WO2004072730A1 - Silver halide photography photosensitive material - Google Patents

Abstract

A silver color photography photosensitive material having a support and, applied thereon, at least one layer containing a silver halide emulsion, characterized in that said silver halide emulsion contains at least one selenium compound and said layer containing a silver halide emulsion contains a specific magenta coupler; and a method for forming an image using the photosensitive material. The silver halide color photography photosensitive material is improved in reciprocity law failure characteristics, and thus is suitable for the digital exposure at high illuminance for a short time by a laser light, and further, even in mass-production, it is reduced in the fluctuation of photography characteristics due to the retention of an emulsion to be applied and can provide a good image

Description

 Description Silver halide photographic light-sensitive material.

 Honkiaki is a digital silver halide photographic material with improved reciprocity failure characteristics suitable for short-time exposure to high illuminance by laser exposure.Especially, even in mass production, photographic characteristics due to stagnation of emulsion coating solution The present invention relates to a silver halide photographic light-sensitive material capable of obtaining a good image with a small fluctuation in image quality and an image forming method thereof. Background art

 In recent years, in the direction of digitization, silver halide photographic light-sensitive materials (hereinafter simply referred to as "light-sensitive materials") have come to be subjected to digital exposure using a laser beam or the like. Along with this, especially for color papers, which are photosensitive materials for color prints, suitability for exposure to high-intensity light in a very short time of about milliseconds to nanoseconds and suitability for scanning exposure are required. It has become. At the same time, with the rapid progress of other non-silver salt output media such as the ink jet system, there is a strong demand for further evolution of photosensitive materials that are advantageous in image quality, cost, and mass productivity.

Conventionally, silver halide emulsions or silver halide emulsions having a high silver chloride content have been used in silver color emulsions as means for achieving faster development processing. . On the other hand, doping with a iridium compound is effective for improving reciprocity failure property, which is one of the problems of silver halide emulsions. It is generally known that For example, JP-A-64-26837 discloses a high silver chloride emulsion having a region having a high silver bromide content near the apex of silver halide grains. No. 940 discloses that a high silver chloride emulsion having excellent latent image stability and reciprocity failure characteristics can be provided by selectively doping a iridium compound in a localized region of silver bromide. ing. Also, US Pat. No. 5,627,020 discloses a method for forming a localized region of silver bromide by using fine particles of silver bromide doped with a iridium compound. It was not enough. In addition, the silver halide grains have a rich phase of silver bromide and silver iodide in the vicinity of the surface, and this rich phase is introduced twice before and after the addition of the antifoggant compound, and the reciprocity law is established. A method for improving the failure and the stagnation of the coating solution is described (for example, see Patent Document 1). However, it has been found that the preservability of the silver halide emulsion is insufficient even with this method.

 There is also a disclosure of a photographic element containing silver chloride particles containing a selenium compound on the particle surface (see, for example, Patent Documents 2 and 3), but the effect of improving photographic performance other than sensitivity is unknown, and especially for printing. Practical silver halide photography that satisfies recently required various performances without mentioning improvement in sensitivity, gamma, latent image, and other performances due to combination with couplers required for color photographic materials It was difficult to provide photosensitive materials. There are also disclosures of silver halide photographic materials in which selenium sensitization and tellurium sensation are applied to silver chloride and silver chlorobromide grains having a high silver chloride content (for example, Patent Documents 4, 5 and 5). 6), and the effect on sensitivity and gamma was insufficient to respond to the recent demand for silver halide photographic materials.

Under such circumstances, silver halide photography applied to digital exposure method Among various studies on photosensitive materials, there has been a problem that performance fluctuations are large in the process of manufacturing a large amount of photosensitive materials. It was found that this was particularly likely to occur when the coating solution was stored over time.

 SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide emulsion having high sensitivity in digital exposure in which short exposure with high illuminance is performed and having excellent stagnation stability of a coating solution, a method for producing a silver halide emulsion, Materials, silver halide color photographic materials.

(Patent Document 1)

 JP 2001-18831 1

 (Patent Document 2)

 JP 5-66513 A

 (Patent Document 3)

 U.S. Pat.No. 5,240,827

 (Patent Document 4)

 JP-A-5-313293

 (Patent Document 5)

 Japanese Patent Application Laid-Open No. Hei 9-5922

 (Patent Document 6)

 Japanese Patent Application Laid-Open No. 9-15924 Disclosure of the Invention

The above object of the present invention is achieved by each of the following constitutions. 3001534

 Four

(1) A silver halide photographic material having at least one layer containing a silver halide emulsion on a support, wherein the silver halide emulsion contains at least one selenium compound, and A silver halide photo-sensitive material characterized in that the emulsion-containing layer contains magenta black and white represented by the following general formula 1 or 2. General formula 1 General formula 2

[Wherein, R a, R b, R c, and R d represent a substituent, and two of R a, R b, and R c may combine to form a ring. X represents a hydrogen atom or a group capable of leaving during a force coupling reaction with an oxidized form of the developing agent. ]

 (2) The silver halide photographic light-sensitive material according to (1), which contains at least one kind of a 2,5-diacylaminophenol type cyan coupler.

(3) The silver halide photographic material as described in (1) or (2) above, comprising a cyan coupler represented by the following general formulas [I] to [IV]. General formula (I)

General formula (Π)

General formula (ΙΠ)

[In the formula, represents a hydrogen atom or a substituent, and R ₂ represents a substituent. m is a substituent R

Indicates the number ₂ . When m is 0, represents an electron-withdrawing group having Hammett's substituent constant and p is 0.20 or more.When m is 1 or more, and at least one of R ₂ is Hammett's substituent. Represents an electron-withdrawing group having a substituent constant p of 0.20 or more.

 Z represents a nonmetallic atom group necessary for forming a nitrogen-containing 5-membered heterocyclic ring which may be condensed with a benzene ring or the like.

Ra represents a hydrogen atom or a substituent; Z ₂ represents a group of non-metallic atoms necessary for forming a nitrogen-containing heterocyclic 6-membered ring by condensing with —NH— with a birazol ring; The membered ring may have a substituent and may be condensed with a benzene ring or the like in addition to the pyrazole ring.

R ₄ and R ₅ represent Hammett's substituent constant and an electron-withdrawing group whose P is 0.20 or more. You. However, the sum of R ₄ and R ₅ spreadability P value of 0. 6 5 above. Z ₃ represents a group of nonmetallic atoms necessary for forming a nitrogen-containing 5-membered heterocyclic ring, and the 5-membered ring may have a substituent.

R ₆ and R ₇ represent a hydrogen atom or a substituent; Z ₄ represents a group of non-metallic atoms necessary for forming a nitrogen-containing 6-membered heterocyclic ring; and the 6-membered ring may have a substituent. Good.

Χ ι, Χ _2, Χ ₃ and chi ₄ each represent a group capable of leaving by the force Ppuringu reaction with an oxidation product of a hydrogen atom or a color developing agent. BEST MODE FOR CARRYING OUT THE INVENTION

 The present inventors have made intensive studies in view of the above problems, and as a result, in a silver halide photographic light-sensitive material having at least one silver halide emulsion-containing layer on a support, A large amount of silver halide photographic light-sensitive material containing at least one selenium compound and having a specific magenta fogging layer in the silver halide agent-containing layer is used even in digital exposure where high illuminance and short time exposure are performed. It has been found that there is little change in sensitivity during production, and the present invention has been reached.

 In addition, it has been found that a clear image can be obtained, and that the effect can be further enhanced by combining with a specific cyan coupler.

 Hereinafter, details of the present invention will be described.

The silver halide photographic light-sensitive material of the present invention comprises a silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, wherein the photosensitive silver halide emulsion comprises at least one kind of silver halide emulsion. The silver halide emulsion-containing layer containing a selenium compound, and a magenta capillar represented by the above general formula 1 or 2 It is characterized by containing.

 First, the silver halide emulsion according to the present invention will be described.

 The composition of the silver halide emulsion according to the present invention has any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodo-iodide, silver chloroiodobromide, and silver chloroiodide. Among them, silver chlorobromide containing substantially 95 mol% or more of silver chloride and substantially containing no silver iodide is particularly preferable since the effect of the present invention is remarkable. Further, from the viewpoint of rapid processing property and processing stability, a silver halide emulsion containing preferably 97 mol% or more, more preferably 98 to 99.9 mol% of silver chloride is preferable.

In the light-sensitive material according to the present invention, from the viewpoint of reducing softening of a characteristic curve in a high-density region in short-time exposure at high illuminance, a silver halide emulsion having a portion containing silver bromide at a high concentration is also used. It can be preferably used. In this case, the portion containing a high concentration of silver bromide may be formed by epitaxy bonding to silver halide grains, a so-called core / shell emulsion, or by forming a partial layer without forming a complete layer. There may be only regions having different compositions. Further, the composition may be changed continuously or discontinuously. The portion where silver bromide is present at a high concentration is particularly preferably at the surface of silver halide grains or at the top of crystal grains. In the light-sensitive material according to the present invention, it is preferable to use silver halide grains containing heavy metal ions from the viewpoint of reducing softening caused by high-illuminance short-time scanning exposure. Heavy metal ions that can be used for such purposes include Group 8 to 10 metals such as iron, iridium, platinum, / \ ° radium, nickel, rhodium, osmium, ruthenium, and cobalt, and force dium and zinc. And Group II transition metals such as mercury and the ions of lead, rhenium, molybdenum, tungsten, gallium and chromium. Among them, iron, iridium, platinum, ruthenium, gas 01534

8 Lium and osmium metal ions are preferred. 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, its ligand or ion may be a cyanide ion, a thiocyanate ion, a cyanate ion, an isothiocyanate ion, a chloride ion, a bromide ion, an iodide ion, or nitric acid. Ions, carbonyl, ammonia and the like. Among them, a cyanide ion, a thiocyanate ion, an isothiocyanate ion, a chloride ion, a bromide ion and the like are preferable.

 In order to allow the above-mentioned heavy metal ions to be contained in the silver halide grains, the heavy metal compound is subjected to physical ripening, such as before the formation of silver halide grains, during the formation of silver halide grains, or after the formation of silver halide grains. May be added at an arbitrary place in each step. In addition, the solution of the heavy metal compound can be continuously added over the whole or a part of the particle forming step.

The amount of time the addition of the heavy metals Ion in a silver halide emulsion Ha port Gen halide per mole 1 X 1 ID- ⁹ mol or more, 1 X 10_ more preferably ² mol or less, particularly 1 X 10- ⁸ mol or 5 X 10- ⁵ moles or less is preferable.

In the light-sensitive material according to the present invention, any shape can be used for the silver halide grains. One preferable example is a cube having a (100) plane as a crystal surface. In addition, U.S. Pat. Nos. 4,183,756 and 4,225,666, JP-A-55-26589, JP-B-55-42737, and the "Journa Nore" Ob "Photographic" Science (J. P hotog r. S ci.) 21 Particles having shapes such as octahedron, tetradecahedron, and dodecahedron are formed by the method described in the literature such as 1, 39 (1973). It can also be used. Sa Furthermore, particles having twin planes may be used.

 In the light-sensitive material according to the present invention, silver halide particles having a single shape are preferably used, but it is particularly preferable to add two or more monodispersed silver halide emulsions to the same layer.

 The particle size of the silver halide grains according to the present invention is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably 0.1 to 1.2 μm, in consideration of other photographic properties such as rapid processing and sensitivity. , 0.2 to 1.0 m.

 This particle size can be measured using the projected area of the particle or its approximate diameter. If the particles are substantially uniform in shape, the particle size distribution can represent this quite accurately as diameter or projected area.

 The particle size distribution of the silver halide grains used in the light-sensitive material according to the present invention is preferably a monodispersed silver halide grain having a coefficient of variation of 0.22 or less, more preferably 0.15 or less. Particularly preferably, two or more monodisperse emulsions having a coefficient of variation of 0.15 or less are added to the same layer. Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation.

 Coefficient of variation = S / R

 (Where S is the standard deviation of the particle size distribution and R is the average particle size.)

 The particle size referred to here is the diameter of a spherical silver halide particle, or the diameter of a cubic or non-spherical particle when the projected image is converted into a circular image of the same area. Represent.

 Various methods known in the art can be used as a device and method for preparing a silver halide emulsion.

The silver halide emulsion used for the light-sensitive material according to the present invention may be prepared by an acid method, a neutral method, It may be obtained by any of the Amonmonier method. The particles may be grown at one time or may be grown after seed particles have been made. The method for producing the seed particles and the method for growing them may be the same or different.

 The form of reacting the soluble silver salt with the soluble halide salt may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like, but a method obtained by a simultaneous mixing method is preferable. Further, as one form of the simultaneous mixing method, a pAg-controllable double-jet method described in JP-A-54-48521 can be used.

 Further, a water-soluble silver salt and a water-soluble silver salt were obtained from an addition device disposed in a reaction mother liquor described in JP-A-57-92523 and JP-A-57-92525. A device for supplying an aqueous solution of a halide salt, a device for continuously changing the concentration of an aqueous solution of a water-soluble silver salt and a water-soluble halide salt described in German Published Patent Application No. 2,921,164, etc. Take the reaction mother liquor out of the reactor as described in JP-B-56-5017-176, etc. and concentrate by ultrafiltration to form grains while keeping the distance between silver halide grains constant. An apparatus or the like may be used.

 If necessary, a silver halide solvent such as polyester 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.

In the silver halide color photographic light-sensitive material according to the present invention, the layer containing a silver halide emulsion contains at least one selenium compound (hereinafter, also referred to as a selenium sensitizer), and the sensitized sensitizer is used for chemical sensitization. One feature is that it contains silver halide. As the selenium sensitizer that can be used in the present invention, particularly, an unstable selenium compound that can react with silver nitrate in an aqueous solution to form a silver selenide precipitate is preferably used. For example, U.S. Patent Nos. 1,574,944, 1,602,592, 1,623,499., JP-A-60-150046, JP-A-4-25832, and JP-A-4-25832. Nos. 109240 and 4-147250.

Useful selenium sensitizers include colloid selenium metal, isoselenone phanates (eg, aryl iselenosinate), selenoureas (eg, N, N-dimethylselenourea, N, N,,) 'Triethylselenourea, Ν, Ν, Ν', Ν '—Tetramethylselenourea, Ν, Ν, N' —Trimethyl-1-N '—Heptafluoroselenourea, Ν, Ν'Dimethyl Ν, Ν'Ibis (force Ruboxymethyl) selenoureas, Ν, Ν, N '—trimethyl-1-NT—heptafluoropropylcarbonylselenourea, N, N, —trimethyl_Ν' — 412-trofenerukalpulonylselenourea, etc.), selenoketones (For example, selenoacetone, selenoacetophenone, etc.), and selenoamide (for example, selenoacetamide, Ν, Ν-dimethylselenobenzamide, Ν, Ν-jetyl-1-) Octylaminosulfonyl selenobenzamide, etc., selenocarboxylic acids and selenoesters (eg, 2-selenopropionic acid, methyl-13-selenobutyrate), and selenophosphites (eg, tri-ρ-tolylseleno) Phosphite, pentafluorene phenyldiphenylselenophosphite, etc., selenides (for example, dimethylselenide, tributylphosphineselenide, triphenylphosphineselenide, triphenyltolylphosphineselenide) , Pentafluorophenyl diphenylphosphine selenide, triflylphosphine selenide, tripi T / JP2003 / 001534

 12

Lysylphosphine selenide). Particularly preferred selenium sensitizers are selenoureas, selenoamides and selenides.

Specific examples of techniques for using these selenium sensitizers are disclosed in the following patents. U.S. Pat.Nos. 1,574,944, 1,602,592, 1,623,499, 3,297,466, 3,297,447, 3 No. 3, 320, 069, No. 3, 408, 196, No. 3, 408, 197, No. 3, 442, 653, No. 3, 420, 670, No. 3, 591, 385 French Patent Nos. 2,693,038, 2,093,209, JP-B Nos. 52-34491, 52-34492, 53-295, 57-22090, and JP-A 59-90 — 180536, 59—185330, 59—181337, 59—187338, 59—192241, 60—150046, 60—151637, 61—246738, and JP-A-3- Nos. 4221, 3-24537, 3--11 1838, 3-116132, 3-148648, 3-237450, 4-16838, 4-25832, 4-25832, 4- — 32831, 4-133043, 4—96059, 4-1109240, 41-140738, 4−140739, 4-1147250, 4-184331, 4 19 0225, 4-19 1929, 41-195035, 5-11 385, 5-40324, 5-24332, 5-24333, 5-30333, 5303157 5-306268, 6-306269, 6-27573, 6-75328, 6-175259, 6-20818 4, 6-208186, 6-317867, 6 7-92599, 7-98483, 7-104415, 7-140579, 7- 2003/001534

13

No. 301879, Week 7-30 1880, Same 8-11,882, Same 9-19 760, Same 9-138475, Same 9-1 66841, Same 9-1 38475, Same 9-189979 No. 10-10666, JP-A-2001-343721, UK Patent Nos. 255,846 and 861,984, and the like. , 31 vol., 158-169 (1983).

The preferred amount of selenium增感agent according to the present ^{invention, 1 X 10- 9 ~1 X 10-} 1 molar Z moles A g X, more preferably 1 X 10- ⁸ ~1 X 10- ² mol / mol A g.

 In order to add the selenium sensitizer according to the present invention to a silver halide emulsion, a method generally used in the art for adding an additive to a photographic emulsion can be applied. For example, when the compound is a water-soluble compound, an aqueous solution having an appropriate concentration is used. When the compound is insoluble or hardly soluble in water, any organic solvent that can be mixed with water, for example, alcohols, glycols, and ketones It can be dissolved in a solvent that does not adversely affect photographic properties such as esters, amides and the like, and added as a solution.

In the silver halide emulsion used in the light-sensitive material according to the present invention, a known chemical sensitization method, for example, a sensitization method using a gold compound, or a chalcogen sensitizer is used together with the above-described sensitizer. Sensitization can be used. As the chalcogen sensitizer applied to the silver halide emulsion, an io sensitizer, a tellurium sensitizer, and the like can be used, and an io sensitizer is preferable. Examples of the thiosensitizer include thiosulfate, arylthiocarbamidothiourea, arylisothiocyanate, cystine, p-.toluenethiosulfonate, lipo-danin, and inorganic dye. Yeah The amount of the sensitizer to be added is preferably changed depending on the type of silver halide emulsion to be applied and the size of the expected effect, but is preferably from 5 × ^{10 to 10 to} 5 × ^{10 to} 5 mol per mole of silver halide. X 1 0- ⁵ mols, preferably ^{5 X 1 0 - 8 ~3 X} 1 0- 5 mole range is preferred.

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 the gold compound, the kind of silver halide emulsion, the type of compound used, but are not and ripening conditions, is usually 1 mol of silver halide per 1 X 1 0- ⁴ mol ~ 1 X 1 It is preferably from 0 to ⁸ mol. More preferably, it is from 1 × 10 to ⁵ mol to 1 × 10 to ⁸ mol.

 The silver halide emulsion layer according to claim 1 of the present invention is characterized in that the silver halide emulsion layer contains the magenta inks represented by the general formulas 1 and 2.

 The magenta coupler according to the present invention will be described.

 In the general formulas 1 and 2, R a, R b, R c, and R d each represent a substituent, and two of R a, R b, and R c may be bonded to form a ring. Good.

 The substituents represented by R a, R b, and R c are not particularly limited, but typically include alkyl, aryl, cycloalkyl, heterocycle, halogen, hydroxy, alkoxy, anilino, acylamino, and sulfonamide. And preferably an alkyl group.

The substituent represented by R d is not particularly limited, but is typically alkyl, aryl, cycloalkyl, heterocyclic, halogen, anilino, acylamino, sulfonamide, alkoxy, aryloxy, or heterocyclic. Ring, alkylthio, aryl —Ruthio, sulfonyl, peridode, rubamoyl ヽ sulfamoyl and the like.

 X i 1 represents a group or an atom which can be eliminated by a reaction with an oxidized form of the developing agent, and is a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a sulfonyloxy group, an alkylthio group, an arylthio group. And the like, preferably a halogen atom, and more preferably a chlorine atom.

 Specific examples of the compounds represented by the general formulas 1 and 2 according to the present invention include the following compounds.

W1- 1

M-1 4

The photosensitive silver halide emulsion layer according to the present invention preferably contains at least one kind of a 2,5-diacylaminophenol-type cyan coupler.

The 2,5-diacylaminophenol type cyan coupler is obtained by reacting phenol with an acylamino group at the 2nd and 5th position, a hydrogen atom at the 4th position or an oxidized form of an aromatic primary amine color developing agent. It represents a phenol compound substituted with a leaving group, and preferred compounds include 2,5-diacylaminophenol type having a spectral absorption maximum wavelength of 6100 nm to 6400 nm. It is a cyan coupler. The preferred 2,5-diacylaminophenol-type cyan coupler is preferably a cyan dye-forming coupler capable of forming an aggregated dye. A particularly preferred 2,5-diaminoaminophenol type cyan coupler is a coupler having an arylsulfonyl group. Particularly preferred cyan couplers include Four

And those represented by the general formula (D).

Wherein R ¹ is a hydrogen atom or an alkyl group; R ² is an alkyl group or an aryl group; n is 1, 2, or 3; Located at the meta or para position of the phenyl ring, independently of alkyl, alkenyl, alkoxy, aryloxy, asiloxy, asilamino, sulfonyloxy, sulfamoylamino, sulfonamide, perylene, oxycarbonyl, Z is a hydrogen atom or a group that can be separated by reaction of the coupler with the oxidized color developing agent.

In the general formula (D), R ¹ is hydrogen or an alkyl group containing a linear or branched, cyclic or acyclic alkyl group, and is preferably methyl, ethyl, n-propyl, isopropyl, decyl, It is a dodecyl or butyl group, most preferably an ethyl group. R ² is an aryl group or an alkyl group (for example, a perfluoroalkyl group). Such alkyl groups typically have 1 to 20 carbon atoms, usually 1 to 4 carbon atoms, and include groups such as methyl, propyl and dodecyl; and perfluoroalkyl have 1 to 20 carbon atoms. Typically having from 3 to 8 carbon atoms and including, for example, trifluoromethyl or perfluorotetradecyl, heptafluoropropyl or heptadecylfluorooctyl; Four

18 A substituted or unsubstituted aryl group typically has 6 to 30 carbon atoms and includes, for example, a halogen atom having 1 to 4 carbon atoms, a cyano group, a carbonyl group, a carbonamide group, a sulfonamide group, It may be substituted with a carboxy group, a sulfo group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group or an arylsulfonyl group. Desirable R ² is a heptafluoropropyl group, a 4-chlorophenyl group, a 3,4-dichlorophenyl group, a 4-cyanophenyl group ヽ 3-chloro-1-4-cyanophenyl group, a pentafluorophenyl group, —It is a bonamidophenyl group, a 4-sulfonamidophenyl group, or an alkylsulfonylphenyl group.

However, when R ¹ is an alkyl group having 4 or more carbon atoms, R ² has an electron-withdrawing group having a Hammett sigma value greater than 0 at the meta or para position relative to the amide group, and It is preferable that the phenyl group has no group having a Hammett sigma value greater than 0 in the ortho position to the phenyl group.

In the general formula (D), each X is located at the meta- or para-position of the phenyl ring, and each independently represents a linear or branched, saturated or unsaturated, alkyl or alkenyl group ( For example, methyl, t-butyl, dodecyl, pentadecyl, or octadecyl); an alkoxy group (eg, methoxy, t-butoxy or tetradecyloxy); an aryloxy group (eg, phenoxy, 4-t-1). Alkyl or aryloxy group (for example, acetooxy or dodecanoyloxy); alkyl or aryloxy group (for example, acetoamide, benzamide, or hexadeoxy); Alkyl) or alkyl or arylsulfonyloxy group (for example, , Methylsulfonyl old carboxymethyl, dodecylsulfonyl O carboxymethyl, if Or 4-methylphenylsulfonyloxy); an alkyl or arylsulfamoylamino group (eg, N-butylsulfamoylamino or N-4t-butylphenylsulfamoylamino); al ^^ Alkyl or aryl sulfonamide groups (eg, methanesulfonamide, 4-chlorophenylsulfonamide or hexadenesulfonamide); peridot groups (eg, methyl or radon); alkoxycarbonyl or Aryloxycarbonylamino group (for example, methoxycarbonylamino or phenoxycarbonylamino); sulfamoyl group (for example, N-butylcarbamoyl or N-methyl-N-dodecylcarbamoyl); Mouth alkyl groups (e.g., Represents fluoromethyl or heptafluoropropyl). Preferably, it is a straight-chained group having 1 to 30 carbon atoms, more preferably 8 to 20 carbon atoms. Most typically, X is a linear alkyl group of 12 to 18 carbon atoms, such as dodecyl, pentadecyl or octadecyl. An alkyl group having no branch is more preferable than an alkyl group having a branch.

 n represents 1, 2, or 3, and when n is 2 or 3, the substituents X may be the same or different. Z represents a hydrogen atom or a group which can be removed by a reaction with an oxidized color developing agent. Examples include halogen, alkoxy, aryloxy, heterocyclyloxy, sulphonyloxy, acyloquin, and acyl. Halogen, alkoxy and aryloxy groups are most suitable.

Examples of specific coupling-off groups, - C l, one F, -B r, - S CN , one OCH _3, one _{OC 6 H 5, ~ OCH 2} C (= 0) NHCH 2 CH 2 OH - OCH ₂ C (= 0) NH CH ₂ CH ₂₀ CH ₃ . A preferred capping leaving group is a chlorine atom.

 Next, examples of the compound of the cyan coupler according to the present invention will be described, but it should not be construed that the invention is limited thereto.

oz

ST

 Οΐ

9i a

s—a "£ Sl00 / C00Zdf / X3d

u_i-SH ^st O u— Η ^οι Ό

.HNOH0- ^Z OS- 《/)

l7CSl00 / C00Zdf / X3d οε ^ ο OA The cyan couplers described above may be used as a mixture of a plurality of compounds, or may be used in combination with other types of cyan couplers.

The coating amount of the cyan coupler is preferably 0.28 g / m ² or less, more preferably 0.25 gZm ² or less.

Further, the photosensitive silver halide emulsion layer according to the present invention preferably contains a cyan coupler represented by the general formulas [I], [II], [ΠΙ], and [IV]. In the above general formula, represents a hydrogen atom or a substituent, and R ₂ represents a substituent. m represents the number of substituents R ₂ . When m is 0, represents a Hammett's substituent constant and an electron-withdrawing group having p of 0.20 or more. When m is 1 or 2 or more, at least one of Ri and R ₂ is substituted for Hammett. The base constant and P represent an electron-withdrawing group of 0.20 or more.

 Represents a group of nonmetallic atoms necessary for forming a nitrogen-containing 5-membered heterocyclic ring which may be condensed with a benzene ring or the like.

R ₃ represents a hydrogen atom or a substituent; Z ₂ represents a group of non-metallic atoms necessary for forming a nitrogen-containing heterocyclic 6-membered ring by condensing with the pyrazole ring together with —NH—; The ring may have a substituent and may be condensed with a benzene ring or the like in addition to the pyrazole ring.

R ₄ and R ₅ represent an electron-withdrawing group having a Hammett's substituent constant and p of 0.20 or more. However, the sum of R ₄ and R ₅ spreadability P value is 0.65 or more. Z ₃ represents a group of nonmetallic atoms necessary for forming a nitrogen-containing 5-membered heterocyclic ring, and the 5-membered ring may have a substituent.

 R 6 and R 7 represent a hydrogen atom or a substituent; Z 4 represents a group of non-metallic atoms necessary for forming a nitrogen-containing 6-membered heterocyclic ring; and the 6-membered ring may have a substituent. Good.

Χι, Χ ₂ , Χ ₃ and Χ ₄ are, respectively, the force with hydrogen It represents a group that leaves by a coupling reaction.

 The substituent constant defined by Hammett and a substituent having a p of +0.20 or more are specifically sulfonyl, sulfinyl, sulfonyloxy, sulfamoyl, phosphophoryl, carpa, moyl, acsyl, acsyloxy, o Examples include groups such as xoxycarbonyl, carboxyl, cyano, nitro, halogen-substituted alkoxy, halogen-substituted aryloxy, pyrrolyl, and tetrazolyl, and halogen atoms. Examples of the sulfonyl group include alkylsulfonyl, arylsulfonyl, halogen-substituted alkylsulfonyl, and halogen-substituted arylsulfonyl; sulfinyl groups include alkylsulfinyl, arylsulfiel and the like; sulfonyloxy groups include alkylsulfonyloxy Sulfamoyl groups such as N, N-dialkylsulfamoyl, N, N-diarylsulfamoyl, N-alkyl-1-N-arylsulfamoyl, etc .; phosphoryl groups such as alkoxy Phosphoryl, aryloxyphosphoryl, alkylphosphoryl, arylphosphoryl, etc .; Examples of the molybamoyl group include N, N-dialkylcarba'moyl, N, N-diarylcarba'moyl, N-alkyl N-arylcarbamoyl, etc. ; A Examples of the alkoxy group include alkylcarbonyl, arylcarbonyl and the like; Examples of the alkoxy group include alkylcarbonyloxy and the like; Examples of the oxycarbonyl group include alkoxycarbonyl and aryloxy groups. A halogen-substituted aryloxy group such as tetrafluoroaryloxy or pentafluoroaryloxy; a pyrrolyl group such as 1-pyrrolyl; a tetrazolyl group such as 1-tetrazolyl; Can be

In addition to the above substituents, trifluoromethyl group, heptafluoroisopropyl group, A nonylfluoro-t-butyl group, a tetrafluoroaryl group, a pentafluoroaryl group and the like are also preferably used.

In the general formula [I], among the substituents represented by or R ₂ , the substituents other than the electron-withdrawing group include various types and are not particularly limited, but typical examples thereof include alkyl, Aryl, Anilino, Annulamino, Sulfonamide, Alkylthio, Arylthio, Alkenyl, Cycloalkyl, Cycloalkenyl, Alkynyl, Heterocycle, Alkoxy, Alyloxy, Heterocyclic Oxy, Siloxy, Amino, Alkylamino, Imid , Peridode, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioperido, hydroxyl and mercapto groups, and Spiro compound residues, bridged hydrocarbon compound residues, etc. .

 The alkyl group preferably has 1 to 32 carbon atoms, and may be linear or branched. The aryl group is preferably a phenyl group.

 Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group; examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group; an alkyl component of the alkylthio group and the arylthio group; Is the above-mentioned alkyl group and aryl group.

 The alkenyl group is preferably one having 2 to 32 carbon atoms, and the cycloalkyl group is preferably one having 3 to 12 carbon atoms, particularly preferably 5 to 7 carbon atoms. The alkenyl group may be straight-chain or branched. As the cycloalkenyl group, those having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms are preferred.

Alkylide groups, aryl groups, etc .; As the moylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, or the like; As the heterocyclic group, a 5- to 7-membered group is preferable, and specifically, a 2-furyl group, a 2-phenyl group, —Pyrimidinyl group, 2-benzothiazolyl group, etc .; As the heterocyclic oxy group, those having a 5- to 7-membered heterocyclic ring are preferable, for example, 3,4,5,6-tetrahydrobiranyl-1-oxy group, 1— A 5- to 7-membered heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, a 2-pyridylthio group, a 2-benzothiazolylthio group, a 2,4-diphenyloxy group; 3,5-triazole-16-thio group, etc .; siloxy groups such as trimethylsiloxy group, tridiethylsiloxy group, dimethylbutylsiloxy group, etc .; imido groups, succinic acid imido group, 3 —Hepta Spiro [3.3] heptane-11-yl, etc .; spiro compound residue; bicyclo [2. succinic acid residue, phthalimid group, daltalimide group, etc .; 2.1] heptane one 1 one I le, tricyclo [3. 3.1.1 ^3.7] decane one 1-I le, 7, 7-dimethyl-one bicyclo [2.2.1] heptane one 1 Iru etc. Are listed.

 These groups may further include a substituent such as a long-chain hydrocarbon group or a non-diffusible group such as a polymer residue.

In the general formula [I], examples of the group capable of leaving by reaction with an oxidized form of the color developing agent represented by X include, for example, a halogen atom (hydrochloric acid, bromine, fluorine, etc.) and alkoxy, aryloxy, heterocyclic oxy, acyloxy, Sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkoxythiocarbonylthio, acylamino , Sulfonamide, N atom Groups such as nitrogen-containing heterocyclic ring, alkoxycarbonylamino, aryloxycarbonylamino, carboxyl, etc., of which preferred are a hydrogen atom and alkoxy, aryloxy, alkylthio, aryl. Chio is a nitrogen-containing heterocyclic group linked by an N atom.

 In the general formula [I], examples of the nitrogen-containing 5-membered heterocyclic ring formed by are a pyrazole ring, an imidazole ring, a benzimidazole ring, a triazole ring, a tetrazole ring and the like.

 More specifically, the compound represented by the general formula [I] is represented by the following general formulas [I] -1 to [I] 17. General formula [I] 1 1 General formula [I] -2 General formula [I] 1 3

-General formula [I] -4 General formula [I]-5

—General formula [I] -6 -General formula [I]-'

In the above general formula, (I) at least one of and R in one 1,;! I! One 2 during and at least one of R ₁₂ - D (I) Rh 11 in one 3 ₁₃及At least one of [11] Ri, Ris and R16 in [I] -14, at least one of [16], [I] at least one of Ri and R17 in 15; At least one of Ri and R ₁₈ in [I] -16 and [I] _-7 is an electron-withdrawing group having a σ 0 of 0.20 or more.

Has the same meaning as X in the general formula [I], and p represents an integer of 0 to 4. Also, in general formula [I]-1 to [I] -17,! ^ And! ^ 丄 ~! ^^ Of, those sigma _[rho is not 0.20 or more electron-withdrawing group, a hydrogen atom or a substituent, of R 10 _18, is not an electron withdrawing group, there is no particular restriction on the substituent Specific examples thereof include those described in the general formula [I] or when R ₂ is other than an electron-withdrawing group, or as a substituent represented by R ₂ .

 The cyan coupler having an electron-withdrawing group according to the present invention can be prepared according to the method described in JP-A-64-554, JP-A-64-555, JP-A-64-557 and JP-A-1-105251. It can be easily synthesized. .

 Next, the cyan coupler represented by the general formula [II] will be described.

The cyan coupler of the general formula (II) has a structure in which a 6-membered heterocyclic ring is condensed with a pyrazole ring, and the substituent represented by R ₃ is not particularly limited. Groups such as alkyl, aryl, anilino, acylamino, sulfonamide, alkynylthio, arylthio, alkenyl, cycloalkyl, etc., and, in addition, halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl. , Sulfinyl, phosphonyl, acyl, carpa, moyl sulfamoyl, cyano, alkoxy, sulfonyloxy, aryloxy, heterocyclic, silo Xy, asiloxy, carbamoyloxy, amino, alkylamino, imido, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclicthio, Examples include groups such as thioperide, carboxyl, hydroxyl, mercapto, nitrate, and sulfonic acid, as well as spiro compound residues and bridged hydrocarbon compound residues.

The alkyl group represented by R ₃ preferably has 1 to 32 carbon atoms, and may be linear or branched. The aryl group is preferably a phenyl group.

Examples of the acylamino group represented by R ₃ include an alkylcarbonylamino group, an arylcarbonylamino group and the like; Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group; an alkylthio group alkyl component definitive in § Li one thio group, § Li - Le component of the alkyl group represented by R _3, include Ryoriichiru group.

The alkenyl group represented by R ₃ is preferably a group having 2 to 32 carbon atoms, and the cycloalkyl group is preferably a group having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms. The alkenyl group may be linear or branched. The cycloalkenyl group preferably has 3 to 12 carbon atoms, particularly preferably 5 to 7 carbon atoms.

Examples of the sulfonyl group represented by R ₃ include an alkylsulfonyl group and an arylsulfonyl group; examples of the sulfinyl group include an alkylsulfinyl group and an arylsulfinyl group; An alkoxyphosphonyl group, an aryloxyphosphonyl group, an arylphosphonyl group, etc .; an alkyl group such as an alkylcarbonyl group, an arylcarbonyl group, etc .; Carbamoyl group; sulfamoyl group As alkylsulfamoyl group, arylsulfamoyl group, etc .; as alkoxy group, as alkylcarbonyloxy group, as arylcarboxyloxy group, etc .; as carbamoyloxy group, as alkylsulfamoyloxy group, as arylcarbamoyloxy group. A perylene group as an alkyl ureido group, an aryl perido group, etc .; a sulfamoylamino group as an alkyl sulfamoylamino group, an arylsulfamoylamino group, etc .; a heterocyclic group as a heterocyclic group. 5- to 7-membered ones are preferred, specifically, 2-furyl, 2-phenyl, 2-pyrimidinyl, 2-benzothiazolyl, 1-pyrrolyl, 1-tetrazolyl, etc .; heterocyclic oxy As the group, those having a 5- to 7-membered heterocyclic ring are preferable, for example, 3,4,5,6-tetrahydroviranyl-l2-oxo. Heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, 2-pyridylthio group, 2-pentazothiazolylthio group, 2,4 —Diphenyloxy 1,1,3,5-triazo-1-yl 6-thio group, etc .; siloxy group such as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; imido group as succinic acid imid group, 3-Heptadecyl succinate imido group, phthalanolimide group, glutarimide group, etc .; Spiro compound residue such as spiro [3.3] heptane-1-yl, etc .; Bridged hydrocarbon compound residue such as bicyclo [ 2.2.1] hept Hmm 1 one I le, preparative Rishikuro [3. 3.1.1 ^{3 '7]} decane one 1-I le, 7, 7 - dimethyl over pin cyclo [2.2.1] heptane one 1-yl and the like. The above group may further have a substituent such as a long-chain hydrocarbon group ゃ a non-diffusible group such as a polymer residue.

Examples of the group capable of leaving by the reaction with the oxidized form of the color developing agent represented by Xz include the same groups as X in the general formula [I]. In the general formula (II), the nitrogen-containing 6-membered heterocyclic ring formed by Z ₂ is preferably a 67-electron system or an 8-electron system, and contains 1 to 4 nitrogen atoms including at least one NH—. And the at least one carbonyl group contained in the 6-membered ring represents a group such as> C = 0 or> C = S. Further, at least one sulfonyl group contained in the 6-membered ring represents a —S 0 ₂ — group.

 Preferred specific examples of the cyan coupler of the present invention include compounds represented by the following general formulas [Π] -1 to [Π] 16.

-General formula [Π]-1-General formula [Π]-2-General formula [Π] 1 3

_{Wherein, R 3, R 2 i,} R 22, R 23, R 2 4, Rss, R 26, R 27 and R ₂₈ are collected by synonymous in the general formula [I], X ₂ is the general formula [I And in the general formula [Π] -15, η represents an integer of 0 to 4. When η is an integer of 2 to 4, a plurality of R ₂₆ may be the same or different.

R ₂₄ , R ₂₅ , R ₂₇ and R ₂₈ in general formulas [II] 1-4 and [II] -6 are general Has the same meaning as in formula [I], but and are not hydroxyl groups.

In the general formula (III), R ₄ and R ₅ represent an electron-withdrawing group having a Hammett's substituent constant and _P of 0.20 or more, and these electron-withdrawing groups are represented by the general formula (I) and The same groups as the electron-withdrawing groups for R ₂ can be exemplified. However, the sum of R ₄ and R ₅ spreadability P value is 0.65 or more.

Examples of the nitrogen-containing 5-membered heterocyclic ring formed by Z ₃ include a pyrazoyl ring, an imidazole ring, and a tetrazole ring. These 5-membered nitrogen-containing heterocyclic rings may have a substituent.

 More specifically, the compound represented by the general formula [III] is represented by the following general formulas [πι]-丄 to [III] -8. General formula [m] 1 1-General formula [m] -2 General formula [m]-3

—General formula [m] 14 'General formula [πι] -5' General formula [ΠΙ] —6

2003/001534

General formula (ΙΠ) 1 7 'General formula (m) --8

In the formula, R ₄ , R ₅ and X ₃ have the same meanings as in the general formula [III]. R 3 i is a hydrogen atom or a substituent, R 3 ₂ represents a Hame' bets substituent constant beauty p is 0.20 or more electron withdrawing groups.

The substituents represented by R ₃ i, formula (II) R ₃ and Ki de include the same groups as the electron-withdrawing group represented by R _32, the general formula [I] in and R ₂ The same groups as the electron-withdrawing groups can be exemplified.

 With respect to the cyan coupler represented by the general formula (III), a cyan coupler represented by the general formula (III) -11, (III) -12 or (III) -13 is preferable, and in particular, the (III) _2 The cyan couplers represented are preferred.

In the general formula [IV], R ₆ and R ₇ each represent a hydrogen atom or a substituent, and examples of these substituents include the same groups as R _{3 in the} general formula [式].

Z ₄ in the general formula [IV] represents a nonmetallic atom group necessary for forming a nitrogen-containing 6-membered heterocyclic ring. Provided that the heterocyclic ring has at least one dissociating group. Examples of four divalent linking groups for forming a nitrogen-containing hetero 6-membered ring include, for example, one NH—, -N (R) one N =, -CH (R)-, one CH =, one C (R ) =, -CO-, one S-, -S O-, - S 0 2 - and the like (R is a substituent group include the substituents exemplified in R a L as an example). Examples of the dissociating group include those having an acidic proton such as 1 NH— and 1 CH (R) — It has a value of pK a 3 to 12.

 Of the couplers represented by the general formula [IV], preferred specific examples include compounds represented by the following general formulas [IV] -1 to [IV] -6. General formula [IV] 1 1 General formula [IV] —2 —General formula [IV] —3

In the formula, R ₆ , R ₇ and X ₄ have the same meanings as in the general formula [IV]. Each R 4 ₁ and R ₄₂ represents a hydrogen atom or a substituent, R ₄₃ represents a Saddle Tsu bets substituent constant beauty P value 0.20 or more electrically attractive group.

Specific examples of the substituents of R ₄₁ and R ₄₂ are the same as those of R _{3 in the} general formula [II]. Specific examples of the electron-withdrawing group represented by R ₄₃ are the same as those of the general formula [I] and R ₂ . It is the same as the attraction group. '

 Examples of the group capable of leaving by reaction with the oxidized form of the color developing agent represented by X4 include the same groups as Xi in the general formula [I].

Hereinafter, cyan couplers represented by the general formulas [I] to [; IV] (hereinafter referred to as the cyan coupler of the present invention) Specific examples are referred to as "uncouplers", but are not limited thereto.

 C-6

Zl-0

 92

l7CSl00 / C00Zdf / X3d οε ^ ο OAV

1633P NHSCH

_H si. ₀ ooHN

Cyan couplers are usually 1 mole of silver halide per 1 X 1 0- ³ ~丄Mo Honoré, preferably in an ^{1 X 1 cr 2 ~8 x 1} o- 1 mole range. It can also be used in combination with another type of cyan coupler.

 The support that can be used in the present invention is preferably a paper support in which a resin coating layer is applied to the rain surface of a substrate.

As the paper support in which the resin coating layer is provided on the rain surface of the base paper, a paper support in which both sides of the base paper are laminated with a polyolefin is preferable, and particularly preferably, a polyethylene support is used. Four

43 Paper support laminated with ren.

 The base paper used for the paper support is made of wood pulp as the main raw material, and if necessary, is made using synthetic pulp such as polypropylene or synthetic fibers such as Nyopen® polyester in addition to wood pulp. . As wood pulp, any of L BKP, LBSP, NBKP, NB SP, LDP, NDP, LUKP, NUKP can be used, but more L BKP NB SPLBSP NDP, LDP should be used. Is preferred. However, the ratio of LBSP and / or LDP is preferably 10% by mass or more and 70% by mass or less.

 As the pulp, a chemical pulp (sulfate pulp or sulfite pulp) having a small amount of impurities is preferably used, and pulp having improved whiteness by a bleaching treatment is also useful. The base paper contains sizing agents such as higher fatty acids and alkyl ketene dimers, white pigments such as calcium carbonate, talc and titanium oxide, paper strength agents such as starch, polyacrylamide and polyvinyl alcohol, and polyethylene glycol. Water holding agents such as celluloses, dispersants, and softening agents such as quaternary ammonium can be added as appropriate.

The freeness of pulp used for papermaking is preferably 200 to 500 m1 according to the CSF regulations, and the fiber length after beating is specified in JIS-P-8207. It is preferable that the sum of the mass% and the residual amount of 42 mesh is 30 to 70%. In addition, the mass% of the 4-mesh residue is preferably 20% by mass or less. The basis weight of the base paper is preferably from 30 to 250 g / m ² , particularly preferably from 50 to 200 gZm ² . The thickness of the base paper is 40-250; «111 is preferred. The base paper can be calendered at the papermaking stage or after papermaking to provide high smoothness. The base paper density is generally 0.7 to 1.2 g / cm ³ (JIS-P-8118). In addition, The paper stiffness is preferably 20 to 200 g under the conditions specified in JIS—P—8143. A surface sizing agent may be applied to the surface of the base paper. As the surface sizing agent, the same sizing agent as that which can be added to the base paper can be used. The pH of the base paper is preferably 5 to 9 when measured by the hot water extraction method specified in JIS-P-8113.

 The polyethylene that covers the front and back surfaces of the base paper is mainly low-density polyethylene (LDPE) and / or high-density polyethylene (HDPE), but also includes LLDPE (linear low-density polyethylene) and polypropylene. Can be used. In particular, as the polyethylene layer on the photosensitive layer side, as is widely used in photographic paper, rutile or anatase type titanium oxide is added to polyethylene to improve opacity and whiteness. preferable. The content of titanium oxide is usually 3 to 20% by mass relative to polyethylene, preferably

It is 4 to 13% by mass.

 Polyethylene-coated paper can be used as glossy paper, or when polyethylene is melted and extruded onto the surface of a base paper, a so-called molding process is performed to obtain a matte surface that can be obtained with ordinary photographic printing paper. Those having a silk surface can also be used in the present invention.

 The amount of polyethylene used on the front and back sides of the base paper is usually in the range of 20 to 40 m on the side of the polyethylene layer on which the photosensitive layer is provided and 10 to 30 m on the side of the back layer. Further, the polyethylene-coated paper support preferably has the following properties.

1. Tensile strength: The strength specified in JIS-P-811 13. It is preferable that the vertical direction is 20 to 30 ON and the horizontal direction is 10 to 20 ON. 2. Tear strength: According to the method specified in JIS-P-811-16, preferably 0.1 to 20 N in the vertical direction and 2 to 20 N in the horizontal direction

 3. Compression modulus 98. I MP a

 4. Surface Beck Smoothness: Under the conditions specified in JIS-P-811, 20 seconds or more is preferable for the glossy surface, but may be less for so-called molded products.

 5.Surface roughness: The surface roughness specified by JIS-B-0601 is preferably not more than 10 m per 2.5 mm of the reference length.

 6. Opacity: 80% or more, particularly preferably 85 to 98%, as measured by the method specified in JIS—P—8138

 7. Whiteness: L * and ab * specified by JIS—Z—8729 are L * = 80 to 95, a * = 3 to 10 and b * =-6 to 10 2 Is preferably

 8. Surface glossiness: The 60-degree specular glossiness specified in JIS-Z-871 is preferably from 10 to 95%.

9. Kura Ichiku stiffness: conveying direction of class Ichiku stiffness of the recording medium ^{5 0~3 0 0 cm 2 / l} 0 0 a a support is preferred

 100. Water content of middle paper: usually 2 to 100% by mass, preferably 2 to 6% by mass with respect to the middle paper

In the present invention, a silver halide emulsion can be optically spectrally sensitized to a desired wavelength region by adding a dye (spectral sensitizing dye) that absorbs light in a wavelength region corresponding to a target spectral sensitivity. Examples of the spectral sensitizing dyes used at this time include, for example, Hemocyc 1—iccompounds — yaninedyesandrelatedcompounds (John Wiley and Sons; New York, 1964). Examples of the spectral sensitizing dye used in the present invention include a cyanine dye, a merocyanine dye, and a complex merocyanine dye. In addition, there are complex cyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. As the cyanine dye, simple cyanine dye, carbocyanine dye, and dicarbocyanine dye are preferably used. In the silver halide photographic light-sensitive material of the present invention, components other than those described above, for example, other silver halide photographic emulsions, emulsion additives, sensitizing methods, anti-capri agents, stabilizers, Dye prevention dye, yellow coupler, magenta black, cyan coupler, spectral dye, emulsification dispersion method, surfactant, anti-turbidity inhibitor, binder, hardener, slipping agent, matting agent, support , Bluing agents and reddish agents, coating methods, color developing agents, processing methods, development processing apparatuses, processing agents, etc. are described in JP-A-11-347615, page 9, left paragraph 22, line 9 Each compound and the method described in paragraph No. 0106 on page 17, left side, line 17, line 17 can be used. In addition, it is described in Research Disc Mouth Jar No. 17643, No. 18716 and No. 308 119 (hereinafter abbreviated as RD 17643, RD 18716 and RD 308 119, respectively). Can be selected and used as appropriate.

 Next, a digital exposure method using the silver halide color photographic light-sensitive material of the present invention will be described.

In order to form a photographic image using the silver halide color photographic light-sensitive material of the present invention or to form a copy image using the color print of the present invention, the image recorded on the negative is printed. Light on silver halide color photographic light-sensitive material It is possible to print the image on a CRT (cathode ray tube) after converting the image into digital information, and then print this image. The image may be printed on a single photographic photosensitive material and printed, or may be printed by changing the intensity of one laser beam based on digital information and scanning. Exposure is preferably based on digital information.

 In the case of performing exposure using one laser beam, the exposure time per pixel is not particularly limited, but the exposure is performed in 100 nanoseconds to 100 microseconds. The exposure time per pixel is defined as the outer edge of the light beam when the light intensity reaches the maximum value of 12 in the spatial change of the light beam intensity, and it is parallel to the scanning line and the light intensity is the maximum. When the distance between two points where the line passing through a point and the outer edge of the light beam intersect is defined as the light beam diameter, the exposure time per pixel is defined as (light beam diameter) / (scanning speed).

 Examples of laser printers that can be applied to such systems include, for example, JP-A-55-4071, JP-A-59-11062, JP-A-63-19977, JP-A-74942, and JP-A-2-74942. 236538, JP-B-56-14963, JP-B-56-40822, European wide-area patent 7710, Department of Electronics and Communication Technology Technical Report 80, No. 244, and Movie and TV Technology Journal 1984/6 (382), 34-36 pages.

In the silver halide color photographic light-sensitive material of the present invention, the horizontal axis: exposure amount (L 0 g E) and the vertical axis: color development obtained by performing exposure and color development processing with an exposure time of 10 to ⁶ seconds or less. It is preferable that the variation of the average gradient of a straight line passing through the point giving the density ◦.5 and the point giving the density 1.5 on the characteristic curve composed of the density be within 10% in the multiple exposure. The characteristic curve in the present invention, was subjected to high-intensity exposure of less than 1 0 ⁶ seconds, the image obtained by performing the color development of the standards, the horizontal axis 1 0 g E (E is the exposure amount) And the vertical axis is D (color density). Multiple exposure means that the same pixel is exposed twice or more at the time of high illuminance exposure of 10 to ⁶ seconds or less. In addition, the fluctuation of the average gradient at that time means that a line passing through a point giving a density of 0.5 and a point giving a density of 1.5 is drawn on a characteristic curve obtained by color development after one exposure. Means the variation of the gradient (tan 6>).

 Fluctuations in the density gradient due to multiple exposures mean color fluctuations in the print, and ideally no average gradient fluctuations.

 As the light source for exposing the silver halide color photographic light-sensitive material of the present invention, in addition to the Xe flash light, a light emitting diode, a gas laser, a solid laser, a semiconductor laser, a HeNe laser, etc. Lasers, dye lasers, etc. Furthermore, it can be used in either the vertical single mode or the horizontal multi mode, and a light source modulated by electric modulation by superposition of high frequency and by SHG (second harmonic element) may be used. Particularly, in order to design an apparatus that is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

The exposure time in such a scanning exposure is defined as the time for exposing a pixel size in the case of the pixel density 4 0 0 dpi, 1 0 ³ sec or less preferred exposure time, more preferably 1 0 ⁶ seconds It is as follows. The dpi in the present invention indicates the number of dots per 2.54 cm.

Next, the present invention will be described specifically with reference to examples, but embodiments of the present invention are not limited thereto. Hereinafter, the present invention will be described with reference to examples, but embodiments of the present invention are not limited thereto.

 << Preparation of silver halide emulsion >>

 Each silver halide emulsion was prepared by the following method.

 (Preparation of red-sensitive silver halide emulsion)

 In one liter of 2% aqueous gelatin solution kept at 40 ° C, 30 minutes while controlling pAg to 7.3 and .pH to 3.0 in 1 liter of a 2% aqueous gelatin solution kept at 40 ° C. Then, the following (solution C) and (solution D) were simultaneously added over 180 minutes while controlling the pAg at 8.0 and the pH at 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 solution of sodium hydroxide.

 (A liquid)

 Sodium chloride 3.42 g bromide power 0.03 g 200 ml with water

(Liquid B)

 Silver nitrate 10 g Add water 200 ml

(C solution)

 Sodium chloride 102.7 g

_{K 2 I r C 16 X 10} _8 mol / mol A g 4F e (CN) 2 X 10- 5 mol / mol A g Nioikaryoku Riumu 3001534

50 ml with water

(D solution)

 After adding 300 g of silver nitrate and 600 ml of water to complete the addition of each of the above solutions, desalting was performed using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas, and gelatin was added. Emulsion EMP-1 was obtained as a monodisperse cubic emulsion having an average particle size of 0.40 m, a coefficient of variation of the particle size distribution of 0.07, and a silver chloride content of 99.5 mol% by mixing with an aqueous solution.

 Next, except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed, the average particle diameter was increased in the same manner as in Emulsion EMP-1. Emulsion EMP-1B was obtained as a monodispersed cubic emulsion having a particle size distribution of 38 m, a coefficient of variation of the particle size of 0.07, and a silver chloride content of 99.5 mol%.

 The above emulsion EMP-1 was subjected to optimal chemical sensitivity at 60 ° C. using the following compounds. Similarly, after optimally chemical sensitizing the emulsion EMP-1B, the emulsion EMP-1 and the emulsion EMP-1B were mixed at a silver content ratio of 1: 1. A red-sensitive silver halide emulsion (10 1 R) was obtained.

Chio sodium sulfate 1 X 1 CI- ⁴ mol mol A g X chloroauric acid 2 X 10- ⁴ mol / mol A g X Stabilizer: STAB - 1 3 X 1 O- 4 mol / mol A g X Stabilizer: STAB - 2 3 X 1 O- ⁴ mol / mol A g X stabilizer: STAB- 3 3 X 10- ⁴ mol / mol A g X增感dye: RS - 1 1 X 10- ⁴ mol / mol A g X增sensitive dye: RS- 2 1 X 10- ⁴ mol / mol A g X 3001534

51

S TAB— 1: 1— (3-acetamidophenyl) 5-mercaptotetrazole

 S TAB—2: 1-phenyl-5-mercaptotetrazole

 S TAB—3: 1-1 (4-ethoxyphenyl) —5-mercaptotetrazole

Also the red-sensitive emulsion, SS- 1 was Π per mol of silver halide 2. 0 X 10 one ³添力.

 (Preparation of green photosensitive silver halide emulsion)

 In the preparation of the above emulsion EMP-1, the average particle size was 0.40 m in the same manner except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. The emulsion EMP-2 was obtained as a monodisperse cubic emulsion having a coefficient of variation of 0.08 and a silver chloride content of 99.5%. Next, in the preparation of the emulsion EMP-1, the average particle size was adjusted in the same manner as above except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. Emulsion EMP-2B was obtained as a monodisperse cubic emulsion having a particle diameter of 50 m, a coefficient of variation of 0.08, and a silver chloride content of 99.5%.

 The emulsion EMP-2 prepared above was optimally chemically sensitized at 55 ° C using the following compounds. Similarly, after optimal chemical sensitization of emulsion EMP-2B, the emulsion EMP-2 and emulsion EMP-2B were mixed at a silver ratio of 1: 1. Thus, a green light-sensitive silver halide emulsion (10 1 G) was obtained.

Chio sodium sulfate 1 X 10- ⁴ mole / / mole A g X

'Chloroauric acid 1.2 X 10— ⁴ mol Z mol Ag X Stabilizer: S TAB— 1 2.5 X 10— ⁴ mol _ mol Ag X Stabilizer: S TAB— 2 3.1 X 10— ⁴ mol / mol A g X Stabilizer: STAB—33.1 X 1 CT ⁴ mol Z mol Ag X X Dye: GS—l 4 X 10 mol / mol Ag X

(Preparation of blue-sensitive silver halide silver halide emulsion)

 In the preparation of the emulsion EMP-1, the average particle size was 0.71 in the same manner except that the addition time of (Solution A) and (Solution B) and the addition time of (Solution C) and (Solution D) were changed. The emulsion EMP-3 was obtained as a monodisperse cubic emulsion having a size of μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5%.

 The emulsion EMP-3 was optimally subjected to chemical sensation at 60 ° C. using the following compounds to obtain a blue-sensitive silver halide emulsion (101B).

Chio sodium sulfate 1 X 1 0- ⁴ mol / mol A g X chloroauric acid 2 X 1 0- ⁴ mol / mol A g X Stabilizer: STAB- 1 2 X 1 0- ⁴ mol / mol A g X stabilizer : STAB- 2 ⁴ X 1 0- 4 mol / mol A g X stabilizer: STAB- 3 1 X 1 mol / mol A g X sensitizing dyes: BS- 1 ⁴ X 1 0_ 4 mol / mol A g X增sensitive dye: BS- the 2 IX 1 0- ⁴ mol / mol a g X above the additives used in the preparation of the color-sensitive emulsion detail, below <

BS-1

(CH ₂ ) ₃ S03 BS-2

(CH ₂ ) ₃ S0 ₃ H ■ N (C ₂ H ₅ ) ₃

GS-1

<< Production of silver halide photographic light-sensitive material >>

[Preparation of Sample 101] High-density polyethylene was laminated on both sides of a paper pulp having a basis weight of 180 gZm ² to produce a paper support. However, on the side to which the emulsion layer was applied, a molten polyethylene containing surface-treated anatase-type titanium oxide dispersed at a content of 15% by mass was laminated to produce a reflective support. After the reflective support is subjected to a corona discharge treatment, a gelatin undercoat layer is provided, and each layer having the following structure is further provided to prepare a silver halide photographic light-sensitive material (101). The coating solution was prepared as described below.

 (First layer coating solution)

 Yellow coupler (Y-1) 23.4 g, dye image stabilizer (ST-1) 3.34 g, (ST-2) 3.34 g, (ST-5) 3.34 g, stin prevention 0.34 g of agent (HQ-1), 5.0 g of image stabilizer A, 3.33 g of high-boiling organic solvent (DBP) and 1.67 g of ethyl acetate 60 m 1 in 1.67 g The solution is emulsified and dispersed in 220 ml of a 10% aqueous gelatin solution containing 7 ml of 20% surfactant (SU-1) using an ultrasonic homogenizer to disperse the yellow coupler. Was prepared. This dispersion was mixed with the blue-sensitive silver halide emulsion 101 B prepared above to prepare a first layer coating solution.

 (Preparation of coating solution for 2nd to 7th layers)

 The second to seventh layer coating solutions were prepared in the same manner as the first layer coating solution, using the following additives.

 (Configuration of sample 101)

7th layer: protective layer> g / m ² gelatin 1.00 DIDP 0.005 silicon dioxide 0.003 <Sixth layer: UV absorbing layer>

Gelatin 0.40 UV absorber (UV-1) 0.12 UV absorber (UV-2) 0.04 UV absorber (UV-3) 0.16 Sting inhibitor (HQ-5) 0.04

PVP (Polyvinyl pigment) 0.03 Anti-irradiation dye (AI-2) 0.01

<Fifth layer: Red photosensitive layer>

Gelatin 1.30 Red photosensitive silver halide emulsion (10 1 R) 0.21 Cyan coupler (Cp-1) 0.25 Cyan coupler (Cp-2) 0.08 Dye image stabilizer ( ST-1) 0.10 Sting inhibitor (HQ-1) 0.004

D 0 P 0.34 Layer 4: UV absorbing layer>

Gelatin 0.94 UV absorber (UV-1) 0.28 UV absorber (UV-2) 0.09 UV absorber (UV-3) 0.38 Anti-stinting agent (HQ-3) 0.10 Anti-dye (AI-2) 0.02 3rd layer: green photosensitive layer>

Gelatin 1.30 Green photosensitive silver halide emulsion (101G) 0.14 Magenta coupler (Mp-1) 0.20 Dye image stabilizer (ST-3) 0.20 Dye image stabilizer (ST-4) 0.17

D I D P 0.1 3

D B P 0.13 Anti-irradiation dye (AI-1) 0.01 Second layer: Intermediate layer>

Gelatin 1.20 Stin inhibitor (HQ-2) 0.03 Stin inhibitor (HQ-3) 0.03 Stin inhibitor (HQ-4) 0.05 Stin inhibitor (HQ-5) 0 . twenty three

D I D P 0.06 Optical brightener (W-1) 0.10 Anti-irradiation dye (AI-3) 0.01 First layer: Blue-sensitive layer>

Gelatin 1.20 Blue-sensitive silver halide emulsion (101B) 0.26 Yellow coupler (Y-1) 0.70 Dye image stabilizer (ST-1) 0.10 Dye image stabilizer (ST—

 Stin inhibitor (HQ-1

 Dye image stabilizer (ST—

 Image stabilizer A

 DNP

D B P

 Support: Reflective support 1 Polyethylene laminated paper (containing a trace amount of colorant) The amount of each silver halide emulsion described above was expressed in terms of silver. Further, (H-1) and (H-2) are added to each of the above coating solutions as a hardening agent, and surfactants (SU-2) and (SU-3) are used as coating aids. Was added to adjust the surface tension. Preservative F-1 was added as appropriate.

 S U-1: Sodium tri-i-propylnaphthalenesulfonate

 S U-2: Di (2-ethylhexyl) sulfosuccinate '' sodium salt

 S U— 3: Sulfosuccinate di (2,2,3,3,4,4,5,5-octafluoropentyl) 'Natrium salt

 DBP: Dibutyl phthalate

 DNP: dinonyl phthalate

 D 0 P: Dioctylphthalate

 D I D P: di-i-decylphthalate

 H—1: Tetrakis (vinylsulfonylmethyl) methane

 H-2: 2,4-dichloro-6-hydroxy-1-s-triazine 'sodium

HQ-1: 2,5-dioctyl high droquinone

HQ-2: 2,5—di-sec—dodecylhydroquinone HQ-3: 2,5-di-sec-tetradecylhydroquinone

HQ—4: 2-sec-dodecyl-5—sec—tetradecylhydroquinone

 HQ-5: 2,5-di [(1,1-dimethyl-14-hexyloxycarbonyl) butyl] hydroquinone

 Image stabilizer A: P-t-octylphenol

 Y one 1

Mp-1

 Cp-1

ST— 1

ST— 2

ST— 3

ST— 4

ST— 5

 UV-1

UV-2

AI-1

 AI-2

AI-3

Four

Molar ratio

Thus, a photosensitive material sample (101) was prepared.

Next, half of the molar amount of sodium thiosulfate used in the preparation of each photosensitive silver halide emulsion was replaced with the selenium compound (1): (phenyl) ₃ — P = Se, A silver halide emulsion was prepared in the same manner except that sodium sulfate and a selenium compound were used in combination.

 Each sample was prepared by changing the silver halide emulsion to be used, the magenta color filter of the third layer, and the cyan coupler of the fifth layer in an equimolar combination as shown in the following table.

 When preparing a silver halide photographic light-sensitive material, in order to evaluate suitability for mass production, immediately after preparation, the coating solution for each layer was overlaid for 12 hours while storing at 38 ° C, and the light-sensitive material was coated. Produced. Each light-sensitive material was exposed and evaluated as follows. 《Evaluation of silver halide silver halide photographic material》

 (Exposure)

For each of the photosensitive material samples prepared in this manner, a blue light source was used as a light source laser (about 422 nm), a green light source was used as a light source and a neon laser (about 5 nm), and a red light source was used as a light source. An optical system using a gallium aluminum arsenide semiconductor laser (about 780 nm) as a light source, a beam diameter of about 80 m, a scanning speed of 16 OmZ seconds using a polygon mirror, and 1 exposure time per pixel is 5 X 1 0- ⁷ seconds Article Exposure was performed on each sample, and the laser exposure sensitivity was measured according to a standard method. [Development Processing] Each of the samples exposed above was subjected to the following development processing. <Development processing> Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C 45 seconds 80 m1 / m “Bleaching and fixing 35, 0 ± 0.5 ° C 45 seconds 1 20 Stable 30-34 ° C 60 seconds 150 m 1 / m ² Drying 60-8 (TC 30 seconds The composition of each processing solution used in the development process is shown below. Color developing solution> Tank solution Replenisher a Pure Water 800 ml 800 ml l Triethylenediamin 2 g 3 g Diethylene glycol 10 g 10 g Potassium bromide 0.0 1 g-Potassium chloride 3.5 g-Potassium sulfite 0.25 g 0.5 g

N-ethyl-N- (3-methanesulfonamidoethyl) -13-methyl-14-anoaniline sulfate 6.0 g 10.0 g

N, N-Getylhydroxylamine 6.8 g 6.0 g Triethanolamine 10.0 g 10.0 g Diethylenetriaminepentaacetic acid pentasodium salt 2.O g 2.0 g Fluorescent whitening agent (4, 4 'diaminostilbene disulfonic acid derivative)

 2.0 g 2.5 g Carbonate 30 g 30 g Water was added to make the whole volume 1 liter. The pH of the tank solution was adjusted to 10.10, and the pH of the replenisher was adjusted to 10.60.

 Bleach-fixer: tank solution and replenisher>

 Diethylenetriaminepentaacetate ammonium dihydrate 65 5 g Diethylenetriaminepentaacetic acid 3 g ammonium thiosulfate (硫酸 0% aqueous solution) 100 m 1

2-amino-5-mercapto-1,3,4-thiadiazol 2 • 0 g ammonium sulfite (40% aqueous solution) 2 7 • 5 m 1 Add water to make 1 liter, and add potassium carbonate or ice Adjust the pH with acetic acid.

 <Stabilizing solution: tank solution and replenisher>

 o—phenylphenol 1 • 0 g

5-Mouth 2-methyl-4-isothiazoline-3-one 0 • 0 2 g

2-Methyl-1-isothiazolin-1-one 0 • 0 2 g Diethylene glycol 1 • 0 g Fluorescent whitening agent (Tinopearl S F P) 2 • 0 g

1-Hydroxyethylidene 1,1-diphosphonic acid 1 • 8 g Bismuth chloride (45% aqueous solution) 0 • 65 g Magnesium sulfate-7 hydrate 0 • 2 g

PVP 10 g Aqueous ammonia (25% aqueous ammonium hydroxide solution) 2.5 g Trisodium triacetate trisodium salt 1.5 g Water was added to make the total volume 1 liter, and the pH was adjusted to 7.5 with sulfuric acid or aqueous ammonia. .

 (Evaluation of sensitivity variation)

 The sensitivity difference (A S) at a reflection density of 0.8 in the neutral image was measured as the sensitivity variation between the immediately prepared sample of each sample and the sample 12 hours after the start of coating. The results are shown in the table below.

 (Image sharpness)

A landscape image was printed on the photosensitive material produced after storage of the coating solution, and the sharpness of the image was visually evaluated in three ranks of Δ, Δ, and ◎.

1534

66

Sample Item III Evaluation Evaluation Equipment

 1 1 2 Number (molar ratio) M force plastic c force bra-ΔS

10 1 1/0 Mp-1 C p-1, Cp-1 23.2 Δ Comparison

1 02 1/0 M- 2 C p-1, C p-1 23.1 Δ Comparison

103 0.5 / 0.5 Mp-1 Cp-1, Cp-1 23.0 Δ Comparison

104 0.5 / 0.5 M- 1 C p-1, C p 1 2 2.1 〇Invention 105 0.5 / 0.5 M- 1 C p- 12.4 〇Invention

1 06 0.5 / 0.5 M-1 D-7 1.8 ◎ The present invention

106 0.5 / 0.5 M-1 C- 7 1.9 ◎ The present invention

1 07 0.5 / 0.5 M-1 C-20 1,9

108 0.5 / 0.5 M- 1 C- 26 1.8 The present invention Item 1: Silver halide emulsion in the first, third and fifth layers

 Sodium thiosulfate selenium compound (1)

 Evaluation 1: Sensitivity variation during manufacturing (%)

 Evaluation 2: Image sharpness (coated product after storage)

 As is clear from the table, the sensitivity variation due to changes in the manufacturing time during digital laser exposure is small, stable and uniform with the sample of the present invention using a selenium compound and a specific force brush. Was reproduced.

In addition, a trial of this festival was performed in which a landscape image was printed on a photosensitive material manufactured after storing the coating solution. With the sample, a clear image with a high density was obtained. Industrial potential

 As described above, according to the configuration of the present invention, even in high-illuminance short-time exposure by a laser, high sensitivity, high color density, and little variation due to stagnation time in emulsion stability in the manufacturing process. A silver halide photographic light-sensitive material can be provided.

Claims

The scope of the claims

1. A silver halide photographic light-sensitive material having at least one silver halide emulsion-containing layer on a support, wherein the silver halide emulsion contains at least one type of selenium.

5. A silver halide photographic emulsion characterized in that the silver halide emulsion-containing layer contains 5 compounds, and the layer containing magenta black and white is represented by the following general formula 1 or 2.

 Light material. Expression

 Two

—General formula 1 丄^u

In the formula, R a, R b, R c, and R d represent a substituent, and two of R a, R b, and R c may combine to form a ring. X represents a hydrogen atom or a group capable of leaving during a 15-force pulling reaction with an oxidized form of the developing agent.

2. The silver halide photographic light-sensitive material according to claim 1, which contains at least one kind of 2,5-diacylaminophenol type cyan coupler.

3. —General formula [I] ~! The haptic silver halide photographic material according to claim 1 or 2, wherein the material contains a cyan coupler represented by the formula: —General formula (I)

General formula (Π)

General formula (mj

In the formula, represents a hydrogen atom or a substituent, and R ₂ represents a substituent. m represents the number of substituents R ₂ . When m is 0, represents a Hammett's substituent constant and an electron-withdrawing group having a p of 0.20 or more.When m is 1 or 2 or more, and at least one of R ₂ is a Hammett's substituent. P represents an electron-withdrawing group of 0.20 or more.

 Zi represents a group of nonmetallic atoms necessary for forming a nitrogen-containing 5-membered heterocyclic ring which may be condensed with a benzene ring or the like.

R 3 represents a hydrogen atom or a substituent, and Z ₂ represents a pyrazole ring and a condensed ring with one NH— Represents a group of non-metallic atoms necessary to form a nitrogen-containing 6-membered heterocyclic ring, wherein the 6-membered ring may have a substituent, and may be condensed with a benzene ring or the like in addition to the pyrazole ring. It may be.

R ₄ and R ₅ represent an electron-withdrawing group having a Hammett's substituent constant and P of 0.20 or more. However, the sum of R ₄ and R ₅ spreadability P value is 0.6 5 above. Z ₃ represents a group of nonmetallic atoms necessary for forming a nitrogen-containing 5-membered heterocyclic ring, and the 5-membered ring may have a substituent.

R ₆ and R ₇ represent a hydrogen atom or a substituent; Z ₄ represents a group of non-metallic atoms necessary for forming a nitrogen-containing 6-membered heterocyclic ring; and the 6-membered ring may have a substituent. Good.

Χι, X ₂ , Χ ₃ and Χ ₄ each represent a hydrogen atom or a group which is released by a force coupling reaction with an oxidized form of a color developing agent.