JP2000310839A - Silver halide color photographic sensitive material and color image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide color photographic sensitive material and color image forming method capable of attaining high image density and superior whiteness and high letter characteristics by rapid processing even in the case of reducing a coating amount of a hydrophilic binder. SOLUTION: This material is formed by laminating at least silver halide emulsion layers containing a yellow dye forming coupler, a magenta dye forming coupler, and a cyan dye forming coupler, and a color mixing preventive layer and a protective layer on a support. The coating amount of a hydrophilic binder in the photographic constituent layers is <=6.5 g/m2 and when the material is subjected to gradation exposure in 10-4 sec, the maximum γ of 1.1-<4.2 in each of yellow, magenta, and cyan in the range where a density after processing is in the range of 1.5-2.0, and the maximum γdifference in yellow, magenta, and cyan are controlled each within 1.0, and a silver chloride content in the silver halide contained in the emulsion is >=95 mol%.

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 material having a small replenishing amount of a processing solution and excellent in rapid processing in a compact exposure processing apparatus, and an image forming method using the same. More specifically,
The present invention relates to a silver halide color photographic light-sensitive material capable of achieving high image density, excellent whiteness and high character quality even when the development processing time is greatly reduced, and a color image forming method using the same.

[0002]

2. Description of the Related Art In recent years, in the photographic processing service industry, there has been a demand for the development of a high-quality photosensitive material which can be processed quickly as a part of improving services to users and as one of means for improving productivity. . At present, a light-sensitive material containing a high silver chloride emulsion is processed with a color development time of 45 seconds, and the total processing time is usually about 4 minutes (for example, color processing C manufactured by Fuji Photo Film Co., Ltd.).
P-45X). However, compared to the processing speed of other color methods (eg, electrostatic transfer method, thermal transfer method, ink jet method), the processing system for high silver chloride print materials is still not satisfactory, and the processing speed of high silver chloride color materials is not satisfactory. It is desired that the total processing time of the printing material be further shortened (ultra-rapid processing).

As means for improving the suitability for ultra-rapid processing in color photographic light-sensitive materials, generally, the use of highly active couplers and the use of couplers having a large molecular extinction coefficient of color-forming dyes reduce the amount of organic material to be applied. Reduction of the amount of the hydrophilic binder applied according to the means, reduction of the thickness of the entire photographic constituent layer, use of a silver halide emulsion having a high developing speed, and the like can be mentioned. In particular, it is considered that the above-mentioned means is important for rapid processing suitability. In this case, it is necessary to develop a technique for obtaining a sufficient image density when the layer is thinned. In addition, in order to improve the suitability of the photosensitive material for ultra-rapid processing in color development and desilvering, efforts are being made to reduce the amount of silver applied to the photosensitive material by adopting a coupler that forms a dye having a high molecular extinction coefficient. I have been. In addition, the silver halide emulsion layer having the largest average grain size (conventionally, the yellow coupler-containing layer in many color print materials) is provided farther from the support in the emulsion layer. Are known to be advantageous, for example, the methods described in JP-A-7-239538 and JP-A-7-239439.

Further, as for the development processing steps, it is necessary to shorten the respective steps of color development, bleach-fixing and washing stabilization. To speed up color development processing, increase the temperature and pH.
Generally, attempts have been made to increase the concentration of the color developing agent, and it is also known to add additives such as a development accelerator. In the bleach-fixing process, it has been generally attempted to lower the pH of the bleach-fixer, increase the temperature, or increase the concentration of components to speed up desilvering. In order to speed up the washing stabilization step, it is necessary to speed up the washing out of the remaining processing solution and sensitizing dyes and dyes from the photosensitive material in order to maintain the whiteness of the white background. For this reason, it is preferable that the coating amount of the dye can be reduced as much as possible in addition to the above means.

On the other hand, miniaturization of an exposure / development processing machine and low discharge of waste liquid are also great demands in the market. Already on the market, the introduction of automatic development processors whose volume has been reduced by a fraction of that of conventional processors such as minilabs (eg, Rocky Series manufactured by Fuji Photo Film Co., Ltd.) has been progressing. It is desired to reduce the installation area, reduce the power consumption, reduce the waste liquid, etc. To reduce the size of such a processing machine, it is effective to reduce the capacity of the processing liquid tank and the washing tank. In addition, this makes it possible to reduce the capacity of the processing liquid heat retaining mechanism, thereby reducing power consumption. It is also known that a reduction in the amount of replenishment and regeneration of the processing solution are effective for lowering the discharge. However, if the capacity and the replenishment amount in the washing stabilization step are reduced in this way, a problem of deterioration in whiteness of a white background occurs. One of the causes
One reason is that the accumulated concentration of the eluate from the photosensitive material is increased. Accordingly, in order to maintain the whiteness of the white background, it is preferable that the amount of the eluted material from the photosensitive material, particularly the amount of the dye, can be reduced to reduce the amount of the eluted material.

[0006] For the above reasons, it is necessary to reduce the amount of a binder and the amount of a dye to be applied to a photosensitive material supplied to a rapidly miniaturized developing processor as compared with a conventional photosensitive material. is there. However, there is a problem in that it is difficult to obtain a high image density under the condition that the amount of the binder applied is small. Problems such as loss of freedom and deterioration of image bleeding occur. In particular, deterioration of image bleeding leads to serious deterioration of print quality, which is a problem to be solved. As a result of intensive studies by the present inventors, it has been found that the influence of image bleeding on character quality is strongly affected. Further deterioration in character quality is caused by laser scanning exposure, LED scanning exposure, DMD (Digital Micromirro
(r Device) It was found that it became remarkable in the case of short-time exposure of about 10 ^-4 seconds assuming scanning exposure or the like.

[0007]

Accordingly, the present invention provides
An object of the present invention is to provide a silver halide color photographic light-sensitive material capable of achieving high image density, excellent whiteness and high character quality by rapid processing even when the amount of a hydrophilic binder applied is reduced. Furthermore, the present invention provides
An object of the present invention is to provide a color image forming method which is excellent in image density and whiteness of a white background portion and enables image formation with high character quality.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to overcome the above-mentioned problems caused by the reduction in the amount of the hydrophilic binder to be applied. When reducing the amount of coating, it is effective to balance the gradation in the high density region of each of the yellow, magenta, and cyan images to prevent the deterioration of the character quality in the short-time high-illumination exposure. It has been found that high image density, excellent whiteness and high character quality can be realized even by rapid processing. The present invention has been made based on this finding. Therefore, the above object of the present invention is achieved by the following means. (1) Halogen having at least a silver halide emulsion layer containing a yellow dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler, a silver halide emulsion layer containing a cyan dye-forming coupler, a color mixture preventing layer and a protective layer on a support In the silver halide color photographic light-sensitive material, the amount of the hydrophilic binder applied to the photographic constituent layer was set to 6.5 g / m ² or less, and
^-4 seconds, the density after processing is 1.5 to 2.
The maximum gamma of the region where it is 0 is 1.1 or more and less than 4.2 for each of yellow, magenta, and cyan, and the difference between the maximum gamma of yellow, magenta, and cyan is 1.0 or less, respectively. A silver halide color photographic light-sensitive material, wherein the silver halide content of the silver halide is 95 mol% or more. (2) thickness ([mu] m) divided by the all of the hydrophilic binder of the layer in the coupler-containing silver halide emulsion layer (g / m ²⁾ silver halide grains contained in the silver halide emulsion Is not less than 1.5, and the value obtained by dividing the amount (g / m ² ) of the hydrophobic photographic material contained in the layer containing the dye-forming coupler by the amount (g / m ² ) of the dye-forming coupler is 4.5 or less. And
Further, the magenta dye-forming coupler has the following general formula (M-
The silver halide color photographic light-sensitive material according to item (1), which is represented by I).

[0009]

Embedded image

In the formula, Za and Zb each represent ＝ C (R ₄ ) — or ＮN—, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a substituent, and X represents hydrogen. It represents an atom or a group which can be removed by a coupling reaction with an oxidized form of a color developing agent. (3) After imagewise exposing the silver halide color photographic material,
In a method of obtaining a color image through color development, bleach-fix, washing and / or stabilization, and drying processing steps,
The silver halide color photographic light-sensitive material described in (1) or (2) above is subjected to a color developing step of 5 seconds to 25 seconds, a bleach-fixing step of 5 seconds to 25 seconds, and a washing and / or stabilizing step of 10 seconds. More than 45 seconds, drying process more than 5 seconds 15
A color image forming method which is performed in each time within seconds. (4) After imagewise exposing the silver halide color photographic light-sensitive material,
In a method for obtaining a color image through color development, bleach-fixing, washing and / or stabilization, and drying processing steps, the silver halide color photographic light-sensitive material described in the above (1) or (2) is used for image information. A color image forming method comprising: performing a scanning process with a light beam modulated on the basis of the light beam; (5) The color image forming method according to (3), wherein the imagewise exposure is scanned and exposed with a light beam modulated based on image information and then developed.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.

In the silver halide color photographic light-sensitive material according to the present invention, gelatin is usually used as a hydrophilic binder.
A hydrophilic colloid such as a graft polymer of gelatin and another polymer, a protein other than gelatin, a sugar derivative, a cellulose derivative, or a synthetic hydrophilic polymer such as a homopolymer or a copolymer can also be used in combination with gelatin.

The gelatin used in the silver halide color photographic light-sensitive material according to the present invention may be lime-processed gelatin or acid-processed gelatin. Gelatin produced as a raw material may be used, but lime-processed gelatin using bovine bone or pork skin as a raw material is preferred.

In the present invention, the photosensitive silver halide from the silver halide emulsion layer closest to the support on the side where the silver halide emulsion layer is coated to the hydrophilic colloid layer farthest from the support is provided. The coating amount of the hydrophilic binder contained in the emulsion layer and the non-photosensitive hydrophilic colloid layer,
From the viewpoint of rapid processing suitability, it is 6.5 g / m ² or less,
More preferably, it is 6.0 g / m ² or less, most preferably 5.5 g / m ² or less and 4.0 g / m ² or more. When the amount of the hydrophilic binder is small, it is particularly effective for speeding up the color development and washing steps.

In the present invention, the maximum gamma of the area where the post-processing density is 1.5 to 2.0 when gradation exposure is performed at 10 ^-4 seconds is 1.1 or more and less than 4.2 for each of yellow, magenta and cyan. , Preferably 2.2 to 3.2. When the maximum gamma is 1.1 or more and less than 4.2, the light emission time is 10 ^-4
In a strobe-type exposure device controlled to 10 seconds or an exposure treatment in which the shutter speed is set to 10 ^-4 seconds and light from the light source is irradiated for 10 ^-4 seconds, gradation exposure of each color is performed through an optical wedge, and color development processing is performed. After performing a process in which the processing solution composition, the processing temperature, and the processing time are adjusted so that the maximum optical density exceeds 2.0 within 25 seconds, the density of the characteristic curve obtained by performing sensitometry is 1%. .5 to 2.
This means that the maximum gamma of the region where the value is 0 is 1.1 or more and less than 4.2 for all of yellow, magenta, and cyan. Here, the density after processing when gradation exposure is performed at 10 ^-4 seconds is specified, but this is limited to the silver halide color photographic light-sensitive material of the present invention which is exposed to high illuminance in 10 ^-4 seconds. It doesn't mean to. In the present invention, the difference between the maximum gammas is within 1.0, preferably within 0.5, and most preferably within 0.3.

In the present invention, the ratio [amount of hydrophilic binder / silver halide emulsion thickness] in at least one, and more preferably all, silver halide emulsion layers is preferably 1.50 or more. Hereinafter, this ratio is referred to as [B / AgX] ratio in the present invention. Here, the amount of the hydrophilic binder refers to the amount of the hydrophilic binder applied (g / m ² ) per 1 m ^{2 of the} silver halide emulsion layer. The amount of the hydrophilic binder is divided by the specific gravity to indicate the thickness, and it is understood that the amount of the hydrophilic binder of the present invention is an amount proportional to the thickness. On the other hand, the term "silver halide emulsion thickness" means a thickness occupied by silver halide emulsion grains in the silver halide emulsion layer in a direction perpendicular to the support. In the present invention, assuming that the silver halide emulsion layer is ideally coated, the side length [μm] of the cube in the case of cubic grains, and the thickness [μm] in the direction perpendicular to the main plane in the case of tabular grains. μm] is the thickness of the silver halide emulsion.
When silver halide emulsion grains of different sizes are used in combination, the weight average of each grain is defined as the silver halide emulsion thickness.

As is clear from the above definition, as the ratio [B / AgX] in the present invention increases, the emulsion thickness in the emulsion layer decreases relatively. In the present invention, the [B / AgX] ratio is preferably 1.50 or more and 15 or less, more preferably 1.70 or more and 13 or less, and even more preferably 1.90 or more 12 from the viewpoint of suppression of pressure fogging streaks and reduction of color mixture during processing. Or less, most preferably 6.0 or more and 10 or less.

In the present invention, the silver halide emulsion layer containing a yellow coupler may be arranged at any position on the support, but the silver halide emulsion layer containing a magenta coupler or the silver halide emulsion layer containing a cyan coupler may be used. It is preferable that the coating is provided at a position more distant from the support than at least one layer. From the viewpoint of accelerating color development, accelerating desilvering, and reducing residual color by the sensitizing dye, the silver halide emulsion layer containing the yellow coupler is coated at a position farthest from the support than the other silver halide emulsion layers. Preferably, it is provided. Further, from the viewpoint of reduction of Blix fading, the cyan coupler-containing silver halide emulsion layer is preferably the center layer of the other silver halide emulsion layers, and from the viewpoint of reduction of photofading, the cyan coupler-containing silver halide emulsion layer is preferably The lowermost layer is preferred. Further, each of the color forming layers of yellow, magenta and cyan may be composed of two or three layers. For example, JP-A-4-75055 and JP-A-9-114
No. 035, 10-246940, U.S. Pat.
As described in JP-A-76-159 and the like, it is also preferable that a coupler layer containing no silver halide emulsion is provided adjacent to the silver halide emulsion layer to form a color-forming layer.

The silver halide emulsion layer containing the yellow coupler is preferably provided farthest from the support than the silver halide emulsion layer. Is preferably 1.35 g / m ² or less, more preferably 1.25 g / m ² or less.
g / m ² or less, most preferably 1.20 g / m ² or less 0.
It is 60 g / m ² or more. Further, the thickness of the silver halide emulsion is preferably 0.80 μm or less, more preferably 0.75 μm or less, most preferably 0.70 μm or less and 0.30 μm or more when cubic grains are used. Is preferably 0.30 μm or less, more preferably 0.20 μm or less, and most preferably 0.15 μm or less.
m and 0.05 μm or more. The aspect ratio of the tabular grains is preferably from 2 to 10, more preferably from 3 to 8. In order to control sensitivity, gradation and other photographic performance, it is preferable to mix silver halide emulsions having different sizes and shapes.

The silver halide emulsion which can be used in the present invention includes silver chloride, silver chlorobromide, silver chloroiodide, or silver chloride having a silver chloride content of 95 mol% or more from the viewpoint of speeding up color development. It is preferable to use silver iodobromide. Among them, more preferred are cubic grains having a silver chloride content of 98 mol% or more and having a silver bromide localized phase on the surface of the silver chloride grains. When tabular grains whose main plane is the (111) plane or the (100) plane are used, [B] of the present invention can be obtained.
/ AgX] ratio can be increased, which is preferable in terms of speeding up color development and reducing color mixing during processing. The tabular high silver chloride emulsion grains having a (111) plane or a (100) main plane are described in JP-A-6-138609, U.S. Pat. Nos. 4,399,215 and 5,061,617, and US Pat. Patent Nos. 5,320,938 and 5,264,33
No. 7, 5,292,632, 5,314,798
No. 5,413,904, WO94 / 22051, and the like.

In the case of high silver chloride cubic grains having 95% by mole or more of silver chloride having the above-mentioned localized phase, the silver bromide localized phase has a total silver bromide content of at least 10% in the silver bromide localized phase. It is preferable that a localized phase of mol% or more is formed by epitaxial growth. The silver bromide content of the silver bromide localized phase is 10 to 6
A range of 0 mol% is preferred, and a range of 20 to 50 mol% is most preferred. The silver bromide localized phase is preferably composed of silver in an amount of 0.1 to 5 mol% of the total silver constituting the silver halide grains in the present invention, and is preferably composed of 0.3 to 4 mol% of silver. More preferably, it is constituted. The silver bromide localized phase preferably contains a Group VIII metal complex ion such as IrCl ₆ ³⁻ or IrCl ₆ ²⁻ .

The silver halide emulsion used in the present invention is:
Various polyvalent metal ion impurities can be introduced during the process of emulsion grain formation or physical ripening. Examples of compounds used include iron, iridium, ruthenium,
Osmium, rhenium, rhodium, cadmium, zinc,
Salts or complex salts of metals of Group VIII of the periodic table such as lead, copper and thallium can be used in combination. In the present invention, metal compounds having at least four cyano ligands, such as iron, ruthenium, osmium, and rhenium, are particularly preferred in that they further increase the high illuminance sensitivity and also suppress the latent image sensitization. In addition, the iridium compound also has a great effect on imparting high illuminance exposure suitability. The addition amount of these compounds varies widely depending on the purpose, but is preferably from 10 ^-9 to 10 ^-2 mol per mol of silver halide. The silver halide emulsion used in the present invention is usually subjected to chemical sensitization. Regarding the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination.
Compounds used for chemical sensitization are described in
Those described in the right lower column of page 18 to the upper right column of page 22 of JP-A-215272 are preferably used. Among them, it is particularly preferable that the material is subjected to gold sensitization. This is because, by performing gold sensitization, fluctuations in photographic performance when scanning exposure is performed with a laser beam or the like can be further reduced. For gold sensitization, compounds such as chloroauric acid or a salt thereof, gold thiocyanate, gold thiosulfate, and gold sulfide colloid can be used. The addition amount of these compounds may vary widely depending on the case, but is from 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, preferably 1 ×, per mol of silver halide.
10 ^-6 to 10 ^-4 mol. In the present invention, gold sensitization may be combined with other sensitization methods, for example, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, or noble metal sensitization using a compound other than a gold compound. Preferred are gold sensitization and sulfur sensitization.

The magenta coupler used in the present invention is particularly preferably one represented by the formula (MI).
One of the objects of the present invention is to provide a light-sensitive material suitable for rapid processing. As described above, for this purpose, it is necessary to use a coupler having high activity and / or a high molecular extinction coefficient. preferable.

The general formula (MI) will be described in detail. R ₁ , R ₂ , R ₃ and R ₄ represent a hydrogen atom or a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group, a sulfo group, an amino group, an alkoxy group, an aryloxy group, an acylamino group, and an alkylamino group. , Anilino group, ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group, sulfonamide group, carbamoyl group,
Sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group, aryloxy It represents a carbonyl group, an acyl group or an azolyl group, and among these groups, a group which can have a substituent may be substituted with the above substituent.

More specifically, a halogen atom (for example, a chlorine atom or a bromine atom) or an aliphatic group (for example, having 1 to 3 carbon atoms)
2 straight-chain or branched-chain alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, for example, methyl, ethyl, propyl, isopropyl, tert-butyl, tridecyl,
2-methanesulfonylethyl, 3- (3-pentadecylphenoxy) propyl, 3- {4-} 2- [4- (4-
Hydroxyphenylsulfonyl) phenoxy] dodecanamido {phenyl} propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl, 3- (2,
4-di-tert-amylphenoxy) propyl), an aryl group (eg, phenyl, 4-tert-butylphenyl, 2,4-di-tert-amylphenyl, 2,
4,6-trimethylphenyl, 3-tridecanamide-
2,4,6-trimethylphenyl, 4-tetradecanamidophenyl, tetrafluorophenyl), heterocyclic group (for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxy group, nitro Group, carboxy group, sulfo group, amino group, alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy, 2-methanesulfonylethoxy), aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 3-tert-butoxycarbamoylphenoxy, 3-methoxycarbamoylphenoxy), acylamino group (for example, acetamido, benzamide, tetradecaneamide, 2- (2,4
-Di-tert-amylphenoxy) butanamide, 4
-(3-tert-butyl-4-hydroxyphenoxy) butanamide, 2- [4- (4-hydroxyphenylsulfonyl) phenoxy] decaneamide), an alkylamino group (for example, methylamino, butylamino, dodecylamino, diethylamino, methyl Butylamino),
Anilino group (for example, phenylamino, 2-chloroanilino, 2-chloro-5-tetradecaneaminoanilino,
2-chloro-5-dodecyloxycarbonylanilino,
N-acetylanilino, 2-chloro-5- [2- (3-
tert-butyl-4-hydroxyphenoxy) dodecanamido] anilino), carbamoylamino group (for example, N-phenylcarbamoylamino, N-methylcarbamoylamino, N, N-dibutylcarbamoylamino), sulfamoylamino group (for example, N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino), alkylthio group (for example, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3-
(4-tert-butylphenoxy) propylthio),
Arylthio groups (for example, phenylthio, 2-butoxy-5-tert-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio, 4-
Tetradecanamidophenylthio), an alkoxycarbonylamino group (eg, methoxycarbonylamino, tetradecyloxycarbonylamino), a sulfonamide group (eg, methanesulfonamide, hexadecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, octadecanesulfone) Amide, 2-methoxy-5-tert-butylbenzenesulfonamide), carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N- Dodecylcarbamoyl, N- [3- (2,4-di-tert
-Amylphenoxy) propyl] carbamoyl), a sulfamoyl group (e.g., N-ethylsulfamoyl,
N, N-dipropylsulfamoyl, N- (2-dodecyloxyethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), sulfonyl group (for example, methanesulfonyl, octane) Sulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group (for example, methoxycarbonyl, butoxycarbonyl, dodecyloxycarbonyl, octadecyloxycarbonyl), heterocyclic oxy group (for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyrani) Oxy), an azo group (eg, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), an acyloxy group (eg,
Acetoxy), a carbamoyloxy group (eg, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), a silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), an aryloxycarbonylamino group (eg, phenoxycarbonylamino), imide Groups (eg, N-succinimide, N-
Phthalimide, 3-octadecenylsuccinimide),
Heterocyclic thio group (for example, 2-benzothiazolylthio,
2,4-di-phenoxy-1,3,5-triazole-
6-thio, 2-pyridylthio), a sulfinyl group (eg, dodecanesulfinyl, 3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), a phosphonyl group (eg, phenoxyphosphonyl,
Octylphosphonyl, phenylphosphonyl), aryloxycarbonyl group (eg, phenoxycarbonyl), acyl group (eg, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), azolyl group (eg, imidazolyl, pyrazolyl) , 3-chloro-pyrazol-1-yl, triazolyl).

Among these substituents, preferred substituents are alkyl, cycloalkyl, aryl, alkoxy, aryloxy, alkylthio, carbamoylamino, aryloxycarbonylamino, alkoxycarbonylamino, Examples thereof include an alkylacylamino group and an arylacylamino group.

X represents a group which can be removed in the reaction with a hydrogen atom or an oxidized form of an aromatic primary amine color developing agent. Acyloxy, alkyl or arylsulfonyloxy, acylamino, alkyl or arylsulfonamido, alkoxycarbonyloxy, aryloxycarbonyloxy, alkyl, aryl or heterocyclic thio, carbamoylamino, 5- or 6-membered There are a nitrogen-containing heterocyclic group, an imide group, an arylazo group, and the like, and these groups may be further substituted with a group allowed as a substituent of R _{1 to} R ₄ .

More specifically, halogen atoms (eg, fluorine, chlorine, bromine atoms), alkoxy groups (eg, ethoxy, dodecyloxy, methoxyethylcarbamoylmethoxy, carboxypropyloxy, methylsulfonylethoxy, ethoxycarbonylmethoxy), aryl An oxy group (for example, 4-methylphenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-carboxyphenoxy, 3-ethoxycarboxyphenoxy,
4-methoxycarbonylphenoxy, 3-acetylaminophenoxy, 2-carboxyphenoxy), acyloxy group (for example, acetoxy, tetradecanoyloxy, benzoyloxy), alkyl or arylsulfonyloxy group (for example, methanesulfonyloxy,
Toluenesulfonyloxy), acylamino groups (eg, dichloroacetylamide, heptafluorobutyrylamino), alkyl or arylsulfonamide groups (eg, methanesulfonamino, trifluoromethanesulfonamino, p-toluenesulfonylamino), alkoxycarbonyloxy Groups (eg, ethoxycarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy groups (eg, phenoxycarbonyloxy), alkyl, aryl or heterocyclic thio groups (eg, dodecylthio, 1-carboxydodecylthio, phenylthio, 2- Butoxy-5-tert
-Octylphenylthio, 2-benzyloxycarbonylaminophenylthio, tetrazolylthio), carbamoylamino group (for example, N-methylcarbamoylamino, N-phenylcarbamoylamino), 5- or 6-membered nitrogen-containing heterocyclic group (for example, 1-imidazolyl,
1-pyrazolyl, 1,2,4-triazol-1-yl, tetrazolyl, 3,5-dimethyl-1-pyrazolyl, 4-cyano-1-pyrazolyl, 4-methoxycarbonyl-1-pyrazolyl, 4-acetylamino- 1-pyrazolyl, 1,2-dihydro-2-oxo-1-pyridyl), imide group (eg, succinimide, hydantoinyl), arylazo group (eg, phenylazo, 4-
Methoxyphenylazo) and the like. Preferred X is a halogen atom, an alkoxy group, an aryloxy group, an alkyl or arylthio group, or a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active site with a nitrogen atom. It is an aryloxy group, a substituted arylthio group or a substituted 1-pyrazolyl group.

In the formula (MI), preferred magenta couplers are those represented by the following formula (M-II) or (M-III)
It is represented by Particularly preferred is represented by the formula (M-II).

[0030]

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(In the formula, R ₁ , R ₂ , R ₃ , and R ₄ have the same meanings as described above.)

[0032]

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(Wherein, R ₁ , R ₂ , R ₃ and R ₄ have the same meanings as described above). Preferred groups in formulas (M-II) to (M-III) are as follows. is there. Preferred groups for X include a halogen atom, an alkoxy group and an aryloxy group, and among them, a chlorine atom is preferred. Preferred substituents for R _{1 to} R ₄ include an alkyl group, an aryl group,
Examples thereof include an anilino group and an alkoxy group. Among them, an alkyl group or an aryl group is preferable, and R ₁ , R ₂ , and R ₃ are particularly preferable.
Is preferably a methyl group, and R ₄ is preferably an alkyl group or an aryl group (preferably substituted). Most preferred R ₄ is an aryl group in the general formula (M-II),
In formula (M-III), it is an alkyl group. The magenta coupler according to the present invention comprises a photosensitive silver halide 1 in the same layer.
0.001-1 mol, preferably 0.001, per mol
It is used in a range of 3 to 0.3 mol. The molecular weight of the coupler is preferably 600 or less. Specific examples of the magenta coupler represented by the general formula (MI) are shown below, but the present invention is not limited thereto.

[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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[0043]

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[0044]

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In the present invention, the hydrophobic photographic material is an oil-soluble component excluding the color-forming coupler, and the oil-soluble component is a lipophilic component remaining in the photographic material after processing. In particular,
These include couplers, color-mixing inhibitors, ultraviolet absorbers, high-boiling organic solvents, lipophilic additives, lipophilic polymer latexes, matting agents, and slip agents, which are usually added to photographic constituent layers as lipophilic fine particles. Therefore, water-soluble dyes, hardeners, water-soluble additives, silver halide emulsions and the like do not fall under oil-soluble components. In addition, a surfactant is usually used when preparing lipophilic fine particles, but in the present invention, the surfactant is not treated as an oil-soluble component.

In the present invention, a preferable total amount of oil-soluble components
Is 4.5 g / m^TwoOr less, more preferably 4.0
g / m^TwoBelow, most preferably 3.8 g / m^Two3.0 below
g / m ^TwoThat is all. Dye-forming coupler in the present invention
Amount of hydrophobic photographic material (g / m^Two)
Amount of dye-forming coupler (g / m^Two) Is 4.5
Hereinafter, it is preferably 0 or more. More preferably
3.5 or less 0.1 or more, most preferably 3.0 or less
0.5 or more. In the present invention, the oil in the photographic constituent layer
The ratio of dissolved to hydrophilic binder can be set arbitrarily.
Wear. The preferred ratio in the photographic constituent layers other than the protective layer is
0.05 to 1.50, more preferably 0.10 by mass ratio
~ 1.40, most preferably from 0.20 to 1.30
You. By optimizing the ratio of each layer, film strength, scratch resistance,
Can be adjusted.

In the present invention, the use of a water-soluble dye for the purpose of preventing irradiation is the same as in ordinary silver halide color photographic light-sensitive materials. Can be. The amount of the water-soluble dye used is determined in consideration of the deterioration of the white background and the deterioration of the sharpness due to the residue, and the preferable range is 0.2 mg / m ² to
30 mg / m ² , more preferably 1 mg / m ² to
15 mg / m ² , most preferably 2 mg / m ^{2 to} 10 mg
/ M ² . Examples of preferred water-soluble dyes for use in the present invention include JP-A-8-21554 and Japanese Patent Application No. 9-2.
No. 76295. In the silver halide color photographic light-sensitive material of the present invention, other conventionally known photographic materials and additives can be used. For example, a transmissive support or a reflective support can be used as a photographic support. Examples of the transmission type support include transmission films such as cellulose nitrate film and polyethylene terephthalate, and 2,6-naphthalenedicarboxylic acid (NDC).
The one in which an information recording layer such as a magnetic layer is provided on polyester of A) and ethylene glycol (EG) or polyester of NDCA, terephthalic acid and EG is preferably used. As the reflective support, a reflective support laminated with a plurality of polyethylene layers or polyester layers, and containing a white pigment such as titanium oxide in at least one of such water-resistant resin layers (laminated layers) is preferable.

It is preferable that the water-resistant resin layer contains a fluorescent whitening agent. The fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material. As the fluorescent whitening agent, preferably, benzoxazole type, coumarin type,
A pyrazoline-based fluorescent whitening agent can be used, and a benzoxazolylnaphthalene-based or benzooxazolylstilbene-based fluorescent whitening agent is more preferable. The amount used is not particularly limited, but is preferably 1 to 100 mg / m ² . The mixing ratio when mixed with the water-resistant resin is preferably 0.0005 to 3% by mass relative to the resin, and more preferably 0.1 to 3% by mass.
001 to 0.5% by mass. As a reflective support,
On a transmissive support, or a reflective support as described above,
It may be provided with a hydrophilic colloid layer containing a white pigment. In addition, the reflection type support has a specular reflection property or a second reflection property.
It may be a support having a seed diffuse reflective metal surface.

The above-mentioned reflection type support comprises a silver halide emulsion,
Further, different metal ion species doped in silver halide grains, storage stabilizers or antifoggants for silver halide emulsions, chemical sensitization (sensitizer), spectral sensitization (spectral sensitizer), Cyan, magenta, yellow couplers and their emulsifying and dispersing methods, color image preservability improvers (anti-stain and anti-fading agents), dyes (colored layers), gelatin species, layer composition of photosensitive material, coating pH of photosensitive material, etc. As described above, those described in the patents of Tables 1 and 2 can be preferably applied to the present invention.

[0050]

[Table 1]

[0051]

[Table 2]

Examples of cyan, magenta and yellow couplers which can be used or used in combination in the present invention are described in JP-A-62-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6; No. 33144, page 3, upper right column, line 14 to page 18, upper left column last line, page 30, upper right column, line 6 to page 35 lower right column, line 11;
5, 660A2, page 4, lines 15 to 27, page 5, 3
Lines 0-28, last line, page 45, lines 29-31, 4
Page 7, line 23 to page 63, line 50, JP-A-8-12298
No. 4, couplers described in JP-A-9-222704 and the like. As the cyan coupler, a pyrrolotriazole coupler is preferably used.
Coupler represented by formula (I) or (II) of JP-A-313324 and formula (I) of JP-A-6-347960.
And the couplers exemplified in these patents are particularly preferred.

In the present invention, known color mixing inhibitors can be used, and among them, those described in the following patents are preferable. For example, high-molecular-weight redox compounds described in JP-A-5-333501, WO98 / 33
No. 760, U.S. Pat. No. 4,923,787, etc .; phenidone and hydrazine compounds;
No. 37, JP-A-10-282615 and German Patent No. 19629142A1 can be used. In particular, the pH of the developer is increased,
In the case of speeding up development, German Patent No. 1961878
No. 6A1, EP 839 623 A1, EP 842975 A1, DE 198 06 846 A1
It is also preferable to use the redox compounds described in US Pat. In the present invention, it is preferable to use a compound having a tridian bone nucleus having a high molar extinction coefficient as an ultraviolet absorber. For example, the compounds described in the following patents can be used. JP 46
Nos. 3335 and 55-152776, JP-A-5-1
97074, 5-232630, 5-3072
No. 32, No. 6-211813, No. 8-53427,
8-234364, 8-239368, 9-
No. 31067, No. 10-1159898, No. 10-14
No. 7577, No. 10-182621, German Patent No. 19
No. 739797A, EP 711804A and JP-T 8-501291.

As the antibacterial and antifungal agents that can be used in the present invention, those described in JP-A-63-271247 are useful.
Gelatin is preferred as the hydrophilic colloid used in the photographic layer constituting the photosensitive material, and particularly, heavy metals contained as impurities such as iron, copper, zinc and manganese are preferably at most 5 ppm, more preferably at most 3 ppm. .
The amount of calcium contained in the light-sensitive material is preferably 20 mg / m ² or less, more preferably 10 mg / m ² or less, and most preferably 5 mg / m ² or less.

The photosensitive material of the present invention is not only used in a printing system using a normal negative printer, but is also developed and processed after being scanned and exposed by a light beam modulated based on image information as described below. It is also preferred.

The photosensitive material of the present invention is also suitable for a scanning exposure system using a cathode ray (CRT). A cathode ray tube exposure apparatus is simpler, more compact, and lower in cost than an apparatus using a laser. Further, adjustment of the optical axis and color is also easy. Various light emitters that emit light in a spectral region are used as necessary for a cathode ray tube used for image exposure. For example, any one of a red light emitter, a green light emitter, and a blue light emitter, or a mixture of two or more thereof is used.
The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in a yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube which emits white light by mixing these light emitters is often used.

When the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions and the cathode ray tube also has a phosphor which emits light in a plurality of spectral regions, a plurality of colors are exposed at a time, that is, the cathode ray tube is exposed. The image signal of a plurality of colors may be input to the display unit to emit light from the display screen. A method of sequentially inputting image signals for each color, sequentially emitting light of each color, and exposing through a film that cuts a color other than that color (plane sequential exposure)
In general, plane-sequential exposure is preferable for high image quality because a cathode ray tube with high resolution can be used.

The photosensitive material of the present invention is a second harmonic generation light source (SHG) obtained by combining a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a solid laser using a semiconductor laser as an excitation light source and a nonlinear optical crystal.
And the like, and is preferably used for a digital scanning exposure method using monochromatic high density light. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, a semiconductor laser or a second harmonic generation light source (SHG) in which a solid-state laser is combined with a nonlinear optical crystal. Particularly, in order to design an apparatus that is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When using such a scanning exposure light source,
The spectral sensitivity maximum wavelength of the light-sensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source used.
In a solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the laser oscillation wavelength can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be provided in the usual three wavelength ranges of blue, green and red. If the exposure time in such scanning exposure is defined as the exposure time for the pixel size when the pixel density is 400 dpi, the preferred exposure time is 10 ^-4 seconds or less, more preferably 10 ^-6 seconds or less.

Preferred scanning exposure methods applicable to the present invention are described in detail in the patents listed in the above table. Further, for processing the light-sensitive material of the present invention, the lower right column of page 26, lower right column of page 26 to the upper right column of page 34 of JP-A-2-207250, and the upper left column of page 5 of JP-A-4-97355 can be used. The processing materials and processing methods described in line 17 to page 20, lower right column, line 20 can be preferably applied. As the preservative used in this developer, the compounds described in the patents listed in the above table are preferably used.

As a method of developing the photosensitive material of the present invention after exposure, there are a conventional method of developing with a developing solution containing an alkaline agent and a developing agent, and an alkaline solution containing a developing agent in the photosensitive material and containing no developing agent. In addition to a wet method such as a method of developing with an activator solution, a thermal developing method without using a processing solution can be used. In particular, since the activator method does not contain a developing agent in the processing liquid, it is easy to manage and handle the processing liquid, and is a preferable method from the viewpoint of environmental protection because it has a small load when processing the waste liquid. In the activator method, examples of the developing agent or its precursor incorporated in the photosensitive material include, for example, JP-A-8-2343.
No. 88, No. 9-152686, No. 9-152693
And hydrazine-type compounds described in JP-A Nos. 9-218814 and 9-160193.

Further, a developing method in which the amount of silver applied to the light-sensitive material is reduced and image amplification processing (intensification processing) using hydrogen peroxide is preferably used. In particular, it is preferable to use this method for the activator method. Specifically, Japanese Patent Application Laid-Open
An image forming method using an activator solution containing hydrogen peroxide described in JP-A-297354 and JP-A-9-152699 is preferably used. In the activator method, after processing with an activator solution, usually a desilvering process is performed, but in an image amplification processing method using a low silver content photosensitive material,
The desilvering process can be omitted, and a simple method such as washing with water or stabilizing process can be performed. Further, in a method in which image information is read from a photosensitive material by a scanner or the like, a processing mode that does not require desilvering processing can be adopted even when a photosensitive material having a high silver content such as a photosensitive material for photography is used.

As the activator solution, desilvering solution (bleaching / fixing solution), washing and stabilizing solution used in the present invention, known processing materials and processing methods can be used. Preferably, Research Disclosure Item 36544
(September 1994) pp. 536-541, JP-A-8
-234388 can be used.

In the present invention, the coating amount of the silver halide emulsion is preferably from 0.60 g / m ^{2 to} 0.10 g / m ^2, more preferably from 0.55 g / m ^{2 to} 0.20 g / m ^2.
m ² or more, most preferably 0.50 g / m ² 0.25
g / m ² or more.

The silver halide emulsion grains used for the cyan color-forming layer and the magenta color-forming layer are preferably cubes, and the side length is preferably 0.50 μm or less, more preferably 0.40 μm or less and 0.10 μm or more. is there.

In the present invention, the film thickness of the photographic constituent layer means
Represents the thickness of the photographic constituent layer above the support before processing. Specifically, it can be determined by any of the following methods. First, it can be obtained by cutting a silver halide color photographic light-sensitive material perpendicularly to a support and observing the cut surface with an electron microscope. A second method is to calculate the film thickness from the coating amount (g / m ² ) of each component in the photographic constituent layer and the specific gravity. For example, the specific gravity of typical gelatin used for photography is 1.34 g / ml, the specific gravity of silver chloride particles is 5.59 g / ml, and other lipophilic additives are measured before coating. By the second
The method can be used to calculate the film thickness.

In the present invention, the thickness of the photographic constituent layer is preferably 9.0 μm or less, more preferably 8.0 μm.
m, most preferably not more than 7.0 μm and not less than 3.5 μm.

Next, an outline of processing steps of development, desilvering, washing with water and / or stabilization in the color image forming method of the present invention will be described. [Development] The color developing solution usable in the developing step in the color image forming method of the present invention is described in JP-A-3-3-3.
No. 3,847, page 9, upper left column, line 6 to page 11, lower right column, line 6 and those described in JP-A-5-197107. As the color developing agent in the color developing step, a known aromatic primary amine color developing agent can be used, and a p-phenylenediamine compound is preferably used. A typical example thereof is 3-methyl-4-amino -N, N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline, 4-amino-3-methyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N- Ethyl-N
-(3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (2-hydroxypropyl) aniline, 4-
Amino-3-ethyl-N-ethyl-N- (3-hydroxypropyl)
Aniline, 4-amino-3-methyl-N-propyl-N- (3-hydroxypropyl) aniline, 4-amino-3-propyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino- 3-
Methyl-N-methyl-N- (4-hydroxybutyl) aniline, 4
-Amino-3-methyl-N-ethyl-N- (4-hydroxybutyl)
Aniline, 4-amino-3-methyl-N-propyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N-ethyl-N
-(3-hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl-N, N-bis (4-hydroxybutyl) aniline, 4-amino-3-methyl-N, N-bis (5- Hydroxypentyl) aniline, 4-amino-3-methyl-N- (5-hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-amino
3-methoxy-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethoxy-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and sulfates, hydrochlorides or p-toluenesulfonates thereof. Among these, in particular, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N
Preferred are-(3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, and their hydrochlorides, p-toluenesulfonates or sulfates. These compounds can be used in combination of two or more depending on the purpose.

[0069] European Patent Publication No. 410450,
Those described in -11255 and the like can also be preferably used. Further, salts of these p-phenylenediamine derivatives with sulfates, hydrochlorides, sulfites, naphthalenedisulfonic acid, p-toluenesulfonic acid and the like may be used. The amount of the aromatic primary amine developing agent to be used is preferably 0.0002 mol to 0.2 mol, more preferably 0.001 mol to 0.1 mol, per liter of the color developer.

In the color developing solution, sodium sulfite, potassium sulfite, sodium bisulfite,
Sulfites such as potassium bisulfite, sodium metasulfite, and potassium metasulfite, and carbonyl sulfite adducts can be added as necessary.

An optional development accelerator can be added to the color developer if necessary. Examples of the development accelerator include thioether compounds described in U.S. Pat. No. 3,813,247 and JP-A-52-49829 and JP-A-50-1555.
4, quaternary ammonium salts described in JP-B-44-30074, U.S. Pat. Nos. 2,482,546, and 2,59.
Amine compounds described in US Pat. Nos. 6,926 and 3,582,346; polyalkylene oxides described in U.S. Pat. No. 3,532,501; and other 1-phenyl-3-pyrazolidones and imidazoles , Etc. can be added as needed.

In addition, various chelating agents can be used in the color developer as an agent for preventing precipitation of calcium or magnesium or for improving the stability of the color developer. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N,
N ', N'-tetramethylenephosphonic acid, transsilohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenyl acid, 2-phosphonobutane-1, -2-, 4 -Tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, -N'-bis (2-hydroxybenzyl) ethylenediamine-N,
N'-diacetate hydroxyethyliminodiacetic acid and the like. These chelating agents may be used in combination of two or more as necessary. These chelating agents may be added in an amount sufficient to block metal ions in the color developer. For example, it is about 0.1 g to 10 g per liter.

In the present invention, an optional antifoggant can be added as required. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, And nitrogen-containing heterocyclic compounds such as -thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adanine.

In the present invention, chlorine ion
3.0 × 10^-2~ 1.5 × 10 ^-1Mol / l
It is preferred to have. Particularly preferably 3.5 × 10^-2
Mol / l to 1.0 × 10^-1Mole / liter
You. Chloride ion concentration is 1.5 × 10^-1Mol / l
If the amount is too high, it has the disadvantage of delaying development,
Preferred for achieving the object of the present invention that the concentration is high
Absent. 3.0 × 10^-2At less than mol / liter,
It is not preferable in preventing fog. In the present invention,
0.5 × 10 bromine ions in color developer^-FiveMol / l
Turtle ~ 1.0 × 10^-3Contains moles / liter
Is preferred. More preferably, 3.0 × 10^-Five~ 5 × 1
0^-FourMol / l. Bromine ion concentration is 1 × 10
^-3If more than mol / l, the development is delayed
0.5 × 10^-FiveMol / l not yet
If it is full, fog cannot be sufficiently prevented.
No.

The chlorine ions and bromine ions may be directly added to the color developer or may be eluted from the photographic material into the color developer during the development processing. When directly added to a color developer, examples of the chloride ion supplying material include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, magnesium chloride, and calcium chloride. Further, it may be supplied from a fluorescent whitening agent added to the color developer. Examples of the bromine ion supply material include sodium bromide, potassium bromide / ammonium bromide, lithium bromide, calcium bromide, and magnesium bromide. When eluted from the light-sensitive material during the development processing, both chlorine ions and bromine ions may be supplied from the emulsion or may be supplied from sources other than the emulsion.

It is preferable that the color developing solution used in the developing step of the present invention does not substantially contain benzyl alcohol. Here, "substantially not contained" means preferably 2 ml / liter or less, more preferably 0.5 m / liter or less.
The benzyl alcohol concentration is less than 1 / liter, most preferably it contains no benzyl alcohol.

The color developer used in the present invention must contain substantially no sulfite ion in order to suppress fluctuations in photographic characteristics due to continuous processing, and to achieve the effects of the present invention (here, substantially no sulfite ion is contained). If not, the sulfite ion concentration is preferably 3.0 × 10 ⁻³ mol / L or less.) Preferably, it contains no sulfite ion at 1.0 × 10 ⁻³ mol / l or less, most preferably no sulfite ion at all. However, in the present invention, a very small amount of sulfite ion used for preventing oxidation of a processing agent kit in which a developing agent is concentrated before preparing a working solution is excluded. The color developer used in the present invention should be substantially free of hydroxylamine in order to suppress the fluctuation of the characteristics due to the fluctuation of the concentration of hydroxylamine. .0
× 10 ^-3 mol / liter or less. Is more preferred. Most preferably it contains no hydroxylamine.

The color developer used in the present invention preferably has a pH of 9 to 13, and more preferably 9 to 12.5. The color developer contains other known developer component compounds. be able to. In order to maintain the above pH, it is preferable to use various buffers.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, and sodium borate. , Potassium borate, sodium tetraborate (borax),
Potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), 5-sulfo-
Potassium 2-hydroxybenzoate (potassium 5-sulfosalicylate) and the like can be mentioned. The amount of the buffer added to the color developer is preferably 0.1 mol / L or more, and more preferably 0.1 mol / L to 0.1 mol / L.
Particularly preferred is 4 mol / l.

The processing temperature of the color developing solution in the present invention is from 20 to 55 ° C., preferably from 30 to 55 ° C. The processing time is 20 seconds to 5 minutes, preferably 3 seconds for the photographic material.
0 second to 3 minutes and 20 seconds. More preferably, 1 minute to 2 minutes 3
0 seconds, 3 to 60 seconds for printing materials,
It is preferably 3 seconds to 45 seconds, and more preferably 5 seconds to 45 seconds.
25 seconds.

[Desilvering Step] Next, the desilvering process will be described. In the desilvering process, the bleaching process and the fixing process may be performed separately or simultaneously (bleach-fixing process). The aspect of the desilvering step in the present invention is preferably a bleach-fixing treatment for the purpose of simplifying the step and reducing the time. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Furthermore, processing in two successive bleach-fixing baths, fixing before bleach-fixing,
Alternatively, bleaching after bleach-fixing can be arbitrarily performed according to the purpose. The desilvering step is generally performed by combining a bleaching step, a bleach-fixing step, and a fixing step.

Examples of the bleaching agent for the processing solution having bleaching ability include:
For example, compounds of a polyvalent metal such as iron (III), peracids, quinones, and nitro compounds are used. Representative bleaching agents include organic complexes of iron (III), for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, glycol etherdiaminetetraacetic acid, JP-A-4-121739, page 4
Bleaching agents such as 1,3-propylenediaminetetraacetic acid iron complex in the lower right column of the fifth page to the upper left column of the fifth page;
Carbamoyl bleach described in U.S. Pat. No. 73647, bleach having a heterocycle described in JP-A-4-174432,
Bleaching agents described in EP-A-520457, including ferric N- (2-carboxyphenyl) iminodiacetic acid complex salt, ethylenediamine-N-2-carboxyphenyl-N, N ', N'-triacetic acid Bleaching agents described in European Patent Publication No. 530828A1, bleaching agents described in European Patent Publication No. 501479, bleaching agents described in European Patent Publication No. 567126, including ferric acetic acid;
Bleaching agent described in JP-A-127145;
The ferric salt of aminopolycarboxylic acid or the salt thereof described on page (11) of JP-A-46 can be mentioned, but is not limited thereto.

A bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and the prebath thereof, if necessary.
Specific examples of useful bleach accelerators include US Pat.
No. 93,858, Research Disclosure No.
Compounds having a mercapto group or a disulfide bond as described in JP-A-17129 (July, 1978);
Thiazolidine derivatives described in U.S. Pat. No. 0,140,129; thiourea derivatives described in U.S. Pat. No. 3,706,561;
Iodide salts described in JP-A-58-16235; polyoxyethylene compounds described in West German Patent No. 2,748,430; polyamine compounds described in JP-B-45-8836; bromide ions and the like can be used. Among them, a compound having a mercapto group or a disulfide group is preferred in view of a large accelerating effect, and in particular, US Pat.
No. 8, West German Patent No. 1,290,812,
Compounds described in No. 95630 are preferred. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material.

The bleaching solution or bleach-fixing solution according to the present invention further includes a bleaching accelerator, a corrosion inhibitor for preventing the corrosion of the processing bath, a buffer for maintaining the pH of the solution, a fluorescent brightening agent, an antifoaming agent, and the like. It is added as needed. Regarding the bleaching accelerator, for example, US Pat. No. 3,893,858,
German Patent 1,290,821, British Patent 1,138,842, JP-A-53-95630
And compounds having a mercapto group or a disulfide group described in Research Disclosure No. 17129 (July 1978), JP-A-50-140129
Thiazolidine derivatives described in U.S. Pat.
No. 06561, thiourea derivatives, iodides described in JP-A-58-16235, polyethylene oxides described in German Patent 2,748,430, JP-B-45-8636. And the like. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography. Particularly preferably, British Patent 1,138,8
Mercapto compounds described in JP-A-42-190, JP-A-2-190856 are preferred.

The bleaching solution and the bleach-fixing solution preferably contain an organic acid in addition to the above compounds for the purpose of preventing bleaching stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5.5, and specifically, acetic acid, propionic acid and the like. As the corrosion inhibitor, a nitrate is preferably used, and ammonium nitrate, sodium nitrate, potassium nitrate and the like are used.
The addition amount is 0.01 to 2.0 mol / l, preferably 0.05 to 0.5 mol / l.

[0086] In recent years, with increasing awareness of the preservation of the global environment, efforts have been made to reduce nitrogen atoms emitted into the environment. From such a viewpoint, it is desired that the treatment liquid of the present invention does not substantially contain ammonium ions. In the present invention, the phrase "contains substantially no ammonium ion" means that the concentration of ammonium ion is 0.1.
1 mol / liter or less, preferably 0.0
8 mol / l or less, more preferably 0.01 mol / l
1 liter or less, particularly preferably a state of not containing any. In order to reduce the ammonium ion concentration in the range of the present invention, alkali metal ions and alkaline earth metal ions are preferable as alternative cation species, and alkali metal ions are particularly preferable, and lithium ion, sodium ion and potassium ion are particularly preferable. However, specifically, sodium salts and potassium salts of a ferric organic acid complex as a bleaching agent, potassium bromide as a rehalogenating agent in a processing solution having bleaching ability, sodium bromide, potassium nitrate, Sodium nitrate and the like. Further, as the alkaline agent used for pH adjustment, potassium hydroxide,
Sodium hydroxide, potassium carbonate, sodium carbonate and the like are preferred.

In the present invention, the pH of the bleaching solution or bleach-fixing solution is from 2.0 to 8.0, preferably from 3.0 to 7.5. In the present invention, a processing solution having a bleaching ability is particularly preferably subjected to aeration during processing, since photographic performance is extremely stably maintained. The bleaching or bleach-fixing step can be performed in a temperature range of 30 ° C to 60 ° C, preferably 35 ° C to 50 ° C.

The light-sensitive material processed with a processing solution having bleaching ability is subjected to fixing or bleach-fixing processing. When the processing solution having the bleaching ability is a bleach-fixing solution, a fixing or bleach-fixing process may or may not be performed thereafter. Such a fixing solution or a bleach-fixing solution is also disclosed in JP-A-3-33847.
It is preferable to use those described on page 6, lower right column, line 16 to page 8, upper left column, line 15.

As a fixing agent in the desilvering step, ammonium thiosulfate has been generally used, but other known fixing agents, for example, mesoionic compounds, thioether compounds, thioureas, a large amount of iodide, hypo and the like May be replaced by These are disclosed in JP-A-60-61749,
Nos. 60-147735, 64-21444, JP-A-1-201659, 1-
Nos. 210951, 2-44355 and U.S. Pat. No. 4,378,424. For example, ammonium thiosulfate, sodium thiosulfate, potassium thiosulfate, guanidine thiosulfate, ammonium thiocyanate, sodium thiocyanate, potassium thiocyanate, dihydroxyethyl-thioether, 3,6-dithia-1,8-octanediol, imidazole and the like. No. Of these, thiosulfates and mesoions are preferred. Ammonium thiosulfate is preferred from the viewpoint of quick fixability, but as described above, sodium thiosulfate and meso ions are more preferred from the viewpoint of environmentally friendly treatment so as to substantially eliminate ammonium ions. Further, by using two or more types of fixing agents in combination, it is possible to perform more rapid fixing. For example, it is preferable to use the above-mentioned ammonium thiocyanate, imidazole, thiourea, thioether and the like in addition to ammonium thiosulfate and sodium thiosulfate. In this case, the second fixing agent is 0.1% based on ammonium thiosulfate and sodium thiosulfate. It is preferably added in the range of 01 to 100 mol%.

The amount of the fixing agent may be bleach-fixing solution or fixing solution 1
0.1 to 3.0 mol per liter, preferably 0.5 to
2.0 moles. Although the pH of the fixing solution depends on the type of the fixing agent, it is generally 3.0 to 9.0, and particularly when thiosulfate is used, 5.8 to 8.0 provides stable fixing performance. Above.

A preservative is added to the bleach-fixing solution or the fixing solution,
The temporal stability of the liquid can also be improved. In the case of a bleach-fixing solution or a fixing solution containing a thiosulfate, a sulfite and / or a bisulfite adduct of hydroxylamine, hydrazine or aldehyde (for example, a bisulfite adduct of acetaldehyde, particularly preferably Is effective to use an aromatic aldehyde bisulfite adduct described in JP-A-1-298935.

In the present invention, the bleach-fixing solution or the fixing solution preferably contains at least one kind of sulfinic acid and a salt thereof. The amount of sulfinic acid and a salt thereof to be added to the bleach-fixing solution or the fixing solution is 1 × 10 ⁻⁴ to 1 mol, preferably 1 × 10 ^{−3 to} 0.5 mol, more preferably 1 × 10 ⁻³ to 1 mol per liter of the processing solution. × 10 ^-2
０．１0.1 mol.

The total time of the desilvering step comprising the bleaching / fixing step in the present invention is preferably as short as possible within the range in which desilvering failure does not occur for the purpose of shortening the processing time. The preferred time is from 5 seconds to 1 minute, more preferably from 5 seconds to 25 seconds. The processing temperature is 25 ° C to 50 ° C, preferably 3 ° C.
5 ° C to 45 ° C. In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented. Further, in each of the above-mentioned processing solutions employed in the present invention, for example, the emulsion is provided so as to face the emulsion surface described in Examples of page 3 lower right column to page 4 lower right column of JP-A No. 62-183460. A method of discharging the liquid pumped by a pump from the slit or nozzle provided can be applied. In addition, the treatment of the present invention has relatively better performance than the combination other than the present invention in any state of the liquid opening ratio [air contact area (cm ² ) / liquid volume (cm ³ )]. From the point of stability, the liquid aperture ratio is 0
~ 0.1 cm ^-1 is preferred. In the continuous treatment, the practical range is preferably 0.001 cm ^{-1 to} 0.05 cm ^-1 , and more preferably 0.002 to 0.03 cm ^-1 .

[Washing and / or Stabilization] Next, the washing and / or stabilizing steps in the color image forming method of the present invention will be described. A processing method in the washing and / or stabilizing step is disclosed in JP-A-57-85.
No. 43, No. 58-14834, No. 60-220345
All known methods described in (1) can be used. Further, a washing step and a stabilizing step may be performed such that a stabilizing bath containing a dye stabilizer and a surfactant is used as a final bath. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely. Various surfactants can be contained in the washing water or the stabilizing solution used in the washing and / or stabilizing step in order to prevent unevenness of water droplets when the processed photosensitive material is dried.
These surfactants include polyethylene glycol type nonionic surfactants, polyhydric alcohol type nonionic surfactants, alkylbenzene sulfonate type anionic surfactants, and higher alcohol sulfate ester type anionic surfactants. Agents, alkyl naphthalene sulfonate type anionic surfactant, quaternary ammonium salt type cationic surfactant, amine salt type cationic surfactant, amino acid type amphoteric surfactant, betaine type amphoteric surfactant The ionic surfactant is preferably used as a nonionic surfactant because it may form an insoluble substance by combining with various ions mixed in with the treatment, and particularly, an alkylphenol ethylene oxide adduct is preferably used. preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferred as alkylphenols, and the number of moles of ethylene oxide added is particularly preferably 8 to 14 mol. It is also preferable to use a silicon surfactant having a high defoaming effect. In the stabilizing solution, an aldehyde such as formalin or glutaraldehyde, an N-methylol compound, hexamethylenetetramine, or an aldehyde sulfite adduct can be used as a dye stabilizer. In addition, the stabilizing solution may further contain a pH adjusting buffer such as boric acid or sodium hydroxide; 1-hydroxyethylidene-1,1-diphosphonic acid; a chelating agent such as ethylenediaminetetraacetic acid; a sulfuric acid such as alkanolamine. An inhibitor, a fluorescent whitening agent, a fungicide, and the like can be contained.

The washing water or the stabilizing solution may contain various antibacterial agents and antifungal agents for preventing generation of water rust and mold generated on the processed photosensitive material. Examples of these antibacterial agents and fungicides include thiazolylbenzimidazole compounds as disclosed in JP-A-57-157244 and JP-A-58-105145, or JP-A-54-27424 and JP-A-54-27424. Kaisho 57
No. 8542, isothiazolone compounds, or chlorophenol compounds represented by trichlorophenol, or bromophenol compounds, or organotin or organozinc compounds, or thiocyanic acid or isothiocyanic acid compounds Compounds, or acid amide compounds, or diazine or triazine compounds, or thiourea compounds, benzotriazole alkylguanidine compounds, or quaternary ammonium salts such as benzalkonium chloride, or penicillin Antibiotics such as those represented by Journal Antibacterial and Antifungus Agent (J. Antibact.A
ntifung.Agents) Voll. No.5, pp.207-223 (1
983) may be used in combination of one or more general-purpose anti-blur agents. Also, various germicides described in JP-A-48-83820 can be used. Further, as a solution to problems such as propagation of bacteria and adhesion of generated suspended matter to a photosensitive material which occur when the amount of washing water is greatly reduced in a multi-stage countercurrent method, JP-A-62-288838 discloses a method. A method for reducing calcium ions and magnesium ions can be used very effectively.

It is preferable to use various chelating agents in a range that does not impair the effects of the compound used in the present invention. Preferred compounds of the chelating agent include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, and 1-hydroxyethylidene-
1,1-diphosphonic acid, ethylenediamine-N, N,
Examples thereof include organic phosphonic acids such as N ', N'-tetramethylenephosphonic acid, and a hydrolyzate of a maleic anhydride polymer described in EP 345172 A1. Further, it is preferable that a preservative which can be contained in the fixing solution or the bleach-fixing solution is contained in the washing water. The water used in these washing or stabilizing steps is tap water, water deionized to a concentration of 5 mg / l or less with an ion exchange resin or the like, sterilized by halogen, an ultraviolet germicidal lamp, or the like. Preferably, water is used.

The pH of the washing water is from 4 to 9, preferably from 5 to 8. The rinsing time can also be variously set depending on the characteristics of the photosensitive material, the application, etc., but is preferably 10 seconds to 90 seconds, more preferably 10 seconds to 45 seconds, and the rinsing water temperature is preferably 15 to 50 ° C., and more preferably 35 to 50 ° C. A range of ５０50 ° C. is selected. The overflow solution resulting from the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step. In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation, it is preferable to add water to correct the concentration. In the present invention, water washed and / or stabilized with a reverse osmosis membrane can be effectively used. As the material of the reverse osmosis membrane, cellulose acetate, crosslinked polyamide, polyether, polysulfone, polyacrylic acid, polyvinylene carbonate and the like can be used.

The liquid sending pressure in the use of these membranes is preferably from ^{2 to} 10 kg / cm ² , and particularly preferably from 3 to 7 in order to prevent stain and to prevent a decrease in the amount of permeated water.
Kg / cm ² . The washing and / or stabilizing step is preferably connected to a multi-stage countercurrent system using a plurality of tanks, but it is particularly preferable to use 2 to 5 tanks.

The drying step in the color image forming method of the present invention may be carried out by any conventionally known method relating to rapid drying of the color photographic material. , Preferably 15
It is preferable that drying can be performed within seconds, more preferably within 5 seconds to 15 seconds, and most preferably within 5 seconds to 10 seconds. Either the contact heating method or the hot air blowing method may be used as the drying method, but the combination of the contact heating method and the hot air blowing method enables quick drying compared to the case of using either method. Is preferable. A further preferred aspect of the present invention relating to the drying method is a method in which the photosensitive material is contact-heated by a heat roller and then blown and dried by warm air blown from the perforated plate or the nozzle group toward the photosensitive material. In the drying section, it is preferable that the mass velocity of the warm air blown per unit area of the heat receiving area of the photosensitive material is 1000 kg / m ² · hr or more. Further, it is preferable that the shape of the blowing outlet is a shape having a small pressure loss, and examples thereof include FIGS. 7 to 15 described in JP-A-9-33998. The light-sensitive material of the present invention has rapid processing properties and high sensitivity,
Since pressure fogging is small and suitable not only for surface exposure but also especially for high illuminance scanning exposure, a good image can be obtained in the above color development time.

In the replenishing method of the developing step, desilvering step, washing and / or stabilizing step in the present invention, a replenisher of a single composition is used, or a replenisher of a plurality of compositions is separated. In the case of replenishment by replenishment, the replenishment can be carried out by any method of separating into one or more replenishers or water replenishment and addition of a solid substance composed of replenishment components. The replenishment amount per step in the present invention is represented by an increase in volume when these are replenished when they are separately replenished into a plurality of replenishers, and a single or a plurality of replenishers or water is replenished. Separation between the replenishment and the addition of the solid material comprising the replenishing components is also represented by the volume increase when they are replenished.

[0102] The low replenishment rate of the processing in the present invention varies depending on the kind of the photosensitive material, for example, in the case of development processing for color printing, replenishing amount per photosensitive material 1 m ² is
The replenishment rate of the color developing solution is 10 to 60 ml / m ² , more preferably 20 to 45 ml / m ² , and at the same time, the replenishment rate of the bleach-fix solution is 20 to 50 ml / m ² , and washing with water and / or stabilization. Replenishment rate of liquid is 50-100ml / m
It is preferably ² . In this case, the total replenishment amount in all the steps is preferably 70 to 200 ml / m ² , and 90 to 1 ml / m ^2.
60 ml / m ² is more preferred.

In the present invention, continuous processing refers to processing of a photosensitive material which requires substantial replenishment of a processing solution. More specifically, it means that a development process in which the replenishment amount accompanying the color printing process is equivalent to 0.1 to 20% of the capacity of the processing tank as an average per day is performed for a plurality of days. In particular, conditions under which the effects of reducing stain and stabilizing photographic performance in simple and rapid processing can be obtained are such that the average replenishment amount per day is preferably 0.1 to 20% of the capacity of the developing tank, more preferably 0 to 20%. 0.2-10%, most preferably 0.5-6%.
At this time, the capacity of the color developing tank is not particularly limited, but is usually 50 liters or less, preferably 0.2 to 20 liters, and most preferably 1 to 10 liters. Also,
The processing amount is determined by the replenishment amount per 1 m ² of the photosensitive machine material and the average replenishment amount per day. Specifically, in the case of a photosensitive material for color printing, the average amount is 0.1 μm per day.
Is preferably 1~80m ^2, more preferably 0.2~60m ^2, and most preferably 0.1 to 30
m ² .

In the present invention, rapid processing means that the time required for developing an exposed photosensitive material and obtaining an image through a drying step is shortened. Specifically, by shortening one or more of the color developing step, desilvering step, washing and / or stabilizing step, and drying step, all the processing steps are performed for 30 to 90 seconds, preferably 50 to 90 seconds. Seconds is a preferred embodiment of the present invention. In each processing step, the processing time in the developing step and the processing time in the desilvering step are each preferably 30 seconds or less, and more preferably 5 to 25 seconds. At this time, the ratio (Tw / Tbf) of the processing time (Tw) of the washing and / or stabilizing step to the processing time (Tbf) of the bleach-fixing step is preferably 1.3 or less. In the present specification, the ultra-rapid processing refers to processing a photosensitive material containing a silver halide emulsion having a silver chloride content of 95 mol% or more in all processing steps in the above-mentioned time.

The processing time of the step in the present invention means the time required from the start of processing of the photosensitive material in one step to the start of processing in the next step. In the present invention, the beginning of the developing step means when the photosensitive material is immersed in the color developing solution, and the end of the drying step means when the photosensitive material has passed through the final transport roller in the drying step.

The actual processing time of an automatic processor usually depends on the linear velocity and the capacity of the processing bath. The standard of the linear velocity in the present invention is 400 to 4000 mm /
In particular, in the case of a small developing machine called a minilab, the speed is preferably 500 to 2500 mm / min.

In the present invention, the washing and / or stabilizing treatment is preferably carried out in a multi-stage countercurrent bath. At this time, it is more preferable that the photosensitive material be moved between the tanks in the liquid so as not to come into contact with air. . As a method of moving between the tanks in the liquid, for example, a photosensitive material passage is provided between the tanks, and the passage can be opened and closed by shutter means. At this time, it is preferable that a pair of flexible blades is provided as the shutter means so that only the leading ends of the blades elastically contact each other.

In the present invention, at least one of the steps of development, desilvering, washing with water and / or stabilization is preferably carried out in the presence of a diaminostilbene-based optical brightener. As the diaminostilbene-based fluorescent whitening agent, specifically, the compounds described in Tables 1 to 6 of JP-A-6-332127 are preferable, and among them, the compound (SR-
1) to (SR-16) are particularly preferred. The diaminostilbene-based fluorescent whitening agent can be contained in both the light-sensitive material and the processing solution, but is preferably contained in the processing solution.
It is preferably contained in any one of the processing solutions of each of the steps of (2) desilvering and (3) washing and / or stabilization, but is preferably substantially contained in the processing solution of a plurality of steps. Here, the desilvering step comprises any of bleaching / fixing or bleach-fixing steps and a combination thereof.

In the present invention, the spraying rate of the circulating treatment liquid is usually from 1 liter / min to 40 liter / min. The circulation amount is 5 to 30 liters / min, preferably 10 to 25 liters / min to achieve the above spraying amount.
And equal to or greater than the spray amount. The circulation amount and the spray amount may be the same. In the present invention, it is necessary that this condition is satisfied at least when the photosensitive material is being processed. This condition may be satisfied when the power of the processing machine is turned on. The circulating and spraying may be in any of a mode of circulating in a processing tank and a mode of spraying a circulating liquid on the photosensitive layer side of the photosensitive material. In the present invention, the circulating liquid is sprayed on at least the photosensitive layer side of the photosensitive material. Spraying is preferably in liquid. The circulating liquid is filtered through a filter by a conventional method, and then returned to the treatment tank. The spray amount of the circulating treatment liquid is preferably 5 to 25 liters /
Minutes. The circulation amount of the processing liquid is 1.0 per processing tank.
４０40 liters / minute, more preferably 5 to 3
0 liter / min. If the spraying amount is small, the effect of the present invention is hardly obtained, while if the spraying amount is too large, the processing liquid tends to deteriorate, which is not preferable. It is preferable that the circulating processing solution blow-out hole is provided immediately at 1 to 4 mm and perpendicularly to the photosensitive layer of the photosensitive material at 10 to 100 locations per tank, more preferably 5 to 100 locations per tank. It is preferable that 50 outlet holes are provided. Further, the distance between the blowing hole and the surface of the photosensitive layer is preferably 1.0 to 50 mm, more preferably 2.0 to 20 mm. Further, the flow rate from one blow hole is preferably 1 to 100 cm / sec or more, more preferably 5 to 50 cm / sec.

In the present invention, the means for spraying the circulating liquid as described above may be provided in any of the processing steps, but is preferably provided at least in the developing step. It is more preferably provided in the steps, and the mode provided in all the steps is most preferable since the effect of improving stain can be obtained. Further, as a preferred embodiment of providing the spraying means in the washing and / or stabilizing step, the washing and / or stabilizing step is divided into at least three tanks, and at least the final tank is provided with a circulating liquid spraying means. It is preferably provided in the final tank and the preceding tank, and most preferably provided in all of the washing and / or stabilizing tanks. Further, the steps of washing and / or stabilizing are 3-12.
It is preferably divided into tanks, and more preferably divided into 3 to 10 tanks. The photosensitive material is preferably transported between the divided washing and / or stabilizing tanks by moving in a liquid via a blade provided on a wall of the tank in view of shortening the aerial time. The nozzle for spraying the liquid is preferably provided between the transport roller and the blade between the tanks. At this time, the spray nozzle may be provided only on the photosensitive layer side of the photosensitive material, but in a multi-chamber washing step or the like, a method of spraying from both sides of the surface of the photosensitive material is preferable because troubles such as jamming during transport hardly occur.

[0110]

Next, the present invention will be described in more detail with reference to examples. Example 1 After a corona discharge treatment was applied to the surface of a support obtained by coating both sides of a paper with a polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and further a first layer to a seventh layer Were sequentially coated to prepare a sample (101) of a silver halide color photographic light-sensitive material having the following layer structure. The coating solution for each photographic constituent layer was prepared as follows. Since the structural formulas and treatment steps of the compounds used in Examples 1 and 2 are the same unless otherwise specified, they are described after Example 2. Examples 3 to 6
In Example 1, the compounds having the same reference numerals as in Example 1 had the same structural formulas and were subjected to the same treatment unless otherwise specified.

Preparation of Coating Solution for Fifth Layer 130 g of cyan coupler (ExC-2) and (ExC-
3) 30 g, color image stabilizer (Cpd-1) 50 g, color image stabilizer (Cpd-6) 60 g, color image stabilizer (Cpd-7)
20 g, 40 g of color image stabilizer (Cpd-9), 10 g of color image stabilizer (Cpd-10), color image stabilizer (Cpd-14)
10 g, 120 g of color image stabilizer (Cpd-15), 30 g of color image stabilizer (Cpd-16), color image stabilizer (Cpd-1)
7) 90 g, 70 g of color image stabilizer (Cpd-18), 150 g of solvent (Solv-5), and 50 g of solvent (Solv-8)
and 350 ml of ethyl acetate, and this solution was emulsified and dispersed in 650 g of a 10% aqueous gelatin solution containing 25 g of a surfactant (Cpd-20) to prepare Emulsion C. On the other hand, silver chlorobromide emulsion C (cubic, average grain size 0.40
μm large size emulsion C and 0.30 μm small size emulsion C
And a 5: 5 mixture (silver molar ratio). The variation coefficients of the particle size distribution are 0.09 and 0.11, respectively. In each size emulsion, 0.5 mol% of silver bromide was locally contained on a part of the surface of the silver chloride-based grain). In this emulsion, the following red-sensitive sensitizing dyes G and H were added in an amount of 9.0 × 10 ⁻⁵ mol per mol of silver, and with respect to the large-sized emulsion C, respectively.
In addition, for small size emulsion C, 12.0 × 10
^-5 mol is added. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion C and the silver chlorobromide emulsion C were mixed and dissolved to prepare a fifth layer coating solution having the composition described below. The emulsion coating amount indicates a coating amount in terms of silver amount.

The coating solutions for the first to fourth layers and the sixth to seventh layers were prepared in the same manner as the coating solution for the fifth layer. Examples of gelatin hardeners for each layer include H-1, H-2 and H-3.
Was used. Ab-1, Ab-2, Ab-3 are formed on each layer.
And Ab-4 in a total amount of 15.0 mg / m ² ,
60.0 mg / m ² , 5.0 mg / m ² and 10.0
mg / m ² .

[0113]

Embedded image

The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

[0115]

Embedded image

(The sensitizing dyes A and C were used in an amount of 0.42 × 1
^0-4 mol, 0.50 × each for small size emulsions
10 ^-4 mol was added. Sensitizing dye B was used in an amount of 3.4 × 10 ^-4 mol per mol of silver halide per mol of silver halide emulsion,
4.1 × 10 ^-4 mol was added to the small size emulsion. Green sensitive emulsion layer

[0117]

Embedded image

(Sensitizing dye D was added per mole of silver halide,
3.0 × 10 for large emulsions ^-FourMol, small size
3.6 × 10 for emulsion^-FourMol and sensitizing dye E
Per mole of silver halide and for large emulsions
4.0 × 10^-Five7.0 × for mole, small size emulsions
10^-FiveMole of sensitizing dye F per mole of silver halide.
2.0 × 10^-FourMol, small sa
2.8 × 10^-FourMole was added. ) Red-sensitive emulsion layer

[0119]

Embedded image

(Sensitizing dyes G and H were converted to silver halide 1
8.0 × 1 for large emulsions per mole
0 ^-5 mol, respectively 10.7 × to the small size emulsion
10 ^-5 mol was added. Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 3.0 × 10 ⁻³ mol per mol of silver halide. )

[0121]

Embedded image

Further, a blue-sensitive emulsion layer, a green-sensitive emulsion layer and
1- (3-methylureidophenyl) was added to the red-sensitive emulsion layer.
) -5-mercaptotetrazole
3.3 × 10 per mole of silver halide^-FourMol, 1.0 × 10^-3
Mol and 5.9 × 10^-FourMole was added. Furthermore, the second
Layer, the fourth layer, the sixth layer and the seventh layer, respectively.
mg / m ^Two 0.2 mg / m^Two , 0.6 mg / m^Two ,
0.1mg / m^Two Was added so that Blue sensitivity
4-hydroxy-6 to the emulsion layer and the green-sensitive emulsion layer
-Methyl-1,3,3a, 7-tetrazaindene
1 × 10 per mol of silver halide^-FourMole, 2
× 10^-FourMole was added. Also, methacrylate is added to the red-sensitive emulsion layer.
Copolymer latex of luic acid and butyl acrylate (mass ratio
1: 1, average molecular weight 200000-400000)
0.05g / m^TwoWas added. The second layer, fourth layer and
Catechol-3,5-disulfonic acid
6 mg / m^Two , 6mg / m^Two , 18mg
/ M^Two Was added so that Also, irradiation
For prevention, the following dyes (in parentheses indicate coating amount)
Was added.

[0123]

Embedded image

(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion is
It represents the silver equivalent coating amount. Support Polyethylene resin laminated paper [A white pigment (TiO ₂ ;
Content: 16% by mass, ZnO; content: 4% by mass] and a fluorescent brightener 4,4'-bis (5-methylbenzoxazolyl)
Stilbene content 0.03 mass%), blue dye (ultramarine)
First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A (cubic, 5: 5 mixture of large-size emulsion A with an average grain size of 0.72 μm and small-size emulsion A with a 0.60 μm size (silver mole The coefficient of variation of the grain size distribution was 0.08 and 0.10, respectively, and 0.3 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride in each size emulsion. ) 0.24 Gelatin 1.25 Yellow coupler (ExY) 0.57 Color image stabilizer (Cpd-1) 0.07 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0 0.07 Color image stabilizer (Cpd-8) 0.02 Solvent (Solv-1) 0.21

Second layer (color mixture preventing layer) Gelatin 0.99 Color mixture inhibitor (Cpd-4) 0.09 Color image stabilizer (Cpd-5) 0.018 Color image stabilizer (Cpd-6) 0.13 Color image stabilizer (Cpd-7) 0.01 Solvent (Solv-1) 0.06 Solvent (Solv-2) 0.22

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion B (cubic, 1: 3 mixture of large-size emulsion B with an average grain size of 0.45 μm and small-size emulsion B of 0.35 μm (silver mole The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively. In each size emulsion, 0.4 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride.) 0.14 Gelatin 1.36 Magenta coupler (ExM-1) 0.15 UV absorber (UV-A) 0.14 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-4) 0 0.002 Color image stabilizer (Cpd-6) 0.09 Color image stabilizer (Cpd-8) 0.02 Color image stabilizer (Cpd-9) 0.03 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) .11 solvent (Solv-4) 0.22 solvent (Solv-5) 0.20

Fourth layer (color mixture prevention layer) Gelatin 0.71 Color mixture prevention agent (Cpd-4) 0.06 Color image stabilizer (Cpd-5) 0.013 Color image stabilizer (Cpd-6) 0.10 Color image stabilizer (Cpd-7) 0.007 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16 Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C (cube, average grain) A 5: 5 mixture (silver molar ratio) of a large emulsion C of 0.40 μm size and a small emulsion C of 0.30 μm, and the coefficient of variation of the grain size distribution is 0.09 and 0.11, respectively. 0.82 mol% of silver bromide is locally contained in a part of the surface of the particle based on silver chloride.) 0.12 Gelatin 1.11 Cyan coupler (ExC-2) 0.13 Cyan coupler (ExC-3) 0.03) Color image stabilizer (Cpd-1) 5 Color image stabilizer (Cpd-6) 0.06 Color image stabilizer (Cpd-7) 0.02 Color image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd-10) 0.01 colors Image stabilizer (Cpd-14) 0.01 Color image stabilizer (Cpd-15) 0.12 Color image stabilizer (Cpd-16) 0.03 Color image stabilizer (Cpd-17) 0.09 Color image stabilizer Agent (Cpd-18) 0.07 Solvent (Solv-5) 0.15 Solvent (Solv-8) 0.05 Sixth layer (ultraviolet absorbing layer) Gelatin 1.66 Ultraviolet absorbing agent (UV-1) 0.19 UV absorber (UV-2) 0.06 UV absorber (UV-3) 0.06 UV absorber (UV-4) 0.05 UV absorber (UV-5) 0.09 Solvent (Solv-7) 0.25 7th layer (protective layer) Gelatin 1.00 Polyvinyl alcohol Acrylic-modified copolymer (modification degree 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01

Next, as shown in Table 3, the gradation at the time of exposure to 10 ^-4 seconds and the coating amount of gelatin as a hydrophilic binder were adjusted with respect to the sample (101).
No. 12 was produced. The gradation at the time of exposure for 10 ^-4 seconds was adjusted by adding potassium hexachloroiridate and yellow blood salt to the silver halide emulsion contained in each color-forming layer. To be the same. The light source and the scanning exposure device used at this time are as follows. Light source for three-color separation: Sensitometer M manufactured by EG & G
ARK VII filter: 480 nm (blue), 550 nm
(Green), 680 nm (Red) band pass filter Laser scanning exposure apparatus: Exposure apparatus described in JP-A-10-20547 In processing A or B of the photosensitive material prepared in this way, the highest density for each of yellow, magenta, and cyan colors Was longer than 2.0, and the processing time required for color development was measured, and the results are shown in Table 3. Further, the photosensitive material 101
To ~ 112, an 8-point large square gothic body, "Fuji Photo Film Photographic Paper FUJIPHOTOFILM COLORPAPER" and a squirrel plate were exposed for ^10-4 seconds with black characters on a white background and white characters on a black background, and the following processing A or processing B Was done.
The print samples thus obtained (samples 101A to 101A)
12A, 101B, 102B, 110B to 112B). The sample 101A was obtained by processing the photosensitive material 101 in the process A, and the sample 101B was obtained by processing the photosensitive material 101 in the process B. In the sensory evaluation method, 10 panelists absolutely evaluated the character quality (contour bleeding, tightness, correctness of fonts, etc.) of each print sample, and were satisfied (O), not satisfactory but acceptable (許 容) In addition, the classification was made into three grades of unsatisfactory and unacceptable (x), and the grade with the largest number of people was used as the evaluation value. At this time, the difference in the evaluation was remarkable due to the difference in character quality in the kanji portion.

[0129]

[Table 3]

As shown in Table 3, the photosensitive material 101 having the gradation specified in the present invention but having a gelatin coating amount exceeding the range specified in the present invention was processed A or B.
(1) Inferior in rapid processing suitability by any of
01A, 101B) Not preferred. Further, it can be seen that even with the gelatin coating amount specified in the present invention, the samples 103A, 104A and 106A having no gradation specified in the present invention are inferior in character quality. On the other hand, the sample 102 of the present invention
A, 105A, 107A to 112A, 102B and 1
When 10B to 112B are used, rapid processing can be performed, and
A print that is satisfactory or acceptable in character quality is obtained.
Furthermore, according to the process B, since the time when the maximum density exceeds 2.0 is shorter than that in the process A, it can be said that this is a more preferable embodiment of the present invention.

Example 2 A photosensitive material 201 was prepared by changing the composition of each layer of the photosensitive material 101 of Example 1 as follows, and 10 ^{-4 was} applied to the photosensitive material 201 in the same manner as in Example 1. Samples 201A to 212A, 201B, 202B and 210B to which the gradation of second exposure and the amount of gelatin applied were adjusted as shown in Table 4.
212B was produced. The notations A and B have the same meaning as in the first embodiment. Subsequently, the same evaluation as in Example 1 was performed.

[0132]

[Table 4]

From the results shown in Table 4, the samples 203A, 204A, and 206A out of the gradation specified by the present invention.
Are inferior in character quality, but the samples 201A and 202 of the present invention
A, 205A, 207A to 212A, 201B, 202
B and 210B to 212B, the time when the maximum concentration exceeded 2.0 was further shortened than each of the samples of Example 1, and the composition was suitable for more rapid processing, and the gelatin coating amount specified in the present invention. It can be seen that the photosensitive material having gradation and gradation is excellent in rapid processing suitability and also excellent in character quality.

Preparation of Sample 201 First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion A (the same emulsion as sample (101)) 0.24 Gelatin 1.25 Yellow coupler (ExY) 0.57 Color image stabilizer (Cpd-1) 0.07 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.07 Color image stabilizer (Cpd-8) 0.02 Solvent (Solv-1) 0.21

Second layer (color mixture preventing layer) Gelatin 0.60 Color mixture inhibitor (Cpd-19) 0.09 Color image stabilizer (Cpd-5) 0.007 Color image stabilizer (Cpd-7) 0.007 UV absorber (UV-C) 0.05 Solvent (Solv-5) 0.11

Third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion B (the same emulsion as in sample (101)) 0.14 gelatin 0.73 magenta coupler (ExM-1) 0.15 ultraviolet absorber (UV- A) 0.05 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-7) 0.008 Color image stabilizer (Cpd-8) 0.07 Color image stabilizer (Cpd-9) 0.03 Color image stabilizer (Cpd-10) 0.009 Color image stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) 0.06 Solvent (Solv-4) 0.11 Solvent (Solv-5) ) 0.06

Fourth layer (color mixture prevention layer) Gelatin 0.48 Color mixture prevention agent (Cpd-4) 0.07 Color image stabilizer (Cpd-5) 0.006 Color image stabilizer (Cpd-7) 0.006 UV absorber (UV-C) 0.04 Solvent (Solv-5) 0.09

Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C (the same emulsion as sample (101)) 0.12 gelatin 0.59 cyan coupler (ExC-2) 0.13 cyan coupler (ExC-3) ) 0.03 Color image stabilizer (Cpd-7) 0.01 Color image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd-15) 0.19 Color image stabilizer (Cpd-18) 0 .04 UV absorber (UV-7) 0.02 Solvent (Solv-5) 0.09

Sixth layer (ultraviolet absorbing layer) Gelatin 0.32 Ultraviolet absorbing agent (UV-C) 0.42 Solvent (Solv-7) 0.08 Seventh layer (protecting layer) Gelatin 0.70 Acrylic of polyvinyl alcohol Modified copolymer (degree of modification 17%) 0.04 Liquid paraffin 0.01 Surfactant (Cpd-13) 0.01 Polydimethylsiloxane 0.01 Silicon dioxide 0.003

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[0145]

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[0146]

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[0147]

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[0148]

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Hereinafter, the processing steps will be described. Processing A The photosensitive material 101 was processed into a 127 mm wide roll, and was imagewise exposed using a minilab printer processor PP1258AR manufactured by Fuji Photo Film Co., Ltd ..
Continuous processing (running test) was performed. This treatment using the running liquid was designated as treatment A. Processing process Temperature Time Replenishment amount ^* Color development 38.5 ° C 45 seconds 45 ml Bleaching and fixing 38.0 ° C 45 seconds 35 ml Rinse (1) 38.0 ° C 20 seconds-Rinse (2) 38.0 ° C 20 seconds - rinse (3) ** 38.0 ℃ 20 seconds - rinse (4) ** 38.0 ℃ 30 seconds 121 ml * phosphorus replenishment rate ** Fuji Photo Film Co., Ltd. rinse cleaning system RC50D per photosensitive material 1 m ² The rinsing liquid is taken out of the rinse (3) and sent to the reverse osmosis membrane module (RC50D) by a pump. The permeated water obtained in the tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. (Rinsing was carried out in a tank countercurrent system from (1) to (4).)

In this example and the following examples, the drying time of the treatment A was 30 seconds. The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml Dimethylpolysiloxane-based surfactant 0.1 g 0.1 g (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Tri (isopropanol) amine 8.8 g 8 8.8 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Polyethylene glycol (molecular weight 300) 10.0 g 10.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.5 g 0.5 g Potassium chloride 10.0 g-odor Potassium iodide 0.040 g 0.010 g Triazinylaminostilbene-based fluorescence 2.5 g 5.0 g Brightener (Hakor FWA-SF / Showa Chemical Co., Ltd.) Sodium sulfite 0.1 g 0.1 g Disodium-N, N- Bis (sulfonatoethyl) hydroxylamine 8.5 g 11.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-amino-4-aminoaniline / 3/2 sulfuric acid monohydrate 5.0 g 15.7 g potassium carbonate 3g 26.3g Add water 1000ml 1000ml pH (25 ° C / adjusted with potassium hydroxide and sulfuric acid) 10.15 12.50

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 700 ml 600 ml iron (III) ammonium ethylenediaminetetraacetate 47.0 g 94.0 g 1.4 g 2.8 g m-carboxybenzeneflufine ethylenediaminetetraacetic acid Acid 8.3 g 16.5 g Nitric acid (67%) 16.5 g 33.0 g Imidazole 14.6 g 29.2 g Ammonium thiosulfate (750 g / l) 107.0 ml 214.0 ml ammonium sulfite 16.0 g 32.0 g Ammonium sulfate 23.1 g 46.2 g Add water 1000 ml 1000 ml pH (adjusted at 25 ° C / acetic acid and ammonia) 6.0 6.0

[Rinse solution] [Tank solution] [Replenisher] 0.02 g 0.02 g of chlorinated sodium isocyanurate Deionized water (conductivity of 5 μS / cm or less) 1000 ml 1000 ml pH 6.5 6.5

Process B The photosensitive material 101 was processed into a roll having a width of 127 mm, and after imagewise exposure, a continuous process (running test) was performed until the capacity of the color developing tank was doubled in the following process. The processing using the running liquid was referred to as processing B. For processing, a minilab printer processor PP1258AR manufactured by Fuji Photo Film Co., Ltd., which was modified to increase the transport speed in order to shorten the processing time, was used. Processing process Temperature Time Replenishment amount ^* Color development 45.0 ° C 12 seconds 45 ml Bleaching and fixing 40.0 ° C 12 seconds 35 ml Rinse (1) 40.0 ° C 4 seconds-Rinse (2) 40.0 ° C 4 seconds - rinse (3) ** 40.0 ℃ 4 seconds - rinse (4) ** 40.0 ℃ 4 seconds 121 ml * phosphorus replenishment rate ** Fuji Photo Film Co., Ltd. rinse cleaning system RC50D per photosensitive material 1 m ² The rinsing liquid is taken out of the rinse (3) and sent to the reverse osmosis membrane module (RC50D) by a pump. The permeated water obtained in the tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. (Rinsing was carried out in a tank countercurrent system from (1) to (4).)

In this example and example 2, the drying time of treatment B was 10 seconds. The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml Dimethylpolysiloxane-based surfactant 0.1 g 0.1 g (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Tri (isopropanol) amine 8.8 g 8 8.8 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g Polyethylene glycol (molecular weight 300) 10.0 g 10.0 g Sodium 4,5-dihydroxybenzene-1,3-disulfonate 0.5 g 0.5 g Potassium chloride 10.0 g-Odor Potassium iodide 0.040 g 0.010 g Triazinylaminostilbene-based fluorescence 2.5 g 5.0 g Brightener (Hakor FWA-SF / Showa Chemical Co., Ltd.) Sodium sulfite 0.1 g 0.1 g Disodium-N, N- Bis (sulfonatoethyl) hydroxylamine 8.5 g 11.1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-amino-4-aminoaniline / 3/2 sulfuric acid monohydrate 10.0 g 22.0 g potassium carbonate 26. 3g 26.3g Add water 1000ml 1000ml pH (25 ° C / adjusted with potassium hydroxide and sulfuric acid) 10.15 12.50

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 700 ml 600 ml iron (III) ammonium ethylenediaminetetraacetate 75.0 g 150.0 g 1.4 g 2.8 g m-carboxybenzeneflufine ethylenediaminetetraacetic acid Acid 8.3 g 16.5 g Nitric acid (67%) 16.5 g 33.0 g Imidazole 14.6 g 29.2 g Ammonium thiosulfate (750 g / l) 107.0 ml 214.0 ml ammonium sulfite 16.0 g 32.0 g meta-weight Potassium sulfite 23.1 g 46.2 g Add water 1000 ml 1000 ml pH (adjusted at 25 ° C / acetic acid and ammonia) 5.5 5.5

[Rinse liquid] [Tank liquid] [Refill liquid] 0.02 g 0.02 g of chlorinated sodium isocyanurate Deionized water (conductivity of 5 μS / cm or less) 1000 ml 1000 ml pH 6.5 6.5

Example 3 Silver halide grains containing a hydrophilic binder (g / m ² ) of a silver halide emulsion layer containing a yellow dye-forming coupler with respect to the light-sensitive material 201 of Example 2 in a silver halide emulsion The value [B / AgX] divided by the thickness (μm) of
The amount of light-sensitive material and a hydrophobic photographic material amount contained in the magenta dye-forming coupler-containing layer (g / m ²⁾ a dye-forming coupler was adjusted coating amount of gelatin to be the values shown in (g / m ² ) And a photosensitive material in which the amount of the hydrophobic photographic material was adjusted so that the value [R / C] divided by the value shown in Table 5 became the value shown in Table 5, and the magenta dye-forming coupler was changed as shown in Table 5 (Sensitive materials 301 to 315), and the same evaluation as in Example 1 was performed for Process A.

[0158]

[Table 5]

[0159]

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From the results shown in Table 5, as [B / AgX] increases, the time to reach the maximum density of yellow is shortened and the character quality is improved (301A to 306A).
As [R / C] becomes smaller, the time required to reach the maximum density of magenta while maintaining the character quality is shortened (30).
7A-310A). Further, when these are combined, similar results are obtained (311A to 312A), which indicates that this is a preferred embodiment of the present invention. Further, in the case of the magenta coupler, it can be seen that the one defined by the general formula (MI) has a short time to reach the maximum density of magenta and can shorten the processing time.

Example 4 A light-sensitive material 401 was prepared by changing the composition of each layer of the light-sensitive material 101 of Example 1 as follows, and the same processing was performed. The same evaluation test as in Example 1 was performed. . As a result, the same result as in Example 1 was obtained. Further, the color mixture preventing agent (Cpd-19) used in the second layer and the fourth layer is added to the photosensitive material 401.
And a color image stabilizer (Cpd-21) were prepared in the same manner as in Example 1 as a result of preparing a photosensitive material 402 which was different only in that the mixture was replaced by an equal mass with a mass ratio of 4: 1. Was obtained.

First Layer (Blue-Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 7: 3 mixture of large-sized emulsion A having an average grain size of 0.60 μm and small-sized emulsion A of 0.52 μm (silver molar ratio) The coefficient of variation of the grain size distribution was 0.10 and 0.11, respectively.Each size emulsion contained 0.3 mol% of silver bromide locally on a part of the grain surface based on silver chloride. 0.25 gelatin 1.35 yellow coupler (ExY) 0.41 yellow coupler (ExY-2) 0.21 color image stabilizer (Cpd-1) 0.08 color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Color image stabilizer (Cpd-8) 0.04 Solvent (Solv-1) 0.23

Second layer (color mixture prevention layer) Gelatin 1.00 Color mixture inhibitor (Cpd-19) 0.05 Color mixture inhibitor (Cpd-4) 0.07 Color image stabilizer (Cpd-5) 0.007 colors Image stabilizer (Cpd-6) 0.14 Color image stabilizer (Cpd-7) 0.006 Solvent (Solv-1) 0.06 Solvent (Solv-2) 0.22

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion B (cubic, 1: 3 mixture of large-size emulsion B having an average grain size of 0.45 μm and small-size emulsion B having a 0.35 μm size (silver mole The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively. In each size emulsion, 0.4 mol% of silver bromide was locally contained in a part of the grain surface based on silver chloride.) 0.12 Gelatin 0.90 Magenta coupler (ExM-1) 0.13 Ultraviolet absorber (UV-1) 0.05 Ultraviolet absorber (UV-2) 0.02 Ultraviolet absorber (UV-3) 0.02 UV absorber (UV-4) 0.03 Color image stabilizer (Cpd-2) 0.01 Color image stabilizer (Cpd-19) 0.002 Color image stabilizer (Cpd-6) 0.08 Color image stabilizer Agent (Cpd-8) 0.01 Color image stabilizer (Cpd-9) 0 03 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-11) 0.0001 Color image stabilizer (Cpd-7) 0.004 Solvent (Solv-4) 0.19 Solvent (Solv- 9) 0.09

Fourth layer (color mixture prevention layer) Gelatin 0.71 Color mixture prevention agent (Cpd-19) 0.04 Color mixture prevention agent (Cpd-4) 0.05 Color image stabilizer (Cpd-5) 0.005 colors Image stabilizer (Cpd-6) 0.10 Color image stabilizer (Cpd-7) 0.004 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion C (cubic, 1: 4 mixture of large-size emulsion C having an average grain size of 0.50 μm and small-size emulsion C of 0.41 μm (silver mole The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively. In each size emulsion, 0.8 mol% of silver bromide was contained locally on a part of the grain surface based on silver chloride.) 0.11 Gelatin 1.13 Cyan coupler (ExC-1) 0.05 Cyan coupler (ExC-2) 0.10 Cyan coupler (ExC-4) 0.01 Color image stabilizer (Cpd-6) 0.06 colors Image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd-7) 0.01 Color image stabilizer (Cpd-14) 0.01 Color image stabilizer (Cpd-15) 0.12 Color image stabilizer Agent (Cpd-16) 0.04 Color image stabilizer (Cpd- 17) 0.07 Color image stabilizer (Cpd-18) 0.07 Solvent (Solv-5) 0.14

Sixth layer (ultraviolet absorbing layer) Gelatin 0.46 Ultraviolet absorbing agent (UV-1) 0.14 Ultraviolet absorbing agent (UV-2) 0.05 Ultraviolet absorbing agent (UV-3) 0.05 Ultraviolet absorbing Agent (UV-4) 0.04 Ultraviolet absorber (UV-5) 0.03 Ultraviolet absorber (UV-7) 0.04 Solvent (Solv-7) 0.18 Seventh layer (protective layer) Gelatin 1. 00 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.02

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Example 5 Emulsion a and emulsion b shown below
Were used in place of the blue-sensitive silver halide emulsions of Samples 102, 202, 305, 401 and 402 of the present invention, and the same tests were performed as in Examples 1-4. In the sample of this example, more excellent effects were obtained. (Emulsion a: Preparation of {111} high silver chloride tabular grains) Water 1.2
2.0 g of sodium chloride and 2.8 g of inert gelatin were added to a liter, and 45 ml of an aqueous silver nitrate solution (18 g of silver nitrate) and 45 ml of an aqueous sodium chloride solution (6.4 g of sodium chloride) were added to a container kept at 33 ° C. while stirring. It was added in one minute by the double jet method. One minute after the completion of the addition, 0.8 mmol of the crystal habit controlling agent 1 and 560 g of a 10% aqueous solution of phthalated gelatin were added. One minute later, 3.0 g of sodium chloride was added. Next, the temperature of the reaction vessel was raised to 60 ° C. in 25 minutes. After aging at 60 ° C. for 16 minutes, 3 g of sodium chloride and 1 × 10 ⁻⁵ mol of sodium thiosulfonate were added. Thereafter, 295 ml of an aqueous silver nitrate solution (118 g of silver nitrate) and 295 ml of an aqueous sodium chloride solution (50.3 g of sodium chloride and 2 × 10 5
^-8 mol of iridium hexachloride) and crystal habit controlling agent 1
160 ml of an aqueous solution (M / 50) were added at an accelerated rate over 13 minutes. Further, after 2 minutes, an aqueous solution of silver nitrate (34 g of silver nitrate) and an aqueous solution of sodium chloride (11.6 g of sodium chloride, 1.27 mg of yellow blood salt, and 0.66 g of potassium iodide) were added over 5 minutes. next,
33.5 ml of a 0.1 N thiocyanic acid solution and 0.32 mmol of sensitizing dye A, 0.48 mmol of sensitizing dye B and 0.05 mmol of sensitizing dye C were added. Temperature 40
The temperature was lowered to ° C., and desalting was carried out by a usual flocculation method. After washing with water, gelatin 67g and phenol (5%)
Was added and 150 ml of distilled water were added. The pH was adjusted to 6.2 and the pAg to 7.5 with sodium hydroxide and silver nitrate solutions. 90% or more of the obtained grains were tabular grains having an average equivalent circle diameter of 0.71 μm, an average thickness of 0.13 μm, and an average equivalent sphere diameter of 0.46 μm.

(Emulsion b: Preparation of {100} silver chloroiodide grains containing 0.4 mol% of iodine based on the total silver after the formation of 95% grains) 1200 ml of H ₂ O and gelatin ( Deionized alkali-treated bone gelatin having a methionine content of about 40 μmol / g) 25 g, sodium chloride 0.4 g, nitric acid
4.5 ml of a 1N solution was added (pH was 4.5), and the temperature was kept at 40 ° C. Next, the Ag-1 solution (silver nitrate 0.2 g / ml) and the X-1 solution (sodium chloride 0.069 g / ml) were added and mixed at 48 ml / min for 4 minutes with vigorous stirring. Fifteen seconds later, an aqueous solution of polyvinyl alcohol [containing 6.7 g of polyvinyl alcohol (hereinafter referred to as PVA-1) having an average degree of polymerization of vinyl acetate of 1700 and an average saponification rate of 98% or more to alcohol, and containing 1 liter of H ₂ O] was added. Fifteen
0 ml was added. Further, 12.3 ml of a 1N nitric acid solution was added to adjust the pH to 3.5. The temperature was raised to 75 ° C in 15 minutes, and sodium hydroxide 1
23 ml of N solution to adjust the pH to 6.5, 4.0 ml of 1- (5-methylureidophenyl) -5-mercaptotetrazole (0.05%), N, N (-dimethylimidazolidin-2-
4.0 ml of thione (1% aqueous solution) was added. Add 4 g of sodium chloride and add silver potential [vs. room temperature calomel electrode]
Was adjusted to 100 mV, and Ag-1 solution and X-1 were used as growth processes.
The solution was added simultaneously for 15 minutes while keeping the silver potential at 100 mV while linearly increasing the flow rate from 40 ml / min to 42 ml / min. Further, 12.5 ml of 1N nitric acid solution was added to adjust the pH to 4.0. After adding 28.8 g of sodium chloride and setting the silver potential to 60 mV, sensitizing dye A 0.38 mmol and sensitizing dye B 0.56
Mmol and 0.06 mmol of sensitizing dye C,
Ag-2 solution (silver nitrate 0.1g / ml) and X-2 solution (sodium chloride 0.03
(45 g / ml) at a flow rate of 40 ml / min for 7 minutes and 30 seconds. Next, 25 ml of an aqueous solution (X-4) containing 31.2 g of potassium iodide in 1 liter was added for 8 seconds. Furthermore, Ag
Solution-2 and Solution X-2 were added at a flow rate of 40 ml / min for 2 minutes and 30 seconds. Then, it was left at 75 ° C. for 10 minutes. Temperature 40 ° C
, And washed by settling and desalination. 79g gelatin
And the emulsion was redispersed to pH 6.0 and pAg 7.3. Then, a part of the emulsion was collected, and an electron microscope image (TEM image) of the grain replica was observed. According to this, 90% of the total projected area of all AgX grains are tabular grains having a principal plane of {100} plane, the average equivalent sphere diameter is 0.47 μm, the average grain thickness is 0.10 μm, and the average aspect ratio is 7 0.9, and the average adjacent side ratio was 1.2.

(Chemical Sensitization) Emulsions a and b were optimally chemically treated at 60 ° C. with sodium thiosulfonate, 1- (5-methylureidophenyl) -5-mercaptotetrazole, sodium thiosulfate and chloroauric acid. I was sensitized.

Example 6 Samples corresponding to the samples of Examples 1 to 5 in which Solv-2 was replaced with tributyl citrate and Solv-6 was replaced with pentaglycerin tribenzoate by the same mass were prepared. When an evaluation test similar to that performed in the example was performed, the same result as that of each corresponding example was obtained.

[0176]

The silver halide color photographic light-sensitive material of the present invention exhibits high image density and high whiteness on a white background in rapid processing despite reduction in the amount of a hydrophilic binder to be applied, and has a high character quality. An excellent function and effect is obtained that does not cause deterioration of image bleeding. This effect of the present invention is particularly remarkable in the case of short-time high-illuminance exposure in which exposure is performed by scanning exposure. According to the image forming method using the silver halide color photographic light-sensitive material, rapid processing is possible, and in particular, ultra-rapid processing which greatly reduces the total processing time is possible. When the silver halide color photographic light-sensitive material of the present invention is subjected to imagewise exposure, it can be applied to both surface exposure and scanning exposure. According to such an image forming method of the present invention, it is possible to form an ultra-rapid processing system in which a silver halide color photographic light-sensitive material is scanned and exposed by a light beam modulated based on image information and then developed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) G03C 5/08 G03C 5/08 7/38 7/38

Claims (5)

[Claims] 1. A support comprising at least a silver halide emulsion layer containing a yellow dye-forming coupler, a silver halide emulsion layer containing a magenta dye-forming coupler, a silver halide emulsion layer containing a cyan dye-forming coupler, a color mixture preventing layer and a protective layer. The silver halide color photographic light-sensitive material had a hydrophilic binder coating amount of 6.5 g / m ² or less in the photographic constituent layer, and when subjected to gradation exposure at 10 ^-4 seconds, the density after processing was 1.5.
From 2.0 to 2.0 for each of yellow, magenta, and cyan, and the difference between the maximum gammas for yellow, magenta, and cyan is 1.0 or less, respectively. A silver halide color photographic light-sensitive material, characterized in that the silver halide content of silver halide is 95 mol% or more. 2. In all the coupler-containing silver halide emulsion layers, the amount (g / m ² ) of the hydrophilic binder in the layer is determined by the thickness (μ) of the silver halide grains contained in the silver halide emulsion.
m) is not less than 1.5, and the amount of hydrophobic photographic material (g / m ² ) contained in the layer containing the dye-forming coupler is divided by the amount of the dye-forming coupler (g / m ² ). 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the value is 4.5 or less, and the magenta dye-forming coupler is represented by the following general formula (MI). Embedded image In the formula, Za and Zb each represent ＣC (R ₄ ) — or ＮN—, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom or a substituent, and X represents a hydrogen atom or a color. It represents a group which can be removed by a coupling reaction with an oxidized form of a developing agent. 3. A method for obtaining a color image through a processing step of color development, bleach-fixing, washing and / or stabilization, and drying after imagewise exposure of a silver halide color photographic light-sensitive material, according to claim 1 or 2, The silver halide color photographic light-sensitive material described above is subjected to a color development processing step of 5 seconds to 25 seconds, a bleach-fixing processing of 5 seconds to 25 seconds, a washing and / or stabilization processing of 10 seconds to 45 seconds, and a drying step of 5 seconds. More than 15
A color image forming method which is performed in each time within seconds. 4. The method according to claim 1, wherein the color image is obtained by subjecting the silver halide color photographic light-sensitive material to imagewise exposure, color development, bleach-fixing, washing and / or stabilization, and drying. 3. A color image forming method, comprising subjecting the silver halide color photographic light-sensitive material described in 1) to scanning exposure with a light beam modulated based on image information, followed by development processing. 5. The color image forming method according to claim 3, wherein the image-wise exposure is scanned and exposed with a light beam modulated based on image information and then developed.