JPH08272026A - Silver halide photographic sensitive material and image forming method using that - Google Patents

Abstract

PURPOSE: To provide a silver halide color photographic sensitive material which attains rapid processing with a decreased amt. of a replenisher, has excellent pressure resistance during swelling and is hardly influenced by temp. during exposure, and to provide an image forming method using this material. CONSTITUTION: This silver halide color photographic sensitive material has at least one silver halide emulsion layer and at least one non-photosensitive layer on a supporting body. The photographic sensitive material has a layer containing a compd. expressed by formula. The layer containing this compd. contains an emulsion substantially comprising such silver halide particles containing at least one kind of such a complex that has a metal element selected from the V group to the X group in the periodical table as the center metal and that among the six unidentate ligand of the complex, at least one ligand on the 4-fold rotation axis is different from others. In formula, R is a hydrogen atom or substituent, R' is a substd. or unsubtd. aryl group, X is a hydrogen atom or substituent which is released by the reaction with the oxidizing group of a color developing agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material and an image forming method using the same, more specifically, it enables rapid processing, is excellent in pressure resistance when wet, and is not affected by temperature during exposure. The present invention relates to a silver halide color photographic light-sensitive material which is difficult to receive and an image forming method using the same.

[0002]

2. Description of the Related Art In recent years, an extremely compact and inexpensive color negative film automatic developing machine and an integrated type minilab system of a printer and a paper automatic developing machine have been developed one after another and have been introduced to camera stores and photo shops. It has become possible for a general user to bring a film taken to the store and finish a color print after only tens of minutes. Therefore, the shorter the required time from the development of the color negative film to the finish of the color print, the more preferable, and the tendency is increasing.

1986 RA-4 from Eastman Kodak Company
The system was announced and pioneered the rapid processing of color photographic paper, but in 1992, Konica Corporation announced the SQA system, which enabled even faster processing. In the future, it is desired to reduce the size of the automatic developing solution, and in order to achieve this, it is necessary to further speed up the developing process, and especially color development has become a technical subject.

In addition, it is also necessary to reduce the replenishment amount of the developing solution for downsizing. Usually, a silver halide color photographic light-sensitive material is replenished with a predetermined amount of replenisher each time it is developed. It is necessary to reduce the amount of the replenisher to reduce the amount of the developing waste liquid, but it has been impossible to reduce the amount of the replenisher to a sufficient amount due to the fluctuation of the components of the color developing solution.

Although it has been conventionally known to reduce the grain size of silver halide grains as a technique for accelerating the color development speed, it is difficult to form fine grains due to the drawback of decreasing the sensitivity. In the magenta couplers with high color development described in JP-A-61-65245 and JP-A-2-60167, the rapid processing suitability is improved as compared with the conventional couplers, but it has not reached a sufficient level. I understood. JP-A-6-43611 describes a magenta coupler that is capable of rapid processing and is excellent in processing stability. However, the inventors of the present invention have found that the processing stability is excellent, but further rapid processing is possible. It turns out that the aptitude is still lacking. It is known that reducing the film thickness of the photosensitive material is effective as a means for increasing the developing speed. When it was applied to the coupler, it was found that the developing speed was accelerated and reached a sufficient level, but the pressure resistance was lost. Precipitants such as developing agents are generated in the color developing solution over time and adhere to the rollers, and when the photosensitive material passes through them, they are rubbed and become scratches. These scratches seriously hinder the image quality, and there has been a constant demand for a photosensitive material that does not generate any scratches.

On the other hand, silver halide color photographic light-sensitive materials, especially color photographic papers, are printed at various temperatures. 9 in the morning
I set up the printer and start working all day, but in the winter, the place where the printer is located is cold, so the printer is set up under cold conditions. It often shifts.
Various sensitizing dyes, inhibitors, and methods of adding a metal compound to silver halide grains are known as means for reducing the influence of temperature, but sufficient desensitization and increased fog are obtained. The current situation is not.

US Pat. No. 4,933,272 has a face-centered cubic lattice containing a complex having a nitrosyl or thionitrosyl ligand as a central metal and having a metal element belonging to Group V to Group X of the periodic table. Although it is disclosed that the reciprocity law failure is improved by the silver halide photographic emulsion having ## STR4 ## no influence on temperature during exposure is mentioned.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material capable of rapid processing with a reduced amount of replenisher, excellent in pressure resistance when wet and hardly affected by temperature during exposure. To provide the material.

[0009]

[Means for Solving the Problems]

(1) A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer and at least one non-photosensitive layer on a support, a compound represented by the following general formula (M) And a layer containing the compound, wherein the layer containing the compound has a metal element of Group V to Group X of the periodic table as a central metal and is a ligand having four rotations among six monodentate ligands. A silver halide color photographic light-sensitive material comprising an emulsion consisting essentially of silver halide grains containing at least one complex in which at least one of them is a ligand different from the other.

[0010]

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[In the formula, R represents a hydrogen atom or a substituent, and R'represents a substituted or unsubstituted aryl group. X represents a hydrogen atom or a substituent capable of leaving by the reaction with the oxidation product of the color developing agent. (2) 50% of the total outer surface of the silver halide grains of the emulsion
The silver halide color photographic light-sensitive material as described in (1) above, which contains silver halide grains having (111) faces.

(3) An image forming method characterized in that in the color development processing of the silver halide color photographic light-sensitive material described in the above (1), the replenishing amount of the color developing solution is 20 to 60 ml per 1 m ^{2 of the} light-sensitive material. .

The present invention will be specifically described below.

The compound represented by the general formula (M) (hereinafter, also referred to as magenta coupler represented by the general formula (M)) will be described.

In the general formula (M), the substituent represented by R is not particularly limited, but is typically alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl. Other groups such as halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, and the like. Carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, and heterocyclic thio groups, as well as spine groups. Compound residue, bridged hydrocarbon compound residue and the like are also mentioned.

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

Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group.

As the sulfonamide group represented by R,
Examples thereof include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R include the alkyl group and aryl group represented by R above.

The alkenyl group represented by R has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 32 carbon atoms.
12, particularly 5 to 7, are preferable, and the alkenyl group may be linear or branched.

The cycloalkenyl group represented by R is preferably a cycloalkenyl group having 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms.

The sulfonyl group represented by R is an alkylsulfonyl group, an arylsulfonyl group, etc .; The sulfinyl group is an alkylsulfinyl group, an arylsulfinyl group, etc .; The phosphonyl group is an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxy group. Phosphonyl group, arylphosphonyl group, etc .; Acyl group, alkylcarbonyl group, arylcarbonyl group, etc .; Carbamoyl group, alkylcarbamoyl group, arylcarbamoyl group, etc .; Sulfamoyl group, alkylsulfamoyl group, arylsulfamoyl group Groups, etc .; acylcarbonyl groups such as alkylcarbonyloxy groups, arylcarbonyloxy groups, etc .; carbamoyloxy groups, such as alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc .; The de group alkylureido group,
Aryl ureido group, etc .; Sulfamoylamino group is alkylsulfamoylamino group, arylsulfamoylamino group, etc .; Heterocyclic group is preferably 5 to 7-membered, specifically, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc .; The heterocyclic oxy group preferably has a 5- to 7-membered heterocycle,
For example, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1-
Phenyltetrazole-5-oxy group, etc .; As the heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable, for example, 2-
Pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5-triazole-6-thio group, etc .; As siloxy group, trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc .; Imide As a group, a succinimide group, a 3-heptadecylsuccinimide group, a phthalimide group, a glutarimide group, etc .; as a spiro compound residue, spiro [3.3] heptan-1-yl, etc .; as a bridged hydrocarbon compound residue Examples include bicyclo [2.2.1] heptan-1-yl, tricyclo [3.3.1.1 ^3.7 ] decan-1-yl, and 7,7-dimethyl-bicyclo [2.2.1] heptan-1-yl.

Among the substituents represented by R, preferred are tertiary alkyl groups, and more preferred is t-butyl group.

The substituent represented by R'is an aryl group, of which the phenyl group is preferred. These groups may have a substituent.

Examples of the group capable of splitting off upon reaction with the oxidant of the color developing agent represented by X are, for example, halogen atom (chlorine atom, bromine atom, fluorine atom, etc.) and alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyl. Oxy, alkoxycarbonyloxy, aryloxycarbonyl, alkyl oxalyloxy, alkoxy oxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring bonded by N atom,
Alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl,

[0026]

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(Wherein R ₁ and R ₄ have the same meanings as R and R ′, respectively, and R ₂ and R ₃ represent a hydrogen atom, an aryl group, an alkyl group or a heterocyclic group) and the like. And a halogen atom, particularly a chlorine atom is preferable.

Among the magenta couplers represented by the general formula (M), preferable ones are represented by the following general formula (M-1).

[0029]

[Chemical 4]

(In the formula, R ₅ represents a group capable of substituting on the benzene ring, and n represents an integer of 1 to 5. When n is 2 or more, R ₅ may be the same or different. ) Examples of the group capable of substituting the benzene ring represented by R ₅ include alkyl, cycloalkyl, alkenyl, aryl, acylamino, sulfonamide, alkylthio, arylthio,
Halogen atom, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, amino,
Examples thereof include groups such as alkylamino, anilino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl and aryloxycarbonyl. Of these groups, preferred are sulfonamide group, sulfonyl group, ureido group and alkoxy group. Among these, more preferable is a sulfonamide group.

The group represented by R ₅ may further have a substituent, and examples of the substituent include alkyl, cycloalkyl, alkenyl, aryl, acylamino, sulfonamide, alkylthio, arylthio, halogen atom,
Heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, anilino, imide, ureido, sulfamoylamino, alkoxy Examples thereof include groups such as carbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl and the like. Of these, a sulfonyl group and a sulfonamide group are preferable.

The typical examples of the magenta coupler represented by the general formula (M) are shown below, but the invention is not limited thereto.

[0033]

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[0034]

[Chemical 6]

[0035]

[Chemical 7]

The composition of the silver halide photographic emulsion used in the present invention is preferably a silver halide emulsion containing silver chloride in an amount of 95 mol% or more. Silver and silver chloroiodobromide are preferred. It is preferably 97 mol% or more, more preferably 98 to 99.
Silver chlorobromide containing 9 mol% silver chloride is preferred.

The complex contained in the silver halide photographic grains used in the present invention has the central metal atom as the origin O.
Considering the O-xyz coordinate space, the z-axis is the axis of rotation four times, and there are two ligands on this axis and four ligands of the same kind on the x and y axes. , At least one of the ligands on the z axis is different from the ligands on the x and y axes.

The central metal of the complex used in the present invention is group V to group X of the periodic table (IUPAC inorganic compound nomenclature revised version (19
89)), and examples thereof include manganese, iron, cobalt, nickel, molybdenum, ruthenium, rhodium, palladium, tungsten, rhenium, osmium, and iridium. Among these, iron, osmium, and ruthenium can be mentioned as preferable metal elements.

Regarding the ligand of the complex used in the present invention, at least one of the ligands present on the z axis is different from the ligands present on the x and y planes. Is characterized by. As the ligand existing on the x and y planes, chloride ion, bromide ion, iodide ion, cyanide ion and the like are preferable, and chloride ion, bromide ion and cyanide ion are particularly preferable. As the ligand existing on the z axis, chloride ion, bromide ion, nitrosyl, thionitrosyl, carbonyl, and water (aco) ligand are preferable. Of these, nitrosyl, thionitrosyl and carbonyl ligands are preferable.

In order to contain the above-mentioned complex in the silver halide grain used in the present invention, the complex is incorporated into the silver halide grain during each step of the physical ripening during the formation of the silver halide grain and after the formation of the silver halide grain. It may be added at any place. To obtain a silver halide emulsion satisfying the above-mentioned conditions, the complex is dissolved together with a halide salt and continuously added during the whole or a part of the grain forming step, or a fine grain silver halide containing a complex in advance is added. Alternatively, after forming the host particles and forming the host particles, the host particles may be added and precipitated on the host particles. As the time for containing the complex,
It is preferably added at the stage where grain growth is occurring.

When the silver halide grain used in the present invention has a portion where silver bromide is localized at a high concentration,
It is advantageous to localize the complex in the concentrated phase.

The above complex is 1 × 1 per mol of silver halide.
It is preferably contained in an amount of 0 ^-9 mol or more and 1 x 10 ^-2 mol or less, and particularly preferably 1 x 10 ^-8 mol or more and 5 x 10 ^-5 mol or less.

Examples of the complex used in the present invention include the followings, but the present invention is not limited thereto.

(I-1) Cs ₂ [Os (NO) Cl ₅ ] (I-2) K ₂ [Ru (NO) Cl ₅ ] (I-3) K ₂ [RuCl ₅ (H ₂ O)] (I -4) K ₄ [Os (SnCl ₃ ) ₅ Cl] (I-5) K ₂ [IrBrCl ₅ ] (I-6) K ₂ [Ir (CN) ₅ Cl] (I-7) K ₂ [Ru ( CO) Cl ₅ ] (I-8) Cs ₂ [Os (CO) Cl ₅ ] (I-9) K ₂ [Fe (NO) (CN) ₅ ] (I-10) K ₂ [Ru (NO) Br ₅ ] (I-11) K ₂ [Ru (NO) I ₅ ] (I-12) K ₂ [Re (NO) (CN) ₅ ] (I-13) K ₂ [Re (NO) Cl ₅ ] ( I-14) K [Ir (NO) Cl ₅ ] (I-15) K ₂ [Ru (NS) Cl ₅ ] (I-16) K ₂ [Os (NS) Br ₅ ] (I-17) K ₂ [Ru (NS) (CN) ₅ ] (I-18) K ₂ [Ru (NS) (SCN) ₅ ] Further, a heavy metal compound other than the above-mentioned complex can be used within a range not impairing the effects of the present invention. . Examples of heavy metal compounds that can be preferably used include the following compounds.

(II-1) FeCl ₂ (II-2) FeCl ₃ (II-3) (NH ₄ ) Fe (SO ₄ ) ₂ (II-4) K ₃ [Fe (CN) ₆ ] (II-5 ) K ₄ [Fe (CN) ₆ ] (II-6) K ₂ [IrCl ₆ ] (II-7) K ₃ [IrCl ₆ ] (II-8) K ₂ [PtCl ₆ ] (II-9) K ₂ [Pt (SCN) ₄ ] (II-10) K ₂ [NiCl ₄ ] (II-11) K ₂ [PdCl ₆ ] (II-12) K ₃ [RdCl ₆ ] (II-13) CdCl ₂ (II- 14) ZnCl ₂ (II-15) K ₃ [Re (CNO) ₆ ] (II-16) K ₃ [Mo (OCN) ₆ ] (II-17) K ₄ [Fe (CNO) ₆ ] (II-18 ) K ₄ [Ru (CNO) ₆ ] (II-19) K ₂ [Ni (CN) ₄ ] (II-20) PbCl ₂ (II-21) K ₃ [Co (NH ₃ ) ₆ ] (II-22 ) K ₅ [Co ₂ (CNO) ₁₁ ] (II-23) K ₃ [Re (CNO) ₆ ] (II-24) K ₄ [Os (CNO) ₆ ] (II-25) K ₂ [Cd (CNO ) ₄ ] (II-26) K ₂ [Pt (CNO) ₄ ] (II-27) K ₃ [IrBr ₆ ] (II-28) K ₂ [IrBr ₆ ] (II-29) Ga (NO ₃ ) ₃ In order to contain these heavy metal compounds in the silver halide grains, the heavy metal compounds are added before the formation of silver halide grains, during the formation of silver halide grains, and during the physical ripening after the formation of silver halide grains. It may be added at any place in the process. Of these, the addition of hexachloroiridium (III), (IV) acid compounds, hexabromoiridium (III), and (IV) acid compounds to the inside of the particles is preferable because the effect of the present invention is large. The addition amount of these compounds is preferably 1 × 10 ^-9 mol or more and 1 × 10 ^-2 mol or less, and particularly preferably 1 × 10 ^-8 mol or more and 5 × 10 ^-5 mol or less per mol of silver halide. .

As described above, as a preferred embodiment of the silver halide grain used in the present invention, one having a portion having a silver bromide content of 30 mol% or more is used. The portion containing silver bromide in a high concentration may form a layer as a so-called core / shell emulsion, or may be epitaxially bonded to a silver halide emulsion grain to form a complete layer and not a partial layer. There may be only regions having different compositions. The portion in which silver bromide is present at a high concentration may be formed in the step of forming silver halide grains, the chemical ripening step thereafter, or the coating solution preparation step.
Further, when the composition of the inside of the particle is different from that of the surface, the composition may be changed continuously or discontinuously.

Although it depends on the composition of the entire silver halide emulsion grains, when the silver bromide content is about 1 mol% with respect to the total silver halide, the silver bromide portion containing a high concentration of silver bromide is used. The content is preferably 40 mol% or more. In order to form such a silver bromide localized phase, a so-called conversion method in which an aqueous solution of a water-soluble bromide salt such as potassium bromide is added may be used, a simultaneous mixing method, or a bromide prepared in advance. A method of adding silver particles and using a recrystallization process may be used. Examples of such silver halide grains include JP-A-58-95736, JP-A-58-108533, and JP-A-1-18364.
There are particles described in No. 7.

The silver bromide content of the portion containing a high concentration of silver bromide can be determined by the method described in JP-A-1-183647, page 22, upper right column. When the thus obtained silver bromide content has a range, the term "silver bromide content in a portion containing a high concentration of silver bromide" as used herein means the maximum value thereof.

In the present invention, any shape of the silver halide grains of the emulsion can be used, but preferably 50% or more of the total outer surface of the emulsion grain is a (111) plane silver halide emulsion. . Furthermore, 80% or more is (11
A silver halide emulsion consisting of plane 1) is preferred. U.S. Pat. Nos. 4,183,756, 4,225,666, JP-A-55-26589, JP-A-6-167790, JP-B-55-42737, The Journal of Photographic Science ( J. Photogr.S
ci. ) 21, 39 (1973) and the like. The ratio of all grains of the (111) plane to the total outer surface area is defined as follows. It is carried out by taking an electron micrograph of silver halide grains (the number of grains is at least 200 or more) and determining the ratio of the outer surface area of the (111) plane to the total outer surface area of all grains. Whether or not a plane is composed of the (111) plane can be determined geometrically or crystallographically.

The silver halide grains of the emulsion of the present invention are (11
1) Any shape may be used as long as the ratio of the faces satisfies the above conditions, and for example, a normal crystal such as an octahedron or a tetradecahedron or a twin crystal such as a tabular grain may be used. It may also be a mixture of materials having various crystal systems.

The grain size of the silver halide grains used in the present invention is not particularly limited, but preferably 3 μm or less and 2.0 μm or less in view of rapid processing property and photographic performance such as sensitivity. More preferably. The grain size of silver halide grains can be measured by various methods generally used in the technical field. A typical method is Loveland's “Particle Size Analysis Method” (ASTM Symposium on Light Microscopy, 94-122, 1955) or “Theory of Photographic Processes, Third Edition” (co-authored by Mies and James). , Second
Chapter, published by Macmillan, 1966).

This particle size can be expressed using the diameter of a circle having the same projected area as the projected area of the particle.

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

The silver halide emulsion used in the present invention is
It may be obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after the seed grains are formed. The method for making seed particles and the method for growing seed particles may be the same or different.

The soluble silver salt and the soluble halide salt may be reacted by any of a forward mixing method, a back mixing method, a double mixing method, and a combination thereof, but those obtained by the double mixing method. Is preferred. Further, the pAg controlled double jet method described in JP-A-54-48521 can be used as one type of the simultaneous mixing method.

Further, a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device arranged in the reaction mother liquor described in JP-A-57-92523 and 57-92524, published in Germany An apparatus for continuously adding and changing the concentration of a water-soluble silver salt and a water-soluble halide salt aqueous solution described in Japanese Patent No. 2921164, and the reaction mother liquor is taken out of the reactor described in Japanese Patent Publication No. 56-501776. You may use the apparatus etc. which perform grain formation, keeping the distance between silver halide grains constant by concentrating by an ultrafiltration method.

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

For the layer containing the silver halide photographic emulsion of the present invention, for the purpose of gradation adjustment and the like, one silver halide emulsion is prepared by mixing a plurality of silver halide emulsions as long as the effects of the present invention are not impaired. A layer may be formed.

The silver halide emulsion used in the present invention is
Sensitizing methods such as a sensitizing method using a gold compound and a chalcogen sensitizer can be used alone or in combination.

As the sulfur sensitizer applied to the silver halide emulsion used in the present invention, thiosulfate, allylthiocarbamidothiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, triethylthiourea. , Inorganic sulfur and the like. The addition amount of the sulfur sensitizer used in the chemical ripening of the silver halide emulsion used in the present invention is preferably changed depending on the silver halide emulsion used, but 5 × 10 ⁻ per mol of silver halide. ^In the range of ^{10 to} 5 × 10 ^-5 mol, preferably 5 ×
The range of 10 ^{−8 to} 3 × 10 ⁻⁵ mol is preferable.

As the gold sensitizer used when chemically sensitizing the silver halide emulsion used in the present invention, various gold complexes such as chloroauric acid and gold sulfide can be added.
Examples of the ligand of the gold complex used include dimethyl rhodanine, thiocyanate, mercaptotetrazole, and mercaptotriazole. Specific compounds of the gold complex, exemplified compounds (I-6), (I-18), (I-19), (I-21), described in JP-A-5-113617, pages 118-123,
(IV-1) and (V-1) can be mentioned. The amount of gold compound used varies depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc., but is usually 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ mol per mol of silver halide. It is preferably molar. More preferably 1 × 10 ^-6 mol to 1 × 10 ^-8
Is a mole.

The silver halide emulsion used in the present invention is capable of preventing fog generated during the process of preparing a silver halide photographic light-sensitive material and reducing performance fluctuation during storage.
Known antifoggants and stabilizers can be used for the purpose of preventing fog that occurs during development. Examples of compounds that can be used for such purposes include compounds represented by the general formula (II) described in JP-A 2-146036, page 7, lower column, and specific compounds thereof include: (IIa-1) to (IIa-8) and (IIb-1) to (IIb-) described on page 8 of the publication.
The compound of 7) and compounds such as 1- (3-methoxyphenyl) -5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole can be mentioned. These compounds are added in steps such as a silver halide emulsion grain preparation step, a chemical sensitization step, the end of the chemical sensitization step, and a coating solution preparation step depending on the purpose. When chemical sensitization is carried out in the presence of these compounds, it is preferably used in an amount of about 1 × 10 ⁻⁵ mol to 5 × 10 ⁻⁴ mol per mol of silver halide. When adding at the end of chemical sensitization,
The amount is preferably about 1 × 10 ⁻⁶ mol to 1 × 10 ⁻² mol, and more preferably 1 × 10 ⁻⁵ mol to 5 × 10 ⁻³ mol, per mol of silver halide. When it is added to the silver halide emulsion layer in the coating liquid preparation step, the amount is preferably about 1 × 10 ^-6 mol to 1 × 10 ^-1 mol, and 1 × 10 ^-5 mol to 1 mol per silver halide. 1
× 10 ^-2 mol is more preferable. When it is added to a layer other than the silver halide emulsion layer, the amount in the coated film is preferably about 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol per 1 m ² .

When the silver halide photographic light-sensitive material of the present invention is a color photographic light-sensitive material, it is spectrally sensitized in a specific region of a wavelength range of 400 to 900 nm and combined with a yellow coupler, a magenta coupler and a cyan coupler. Is provided. Usually, the silver halide emulsion often contains one kind or a combination of two or more kinds of sensitizing dyes.

As the spectral sensitizing dye used in the silver halide emulsion used in the present invention, any known compound can be used, but as the blue-sensitive sensitizing dye, JP-A-3-251840, page 28 BS-1 to BS-8 described in 1 above can be preferably used alone or in combination. As the green sensitizing sensitizing dye, GS-1 described on page 28 of the same publication is used.
~ 5 are preferably used. As the red-sensitive sensitizing dye, RS-1 to RS-8 described on page 29 of the same publication are preferably used. When image exposure is performed by infrared light using a semiconductor laser or the like, an infrared-sensitive sensitizing dye needs to be used. The dyes of IRS-1 to 11 described in No. 6 to 8 are preferably used. Further, it is preferable to use the supersensitizers SS-1 to SS-9 described on pages 8 to 9 of the publication in combination with these dyes.

The addition amount of the sensitizing dye varies depending on the kind of the sensitizing dye, the halogen composition of the silver halide emulsion to be applied, the grain size, etc., but is preferably 5 per mol of silver halide.
× 10 ^-5 to 4 × 10 ^-3 mol, more preferably 1 × 10 ^-4 to 1 × 10
Used in the range of ^-3 mol.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization. Further, as a method of adding these dyes, water or methanol, ethanol, fluorinated alcohol, acetone, may be dissolved in a water-miscible organic solvent such as dimethylformamide and added as a solution, or dissolved. Alternatively, it may be added as a dispersed suspension. A method of adding a sensitizing dye as a solution, emulsion or suspension of a water-miscible solvent having a density of more than 1.0 g / ml is preferably used from the viewpoint of the effect of the present invention.

As the dispersion method of the sensitizing dye, other than the method of mechanically pulverizing and dispersing into fine particles of 1 μm or less in an aqueous system using a high-speed stirring type disperser, as described in JP-A-58-105141 A method of mechanically pulverizing and dispersing fine particles of 1 μm or less in a water system under conditions of pH 6 to 8 and 60 to 80 ° C.
-6496, a method of dispersing in the presence of a surfactant which suppresses the surface tension to 38 dyne / cm or less, and substantially no water as described in JP-A-50-80826, and pKa of which does not exceed 5. It is possible to use a method of dissolving in an acid, adding and dispersing the solution in an aqueous solution, and adding this dispersion to a silver halide emulsion.

Water is preferably used as the dispersion medium for dispersion, but a small amount of an organic solvent may be included to adjust the solubility, or a hydrophilic colloid such as gelatin may be added to enhance the stability of the dispersion. .

As a dispersing device that can be used to prepare a dispersion liquid, for example, Japanese Patent Laid-Open No. 4-125631 can be used.
In addition to the high-speed stirring type disperser shown in the figure, a ball mill, a sand mill, an ultrasonic disperser, etc. may be mentioned.

When using these dispersing devices, as described in Japanese Patent Laid-Open No. 4-125632, a method of performing wet dispersion after performing pretreatment such as dry pulverization in advance may be adopted.

When a plurality of sensitizing dyes are used in combination, the two sensitizing dyes may be added separately or may be mixed in advance and then added. One of the sensitizing dyes can be added as a solution.

The amount of silver coated on the silver halide color photographic light-sensitive material of the present invention is desirably 0.9 g / m ² or less, preferably 0.7 g / m ² or less, in view of suitability for rapid processing.

For the silver halide emulsion according to the present invention, a sensitization method using a sulfur compound, a sensitization method using a gold compound, and a sensitization method using both a sulfur compound and a gold compound can be used.

Examples of the sulfur sensitizer applied to the silver halide emulsion according to the present invention include thiosulfate, allylthiocarbamidourea, allylisothiacyanate, cystine, p-toluenethiosulfonic acid, rhodanine and inorganic sulfur. Can be mentioned.

As the gold sensitizer applied to the silver halide emulsion according to the present invention, various gold complexes other than chloroauric acid, gold sulfide and the like and the above gold compounds can be preferably used.

Particularly, it is desirable to use a gold sensitizer and a sulfur sensitizer in combination from the viewpoint of pressure resistance during drying.

The silver halide emulsion according to the present invention has the purpose of preventing fog that occurs during the process of preparing a silver halide photographic light-sensitive material, reducing performance fluctuations during storage, and preventing fog that occurs during development. Antifoggant known in
Stabilizers can be used. Examples of compounds that can be used for such purpose include compounds represented by the general formula (II) described in JP-A 2-146036, page 7, lower column, and specific examples thereof include: 8 of the publication
(IIa-1) to (IIa-8) and (IIb-1) described on page
~ (IIb-7) compounds and 1- (3-methoxyphenyl)
Examples thereof include compounds such as -5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole. These compounds are added in steps such as a silver halide emulsion grain preparation step, a chemical sensitization step, the end of the chemical sensitization step, and a coating solution preparation step depending on the purpose.

The support used in the present invention is a paper support based on paper and having resin layers on both sides. The resin layer on the side coated with the silver halide emulsion layer contains a white pigment. It is a paper support.

The base paper used in the paper support of the present invention can be selected from the raw materials generally used for photographic printing paper. Examples thereof include natural pulp, synthetic pulp, a mixture of natural pulp and synthetic pulp, and various raw materials for laminated paper. Generally, natural pulp mainly composed of softwood pulp, hardwood pulp, mixed pulp of softwood pulp and hardwood pulp, etc. can be widely applied. Any type of paper such as neutral paper and acid paper may be used.

The thickness of the paper is preferably 40 μm to 250 μm.

Further, the support may be blended with additives such as a sizing agent, a fixing agent, a tension enhancer, a denaturant, an antistatic agent, a dye and an antifoggant, which are generally used in papermaking, Further, a surface sizing agent, a surface tension agent, an antistatic agent, or the like may be appropriately applied to the surface.

As a method of applying a resin coating layer on the support used in the present invention, a method of laminating a polyolefin resin or a polyethylene terephthalate resin is known.

The olefin resin mainly used for lamination may be selected from ethylene, α-olefins and a mixture of at least two of them. Among them, the widely used polyolefin resin is low density polyethylene, high density polyethylene or a mixture thereof.

Generally, a resin laminate can be formed by melt-extruding a resin composition on a support and coating the support. In order to carry out this melt extrusion coating method, usually, a resin composition is melt extrusion coated in a form of a single layer or a plurality of layers from a slit die of an extruder on a running support. Usually, the melt extrusion temperature is preferably 200 to 250 ° C.

The thickness of the resin coating layer is not particularly limited and is usually 15 to 60 μm.

Examples of white pigments used in the resin coating layer of the support used in the present invention include rutile type titanium dioxide, anatase type titanium dioxide, barium sulfate, and the like.
Barium stearate, silica, alumina, zirconium oxide, kaolin and the like can be used, but titanium dioxide is particularly preferable.

Titanium dioxide may or may not be surface-treated with aluminum hydroxide, alcohol, a surfactant or the like. These white pigments are normally contained in an amount of 16% by weight or less, preferably 13% by weight or less, more preferably 10% by weight or less, based on the resin of the resin coating layer on the side of the reflective support on which the photographic emulsion is coated. Most preferred is 7% by weight or less.

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

The coupler used in the silver halide color photographic light-sensitive material of the present invention forms a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by a coupling reaction with an oxidant of a color developing agent. Although any compound that can be used can be used, as a particularly typical example, a yellow coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a magenta coupler having a spectral absorption maximum wavelength in a wavelength range of 500 to 600 nm, A typical one is known as a cyan coupler having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm.

As the yellow coupler, various acylacetanilide type couplers and the like can be used.

As the cyan dye forming coupler, a naphthol type coupler, a phenol type coupler, an imidazole type coupler and the like can be used.

Yellow couplers which can be preferably used in the silver halide color photographic light-sensitive material of the present invention include couplers represented by formula (Y-I) described on page 8 of JP-A-4-114154. You can Specific compounds include those described as YC-1 to YC-9 on pages 9 to 11 of the same publication. Above all, the publication 11
YC-8 and YC-9 described on the page are preferable because they can reproduce a preferable yellow color, but the present invention is not limited thereto.

Cyan couplers that can be preferably used in the silver halide color photographic light-sensitive material of the present invention are described by the general formula (C-C) described on page 17 of JP-A-4-114154.
Examples thereof include couplers represented by I) and (C-II). Specific compounds are described in CC-1 to 18-18 of the publication.
The compounds described as CC-14 can be mentioned, but the present invention is not limited thereto.

When the oil-in-water type emulsion dispersion method is used to add the coupler used in the silver halide photographic light-sensitive material of the present invention, it is usually necessary to use a water-insoluble high-boiling point organic solvent having a boiling point of 150 ° C. or higher. According to the above, a low boiling point and / or a water-soluble organic solvent is also used in combination to dissolve, and a surfactant is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser or the like can be used. After the dispersion or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be added. As the high boiling point organic solvent that can be used for dissolving and dispersing the coupler, phthalic acid esters such as dioctyl phthalate and phosphoric acid esters such as tricresyl phosphate are preferably used.

Further, instead of the method using a high boiling point organic solvent, the coupler and the water-insoluble and organic solvent-soluble polymer compound are dissolved in a low boiling point and / or water-soluble organic solvent, if necessary, to prepare a gelatin aqueous solution or the like. It is also possible to employ a method of emulsifying and dispersing by using various dispersing means using a surfactant in a hydrophilic binder. Examples of the water-insoluble organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

For the purpose of shifting the absorption wavelength of the color forming dye, the compound (d-1 described in JP-A-4-114154, page 33)
Compounds such as the compound (A′-1) described in 1) and page 35 of the same publication can be used. In addition to this, U.S. Pat.
The fluorescent dye-releasing compound described in 4,187 can also be used.

Gelatin is used as a binder in the silver halide color photographic light-sensitive material of the present invention. If necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, proteins other than gelatin,
Hydrophilic colloids such as sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymeric substances such as homopolymers or copolymers can also be used in combination with gelatin.

The gelatin used in the silver halide color photographic light-sensitive material of the present invention may be lime-processed gelatin or acid-processed gelatin.
Gelatin produced from any source such as pig skin may be used, but lime-processed gelatin produced from cow bone or pig skin is preferred.

In the present invention, the photosensitive silver halide from the silver halide emulsion layer closest to the support on the side coated with the silver halide emulsion layer to the hydrophilic colloid layer farthest from the support in the present invention. From the viewpoint of suitability for rapid processing and sensitivity, the total amount of gelatin contained in the emulsion layer and the non-photosensitive hydrophilic colloid layer is preferably 7.5 g or less per 1 m ^{2 of the} silver halide color photographic light-sensitive material of the present invention.

In the photographic emulsion layer and other hydrophilic colloid layers of the silver halide color photographic light-sensitive material of the present invention, an N-nitroethylmorpholine compound, an isothiazolone compound, for the purpose of preventing the decay of hydrophilic colloid such as gelatin. Antifungal agents such as phenol compounds and phenoxyethanol compounds can be used.

In the photographic emulsion layer and other hydrophilic colloid layers of the silver halide color photographic light-sensitive material of the present invention, a hardener which crosslinks a binder (or protective colloid) molecule and enhances film strength is used alone or in combination. It is a dura.

In addition to the above compounds, various photographic additives can be added to the silver halide color photographic light-sensitive material of the present invention.

As such examples, for example, an ultraviolet absorber (for example, benzophenone compound, benzotriazole compound, etc.), a development accelerator (for example, 1-aryl-3-pyrazolidone compound, etc.), a water-soluble anti-irradiation dye (For example, azo compound, styryl compound, oxonol compound, etc.), film physical property improving agent (liquid paraffin, polyalkylene glycol, etc.), color turbidity preventing agent (diffusion-resistant hydroquinone compound, etc.), color image stabilizer (for example, Hydroquinone derivatives, gallic acid derivatives, etc.), water-soluble or oil-soluble optical brighteners, and ground color tone adjusting agents.

In addition to these, competing couplers, fogging agents, development inhibitor releasing couplers (so-called DIR)
A coupler), a development inhibitor releasing compound and the like can be added.

In the silver halide color photographic light-sensitive material of the present invention, the coatability is improved when the silver halide emulsion layer and the hydrophilic colloid layer used in the present invention are coated on the support used in the present invention. A thickener may be used for this purpose. As a coating method, extrusion coating and curtain coating which can simultaneously coat two or more layers are useful.

To form a photographic image using the silver halide color photographic light-sensitive material of the present invention, the image recorded on the negative is optically combined with the silver halide photographic light-sensitive material to be printed. It may be imaged and printed, or after the image is once converted into digital information, the image is formed on a CRT (cathode ray tube) and then formed on the silver halide photographic light-sensitive material to be printed. Printing may be performed, or the scanning may be performed by changing the intensity of the laser light based on digital information and scanning.

The silver halide color photographic light-sensitive material of the present invention can form an image by performing color development processing known in the art.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds may be mentioned as examples of these compounds.

(CD-1) N, N-diethyl-p-phenylenediamine (CD-2) 2-amino-5-diethylaminotoluene (CD-3) 2-amino-5- (N-ethyl-N-lauryl amino)
Toluene (CD-4) 4-amino-3-methyl-N-ethyl-N- (β-butoxyethyl) aniline (CD-5) 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl ) Amino] aniline (CD-6) 4-amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] aniline (CD-7) N- (2-amino-5-diethylaminophenyl Ethyl) methanesulfonamide (CD-8) N, N-dimethyl-p-phenylenediamine (CD-9) 4-amino-3-methyl-N-ethyl-N-methoxyethylaniline (CD-10) 4-amino -3-Methyl-N-ethyl-N- (β-ethoxyethyl) aniline (CD-11) 4-amino-3-methyl-N-ethyl-N- (γ-hydroxypropyl) aniline Color developing agents are usually , 1 × 10 ^-2 per liter of developer
It is used in the range of from 2 × 10 ^-1 mol, and from the viewpoint of rapid processing, it is preferably used in the range of from 1.5 × 10 ^-2 to 2 × 10 ^-1 mol per liter of the color developing solution. The color developing agent may be used alone or in combination with other known p-phenylenediamine derivatives.

The color developer used in the present invention may contain the following developer components in addition to the above components. As the alkaline agent, for example, sodium hydroxide, potassium hydroxide, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, silicates, etc. may be used alone or in combination to prevent precipitation. , P
It can be used in combination within a range that maintains the H stabilizing effect. Further, disodium hydrogen phosphate, for the purpose of preparation or for the purpose of increasing ionic strength,
Various salts such as dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate and borate can be used.

If necessary, inorganic and organic antifoggants can be added. For the purpose of suppressing development, halide salt ions are often used,
To finish the development in a very short time, chloride ions are mainly used, and potassium chloride, sodium chloride, etc. are used. The amount of chloride ion is approximately 3.0 × 10 ^-2 mol or more, preferably 4.0 × 10 ^-2 , per liter of color developing solution.
It is about 5.0 × 10 ^-1 mol. Bromide ions can be used within a range that does not impair the effects of the present invention, but have a large effect of suppressing development, and are approximately 1.0 × 10 ⁻³ mol or less, preferably 5.0 × 10 ⁻⁴ mol, per liter of color developing solution. It is desirable that the amount is not more than mol.

If necessary, a development accelerator can be used. As the development accelerator, US Pat.
648,604, 3,671,247, various pyridinium compounds represented by JP-B-44-9503, other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, U.S. patents 2,533,990
No. 2,531,832, No. 2,950,970, No. 2,577,127 and polyethylene glycol and its derivatives described in JP-B-44-9504, nonionic compounds such as polythioethers,
Organic solvents and organic amines described in JP-B-44-9509, ethanolamine, ethylenediamine, diethanolamine,
Triethanolamine and the like are included. Also, US Patent 2,
Phenethyl alcohol and others described in 304,925, acetylene glycol, methyl ethyl ketone,
Examples thereof include cyclohexanone, pyridine, ammonia, hydrazine, thioethers, amines and the like.

Further, in the color developing solution, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin and other compounds described in JP-B-47-33378 and 44-9509. Can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developing agent may be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminophenol sulfate, phenidone, N, N'-diethyl-p-aminophenol hydrochloride, N, N,
N ', N'-tetramethyl-p-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually 0.01 to 1.0 g per liter of the developing solution.

Each component of the color developing solution can be prepared by sequentially adding and stirring to a fixed amount of water. In this case, the component having low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. Further, more generally, a color developing solution is prepared by adding a plurality of components, each of which can coexist stably, in a concentrated aqueous solution or in a small container prepared in advance in a solid state into water and stirring. You can also

In processing the silver halide color photographic light-sensitive material of the present invention, the color developer can be used in any pH range, but from the viewpoint of rapid processing, it is preferably pH 9.5 to 13.0, more preferably Is used in the range of pH 9.8 to 12.0.

The processing temperature for color development adopted in the present invention is
The temperature is preferably 15 ° C or higher and 45 ° C or lower, and particularly preferably 20 ° C or higher and 45 ° C or lower.

The color development time is conventionally about 3 minutes and 30 seconds, but in the present invention, it is within 1 minute. Further, it is preferable to perform the treatment within 50 seconds.

When the silver halide photographic light-sensitive material of the present invention is subjected to a running process while continuously replenishing the color developing solution, in order to reduce the overflow solution of the color developing solution and the environmental destruction due to the waste solution, The color developer replenishment amount is preferably 20 to 150 ml per 1 m ² of the light-sensitive material. It is more preferable to further waste by substantially overflow replenishment amount that does not occur, per photosensitive material 1 m ² as the specific replenishing amount from 20 to 60
More preferably there is ml. Under such conditions, the performance of the silver halide photographic light-sensitive material is likely to change, and the silver halide photographic light-sensitive material according to the present invention can be particularly advantageously used under such conditions.

The silver halide photographic light-sensitive material of the present invention is subjected to bleaching treatment and fixing treatment after color development. The bleaching process may be performed simultaneously with the fixing process. After the fixing process,
Usually, a washing process is performed. Further, as a substitute for the water washing treatment, a stabilizing treatment may be performed. As a development processing apparatus used for the development processing of the silver halide photographic light-sensitive material of the present invention, even if it is a roller transport type that conveys the light-sensitive material sandwiched between rollers arranged in a processing tank,
The endless belt method may be used in which the photosensitive material is fixed and conveyed on a belt, but the processing tank is formed in a slit shape and the processing solution is supplied to the processing tank and the processing solution is conveyed. A spray method for atomizing, a web method by contact with a carrier impregnated with a treatment liquid, a method with a viscous treatment liquid, and the like can also be used.

[0121]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

Example 1 A paper support was prepared by laminating high density polyethylene on both sides of a paper pulp weighing 180 g / m ² . However, a reflective support was prepared by laminating molten polyethylene containing 13% by weight of surface-treated anatase type titanium oxide dispersed on the side on which the emulsion layer was coated. Each layer having the following constitution was coated on this reflective support to prepare a silver halide photographic light-sensitive material. The coating liquid was prepared as follows.

First Layer Coating Liquid Yellow coupler (Y-1) 23.4 g, dye image stabilizer (ST-1) 3.34 g, (ST-2) 3.34 g, (ST-
5) Ethyl acetate (60 cc) was added to 3.34 g, stain inhibitor (HQ-1) 0.33 g, compound A 5.0 g, and high boiling point organic solvent (DBP) 5.0 g to dissolve, and this solution was dissolved in 20% surfactant (SU). -1) 220cc of 10% gelatin aqueous solution containing 7cc
A yellow coupler dispersion was prepared by emulsifying and dispersing with an ultrasonic homogenizer. This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a coating solution for the first layer.

The coating liquids for the second to seventh layers were prepared in the same manner as the coating liquid for the first layer so that the coating amounts were as shown in Tables 1 and 2.

Further, as a hardener (H-1), (H-2)
Was added. As a coating aid, a surfactant (SU-
2) and (SU-3) were added to adjust the surface tension. Further, F-1 was added to each layer so that the total amount was 0.04 g / m ² .

[0126]

[Table 1]

[0127]

[Table 2]

SU-1: Sodium tri-i-propylnaphthalene sulfonate SU-2: Di (2-ethylhexyl) sulfosuccinate / sodium salt SU-3: Di (2,2,3,3,4) sulfosuccinate , 4,5,5-Octafluoropentyl) -sodium salt DBP: dibutylphthalate DOP: dioctylphthalate DIDP: di-i-decylphthalate H-1: tetrakis (vinylsulfonylmethyl) methane H-2: 2,4-dichloro -6-hydroxy-s-triazine
Sodium Compound A: pt-octylphenol

[0129]

Embedded image

[0130]

[Chemical 9]

[0131]

[Chemical 10]

[0132]

[Chemical 11]

[0133]

[Chemical 12]

[0134]

[Chemical 13]

(Preparation of blue-sensitive silver halide emulsion) In one liter of a 2% gelatin aqueous solution kept at 40 ° C., the following (A
30) while controlling the liquids) and (B liquid) to pAg = 7.3 and pH = 3.0
Simultaneously added over the course of minutes,
Simultaneous addition was carried out over 180 minutes while controlling pAg = 8.0 and pH = 5.5. At this time, pAg was controlled by the method described in JP-A-59-45437, and pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water added 200 cc (Solution B) Silver nitrate 10 g Water added 200 cc (Solution C) K ₂ IrCl ₆ 2 × 10 ^-8 mol / mol Ag Chloride Sodium 102.7 g K ₄ Fe (CN) ₆ 1 × 10 ^-5 mol / mol Ag potassium bromide 1.0 g Water added 600 cc (D liquid) Silver nitrate 300 g Water added 600 cc After addition of Kao Atlas Demol N 5% aqueous solution of magnesium sulfate and 20% aqueous solution of magnesium sulfate were used for desalting, and then mixed with an aqueous solution of gelatin to obtain a single particle having an average particle size of 0.85 μm, a particle size distribution variation coefficient of 0.07, and a silver chloride content of 99.5 mol%. A dispersed cubic emulsion EMP-1 was obtained.

The following compounds were used for EMP-1.
Optimal chemical sensitization was performed at 60 ° C. to obtain a blue-sensitive silver halide emulsion for comparison (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-3 8 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX sensitization Dye BS-2 1 × 10 ^-4 mol / mol AgX (preparation of green-sensitive silver halide emulsion) 2 kept at 40 ° C.
% Gelatin aqueous solution 1 liter, the following (G liquid) and (H
(Solution) is added simultaneously while controlling pAg = 7.3 and pH = 3.0, and the following (solution I) and (solution J) and solution (K) and solution (L) are pAg = 8.0, Simultaneous addition was carried out while controlling pH = 5.5. At this time, the control of pAg is disclosed in JP-A-59-45.
No. 437, and the pH was controlled using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution G) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (solution H) Silver nitrate 10.0 g Water was added to 200 ml (solution I) Sodium chloride 92.1 g Potassium bromide 0. 87 g Water was added 538 ml (J liquid) Silver nitrate 269 g Water was added 538 ml (K liquid) Sodium chloride 10.6 g Potassium bromide 0.13 g Water was added 62 ml (L liquid) Silver nitrate 31 g Water was added 62 ml After that, desalting was performed using a 5% aqueous solution of Demol N and a 20% aqueous solution of magnesium sulfate manufactured by Kao Atlas Co., and then mixed with a gelatin aqueous solution to obtain an average particle size of 0.43 μm.
m, coefficient of variation (S / R) = 0.08, silver chloride content 9
A 9.5 mol% monodisperse cubic emulsion (EMP-11) was obtained.

In the preparation of (EMP-11) (K
Solution) and (Liquid L) were mixed with 8.0 × 10 ⁻⁷ mol of the exemplified compound (metal complex) of the present invention (shown in Table 3) to prepare a monodisperse cubic emulsion (EMP-12 to 17). did. When the exemplified compounds (metal complexes) I and II are used in combination, I is 2.0 × 10 ⁻⁸ mol and II is 8.0 × 10.
^-Prepared using ⁸ moles.

Then, the above emulsions (EMP-11) to (EM
P-17) was optimally chemically sensitized at 62 ° C. using the following compound to obtain a green-sensitive silver halide emulsion (Em-G
-11) to (Em-G-17) were obtained.

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer (STAB-1) 6 × 10 ⁻⁴ mol / mol AgX stabilizer (STAB-2) 3 × 10 ⁻⁴ mol / Mol AgX sensitizing dye (GS-1) 4 × 10 ⁻⁴ mol / mol AgX The above compound EMP-2 was optimally chemically sensitized at 55 ° C. with a green-sensitive silver halide emulsion ( Em-
G) was obtained.

Sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ^-4 mol / mol AgX (preparation of red-sensitive silver halide emulsion) (solution A) and solution (B)
A monodisperse cubic emulsion E having an average grain size of 0.50 μm, a coefficient of variation of 0.08, and a silver chloride content of 99.5% in the same manner as EMP-1 except that the addition time of (C solution) and the addition time of (C solution) are changed.
MP-3 was obtained.

The following compounds were used for EMP-3.
Optimal chemical sensitization was carried out at 60 ° C. to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX supersensitizer RS-2 3 × 10 ⁻³ mol / mol AgX STAB-1: 1- (3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole

[0146]

Embedded image

<Coloring property> The sample prepared in this manner was subjected to optical wedge exposure by a conventional method, and the replenishing liquid amount was 2 times the tank liquid amount using CL-PP1701 manufactured by Konica Corporation according to the following development processing steps. Continuous processing was performed until the double amount was replenished.

Treatment process Treatment temperature Time Replenishment amount Color development 38.0 ± 0.3 ℃ 45 seconds 80cc Bleach fixing 35.0 ± 0.5 ℃ 45 seconds 120cc Stabilization 30-34 ℃ 60 seconds 150cc Dry 60-80 ℃ 30 seconds Development processing The composition of the liquid is shown below.

Color developer tank solution and replenisher tank solution Replenisher pure water 800cc 800cc triethylenediamine 2g 3g diethylene glycol 10g 10g potassium bromide 0.01g-potassium chloride 3.5g-potassium sulfite 0.25g 0.5g N-ethyl-N- ( β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g triethanolamine 10.0 g 10.0 g Diethylenetriamine pentaacetic acid sodium salt 2.0 g 2.0 g Fluorescence enhancement Whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 2.0g 2.5g Potassium carbonate 30g 30g Add water to bring the total volume to 1 liter. Adjust the tank solution to pH = 10.10 and the replenisher to pH = 10.60. .

Bleach-fixing solution Tank solution and replenishing solution Diethylenetriamine pentaacetate ammonium ferric dihydrate 65 g Diethylenetriamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 cc 2-Amino-5-mercapto-1,3,4-thiadiazole 2.0 g Ammonium sulfite (40% aqueous solution) 27.5cc Add water to make the total volume 1 liter, and adjust the pH to 6.5 with potassium carbonate or glacial acetic acid.

Stabilizing solution tank solution and replenishing solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.8g Bismuth chloride (45% aqueous solution) 0.65g Magnesium sulfate heptahydrate 0.2g PVP 1.0g Ammonia water (ammonium hydroxide 25 % Aqueous solution) 2.5 g nitrilotriacetic acid trisodium salt 1.5 g Add water to make the total volume 1 liter, and adjust the pH to 7.5 with sulfuric acid or aqueous ammonia.

The minimum and maximum densities of the magenta image of the sample after the completion of the continuous processing were measured with PDM-5 (Konica Corporation).
The results are shown in Table 3. Similar evaluations were performed for other samples.

<Pressure resistance> A sample subjected to uniform exposure so that the color density of magenta after development is 0.1 to 0.3 is subjected to color development at 35 ° C. using the above color developing solution. A ball point needle having a diameter of 0.3 mm is moved in parallel with the sample surface in the color developing solution at a speed of 1 cm / sec, and at the same time, a load of 0 to 50 g is continuously changed and applied to the ball point needle. Record the load on the ballpoint needle as the increase in magenta density due to pressure occurs. It is evaluated that the larger the value of the load, the better the pressure resistance.

<Effect of Temperature During Exposure> The above sample was left for 2 hours under the conditions of 5 ° C. and 40 ° C. (50% RH in each case) and then subjected to optical wedge exposure by a conventional method. After that, development processing was performed with the above processing solution. The reflection density (magenta) when exposed at 5 ° C. [using the above densitometer] was calculated from the change from 1.0.

[0155]

[Table 3]

[0156]

[Chemical 15]

As is clear from Table 3, the samples using the magenta coupler and heavy metal of the present invention have a low minimum concentration,
It can be seen that the maximum density is high, the color development is excellent, the pressure resistance is excellent, and the influence of the temperature during exposure is less likely to occur. It can be seen that the maximum concentration is high in the samples using M-12 and M-21 in which R is a tertiary alkyl group. Further, it can be seen that the maximum concentration of M-12 in which R ′ contains an aryl group containing a sulfonamide group is higher. It can also be seen that the effect of temperature upon exposure is further reduced by using a heavy metal together.

Example 2 In the method of preparing the green-sensitive silver halide emulsion prepared in Example 1, 0.2 g of 3-amino-1,2,4-triazole was added to (solution G), and pAg = 9. In the same manner as above, the tetrahedral grains thus obtained (average particle size 0.43
μm, coefficient of variation 0.08, silver chloride content 99.5 mol%) was designated as Em-G-21. Next, the silver halide emulsions shown in Table 4 were prepared by changing the types of heavy metals (the addition amounts are the same as in Example 1), the amounts of 3-amino-1,2,4-triazole, and pAg, to prepare Examples 1 and 2. The same chemical ripening was performed. All had the same average particle size and coefficient of variation as Em-G-21. Regarding the prepared emulsion, JP-A-6-167790
The ratio of the (111) plane was obtained by the method described in the specification.

[0159]

[Table 4]

Using these emulsions, samples were prepared in the same manner as in Example 1 and evaluated in the same manner. The results are shown in Table 5.

[0161]

[Table 5]

[0162]

Embedded image

As is clear from Table 5, the pressure resistance is further improved by using silver halide grains having a (111) plane ratio of 50% or more.

Example 3 The samples prepared in Example 1 were evaluated in the same manner as in Example 1 except that the treatment liquid was changed as follows. The results are shown in Table 6.

Treatment Process A Treatment Process B Treatment Process C Tank Solution Replenisher Tank Solution A Replenisher Tank Solution A Replenisher Color developer Replenishment amount 70 ml / m ² 55 ml / m ² 40 ml / m ² Color developer CD-3 * 7.5g 11.0g 8.2g 12.0g 8.9g 12.9g pH 10.10 10.60 10.20 10.65 10.20 10.65 Treatment temperature 38.5 ± 0.3 ℃ 38.5 ± 0.3 ℃ 38.5 ± 0.3 ℃ ※ CD-3 is 2-amino-5- (N-ethyl-N -Laurylamino) toluene.

[0166]

[Table 6]

As is clear from Table 6, the sample of the present invention showed no increase in the minimum density and no decrease in the maximum density even when the replenisher amount of the color developing solution was 60 ml / m ² or less. . The effects of pressure resistance and temperature during exposure were the same as in Example 1.

[0168]

Industrial Applicability According to the present invention, a silver halide color photographic light-sensitive material capable of rapid processing with a reduced amount of replenisher, excellent in pressure resistance during wetting, and less susceptible to temperature during exposure, and the same are used. An image forming method can be provided.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location G03C 7/44 G03C 7/44

Claims (3)

[Claims] 1. A silver halide color photographic light-sensitive material comprising at least one silver halide emulsion layer and at least one light-insensitive layer on a support, represented by the following general formula (M): And a layer containing the compound, wherein the layer containing the compound has a metal element of Group V to Group X of the periodic table as a central metal and is arranged four times out of six monodentate ligands on the rotation axis. A silver halide color photographic light-sensitive material comprising an emulsion consisting essentially of silver halide grains containing at least one complex in which at least one ligand is a ligand different from the other. Embedded image [In the formula, R represents a hydrogen atom or a substituent, and R'represents a substituted or unsubstituted aryl group. X represents a hydrogen atom or a substituent capable of leaving by the reaction with the oxidation product of the color developing agent. ] 2. The silver halide color photographic light-sensitive material according to claim 1, wherein 50% or more of all outer surfaces of the silver halide grains of the emulsion are (111) planes. 3. An image forming method, wherein the replenishing amount of the color developing solution in the color development processing of the silver halide color photographic light-sensitive material according to claim 1 is ^{20 to} 60 ml per 1 m ^{2 of the} light-sensitive material.