JP2005077863A - Processing method for silver halide color photosensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a processing method for a silver halide color photosensitive material, by which a high quality color image is obtained which improves dotwise image defects caused by desilvering of the silver halide color photosensitive material. <P>SOLUTION: In the processing method for the silver halide color photosensitive material in which the silver halide color photosensitive material having at least one image forming layer on a support is developed and desilvered with a desilvering solution, the silver halide color photosensitive material contains a compound represented by formula (Cp-A), and the desilvering solution contains a ferric complex salt of a compound represented by formula (B-1). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for processing a silver halide color light-sensitive material, and more particularly to a method for processing a silver halide color light-sensitive material that provides a high-quality color image free from point image defects caused by desilvering. is there.

  Silver halide light-sensitive materials are actively used today because of their high sensitivity, excellent color reproducibility, and suitability for continuous processing. Conventionally, in the method of printing an image taken with a color negative using an optical system, if the conditions are set in advance, the conditions are easily adjusted from the result of measuring the density of the color negative, and the full color is excellent with one exposure. Therefore, it is possible to continuously obtain print images with high image quality and high productivity. Recently, it has also been used for digital image formation in which an image is formed by modulating the amount of light from an exposure light source such as a laser or LED based on image data taken by a digital camera. Also in digital image exposure, normally, modulated three-color light of B, G, and R is mixed, and an image is formed by one scan, which shows high productivity similar to the conventional one.

  In addition, it is known that a recording material using a silver halide light-sensitive material has little noise particularly at a low density, and has a feature that a very smooth gradation reproduction is possible. When has a sufficient gradation reproduction capacity, it has a feature that it is particularly excellent in the depiction of highlights. Because of these characteristics, silver halide 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 proofs for checking the state of finished printed matter in the middle of printing. ing.

  In the field of proofing, each image of yellow (Y), magenta (M), and cyan (C) is output by outputting an image edited on a computer to a printing film and separating and exposing the developed film as appropriate. An 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.

  Recently, a method of directly outputting an image edited on a computer directly to a printing plate has been gradually spread. In such a case, it is desired to obtain a color image directly from the data on the computer without using a film. It was rare.

  For such purposes, 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. There is a drawback, and the cost is low, and the method with excellent productivity has the disadvantage that the image quality is inferior. A system using a silver halide light-sensitive material can form an image with high image quality such as an accurate halftone image due to excellent sharpness and the like, while being capable of continuous processing as described above. In addition, high productivity can be realized because images can be simultaneously written in 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 an image directly from data in a computer has increased. For the reasons described above, silver halide photosensitive materials have begun to be used advantageously in this field. Proof using a silver halide photosensitive material is a printing ink because it forms a color image with an azomethine dye or indoaniline dye formed by a coupling reaction between a coupler contained in the photosensitive material and an oxidized form of a color developing agent. Although it is extremely difficult to make the color tone completely coincide with the color tone, as proposed in Japanese Patent Application Laid-Open No. 11-184043, in recent years, there is a material that closely approximates the color tone of the printing ink due to technological innovation. However, further improvement in color reproduction is desired in the market, and a photosensitive material that more closely approximates the color tone of printing ink is required.

  Patent Documents 1 and 2 disclose that a specific yellow coupler can provide a dye having excellent hue, large molecular extinction coefficient, and excellent storage stability, particularly light fastness. A silver halide color light-sensitive material is prepared using the yellow coupler described in the publication, and after color development and desilvering is performed, color reproduction that more closely approximates the color tone of the printing ink can be obtained. It was found that dotted brown stains were generated. Even when the conventionally used acylacetanilide type couplers described in JP-A-63-123047 and malondiamide type couplers described in US Pat. No. 4,149,886 are used, brown stains may be generated. It has been found that when the specific yellow coupler described in Patent Documents 1 and 2 is used, the degree of occurrence is significantly deteriorated.

  In the processing method in which the replenisher is replenished in accordance with the processing amount of the light-sensitive material, dotted brown stains may become more noticeable when the squeeze of the developer is insufficient. The squeeze here is performed to reduce the amount of processing solution adhering to the photosensitive material brought into the rear tank when the photosensitive material is processed by an automatic developing machine typified by a roller conveyance type. A thing by a thing and a blade is known. The squeeze may be insufficient due to the deterioration of the spring that tightens the roller or the blade. Brown stains may also be observed when the conventionally used acylacetanilide type couplers described in JP-A-63-123047 and malondiamide type couplers described in US Pat. No. 4,149,886 are used. However, it has been found that when the specific yellow couplers described in Patent Documents 1 and 2 are used, the degree of occurrence is significantly deteriorated. These are not mentioned in Patent Documents 1 and 2.

  Japanese Patent Application Laid-Open No. H10-228707 consists of an area gradation image with improved color variation and excellent stability by a processing method of a silver halide photosensitive material in which a photosensitive material having a specific size or more is processed in the presence of a specific chelating agent. A method for processing a silver halide photosensitive material for forming a color proof image is described. When the present inventors processed the above-described photosensitive material using the chelating agent described in Patent Document 3, it was confirmed that the degree of occurrence of brown stain was remarkably reduced. Further, Patent Document 4 discloses that a bleach-fixing solution can be provided by using two types of chelating agents in combination to provide quick desilvering and little yellow stain after image storage. When the present inventors processed the above-mentioned photosensitive material using one of the chelating agents described in Patent Document 4, it was confirmed that the degree of occurrence of brown stain was remarkably reduced.

However, none of the patent documents mentions the yellow coupler according to the present invention.
JP 2002-296740 A JP 2003-173007 A JP 2003-29385 A JP 2003-84405 A

  An object of the present invention is to provide a method for processing a silver halide color light-sensitive material that obtains a high-quality color image with improved dot image defects caused by desilvering processing of the silver halide color light-sensitive material.

The above object of the present invention is achieved by the following configurations.
(Claim 1)
In a method for processing a silver halide color light-sensitive material, a silver halide color light-sensitive material having at least one image forming layer on a support is developed and then desilvered using a desilvering solution. The photosensitive material contains a compound represented by the following general formula (Cp-A), and the desilvering treatment solution contains a ferric complex salt of a compound represented by the following general formula (B-1). A method for processing a silver halide color light-sensitive material.

(In the formula, R represents a substituent, 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 when coupled with an oxidized form of a color developing agent.

(In the formula, A ¹ , A ² , A ³ and A ⁴ each represent —CH ₂ OH, —PO ₃ M ₂ or —COOM, and may be the same or different. M represents a hydrogen atom. Represents an alkali metal atom, an organic ammonium group or other cationic group, X represents an alkylene group having 2 to 6 carbon chains or — (B ₁ O) n—B ₂ —, where n is an integer of 1 to 8. And each B ₁ and B ₂ may be the same or different and each represents an alkylene group having 1 to 8 carbon atoms.)
(Claim 2)
In a method for processing a silver halide color light-sensitive material, a silver halide color light-sensitive material having at least one image forming layer on a support is developed and then desilvered using a desilvering solution. The photosensitive material contains a compound represented by the above general formula (Cp-A), and the desilvering treatment solution has 1 to 3 carbon atoms represented by the following general formula (B-2). A method for processing a silver halide color light-sensitive material comprising a ferric complex salt of diacetate.

(In the formula, R represents an alkyl group having 1 to 3 carbon atoms or a substituted alkyl group.)
(Claim 3)
Z in the compound represented by the general formula (Cp-A) is a residue forming a 3H-pyrimidin-4-one ring or a residue forming a 1H-pyrimidin-4-one ring A processing method for a silver halide color light-sensitive material according to claim 1 or 2.
(Claim 4)
Z in the compound represented by the general formula (Cp-A) is a residue forming a 2H- [1,2,4] thiadiazine-1,1-dioxide ring, or 4H- [1,2,4]. 3. The method for processing a silver halide color light-sensitive material according to claim 1, wherein the residue is a residue forming a thiadiazine-1,1-dioxide ring.

  According to the present invention, it is possible to provide a method for processing a silver halide color light-sensitive material for obtaining a high-quality color image with improved dot image defects caused by desilvering processing of the silver halide color light-sensitive material.

  As a result of intensive studies, the present inventors have conducted processing of silver halide color photosensitive materials (hereinafter also referred to as photosensitive materials) containing a compound represented by the general formula (Cp-A), which is excellent in color reproduction. By using a treatment solution containing a ferric complex salt of a specific chelating agent, it is possible to specifically improve the occurrence of punctate brown stains associated with desilvering treatment, and the punctuation that occurs when squeeze shortage occurs It was found that the deterioration of brown stains can be remarkably suppressed. The ferric complex salt of this specific chelating agent is biodegradable and is a preferred compound from the viewpoint of environmental conservation.

  Moreover, in order to exhibit the effect of this invention more, it is preferable that the compound represented by the said general formula (Cp-A) is further a specific compound.

  Hereinafter, the present invention will be described in detail.

[Compound represented by formula (Cp-A)]
The compound represented by the general formula (Cp-A) is a dye-forming coupler.

  R in the general formula (Cp-A) represents a substituent, and the substituent represented by R is not particularly limited, but an alkyl group (for example, a methyl group, an isopropyl group, a (t) butyl group, a 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, A thiazolyl group, an oxazolyl group, an imidazolyl group, a furyl group, a pyrrolyl group, a pyrazinyl group, a selenazolyl group, a sulfolanyl group, a piperidinyl group, a tetrazolyl group, etc.), a halogen atom (for example, a chlorine atom, a fluorine atom, etc.), an alkoxy group (for example, 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.), aryloxy A carbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), a 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) ), Ureido group (for example, methylureido group, ethylureido group, cyclohexylureido group, octylureido group, phenylureido group, naphthylureido group, etc.), acyl group (for example, acetyl group, propylcarbonyl group, cyclohexylcarbonyl group, octyl group) Carbonyl group, 2-ethylhexylcarbonyl group, phenylcarbonyl group, pyridylcarbonyl group and the like), acyloxy group (for example, acetyloxy group, ethylcarbonyloxy group, octylcarbonyloxy group, phenylcarbonyloxy group and the like), carbamoyl group (for example, Aminocarbonyl group, dimethylaminocarbonyl group, cyclohexylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.) An acylamino group (eg, methylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, 2-ethylhexylcarbonylamino group, dodecylcarbonylamino group, naphthylcarbonylamino group, etc.), alkylsulfonyl group or arylsulfonyl group (eg, Ethylsulfonyl 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, Dodecylamino group, anilino group, 2-pyridylamino group, etc.), cyano group, nitro group, sulfo group, carboxyl group, hydroxyl group and the like. These groups are further substituted by the above substituents. It may be.

  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. Of the aryl group. 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 by R may include a hetero atom, and the total number of carbon atoms does not include the number of hetero atoms.

  In the general formula (Cp-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 similar to the group quoted by R in general formula (Cp-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] thiazine-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] thiazine-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 preferred is a 6-membered aromatic ring, and most preferred is 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 the same groups as the substituent represented by R ′ described above.

  In the general formula (Cp-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 include, for example, phenoxy group, alkoxy group, acyloxy group, carbamoyl group, sulfonyl group, or nitrogen-containing heterocyclic 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 described for the group represented by R in the general formula (Cp-A). More specifically, those having the same meaning as the group represented by W described in JP-A-8-29932, 0033 to 0043 can be mentioned.

  Specific examples of the compound represented by the general formula (Cp-A) of the present invention are shown below, but the present invention is not limited thereto.

  These compounds can be synthesized, for example, according to the methods described in US Pat. No. 5,455,149, Japanese Patent Publication No. 2003-64332, and the like.

These compounds can be used usually in the range of 1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻¹ mol, per mol of silver halide. It can also be used in combination with other types of couplers. In order to use the coupler represented by the general formula (Cp-A) of the present invention for a light-sensitive material, the methods and techniques used in ordinary dye-forming couplers are similarly applied.

[Compound represented by formula (B-1)]
In the formula, A ₁ , A ₂ , A ₃ and A ₄ each represent —CH ₂ OH, —PO ₃ M ₂ or —COOM, and may be the same or different. M represents a hydrogen atom, an alkali metal atom, an organic ammonium group, or other cationic group. X represents an alkylene group having 2 to 6 carbon chains or — (B ₁ O) n—B ₂ —. Here, n represents an integer of 1 to 8, and each B ₁ and B ₂ may be the same or different and each represents an alkylene group having 1 to 8 carbon atoms. Examples of the alkylene group represented by X include ethylene, trimethylene, and tetramethylene. Examples of the substituent of the alkylene group represented by X, B ₁ or B ₂ include a hydroxyl group and an alkyl group having 1 to 3 carbon atoms (for example, a methyl group, an ethyl group, etc.). n represents an integer of 1 to 8, preferably 1 to 4.

  Although the specific example of a compound represented by general formula (B-1) of this invention below is shown, this invention is not limited to these.

  The compounds represented by B-1-1 to 17 have various optical isomers, and the S and S-isomers are most preferable from the viewpoint of biodegradability.

[Compound represented by formula (B-2)]
Specific examples of the compound represented by formula (B-2) of the present invention are shown below, but the present invention is not limited to these.

B-2-1: N-methyliminodiacetic acid B-2-2: N-ethyliminodiacetic acid B-2-3: N-hydroxymethyliminodiacetic acid B-2-4: N-β-hydroxyethyliminodiacetic acid B- 2-5: N-propyliminodiacetic acid B-2-6: N-α, β-dihydroxyethyliminodiacetic acid B-2-7: N-α-hydroxyethyliminodiacetic acid B-2-8: β- Alanine diacetic acid Among the above compounds, B2-1, 2, 3, and 8 are particularly preferable.

  The compounds represented by the general formula (B-1) and general formula (B-2) are used as ferric complex salts in the present invention, and these are added in the form of ammonium salt, potassium salt, sodium salt and the like. Alternatively, it may be produced by mixing the free compound and a compound that donates ferric ions in a liquid.

  The preferable addition amount of the compound represented by General Formula (B-1) or General Formula (B-2) is 0.01 to 5.0 mol / L, preferably 0.1 to 2.5 mol in terms of iron ion concentration. / L.

  The processing method using the compounds represented by formulas (B-1) and (B-2) is preferably used in a bleach-fixing step subsequent to color development. Moreover, it is preferable that pH of a use liquid is 3.0-9.0, More preferably, it is 4.0-7.5.

  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. Still other specific examples include compounds M-1 to M-61 described in European Patent No. 273712, pages 6 to 21, and compounds 1 to 223 described in pages 235913 to 36-92. There are other than the specific examples described above.

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

Λmax of the spectral absorption of a magenta image formed in the light-sensitive material according to the present invention is preferably a 530～560Nm, also .lambda.L _0.2 is preferably 580～635Nm. λL _0.2 means a wavelength at which the absorbance is 0.2 longer than the wavelength indicating the maximum absorbance when the maximum absorbance is 1.0 in the spectral absorbance curve of the image dye. This amount is a measure indicating the magnitude of unnecessary absorption on the long wave side of the image dye, and a wavelength closer to λmax is preferable because unnecessary absorption is smaller.

  The magenta image forming layer of the light-sensitive material according to the present invention preferably contains a yellow coupler in addition to a magenta coupler. Preferred yellow couplers to be contained in the magenta image forming layer include known pivaloyl acetanilide type or benzoyl acetanilide type couplers. Specific examples of preferable yellow couplers to be contained in the magenta image forming layer include couplers represented by YCP-1 to YCP-39 described in JP-A-8-314079, pages 6 to 15, right column. 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 an alkyl group, acylamino group, or ureido group, 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 in page 2 of JP-A-8-171185, or a general formula (I) described in JP-A-11-282138 is used. The pyrroloazole couplers represented can be mentioned.

The cyan coupler is usually 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, phenol 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.

  In the case of using an oil-in-water emulsion dispersion method to add a stain inhibitor or other organic compound used in the light-sensitive material according to the present invention, usually, a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher is used. If necessary, it is dissolved in combination with a low boiling point and / 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 organic solvent after the dispersion or simultaneously with the dispersion may be added. Examples of the high-boiling organic solvent that can be used for dissolving and dispersing the stain inhibitor include phosphate esters such as tricresyl phosphate and trioctyl phosphate, phosphine oxides such as trioctyl phosphine oxide, Higher alcohol compounds represented by (ai) to (ax) described on page 5 of No. 4-265,975 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 organic solvents can be used in combination.

  The silver halide emulsion used in the light-sensitive material according to the present invention is preferably a silver halide emulsion comprising at least 95 mol% of silver chloride. Silver chloride, silver chlorobromide, silver chloroiodobromide, silver chloroiodide Those having an arbitrary halogen composition are 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.

  The silver halide emulsion used in the present invention preferably 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, and cobalt, and group 12 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 the 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 forming silver halide fine particles containing these heavy metal compounds in advance and adding them. The addition amount of the heavy metal ions is more preferably 1 × 10 ⁻⁹ to 1 × 10 ⁻² mol, and particularly preferably 1 × 10 ^{−8 to} 5 × 10 ⁻⁵ mol, per mol of silver halide.

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

  The silver halide 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 grain size of the silver halide grains used in the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably 0 in consideration of other photographic performance such as rapid processability and sensitivity. .2 to 1.0 μm.

  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 0.1. 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 represents the standard deviation of the particle size distribution, and R represents 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 silver halide grains may be grown at a time, or may be grown after the seed grains are formed. The method for making seed particles and the method for growing them may be the same or different.

  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 and a water-soluble halide salt aqueous solution from an adding apparatus disposed in a reaction mother liquor described in JP-A-57-92523 and JP-A-57-92524, German Patent No. 2 , 921,164, etc., an apparatus for continuously adding an aqueous solution of a water-soluble silver salt and a water-soluble halide salt, and a reaction mother liquor outside the reactor described in JP-B-56-501776, etc. An apparatus or the like that forms grains while keeping the distance between silver halide grains constant by taking out and concentrating by ultrafiltration 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 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 preferable to change the size of the applied silver halide emulsion types and expected effects, per mol of silver halide 5 × 10 ^-10 ~5 × 10 ^{- 5} mol, preferably 5 × 10 ^{−8 to} 3 × 10 ⁻⁵ mol are 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 to 1 × 10 ⁻⁸ mol per mol of silver halide. It is preferable that More preferably, it is 1 * 10 < ^-5 > -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 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 a known antifoggant for the purpose of preventing fogging during the preparation process of the light-sensitive material, reducing performance fluctuation during storage, and preventing fogging during development. 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 performed in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ^{−5 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 to 1 × 10 ⁻² mol per mol of silver halide, more preferably 1 × 10 ^{−5 to} 5 × 10 ⁻³ mol. . In the coating solution preparation step, when added to the silver halide emulsion layer, the amount is preferably about 1 × 10 ⁻⁶ to 1 × 10 ⁻¹ mol per mol of silver halide, and 1 × 10 ⁻⁵ 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 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, polysulfide compounds such as A-20, C-1, C-9, C-14, C-15, C-16, and C-40, which are specifically described in JP-A-2-146036, It is preferable to use thiosulfonic acid compounds such as D-1, D-3, D-6, D-8, inorganic sulfur, and the like.

  In the photosensitive 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, 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 light-sensitive material according to the present invention has at least one hydrophilic colloid layer colored with a non-diffusible compound on the side closer to the support than the silver halide emulsion layer closest to the support among the silver halide emulsion layers. It is preferable. As the coloring substance, a dye or other organic or inorganic coloring substance can be used. 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. Among these, titanium dioxide is preferred for various reasons. The white pigment is dispersed in a hydrophilic colloid aqueous solution binder such as gelatin so that the treatment liquid can penetrate. The coating amount of the white pigment is preferably 0.1 to 50 g / m ² , more preferably 0.2 to 5 g / 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 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 photosensitive material. Another preferred form is a solid particulate compound having a fluorescent whitening effect.

  The 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 solution, emulsion or suspension of a water-miscible solvent 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.

  In using these dispersing devices, as described in JP-A-4-125632, a pre-treatment such as dry pulverization may be 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 it is better that the time until dispersion is added to the coating solution after dispersion and the time after addition to the coating solution is short. It is preferably within 10 hours, more preferably within 3 hours, and even more preferably within 20 minutes.

  In the light-sensitive material according to the present invention, a compound that reacts with the oxidized developer is added to the layer between the light-sensitive layer to prevent color turbidity, or added to the silver halide emulsion layer to cause fogging, etc. It is preferable to improve. 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 on pages 8-9 of JP-A-2-842.

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

  As the binder hardener, it is preferable to use a vinylsulfone type hardener or a chlorotriazine type hardener alone or in combination. It is preferable to use compounds described in JP-A Nos. 61-249054 and 61-245153. In order to prevent the growth of mold 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 to the colloid layer. 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 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 or the like which may be contained can be used. Among these, a support having a water-resistant resin coating layer on both sides of the 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 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 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 value of the center plane average roughness (SRa) of the support is 0.15 μm or less, and further 0.12 μm or less, because the effect of good gloss is obtained.

  The photosensitive 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 properties, dimensional stability) 1 or 2 or more subbing layers for improving the properties, friction resistance, hardness, antihalation properties, frictional properties and / or other properties.

  In coating the 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 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.

  The term “area gradation image” is used in the background section above, but this does not represent the shading on the image with the shading of the colors of individual pixels, but the size of the area of the portion that has developed to a specific density. It can be considered as synonymous with a halftone dot. 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 values. In printing, a special color plate may be used, but in order to reproduce this, it is preferable to perform exposure using different exposure values of four or more values.

  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 photosensitive material with a light beam. The photosensitive material is wound around a cylindrical drum and rotated at a high speed to move the light beam in a direction perpendicular to the rotation direction. A cylindrical outer surface scanning method may be employed, and a cylindrical inner surface scanning method in which a 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 polyhedral mirror is rotated at high speed to expose the 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 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 light-sensitive 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 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 photosensitive material to be exposed. The number of rotations of the drum can also be set arbitrarily, but an appropriate number of rotations can be selected depending on the beam diameter of laser light, energy intensity, writing pattern, sensitivity of photosensitive material, and the like. 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 photosensitive material may be fixed to the drum by mechanical means, or a number of fine holes that can be sucked on the drum surface are provided according to the size of the photosensitive material, and the photosensitive material is sucked. It can also be adhered. In order to prevent troubles such as image unevenness, it is important to make the photosensitive material as close as possible to the drum.

  As the aromatic primary amine developing agent used in the present invention, known compounds can be used. Examples of these compounds include the following compounds.

CD-1: N, N-diethyl-p-phenylenediamine CD-2: 2-amino-5-diethylaminotoluene CD-3: 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4 : 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5: 2-methyl-4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-6: 4 -Amino-3-methyl-N-ethyl-N- (β- (methanesulfonamido) ethyl) -aniline CD-7: N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide CD-8: N , N-dimethyl-p-phenylenediamine CD-9: 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline CD-10: 4-amino-3-methyl-N Ethyl-N- (β-ethoxyethyl) aniline CD-11: 4-amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline In the present invention, a color developer containing the above compound is arbitrarily selected. However, it is preferably pH 9.5 to 13.0, more preferably pH 9.8 to 12.0 from the viewpoint of rapid processing.

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

  The color development time is generally about 210 seconds, but in the present invention, it is preferably within 120 seconds, and more preferably within 90 seconds.

  In addition to the above 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 light-sensitive material according to the present invention is subjected to desilvering (bleaching) and fixing after color development. The desilvering 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.

(Desilvering solution)
The present invention is characterized in that the desilvering solution contains a ferric complex salt of the compound represented by the general formula (B-1) or (B-2).

  The addition amount of the ferric complex salt of these compounds is preferably contained in the range of 0.01 to 5.0 mol / l, more preferably 0.1 to 2.5 mol / l in terms of iron ion concentration. It is a range.

In the present invention, a ferric complex salt of the following compound can be used as a bleaching agent in addition to the iron complex salt of the compound represented by the general formula (B-1) or (B-2) as a bleaching agent. .
[A′-1] ethylenediaminetetraacetic acid [A′-2] trans-1,2-cyclohexanediaminetetraacetic acid [A′-3] dihydroxyethylglycine [A′-4] ethylenediaminetetrakismethylenephosphonic acid [A′-5 Nitrilotrismethylenephosphonic acid [A'-6] diethylenetriaminepentakismethylenephosphonic acid [A'-7] diethylenetriaminepentaacetic acid [A'-8] ethylenediaminediorthydroxyphenylacetic acid [A'-9] hydroxyethylethylenediaminetriacetic acid [A'-10] ethylenediaminepropionic acid [A'-11] ethylenediaminediacetic acid [A'-12] hydroxyethyliminodiacetic acid [A'-13] nitrilotriacetic acid [A'-14] nitrilotripropionic acid [A ' -15] triethylenetetramine hexaacetic acid [ '-16] ethylenediaminetetrapropionic acid [A'-17] 1,3-propylenediaminetetraacetic acid [A'-18] glycol etherdiaminetetraacetic acid As one of the preferred embodiments of the present invention, Japanese Patent Application No. 60-256383 is disclosed. And examples of compounds (I-1) to (VII-20) described on pages 79 to 142 are added to the desilvering solution of the present invention. Among these compounds, particularly preferred compounds are (C-1) to (C-30) shown below.

  These compounds are suitably used in an amount of 0.05 to 50 g per liter of treatment liquid, and more preferably in the range of 0.1 to 20 g.

  The desilvering solution is preferably used at a temperature of 20 to 50 ° C, preferably 25 to 45 ° C.

  The pH of the desilvering treatment solution (bleaching solution) having no fixing function is preferably 6.0 or less, more preferably 1.0 to 5.5. The pH of the desilvering processing solution (bleaching fixing solution) having a fixing function is preferably 3.0 to 9.0, more preferably 4.0 to 7.5. The pH of the bleaching solution or bleach-fixing solution is the pH of the processing tank at the time of processing the photosensitive material, and can be clearly distinguished from the so-called replenishing solution.

  In addition to the above, the bleaching solution or the bleach-fixing solution may contain various optical brighteners, antifoaming agents or surfactants.

The preferred replenishing amount of the bleaching solution or the bleach-fixing solution is 1000 ml or less per 1 m ² of the light-sensitive material, more preferably 20 to 600 ml, most preferably 40 to 500 ml, and the lower the replenishing amount, the more the present invention. The effect becomes more prominent.

  Further, compounds known to be added to normal fixing solutions or bleach-fixing solutions such as alkylamines and polyethylene oxides can be appropriately added.

  Silver may be recovered from the bleach-fixing solution according to the present invention by a known method.

  The processing time with the bleaching solution and the fixing solution is arbitrary, but it is preferably 3 minutes 30 seconds or less, more preferably 10 seconds to 2 minutes 20 seconds, particularly preferably 20 seconds to 1 minute 20 seconds. is there. The processing time with the bleach-fixing solution is preferably 4 minutes or less, more preferably in the range of 10 seconds to 2 minutes and 20 seconds.

  The development processing apparatus used for the development processing of the photosensitive material of the present invention is a roller transport type that conveys the photosensitive material between the rollers disposed in the processing tank, and conveys the photosensitive material fixed to the belt. 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, the spraying method of spraying the processing liquid, the processing liquid It is also possible to use a web system by contact with a carrier impregnated with, a system using a viscous treatment liquid, or the like. 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 The present invention will be specifically described below with reference to examples, but the present invention is not limited to these embodiments.

Example 1
A polyethylene laminated paper reflective support with a mass of 115 g / m ² , in which high-density polyethylene is laminated on one side and molten polyethylene containing 15% by mass of anatase-type titanium oxide is laminated on the other side. (Stiffness = 3.5, PY value = 2.7 μm), each layer having the layer structure shown in Table 1 below was coated on the side of the polyethylene layer containing titanium oxide. m ² , photosensitive material No. 1 coated with 0.65 g / m ² of silica matting agent. 1 was produced.

The coupler was dissolved in a high boiling point solvent, ultrasonically dispersed, and added as a dispersion. At this time, (SU-1) was used as a surfactant. Moreover, (H-1) and (H-2) were added as a hardening agent. As coating aids, surfactants (SU-2) and (SU-3) were added to adjust the surface tension. Further, (F-1) was added to each layer so that the total amount was 0.04 g / m ² .

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. Q-4: 2,5-di -t- butyl hydroquinone PVP: Polyvinylpyrrolidone

(Preparation of blue-sensitive silver halide emulsion)
The following (A liquid) and (B liquid) were simultaneously added to 1 liter of a 2% by weight gelatin aqueous solution kept at 40 ° C. while controlling pAg = 7.3 and pH = 3.0, and the following (C liquid) And (Liquid D) were 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 the addition, desalting was performed using a 5% by weight aqueous solution of Demol N made by Kao Atlas and a 20% by weight aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to obtain an average particle size of 0.71 μm. A monodispersed cubic emulsion EMP-101 having a coefficient of variation of 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
Next, 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.

STAB-1: 1-phenyl-5-mercaptotetrazole STAB-2: 1- (4-Ethoxyphenyl) -5-mercaptotetrazole STAB-3: 1- (3-acetamidophenyl) -5-mercaptotetrazole (green sensitive halogen Preparation of 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-102 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
Sensitizing dye GS-3 2 × 10 ⁻⁴ mol / mol AgX
Sodium chloride 0.5g / mol AgX
Next, in the preparation of EMP-103, the average particle size was set to 0. 0 as in EMP-103, 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-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-4: p-toluenethiosulfonic acid A 1: 1 mixture of Em-R101 and Em-R102 was used as the red sensitive emulsion.

  Photosensitive material No. As in the case of the photosensitive material No. No. 1 was prepared by replacing Y-1 and Y-2 of the seventh layer with the compounds shown in Table 2 so that the addition amount was 65% by mole. 2-6 were produced.

  The photosensitive material thus produced was exposed as follows. As the light source, 10 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 10 LEDs. In addition, an exposure head was prepared in which 10 LEDs were arranged in the sub-scanning direction, and exposure for 10 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 100 μm. The exposure time per pixel was about 100 nanoseconds.

  After the exposure, the following development processing was performed, and continuous processing (so-called running processing) was performed until the replenishment amount of the bleach-fixing replenisher was twice the capacity of the bleach-fixing tank. The exposure image in the continuous processing was adjusted so that the exposure area was 80% white background and the black color development portion was 20% with respect to the processing area. The density of each color component of the black color development portion is 550 type densitometer manufactured by X-rite, Y component: 1.60 to 1.70, M component: 1.85 to 1.95, C component under spectral condition status T: The exposure amount was adjusted to be 1.80 to 1.90. The treatment liquid according to this production pattern is referred to as pattern A.

Processing step Processing temperature Time Replenishment amount Color development 37.0 ± 0.3 ° C 90 seconds 80 ml / m ²
Bleach fixing 37.0 ± 0.5 ° C. 60 seconds 120 ml / m ²
Stabilization 30-34 ° C 90 seconds 150ml / m ²
Drying 60-80 ° C 30 seconds Color developer tank solution and replenisher Tank solution Replenisher Pure water 800 ml 800 ml
Triethylenediamine 2g 3g
Diethylene glycol 10g 10g
Potassium bromide 0.3g 0.3g
Potassium chloride 3.5g 1.0g
Potassium sulfite 0.02g 0.03g
N-ethyl-N- (β-hydroxyethyl)
-4-aminoaniline sulfate 2.9 g 4.8 g
N, N-disulfoethylhydroxylamine
20.4g 18.0g
Triethanolamine 10.0 g 10.0 g
Diethylenetriaminepentaacetic acid sodium salt 2.0 g 2.0 g
Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g
Potassium carbonate 30g 30g
Add water to bring the total volume to 1 liter, adjust the tank solution to pH = 10.0, and the replenisher to pH = 10.6.

Bleach-fixer tank solution and replenisher solution Diethylenetriaminepentaacetic acid ferric ammonium dihydrate 65g
Diethylenetriaminepentaacetic acid 3.0g
Ammonium thiosulfate (70% by weight aqueous solution) 100 ml
2-amino-5-mercapto-1,3,4-thiadiazole 2.0 g
Ammonium sulfite (40% by weight aqueous solution) 27.5 ml
Water is added to make a total volume of 1 liter, and the pH is adjusted to 5.5 with aqueous ammonia 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
Fluorescent whitening agent (Chinopearl SFP) 0.5g
1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g
Magnesium sulfate heptahydrate 0.2g
PVP (Polyvinylpyrrolidone) 1.0g
Ammonia water (25% by weight aqueous solution of ammonium hydroxide) 2.5g
Nitrilotriacetic acid trisodium salt 1.5g
Water is added to make a total volume of 1 liter, and the pH is adjusted to 7.0 with sulfuric acid or potassium hydroxide solution.

  Further, continuous processing was performed in the same manner as in the preparation of Pattern A except that the spring of the squeeze roller between color development and bleach-fixing was weakened. The treatment liquid according to this production pattern is referred to as pattern B.

  In the bleach-fixing replenisher and tank solution, diethylenetriaminepentaacetic acid ferric ammonium dihydrate is replaced with equimolar amounts of the ferric salts of the compounds shown in Table 2, and diethylenetriaminepentaacetic acid is replaced with equimolar amounts of the compounds shown in Table 2. Each pattern A and B liquid was produced in the same manner except that.

  Similarly, diethylenetriaminepentaacetic acid ferric ammonium dihydrate was replaced with equimolar amounts of the ferric salts of the compounds shown in Table 3, and diethylenetriaminepentaacetic acid was replaced with equimolar amounts of the compounds shown in Table 3 in the same manner. Patterns A and B were prepared.

  From the analysis of iron content in each bleach-fixing solution, the dilution with Pattern A developer was 5%, and the dilution with Pattern B (a group in which the squeeze between color development and bleach-fixing was weakened) was 10%.

Subsequently, the exposure amount was adjusted so that the Y density was 0.85, and the entire surface was exposed and processed with the processing solutions. Table 2 shows the results of measuring the number of brown fault points (pieces / m ² ) of the treated sample. Measurements represent the mean value of the measured number of 10 m ^2.

Regarding the measured value, if the number of failure points exceeds 5 pieces / m ² , there is a possibility that a practical concern may arise, and if it is 9 to 10 pieces / m ² , it is clearly a problem.

  Photosensitive material No. When 1 is processed with the comparative liquid pattern A, the number of failure points is 2.5, which is almost inconspicuous (no problem in practical use) in an actual image, but the processing liquid is fatigued, such as weakening the squeeze. In this state (comparative liquid pattern B), the number of failure points increases to 7.8, and there is a concern that the failure may occur in the actual image.

  Photosensitive material No. 2 to 6 were processed with the comparative liquid pattern A, the number of failure points was 6.8 to 9.0. Degraded compared to 1. Similarly, the number of failure points further increases in the processing with the comparative liquid pattern B that is fatigued.

  However, the photosensitive material No. When the result of treating 2 with the treatment liquid B-1-1 to 3 is seen, it becomes 0.5 to 2.3 in the pattern A and 1.0 to 2.7 in the pattern B which is the deterioration treatment liquid. It was found that both levels were practically acceptable. Similarly, the photosensitive material No. As a result of treating 1 with the treatment liquid B-1-1 to 3, it was 2.3 to 2.7 in the pattern A, and 7.6 to 9.2 in the pattern B. It can be seen that the failure level is greatly degraded. This is a result showing that the effect of improving the failure is not manifested only by changing the chelating agent of the liquid.

  In other words, it can be said that the effect of the present invention is a phenomenon obtained specifically by using a material using a specific Cp described in the present application in combination with a ferric salt-containing bleach-fixing solution of a specific chelating agent. . In each of the examples in which the photosensitive material using the specific Cp described in the present application and the ferric salt-containing bleach-fixing solution of the specific chelating agent are used in combination, the number of failures is clearly reduced with respect to the comparative solution. In addition, the effect of reducing the degree of deterioration is clear with respect to the phenomenon in which the number of failure points deteriorates due to liquid dilution caused by carryover of the liquid in the front tank (color development).

  The results of further investigation on the B-2 chelating agent are shown in Table 3.

  Similar to the liquid containing B-1 chelate iron, the same phenomenon as seen in Table 3 was also observed in the liquid containing B-2 chelate iron. It can be seen that this phenomenon is obtained specifically by using a combination of a photosensitive material using a specific Cp described in the present application and a ferric salt-containing bleach-fixing solution of a specific chelating agent.

Claims (4)

In a method for processing a silver halide color light-sensitive material, a silver halide color light-sensitive material having at least one image forming layer on a support is developed and then desilvered using a desilvering solution. The photosensitive material contains a compound represented by the following general formula (Cp-A), and the desilvering treatment solution contains a ferric complex salt of a compound represented by the following general formula (B-1). A method for processing a silver halide color light-sensitive material.

(In the formula, R represents a substituent, 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 when coupled with an oxidized form of a color developing agent.

(In the formula, A ¹ , A ² , A ³ and A ⁴ each represent —CH ₂ OH, —PO ₃ M ₂ or —COOM, and may be the same or different. M represents a hydrogen atom. Represents an alkali metal atom, an organic ammonium group or other cationic group, X represents an alkylene group having 2 to 6 carbon chains or — (B ₁ O) n—B ₂ —, where n is an integer of 1 to 8. And each B ₁ and B ₂ may be the same or different and each represents an alkylene group having 1 to 8 carbon atoms.) In a method for processing a silver halide color light-sensitive material, a silver halide color light-sensitive material having at least one image forming layer on a support is developed and then desilvered using a desilvering solution. The photosensitive material contains a compound represented by the above general formula (Cp-A), and the desilvering treatment solution has 1 to 3 carbon atoms represented by the following general formula (B-2). A method for processing a silver halide color light-sensitive material comprising a ferric complex salt of diacetate.

(In the formula, R represents an alkyl group having 1 to 3 carbon atoms or a substituted alkyl group.) Z in the compound represented by the general formula (Cp-A) is a residue forming a 3H-pyrimidin-4-one ring or a residue forming a 1H-pyrimidin-4-one ring A processing method for a silver halide color light-sensitive material according to claim 1 or 2. Z in the compound represented by the general formula (Cp-A) is a residue forming a 2H- [1,2,4] thiadiazine-1,1-dioxide ring, or 4H- [1,2,4]. 3. The method for processing a silver halide color light-sensitive material according to claim 1, wherein the residue is a residue forming a thiadiazine-1,1-dioxide ring.