsion EMP-101 having 0.07 and a silver chloride content of 99.5 mol% was obtained.

  The above (EMP-101) was optimally chemically sensitized at 60 ° C. using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B101).

Sodium thiosulfate 0.8mg / mol AgX
Chloroauric acid 0.5mg / mol AgX
Stabilizer (STAB-1) 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer (STAB-2) 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer (STAB-3) 3 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye (BS-1) 4 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye (BS-2) 1 × 10 ⁻⁴ mol / mol AgX
Potassium bromide 0.2g / mol AgX
Subsequently, in the preparation of EMP-101, the average particle size of 0. 0 was changed in the same manner as EMP-101 except that the addition time of (A liquid) and (B liquid) and the addition time of (C liquid) and (D liquid) were changed. A monodispersed cubic emulsion EMP-102 having a diameter of 64 μm, a coefficient of variation of grain size distribution of 0.07, and a silver chloride content of 99.5 mol% was obtained. Em-B102 was obtained in the same manner as in the preparation of Em-B101 except that EMP-102 was used instead of EMP-101, and a 1: 1 mixture of Em-B101 and 102 was used as a blue-sensitive emulsion.

(Preparation of green sensitive silver halide emulsion)
In the preparation of EMP-101, the average particle size was 0.40 μm, the coefficient of variation was 0.08, chloride was changed except that the addition times of (A liquid), (B liquid), (C liquid) and (D liquid) were changed. A monodispersed cubic emulsion (EMP-103) having a silver content of 99.5% was obtained.

  The EMP-103 was optimally chemically sensitized at 55 ° C. using the following compound to obtain a green sensitive silver halide emulsion (Em-G101).

Sodium thiosulfate 1.5mg / mol AgX
Chloroauric acid 1.0mg / mol AgX
Stabilizer (STAB-1) 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer (STAB-2) 3 × 10 ⁻⁴ mol / mol AgX
Stabilizer (STAB-3) 3 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye (GS-1) 2 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye (GS-2) 2 × 10 ⁻⁴ mol / mol AgX
Sodium chloride 0.5g / mol AgX
Next, in the preparation of EMP-103, the average particle size of 0. 0 was changed in the same manner as EMP-103, except that the addition time of (Liquid A) and (Liquid B) and the addition time of (Liquid C) and (Liquid D) were changed. A monodispersed cubic emulsion EMP-104 having a thickness of 50 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% was obtained. Em-G102 was obtained in the same manner as in the preparation of Em-G101 except that EMP-104 was used instead of EMP-103, and a 1: 1 mixture of Em-G101 and 102 was used as a green-sensitive emulsion.

(Preparation of red-sensitive silver halide emulsion)
The EMP-103 was optimally chemically sensitized at 60 ° C. using the following compound to obtain a red-sensitive silver halide emulsion (Em-R101).

Sodium thiosulfate 1.8mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer (STAB-1) 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer (STAB-2) 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer (STAB-3) 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer (STAB-4) 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye (RS-1) 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye (RS-2) 1 × 10 ⁻⁴ mol / mol AgX
Supersensitizer (SS-1) 2 × 10 ⁻⁴ mol / mol AgX
Next, in the preparation of (Em-R101), chemical sensitization was optimally performed at 60 ° C. using the following compound to obtain a red-sensitive silver halide emulsion (Em-R102).

Sodium thiosulfate 1.8mg / mol AgX
Chloroauric acid 2.0mg / mol AgX
Stabilizer (STAB-1) 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer (STAB-2) 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer (STAB-3) 2 × 10 ⁻⁴ mol / mol AgX
Stabilizer (STAB-4) 1 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye (RS-1) 2 × 10 ⁻⁴ mol / mol AgX
Sensitizing dye (RS-2) 2 × 10 ⁻⁴ mol / mol AgX
Supersensitizer (SS-1) 2 × 10 ⁻⁴ mol / mol AgX
STAB-1: 1-phenyl-5-mercaptotetrazole STAB-2: 1- (4-Ethoxyphenyl) -5-mercaptotetrazole STAB-3: 1- (3-acetamidophenyl) -5-mercaptotetrazole STAB-4: p-Toluenethiosulfonic acid

  A 1: 1 mixture of Em-R101 and Em-R102 was used as the red sensitive emulsion.

[Production of Samples 102 to 118]
In the preparation of Sample 101, the same procedure was performed except that the same amount (g) of the compound represented by the general formula (a) of the present invention was used instead of the yellow coupler of the seventh layer (blue photosensitive layer). Samples 102 to 118 were prepared in the same manner as shown in Table 2, except that after the yellow coupler dispersion was prepared, ethyl acetate was distilled off under reduced pressure and the ethyl acetate content was adjusted. The residual concentration of ethyl acetate in the yellow coupler dispersion was determined by a gas chromatograph calibrated with an aqueous solution sample.

In each of the above samples, 2000 L of coating solution for each layer was prepared, stored at 30 ° C. for 5 hours, and then coated simultaneously, and the number of coating failures per 1000 m ² was measured. Further, each of the above samples was stored for 3 weeks under the conditions of 40 ° C. and 55 RH%, and then exposed and developed by the following method to obtain the density fluctuation range of the Y density.

<Evaluation of silver halide photosensitive material sample>
[Exposure apparatus and exposure method]
A drum exposure type exposure apparatus having the following light source was used. As the light source, five LEDs of B were arranged in the main scanning direction, and the exposure timing was gradually delayed so that the same place could be exposed with five LEDs. Further, an exposure head was prepared in which 20 LEDs were arranged in the sub-scanning direction, and exposure for 20 adjacent pixels could be performed at once. Similarly, for G and R, exposure heads were prepared by combining LEDs. The diameter of each beam was about 10 μm, the beams were arranged at this interval, and the sub-scanning pitch was about 200 μm.

  As image data used for exposure, a uniform image having a condition that the yellow (Y) solid density is 0.75 was prepared.

  The sample cut into a sheet of 670 mm × 970 mm with the exposure apparatus and the exposure method described above was wound around a drum and exposed in an atmosphere of 23 ° C. and 55 RH%, and then subjected to the following development processing. An image was obtained in the same manner except that the temperature condition of the sample wound around the drum during exposure was changed to 30 ° C. and 55 RH%.

[Development 1]
Development processing after exposure was performed using an automatic processor under the following conditions.

Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C 45 seconds 100ml
Bleach fixing 38.0 ± 0.5 ° C 45 seconds 75 ml
Stabilization 30-34 ° C 30 seconds 200ml
Drying 60 to 80 ° C. 30 seconds Color developer starter and replenisher Starter replenisher Triethylenediamine 3.0 g 4.0 g
Diethylene glycol 6.0g 8.0g
Potassium bromide 0.15g 0.2g
Potassium chloride 3.5g 0.2g
Potassium sulfite 0.3g 0.4g
Developing agent: 4-amino-3-methyl-N-ethyl-N-β-methanesulfonamidoethylaniline 1.5 sulfate monohydrate (hereinafter abbreviated as CD-1)
3.0g 4.0g
N, N-disulfoethylhydroxylamine 15.0 g 20.0 g
Triethanolamine 6.0g 8.0g
Diethylenetriaminepentaacetic acid sodium salt 1.5 g 2.0 g
Potassium carbonate 30g 40g
Water is added to make the total volume 1 liter, and the tank liquid is adjusted to pH = 10.2 and the replenisher is adjusted to pH = 10.5.
Bleach-fixer tank solution and replenisher solution Diethylenetriaminepentaacetic acid ferric ammonium dihydrate 65g
Diethylenetriaminepentaacetic acid 3g
Ammonium thiosulfate (70% aqueous solution) 100 ml
2-amino-5-mercapto-1,3,4-thiadiazole 2.0 g
Ammonium sulfite (40% aqueous solution) 27.5 ml
Add water to bring the total volume to 1 liter, and adjust to pH = 5.0 with potassium carbonate or glacial acetic acid.
Stabilizing liquid tank liquid and replenishing liquid o-phenylphenol 1.0 g
5-Chloro-2-methyl-4-isothiazolin-3-one 0.02 g
2-Methyl-4-isothiazolin-3-one 0.02 g
Diethylene glycol 1.0g
1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g
Zinc sulfate 0.5g
Magnesium sulfate heptahydrate 0.2g
PVP (Polyvinylpyrrolidone) 1.0g
Ammonia water (25% ammonium hydroxide aqueous solution) 2.5 g
Nitrilotriacetic acid trisodium salt 1.5g
Water is added to make a total volume of 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or ammonia water.

[Evaluation of treated sample]
In order to see the exposure temperature dependence of the density after storage of the raw sample, for the obtained images, a solid image of Y density around 0.75 at the time of exposure of each sample at 23 ° C. After measuring the status T density using a densitometer, the Y density at the same position of the entire solid image at the time of exposure at 30 ° C. was measured, and the fluctuation range of the density was obtained and expressed as an absolute value. The smaller the difference, the better the temperature dependency.

The results obtained as described above are also shown in Table 2 below for the number of coating failures per 1000 m ^{2 of} each sample.

  As is clear from Table 2, it can be seen that the sample of the present invention has both coating properties and temperature dependency upon exposure after storage of the raw sample.

Claims (3)

In a silver halide color light-sensitive material having at least one each of a yellow color-sensitive silver halide emulsion layer, a magenta color-sensitive silver halide emulsion layer, and a cyan color-sensitive silver halide emulsion layer on a reflective support. The dye-forming coupler contained in at least the yellow color-forming photosensitive silver halide emulsion layer is at least one represented by the following general formula (a), and the dye-forming coupler is used as a high-boiling solvent or a low-boiling solvent. It is added as a coupler dispersion dispersed in an aqueous hydrophilic colloid solution after being dissolved, and the low boiling point solvent content in the coupler dispersion is 2 to 10% by mass. Silver halide color light-sensitive material.

(In the general formula (a), R represents a substituent, and Z represents an atomic group necessary for forming a nitrogen-containing 6-membered ring or 7-membered ring together with the —N—C═N part. R ′ represents a substituent. N represents an integer of 0 to 4, X represents a hydrogen atom or a substituent, and A represents a hydrogen atom or a group that can be eliminated by coupling with an oxidized form of a color developing agent. The silver halide color photographic material according to claim 1, wherein, in the general formula (a), Z is a 3H-pyrimidin-4-one ring or a 1H-pyrimidin-4-one ring residue. In the general formula (a), Z is a 2H- [1,2,4] thiadiazine-1,1-dioxide ring or a 4H- [1,2,4] thiadiazine-1,1-dioxide ring residue. The silver halide color light-sensitive material according to claim 1.