DE69612061T2 - Color photographic light-sensitive silver halide material - Google Patents

Description

The present invention relates to a color photography technology, and more particularly, the present invention relates to a silver halide color photography material which is resistant to environmental influences and can be processed easily and quickly and also has a good color forming property, a good storage stability and a good color tone, and a color image forming method therefor.

Generally, color photographic materials are color developed after exposure, whereby an oxidized p-phenylenediamine derivative reacts with a coupler to form an image. In this process, color reproduction is achieved by a subtractive color process, and yellow, magenta and blue-green color images are formed, respectively, which are in a complementary relationship to each other, to reproduce blue, green and red colors.

Color development is achieved by immersing an exposed color photographic light-sensitive material in an aqueous alkali solution having a p-phenylenediamine derivative (color developer) dissolved therein. However, the p-phenylenediamine derivative formed in the aqueous alkali solution is unstable and easily degrades with aging, and in order to maintain a stable developing capacity, there is a problem that the color developer must be frequently refreshed.

In addition, the disposal of the used color developer containing the p-phenylenediamine derivative requires cumbersome procedures, and in combination with the frequent replenishment described above, the disposal of the used color developer generated in large quantities causes a serious problem. Therefore, low replenishment and low generation of the color developer are highly sought after.

An effective means for solving the issue of low replenishment and low consumption of the color developer is a method of adding an aromatic primary amine or a precursor thereof into a hydrophilic colloid layer, and examples of an aromatic primary amine developing agent capable of addition and the precursor therefor include the compounds described in U.S. Patent No. 4,060,418. However, since these aromatic primary amines and precursors thereof are unstable, stains are disadvantageously formed during long-term storage of an unprocessed photosensitive material or in color development. Another effective means is a method of adding a sulfonylhydrazine type compound described in, for example, EP-A-0 545 491 and EP-A-0 565 165 into a hydrophilic colloid layer. However, the sulfonylhydrazine type compounds described in these patent publications are not sufficiently stable, and staining due to high temperature, high humidity or light during long-term storage after processing is still at a problematic level. In addition, the sulfonylhydrazine type compound has a problem that almost no color formation is achieved when a 2-equivalent coupler is used. The 2-equivalent coupler is advantageous compared with the 4-equivalent coupler in that the spots attributable to the coupler can be reduced, the activity of the coupler can be easily regulated, and various functions can be transferred to the split-off group.

EP-A-0 554 778 describes a silver halide photographic material comprising a support having thereon at least one layer containing a hydrazide compound of the formula RNHNHC(O)(PA) wherein R represents an alkyl group, an aryl group or an aromatic heterocyclic group and (PA) represents a pyrazoloazole coupler residue or an indazolone coupler residue.

EP-A-0 167 762 describes a silver halide color photographic material to which an ether compound is added either in a silver halide emulsion layer or in a layer adjacent thereto or in both.

In order to solve the problems described above, it was demanded to develop a technique for increasing the color forming properties and a technique that allows the use of a 2-equivalent coupler.

The object of the present invention is to provide a photosensitive material capable of low replenishment and low consumption, having a good color forming property and further reduced in stains due to high temperature/high humidity or light during long-term storage of the photosensitive material.

The object of the present invention can be achieved by the following structure:

a silver halide color photographic light-sensitive material comprising a support having at least one layer containing photographic components, wherein at least one of the layers containing photographic components contains at least one reducing agent for color formation, at least one dye-forming coupler and at least one compound having an erasure rate constant (Kq) to singlet oxygen of 1 x 10⁷ M⁻¹·s⁻¹ or more; characterized in that the reducing agent for color formation is represented by the formulas (II) or (III):

wherein Z¹ represents an acyl group, a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, Z² represents a carbamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, X¹, X², X³, X⁴ and X⁵ each represent a hydrogen atom or a substituent, with the proviso that the sum of the values of the Hammett constants σp of X¹, X³ and X⁵ and the values of the Hammett constants σm of X² and X⁵ is 0.80 to 3.80, and R³ represents a heterocyclic group.

Preferred features are as defined in the subclaims.

The reducing agent for color formation for use in the present invention is dispersed in the same layer as or a different layer from the above-described compound having a specific erasure rate constant (compound for use in the present invention), and it can then achieve a high color formation property upon formation of a dye with a coupler and also reduce the formation of stains during long-term storage of the unexposed light-sensitive material (improvement of storability). In particular, the reducing agent for color formation represented by the formula (IV) or (V) is dispersed together with the above-described compound having a specific erasure rate constant and can thereby provide higher effects for the above-described color formation property and storage stability and give a good oxidation coupling reaction not only with a 4-equivalent coupler but also with a 2-equivalent coupler to form a dye having high color density.

When the reducing agent represented by formula (VI) or (VII) is used for color formation, the effect resulting from the use together with the compound of the invention having the specific erasure rate constant is particularly great.

In a preferred embodiment of the invention, at least one reducing agent for color formation and at least one coupler in the form of oil droplets obtained by dissolution in an organic solvent are mixed together with the compound described above with the specific erasure rate constant. In a further preferred embodiment, the reducing agent for color formation, the coupler and the compound having the specific erasure rate constant are dispersed in the form of oil droplets obtained by dissolving the elements in the organic solvent described above.

In addition, the present invention is environmentally friendly because a good image can be obtained even with a low-silver photosensitive material with a coated silver amount of 0.003 to 0.3 g/m², and it is also suitable for digital processing because when an image is formed by scanning exposure, the obtained image can have a high density and be reduced in stains after storage.

The reducing agent for color formation represented by formula (II) or (III) is a compound which directly reacts with exposed silver halide in an alkali solution and is oxidized thereby, or which causes an oxidation-reduction reaction with an auxiliary developing agent which has been oxidized by exposed silver halide and is oxidized thereby, and the resulting oxidation product reacts with a dye-forming coupler to form a dye.

Among the compounds represented by the formula (II) or (III), the compounds represented by the formula (IV) or (V) are preferred, and the compounds represented by the formula (VI) or (VII) are particularly preferred.

The compounds represented by formulas (II), (II), (IV), (V), (VI) or (VII) are described in detail below.

In formulas (II) and (III), Z¹ represents an acyl group, carbamoyl group, alkoxycarbonyl group or aryloxycarbonyl group, Z² represents a carbamoyl group, alkoxycarbonyl group or aryloxycarbonyl group. The acyl group is preferably an acyl group having 1 to 50, particularly preferably 2 to 40 carbon atoms. Specific examples thereof include an acetyl group, 2-methylpropanoyl group, cyclohexylcarbonyl group, n-octanoyl group, 2-hexyldecanoyl group, dodecanoyl group, chloroacetyl group, trifluoroacetyl group, benzoyl group, 4-dodecyloxybenzoyl group, 2-hydroxymethylbenzoyl group and 3-(N-hydroxy-N-methylaminocarbonyl)propanoyl group.

The case where Z¹ and Z² are each a carbamoyl group is described in detail with reference to formulas (VI) and (VII).

The alkoxycarbonyl or aryloxycarbonyl group for Z¹ or Z² is preferably an alkoxycarbonyl or aryloxycarbonyl group having 2 to 50, particularly preferably 2 to 40 carbon atoms. Specific examples thereof include a methoxycarbonyl group, ethoxycarbonyl group, isobutyloxycarbonyl group, cyclohexyloxycarbonyl group, dodecyloxycarbonyl group, benzyloxycarbonyl group, phenoxycarbonyl group, 4-octyloxyphenoxycarbonyl group, 2-hydroxymethylphenoxycarbonyl group and 2-dodecyloxyphenoxycarbonyl group.

X¹, X², X³, X⁴ and X⁵ each represents a hydrogen atom or a substituent. Examples of the substituent include a linear or branched, chain or cyclic alkyl group having 1 to 50 carbon atoms (e.g. trifluoromethyl, methyl, ethyl, propyl, heptafluoropropyl, isopropyl, butyl, t-butyl, t-pentyl, cyclopentyl, cyclohexyl, octyl, 2-ethylhexyl, dodecyl), a linear or branched, chain or cyclic alkenyl group having 2 to 50 carbon atoms (e.g. vinyl, 1-methylvinyl, cyclohexen-1-yl), an alkynyl group having a total carbon number of 2 to 50 (e.g. ethynyl, 1-propynyl), an aryl group having 6 to 50 carbon atoms (e.g. phenyl, naphthyl, anthryl), an acyloxy group having 1 to 50 carbon atoms (e.g. acetoxy, tetradecanoyloxy, benzoyloxy), a carbamoyloxy group with 1 to 50 carbon atoms (e.g. N,N-dimethylcarbamoyloxy), a carbonamido group with 1 to 50 carbon atoms (e.g. formamido, N-methylacetamido, acetamido, N-methylformamido, benzamido), a sulfonamido group with 1 to 50 carbon atoms (e.g. B. methanesulfonamido, dodecanesulfonamido, benzenesulfonamido, p-toluenesulfonamido), a carbamoyl group with 1 to 50 carbon atoms (e.g. N-methylcarbamoyl, N,N-diethylcarbamoyl, N-mesylcarbamoyl), a sulfamoyl group with 0 to 50 carbon atoms (e.g. N-butylsulfamoyl, N,N-diethylsulfamoyl, N-methyl-N-(4-methoxyphenyl)sulfamoyl), an alkoxy group with 1 to 50 carbon atoms (e.g. methoxy, propoxy, isopropoxy, octyloxy, t-octyloxy, dodecyloxy, 2-(2,4-di-t-pentylphenoxy)ethoxy), an aryloxy group with 6 to 50 carbon atoms (e.g. phenoxy, 4-methoxyphenoxy, naphthoxy), a Aryloxycarbonyl group with 7 to 50 carbon atoms (e.g. phenoxycarbonyl, naphthoxycarbonyl), an alkoxycarbonyl group with 2 to 50 Carbon atoms (e.g. methoxycarbonyl, t-butoxycarbonyl), an N-acylsulfamoyl group with 1 to 50 carbon atoms (e.g. N-tetradecanoylsulfamoyl, N-benzoylsulfamoyl), an alkylsulfonyl group with 1 to 50 carbon atoms (e.g. methanesulfonyl, octylsulfonyl, 2-methoxyethylsulfonyl, 2-hexyldecylsulfonyl), an arylsulfonyl group with 6 to 50 carbon atoms (e.g. benzenesulfonyl, p-toluenesulfonyl, 4-phenylsulfonylphenylsulfonyl), an alkoxycarbonylamino group with 2 to 50 carbon atoms (e.g. ethoxycarbonylamino), an aryloxycarbonylamino group with 7 to 50 carbon atoms (e.g. phenoxycarbonylamino, naphthoxycarbonylamino), an amino group with 0 to 50 carbon atoms (e.g. amino, methylamino, diethylamino, diisopropylamino, anilino, morpholino), a cyano group, a nitro group, a carboxyl group, a hydroxy group, a sulfo group, a mercapto group, an alkylsulfinyl group having 1 to 50 carbon atoms (e.g. methanesulfinyl, octanesulfinyl), an arylsulfinyl group having 6 to 50 carbon atoms (e.g. B. benzenesulfinyl, 4-chlorophenylsulfinyl, p-toluenesulfinyl), an alkylthio group with 1 to 50 carbon atoms (e.g. methylthio, octylthio, cyclohexylthio), an arylthio group with 6 to 50 carbon atoms (e.g. phenylthio, naphthylthio), a ureido group with 1 to 50 carbon atoms (e.g. 3-methylureido, 3,3-dimethylureido, 1,3-diphenylureido), a heterocyclic group with 2 to 50 carbon atoms (a 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11- or 12-membered monocyclic or fused ring which contains as a heteroatom at least one representative of e.g. nitrogen, oxygen and sulfur, e.g. 2-furyl, 2-pyranyl, 2-pyridyl, 2-thienyl, 2-imidazolyl, morpholino, 2-quinolyl, 2-benzimidazolyl, 2-benzothiazolyl, 2-benzoxazolyl), an acyl group with 1 to 50 Carbon atoms (e.g. acetyl, benzoyl, trifluoroacetyl), a sulfamoylamino group having 0 to 50 carbon atoms (e.g. N-butylsulfamoylamino, N-phenylsulfamoylamino), a silyl group having 3 to 50 carbon atoms (e.g. trimethylsilyl, dimethyl-t-butylsilyl, triphenylsilyl) and a halogen atom (e.g. fluorine, chlorine, bromine). These substituents may each have another substituent, and examples of the substituent include the substituents described above. X¹, X², X³, X⁴ or X⁵ may be combined with each other to form a fused ring. The fused ring is preferably a 5-, 6- or 7-membered ring, particularly preferably a 5- or 6-membered ring.

The substituent preferably has 50 or fewer carbon atoms, more preferably 42 or fewer carbon atoms, most preferably 34 or fewer carbon atoms, and preferably has 1 or more carbon atoms.

With respect to X¹, X², X³, X⁴ and X⁵, the sum of the values of the Hammett constants σp of X¹, X³ and X⁵ and the values of the Hammett constants σm of X² and X⁴ is 0.80 to 3.80. In formula (VI), X⁶, X⁷, X⁹⁰, X⁷⁴, X⁹⁰ represent each represents a hydrogen atom, a cyano group, a sulfonyl group, a sulfinyl group, a sulfamoyl group, a carbamoyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, a trifluoromethyl group, a halogen atom, an acyloxy group, an acylthio group or a heterocyclic group, and these groups may each have a substituent or may be combined with each other to form a fused ring. Specific examples thereof are the same as those described for X¹, X², X³, X⁴ and X⁵. However, in formula (VI), the sum of the values the Hammett constants σp of X⁶, X⁸ and X¹⁰ and the values of the Hammett constants σm of X⁷ and X⁹⁹ are 1.20 to 3.80, preferably 1.50 to 3.80, particularly preferably 1.70 to 3.80.

If the sum of the σp values and the σm values is less than 0.80, the color forming property is insufficient, whereas if the sum exceeds 3.80, the compound itself is difficult to synthesize and difficult to obtain.

The Hammett constants σp and σm of substituents are described in detail in publications such as Naoki Inamoto, Hammett Soku - Kozo to Han'no Sei - (Hammett's Rule - Structure and Reactivity -), Maruzen; Shin Jikken Kagaku Koza 14, Yuki Kagobutsu no Gosei to Han'no V (New Experimental and Chemistry Lecture 14, Synthesis and Reaction of Organic Compounds V), page 2605, Nippon Kagaku Kai (author), Maruzen; Tadao Nakaya, Riron Yuki Kagaku Kaisetsu (Review of Theoretical Organic Chemistry), page 217, Tokyo Kagaku Dojin; and Chemical Review, vol. 91, pages 165 to 195 (1991).

R¹ and R² in formulas (IV) and (V) and R⁴ and R⁵ in formulas (VI) and (VII) each represent a hydrogen atom or a substituent, and examples of the substituents include the same groups as described for X¹, X², X³, X⁴ and X⁵. R¹ and R² in formulas (IV) and (V) and R⁴ and R⁵ in formulas (VI) and (VII) each preferably represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 1 to 50 carbon atoms, and particularly preferably at least one of R¹ and R² or at least one of R⁴ and R⁵ is a hydrogen atom.

In formulas (III) and (V), R³ represents a heterocyclic group. The heterocyclic group is preferably a heterocyclic group having 1 to 50 carbon atoms which is a 3-, 4-, 5-, 6-, 7-, 8-, 9-, 10-, 11- or 12-membered (preferably 3-, 4-, 5-, 6-, 7- or 8-membered) monocyclic or fused ring containing as a heteroatom at least one of e.g. B. nitrogen, oxygen and sulfur, and specific examples of the heterocyclic ring include furan, pyran, pyridine, thiophene, imidazole, quinoline, benzimidazole, benzothiazole, benzoxazole, pyrimidine, pyrazine, 1,2,4-thiadiazole, pyrrole, oxazole, thiazole, quinazoline, isothiazole, pyridazine, indole, pyrazole, triazole and quinoxaline. These heterocyclic groups may each have a substituent and preferably one or more electron-withdrawing groups. The term "electron-withdrawing group" as used here means a group having a positive Hammett value σp.

When adding the reducing agent for color formation according to the present invention to a light-sensitive material, preferably at least one group of Z¹, Z², R¹ to R⁵ and X¹ to X¹⁰ has a ballast group.

Examples of the heterocyclic ring completed by Q1 are specifically shown in compounds (I-16) to (I-74).

Specific examples of the novel color-forming reducing agent used in the present invention are shown below.

Examples of the couplers preferably used in the present invention include the compounds having a structure represented by formula (1), (2), (3), (4), (5), (6), (7), (8), (9), (10), (11) or (12). Generally, these compounds are collectively called active methylene, pyrazolone, pyrazoloazole, phenol, naphthol or pyrrolotriazole and are known in the relevant field.

Couplers having a structure of formula (1), (2), (3) or (4) are called active methylene-based couplers. In the formulas, R¹⁴ represents an acyl group, aryl group, heterocyclic group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, sulfamoyl group, alkylsulfonyl group or arylsulfonyl group, each of which may have a substituent, or a cyano group or nitro group.

In formulas (1) to (3), R¹⁵ represents an alkyl group, aryl group or heterocyclic group, each of which may have a substituent. In formula (4), R¹⁶ represents an aryl group or heterocyclic group, each of which may have a substituent. Examples of the substituent of R¹⁴, R¹⁵ or R¹⁵ include those described above for X¹ to X⁵.

In formulas (1) to (4), Y represents a hydrogen atom or a group capable of being split off in the coupling reaction with an oxidation product of the reducing agent to form color. Examples of Y include: a heterocyclic group (a saturated or unsaturated 5-, 6- or 7-membered, monocyclic or condensed ring containing as a heteroatom at least one of nitrogen, oxygen and sulfur, e.g. succinimido, maleimido, phthalimido, diglycolimido, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, benzopyrazole, benzimidazole, benzotriazole, imidazolin-2,4-dione, oxazolidin-2,4-dione, thiazolidin-2,4-dione, imidazolidin-2-one, oxazolin-2-one, thiazolin-2-one, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazolin-2-one, 2-pyrrolin-5-one, 2-imidazolin-5-one, Indoline-2,3-dione, 2,6-dioxypurine, parabanic acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6-pyridazone, 2-pyrazone, 2-amino-1,3,4-thiazolidine, 2-imino-1,3,4-thiazolidine-4- on), a halogen atom (e.g. chlorine, bromine), an aryloxy group (e.g. phenoxy, 1-naphthoxy), a heterocyclic oxy group (e.g. pyridyloxy, pyrazolyloxy), an acyloxy group (e.g. acetoxy, benzoyloxy), an alkoxy group (e.g. methoxy, dodecyloxy), a carbamoyloxy group (e.g. N,N-diethylcarbamoyloxy, morpholinocarbonyloxy), an aryloxycarbonyloxy group (e.g. phenoxycarbonyloxy), an alkoxycarbonyloxy group (e.g. methoxycarbonyloxy, ethoxycarbonyloxy), an arylthio group (e.g. phenylthio, naphthylthio), a heterocyclic thio group (e.g. tetrazolylthio, 1,3,4-thiadiazolylthio, 1,3,4-oxadiazolylthio, benzimidazolylthio), a Alkylthio group (e.g. methylthio, octylthio, hexadecylthio), an alkylsulfonyloxy group (e.g. methanesulfonyloxy), an arylsulfonyloxy group (e.g. benzenesulfonyloxy, toluenesulfonyloxy), a carbonamido group (e.g. acetamido, trifluoroacetamido), a sulfonamido group (e.g. methanesulfonamido, benzenesulfonamido), an alkylsulfonyl group (e.g. methanesulfonyl), an arylsulfonyl group (e.g. benzenesulfonyl), an alkylsulfinyl group (e.g. methanesulfinyl), an arylsulfinyl group (e.g. benzenesulfinyl), an arylazo group (e.g. phenylazo, naphthylazo) and a carbamoylamino group (e.g. N-methylcarbamoylamino).

Y may be substituted with a substituent, and examples of the substituent of Y include those described for X¹ to X⁵.

Y is preferably a halogen atom, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an aryloxycarbonyloxy group, an alkoxycarbonyloxy group or a carbamoyloxy group.

In formulas (1) to (4), R¹⁴ and R¹⁵ or R¹⁴ and R¹⁵6 may be combined to form a ring.

Couplers having a structure of formula (5) are called 5-pyrazolone-based couplers. In the formula, R¹⁹7 represents an alkyl group, an aryl group, an acyl group or a carbamoyl group, and R¹⁹8 represents a phenyl group or a phenyl group substituted with one or more halogen atoms, alkyl groups, cyano groups, alkoxy groups, alkoxycarbonyl groups or acylamino groups.

Among the 5-pyrazolone-based couplers represented by formula (5), preferred are those wherein R¹⁷ is an aryl group or an acyl group and R¹⁸ is a phenyl group substituted with one or more halogen atoms.

Specifically, in these preferred groups, R¹⁷ is an aryl group such as a phenyl group, 2-chlorophenyl group, 2-methoxyphenyl group, 2-chloro-5- tetradecanamidophenyl group, 2-chloro-5-(3-octadecenyl-1-succinimido)phenyl group, 2-chloro-5- octadecylsulfonamidophenyl group and 2-chloro-5-[2-(4-hydroxy-3-t-butylphenoxy)tetradecanamido]phenyl, or an acyl group such as an acetyl group, 2-(2,4-di-t-pentylphenoxy)butanoyl group, benzoyl group and 3-(2,4-di-t-amylphenoxyacetamido)benzoyl group. These groups may each further have a substituent, and examples thereof include an organic substituent linked through a carbon atom, oxygen atom, nitrogen atom or sulfur atom and a halogen atom. Y has the same meaning as defined above.

R¹⁸ is preferably a substituted phenyl group such as 2,4,6-trichlorophenyl group, 2,5-dichlorophenyl group and 2-chlorophenyl group.

Couplers having a structure of formula (6) are called pyrazoloazole-based couplers. In the formula, R¹⁹9 represents a hydrogen atom or a substituent, Q³ represents a non-metal atom group necessary to form a 5-membered azole ring containing 2 to 4 nitrogen atoms. The azole ring may have a substituent (including a condensed ring).

Among the pyrazoloazole-based couplers represented by formula (6), the imidazo[1,2-b]pyrazoles described in U.S. Patent No. 4,500,630, the pyrazolo[1,5-b]-1,2,4-triazoles described in U.S. Patent No. 4,500,654, and the pyrazolo[5,1-c]-1,2,4-triazoles described in U.S. Patent No. 3,725,067 are preferred in terms of the spectral absorption characteristics of the colored dye.

The substituent represented by R¹⁹9 and the substituent represented by Q³ of the azole ring are described in detail, for example, in U.S. Patent No. 4,540,654, column 2, line 41 to column 8, line 27. Preferred are a pyrazoloazole coupler having a branched alkyl group directly bonded to the 2-, 3- or 6-position of the pyrazolotriazole group described in JP-A-61-65245 (the term "JP-A" as used herein means an "unexamined published Japanese patent application"), a pyrazoloazole coupler containing a sulfonamido group in the molecule described in JP-A-61-65245, a pyrazoloazole coupler having an alkoxyphenylsulfonamido ballast group described in JP-A-61-147254, a pyrazolotriazole coupler having a alkoxy group or an aryloxy group at the 6-position described in JP-A-62-209457 and JP-A-63-307453, and a pyrazolotriazole coupler having a carbonamido group in the molecule described in JP-A-2-201443. Y has the same meaning as described above.

Couplers having a structure of formulas (7) or (8) are called phenol-based couplers and naphthol-based couplers, respectively. In the formulas, R²⁰ represents a hydrogen atom or a group selected from -CONR²²R²³, -SO₂NR²²R²³, -NHCOR²², -NHCONR²²R²³ and -NHSO₂R²²R²³ (wherein R²² and R²³ each represent a hydrogen atom or a substituent). In formulas (7) and (8), R²¹ represents a substituent, l represents 0 or an integer of 1 or 2, and m represents 0 or an integer of 1 to 4. When l or m is 2 or more, the R²¹ groups may be the same or different. Examples of the substituent represented by R²¹, R²² or R²³ include those described above for X¹ to X⁵ in formula (II) or (IV). Y has the same meaning as described above.

Preferred examples of the phenol-based coupler represented by formula (7) include 2-acylamino-5-alkylphenol-based couplers described in U.S. Patents 2,369,929, 2,801,171, 2,772,162, 2,895,826 and 3,772,002, 2,5-diacylaminophenol-based couplers described in U.S. Patents 2,772,162, 3,758,308, 4,126,396, 4,334,011 and 4,327,173, German Patent Application Laid-Open No. 3,329,729 and JP-A-59-166956, and 2-phenylureido-5-acylaminophenol-based couplers described in U.S. Patent Nos. 3,446,622, 4,333,999, 4,451,559 and 4,427,767. Y is the same as described above.

Preferred examples of the naphthol coupler represented by formula (8) include 2-carbamoyl-1-naphthol-based couplers described in U.S. Patent Nos. 2,474,293, 4,052,212, 4,146,396, 4,282,233 and 4,296,200, and 2-carbamoyl-5-amido-1-naphthol-based couplers described in U.S. Patent No. 4,690,889. Y is the same as described above.

Couplers having a structure of formula (9), (10), (11) or (12) are called pyrrolotriazoles. In the formulas, R³², R³³ and R³⁴ each represents a hydrogen atom or a substituent, and Y has the same meaning as defined above. Examples of the substituents represented by R³², R³³ or R³⁴ include those described above for X¹ to X⁵. Preferred examples of the pyrrolotriazole-based couplers represented by formulas (9) to (12) include couplers wherein at least one of R³² and R³³ is an electron-withdrawing group described in EP-A-488 248, EP-A-491 197 and EP-B-545 300. Y is the same as described above.

In addition, couplers having a structure such as a ring-condensed phenol, an imidazole, pyrrole, 3-hydroxypyridine, active methylene other than those described above, an active methine, 5,5-condensed heterocyclic ring or 5,6-condensed heterocyclic ring can be used.

The ring-condensed phenol-based couplers include the couplers described in U.S. Patent Nos. 4,327,173, 4,564,586, and 4,904,575.

The imidazole-based couplers include the couplers described in U.S. Patent Nos. 4,818,672 and 5,051,347.

The 3-hydroxypyridine-based couplers include the couplers described in JP-A-1-315736.

The active methylene and active methine based couplers include the couplers described in U.S. Patent Nos. 5,104,783 and 5,162,196.

The 5,5-fused heterocyclic ring-based couplers include the pyrrolopyrazole-based couplers described in U.S. Patent No. 5,164,289 and the pyrroloimidazole-based couplers described in JP-A-4-174429.

The 5,6-fused heterocyclic ring-based couplers include the pyrazolopyrimidine-based couplers described in U.S. Patent No. 4,950,585, the pyrrolotriazine-based couplers described in JP-A-4-204730, and the couplers described in EP-B-556,700.

In addition to the couplers described above, the couplers described in German Offenlegungsschrifts 3,819,051 and 3,823,049, US Pat. Nos. 4,840,883, 5,024,930, 5,051,347 and 4,481,268, EP-A-304,856, EP-B-329,036, EP-A-354,549, EP-A-374,781, EP-A-379,110, EP-A-386,930, JP-A-63-141055, JP-A-64-32260, JP-A-64-32261, JP-A-2-297547, JP-A-2-44340, JP-A-2-110555, JP-A-3-7938, JP-A-3-160440, JP-A-3-172839, JP-A-4-172447, JP-A-4-179949, JP-A-4-182645, JP-A-4-188138, JP-A-4-188139, JP-A-4-194847, JP-A-4-204532, JP-A-4-204731 and JP-A-4-204732.

Specific examples of the couplers which can be used in the present invention are shown below.

The reducing agent for color formation according to the invention is, in order to obtain a satisfactory color density, preferably used in an amount of 0.01 to 10 mmol/m², particularly preferably 0.05 to 5 mmol/m², even more preferably 0.1 to 1 mmol/m² per color formation layer. Within this range, a satisfactory color density is advantageously obtained.

The amount of the coupler used in the color-forming layer in which the reducing agent for color formation according to the invention is used is preferably 0.05 to 20 times, particularly preferably 0.1 to 10 times, even more preferably 0.2 to 5 times, as a molar ratio to the reducing agent for color formation. Within this range, a satisfactory color density is advantageously obtained.

The color light-sensitive material of the present invention basically comprises a support coated with at least one photographic component layer comprising a hydrophilic colloid layer, and one of the photographic component layers contains a light-sensitive silver halide, a dye-forming coupler and a reducing agent for color formation.

In the most representative embodiment, the color forming coupler and the reducing agent for color formation used in the present invention are added to the same layer, but if they are in a reactive state, they may be added separately to different layers. These components are preferably added to a silver halide emulsion layer of the light-sensitive material or an adjacent layer, particularly preferably a silver halide emulsion layer.

The reducing agent for color formation, the compound having a specific Kq value and the coupler according to the present invention can be added to a light-sensitive material by various known dispersion methods, and an oil-in-water dispersion method in which they are dissolved in a high boiling point organic solvent (if desired, using a low boiling point organic solvent in combination), emulsion-dispersed in an aqueous gelatin solution and then added to a silver halide emulsion is preferred. The high boiling point organic solvent that can be used in the present invention is a water-immiscible compound having a melting point of 100°C or lower, preferably 80°C or lower, and a boiling point of 140°C or higher, preferably 160°C or higher, particularly preferably 170°C or higher, and it can be used if it is a good solvent for the reducing agent for color formation and the coupler. The high boiling point organic solvent is described in detail in JP-A-62-215272 from page 137, right lower column to page 144, right upper column. In the present invention, when a high boiling point organic solvent is used, the high boiling point organic solvent can be used in any amount, but the weight ratio of the high boiling point organic solvent to the color-forming reducing agent to the color-forming reducing agent is 20 or less, particularly preferably 0.02 to 5, even more preferably 0.2 to 4.

In the present invention, a known polymer dispersion method can be used. The method and effect of the latex dispersion method as a polymer dispersion method and specific examples of the latex for impregnation are described in U.S. Patent No. 4,199,363, German Laid-Open Nos. 2,541,274 and 2,541,230, JP-B-53-41091 and EP-A-029,104, and a dispersion method using a water-insoluble and organic solvent-soluble polymer is described in PCT International Patent Publication WO88/00723.

The average particle size of the lipophilic fine particles containing the reducing agent for color formation according to the present invention is not particularly limited, but it is preferably 0.05 to 0.3 µm, particularly preferably 0.05 to 0.2 µm in view of the color formation property.

In order to achieve a reduction in the average particle size of the lipophilic fine particles, the type of surfactant is generally selected, the amount of surfactant used is increased, the viscosity of the hydrophilic colloid solution is increased, the viscosity of the lipophilic organic layer is reduced, e.g. by using an organic solvent with a low boiling point in combination, the shear force is increased, e.g. by increasing the number of revolutions of the stirring blade of an emulsifying device, or the emulsification time is prolonged.

The particle size of the lipophilic fine particles can be measured by a device such as a Nanosizer manufactured by British Coulter Company.

The compound having a quenching rate constant for singlet oxygen of 1 x 10⁷ M⁻¹·s⁻¹ or more for use in the present invention is described below.

The quenching rate constant (Kq) for singlet oxygen (1O2) can be obtained by a method described in J. Phys. Chem., 83(5), 591 (1979). Specifically, a chloroform solution of rubrene and a chloroform solution of a mixture of rubrene with a compound whose Kq value is sought are irradiated with light of equal energy. Assuming that the initial concentration of rubrene is [R], the concentration of the compound whose Kq value is sought is [Q], the rubrene concentration in the solution containing only rubrene after irradiation with light is [R]FO, and the rubrene concentration in the mixed solution of rubrene with the compound whose Kq value is sought is [R]FQ, the Kq value can be expressed by the following equation:

The compound for use in the present invention has a Kq value of 1 x 10⁷ M⁻¹·s⁻¹ or more, preferably 2 x 10⁷ M1·s'1 or more, particularly preferably 3 x 10⁷ M⁻¹·s⁻¹ or more. The upper limit is preferably 1 x 10¹¹ M⁻¹·s⁻¹ or less, particularly preferably 1 x 10¹⁰ M⁻¹·s⁻¹ or less. By using the compound having the above-described Kq value, the object of the present invention can be effectively achieved.

The compound particularly preferred in view of the effect of the present invention is represented by formula (A).

The compound represented by formula (A) for use in the present invention will be described in detail.

The alkyl group in formula (A) is a linear, branched or cyclic alkyl group, and examples thereof include methyl, isopropyl, t-butyl, cyclohexyl, n-octyl, dodecyl, hexadecyl and octadecyl.

The alkenyl group in formula (A) is a linear, branched or cyclic alkenyl group, and examples include vinyl, allyl, cyclohexenyl and oleyl.

Examples of the aryl group in formula (A) include phenyl and naphthyl. The heterocyclic group is a 5-, 6- or 7-membered ring containing as a ring atom at least one of an oxygen atom, nitrogen atom and sulfur atom, and examples thereof include pyrrolidyl, pyrazolidyl, imidazolidyl, piperazyl, thienyl, furyl and chromanyl.

Examples of the arylene group in formula (A) include phenylene and naphthylene.

Each group in formula (A) may be substituted with a substituent, and examples of the substituent include: an alkyl group, alkenyl group, aryl group, heterocyclic group, a halogen atom, an alkoxy group, alkenyloxy group, aryloxy group, heterocyclic oxy group, alkylthio group, alkenylthio group, arylthio group, heterocyclic Thio group, amino group, alkylamino group, alkenylamino group, arylamino group, heterocyclic amino group, acylamino group, sulfonamido group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, acyloxy group, silyloxy group, carboxy group, carbamoyl group, sulfamoyl group, cyano group, nitro group, sulfo group, sulfonyl group, sulfinyl group and hydroxyl group.

The compound represented by formula (A) is particularly preferably a compound represented by formula (AI), (A-II), (A-III) or (A-IV):

wherein Ra, Rb, Rc, Xa and Xb each represents a group defined in formula (A), R represents a substituent, R' represents a substituent other than -Xb-Rb, with the proviso that when there are a plurality of R or R' groups, they may be the same or different or the groups may be combined in the ortho position to each other to form a 5- or 6-membered ring, l represents 0 or an integer from 1 to 4, and m represents 0 or an integer from 1 to 5.

Regarding the substituents in formulas (A-I) to (A-IV), Ra, Rb and Rc are each preferably an alkyl group, alkenyl group or aryl group, R is preferably an alkyl group, aryl group or group represented by -Xa-Ra, and R' is preferably an alkyl group, aryl group, alkylthio group or arylthio group.

The compounds represented by any one of the formulas (A-I) to (A-IV) each preferably have a total carbon number of 12 or more, more preferably 15 or more, even more preferably 20 or more.

Among the compounds represented by any one of formulas (A-I) to (A-IV), preferred are those represented by formula (A-I), (A-II) or (A-IV), and particularly preferred are those represented by formula (A-I) or (A-II).

In formula (A-I) or (A-II), Xa and Xb are particularly preferably both -O-, or one of Xa and Xb is -O- and the other is -N(Rc)-.

Specific examples of the compound for use in the present invention are listed below.

The addition amount of the compound having a singlet oxygen quenching rate constant of 1 x 10⁷ M⁻¹ s⁻¹ according to the present invention is not particularly limited, but it is preferably added in an amount of 0.002 to 10 mol, particularly preferably 0.01 to 2 mol, even more preferably 0.02 to 0.5 mol times the amount of the reducing agent for color formation according to the present invention. Within this range, the object of the present invention can be effectively achieved.

The compound of the present invention having a specific Kq value can be added to either a light-sensitive layer or a light-insensitive layer, but it is preferred that it be contained in the same light-sensitive layer as the reducing agent for color formation.

In the present invention, in the case where the dye formed from the reducing agent for color formation and the dye-forming coupler is a diffusible dye, a mordant is preferably added to the light-sensitive material. When the present invention is applied to such a case, color formation eliminates the need for immersion in an alkali, and therefore, the image stability after processing is superiorly improved. The mordant may be used in any layer, but if it is added to a layer in which the reducing agent for color formation in the present invention is contained, the stability of the reducing agent for color formation deteriorates, and therefore the mordant is preferably used in a layer in which the reducing agent for color formation for use in the present invention is not contained. The mordant formed from the The dye produced by the reducing agent for color formation and the coupler diffuses in the gelatin layer, which swells during processing, to color the mordant. In order to obtain good sharpness, the diffusion distance is preferably small. For this effect, the layer to which the mordant is added is preferably a layer adjacent to the layer in which the reducing agent for color formation is contained.

The dye produced from the reducing agent for color formation for use in the present invention and the coupler for use in the present invention is a water-soluble dye, and therefore the dye may flow out into the processing solution. To prevent this, the layer to which the mordant is added is preferably positioned on the side opposite to the support from the layer in which the reducing agent for color formation is contained. However, when a barrier layer is provided on the side opposite to the support from the layer to which the mordant is added as described in JP-A-7-168335, the layer to which the mordant is added may preferably be provided on the same side as the support from the layer in which the reducing agent for color formation is contained.

The mordant for use in the present invention may be added to a plurality of layers, and particularly when a plurality of layers contain the reducing agent for color formation, the mordant may preferably be added to respective adjacent layers.

The coupler for forming a diffusible dye can be any coupler, as long as the coupler used in the coupling with the reducing agent for color formation for use in the present invention can reach the mordant, however, the diffusible dye formed preferably has one or more dissociation groups having a pKa (acid dissociation constant) of 12 or less, more preferably one or more dissociation groups having a pKa of 8 or less, still more preferably a dissociation group having a pKa of 6 or less. The diffusible dye formed preferably has a molecular weight of 200 to 2,000, and (the molecular weight of the dye formed/the number of dissociation groups having a pKa of 12 or less) is preferably 100 to 2,000, more preferably 100 to 1,000. The pxa used here is measured using a solvent of dimethylformamide/water = 1:1.

The coupler for forming a diffusible dye couples with the reducing agent for color formation for use in the present invention to form a diffusible dye, which preferably has a solubility such that the dye is dissolved in an alkali solution having a pH of 11 at up to 25°C in a concentration of 1 x 10-6 mol/L or more, more preferably 1 x 10-5 mol/L or more, even more preferably 1 x 10-4 mol/L. Furthermore, the coupler for forming a diffusible dye couples with the reducing agent for color formation for use in the present invention to form a diffusible dye which preferably has a diffusion constant, measured when the dye is dissolved in a concentration of 10-4 mol/l in an alkali solution having a pH of 11 at 25°C, of 1 x 10-8 m2/s-1 or more, more preferably 1 x 10-7 m2/s-1 or more, even more preferably 1 x 10-6 m2/s-1 or more.

The mordant that can be used in the present invention can be freely selected from generally used mordants, and among them, a polymer mordant is preferred. The term "polymer mordant" as used herein includes a polymer having a tertiary amino group, a polymer having a nitrogen-containing heterocyclic unit, and a polymer containing a quaternary group thereof.

Specific examples of the homopolymer or copolymer containing a vinyl monomer unit having a tertiary imidazole group include the mordants described in U.S. Patents 4,282,305, 4,115,124 and 3,148,061, JP-A-60-118834, JP-A-60-122941, JP-A-62-244043 and JP-A-62-244036 and those described below.

Specific preferred examples of the homopolymer or copolymer containing a vinyl monomer unit with a quaternary imidazolium salt include the mordants described in British Patents 2,056,101, 2,093,041 and 1,594,961, U.S. Patents 4,124,386, 4,115,124 and 4,450,224 and JP-A-48-28325 and those described below.

Specific preferred examples of the homopolymer or copolymer containing a vinyl monomer unit with a quaternary ammonium salt include the mordants described in U.S. Patent Nos. 3,709,690, 3,898,088 and 3,958,995, JP-A-60-57836, JP-A-60-60643, JP-A-60-122940, JP-A-60-122942 and JP-A-60-235134 and those described below.

Other examples include vinylpyridine polymers and vinylpyridinium cation polymers disclosed in U.S. Patents 2,548,564, 2,484,430, 3,148,161 and 3,756,814; polymer mordants crosslinkable with gelatin or the like disclosed in U.S. Patents 3,625,694, 3,859,096 and 4,128,538 and British Patent 1,277,453; aqueous sol type mordants disclosed in U.S. Patent Nos. 3,958,995, 2,721,852 and 2,798,063, JP-A-54-115228, JP-A-54-145529 and JP-A-54-26027; water-insoluble mordants disclosed in U.S. Patent No. 3,898,088; reactive mordants capable of covalently bonding with a dye disclosed in U.S. Patent No. 4,168,976 (corresponding to JP-A-54-137333); and the mordants disclosed in U.S. Patent Nos. 3,709,690, 3,788,855, 3,642,482, 3,488,706, 3,557,066 and 3,271,147, JP-A-50-71332, JP-A-53-30328, JP-A-52-155528, JP-A-53-125 and JP-A-53-1024.

Still other examples include the mordants described in U.S. Patent Nos. 2,675,316 and 2,882,156.

The polymer mordant for use in the present invention suitably has a molecular weight of from 1,000 to 1,000,000, preferably from 10,000 to 200,000.

The above-described polymer mordant for use in the present invention is usually mixed with a hydrophilic colloid before use. The hydrophilic colloid may be a hydrophilic colloid, a highly hygroscopic polymer or a combination thereof, but gelatin is the most representative example. The mixing ratio of the polymer mordant to the hydrophilic colloid and the coating amount of the polymer mordant can be easily determined by those skilled in the art according to the amount of the dye to be mordant, the type or composition of the polymer mordant or the used, however, the ratio of mordant/hydrophilic colloid is suitably 20:80 to 80:20 (by weight), and the coating amount of the mordant is suitably 0.2 to 15 g/m², preferably 0.5 to 8 g/m².

In the present invention, an auxiliary developing agent or a precursor thereof is preferably used in the light-sensitive material, and these compounds are described below.

The auxiliary developing agent for use in the present invention is a compound having an effect of accelerating the transfer of electrons from the reducing agent for color formation to silver halide during the development of silver halide grains, preferably a compound capable of developing exposed silver halide grains and oxidizing the reducing agent for color formation by the resulting oxidation product (hereinafter referred to as "cross-oxidation").

The auxiliary developing agent for use in the present invention is preferably a pyrazolidone, hydroxybenzene, reductone or aminophenol, particularly preferably a pyrazolidone. These compounds are preferably lower in diffusibility in a hydrophilic colloid layer, and, for example, the solubility (25°C) thereof in water is preferably 0.1% or less, particularly preferably 0.05% or less, most preferably 0.01% or less.

The precursor for the auxiliary developing agent for use in the present invention is a compound which is stable in the light-sensitive material but rapidly releases the auxiliary developing agent described above when processed with a developing solution, and also in the case of using this compound, the diffusibility thereof in a hydrophilic colloid layer is preferably lower. For example, the solubility (25°C) thereof in water is preferably 0.1% or less, particularly preferably 0.05% or less, still more preferably 0.01% or less. The auxiliary developing agent released from the precursor is not particularly limited in its solubility, but the auxiliary developing agent itself is preferably lower in solubility.

The auxiliary developing agent precursor for use in the present invention is preferably represented by formula (A):

A-(L)n-PUG (A)

wherein A represents a blocking group which cleaves the bond to (L)n-PUG upon development, L represents a linking group which cleaves the bond between L and PUG after cleavage of the bond between L and A, n represents 0 or an integer of 1 to 3, and PUG represents an auxiliary developing agent.

As auxiliary developing agents, electron-releasing compounds according to the Kendall-Perutz law, other than p-phenylenediamines, are used, and the pyrazolidones described above are preferably used.

The following known block groups can be used as the block group represented by A. In particular, the block group includes the block groups such as a acyl group and a sulfonyl group described in U.S. Patent No. 3,311,476, the block groups using a reverse Michael reaction described in JP-A-59-105642, the block groups using quinone methide or a compound analogous to quinone methide through the intramolecular electron transfer described in JP-A-2-280140, the block groups using the intramolecular nucleophilic substitution reaction described in JP-A-63-318555 (corresponding to EP-A-0 295 729), the block groups using the addition reaction of a nucleophilic agent to a conjugated unsaturated bond described in JP-A-4-186344, the block groups using the β-elimination reaction described in JP-A-62-163051, the block groups the block groups using the nucleophilic substitution reaction of diarylmethanes described in JP-A-61-188540, the block groups using a Lossen rearrangement reaction described in JP-A-62-187850, the block groups using the reaction of an N-acyl form of thiazolidine-2-thione with an amine described in JP-A-62-147457, and the block groups having two electrophilic groups reacting with a dinucleophile reagent described in International Patent Publication WO93/03419.

The group represented by L is a linking group capable of cleaving the bond of (L)n-1-PUG after release of the group represented by A upon development, and the group is not particularly limited if it has this function.

Specific examples of the ADC and its precursor are listed below.

These compounds may be added to any of the photosensitive layer, the intermediate layer, the undercoat layer and the protective layer, but when the auxiliary developing agent is added, they are preferably added to a photosensitive layer.

The compound can be incorporated into the light-sensitive material by a method in which the compound is dissolved in a water-miscible organic solvent such as methanol and then added directly to a hydrophilic colloid layer, a method in which the compound is formulated into an aqueous solution or colloid dispersion in the presence of a surfactant and then added, a method in which the compound is dissolved in a substantially water-immiscible solvent or oil, then dispersed in water or a hydrophilic colloid and then added, or by a method in which the compound is added in the state of a solid fine particle dispersion, and these conventionally known methods can be used individually or in combination. The preparation method for a solid fine particle dispersion is described in detail in JP-A-2-235044, page 20.

The amount of the auxiliary developing agent added to the light-sensitive material is 1 to 200 mol%, preferably 5 to 100 mol%, particularly preferably 10 to 50 mol%, based on the reducing agent for color formation.

The support for use in the present invention may be any transparent or reflective support as long as it is a support on which photographic emulsion layers can be coated, such as glass, Paper or plastic film. The plastic film for use in the present invention includes a polyester film such as polyethylene terephthalate, polyethylene naphthalate, cellulose triacetate and cellulose nitrate, a polyamide film, a polycarbonate film and a polystyrene film.

The "reflective support" that can be used in the present invention means a support whose reflectivity is increased so that the dye image formed on the silver halide emulsion layer is sharply displayed, and the reflective support includes a support covered with a hydrophobic resin having a light-reflecting substance dispersed therein, such as titanium oxide, zinc oxide, calcium carbonate or calcium sulfate, and the hydrophobic resin itself having a light-reflecting substance dispersed therein and used as a support. Examples thereof include polyethylene-coated paper, polyester-coated paper, polypropylene-based synthetic paper, and a support provided with a reflective layer or using a reflective substance in combination, such as a glass plate, a polyester film (e.g., polyethylene terephthalate, cellulose triacetate, cellulose nitrate), a polyamide film, a polycarbonate film, a polystyrene film, and a vinyl chloride resin. As the polyester-coated paper, the polyester-coated paper described in EP-B-0 507 489, which comprises polyethylene terephthalate as a main component, is particularly preferred.

The reflective support for use in the present invention is preferably a paper support, both surfaces of which are coated with waterproof resin layers, at least one of the waterproof resin layers containing fine white pigment particles. The white pigment particles are preferably contained in a density of 12% by weight or more, particularly preferably 14% by weight or more. The light-reflecting white pigment is preferably obtained by thoroughly kneading a white pigment in the presence of a surfactant and further by treating the surface of the pigment particles with 2-, 3- or 4-hydric alcohol.

In the present invention, a support having a second-order diffuse reflection is preferably used. Second-order diffuse reflection means a diffuse reflection obtained when the mirror surface is made uneven to obtain finely divided mirror surfaces facing in different directions. The unevenness of the second-order diffuse reflection surface is preferably such that the three-dimensional average height to the central plane is 0.1 to 2 µm, preferably 0.1 to 1.2 µm, and such a support is described in detail in JP-A-2-239244.

In order to obtain colors over a wide range on the color triangle using the three primary colors yellow, magenta and blue-green, at least three silver halide emulsion layers with sensitivity in different spectral regions are used in combination. For example, a three-layer combination consisting of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer or of a green-sensitive layer, a red-sensitive layer and an IR-sensitive layer can be applied to the above-described support Respective photosensitive layers can be arranged in various orders known for ordinary photosensitive color materials. In addition, each photosensitive layer can be divided into two or more layers if desired.

The light-sensitive material may comprise layers containing photographic components comprising the above-described light-sensitive layer and various light-insensitive layers such as a protective layer, an underlayer, an interlayer, an antihalation layer and a backing layer. In addition, various filter dyes may be added to the layer containing photographic components to improve color separation.

Gelatin is advantageously used as a binder or protective colloid that can be used in the light-sensitive material of the present invention, but a hydrophilic colloid other than gelatin may be used alone or in combination with gelatin. The calcium content of the gelatin is preferably 800 ppm or less, more preferably 200 ppm or less, and the iron content of the gelatin is preferably 5 ppm or less, more preferably 3 ppm or less. In addition, an anti-mold agent as described in JP-A-63-271247 is preferably added for preventing the growth of various molds or bacteria in the hydrophilic colloidal layer which destroy the image.

At the time when the light-sensitive material of the present invention is exposed to a printer, it is preferable to use a method as described in US-PS 4 880 726. Bandstop filter is used. Using this filter prevents color mixing and greatly improves color reproduction.

The photosensitive material of the present invention is used in a printing system using a normal negative printer, and in addition, it is preferably used in digital scanning exposure using high intensity monochromatic light such as a gas laser, a light emitting diode, a semiconductor laser or a second harmonic generation (SHG) light source as a combination of a semiconductor laser or a solid laser using a semiconductor laser as an excitation light source with a non-linear optical crystal. In order to achieve a compact and inexpensive system, it is preferable to use the semiconductor laser or the second harmonic generation (SHG) light source as a combination of a semiconductor laser or a solid laser with a non-linear optical crystal. In particular, in order to create a compact and inexpensive device with a long service life and high stability, the semiconductor laser is preferably used, and at least one of the light sources for exposure is preferably a semiconductor laser.

When using the above-described light source for scanning exposure, the spectral sensitivity maximum of the photosensitive material according to the invention can be freely selected depending on the wavelength of the light source used for scanning exposure. In the case of a SHG light source obtained by combining a solid laser using a semiconductor laser as an excitation light source or a semiconductor laser with a non-linear optical Crystal, the oscillation wavelength of the laser can be reduced to half, and thereby blue light and green light can be obtained. Accordingly, the photosensitive material can have a spectral sensitivity peak in the normal three regions of blue, green and red. When a semiconductor laser is used as a light source to achieve a low-cost, highly stable and compact device, it is preferable that at least two layers having a spectral sensitivity peak at 670 nm or more are used. The reason is that the Group III-V series semiconductor laser, which is available, low-cost and stable, currently has an emission wavelength range in the range from red to infrared. However, on a laboratory scale, the oscillation of Group II-VI series semiconductor lasers in green and blue regions has been confirmed, and it is expected that the semiconductor lasers described above can be used inexpensively and stably if the production technology of semiconductor lasers is developed. If this is the case, the need for at least two layers to have a spectral sensitivity maximum at 670 nm or more would be eliminated.

In scanning exposure, the exposure time for the silver halide in the photosensitive material is the time required to expose a certain small area. The small area is generally the minimum unit capable of controlling the amount of light from corresponding digital data and is called a pixel. Accordingly, the exposure time per pixel varies depending on the size of the pixel. The size of the pixel depends on the pixel density, which is practically in the range of 50 to 2,000 dpi. If the If exposure time is defined as the time required to expose a pixel of a size such that the pixel density is 400 dpi, then the exposure time is preferably 10⁻⁴ seconds or less, more preferably 10⁻⁴ seconds or less.

The silver halide grain for use in the present invention is silver bromide, silver chloride, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide or silver chloroiodobromide. A silver salt other than these, e.g. silver rhodanide, silver sulfide, silver selenide, silver carbonate, silver phosphate or silver salt of an organic acid, may be contained as a separate grain or as a part of the silver halide grains. When rapid development and desilvering (e.g. bleaching, fixing, bleach-fixing) are desired, a so-called high silver chloride grain having a silver chloride content of 90 mol% or more is preferred. In addition, when development is adequately suppressed, silver iodide is preferably contained. The preferred silver iodide content varies depending on the light-sensitive material as a target.

The high silver chloride emulsion for use in the present invention preferably has such a structure that a localized silver bromide phase in a layered or non-layered form is present in the interior and/or on the surface of a silver halide grain. The halogen composition of the localized phase described above preferably has a silver bromide content of at least 10 mol%, particularly preferably more than 20 mol%. The silver bromide content in a localized silver bromide phase can be analyzed using an X-ray diffraction method [e.g., described in Nippon Kagaku-kai (author), Shin Jikken Kagaku Koza 6, Kozo Kaiseki (New Experimental and Chemistry Lecture 6, Structural Analysis), Maruzen]. The localized phase may exist in the interior of a grain or at the edges, corners or on the planes of the grain surface. A preferred example is a localized phase grown epitaxially at the corners of a grain.

It is also effective to further increase the silver chloride content of the silver halide emulsion to reduce the replenishment amount of the development processing solution. If this is the case, an almost pure silver chloride emulsion having a silver chloride content of 98 to 100 mol% is also used.

The silver halide emulsion for use in the present invention preferably has a distribution or structure with respect to the halogen composition in the grain. Typical examples thereof are disclosed in JP-B-43-13162 (the term "JP-B" as used herein means an "examined Japanese patent publication"), JP-A-61-215540, JP-A-60-222845, JP-A-60-143331, JP-A-61-75337 and JP-A-60-222844.

In order to provide the interior of a grain with a structure, not only the shell structure as described above, but also a so-called transition structure can be formed in the grain. Examples of this are described in JP-A-59-133540, JP-A-58-108526, EP-A-199290, JP-B-58-247772 and JP-A-59-16254.

In the case of a transition structure, a silver halide and a silver halide can of course be combined, but a silver salt compound that does not only have a rock salt structure, such as Silver rhodanide and silver carbonate can be combined with silver halide to provide the transition structure.

In the case of a silver iodobromide grain or the like having the structure described above, the silver iodide content of the core portion is preferably higher than that of the shell portion. In contrast, in some cases, it is preferable that the silver iodide content of the core portion is low and that of the shell portion is high. Similarly, in the case of a grain having a transition structure, the host crystal may have a high silver iodide content and the bonded crystal may have a relatively low silver iodide content, and the reverse thereof may also be used. The boundary between parts having different halogen compositions of a grain having the structure described above may be either clear or blurred. It is also a preferable embodiment to positively provide a continuous change in composition.

In the case of a silver halide grain in which two or more silver halides exist as a solid solution or to form a structure, control of the distribution of the halogen composition between the grains is important. The measuring method of the distribution of the halogen composition between the grains is described in JP-A-60-254032. In particular, an emulsion having a high uniformity such as that having a coefficient of variation of 20% or less is preferred.

Control of the halogen composition near the grain surface is important. Increasing the silver iodide or silver chloride content near the surface is accompanied by a change in the adsorption ability for a dye or the development speed, and therefore the control can be selected depending on the purpose.

The silver halide grain for use in the present invention may be a regular crystal having no twin planes or a crystal described in Nippon Shashin Gakkai (author), Shashin Kogyo no Kiso, Gin-en Shashin Hen (Primary Study of Photographic Industry, Silver Salt Photography), page 163 (Corona Sha) (1979), such as a parallel multiple twin crystal containing two or more parallel twin planes or a non-parallel multiple twin crystal containing two or more non-parallel twin planes, and these crystals may be selected depending on the purpose. An example of the method of mixing grains having different shapes is disclosed in U.S. Patent No. 4,865,964. In the case of a regular crystal, a cubic grain comprising a (100) face, an octahedral grain comprising a (111) face, or dodecahedral grain comprising a (110) face may be used, disclosed in JP-B-55-42737 and JP-A-60-222842. In addition, a grain having (hlm) face may also be selected, as reported in Journal of Imaging Science, Vol. 30, p. 247 (1986). A grain having two kinds or a plurality of faces together can also be selected and used depending on the purpose, and examples thereof include a tetradecahedral grain having a (100) face and a (111) face together in one grain, a grain having a (100) face and a (110) face together, and a grain having a (111) face and a (110) face together.

The value obtained by dividing the diameter of a projected area corresponding to a circle by the grain thickness is called the aspect ratio, and the shape of a tabular grain is defined by the aspect ratio. Tabular grains having an aspect ratio of 1 or more can be used in the present invention. The tabular grain can be prepared according to methods described in Cleve, Photography Theory and Practice, page 131 (1930), Gutoff, Photographic Science and Engineering, vol. 14, pages 248-257 (1970), U.S. Patents 4,434,226, 4,414,310, 4,433,048 and 4,439,520 and British Patent 2,112,157. The use of a tabular grain is advantageous in that the hiding power is increased or the spectral sensitization efficiency is increased by a sensitizing dye, and U.S. Patent 4,434,226 described above describes this in detail. The average aspect ratio of 80% or more of the total projected area of the grains is preferably 1 to less than 100, more preferably 2 to less than 20, most preferably 3 to less than 10. The shape of the tabular grain can be selected from a triangle, a hexagon or a circle. An equilateral hexagon consisting of six sides of approximately the same length, described in U.S. Patent No. 4,797,354, is a preferred embodiment.

The diameter of the projected area corresponding to a circle is often used as the grain size of a tabular grain, and grains having an average diameter of 0.6 µm or less described in U.S. Patent No. 4,748,106 are preferred for achieving high image quality. Also, an emulsion having a narrow grain size distribution described in U.S. Patent No. 4,775,617 is preferred. Regarding the shape of a tabular grain the grain thickness is preferably reduced to 0.5 µm or less, particularly preferably 0.3 µm or less, in order to increase sharpness. An emulsion having a high uniformity such that the coefficient of variation of the grain thickness is 30% or less is also preferred. In addition, a grain whose grain thickness and face-to-face dimension of the twin planes are prescribed as described in JP-A-63-163451 is also preferred.

It is preferable to select a grain containing no dislocation line, a grain containing a plurality of dislocation lines, or a grain containing a large number of dislocation lines, depending on the purpose. A grain containing dislocation lines linearly integrated in or twisted to a specific direction of crystal orientation may also be selected. The dislocation lines may be integrated throughout the grain or may be integrated in a specific part of the grain, for example, the dislocation lines may be integrated only in a peripheral portion of the grain. The dislocation lines are preferably integrated not only in a tabular grain but also in a regular crystal grain or an amorphous grain represented by a siliceous grain.

The silver halide emulsion for use in the present invention may be subjected to a grain rounding treatment as disclosed in EP-B-96 727 and EP-B-64 412, or may be subjected to a surface modification as disclosed in DE-PS 23 06 447 and JP-A-60-221320.

The grain surface generally has a flat structure, but in some cases, unevenness is intentionally provided thereon. This is described in JP-A-58-106532, JP-A-60-221320 and US-PS 4,643,966.

The grain size of the emulsion for use in the present invention can be verified by the diameter of the projected area corresponding to a circle measured using an electron microscope, by the diameter of the grain volume corresponding to a sphere calculated from the projected area and the grain thickness, or by the diameter of the volume corresponding to a sphere according to the Coulter Counter method. With respect to the diameter corresponding to a sphere, a grain can be selected over a wide range from an ultrafine grain having a grain size of 0.01 µm or less to a giant grain having a grain size of more than 10 µm. Preferably, a grain having a grain size of 0.1 to 2 µm is used as the photosensitive silver halide grain.

The emulsion for use in the present invention can be selected from a so-called polydisperse emulsion having a broad grain size distribution and a monodisperse emulsion having a narrow size distribution depending on the purpose. As a measure for expressing the size distribution, the coefficient of variation of the diameter of the projected area of a grain corresponding to a circle or the diameter of the volume of a grain corresponding to a sphere can be used. In the case of using a monodisperse emulsion, the emulsion used preferably has a coefficient of variation of the size distribution of 25% or less, particularly preferably 20% or less, more preferably 15% or less.

In order to satisfy the gradation required for the light-sensitive material, within the emulsion layers having substantially the same spectral sensitivity, two or more kinds of monodisperse silver halide emulsions having different grain sizes may be mixed in the same layer or coated as separate layers by superposition. In addition, two or more kinds of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or superposed.

The photographic emulsion for use in the present invention can be prepared according to the methods described in P. Glafkides, Chimie et Phisique Photographique, Paul Montel (1967), G. F. Duffin, Photographic Emulsion Chemistry, The Focal Press (1966) and V. L. Zelikman et al., Making and Coating Photographic Emulsion, The Focal Press (1964). Also, a method of forming grains in excess of silver ions (so-called reverse mixing method) can be used. A so-called controlled double jet method, which is a system of double jet method of keeping the pAg of the liquid phase constant when the silver halide is formed, can also be used. According to this method, the obtained silver halide emulsion can have a regular crystal form and an almost uniform grain size.

In some cases, a process of adding silver halide grains previously dissolved in a reaction vessel to prepare an emulsion, preferably those described in U.S. Patents 4,334,012, 4,301,241 and 4,150,994. The grain may be used as a seed crystal or may be supplied as silver halide for growth, and this is effective. In addition, to modify the surface, it is effective in some cases to add fine grains of various halogen compositions.

A process for converting a large part or only a part of the halogen composition of a silver halide grain by halogen conversion is disclosed in US Patents 3,477,852 and 4,142,900, EP Patents 273,429 and 273,430 and DE-OS 38 19 241. To effect conversion to a less soluble silver salt, a soluble halogen solution or silver halide grains can be added.

With respect to grain growth, in addition to the method of adding a soluble silver salt and a halogen salt at a constant concentration and a constant flow rate, a method of forming grains by varying the concentration or varying the flow rate is preferred, as described in British Patent No. 1,469,480 and US Patent Nos. 3,650,757 and 4,242,445. By increasing the concentration or increasing the flow rate, the amount of silver halide supplied can be varied according to a linear function, secondary function or a more complicated function of the addition time.

The mixing vessel used in the reaction of a soluble silver salt with a soluble halogen salt solution can be selected from those described in U.S. Patents 2,996,287, 3,342,605, 3,415,650 and 3,785,777 and the processes described in DE-OSs 2 556 885 and 2 555 364 can be used.

For the purpose of accelerating ripening, a silver halide solvent is useful. For example, it is known to introduce an excess amount of halogen ions into a reaction vessel to accelerate ripening. Other ripening agents can also be used. The ripening agent can be completely mixed into the dispersion medium in the reaction vessel before the addition of silver salt and halide salt, or can be introduced into the reaction vessel together with the addition of halide salt, silver salt or deflocculant.

Examples thereof include ammonia, thiocyanates (e.g. potassium thiocyanate, ammonium thiocyanate), organic thioether compounds (e.g. the compounds described in U.S. Patents 3,574,628, 3,021,215, 3,057,724, 3,038,805, 4,276,374, 4,297,439, 3,704,130 and 4,782,013, JP-A-57-104926), thione compounds (e.g. tetrasubstituted thiourea described in JP-A-53-82408, JP-A-55-77737 and U.S. Patent 4,221,863, compounds described in JP-A-53-144319), mercapto compounds capable of accelerating the growth of silver halide grains described in JP-A-57-202531, and amine compounds, e.g. those described in JP-A-54-100717. Gelatin is advantageous as a protective colloid for use in the preparation for use in the emulsion for use in the present invention or as a binder in other hydrophilic colloid layers, but a hydrophilic colloid other than gelatin may also be used.

Examples include proteins such as gelatin derivatives, graft polymers of gelatin to other polymers, albumin and casein; saccharide derivatives such as cellulose derivatives (e.g. hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfate), sodium alginates and starch derivatives; and various synthetic hydrophilic polymer materials such as homopolymers and copolymers of polyvinyl alcohol, polyvinyl alcohol hemiacetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole or polyvinylpyrazole.

The gelatin may be a lime-treated gelatin, acid-treated gelatin or enzyme-treated gelatin as described in Bull. Soc. Sci. Photo. Japan, No. 16, page 30 (1966), and a hydrolysate or enzymolysate of gelatin may also be used. A low molecular weight gelatin described in JP-A-1-158426 is preferably used in the preparation of tabular grains.

The silver halide emulsion is preferably washed with water to remove salts and processed into a new protective colloid dispersion. The temperature for washing with water can be selected depending on the purpose, but it is preferably 5 to 50°C. The pH at the time of washing with water can also be selected depending on the purpose, but it is preferably 2 to 10, particularly preferably 3 to 8. The pAg at the time of washing with water can also be selected depending on the purpose, but it is preferably 5 to 10. The method of washing with water can be selected from a noodle washing method with water, a dialysis method using a semipermeable membrane, a centrifugal separation method, a Coagulation precipitation method and an ion exchange method. The coagulation precipitation method can be selected from a method using sulfate, a method using an organic solvent, a method using a water-soluble polymer and a method using a gelatin derivative.

Depending on the purpose, it is preferable to provide a metal ion salt at the time of preparing the silver halide emulsion, e.g., during grain formation, in desilvering, in chemical sensitization, or before coating. The metal ion salt is preferably added during grain formation when it dopes the grain, and in the interval between grain formation and before the completion of chemical sensitization when it is used to modify the grain surface or as a chemical sensitizer. The metal ion salt may be doped on the entire grain, only on the core, shell or epitaxial region of a grain, or only on the substrate grain. Examples of the metal include: Mg, Ca, Sr, Ba, Al, Sc, Y, La, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, Pt, Au, Cd, Hg, Tl, In, Sn, Pb and Bi. These metals may be added if they are in a form of a salt capable of dissolving during grain formation, such as an ammonium salt, acetate, nitrate, sulfate, phosphate, hydroxy salt, 6-coordinate complex salt or 4-coordinate complex salt. Examples include: CdBr2, CdCl2, Cd(NO3)2, Pb(NO3)2, Pb(CH3COO)2, K3[Fe(CN)6], (NH4)4[Fe(CN)6], K3IrCl4, (NH4)3RhCl6 and K4Ru(CN)6. The ligand of the coordination compound can be selected from halogen, H2O, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo and carbonyl.

These metal compounds can be used individually or in combination of two or more.

A method of adding a chalcogen compound during the preparation of an emulsion, described in U.S. Patent 3,772,031, is also useful in some cases. Apart from S, Se and Te, a cyanate, thiocyanate, selenocyanate, carbonate, phosphate or acetate may also be present.

The silver halide grain for use in the present invention may be subjected to at least sulfur sensitization, selenium sensitization, tellurium sensitization (these three sensitizations are collectively called chalcogen sensitization), noble metal sensitization and reduction sensitization in each step during the preparation of the silver halide emulsion. A combination of two or more sensitization methods is preferred. By selecting the step in which the chemical sensitization is carried out, various types of emulsions can be prepared. The chemical sensitization spots are embedded in one type inside the grain, embedded in another type in the superficial part of the grain surface, and formed on the grain surface in still another type. In the emulsion for use in the present invention, the location of the chemical sensitization spots can be appropriately selected.

The chemical sensitization which can preferably be used in the present invention is chalcogen sensitization, noble metal sensitization or a combination thereof, and it can be carried out using an active gelatin as described in TH James, The Theory of the Photographic Process, 4th edition, Macmillan, pages 67-76 (1977), or using sulfur, selenium, tellurium, gold, platinum, palladium, iridium or a combination of these sensitizers in a plurality at a pAg of 5 to 10, a pH of 5 to 8 and a temperature of 30 to 80ºC as described in Research Disclosure, Item 12008 (April 1974), ibid., Item 13452 (June 1975), ibid., Item 307105 (November 1989), U.S. Patents 2,642,361, 3,297,446, 3,772,031, 3,857,711, 3,901,714, 4,266,018 and 3 904 415 and GB-PS 1 315 755.

In sulfur sensitization, a labile sulfur compound is used, and specific examples include: thiosulfates (e.g., hypo-), thioureas (e.g., diphenylthiourea, triethylthiourea, allylthiourea), rhodanines, mercapto compounds, thioamides, thiohydantoins, 4-oxooxazolidine-2-thiones, disulfides, polysulfides, polythionates, elemental sulfur, and known sulfur-containing compounds described in U.S. Patents 3,857,711, 4,266,018, and 4,054,457. Sulfur sensitization is used in many cases in combination with noble metal sensitization.

The amount of the sulfur sensitizer used is, based on the silver halide grain, preferably 1 x 10⁻⁷ to 1 x 10⁻³ mol, particularly preferably 5 x 10⁻⁷ to 1 x 10⁻⁴ mol per mol of silver halide.

In selenium sensitization, a known labile selenium compound is used, such as the selenium compounds described in U.S. Patents 3,297,446 and 3,297,447, and specific examples thereof include colloidal selenium metal, selenoureas (e.g., N,N- Dimethylselenourea, tetramethylselenourea), selenoketones (e.g. selenoacetone), selenoamides (e.g. selenoacetamide), selenocarboxylic acids and esters, isoselenocyanates, selenides (e.g. diethylselenide, triphenylphosphineselenide) and selenophosphates (e.g. tri-p-tolylselenophosphate). Selenium sensitization is preferably used in some cases in combination with sulfur sensitization, noble metal sensitization or both of these sensitizations.

The amount of the selenium sensitizer used varies depending on the kind of selenium compound or silver halide grain used or chemical ripening conditions, but it is usually 10-8 to 10-4 mol, preferably on the order of 10-7 to 10-5 mol per mol of silver halide.

As the tellurium sensitizer for use in the present invention, the compounds described in Canadian Patent No. 800,958, British Patent Nos. 1,295,462 and 1,396,696, and JP-A-4-204640 and JP-A-4-333043 can be used.

In the noble metal sensitization, a noble metal salt such as gold, platinum, palladium or iridium may be used, and in particular, gold sensitization, palladium sensitization and combination use of these two sensitizations are preferred. In the case of gold sensitization, a known compound such as chloroaurate, potassium chloroaurate, potassium aurithiocyanate, gold sulfide or gold selenide may be used. The palladium compound means a divalent or tetravalent palladium salt. The preferred palladium compound is represented by R₂PdX₄ or R₂PdX₄, wherein R is a hydrogen atom, alkali metal atom or an ammonium group and X represents a halogen atom such as chlorine, bromine or iodine.

In particular, K₂PdCl₄, (NH₄)₂PdCl₆, Na₂PdCl₄, (NH₄)₂PdCl₄, Li₂PdCl₄, Na₂PdCl₆, and K₂PdBr₄ are preferred. The gold compound and palladium compound are each preferably used in combination with a thiocyanate or selenocyanate.

To the emulsion for use in the present invention, gold sensitization is preferably applied in combination. The amount of the gold sensitizer is preferably 1 x 10-7 to 1 x 10-3 mol, particularly preferably 5 x 10-7 to 5 x 10-4 mol per mol of silver halide. The amount of the palladium compound is preferably 5 x 10-7 to 1 x 10-3 mol per mol of silver halide. The amount of the thiocyanate compound or the selenocyanate compound is preferably 1 x 10-6 to 5 x 10-2 mol per mol of silver halide.

The silver halide emulsion is preferably subjected to reduction sensitization during grain formation, before or during chemical sensitization after grain formation, or after chemical sensitization.

The reduction sensitization can be carried out by one of a method of adding a reduction sensitizer to the silver halide emulsion, a method of growing or ripening the emulsion in a low pAg environment at a pAg of 1 to 7 called silver ripening, and a method of growing or ripening the emulsion in a high pH environment at a pH of 8 to 11 called high pH ripening. Two or Several of the methods described above can also be used in combination.

The reduction sensitizer can be selected from known reduction sensitizers such as a stannous salt, ascorbic acid and a derivative thereof, amines and polyamines, a hydrazine and a derivative thereof, a formamidine sulfinic acid, a silane compound and a borane compound, and these compounds can be used in combination of two or more. Preferred compounds as the reduction sensitizer are a stannous chloride, an aminoiminomethanesulfinic acid (common name: thiourea dioxide), a dimethylamine borane, ascorbic acid and a derivative thereof.

Chemical sensitization can also be carried out in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fogging while increasing sensitivity during chemical sensitization, such as azaindene, azapyridazine and azapyrimidine. Examples of the chemical sensitization aid are described in U.S. Patent Nos. 2,131,038, 3,411,914 and 3,554,757, JP-A-58-126526 and G. F. Duffin, Photographic Emulsion Chemistry (10c. cit.), pages 138-143.

An oxidizing agent for silver is preferably used during the preparation of the emulsion. The oxidizing agent for silver means a compound capable of acting on metallic silver to convert it to a silver ion. In particular, a compound is useful which oxidizes very fine silver grains formed during grain formation and chemical sensitization of silver halide grains as byproduct, converted to silver ions. The silver ion produced here can be in the form of a poorly water-soluble silver salt, such as silver halide, silver sulfide or silver selenide, or in the form of a readily water-soluble silver salt, such as silver nitrate. The oxidizing agent for silver can be either an inorganic substance or an organic substance. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and an adduct thereof (e.g. NaBO₂·H₂O₂·3H₂O, 2NaCO₃·3H₂O₂, Na₄P₂O�7·2H₂O₂, 2Na₂SO₄·H₂O₂·2H₂O), a peroxy acid salt (e.g. K₂S₂O�8, K₂C₂O�6, K₂P₂O�8), a peroxy complex compound (e.g. K₂[Ti(O₂)C₂O₄]₃3H₂O, 4K₂SO₄·Ti(O₂)OH·SO₄·2H₂O, Na₃[VO(O₂)(C₂H₄)₂·6H₂O), a permanganate (e.g. KMnO₄), an oxyacid salt such as chromate (e.g. K₂Cr₂O₇), a halogen element such as iodine and bromine, a perhalogenic acid salt (e.g. potassium periodate), a salt of a high valence metal (e.g. potassium hexacyanoferrate) and a thiosulfonate.

Examples of the organic oxidizing agent include: quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and active halogen releasing compounds (e.g. N-bromosuccinimide, chloramine-T, chloramine-B).

The combination use of the above-described reduction sensitization with the oxidizing agent for silver is a preferred embodiment.

Various compounds may be incorporated into the photographic emulsion for use in the present invention to prevent fogging during manufacture, storage or photographic processing of the light-sensitive material, or to photographic performance. In particular, a wide variety of compounds known as antifoggants or stabilizers can be added, for example thiazoles such as benzothiazolium salt, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles and mercaptotetrazoles (e.g. 1-phenyl-5-mercaptotetrazole, 1-(5-methylureidophenyl)-5-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinethione; and azaindenes such as triazaindenes, tetraazaindenes [especially 4-hydroxy-6-methyl-(1,3,3a,7)tetraazaindenes] and pentaazaindenes. For example, those described in U.S. Patents 3,954,474 and 3,982,947 and JP-B-52-28660 can be used. One of the preferred compounds is the compound described in JP-A-63-212932. The antifoggant and the stabilizer can be added respectively at various stages depending on the purpose, such as before grain formation, during grain formation, after grain formation, at water washing, at dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization or before coating.

The photographic emulsion for use in the present invention is preferably spectrally sensitized by a methine dye or others. Examples of the dye used include a cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, holopolar cyanine dye, hemicyanine dye, styryl dye and hemioxonol dye. Among them, Particularly useful dyes are those belonging to cyanine dye, merocyanine dye and complex merocyanine dye. For these dyes, any nucleus which is commonly used for cyanine dyes as a heterocyclic base nucleus can be used. Examples thereof include a pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus and pyridine nucleus; a nucleus resulting from the fusion of an alicyclic hydrocarbon ring to the nuclei described above; and a nucleus resulting from the fusion of an aromatic hydrocarbon ring to the nuclei described above, e.g. an indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus and quinoline nucleus. These nuclei may have a substituent on the carbon atom.

For the merocyanine dye or complex merocyanine dye, a 5- or 6-membered heterocyclic nucleus such as a pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thioxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus or thiobarbituric acid nucleus can be used as the nucleus having a ketomethylene structure.

These sensitizing dyes may be used individually or in combination thereof, and the combination of sensitizing dyes is often used for the purpose of supersensitization. Representative examples thereof are described in U.S. Patent Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628,946, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,769,301, 3,814,609, 3,837,862 and 4 026 707, GB-PSs 1 344 281 and 1 507 803, JP-B-43-4936, JP-B-53-12375, JP-A-52-110618 and JP-A-52-109925.

In combination with a sensitizing dye, a dye which does not itself provide a spectral sensitizing effect or a material which does not substantially absorb visible light but exerts a hypersensitizing effect may be included in the emulsion.

The time at which the spectral sensitizing dye is added to the emulsion can be any stage known to date that is useful during the preparation of the emulsion. Most commonly, spectral sensitization is effected after completion of chemical sensitization and before coating, but the dye can be added at the same time as the chemical sensitizer to effect simultaneous spectral sensitization and chemical sensitization, as described in U.S. Patents 3,628,969 and 4,225,666, spectral sensitization can be effected before chemical sensitization, as described in JP-A-58-113928, or the dye can be added before completion of precipitation and formation of silver halide grains to start spectral sensitization. Furthermore, the compound described above may be added in parts, in particular, a part of the compound may be added before chemical sensitization and the rest may be added after chemical sensitization as described in US Patent No. 4,225,666, and the compound may be added at any time during the formation of the silver halide grains. as in the process described in US Pat. No. 4,183,756.

The addition amount of the compound may be 4 x 10-6 to 8 x 10-3 mol per mol of silver halide, but in the case of silver halide grains in the size of 0.2 to 1.2 µm, which is a particularly preferred embodiment, it is effectively 5 x 10-5 to 2 x 10-3 mol per mol of silver halide.

The light-sensitive material of the present invention uses various additives as described above, but apart from these, various additives may be used appropriately.

These additives are described in more detail in Research Disclosure, Item 17643 (December 1978), ibid., Item 18716 (November 1979), and ibid., Item 307105 (November 1989), and the relevant amounts thereof are summarized in the table below. TABLE 1

The total coated amount of silver of the photosensitive material of the present invention is preferably 0.003 to 12 g/m² in terms of silver. In the case of a transmissive material such as color negative film, it is preferably 1 to 12 g/m², particularly preferably 3 to 10 g/m². In the case of a reflective material such as color paper, it is preferably 0.003 to 1 g/m² in view of rapid processing and low replenishment, and in this case the amount added to the respective layers is preferably 0.001 to 0.4 g per photosensitive layer. Particularly when the photosensitive material of the present invention is subjected to amplification processing, the total amount of silver coated is preferably 0.003 to 0.3 g/m², particularly preferably 0.01 to 0.1 g/m², even more preferably 0.015 to 0.05 g/m². In this case, the addition amount is preferably 0.001 to 0.1 g, preferably 0.003 to 0.03 g per photosensitive layer.

In the present invention, if the coated amount of silver of each photosensitive layer is less than 0.001 g/m², the dissolution of silver salt progresses and a sufficiently high color density cannot be obtained, and if it exceeds 0.1 g/m², in the case of the amplification process, an increase in Dmin or generation of bubbles is caused and the appearance is often poor.

The total amount of gelatin in the light-sensitive material according to the invention is 1.0 to 30 g/m², preferably 2.0 to 20 g/m². When swelling the light-sensitive material according to the invention using an alkali solution with a pH of 12, the amount of gelatin required to achieve half saturation of the swollen layer thickness (corresponding to 90% of the maximum swollen layer thickness) is The time required for swelling (maximum swollen layer thickness - layer thickness) is preferably 15 seconds or less, particularly preferably 10 seconds or less. The swelling ratio [(maximum swollen layer thickness - layer thickness) / layer thickness x 100] is preferably 50 to 300%, particularly preferably 100 to 200%.

The processing materials and the processing method for use in the present invention are described in detail below. In the present invention, the photosensitive material is processed by development (silver development / cross-oxidation of the isolated reducing agent), desilvering and water washing or stabilization. In some cases, the photosensitive material may be subjected to processing for intensifying color formation such as alkali transfer after water washing or stabilization.

In developing the light-sensitive material of the present invention, the developer may use a compound which can function as a developing agent for silver halide and/or has a function such that the oxidation product of the developing agent generated during silver development cross-oxidizes the reducing agent contained in the light-sensitive material to form color. Preferred examples of the compound include pyrazolidones, dihydroxybenzenes, reductones and aminophenols, with pyrazolidones being particularly preferred.

The pyrazolidones are preferably 1-phenyl-3-pyrazolidones and examples thereof include: 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1-phenyl-5-methyl-3- pyrazolidone, 1-phenyl-5-phenyl-3-pyrazolidone, 1-p-tolyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-p-chlorophenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-2-hydroxymethyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-2-acetyl-3-pyrazolidone and 1-Phenyl-2-hydroxymethyl-5-phenyl-3-pyrazolidone.

Examples of the dihydroxybenzenes include: hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3- dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,5-dimethylhydroquinone and potassium hydroquinone monosulfonate.

The reductones are preferably an ascorbic acid and a derivative thereof, and examples thereof include the compounds described in JP-A-6-148822, pages 3-10, particularly sodium L-ascorbate and sodium erythorbate are preferred.

Examples of the p-aminophenols include N-methyl-p-aminophenol, N-(β-hydroxyethyl)-p-aminophenol, N-(4-hydroxyphenyl)glycine and 2-methyl-p-aminophenol.

These compounds are usually used individually, but they are preferably used in combination of two or more of them for the purpose of increasing the developing and cross-oxidation activity.

The amount of the above-described compound used in the developer is generally 2.5 x 10-4 to 0.2 mol/l, preferably 0.0025 to 0.1 mol/l, particularly preferably 0.001 to 0.05 mol/l.

Examples of the preservative used in the developer include sodium sulfite, Potassium sulfite, lithium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, sodium formaldehyde bisulfite and hydroxylamine sulfate, and the amount of the compound used is usually 0.1 mol/L or less, preferably 0.001 to 0.002 mol/L. In the case of using a high silver chloride emulsion in the light-sensitive material, the amount of the compound used is usually 0.001 mol/L or less, and preferably the compound is not used at all.

In the present invention, an organic preservative such as diethylhydroxylamine and the dialkylhydroxylamines described in JP-A-4-97355 is preferably contained instead of the above-described hydroxylamine or sulfite ion.

The developer may contain halogen ions such as chloride ions, bromine ions or iodine ions.

The halide can be added directly to the developer or can be eluted from the light-sensitive material into the developer during development processing.

The developer for use in the present invention preferably has a pH of 8 to 13, more preferably 9 to 12.

To maintain the pH described above, various buffer solutions are preferably used. Examples include carbonate, phosphate, tetraborate and hydroxybenzoate.

The amount of the buffer agent for the developer is preferably 0.05 mol/l or more, particularly preferably 0.1 to 0.4 mol/l.

In addition, the developer may contain various complexing agents as precipitation inhibitors for calcium or magnesium or to improve the stability of the developer.

The amount of complexing agent added may be sufficient if it is an amount sufficiently high to retain the metal ions in the developer, and is, for example, about 0.1 to 10 g/l.

In the present invention, a freely selected antifoggant may be added if desired. The antifoggant includes alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and nitrogen-containing heterocyclic compounds.

The amount of the nitrogen-containing heterocyclic compound added is 1 x 10⁻⁵ to 1 x 10⁻² mol/l, preferably 2.5 x 10⁻⁵ to 1 x 10⁻³ mol/l.

An optional development accelerator can be added to the developer if desired.

The developer preferably contains a brightening agent. In particular, compounds based on 4,4'-diamino-2,2'-disulfostilbene are preferably used.

The processing temperature of the developer for use in the present invention is 20 to 50°C, preferably 30 to 45°C. The processing time is 5 Seconds to 2 minutes, preferably 10 seconds to 1 minute. The replenishment amount is preferably less, but it is usually 15 to 600 ml, preferably 25 to 200 ml, particularly preferably 35 to 100 ml per m² of the photosensitive material.

Development is followed by desilvering. Desilvering may include fixing or bleaching and fixing. If it includes bleaching and fixing, bleaching and fixing may be carried out separately or simultaneously (bleach-fixing). In addition, processing in a bleach-fix bath consisting of two continuous tanks, processing of carrying out fixation before bleach-fixing, or processing of carrying out bleaching after bleach-fixing can be freely selected as appropriate.

In some cases, it is preferable to perform stabilization after development without effecting desilvering in order to stabilize the silver salt or dye image.

Image enhancement processing (intensification) can also be carried out after development using peroxides, halogen acids, iodoso compounds and cobalt(III) complex compounds described in DE-OSs 1 813 920, 2 044 993 and 2 735 262, JP-A-48-9728, JP-A-49-84240, JP-A-49-102314, JP-A-51-53826, JP-A-52-13336 and JP-A-52-73731. To further intensify image enhancement, the above-described oxidizing agent for image enhancement can be added to the developer to effect development and image intensification simultaneously in a single bath. In particular, hydrogen peroxide is preferred because of its high amplification factor. The above-described Image intensification is a preferred processing method in terms of environmental protection because the amount of silver in the photosensitive material can be greatly reduced to avoid bleaching and at the same time does not involve the release of silver (or silver salt), for example during stabilization.

Examples of the bleaching agent for use in the bleaching solution or the bleach-fixing solution include polyvalent metal compounds such as iron(III), cobalt(III), chromium(IV) and copper(II), peracids, quinones and nitro compounds. Among them, aminopolycarboxylic acid ferrate such as ethylenediaminetetraacetatoferrate complex salt and 1,3-diaminopropanetetraacetatoferrate complex salt, hydrogen peroxide and persulfate are preferred in view of rapid processing and prevention of environmental pollution.

The bleaching solution or bleach-fixing solution using the aminopolycarboxylic acid ferrate complex salt is used at a pH of 3 to 8, preferably 5 to 7. The bleaching solution using persulfate or hydrogen peroxide is used at a pH of 4 to 11, preferably 5 to 10.

The bleach solution, bleach-fix solution or a prebath thereof may use a bleach accelerator if desired.

The bleaching solution, the bleach-fixing solution or the fixing solution may employ conventionally known rehalogenating agents or additives such as a pH buffer and a metal corrosion inhibitor. In particular, the solutions each preferably contain a organic acid with an acid dissociation constant (pKa) of 2 to 7 to prevent bleach stains.

Examples of the fixing agent for use in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioureas, a large number of iodide salts and nitrogen-containing heterocyclic compounds having a sulfide group, mesoionic compounds and thioether-based compounds described in JP-A-4-365037, pages 11-21, JP-A-5-66540, pages 1088-1092.

As preservatives for the fixing solution or the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts and sulfinic acid compounds, described in EP-A-294 769, are preferred.

In addition, the fixing solution or the bleach-fixing solution may contain various brightening agents, defoaming agents, surfactants, polyvinylpyrrolidones or methanols.

The processing temperature for desilvering is 20 to 50ºC, preferably 30 to 45ºC. The processing time is 5 seconds to 2 minutes, preferably 10 seconds to 1 minute. The amount of replenishment is preferably less, but it is usually 15 to 600 ml, preferably 25 to 200 ml, particularly preferably 35 to 100 ml per m² of the photosensitive material. Processing without replenishment only with compensation for the evaporation loss of water is also preferred.

The light-sensitive material of the present invention is usually washed with water after desilvering. When stabilization is carried out, the Water washing can be omitted. In the stabilization, any of the known methods described in JP-A-57-8543, JP-A-58-14834, JP-A-60-220345, JP-A-58-127926, JP-A-58-127837 and JP-A-58-140741 can be used. Stabilization by water washing as exemplified by processing a color light-sensitive material for photographing can also be carried out using the stabilizing bath containing a dye stabilizer and a surfactant as a final bath.

The water washing solution and the stabilizing solution may contain a sulfite; a hard water softener such as inorganic phosphoric acid, polyaminocarboxylic acid and organic aminophosphonic acid; a metal salt such as Mg salt, Al salt and Bi salt; a surfactant; a hardening agent, a pH buffer; a brightener; and a silver salt forming agent such as a nitrogen-containing heterocyclic compound.

Examples of the dye stabilizer for the stabilizing solution include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine and aldehyde-sulfurous acid adducts.

The pH of the washing water or the stabilizing solution is 4 to 9, preferably 5 to 8. The processing temperature is generally 15 to 45ºC, preferably 25 to 40ºC. The processing time is 5 seconds to 2 minutes, preferably 10 to 40 seconds.

The refreshment of the washing water and/or stabilizing solution described above Excess solution can be reused in other steps such as desilvering.

The amount of the washing water and/or the stabilizing solution can be selected in a wide range depending on various conditions, but the replenishment amount is preferably 15 to 360 ml, particularly preferably 25 to 120 ml per m² of the photosensitive material. In order to reduce the amount of replenishment water, it is preferable to use a plurality of tanks in a countercurrent system.

In the present invention, the water resulting from the treatment of the overflow solution or solution within the containers with a reverse osmosis membrane can be used for saving water. For example, the treatment with a reverse osmosis membrane is preferably applied to water in the second or subsequent container for water washing and/or stabilization in a multi-stage countercurrent system.

In the present invention, stirring is preferably intensified as high as possible. Specific examples of the method for intensifying stirring include a method of colliding a jet stream of a processing solution against the emulsion surface of the photosensitive material described in JP-A-62-183460 and JP-A-62-183461, a method of increasing stirring efficiency by using a rotating means described in JP-A-62-183461, a method of increasing stirring efficiency by causing turbulence on the emulsion surface while moving the photosensitive material with the emulsion surface brought into contact with a wiping blade provided in the solution, and a method of Increasing the circulation flow rate of the entire processing solutions. Such a means of intensifying the agitation is effective in any of the developer, the bleaching solution, the fixing solution, the bleach-fixing solution, the stabilizing solution and the washing water. These methods are advantageous in that the addition of the effective components in the solution to the photosensitive material or the diffusion of unnecessary components of the photosensitive material is accelerated.

The present invention has superior performance no matter what state the solution opening ratio [contact area with air (cm²)/solution volume (cm³)] of any bath is, however, the solution opening ratio is preferably 0 to 0.1 cm⁻¹ in view of the stability of the solution components, and in the case of continuous processing, it is practically preferably 0.001 to 0.05 cm⁻¹, particularly preferably 0.002 to 0.03 cm⁻¹.

The automatic developing machine used for the light-sensitive material of the present invention preferably comprises a transporting means for the light-sensitive material described in JP-A-60-191257, JP-A-60-191258 and JP-A-60-191259. The transporting means can extremely reduce the amount of the processing solution carried over from a previous bath to the next bath and provides a remarkable effect in preventing the performance of the processing solution from falling. Such an effect is particularly useful in reducing the processing time or reducing the amount of replenishment of the processing solution in each step. In addition, in order to reduce the processing time, the transfer time (ventilation time) is reduced. is preferably shortened, and, for example, a method described in JP-A-4-86659, Fig. 4, 5 or 6 and JP-A-5-66540, Fig. 4 or 5, in which a photosensitive material is transferred through blades having a shielding effect, is preferably used.

In case each processing solution is concentrated due to evaporation during continuous processing, it is preferable to correct the concentration by adding water.

The processing time in one step as used in the present invention means the time required from the start of processing of the photosensitive material in a certain step to the start of processing in the next step. The practical processing time in an automatic developing machine is usually determined by the linear speed and the volume of the processing bath, and in the present invention, the linear speed is 500 to 4,000 mm/min as a standard. In the case of a small developing machine, the linear speed is preferably 500 to 2,500 mm/min.

The total processing time, in other words the processing time from development to drying, is preferably 360 seconds or less, more preferably 120 seconds or less, still more preferably 30 to 90 seconds. The processing time used here means the period of time from when the photosensitive material is immersed in a developer until it comes out of the drying zone of the processing device.

In the processing applied to the present invention, various additives are used, and they are described in more detail in Research Disclosure, Item 36544 (September 1994). The relevant parts of this are summarized in the table below.

Type of processing equipment Page

Development funds 536

Preservative for developing agent 537, left column.

Antifoggant 537

Complexing agent 537, right sp.

Buffer 537, right column

Surfactant 538, left column and 539, right column

Bleach 538

Bleaching accelerator 538, right column to 539, left column

Complexing agent for bleaching 539, li.sp.

Rehalogenating agent 539, li.sp.

Fixative 539, right sp.

Preservative for fixative 539, right sp.

Complexing agent for fixative 540, left column.

Surfactant for stabilization 540, left sp.

Foam inhibitor for stabilization 540, re.Sp.

Complexing agent for stabilization 540, re.Sp.

Antiseptic, anti-mold agent 540, re.Sp.

Color image stabilizer 540, re.Sp.

The water saving technique used in the present invention is described in detail in Research Disclosure, Item 36544 (September 1994), page 540, right column to page 541, left column.

The present invention will be described in more detail with reference to the following examples.

EXAMPLE 1

The surface of a paper support having polyethylene laminated on both surfaces thereof was subjected to corona glow discharge treatment, a gelatin undercoat layer containing sodium dodecylbenzenesulfonate was coated thereon, and two kinds of layers containing photographic components were coated thereon to prepare a photographic printing paper (100) having the two-layer structure described below. The coating solutions were prepared as follows.

Coating solution for the first layer:

In ethyl acetate were dissolved 17 g of coupler (C-76), 20 g of reducing agent (I-16) for color formation and 80 g of solvent (Solv-1), and the resulting solution was emulsion-dispersed in 400 g of a 16% aqueous gelatin solution containing 10% sodium dodecylbenzenesulfonate and citric acid to prepare emulsion dispersion A. Separately, a silver chlorobromide emulsion A was prepared [cubic, a 3:7 mixture (on silver mole) of large emulsion A having an average grain size of 0.88 µm and small emulsion A having an average grain size of 0.70 µm; these emulsions having a coefficient of variation in grain size distribution of 0.08 and 0.10, respectively; wherein the emulsion of each size contains 0.3 mol% silver bromide localized on a portion of the grain surface comprising a substrate of silver chloride]. To this emulsion were added the blue sensitizing dyes A, B and C shown below were added in an amount of 1.4 x 10-4 mol for the large emulsion A and 1.7 x 10-4 mol for the small emulsion A per mol of silver halide, respectively. The resulting emulsion was subjected to optimum chemical ripening by adding a sulfur sensitizer and a gold sensitizer. Emulsion dispersion A and silver chlorobromide emulsion A were mixed and dissolved to prepare a first layer coating solution having the following composition. The emulsion coating amount is the coating amount calculated in terms of silver.

A coating solution for the second layer was prepared in the same manner as the coating solution for the first layer. In each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was added as a gelatin hardener.

In addition, Cpd-2, Cpd-3, Cpd-4 and Cpd-5 were added to each layer to show a total coverage of 15.0 mg/m², 60.0 mg/m², 50.0 mg/m² and 10.0 mg/m², respectively.

In addition, 1-(5-methylureidophenyl)-5- mercaptotetrazole was added to the first layer in an amount of 3.0 x 10-3 mol per mol of silver halide.

Layer structure:

The composition of each layer is shown below. The reference numerals indicate the amount coated (g/m²). In the case of silver halide emulsions, the amount coated is in terms of silver.

Carrier:

Polyethylene-coated paper [polyethylene on the side of the first layer contained a white pigment (TiO2, 15 wt.%) and a bluish dye (Ultramarine)].

First layer:

Silver chlorobromide emulsion A, described above 0.20

Gelatine 1.50

Yellow coupler (C-76) 0.17

Reducing agent (I-16) for color formation 0.20

Solvent (Solv-1) 0.80

Second layer: protective layer

Gelatin 1.01

Acrylic-modified copolymer of polyvinyl alcohol (modification level: 17%) 0.04

liquid paraffin 0.02

Surfactant (Cpd-1) 0.01

Samples (101) to (131) were carefully prepared in the same manner as Sample (100), except that the yellow coupler and the reducing agent for color formation in the coating solution for the first layer were replaced with an equimolar amount of the yellow coupler and the reducing agent for color formation shown in Tables a-1 and a-2, respectively, and that the compound shown in Tables a-1 and a-2 was added in addition to the solvent in an amount of 20 mol% based on the reducing agent for color formation and co-emulsified.

Samples (200) to (231) were carefully prepared in the same manner as sample (100), except that the silver chlorobromide emulsion A in the coating solution for the first layer was replaced by the same amount, in terms of silver, of the silver chlorobromide emulsion B shown below, that the coupler and the reducing agent for color formation were replaced by an equimolar amount of the magenta coupler shown in Tables b-1 and b-2 and the reducing agent for color formation were exchanged, and that the compound shown in Tables b-1 and b-2 was added in addition to the solvent in an amount of 20 mol% based on the reducing agent for color formation and co-emulsified.

Silver chlorobromide emulsion B:

cubic; a 1:3 mixture (in moles of Ag) of high size emulsion B having an average grain size of 0.55 µm and low size emulsion B having an average grain size of 0.39 µm; the emulsions have a coefficient of variation in the grain size distribution of 0.10 and 0.08, respectively; and the emulsion of the respective size contains 0.8 mol% AgBr localized on a portion of the grain surface comprising a substrate of silver chloride.

In silver chlorobromide emulsion B, the following spectral sensitizing dyes were used for the emulsions of each size.

(Sensitizing dye D was added in an amount of 3.0 x 10⁻⁴ mol for the large grain size emulsion and 3.6 x 10⁻⁴ mol for the small grain size emulsion per mol of silver halide; sensitizing dye E was added in an amount of 4.0 x 10⁻⁴ mol for the large grain size emulsion and 7.0 x 10⁻⁴ mol for the small grain size emulsion per mol of silver halide; and sensitizing dye F was added in an amount of 2.0 x 10⁻⁴ mol for the large grain size emulsion and 2.8 x 10⁻⁴ mol per mole of silver halide added)

Samples (300) to (331) were carefully prepared in the same manner as sample (100), except that the Silver chlorobromide emulsion A in the first layer coating solution was replaced with the same amount, in terms of silver, of silver chlorobromide emulsion C shown below, the coupler and the reducing agent for color formation were replaced with an equimolar amount of the cyan coupler and the reducing agent for color formation shown in Tables c-1 and c-2, respectively, and the compound shown in Tables c-1 and c-2 was added and co-emulsified in addition to the solvent in an amount of 20 mol% based on the reducing agent for color formation.

Silver chlorobromide emulsion C:

Cubic; a 1:4 mixture (in moles of Ag) of high size emulsion C having an average grain size of 0.5 µm and low size emulsion C having an average grain size of 0.41 µm; the emulsions have a coefficient of variation in the grain size distribution of 0.09 and 0.11, respectively; and the emulsion of each size contains 0.8 mol% AgBr localized on a portion of the grain surface comprising a substrate of silver chloride.

In silver chlorobromide emulsion C, the following spectral sensitizing dyes were used for the emulsions of each size.

(each sensitizing dye was added in an amount of 5.0 x 10-5 mol for the large size emulsion and 8.0 x 10-5 mol for the small size emulsion per mol of silver halide)

Surfactant (Cpd-1): A 7 : 3 mixture (by weight) of

The samples thus prepared were immediately subjected to gradation exposure using a sensitometer, Model FWH (color temperature of light source: 3,200ºK), manufactured by Fuji Photo Film Co., Ltd., through a blue filter for sensitometry in the case of samples (100) to (131), through a green filter for sensitometry in the case of samples (200) to (231), and through a red filter for sensitometry in the case of samples (300) to (331).

After exposure, the samples were processed through the following processing steps using the processing solutions described below.

Developer:

Water 600ml

Potassium phosphate 40 g

Disodium N,N-bis(sulfonatoethyl)-hydroxylamine 10 g

KCl 5g

Hydroxyethylidene-1,1-diphosphonic acid (30%) 4 ml

1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1 g

Water to 1000 ml

pH (at 25ºC, with potassium hydroxide) 12

Bleach-fixing solution:

Water 600ml

Ammonium thiosulfate (700 g/l) 93 ml

Ammonium sulphite 40 g

Ammonium ethylenediaminetetraacetatoferrate 55 g

Ethylenediaminetetraacetic acid 2 g

Nitric acid (67%) 30 g

Water to 1000 ml

pH (at 25ºC, with acetic acid and aqueous solution) 5.8

Watering solution:

chlorinated sodium isocyanurate 0.02 g

Deionized water (electrical conductivity: 5 uS/cm or less) 1000 ml

pH6.5

Alkali treatment solution:

Water 800 ml

Potassium carbonate 30 g

Water to 1000 ml

pH (with 1N sulfuric acid or 1N potassium hydroxide) 10

After processing, the samples were measured on the maximum color density area (Dmax) with blue light in the case of samples (100) to (131), with green light in the case of samples (200) to (231), and with red light in the case of samples (300) to (331). The results obtained are shown in Tables a-1 and a-2, Tables b-1 and b-2, and Tables c-1 and c-2, respectively.

In addition, each of the unprocessed samples was left at a temperature of 80ºC and a humidity of 70% for one week and then subjected them to bleach-fixing, washing and alkali treatment at the same temperature with the same processing time using the same formulation as above.

After processing, the samples were measured for density (Dmin) with blue light in the case of samples (100) to (131), with green light in the case of samples (200) to (231), and with red light in the case of samples (300) to (331). The results obtained are shown in Tables a-1 and a-2, Tables b-1 and b-2, and Tables c-1 and c-2, respectively. TABLE a-1 TABLE a-2 TABLE b-1 TABLE b-2 TABLE c-1 TABLE c-2

It is clearly apparent from the results in Tables a-1 to c-2 that when the reducing agent of the present invention was used for color formation, the unprocessed photosensitive material experienced an increase in stains (post-coloring) in the unexposed areas after storage for a long period of time at high temperature and high humidity, but that this increase in post-coloring could be suppressed by using the compound of the present invention. It is also apparent that when the compound of the present invention was used, the color density was not reduced.

Furthermore, the subsequent coloration in a similar experiment under irradiation with light could be suppressed by using the compound according to the invention.

EXAMPLE 2

The surface of a paper support with polyethylene laminated on both surfaces was subjected to a glow discharge treatment, a gelatin undercoat layer containing sodium dodecylbenzenesulfonate was coated thereon, and three kinds of layers containing photographic components were coated to prepare color photographic printing paper 400 having the three-layer structure described below. The coating solutions were prepared as follows.

Coating solution for the second layer:

In ethyl acetate were added 17 g of yellow coupler (C-76), 20 g of reducing agent (I-16) for color formation and 80 g Solvent (Solv-2), and the resulting solution was emulsion-dispersed in a 16% aqueous gelatin solution containing 10% sodium dodecylbenzenesulfonate and citric acid to prepare Emulsion Dispersion D. Emulsion Dispersion D and silver chlorobromide emulsion A used in Example 1 were mixed and dissolved to prepare a second layer coating solution having the following composition. The coated amount of the emulsion is the coated amount calculated as silver.

The coating solutions for the first and third layers were prepared in the same manner as the coating solution for the second layer. In each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used as the gelatin hardener.

In addition, Cpd-2, Cpd-3, Cpd-4 and Cpd-5 used in Example 1 were added to each layer to a total coating of 15.0 mg/m², 60.0 mg/m², 50.0 mg/m² and 10.0 mg/m², respectively.

In the silver chlorobromide emulsion of the second layer, the blue sensitizing dyes A, B and C used in Example 1 were used in the same amount as used in Example 1.

In addition, 1-(5-methylureidophenyl)-5- mercaptotetrazole was added to the second layer in an amount of 3.0 x 10-3 mol per mol of silver halide.

Layer structure:

The composition of each layer is shown below. The reference numerals indicate the amount applied (g/m²). In the case of silver halide emulsions, the amount applied is based on silver.

Carrier:

Polyethylene-coated paper [the polyethylene on the side of the first layer contained a white pigment (TiO2, 15 wt.%) and a bluish dye (Ultramarine)],

First layer:

Gelatin 1.12

1,5-Diphenyl-3-pyrazolidone (ETA-6, described above) (in the state of a solid dispersion of fine particles) 0.02

Second layer:

Silver chlorobromide emulsion A, described above 0.20

Gelatine 1.50

Yellow coupler (C-76) 0.17

Reducing agent (I-16) for color formation 0.20

Solvent (Solv-2) 0.80

Third layer: protective layer

Gelatin 1.01

Acrylic-modified copolymer of polyvinyl alcohol (modification level: 17%) 0.04

liquid paraffin 0.02

Surfactant (Cpd-1) used in Example 1 0.01

Samples (401) to (413) were carefully prepared in the same manner as Sample (400), except that the yellow coupler and the reducing agent for color formation in the coating solution for the second layer were replaced with an equimolar amount of the yellow coupler and the reducing agent for color formation shown in Table d, respectively, and the compound shown in Table d was added in addition to the solvent in an amount of 20 mol% based on the reducing agent for color formation and co-emulsified.

Samples (500) to (513) were carefully prepared in the same manner as Sample (400), except that the silver chlorobromide emulsion A in the coating solution for the second layer was replaced with the same amount, in terms of silver, of the silver chlorobromide emulsion B used in Example 1, the coupler and the color-forming reducing agent were replaced with an equimolar amount of the magenta coupler and the color-forming reducing agent shown in Table e, respectively, and the compound shown in Table e was added and co-emulsified in addition to the solvent in an amount of 20 mol% based on the color-forming reducing agent. In the silver chlorobromide emulsion B, the green sensitizing dyes D, E and F used in Example 1 were used in the same amount as used in Example 1.

Samples (600) to (613) were carefully prepared in the same manner as Sample (400), except that the silver chlorobromide emulsion A in the coating solution for the second layer was replaced by the same amount, in terms of silver, of the silver chlorobromide emulsion C used in Example 1, that the coupler and the reducing agent for color formation were replaced by an equimolar amount of the cyan coupler or reducing agent for color formation shown in Table f was exchanged and that the compound shown in Table f was added in addition to the solvent in an amount of 20 mol% based on the reducing agent for color formation and co-emulsified. In the silver chlorobromide emulsion C, the red sensitizing dyes G and H used in Example 1 were used in the same amount as used in Example 1.

The samples thus prepared were immediately subjected to gradation exposure using a sensitometer, Model FWH (color temperature of light source: 3,200ºC), manufactured by Fuji Photo Film Co., Ltd., through a blue filter for sensitometry in the case of samples (400) to (413), through a green filter for sensitometry in the case of samples (500) to (513), and through a red filter for sensitometry in the case of samples (600) to (613).

After exposure, the samples were processed through the following processing steps using the processing solutions described below.

Developer (alkali activation solution):

Water 600ml

Potassium phosphate 40 g

KCl 5g

Hydroxyethylidene-1,1-diphosphonic acid (30%) 4 ml

Water to 1000 ml

pH (at 25ºC, with potassium hydroxide) 12

The bleach-fixing solution and the washing solution were the same as the bleach-fixing solution and the washing solution used in Example 1.

After processing, the samples were measured for the maximum color density range with blue light in the case of samples (400) to (413), with green light in the case of samples (500) to (513) and with red light in the case of samples (600) to (613). The results obtained are shown in Tables d, e and f, respectively.

In addition, similarly to Example 1, each of the unprocessed samples was stored at a temperature of 80°C and a humidity of 70% and then subjected to bleach-fixing and washing in the same manner as in Example 1. After processing, the samples were measured for density (Dmin) with blue light in the case of samples (400) to (413), with green light in the case of samples (500) to (513), and with red light in the case of samples (600) to (613). The results obtained are shown in Tables d, e, and f, respectively. TABLE d TABLE e TABLE f

It is clearly evident from the results in Tables d, e and f that even when an auxiliary developing agent was added to the light-sensitive material, an increase in the subsequent coloration could be suppressed by using the compound of the invention similarly to Example 1. In addition, it is evident that in this case, too, the color density was not reduced.

Furthermore, in a similar experiment under irradiation with light, the subsequent coloration could be suppressed by using the compound according to the invention.

EXAMPLE 3

The surface of a paper support with polyethylene laminated on both surfaces was subjected to a glow discharge treatment, a gelatin undercoat layer containing sodium dodecylbenzenesulfonate was coated thereon, and various layers containing photographic components were coated thereon to prepare multilayer color printing photographic paper (700) having the layer structure described below. Coating solutions were prepared as follows.

Coating solution for the first layer:

In ethyl acetate, 17 g of coupler (C-76), 20 g of reducing agent (I-16) for color formation and 80 g of solvent (Solv-2) used in Example 2 were dissolved, and the resulting solution was dissolved in a 16% aqueous gelatin solution containing 10% sodium dodecylbenzenesulfonate and citric acid to prepare Emulsion Dispersion D. Emulsion Dispersion D and silver chlorobromide emulsion A used in Example 1 were mixed and dissolved to prepare a first layer coating solution having the following composition. The emulsion coated amount is the coated amount calculated as silver.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. In each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardener.

In addition, Cpd-2, Cpd-3, Cpd-4 and Cpd-5 used in Example 1 were added to each layer to a total coverage of 15.0 mg/m², 60.0 mg/m², 50.0 mg/m² and 10.0 mg/m², respectively.

In the silver chlorobromide emulsion of the first layer, the third layer and the fifth layer, the blue sensitizing dyes A, B and C, the green sensitizing dyes D, E and F and the red sensitizing dyes G and H used in Example 1 were used in the same amount as used in Example 1.

In the fifth layer (red-sensitive layer), the following compound was additionally added in an amount of 2.6 x 10⁻² mol per mol of silver halide.

In addition, 1-(5-methylureidophenyl)-5- mercaptotetrazole was added to the blue-sensitive emulsion layer, green-sensitive emulsion layer and red-sensitive emulsion layer in an amount of 3.5 x 10-4 mol, 3.0 x 10-3 mol and 2.5 x 10-4 mol, respectively, per mol of silver halide.

In addition, 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in an amount of 1 x 10-4 mol and 2 x 10-4 mol, respectively, per mol of silver halide.

For the purpose of preventing irradiation, the following dyes (the applied amount is shown in parentheses) were added to each emulsion layer.

Layer structure:

The composition of each layer is shown below. The reference numerals indicate the coated amount (g/m²). In the case of the silver halide emulsion, the coated amount is in terms of silver.

Carrier:

Polyethylene-coated paper [the polyethylene on the side of the first layer contained a white pigment (TiO2, 15 wt.%) and a bluish dye (Ultramarine)].

First layer: blue-sensitive emulsion layer

Silver chlorobromide emulsion A, described above 0.20

Gelatine 1.50

Yellow coupler (C-76) 0.17

Reducing agent (I-16) for color formation 0.20

Solvent (Solv-2) 0.80

Second layer: layer to prevent color mixing

Gelatin 1.09

Color mixing inhibitor (Cpd-6) 0.11

Solvent (Solv-2) used in Example 0.19

Solvent (Solv-3) 0.07

Solvent (Solv-4) 0.25

Solvent (Solv-5) 0.09

1,5-Diphenyl-3-pyrazolidone (in the state of a solid dispersion of fine particles) 0.03

Third layer: green-sensitive emulsion layer

Silver chlorobromide emulsion B, described above 0.20

Gelatine 1.50

Purple coupler (C-56) 0.24

Reducing agent (I-16) for color formation 0.20

Solvent (Solv-2) 0.80

Fourth layer: layer to prevent color mixing

Gelatin 0.77

Color mixing inhibitor (Cpd-6) 0.08

Solvent (Solv-1) 0.14

Solvent (Solv-3) 0.05

Solvent (Solv-4) 0.14

Solvent (Solv-5) 0.06

1,5-Diphenyl-3-pyrazolidone (in the state of a solid dispersion of fine particles) 0.02

Fifth layer: red-sensitive emulsion layer

Silver chlorobromide emulsion C, described above 0.20

Gelatin 0.15

Blue-green coupler (C-43) 0.21

Reducing agent (I-16) for color formation 0.20

Solvent (Solv-2) 0.80

Sixth layer: UV absorbent layer

Gelatin 0.64

UV absorber (UV-1) 0.39

Solvent (Solv-6) 0.05

Seventh layer: protective layer

Gelatin 1.01

Acrylic-modified copolymer of polyvinyl alcohol (modification level: 17%) 0.04

liquid paraffin 0.02

Surfactant (Cpd-1) used in Example 1 0.01

Color mixing inhibitor (Cpd-6):

A 1 : 1 : 1 mixture (by weight) of (1), (2) and (3)

UV absorbers (UV-1):

A 1 : 2 : 2 : 3 : 1 mixture (by weight) of (1), (2), (3), (4) and (5)

Samples (701) to (709) were carefully prepared in the same manner as sample (700), except that the coupler and the color-forming reducing agent of sample (700) were replaced with an equimolar amount of the coupler and the color-forming reducing agent shown in Table g, respectively, and that the compound shown in Table g was added in addition to the solvent in an amount of 20 mol% based on the color-forming reducing agent and co-emulsified.

The samples thus prepared were all immediately subjected to gradation exposure using a sensitometer, Model FWH (color temperature of light source: 3,200ºC), manufactured by Fuji Photo Film Co., Ltd., through a three-color separation filter for sensitometry.

After exposure, the samples were processed through the following processing steps using the processing solutions described below.

The color developer, bleach-fix solution and wash solution were the same as the developer, bleach-fix solution and wash solution used in Example 2.

After processing, the samples were measured for the maximum color density range using red light, green light or blue light. The results obtained are shown in Table g.

In addition, each of the unprocessed samples was stored at a temperature of 80ºC and a humidity of 70% similarly to Example 1 and then subjected to bleach-fixation and washing in the same manner as Example 1.

After processing, the samples were measured for density (Dmin) using blue light, green light or red light. The results obtained are shown in Table g. TABLE g

It is clearly apparent from the results in Table g that even in the case of a multilayer photosensitive material in which an auxiliary developing agent was incorporated into the photosensitive material, similarly to Example 1, an increase in post-coloring could be suppressed by using the compound of the present invention. Furthermore, it is apparent that the color density was not reduced by using the compound of the present invention.

Furthermore, in a similar experiment under irradiation with light, the subsequent coloration could be suppressed by using the compound according to the invention.

EXAMPLE 4

Sample (800) was carefully prepared in the same manner as Sample (700) in Example 3, except that the silver chlorobromide emulsions A, B and C in the first, third and fifth layers of Sample (700) were replaced by the silver chlorobromide emulsions D, E and F shown below, respectively, and the coated amounts of silver of the respective emulsions were 0.01 g/m², 0.01 g/m² and 0.015 g/m², respectively.

Silver chlorobromide emulsion D:

Cubic; a 3 : 7 mixture (in moles of Ag) of the high size emulsion D with an average grain size of 0.10 µm and the low size emulsion D with an average grain size of 0.08 µm; the emulsions have a coefficient of variation in the Grain size distribution of 0.08 and 0.10, respectively; and the emulsion of each size contains 0.3 mol% AgBr localized on a portion of the grain surface comprising a silver chloride substrate. Chemical ripening of this emulsion was optimally carried out by adding a sulfur sensitizer and a gold sensitizer.

In the silver chlorobromide emulsion D, the blue sensitizing dyes A, B and C used in Example 1 were each used in an amount of 7.0 x 10-4 mol for the large size emulsion D and 8.5 x 10-4 mol for the small size emulsion D per mol of silver halide.

Silver chlorobromide emulsion E:

Cubic; a 1:3 mixture (in moles of Ag) of high size emulsion E having an average grain size of 0.10 µm and low size emulsion E having an average grain size of 0.08 µm; the emulsions have a coefficient of variation in the grain size distribution of 0.10 and 0.08, respectively; and the emulsion of the respective size contains 0.8 mol% AgBr localized on a portion of the grain surface comprising a substrate of silver chloride.

In the silver chlorobromide emulsion E, the green sensitizing dyes D, E and F used in Example 1 were used. The sensitizing dye D was added in an amount of 1.5 x 10⁻³ mol for the large size emulsion and 1.8 x 10⁻³ mol for the small size emulsion per mol of silver halide. The sensitizing dye E was added in an amount of 2.0 x 10⁻⁴ mol for the large size emulsion and 3.5 x 10⁻⁴ mol for the small size emulsion per mol of silver halide. The Sensitizing dye F was added in an amount of 1.0 x 10⁻³ mol for the large size emulsion and 1.4 x 10⁻³ mol for the small size emulsion per mole of silver halide.

Silver chlorobromide emulsion F:

Cubic; a 1:4 mixture (in moles of Ag) of the high size emulsion F having an average grain size of 0.10 µm and the low size emulsion F having an average grain size of 0.08 µm; the emulsions have a coefficient of variation in the grain size distribution of 0.09 and 0.11, respectively; and the emulsion of the respective size contains 0.8 mol% AgBr localized on a portion of the grain surface comprising a substrate of silver chloride.

In the silver chlorobromide emulsion F, the red sensitizing dyes G and H used in Example 1 were each used in an amount of 2.5 x 10-4 mol for the large size emulsion and 4.0 x 10-4 mol for the small size emulsion per mol of silver halide.

Samples (801) to (809) were prepared in the same manner as Sample (800), except that the reducing agent for color formation and the coupler of Sample (800) were replaced with an equimolar amount of the coupler and reducing agent for color formation shown below, respectively, and the compound of the present invention was added and co-emulsified in addition to the solvent in the first, third and fifth layers in an amount of 20 mol% based on the reducing agent for color formation in each layer.

Each sample was exposed in the same manner as in Example 3 and processed with an amplifier which was a 0.3% aqueous solution of hydrogen peroxide having a pH of 12.0 obtained by adding hydrogen peroxide to the developer used in Example 3. Then, even with a light-sensitive material greatly reduced in the amount of silver used, an image having a similarly high maximum density as in Example 3 could be obtained. In addition, the image in the samples to which the compound of the present invention was added had good durability, whereby a sharp image with reduced post-coloring could be obtained even after storage under high temperature and high humidity or conditions of irradiation with light.

The photosensitive material of the present invention was verified to be suitable for image formation enhanced by the amplification processing for a low-silver photosensitive material.

EXAMPLE 5

Using samples (700) to (709) in Example 3, the same processing and evaluation as in Example 3 were performed, except that the exposure was carried out as follows.

Exposure:

The light sources used were a YAG solid laser (oscillation wavelength: 946 nm) which used a GaAlAs semiconductor laser (oscillation wavelength: 808.5 nm) as an excitation light source and emitted to 473 nm after wavelength conversion by a SHG crystal made of KNbO₃, a YVO₄ solid laser (oscillation wavelength: 1,064 nm) which used a GaAlAs semiconductor laser (oscillation wavelength: 808.7 nm) as an excitation light source and emitted to 532 nm after wavelength conversion by a SHG crystal made of KTP, and AlGaInP (oscillation wavelength: approximately 670 nm; type No. TOLD9211, manufactured by Toshiba KK). The laser light source in each case was a device capable of exposing the color photographic paper moving in the vertical direction to the scanning direction line by line by line by means of a rotating polyhedron. Using these devices, the relationship D-logE between the density (D) of the photosensitive material and the light energy (E) was obtained by varying the amount of light. In this case, the laser light sources of the three wavelengths were modulated in the amount of light using an external modulator to control the amount of exposure. The line by line exposure was carried out at 400 dpi, and the average exposure time per pixel was about 10 minutes. 5 · 10⊃min;⊃8; s. The semiconductor lasers were kept at a constant temperature using a Peltier element to suppress a change in the amount of light due to temperature.

As a result, the image formed by digital exposure at high illuminance could also have a high maximum density, and when the compound of the present invention was used, the image in the post-coloring was reduced even after storage at high temperature and high humidity or under conditions of irradiation with light.

According to the invention, low refreshing and low consumption can be achieved, subsequent coloring after long-term storage of the light-sensitive material is reduced, and an image with high color density can be obtained.

Claims (12)

1. A silver halide color photographic light-sensitive material comprising a support having thereon at least one layer containing photographic components, wherein each of the layers containing photographic components contains at least one reducing agent for color formation, at least one dye-forming coupler and at least one compound having a quenching rate constant (Kq) for singlet oxygen of 1 x 10⁷ M⁻¹·s⁻¹ or more, characterized in that the reducing agent for color formation is represented by formula (II) or (III): wherein Z¹ represents an acyl group, carbamoyl group, alkoxycarbonyl group or aryloxycarbonyl group, Z² represents a carbamoyl group, alkoxycarbonyl group or aryloxycarbonyl group, X¹, X², X³, X⁴ and X⁵ each represent hydrogen atom or a substituent, with the proviso that the sum of the values of the Hammett constants σp of X¹, X³ and X⁵ and the values of the Hammett constants σm of X² and X⁴ is 0.80 to 3.80, and R³ represents a heterocyclic group. 2. A silver halide color photographic light-sensitive material according to claim 1, wherein the compounds represented by the formulas (II) and (III) are represented by the formulas (IV) and (V), respectively: wherein R¹ and R² each represent a hydrogen atom or a substituent, X¹, X², X³, X⁴ and X⁵ each represent a hydrogen atom or a substituent, provided that the sum of the values of the Hammett constants σp of X¹, X³ and X⁵ and the values of the Hammett constants σm of X² and X⁵ is 0.80 to 3.80, and R³ represents a heterocyclic group. 3. A silver halide color photographic light-sensitive material according to claim 2, wherein the alkyl groups represented by formulas (IV) and (V) Compounds represented by the formulas (VI) and (VII): wherein R⁴ and R⁵ each represent a hydrogen atom or a substituent, X⁶, X⁷, X⁹⁸, X⁹⁸ and X¹⁸ each represent a hydrogen atom, a cyano group, sulfonyl group, sulfinyl group, sulfamoyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, trifluoromethyl group, a halogen atom, an acyloxy group, acylthio group or heterocyclic group, with the proviso that the sum of the values of the Hammett constants σp of X⁶, X⁹⁸ and X¹⁸ and the values of the Hammett constants σm of X⁷ and X⁹⁸ 1.20 to 3.80, and Q¹ represents a non-metallic atom group necessary to form a nitrogen-containing 5-, 6-, 7- or 8-membered heterocyclic ring together with C. 4. A silver halide color photographic light-sensitive material according to any one of claims 1 to 3, wherein the compound having an erasure rate constant (Kq) for singlet Oxygen of 1 · 10⁻ M⁻¹·s⁻¹ or more is represented by formula (A): Ra-Xa-L-Xb-Rb (A) wherein L represents a single bond or an arylene group, Xa and Xb, which may be the same or different, each represent -O- or -N(Rc)-, Ra, Rb and Rc, which may be the same or different, each represent an alkyl group, alkenyl group, aryl group or heterocyclic group, and Ra and L, Ra and Rc, Rb and Rc or Rc and L may be combined with each other to form a 5- or 6-membered ring, with the proviso that L is an arylene group when Xa and Xb are simultaneously -O-, and that -XbRb itself may be a hydrogen atom when Xa is -N(Rc)- and L is an arylene group. 5. A silver halide color photographic light-sensitive material according to any one of claims 1 to 4, wherein the total coated silver amount of all coated layers as silver is 0.003 to 0.3 g/m². 6. Color photographic light-sensitive silver halide material according to one of claims 1 to 5, which is exposed line by line for an exposure time of 10⁻⁶ to 10⁻⁴ seconds per pixel. 7. The silver halide color photographic light-sensitive material according to claim 4, wherein the compound represented by formula (A) is a compound represented by formula (AI), (A-II), (A-III) or (A-IV): wherein Ra, Rb, Rc, Xa and Xb each represent a group defined in formula (A), R represents a substituent, R' represents a substituent other than -Xb-Rb, with the proviso that when a plurality of groups R or R' are present, they may be the same or different or the groups may be combined in the ortho position to each other to form a 5- or 6-membered ring, l is 0 or an integer from 1 to 4 and m represents 0 or an integer from 1 to 5. 8. The silver halide color photographic light-sensitive material according to claim 1, wherein the at least one compound having an extinguishing rate constant (Kq) for singlet oxygen of 1 x 10⁷ M⁻¹·s⁻¹ or more is added to a light-sensitive layer containing the reducing agent for color formation. 9. The silver halide color photographic light-sensitive material according to claim 1, wherein the at least one compound having a singlet oxygen quenching rate constant (Kq) of 1 x 10⁷ M⁻¹·s⁻¹ or more is added in a molar amount of 0.002 to 10 times the reducing agent for color formation. 10. The silver halide color photographic light-sensitive material according to claim 1, wherein the at least one layer containing photographic components comprises at least one silver halide emulsion layer comprising a silver halide emulsion having a silver chloride content of 90 mol% or more. 11. The silver halide color photographic light-sensitive material according to claim 1, wherein R¹³ is a hydrogen atom. 12. A silver halide color photographic light-sensitive material according to claim 1, wherein the reducing agent for color formation, the dye-forming coupler and the compound with a singlet oxygen quenching rate constant (Kq) of 1 x 10⁻ M⁻¹·s⁻¹ or more in the same layer as photographic components.