JP2000250163A - Silver halide color photographic sensitive material and color image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide color photographic sensitive material which prevents plane trouble after processing, suppresses the stain of the white ground and is excellent in rapid processability by using a silver halide emulsion containing a specified spectral sensitizing dye and having a specified silver chloride content and specifying the amount of a hydrophilic binder and the amount of calcium. SOLUTION: The silver halide color photographic sensitive material has silver halide emulsion layers at least one of which comprises a silver halide emulsion containing at least one spectral sensitizing dye of the formula and having >=95 mol% silver chloride content. The amount of a hydrophilic binder in the photographic constituent layers of the sensitive material is 3.0-6.0 g/m2 and the amount of calcium is <=6.0 mg/m2. In the formula, Z1 and Z2 are each S or the like, V1 and V2 are each a monovalent substituent, R1 and R2 are each alkyl, M1 is a counter ion balanced with an electric charge, m1 is a number of >=0 and n1 and n2 are each an integer of 0-4.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material excellent in rapid processing and a color image forming method. More specifically, the present invention reduces white background contamination due to residual spectral sensitizing dye after processing, reduces the occurrence of surface failure due to the generation of aggregates of spectral sensitizing dye, and further reduces the use of unused state. The present invention relates to a silver halide color photographic light-sensitive material in which the rise of the light-sensitive material during storage is prevented, and a color image forming method using the light-sensitive material.

[0002]

2. Description of the Related Art In recent years, in the field of photo processing services, as a part of improving services for users,
As means for improving productivity, a high-quality photosensitive material that can be processed quickly is desired. At present, a photosensitive material containing a high silver chloride emulsion is processed with a color development time of 45 seconds and a total processing time of less than 4 minutes is generally used (for example, color processing CP45X manufactured by Fuji Photo Film Co., Ltd.). ).
However, compared to the total processing time of other color systems (for example, an electrostatic transfer system, a thermal transfer system, and an ink jet system), the processing time is still not satisfactory, and ultra-rapid processing with a total processing time of less than one minute is desired. It is rare. In order to achieve the above ultra-rapid processing, various studies have been made on two aspects of processing solutions and photosensitive materials. It is known in the art that from the viewpoint of the design of a photosensitive material, reducing the amount of the hydrophilic binder to be applied is advantageous in some aspects in realizing rapid processing. In JP-A-3-21947, it is possible to increase the initial swelling speed of a light-sensitive material by limiting the amount of a hydrophilic colloid to be applied, and to promote penetration of a developing agent and an alkali required at the time of development. It is stated that the washing step is advantageous because the amount of the residual active substance brought into the washing bath can be reduced.

However, even when such a photosensitive material is used, if the ultra-rapid processing as described above is applied, it is not sufficient to wash out elutes and the like from the photosensitive material in the processing step. The problem of so-called residual color, in which the blue-sensitive dye remains and contaminates the white background to impair image quality, has been insufficient. JP-A-3-1386
No. 46 also contains a fluorescent whitening agent with a specific structure in the photosensitive material, which also defines the amount of binder applied to the photosensitive material, to suppress the deterioration of the white background even in a process in which the replenishment amount of the color developer is reduced. It is disclosed that it is possible.
However, even in this light-sensitive material, the residual color level when subjected to ultra-rapid processing cannot be said to be sufficient. There is a problem that coloring is more conspicuous, and further improvement has been desired.

[0004] As for the problem of residual color due to the spectral sensitizing dye as described above, it is known that the level thereof can vary depending on the structure of the spectral sensitizing dye, and a spectral sensitizing dye having an appropriate structure is selected. Japanese Patent Application Laid-Open No. 6-230501 discloses that the residual color can be reduced by this. The present inventors intended to develop a light-sensitive material having the above-mentioned ultra-rapid processing suitability and further solving the problem of residual color. A photosensitive material using a blue-sensitive dye, which is preferable for reducing the residual color and reducing the residual color, was studied.

As a result of investigation, it has been found that these photosensitive materials have serious defects and are not practically usable, although they have excellent super-rapid processability and can reduce residual color. In other words, the use of a dye which is preferable for the residual color by reducing the amount of the coating binder, causes an agglomerate of these sensitizing dyes to be formed on the light-sensitive material after coating, which impairs the surface state. Was found to occur. Therefore, in the range of the prior art, it has been difficult to obtain a practically usable photosensitive material which has ultra-rapid processing suitability and further resolves contamination of a white background due to residual spectral sensitizing dye after processing. On the other hand, it is known that silver halide grains having a high silver chloride content suitable for rapid processing are susceptible to flaws, and various measures have been taken to reduce the fog of light-sensitive materials immediately after production and in an unused and stored state. Has been done so far. It is important to reduce the residual of spectral sensitizing dyes, and at the same time, reduce the fogging of photosensitive materials, especially during storage, in order to improve the white background of photosensitive materials. Was desired.

JP-A-1-303438 discloses that the generation of suspended matter and tar in a processing solution can be prevented by limiting the calcium content in a photosensitive material. Also, JP-A-3-29943, JP-A-3-555
No. 38 discloses that by setting the calcium content in the light-sensitive material to a certain level or more, the fogging during storage of the light-sensitive material can be suppressed. However, there is no description in these documents regarding the effect on the dye precipitate during coating which specifically occurs in the photosensitive material in which the coating amount of the hydrophilic binder is reduced as described above.

[0007]

SUMMARY OF THE INVENTION The present invention firstly provides a silver halide color photographic light-sensitive material excellent in rapid processability, in which surface failure after processing is prevented and contamination of a white background is reduced. The purpose is to: A second object of the present invention is to provide a silver halide color photographic light-sensitive material capable of preventing an increase in fogging due to storage in addition to the above-described surface failure and prevention of white background contamination. A third object of the present invention is to provide a color image forming method capable of obtaining a high-quality image in which surface failure and white background contamination are prevented even by ultra-rapid processing.

[0008]

The above objects have been achieved by the following inventions. (1) In a silver halide color photographic material having at least three silver halide emulsion layers having different color sensitivity on a support, the silver halide emulsion in at least one of the silver halide emulsion layers is as follows: It is composed of a silver halide emulsion containing at least one kind of spectral sensitizing dye represented by the general formula (I) and having a silver chloride content of 95 mol% or more, and has a hydrophilic property in a photographic constituent layer of a silver halide color photographic light-sensitive material. When the amount of the binder is 3.0 g / m ² or more and 6.0 g / m ² or less,
A silver halide color photographic light-sensitive material, wherein the calcium content is 6.0 mg / m ² or less.

[0009]

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(Wherein, Z₁And Z_TwoAre independently sulfur fields
Represents a selenium atom or an oxygen atom. V₁And V_Two
Represents a monovalent substituent. Where V₁And V_TwoIs aromatic
Is not a group, and is condensed with two or more adjacent groups.
It does not form a fused ring. R ₁, R_TwoAre each independently
Represents a kill group;₁Represents a charge-balancing counter ion. m₁
Represents the number of zero or more necessary to neutralize the molecular charge
Then n₁And n_TwoRepresents an integer of 0 to 4. (2) The pH of the film composed of the photographic constituent layer is 4.0 to 6.5.
The silver halide powder according to item (1),
Color photographic material. (3) It contains an antioxidant having a molecular weight of 330 or less.
Silver halide color according to (1) or (2),
-Photosensitive materials. (4) The antioxidant is represented by the following general formula (II)
(3) The silver halide color photographic feeling as described in (3) above,
Light material.

[0011]

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(In the formula, Z ₁₁ represents an atom group necessary for completing a carbocyclic or heterocyclic ring, and may be further substituted by a substituent.) (5) Silver chloride content of 95 mol% or more The silver halide emulsion according to any one of (1) to (4), wherein the silver halide emulsion contains 0.01 to 1 mol% of silver iodide per 1 mol of the silver halide. Color photographic light-sensitive material. (6) In an image forming method in which a silver halide color photographic light-sensitive material is scanned and exposed with a light beam modulated based on image information, and then developed, the silver halide color photographic light-sensitive material is (1) to (5). 13. A color image forming method, comprising the silver halide color photographic light-sensitive material according to any one of the above items. (7) A color image forming method, wherein the silver halide color photographic material according to any one of (1) to (5) is processed with a color development time of 20 seconds or less.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION

First, the spectral sensitizing dye of the present invention represented by formula (I) will be described in detail. In the general formula (I), Z ₁ and Z ₂ represent a sulfur atom, a selenium atom or an oxygen atom. Preferably, at least one of Z ₁ and Z ₂ is a sulfur atom.

V ₁ and V ₂ represent a monovalent substituent. However,
V ₁ and V ₂ are not aryl groups, and _two adjacent groups do not bond to each other to form a fused ring. n ₁ and n ₂ represents an integer of 0-4. R ₁ and R ₂ represent an alkyl group. M ₁ represents a charge balancing counter ion, and m ₁ represents a number of 0 or more necessary to neutralize the charge of the molecule.

Hereinafter, the compounds used in the present invention will be described in detail. Z ₁ and Z ₂ represent a sulfur atom, a selenium atom or an oxygen atom. Preferably, at least one of Z ₁ and Z ₂ is a sulfur atom. More preferably, both Z ₁ and Z ₂ are sulfur atoms.

As V ₁ and V ₂ , any monovalent substituent may be used as long as it does not form an aromatic group or a condensed ring when two adjacent groups are fused to each other. V is a monovalent substituent
Then, for example, a halogen atom (for example, chlorine, bromine,
Iodine, fluorine), mercapto group, cyano group, carboxyl group, phosphate group, sulfo group, hydroxy group, carbamoyl group having 1 to 10, preferably 2 to 8, more preferably 2 to 5 carbon atoms ( For example, methylcarbamoyl, ethylcarbamoyl, morpholinocarbonyl), having 0 to 10 carbon atoms, preferably 2 to 8 carbon atoms,
More preferably, a sulfamoyl group having 2 to 5 carbon atoms (eg, methylsulfamoyl, ethylsulfamoyl), a nitro group, 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms. Alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-phenylethoxy)

An acyl group having 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (eg, acetyl, benzoyl, trichloroacetyl), 1 to 20 carbon atoms, preferably 2 to 20 carbon atoms 1
2, more preferably an acyloxy group having 2 to 8 carbon atoms (eg, acetyloxy), an acylamino group having 1 to 20, preferably 2 to 12, and more preferably 2 to 8 carbon atoms (eg, acetylamino); C1 to C20, preferably C1 to C10, more preferably C1 to C8 sulfonyl group (for example, methanesulfonyl, ethanesulfonyl, benzenesulfonyl, etc.), C1 to C20, preferably C1 to C20 1
0, more preferably a sulfinyl group having 1 to 8 carbon atoms (for example, methanesulfinyl, benzenesulfinyl), 1 to 20 carbon atoms, preferably 1 to 1 carbon atom
0, more preferably a sulfonylamino group having 1 to 8 carbon atoms (eg, methanesulfonylamino, ethanesulfonylamino, etc.);

An amino group, a substituted amino group having 1 to 20, preferably 1 to 12, more preferably 1 to 8 carbon atoms (eg, methylamino, dimethylamino,
Benzylamino, anilino), an ammonium group having 0 to 15 carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 6 carbon atoms (for example, trimethylammonium group, triethylammonium group), and 0 to 15 carbon atoms.
Preferably, the hydrazino group has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms (for example, trimethylhydrazino group), 1 to 15 carbon atoms, preferably 1 to 1 carbon atoms.
0, more preferably a ureido group having 1 to 6 carbon atoms (e.g., ureido group, N, N-dimethylureido group), 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. An imide group (eg, a succinimide group), an alkyl or arylthio group having 1 to 20, preferably 1 to 12, and more preferably 1 to 8 carbon atoms (eg, methylthio, ethylthio, carboxyethylthio, sulfobutylthio, etc.) An alkoxycarbonyl group having 2 to 20 carbon atoms, preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms (for example, methoxycarbonyl, ethoxycarbonyl);

An unsubstituted alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methyl, ethyl, propyl, butyl), and 1 to 18 carbon atoms, preferably 1 to 1 carbon atoms
0, more preferably a substituted alkyl group having 1 to 5 carbon atoms (hydroxymethyl, trifluoromethyl, benzyl,
Carboxyethyl, ethoxycarbonylmethyl, acetylaminomethyl, and here, preferably, an unsaturated hydrocarbon group having 2 to 18 carbon atoms, more preferably 3 to 10 carbon atoms, particularly preferably 3 to 5 carbon atoms (for example, vinyl group Ethynyl group and 1-cyclohexenyl group) are also included in the substituted alkyl group. ),

An optionally substituted heterocyclic group having 1 to 20 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 4 to 6 carbon atoms (eg, pyridyl, 5-methylpyridyl, thienyl, furyl, morpholino, tetrahydro Furfuryl). Further, V may be further substituted on these substituents.

Preferred as V ₁ and V ₂ are the aforementioned alkyl groups, alkoxy groups, halogen atoms, acyl groups,
It is a cyano group, more preferably an alkyl group, an alkoxy group, a cyano group, and a halogen atom, and particularly preferably a methyl group, a methoxy group, a cyano group, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. n ₁ and n ₂ are 0,
1, 2, 3 or 4, preferably 0, 1, 2, more preferably 1, 2 and particularly preferably 1
It is. When n ₁ and n ₂ are 2 or more, V ₁ and V ₂ are repeated, but need not be the same.

M ₁ is included in the formula to indicate the presence of a cation or an anion when necessary to neutralize the ionic charge of the dye. Typical cations include inorganic ions such as hydrogen ions (H ⁺ ), alkali metal ions (eg, sodium ion, potassium ion, lithium ion), alkaline earth metal ions (eg, calcium ion), and ammonium ions (eg, Organic ions such as ammonium ion, tetraalkylammonium ion, pyridinium ion, and ethylpyridinium ion. The anion may be either an inorganic anion or an organic anion,
Halogen anions (for example, fluorine ions, chlorine ions,
Iodine ion), substituted arylsulfonate ion (eg, p-toluenesulfonic acid ion, p-chlorobenzenesulfonate ion), aryldisulfonic acid ion (eg, 1,3-benzenesulfonic acid ion, 1,5-naphthalenedisulfonic acid ion) , 2,6-naphthalenedisulfonic acid ion), alkyl sulfate ion (eg, methyl sulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, trifluoromethanesulfonic acid Ions. Further, another dye having a charge opposite to that of the ionic polymer or the dye may be used. In addition, CO ₂ ^-,
SO ₃ ^-, when having a hydrogen ion as a counter ion CO ₂ H,
It can be written as SO ₃ H. m ₁ represents the number necessary to balance the charges, and is 0 when a salt is formed in the molecule. It is preferably 0 to 10, more preferably 0 to 4, and particularly preferably 0 or 1.

R ₁ and R ₂ each represent an alkyl group, for example, an unsubstituted alkyl group having 1 to 18, preferably 1 to 7, and particularly preferably 1 to 4 carbon atoms (eg, methyl, ethyl, propyl, isopropyl) Butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), substituted alkyl groups of 1 to 18, preferably 1 to 7, particularly preferably 1 to 4 carbon atoms, such as V mentioned as substituents such as Z ₁ above. _And a heterocyclic group substituted by ₁ . Preferably, an aralkyl group (eg, benzyl, 2-phenylethyl), an unsaturated hydrocarbon group (eg, an allyl group), a hydroxyalkyl group (eg, 2-
Hydroxyethyl, 3-hydroxypropyl), carboxyalkyl group (eg, 2-carboxyethyl, 3-
Carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxyalkyl group (for example, 2-methoxyethyl, 2- (2-methoxyethoxy) ethyl),
Acyloxyalkyl group (eg, 2-acetyloxyethyl), acylalkyl group (eg, 2-acetylethyl), carbamoylalkyl group (eg, 2-morpholinocarbonylethyl), sulfamoylalkyl group (eg, N, N-dimethylcarbamoylmethyl) , A sulfoalkyl group (for example, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, 2- [3-
Sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl),
Sulfoalkenyl group, sulfatoalkyl group (for example,
2-sulfatoethyl group, 3-sulfatopropyl, 4
-Sulfatobutyl), a heterocyclic-substituted alkyl group (eg, 2- (pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl), an alkylsulfonylcarbamoylmethyl group (eg, a methanesulfonylcarbamoylmethyl group)}. .

The alkyl group of R ₁ and R ₂ is preferably a carboxyalkyl group, a sulfoalkyl group,
It is an unsubstituted alkyl group, and more preferably a sulfoalkyl group. Hereinafter, specific examples of the compound of the general formula (I) of the present invention are shown, but the present invention is not limited thereto.

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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The compound represented by the general formula (I) of the present invention can be prepared by the method described in FM Harmer, "Heterocyclic Compounds-Cysteine Soybeans and Related Compounds (Heterocyclic Compounds-Cy).
anine Dyes and Related Compounds), John Wiley & Sons, New York, London, 1964, DMSturmer, Heterocyclic Compounds-Special Topics. In Heterocyclic Compounds-Special top
ics in heterocyclic chemistry) ", Chapters 18, 14
Verses 482-515, John Wiley & Sons, Inc.-New York, London, 1977, "Rods Chemistry of
Carbon Compounds (Rodd's Chemistry of Carbon)
Vol. IV, part B, 1977, Chapter 15, pages 369-422, Elsevier Scien Public Company, Inc.
ce Publishing Company Inc.), New York, and the like.

To incorporate the sensitizing dye used in the present invention into silver halide, the sensitizing dye may be directly dispersed in the emulsion, or may be dispersed in water, methanol, ethanol, propanol, acetone, methylcellosolve. , 2,2,3
3-tetrafluoropropanol, 2,2,2-trifluoroethanol, 3-methoxy-1-propanol,
3-methoxy-1-butanol, 1-methoxy-2-propanol, acetonitrile, tetrahydrofuran,
It may be added by dissolving in a solvent such as N, N-dimethylformamide alone or in a mixed solvent. Further, as described in U.S. Pat. No. 3,469,987, a dye is dissolved in a volatile organic solvent, the solution is dispersed in water or a hydrophilic colloid, and this dispersion is added to an emulsion. As described in JP-B-46-24185, a method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it and adding this dispersion to an emulsion, US Pat. No. 3,822 No. 135, U.S. Pat. No. 4,006,025.
JP-A-53-102733, JP-A-58-102, a method of adding an aqueous solution or colloidal dispersion in the presence of a surfactant to an emulsion as described in
No. 105141, a method of directly dispersing a dye in a hydrophilic colloid and adding the dispersion to an emulsion, and a method of using a red-shifting compound as described in JP-A-51-74624. A method of dissolving and adding the solution to the emulsion may be used. Also, ultrasonic waves can be used for dissolution. A more preferred method of incorporating the dye used in the present invention into the silver halide of the present invention is an aqueous solution in which the dye is dissolved in water or a hydrophilic colloid, or a solution having a solubility at 25 ° C. of 1.5 × 10 ⁻² mol / mol. In the case of a dye of 1 liter or less, this is a method of dispersing as fine particles of 1 μm or less in water or a hydrophilic colloid, and adding it as a dispersion. A method of dissolving or dispersing in a water-soluble organic solvent or an aqueous solution of a water-soluble organic solvent is also preferably used, but the amount of the added organic solvent is more preferably 5% by volume or less of the amount of the prepared silver halide emulsion. . Furthermore, when the solubility of the dye used in the present invention at 25 ° C. is 5 × 10 ⁻⁴ mol / l or more, a method in which these cyanine dyes are directly added to a silver halide emulsion in a finely pulverized solid state Is also preferred.

The sensitizing dye to be used in the present invention may be added to the silver halide emulsion of the present invention at any time during the preparation of the emulsion which has been found to be useful. For example, US Pat. No. 2,735,766, US Pat. No. 3,628,960, US Pat.
756, U.S. Pat. No. 4,225,666;
As disclosed in the specification of JP-A-8-184142 and JP-A-60-196749, the stage before silver halide grain formation and / or before desalination, during and / or after desalination. Until the start of chemical ripening,
As disclosed in the specification such as -113920,
It may be added at any time during the process just before or during the chemical ripening, during the process, or before the application of the emulsion before the coating after the chemical ripening. Preferably, it is before the desalting step for removal. No. 4,225,666;
As disclosed in the specification such as No. 8-7629, the same compound may be used alone or in combination with a compound having a different structure, for example, during the same step, or during the particle formation step and during the chemical ripening step or during the chemical ripening step. After completion, or may be divided and added to different steps such as before or during chemical ripening or during and after the process, and also by changing the type of compound and compound combination to be divided and added. It may be added. Further, a predetermined amount may be added in a short time, or for a long time, for example, continuously in any step from the nucleation in the particle forming step to the completion of the particle formation or most of the chemical ripening step. It may be added. In such a case, the addition speed may be a constant flow rate, or the flow rate may be accelerated or decelerated.
The temperature at which the sensitizing dye is added to the silver halide emulsion is not particularly limited, but is usually 35 ° C. to 70 ° C., and the addition temperature and the ripening temperature may be changed. After adding at 45 ° C. or less, a method of raising the temperature and aging is more preferable.

The total amount of the dye used in the present invention is as follows:
Depending on the shape and size of the silver halide grains, 5.5 × 10 ^{−6 to} 1.2 × 10 per mol of silver halide.
^-2 moles can be used. For example, when the silver halide grain size is 0.2 to 2.0 μm, 4.0 × 10 ^{−7 to} 6.5 per 1 m ² of the surface area of the silver halide grains.
The addition amount of × 10 ⁻⁶ mol is preferred, and 1.0 × 10 ⁻⁶ to
An addition amount of 4.2 × 10 ⁻⁶ mol is more preferred.

In the silver halide color photographic light-sensitive material of the present invention, gelatin is used as a hydrophilic binder. If necessary, other gelatins, gelatin derivatives, graft polymers of gelatin and other high polymers, and non-gelatin Hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as homopolymers and copolymers 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, and may be produced using any of bovine bone, cowhide, pork skin and the like. Although gelatin may be used, lime-processed gelatin obtained from cow bone and pig skin is preferred. In the present invention, a photosensitive silver halide emulsion layer ranging from a 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 from the support; The total amount of the hydrophilic binder contained in the non-photosensitive hydrophilic colloid layer is 3.0 g / m ² or more and 6.0 g / m ² or less from the viewpoint of rapid processing suitability.
More preferably, it is 3.0 g / m ² or more and 5.8 g / m ² or less, most preferably 4.0 g / m ² or more and 5.5 g / m ² or less. 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 silver halide emulsion layer farthest from the support is defined as a halide such that the silver halide emulsion contained in the layer is developed and substantially contributes to dye formation by reaction with a coupler. Refers to a layer containing a silver emulsion. Therefore, a fine grain emulsion having substantially no sensitivity or a layer containing only colloidal silver and no coupler is not applicable.

In the present invention, the ratio [amount of hydrophilic binder / silver halide emulsion thickness] in the silver halide emulsion layer containing a yellow coupler is preferably 1.50 or more. Hereinafter, this ratio is referred to as [B /
AgX] ratio. Here, the hydrophilic binder amount is
The amount of hydrophilic binder per 1 m ^{2 of the} silver halide emulsion layer (g / m ² ). The amount of the hydrophilic binder is divided by the specific gravity to represent the thickness, and it is understood that the amount of the hydrophilic binder in 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, the [B / AgX] ratio in the present invention indicates that as the ratio increases, the emulsion thickness in the emulsion layer relatively decreases. In the present invention, the [B / AgX] ratio is preferably 1.50 or more, more preferably 1.70 or more, still more preferably 1.90 or more, and most preferably 6 from the viewpoint of suppressing pressure fogging streaks and reducing color mixture during processing. 0.0 or more.

In the silver halide emulsion layer containing a yellow coupler in the present invention, the amount of hydrophilic binder is preferably 1.35 g / m ² or less, more preferably 1.25 g / m ^2.
/ M ² or less, most preferably 1.20 g / m ² or less 0.6
0 g / m ² or more. The silver halide emulsion thickness is preferably 0.80 μm or less when cubic grains are used,
More preferably, it is 0.75 μm or less, most preferably 0.1 μm or less.
70 μm or less and 0.30 μm or more. When tabular grains are used, the particle size is preferably 0.30 μm or less, more preferably 0.20 μm or less, and most preferably 0.15 μm or less 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, and 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.

More preferably, the silver halide grains of the present invention contain at least 0.1 mol% of silver iodide per mol of total silver halide of the grains on the surface portion outside 50% or more by volume. This is the case where a silver iodide-containing phase is contained. The term “silver iodide-containing phase” as used herein means a region in which the local content of silver iodide is relatively higher in other regions in the grain. The local silver iodide content in the silver iodide-containing phase is not particularly limited, but is preferably in the range of 0.2 mol to 100 mol% of the silver halide in the phase, more preferably 0 mol%. It is from 0.4 mol% to 13 mol%, more preferably from 1 mol% to 5 mol%. The halogen composition other than silver iodide in the silver iodide-containing phase comprises silver chloride or silver bromide, and the ratio of silver chloride to silver bromide is preferably 90% or more.

It is desirable that the local silver iodide content in the silver iodide-containing phase is uniform in order to avoid the occurrence of desensitizing lines due to external pressure. The silver iodide-containing phase is
It does not have a layer containing no silver iodide on its outside and has a shell structure composed of uniform silver iodochloride or silver iodochlorobromide located 50% or more by volume from the center of the grain. Is desirable. When a layer not containing silver iodide is further provided outside the silver iodide-containing phase, the thickness of the layer not containing silver iodide is 0.002 μm or less. The ratio of the volume of the silver iodide-containing phase to the grain volume is less than 50%, preferably less than 20%, and more preferably less than 10%. Reducing the volume ratio of the silver iodide-containing phase while maintaining the local silver iodide content of the silver iodide-containing phase can reduce the total amount of iodide used while maintaining the effects of the present invention. It is preferable from the viewpoint of quick processing and the like. However, when the volume ratio of the silver iodide-containing phase is extremely reduced,
Care must be taken since the influence of the intergranular distribution on the formation state of the silver iodide-containing phase may increase. It is desirable that the total amount of silver iodide in the present invention does not exceed 1 mol% per mol of silver halide grains. Further, the distribution of silver iodide content between grains is preferably as narrow as possible.
% Is desirable. The formation of the silver iodide-containing phase
It is preferably carried out by simultaneously adding a soluble silver salt and a soluble halide salt containing iodide ions to the reaction vessel during the formation of high silver chloride grains by a simultaneous mixing method.
Alternatively, it can be preferably formed by adding a previously prepared fine grain emulsion containing silver iodide alone or simultaneously with the addition of a soluble silver salt and / or a soluble halide salt. When a silver iodide-containing phase is formed by adding a previously prepared fine grain emulsion, it is preferable that the silver halide grains in the fine grain emulsion have no twin plane. Further, from the viewpoint of enhancing the intergranularity of the silver iodide-containing phase, a sustained release iodine compound as described in JP-B 1-285942 can be preferably used.

The silver halide grains in the present invention preferably further have a localized phase in which the silver bromide content exceeds at least 10 mol%. Such an arrangement of the localized phase having a high silver bromide content is desirably in the vicinity of the grain surface from the viewpoints of pressure properties, processing solution dependence and the like. Here, “near the grain surface” means a position within 1/5 of the grain volume of the silver halide grains to be used, as measured from the outermost surface. 1 of the volume of the silver halide grains used, measured from the outermost surface
The position is preferably within / 10. The most preferred configuration of the silver bromide containing phase is cubic, tetradecahedral, (100)
Tabular grains having major planes or (11
1) A localized phase having a silver bromide content exceeding at least 10 mol% is epitaxially grown at a corner of a tabular grain having a (100) main plane having a plane. The silver bromide content of the localized phase having a high silver bromide content is preferably more than 10 mol%, but if the silver bromide content is too high, desensitization occurs when pressure is applied to the light-sensitive material. In addition, characteristics unfavorable for a photographic light-sensitive material such as a change in sensitivity and gradation due to a change in the composition of the processing solution may be imparted. Taking these points into consideration, the silver bromide content of the localized phase having a high silver bromide content is preferably in the range of 10 to 60 mol%, and 20 to 50 mol%.
A mole% range is most preferred.

The localized phase having a high silver bromide content is 0.1% of the total silver constituting the silver halide grains contained in the emulsion of the present invention.
It is preferably composed of 1% to 10% silver, more preferably 0.5% to 5% silver. Various methods can be used to form such a localized phase having a high silver bromide content. For example, a localized phase can be formed by reacting a soluble silver salt and a soluble halogen salt by a one-side mixing method or a simultaneous mixing method. Furthermore, the silver halide grains already formed are
It can also be formed by using a conversion method for converting into silver halide having a lower solubility product. For example, cubic, tetrahedral, tabular grains having a (100) major plane,
A water-soluble bromide solution is added to a tabular silver halide host grain having a (100) major plane having a (111) plane at a corner, or the grain size is smaller than the silver halide host grain, and Silver bromide with a high silver chloride content,
A mixed phase of silver chlorobromide, silver iodobromide, or silver iodochlorobromide fine grains is mixed and then ripened to form a localized phase having a high silver bromide content.

The interface between the silver iodide-containing phase and the silver bromide localized phase and the other phase having a different halogen composition forms a mixed crystal due to the difference in composition, even if the interface has a clear phase boundary. The boundary may be an unclear boundary, or may have a positively continuous structural change. The silver iodide content in the silver iodide-containing phase and the silver bromide content in the silver bromide-localized phase were determined by X-ray diffraction (for example, “The Chemical Society of Japan, New Experimental Chemistry Course 6, Structural Analysis” Maruzen, And the like.). When the iridium compound is contained in the silver halide grains of the present invention,
Preferably, at least 50% of the iridium compound is present at the time of deposition of the silver bromide localized phase, and more preferably, 80% or more of the iridium compound is present at the time of deposition of the silver bromide localized phase. It is particularly preferable in the present invention to form a silver bromide localized phase by adding a silver bromide fine grain emulsion containing an iridium compound in advance. The silver halide grains of at least one layer (preferably all layers) of the silver halide emulsion layer used in the present invention include:
Silver iodochloride or silver iodochlorobromide comprising 95 mol% or more of silver chloride is also preferable. The silver chloride content is preferably at least 95 mol%, more preferably at least 98 mol%. The emulsion is preferably used in an amount of 0.01 to 1 based on the silver halide.
Mol%, more preferably 0.02 to 0.08 mol%. In the present invention, the halogen composition of the emulsion may be different or the same between grains. However, when an emulsion having the same halogen composition between grains is used, it is easy to make the properties of each grain uniform.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0.1. 1 μm to 2 μm is preferred. The particle size distribution is preferably a so-called monodisperse coefficient of variation (a standard deviation of the particle size distribution divided by the average particle size) of 20% or less, preferably 15% or less, and more preferably 10% or less. It is desirable to make the grain size distribution monodisperse from the viewpoint of forming a silver iodide-containing phase or a silver bromide localized phase uniformly among grains in the present invention. In order to obtain a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to apply a multilayer coating. The present invention can be applied to octahedral, tabular grains having a (111) major plane or grains having a higher crystal plane. (1) Plane, flat plate having (100) main plane or (111) plane at corners
00) It is preferably a flat plate having a main plane. More preferably, the shape of the silver halide grains in the present invention is a cubic or tabular grain substantially containing no higher-order planes other than the (100) plane. Here, the expression that substantially no higher-order planes other than the (100) plane are included means that 95% or more of the total surface area of the silver halide grains is composed of the (100) plane. Further, the shape of the silver halide grains in the present invention is preferably a cubic or tabular grain in which the (100) plane accounts for 98% or more of the total surface area. When the silver halide grains in the present invention are tabular grains, the tabular grains having an aspect ratio of 2 or more, more preferably 5 or more, have a total projected area of 5 or more.
Preferably, it is occupied by 0% or more. The aspect ratio referred to here is a value obtained by dividing the diameter of a circle having an area equal to the area of the main plane of the tabular grains by the distance between the main planes of the tabular grains (ie, the thickness of the tabular grains).

The silver iodochloride emulsion or silver iodochlorobromide emulsion used in the present invention is preferably a P.I. Chimi by Glafkides
e et Physique Photographi
que (Paul Montel, 1967),
G. FIG. F. Photographic by Duffin
Emulsion Chemistry (FocalP
Res., 1966); L. Zelikma
Making and Coatin by net et al
g Photographic Emulsion (F
ocal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt with a soluble halide salt includes any method such as a one-sided mixing method, a simultaneous mixing method, and a combination thereof. May be used. A method of forming particles in an atmosphere containing excess silver ions (so-called reverse mixing method) can also be used. As one type of the double jet method, a method in which pAg in a liquid phase in which silver halide is formed is kept constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained. Furthermore, tabular grains having a (100) major plane can be formed by referring to, for example, the method described in JP-A-7-168296.

It is preferable that the localized phase of the silver halide grains of the present invention or the substrate thereof contains a foreign metal ion or a complex ion thereof. Preferred metals are selected from metal ions or metal complexes belonging to Groups VIII and IIb of the periodic table, lead ions and thallium ions. Ion selected from iridium, rhodium, iron, etc. or its complex ion for the localized phase, and metal ion selected from osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel, iron, etc. for the substrate Alternatively, the complex ions can be used in combination. Further, the type and concentration of the metal ion can be changed depending on the localized phase and the substrate. A plurality of these metals may be used. In particular, the iron and iridium compounds are preferably present in the localized phase of silver bromide and / or in the phase containing silver iodide. In particular, the iridium compound has at least 5
Preferably 0% is present in the localized silver bromide phase, more preferably at least 80% is present in the localized silver bromide phase. The amount of the iridium compound used in the present invention depends on the grain size, but is 1 × 1 per mol of silver halide.
0 ^-9 mol to 10 ^-3 mol, preferably 5 × 10 ^-8 to
It is in the range of 1 × 10 ^-5 mol. These metal ion-providing compounds may be used in the form of an aqueous gelatin solution, an aqueous halide solution, an aqueous silver salt solution, or other aqueous solutions that serve as a dispersion medium when forming silver halide particles, or silver halide fine particles containing metal ions in advance. And dissolving the fine particles in the localized phase of the silver halide grains of the present invention and / or other grains (substrate). The metal ions used in the present invention can be contained in the emulsion grains either before, during or immediately after grain formation. This can be changed depending on where the metal ions are contained in the particles.

Chemical sensitization and spectral sensitization can be carried out according to the compounds described in paragraphs (0045) to (0067) of JP-A-7-168296 and the use thereof. To the silver halide emulsion used in the present invention, various compounds or their precursors are added for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. be able to. As specific examples of these compounds, those described in paragraph (0060) of JP-A-7-168296 and pages 39 to 72 of JP-A-62-215272 are preferably used. Further, a 5-arylamino-1,2,3,4-thiatriazole compound (the aryl residue has at least one electron-withdrawing group) described in European Patent (EP) 447647 is also preferably used.

The amount of calcium in the photographic constituent layer referred to in the present invention refers to the sum of calcium ion and calcium in water-soluble calcium. In the present invention, it is necessary that the total amount of calcium atoms in the light-sensitive material is 6.0 mg / m ² or less. A method for determining total calcium atoms in a photosensitive material is ICP (Inductively Coupled P).
lasma) emission spectroscopy is preferred. This analysis method is described in Chemistry Special Edition 127 (Nankodo 1980) and V. A. Fassel: Anal. Che
m. , 46, 1110 (1974) (title Indu
Ctively Coupled Plasma Em
issue Spectroscopy). Gelatin used as a binder in a silver halide color photographic light-sensitive material usually contains, for example, a considerable amount of a calcium salt coming from, for example, a raw material bone or the like (thousands of ppm in terms of calcium atoms). degree.
Hereinafter, in this specification, the amount of calcium (calcium salt amount)
Represents a calcium atom unless otherwise specified).
For this reason, in practically used color photographic materials, although it depends of course on the amount of gelatin applied, usually 15 mg /
m ² or more calcium is contained.

The calcium content in the light-sensitive material is specified, for example, in JP-A-60-159850, which relates to a change in photographic properties during continuous processing of a specific magenta coupler. It was completely unexpected that the use of a preferred dye for preventing color and the reduction of the amount of the hydrophilic binder could change the occurrence of unexpected dye agglomerates. In the present invention, the calcium content in the light-sensitive material is 6.0 mg /
m ² or less, preferably 4.0 mg / m ² or less, more preferably 3.0 mg / m ² or less. By defining the amount of calcium in this way, it is possible to prevent the occurrence of aggregates of the spectral sensitizing dye represented by the general formula (I) and to provide a photosensitive material with reduced planar failure.

Various methods are conceivable for realizing the embodiment of the present invention. For example, the following methods can be mentioned. (1) A raw material gelatin having a low calcium content is used in the production of a photosensitive material. (2) Additives containing gelatin, such as gelatin solutions, emulsions, silver halide emulsions, etc., are desalted in advance during the production of photosensitive materials by noodles, washing with water, dialysis or the like.

Of the above, in terms of the production stability of the photosensitive material (1)
Is preferred. The calcium content in gelatin is reduced, so-called deionized gelatin (Ca content of 100 pp.
m) or less, for example, treatment with an Na ⁺ type or H ⁺ type ion exchange resin, or dialysis treatment, etc. It can be advantageously used in the present invention.

At the time of producing a light-sensitive material, gelatin is added in the form of a gelatin solution or the like as an emulsion containing a silver halide emulsion, a coupler or the like, or as a simple binder. Therefore, the photosensitive material of the present invention can be prepared by using gelatin having a low calcium content for all or a part of these additives.

The antioxidant used in the present invention preferably has a molecular weight of 330 or less. Although the lower limit is not particularly limited, a molecular weight of 40 or more is preferable. Particularly preferred are those having a molecular weight of 200 to 330.

Further, the antioxidant used in the present invention is preferably a compound having an oxidation potential Eox of Eox ≦ 1.5 (V). More preferably, Eox ≦ 1.2 (V). More preferably, 0.3 ≦ Eox ≦ 0.8 (V). The oxidation potential Eox of the antioxidant can be easily measured by those skilled in the art. The method is described, for example, in A. Stanienda's dissertation "Naturwissenschaften" (Naturwissens).
chaften) 47, 353 and 512 (19
1960), "New Instrumental Methods in Electrochemistry" by P. Delahay (New Instrument)
al Methods in Electrochem
Istry) (1954), Interscience Publisher
ishers) and L. Mites
s) "Polarographic Techniques" (Po
Larographic Techniques) Second
Edition (1965), Interscience Publisher
s) Published in company publications. The value of Eox is:
The potential at which the compound abstracts its electrons at the anode in portammetry, and is primarily related to the highest occupied electron energy level in the ground state of the compound.

Eox in the present invention is defined by the following conditions:
Is the value obtained from the polarographic half-wave potential at
You. That is, acetonitrile as a solvent for the antioxidant,
Using 0.1N sodium perchlorate as a supporting electrolyte,
Antioxidant concentration 10^-3-10 ^-FourMol / l, see
An Ag / AgCl electrode was used as the electrode, and Eox was measured.
The measurement was performed at 25 ° C. using a rotating platinum plate electrode.

This antioxidant is most preferably added directly to the silver halide emulsion layer of the photographic light-sensitive material of the present invention and contained therein, but the intermediate layer, the protective layer, the yellow filter layer,
It may be added to a non-photosensitive layer using a hydrophilic colloid as a binder, such as an antihalation layer. It is also effective to add it to both the photosensitive emulsion layer and the non-photosensitive layer. When the antioxidant is added to the photosensitive emulsion layer, it may be added at any time before coating, but is preferably added from chemical ripening to coating, and more preferably added after chemical ripening. Just fine. Further, it may be added to the non-photosensitive layer and diffused throughout the photographic constituent layer at the time of coating.

The antioxidant is water or a low water-compatible low-oxidant.
Grade alcohols, esters or ketones or these
May be added after dissolving in a mixed solvent. Also high boiling point
It may be dispersed and added after dissolving in a solvent or the like. Addition amount is halogen
10 per mole of silver halide^-2-10 ^-8Molar ranges are preferred,
10^-3-10^-FiveThe molar range is particularly preferred, but the amount added is
Depending on the type of silver halide, antioxidant, etc.
Just choose. When it is contained in the non-photosensitive layer,
In the range of 0.01 to 50 g / g of hydrophilic colloid,
More preferably, in the range of 0.05 to 10 g, an antioxidant
Good by applying aqueous solution of hydrophilic colloid containing
Good results can be obtained. In addition, the antioxidant alone
May be used, or may be used in combination.

Specific examples of the antioxidant include the following compounds, but are not limited thereto.

[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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[0080]

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Preferred antioxidants are represented by the above general formula (II). In the formula, Z ₁₁ represents a group of atoms necessary to form a carbocyclic or heterocyclic ring. Preferred specific examples of the carbon ring include a benzene ring and a naphthalene ring, and preferable specific examples of the heterocyclic ring include Is a 7-membered ring containing an oxygen atom as a hetero atom. Specific examples of the substituent that can be substituted on these rings include an alkyl group, an alkoxy group, an alkoxycarbonyl group, a hydroxyl group,
And sulfonic acid groups.

Among the compounds of the general formula (II), at least one sulfonic acid group (sulfonic acid salt) on the aromatic carbon ring
Are particularly preferred. Particularly preferred specific examples of the antioxidant include the specific examples II- (19) and II-
(22), II- (39) and the like. As the antioxidant having a molecular weight of 330 or less, the following antioxidants (1) and (2) are preferable in addition to the compound represented by the general formula (II). (1) One of the substituents at the 2-position is a group selected from a hydroxy group, an amino group and a substituted amino group, the other is a hydrogen atom, and one of the substituents at the 3-position is a hydroxy group, an amino group and A 2-cyclopenten-1-one derivative which is a group selected from substituted amino groups and the other is a hydrogen atom. (2) One of the substituents at the 2-position is a group selected from a hydroxy group, an amino group and a substituted amino group, the other is a hydrogen atom, and one of the substituents at the 3-position is a hydroxy group, an amino group and A 2-cyclohexen-1-one derivative which is a group selected from substituted amino groups and the other is a hydrogen atom.
In (1) and (2), a compound in which the 2-position is a hydroxy group and the 3-position is an amino group or a substituted amino group is more preferable. Among (1) and (2), (1) is preferable,
Among them, the 3-position is pyrrolidin-1-yl, piperidin-1-yl or morpholin-1-yl, and 2
Most preferred is a hydroxy group. Specific examples include (II)-(48) and (II)-(49) of exemplary compounds.

In the present invention, the oil-soluble component in the photographic constituent layer is a lipophilic component remaining in the photographic material after processing. Specific examples include couplers, color mixture inhibitors, ultraviolet absorbers, lipophilic additives, lipophilic polymer latexes, matting agents, slip agents, and the like, 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 generally 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 the oil-soluble component is 4.5 g / m ² or less, more preferably 4.0 g / m ^2.
m ² or less, most preferably 3.8 g / m ² or less 3.0 g /
m ² or more.

In the present invention, the ratio of the oil content in the photographic constituent layer to the hydrophilic binder can be arbitrarily set.
The preferred ratio in the photographic constituent layers other than the protective layer is 0.05 to 1.50 by weight, more preferably 0.10 to 1.
40, most preferably 0.20 to 1.30. By optimizing the ratio of each layer, the film strength, scratch resistance and curl characteristics can be adjusted.

In the present invention, the film thickness of the photographic constituent layer means
It 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 preferred thickness of the photographic constituent layer is 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.

In the present invention, the coating position of the silver halide emulsion layer containing the yellow dye-forming coupler is not particularly limited. However, the silver halide emulsion layer containing the magenta dye-forming coupler or the silver halide containing the cyan dye-forming coupler is not limited. It is preferably provided at a position farther from the support than at least one of the emulsion layers. From the viewpoint of accelerating color development, accelerating desilvering, and reducing the residual color of the sensitizing dye, the silver halide emulsion layer containing the yellow dye-forming coupler is preferably provided at a position farthest from the support. Further, from the viewpoint of reduction of Brix discoloration, the silver halide emulsion layer containing a cyan color-forming coupler is preferably a central layer,
From the viewpoint of reducing photobleaching, the silver halide emulsion layer containing a cyan color-forming coupler is preferably the lowermost layer. Further, each of the color forming layers of yellow, magenta and cyan may be composed of two or three layers. For example, JP-A-4-7505
No. 5, 9-114035 and 10-246940
It is also preferable to provide a coupler layer containing no silver halide emulsion adjacent to the silver halide emulsion layer to form a color forming layer, as described in U.S. Pat. No. 5,576,159.

[0089] The coating amount of silver halide emulsion in the present invention is preferably 0.60 g / m ² or less, more preferably 0.55 g / m ² or less, most preferably 0.50 g / m ²
It is as follows.

The silver halide emulsion grains used for the cyan color-forming layer and the magenta color-forming layer are preferably cubic, 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. The pH of the coating comprising the photographic component layer of the light-sensitive material of the present invention is preferably 4.0 to 6.5, more preferably 5.0 to 6.3.
It is. If the pH is too low, the fogging of the photosensitive material may be increased due to so-called raw preservation, and it may be necessary to use an anti-fogging agent, but only by adjusting the coating pH as described above. This problem can be avoided. The pH can be adjusted by adding a solution of a known acid (eg, sulfuric acid, citric acid, etc.) or an alkali (eg, sodium hydroxide, potassium hydroxide, etc.).

The silver halide photographic light-sensitive material of the present invention is used for a color negative film, a color positive film, a color reversal film, a color reversal photographic paper, a color photographic paper, etc., and among them, a color photographic paper is preferable.
As the photographic support used in the present invention, a transmission type support or a reflection type support can be used. As the transmission type support, a transmission film such as a cellulose triacetate film or polyethylene terephthalate,
A material in which an information recording layer such as a magnetic layer is provided on a polyester of 6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG) or a polyester of NDCA, terephthalic acid and EG is preferably used. As the reflective support, a reflective support that is laminated with a plurality of polyethylene layers or polyester layers, and contains 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 and benzooxazolylstilbene-based fluorescent whitening agent is more preferable. Specific examples of the fluorescent whitening agent contained in the water-resistant resin layer include, for example, 4,4 ′
-Bis (benzoxazolyl) stilbene and 4,4'-
Bis (5-methylbenzoxazolyl) stilbene and mixtures thereof; 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 weight, more preferably 0.001 to 0.5% by weight, based on the resin. The reflective support may be a transmissive support or a reflective support as described above, on which a hydrophilic colloid layer containing a white pigment is applied. Further, the reflective support may be a support having a mirror-reflective or second-class diffuse-reflective metal surface.

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

[0094]

[Table 1]

[0095]

[Table 2]

The cyan, magenta and yellow couplers used in the present invention include those described in
JP-A-2-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6; JP-A-2-33144, page 3, upper right column, line 14 to page 18, upper left column last line and page 30, upper right Lines 6 to 35, lower right column, line 11, EP 0355, 660A2, page 4, lines 15 to 27, page 5, line 30 to page 28, last line, page 45, lines 29 to 31 Eye, page 47, lines 23-6
The couplers described on page 3, line 50 are also useful.

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 light-sensitive material. 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 light-sensitive material of the present invention is suitable for a scanning exposure method using a cathode ray (CRT) in addition to being used for a printing system using a normal negative printer. 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 that emits light in a plurality of spectral regions, a plurality of colors are exposed at a time, ie, the cathode ray tube is exposed. The image signals 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) in which a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a solid-state laser using a semiconductor laser as an excitation light source is combined with 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. When 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.

The preferred scanning exposure method applicable to the present invention is described in detail in the patent publications 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 the developer, compounds described in the patent publications listed in the above table are preferably used.

The method of developing the light-sensitive material of the present invention after exposing the light-sensitive material includes a conventional method of developing with a developer containing an alkali agent and a developing agent, an alkali solution containing the developing agent in the light-sensitive 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, Japanese Patent Application No. 7-334190, 7-33419
The hydrazine-type compounds described in Nos. 2, 7-334197, and 7-344396 are preferable.

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 Japanese Patent Application No. 297354/1997 and Japanese Patent Application No. 7-334202 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), water washing and stabilizing solution used in the present invention, known materials and processing methods can be used. Preferably, Research Disclosure Item 36544
(September 1994) pp. 536-541, JP-A-8
-234388 can be used.

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 of the present invention is described in JP-A-3-33847, 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 applied, and p-phenylenediamine compounds are preferably used, and 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-hydroxy Pentyl) 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 these Sulfate, hydrochloride or p
-Toluenesulfonate and the like. Among these, in particular, 3-methyl-4-amino-N-ethyl-N-β-
Hydroxyethylaniline, 4-amino-3-methyl-N
-Ethyl-N- (3-hydroxypropyl) aniline, 4-
Amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline and the hydrochloride, p-toluenesulfonate or sulfate thereof are preferred. These compounds can be used in combination of two or more depending on the purpose.

[0108] 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, as a preservative, 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 inhibitor for preventing precipitation of calcium and 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 etherdiaminetetraacetic 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.

Here, the chlorine ions and bromine ions may be added directly to the color developer, or may be eluted from the photosensitive 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 may contain other known developer component compounds. be able to. In order to maintain the above pH, it is preferable to use various buffer materials.

Specific examples of these buffer materials 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. 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 second, 3 to 60 seconds, preferably 3 to 45 seconds, and more preferably 5 to 25 seconds for a printing material.

[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.

In the bleaching solution, the bleach-fixing solution and their prebaths, a bleaching accelerator can be used 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 may further contain a bleaching accelerator, a corrosion inhibitor for preventing 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.

In recent years, with increasing awareness of the preservation of the global environment, efforts have been made to reduce nitrogen atoms discharged 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 containing no liter. 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.

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

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. However, other known fixing agents such as mesoionic compounds, thioether compounds, thioureas, a large amount of iodide, hypo and the like can be used. May be replaced by These are disclosed in JP-A-60-61749,
Nos. 60-147735, 64-21444, JP-A-1-201659, 1-2
Nos. 10951 and 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 is 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. Preferred 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.

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 1 mol per liter of the processing solution.
It is 0.5 mol, more preferably 1 × 10 ^{-2 to} 0.1 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 combinations other than the present invention in any state of the liquid opening ratio [air contact area (cm ² ) / liquid volume (cm ² )]. 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 steps of washing and / or stabilization 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 fungicides in order to prevent generation of water rust and mold generated in the photosensitive material after processing. 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) Vol.No.5, pp.207-223 (19
One or more general-purpose anti-microbial agents described in 83) may be used in combination. 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.

Further, various chelating agents are preferably used in combination as long as the effects of the compound of the present invention are not impaired.
Preferred compounds of the chelating agent include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, and ethylenediamine-N, N, N ', N'-.
Examples thereof include organic phosphonic acids such as tetramethylene phosphonic acid, and hydrolysates 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. As water used in these washing steps or stabilizing steps,
In addition to tap water, it is preferable to use water deionized to a Ca or Mg concentration of 5 mg / liter or less with an ion-exchange resin or the like, water sterilized by halogen, an ultraviolet germicidal lamp, or the like.

The pH of the washing water is from 4 to 9, preferably from 5 to 8. The washing temperature and washing time can be variously set depending on the characteristics of the photosensitive material, the use, and the like, but are preferably 15 to 50.
The range is 10 seconds to 90 seconds at C, more preferably 10 to 45 seconds at 35 to 50C. 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.

[0137] The liquid sending pressure in the use of these membranes is preferably ^{2 to} 10 kg / cm ² , particularly preferably 3 to 7 kg, for the effect of preventing stain and preventing the reduction of 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.

In the replenishing method of the developing step, desilvering step, washing and / or stabilizing step in the present invention, apart from replenishing a replenisher having a single composition, the replenishing method may be performed by separating into a plurality of replenishers having a plurality of compositions. In the case of replenishment by replenishment, the replenishment can be carried out by any method in the case of separating into one or more replenishers or water replenishment and the addition of a solid substance composed of replenishment components. In the present invention, the replenishment amount per step 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.

Although the replenishment of the processing in the present invention differs depending on the type of the photosensitive material, for example, in the case of the development processing for color printing, the replenishment amount per m ^{2 of} the photosensitive material is as follows.
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 light-sensitive 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 .

The rapid processing in the present invention 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. Of these, in the ultra-rapid processing aimed at by the present invention, the color development time can be 50 seconds or less, preferably 30 seconds or less, more preferably 20 seconds or less, and most preferably 15 seconds or less and 6 seconds or more. It is. Similarly, the bleach-fixing time is preferably 30 seconds or less, more preferably 20 seconds or less, and most preferably 15 seconds or less and 6 seconds or more. The washing or stabilizing time is preferably 40 seconds or less, more preferably 30 seconds or less, and most preferably 20 seconds or less and 6 seconds or more.

The processing time of a step in the invention does not mean 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 preferred 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 includes any one of bleaching / fixing and bleach-fixing steps and a combination thereof.

In the present invention, as described above, the spraying amount of the circulating treatment liquid is usually 1 liter / min to 40 liter / min.
Minutes or less. The circulation amount is 5 to achieve the above spray amount.
３０30 liters / min, preferably 10 to 25 liters / min, which is 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.
L / min. The circulation rate of the processing liquid is preferably 1.0 to 40 liter / min per one processing tank, and more preferably 5 to 30 liter / min. If the spray amount is small, it is difficult to obtain the effect of the present invention. On the other hand, if the spray amount is too large, the processing liquid tends to deteriorate, which is not preferable. The outlet of the circulated processing solution is 1 to 4 mm immediately and the direction perpendicular to the photosensitive layer of the photosensitive material is 10 to 10 per tank.
It is preferable that 100 outlets are provided, and more preferably, 5 to 50 outlets are provided per tank. 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 outlet 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 in at least the developing step. It is more preferably provided in the steps, and the aspect provided in all the steps is most preferable because the effect of improving the stain of the present invention 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 washing and / or stabilizing step is preferably divided into 3 to 12 tanks.
More preferably, it is divided into 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.

[0147]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Example 1 Emulsions of the present invention and comparative emulsions were prepared as follows. Preparation of Emulsion A-01 32 g of lime-processed gelatin was added to 800 ml of distilled water,
After dissolving at 40 ° C., 3.3 g of sodium chloride and N, N ′
0.02 g dimethyl imidazolidine-2-thione was added and the temperature was raised to 60 ° C. A solution obtained by dissolving 10 g of silver nitrate in 30 ml of distilled water and a solution obtained by dissolving 3.5 g of sodium chloride in 30 ml of distilled water were added to the above solution at 60 ° C. over 7 minutes and mixed. Subsequently, silver nitrate 206
g in 600 ml of distilled water and sodium chloride 7
A solution prepared by dissolving 3 g in 600 ml of distilled water was added and mixed at 60 ° C. for 45 minutes. Next, a solution prepared by dissolving 24 g of silver nitrate in 100 ml of distilled water and sodium chloride 8.5.
g in 100 ml of distilled water was further added and mixed for 8 minutes. After the temperature was lowered to 40 ° C., desalting and washing were performed by a sedimentation method, and 120 g of lime-processed gelatin was added and redispersed. A silver bromide fine grain emulsion prepared in advance (having an average sphere equivalent diameter of 0.03 μm,
^Per mole, containing 1 × 10 ⁻⁷ mol of potassium hexachloroiridate (IV)), and heated to 60 ° C.
Optimally gold-sulfur sensitized. Then, 4.2 × 10 ^-4 mol of the following sensitizing dye A for comparison was added per mol of silver halide, and 1-phenyl-5-mercaptotetrazole and 1- (5-methylureidophenyl) -5- were added.
Mercaptotetrazole per mole of silver halide,
1.7 × 10 ^-4 mol of each was added. The pure silver chloride emulsion thus obtained was named Emulsion A-01. Emulsion A-0
Sample No. 1 was composed of a cubic emulsion having an average side length of 0.73 μm. X-ray diffraction showed weak diffraction at a portion corresponding to a silver bromide content of 10 mol% to 40 mol%.

Preparation of Emulsion A-02 An emulsion was prepared in the same manner as Emulsion A-01 except that Comparative Sensitizing Dye B was used instead of Comparative Sensitizing Dye A. −02.

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Preparation of Emulsions A-03 to A-06 In the method for preparing Emulsion A-01, sensitizing dyes I- (1), I- (2) and I- (3) were used in place of comparative sensitizing dye A. )
Alternatively, emulsions differing only by using I- (4) were prepared, and the obtained emulsions were designated as A-03 to A-06, respectively.

Preparation of Emulsions A-13 and A-15 In the method of preparing Emulsion A-03, emulsions were prepared which differed only in that 0.28 g of potassium iodide was added to the sodium chloride solution added a third time. The obtained emulsion is
-13. In the method of preparing Emulsion A-05, an emulsion was prepared which differed only in that 0.28 g of potassium iodide was added to the sodium chloride solution added for the third time, and the obtained emulsion was designated as A-15. Emulsions A-13 and A-15
Has a silver iodide containing 0.1 mol% of silver iodide per mol of silver halide and has a silver iodide-containing layer having an average silver iodide content of 2 mol% in contact with the surface. Was.

For each emulsion, the particle shape, particle size, and particle size distribution were determined from electron micrographs.
The particle size was represented by the average value of the diameter of a circle equivalent to the projected area of the particle, and the particle size distribution was obtained by dividing the standard deviation of the particle size by the average particle size. Emulsions A-01 to A
-06 and Emulsions A-13 and A-15 all had substantially the same grain size and grain size distribution, with a grain size of 0.73μ and a grain size distribution of 0.09. The grain shape of each emulsion consisted of isotropic grains mainly surrounded by (100) crystal planes.

Emulsions A-21, A-23, A-25, A-
Preparation of 31, A-33 Emulsions A-01, A-03, A-05, A-11, A-1
3 In each of the preparation methods, the grain size was reduced, and the addition amounts of the sensitizing dyes 1-phenylmercaptotetrazole and 1- (5-methylureidophenyl) -5-mercaptotetrazole were each set to 5.2 × per mol of silver halide. 1
Emulsions were prepared by changing only ^0-4 mol, 2.0 × 10 ⁻⁴ mol, and 2.0 × 10 ⁻⁴ mol except that the total sulfur sensitization was optimally performed. 21, A-23, A-
25, A-31 and A-33. At this time, the grain size was changed by changing the addition speed and the addition temperature of the silver nitrate aqueous solution and the sodium chloride solution for the first time, and all emulsions had a grain size of 0.59 μm and a grain size distribution of 0.09 μm.
It consisted of 9 cubic emulsions. Table 3 summarizes the properties of the obtained emulsion.

[0154]

[Table 3]

Preparation of Photosensitive Material A corona discharge treatment was applied to the surface of a support in which both sides of paper were coated with polyethylene resin, and then a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. The silver halide color photographic light-sensitive material sample (101) having the following layer structure was prepared by sequentially coating the photographic constituent layers from the seventh layer to the seventh layer. The coating solution for each photographic constituent layer was prepared as follows.

Preparation of Coating Solution for Fifth Layer 300 g of cyan coupler (EXC-1), 250 g of color image stabilizer (Cpd-1), 1 color image stabilizer (Cpd-9)
0 g, color image stabilizer (Cpd-10) 10 g, color image stabilizer (Cpd-12) 20 g, ultraviolet absorber (UV-1) 1
4 g, UV absorber (UV-2) 50 g, UV absorber (UV-3) 40 g and UV absorber (UV-4) 6
0 g was dissolved in 230 g of a solvent (Solv-6) and 350 ml of ethyl acetate.
6-20% aqueous solution of gelatin containing 25 g of d-20)
The resulting mixture was emulsified and dispersed in the resulting mixture to prepare an emulsified dispersion C. On the other hand, silver chlorobromide emulsion C (cubic, a 5: 5 mixture (silver molar ratio) of large-size emulsion C having an average grain size of 0.40 μm and small-size emulsion C having an average grain size of 0.40 μm. The variation coefficient of the grain size distribution is 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 grain having silver chloride as a base material). This emulsion contains the following red-sensitive sensitizing dyes G and H in an amount of 9.0 × 10 ⁻⁵ mol per mol of silver for the large-sized emulsion C and 9.0 × 10 ^-5 mol for the small-sized emulsion C, respectively, per mol of silver. 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 and 6 respectively.
0.0 mg / m ² , 5.0 mg / m ² and 10.0 m
g / m ² .

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

[0160]

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(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

[0162]

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(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. )

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In addition, the green-sensitive emulsion layer and the red-sensitive emulsion layer
On the other hand, 1- (3-methylureidophenyl) -5-mer
Captotetrazole was added in an amount of 1 mol
5.9 × 10^-FourMole was added. In addition, the second layer, the fourth
0.2 mg / m2 for the layer, the sixth layer and the seventh layer, respectively.
^Two 0.2 mg / m^Two, 0.6 mg / m^Two0.1 mg /
m^TwoWas added so that In addition, a blue-sensitive emulsion layer and
With respect to the green-sensitive emulsion layer, 4-hydroxy-6-methyl-
1,3,3a, 7-tetrazaindene is converted to halo
1 × 10^-FourMole, 2 × 10^-FourMo
Was added. Also, methacrylic acid and acrylic acid were added to the red-sensitive emulsion layer.
Butyl acrylate copolymer latex (weight ratio 1: 1, flat
Average molecular weight of 200,000 to 400,000) is added to 0.05 g /
m^TwoWas added. Also, to prevent irradiation,
The following dyes (in parentheses indicate the coating amount) were added.

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(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 weight, ZnO; content: 4% by weight), fluorescent whitening agent (4,4'-bis (5-methylbenzoxazolyl) stilbene; content: 0.03% by weight), bluish dye ( Ultramarine blue)] First layer (blue-sensitive emulsion layer) Emulsion A-01 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 0.99 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 having an average grain size of 0.45 μm and large-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.Each size emulsion contained 0.4 mol% of silver bromide in a part of the grain surface based on silver chloride. 0.1) Gelatin 1.36 Magenta coupler (ExM) 0.15 UV absorber (UV-A) 0.14 Color image stabilizer (Cpd-2) 0.02 Color image stabilizer (Cpd-4) 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 colors Image stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) 0 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 (cubic, 5: 5 mixture of large-size emulsion C with an average grain size of 0.40 μm and large-size emulsion C with a 0.30 μm size (silver mole The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively. In each size emulsion, 0.5 mol% of silver bromide was contained locally on a part of the grain surface based on silver chloride. 0.20 gelatin 1.11 cyan coupler (ExC-1) 0.30 ultraviolet absorber (UV-A) 0.29 color image stabilizer (Cpd-1) 0.25 color image stabilizer (Cpd-9) 0.01 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-12) 0.02 Solvent (Solv-6) 0.23

Sixth layer (ultraviolet absorbing layer) Gelatin 0.46 Ultraviolet absorbing agent (UV-B) 0.45 Solvent (Solv-7) 0.25 Seventh layer (protective layer) Gelatin 1.00 Acrylic of polyvinyl alcohol Modified copolymer (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01

Table 4 shows the gelatin coating amount (= hydrophilic binder coating amount), calcium coating amount, coating pH, antioxidant, and emulsion used (blue-sensitive dye type) for the sample 101 prepared as described above. Samples differing only in the manner described above were prepared, and were set as samples 102 to 142. Here, the amount of gelatin applied was changed by uniformly changing the amount of gelatin applied to each layer. The amount of calcium applied was changed by preparing two kinds of gelatins having different calcium contents (calcium contents of 3000 ppm and 10 ppm) and changing the mixing ratio thereof. The pH of the coating was adjusted by adding a sulfuric acid or sodium hydroxide solution to the coating solutions of the second and fourth layers. The antioxidant was used in an amount of 1 × 10 5 per mole of all silver halide in the coating film.
^{A -4} mole amount was added to each of the second and fourth layers.

The following evaluation test was performed on each of the obtained samples. Evaluation test: Applied surface condition test The occurrence frequency of blue-sensitive dye aggregates on the applied surface was visually counted, and the following ranking was performed. Rank Frequency of occurrence of aggregates ◎ → about 0 to 5 pieces / m ² ○ → about 6 to 10 pieces / m ² × → about 11 to 30 pieces / m ² XX → more than 31 pieces / m ²

Evaluation Test: Development Progress Test After coating, each sample after storage at 25 ° C. and 55% RH for 10 days was subjected to a sensitometer (using a color temperature of 3200 ° K of a light source of FWH type sensitometer manufactured by Fuji Photo Film Co., Ltd.). The sample after the exposure was subjected to a running process A (color development time 45 seconds) and a process B (color development time 1
(2 seconds). The color density of the sample after the processing was measured, and the yellow density (D
mA) and the yellow density (DmB) in the processing step B (DmB / DmA) were determined and used as a measure of the development progress. The higher the DmB / DmA, the closer to 1, the more excellent the rapid processability.

Evaluation test: Residue test of blue-sensitive dye The reflection spectrum of the unexposed part of the sample treated with the treatment B used in the evaluation test was measured by a spectrophotometer (U-3 manufactured by Hitachi, Ltd.).
Measured at 410) to determine the reflection density Dy ₁ at 450nm. Next, these samples were washed with water at 40 ° C. for 5 minutes, the reflection spectrum was measured again, the reflection density Dy ₂ at 450 nm was obtained, the difference ΔY = Dy ₁ −Dy ₂ between them, and the value of sample 101 was calculated. It was determined as a relative value when 100.
The smaller the value is, the less the white background contamination due to the residual sensitizing dye is. Evaluation test Test of storage cover After application, the sample was stored at 25 ° C and 55% for 10 days, and further forcibly stored at 60 ° C and 30% for 1 day, and then subjected to the treatment A used in the above evaluation test. The color density was measured. Yellow density Fog of the obtained unexposed portion
₂ and the difference ΔFog = Fog ₂ −F between the yellow density Fog ₁ of the unexposed portion of the sample processed by the process A in the evaluation test
og ₁ was determined, and was used as a measure of the ease with which the cover was raised when the photosensitive material was stored for a long time after coating. The smaller the ΔFog, the better the occurrence of fogging during storage of the light-sensitive material, which is more preferable.

The processing method used in this embodiment will be described below. [Processing A] The photosensitive material 103 is processed into a roll having a width of 127 mm, and is imagewise exposed using a minilab printer processor PP1258AR manufactured by Fuji Photo Film Co., Ltd., and then replenished to twice the capacity of the color developing tank in the following processing steps. Until this was done, 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).)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml dimethylpolysiloxane-based surfactant (silicone KF351A / Shin-Etsu Chemical Co., Ltd.) 0.1 g 0.1 g 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 fluorescent brightener (Hakkol FWA-SF / Showa Kagaku) 2.5 g 5.0 g Sodium sulfite 0.1 g 0.1 g Disodium-N, N- Bis (sulfonatoethyl) hydroxylamine 0.5 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 26 Addition of water 1000ml 1000ml pH (adjusted with potassium hydroxide and sulfuric acid at 25 ° C) 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-carboxybenzenesulfinic 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 bisulfite 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

[Processing B] The photosensitive material 103 was 127 m
After processing into a roll having a width of m and imagewise exposure, continuous processing (running test) was carried out until replenishment of twice the capacity of the color developing tank in the following processing step. The processing using the running liquid was referred to as processing B. The processing was mini-lab printer processor PP125 manufactured by Fuji Photo Film Co., Ltd.
8AR was used.

Processing Step 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 ° C for 4 seconds-Rinse (4) ** 40.0 ° C for 4 seconds 121 ml * Replenishment amount per 1 m ^{2 of} photosensitive material ** Rinse phosphorus screening system RC50D manufactured by Fuji Photo Film Co., Ltd. Install in 3), take out the rinse liquid from rinse (3), and send it to reverse osmosis membrane module (RC50D) by 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).)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 ml 800 ml dimethylpolysiloxane-based surfactant (silicone KF351A / Shin-Etsu Chemical Co., Ltd.) 0.1 g 0.1 g 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 fluorescent brightener (Hakkol FWA-SF / Showa Kagaku) 2.5 g 5.0 g Sodium sulfite 0.1 g 0.1 g Disodium-N, N- Bis (sulfonatoethyl) hydroxylamine 0.5 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 Addition of water 1000ml 1000ml pH (adjusted with potassium hydroxide and sulfuric acid at 25 ° C) 10.15 12.50

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 700 ml 600 ml ammonium ethylenediaminetetraacetate (III) ammonium 75.0 g 150.0 g ethylenediaminetetraacetic acid 1.4 g 2.8 g m-carboxybenzenesulfinic 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 metabisulfite Potassium 23.1 g 46.2 g Water was added to add 1000 ml 1000 ml pH (adjusted at 25 ° C./acetic acid and ammonia) 5.5 5.5

[Rinse liquid] [Tank liquid] [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

Tables 4 and 5 show the results. Table 4 and Table 5
From this, the excellent effects of the present invention can be known. That is, samples 101 to 106 having a relatively large amount of gelatin applied were DmB
/ DmA value is generally low and the development progress is inferior. On the other hand, the sample in which the amount of gelatin applied is within the range of the present invention has an increased DmB / DmA value and is advantageous for the development progress.
Further, at this time, by using the dye represented by the general formula (I), the dye residual ΔY is also reduced, which is preferable for rapid processing. However, in a sample in which the amount of calcium applied exceeds the regulation of the present invention, when the amount of gelatin applied is lowered and at the same time the dye represented by the general formula (I) is used,
It is not preferable because the surface is deteriorated (samples 109 to 109).
112, 133, 134). That is, only when the gelatin coating amount satisfies the stipulation of the present invention, the sensitizing dye represented by the general formula (I) is used, and the calcium coating amount is limited to the range of the present invention, the rapid processing property is excellent.
A sample without planar failure was obtained. Here, it should be noted that the effect of improving the surface condition by reducing the calcium content is an effect obtained only when the dye represented by the general formula (I) is used at the gelatin coating amount specified in the present invention. is there. This surface effect is more remarkable when the amount of dye used in the emulsion used is large (Sample 13).
Samples 135 and 136 with respect to 3,134), and when the emulsion used further has a silver iodide-containing phase, it is shown that the surface state is further improved (Samples 141 and 142).

On the other hand, the reduction in the amount of calcium applied, which has the effect of preventing planar failure, also causes deterioration of storage coverage. The occurrence of the storage fog becomes more remarkable when the coating pH does not satisfy the preferred range of 4 to 6.5 of the present invention (sample 124 for sample 119 and sample 126 for sample 120). This can be prevented by adding an appropriate amount of the antioxidant (Sample 125). However, even when the calcium content is reduced, by selecting the coating pH within a preferable range, it is possible to prevent deterioration of the storage cover without adding any additive. In addition, it can be seen that the deterioration of the storage cover seen when the calcium content is reduced can be suppressed by adding the antioxidant represented by the general formula (II) to the sample (samples 121 to 123 with respect to sample 115). ).
Also, from Tables 4 and 5, it is found that the emulsion used preferably has a silver iodide phase in the present invention. That is, by using an emulsion having a silver iodide-containing phase,
It can be seen that the deterioration of the surface state when the amount of gelatin applied was reduced using the dye of the present invention was further improved (Sample 1).
Samples 128, 129 for 15, 117). Although the storage fogging tends to be slightly deteriorated by the provision of the silver iodide-containing phase, it can be understood that this can be improved by using the antioxidant represented by the general formula (II) (Sample 1).
Samples 130, 131 for 28, 129).

[0188]

[Table 4]

[0189]

[Table 5]

Example 2 Preparation of Sample 201 Sample 201 was prepared by changing the composition of the fifth layer from Sample 101 of Example 1 as follows. Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion C (cubic, 5: 5 mixture of large-size emulsion C with an average grain size of 0.40 μm and large-size emulsion C with a 0.30 μm size (silver molar ratio). 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.) 12 Gelatin 1.11 Cyan coupler (ExC-1) 0.13 Cyan coupler (ExC-3) 0.03 Color image stabilizer (Cpd-1) 0.05 Color image stabilizer (Cpd-6) 0.06 colors Image stabilizer (Cpd-7) 0.02 Color image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-14) 0.01 Color image stabilizer Agent (Cpd-15) 0.12 Color image stabilizer (Cpd-16) 0.0 Color Image Stabilizer (Cpd-17) 0.09 Color Image Stabilizer (Cpd-18) 0.07 solvent (Solv-5) 0.15 solvent (Solv-8) 0.05

The amount of gelatin applied on the sample 201 was 6.92 g.
/ M ² , calcium application amount is 8.0 mg / m ² , coating pH
Was 6.8, which was the same value as that of the sample 101 of Example 1. For sample 201, a sample was prepared in which the amount of gelatin applied, the amount of calcium applied, the coating pH, the antioxidant, and the emulsion used were changed in the same manner as in Example 1, and the same evaluation test as in Example 1 was performed. As in Example 1, it was shown that each sample of the present invention was excellent in each property.

Example 3 Preparation of Emulsion B-01 1200 ml of an aqueous gelatin solution (20 g of a deionized alkali-treated gelatin having a methionine content of about 40 μmol / g, containing 0.8 g of NaCl, and having a pH of 6.0) was placed in a reaction vessel. Ag-1 solution (100 ml
Silver nitrate 20 g, gelatin 0.8 g, HNO ₃ 1
Liquid N (including 0.2 ml) and liquid X-1 (6.9 g of sodium chloride in 100 ml, 0.8 g of the same gelatin as above)
NaOH 1N solution (including 0.3 ml) at 50 ml / min.
Simultaneous addition was performed for 5 seconds. After stirring for 2 minutes, Ag
-2 solution (silver nitrate in 100 ml 4g, the same gelatin 0.8 g, containing HNO ₃ 1N solution 0.2 ml) and X
Solution-2 (containing 2.8 g of potassium bromide, 0.8 g of the same gelatin as described above, and 0.3 ml of 1N NaOH solution in 100 ml) was added simultaneously at 70 ml / min for 15 seconds.
After stirring for 2 minutes, the Ag-1 solution and the X-1 solution were mixed at 25 ml /
For 2 minutes. NaCl-solution (100
15 ml of sodium chloride in 10 ml) was added, the temperature was raised to 55 ° C., and the mixture was aged for 5 minutes. Then, an Ag-3 solution (containing 100 g of silver nitrate in 100 ml) and an X-3 solution (1 ml) were added.
Ag-3 solution (containing 7 g of sodium chloride in 00 ml) was added in 400 ml portions, and the mixture was added simultaneously over 30 minutes. Then, a sedimentation agent was added, the temperature was lowered to 30 ° C., the precipitate was washed by settling, and an aqueous gelatin solution was added.
2, adjusted to pCl 3.0. A previously prepared silver bromide fine grain emulsion (having an average equivalent sphere diameter of 0.03 μm and containing 1 × 10 ⁻⁷ mol of potassium hexachloroiridate (IV) per mol of the finished silver halide) was added thereto, and the mixture was heated to 60 ° C. After heating, gold-sulfur sensitization was optimally performed. Next, the comparative sensitizing dye A was used per 1 mol of silver halide,
7.9 × 10 ^-4 mol was added, and 1-phenyl-5-
Mercaptotetrazole and 1- (5-methylureidophenyl) -5-mercaptotetrazole were each added in an amount of 3.2 × 10 ^-4 mol per mol of silver halide. The addition amount of these compounds in Emulsion B-01 was
Emulsion A-0 in the amount added per silver halide surface area
Adjusted to be approximately equal to 1. The pure silver chloride emulsion thus obtained was designated as Emulsion B-01. Emulsion B-0
X-ray diffraction of No. 1 showed weak diffraction in a portion corresponding to a silver bromide content of 10 mol% to 40 mol%.

Preparation of Emulsions B-03 to B-06 In the method of preparing Emulsion B-01, sensitizing dyes I- (1), I- (2), I- (3), I
-Emulsions differing only in the use of (4) were prepared, and the obtained emulsions were named B-03 to B-06. Preparation of Emulsion B-13 In the method of preparing Emulsion B-03, Ag-3 solution and X
After adding 350 cc of the X-3 solution, the X-3 solution was added to X-4.
The solution was replaced with a solution (containing 7 g of sodium chloride and 0.19 g of potassium iodide in 100 ml), and emulsions were prepared only by adding 50 cc of an Ag-3 solution and 50 cc of an X-4 solution, respectively. Emulsion B-13 was obtained. Emulsion B-13 contained 0.1 mol per mol of silver halide.
A silver iodide-containing phase (silver iodochloride shell) composed of silver chloroiodobromide containing 1 mol of silver iodide and having an average silver iodide content of 2 mol% in contact with the surface from about 90% from the center of the grain. Had on the outside.

Emulsions B-01, B-03 to B-06, B-
11 and B-13 have almost the same particle size and particle size distribution, and the average particle size is 0.5
The particle size distribution was 3 μm and the particle size distribution was 0.28. Regarding the grain shape, 80% or more of the total projected area of all grains in each emulsion was (1).
00) The particles were occupied by tabular grains having a main plane and an aspect ratio of 2 or more. The tabular grains had an average equivalent circle diameter of 1.02 μm and an average aspect ratio of 7.3.

Table 6 summarizes the characteristics of the obtained emulsion.

[0196]

[Table 6]

Preparation of Sample 301 A sample 301 was prepared by changing the composition of each layer from the sample 101 of Example 1 as follows. First layer (blue-sensitive emulsion layer) Silver chlorobromide emulsion B-01 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 prevention layer) Gelatin 0.60 Color mixture prevention agent (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) 0.15 ultraviolet absorber (UV-A) 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 colors Image stabilizer (Cpd-10) 0.009 Color image stabilizer (Cpd-11) 0.0001 Solvent (Solv-4) 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 in sample 101) 0.12 gelatin 0.59 cyan coupler (ExC-2) 0.13 cyan coupler (ExC-3) 0 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 (protective 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

[0203]

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[0204]

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[0205]

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[0206]

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[0207]

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[0208]

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[0209]

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[0210]

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[0211]

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Table 7 shows the gelatin coating amount (= hydrophilic binder coating amount), calcium coating amount, coating pH, antioxidant, and emulsion used (blue-sensitive dye type) for the sample 301 prepared as described above. Samples differing only in the manner described above were prepared, and used as samples 301 to 320. Here, the amount of gelatin applied was changed by uniformly changing the amount of gelatin applied to each layer. The amount of calcium applied was changed by preparing two kinds of gelatins having different calcium contents (calcium contents of 3000 ppm and 10 ppm) and changing the mixing ratio thereof. The pH of the coating was adjusted by adding a sulfuric acid or sodium hydroxide solution to the coating solutions of the second and fourth layers. The antioxidant was used in an amount of 1 × 1 per mol of all silver halide in the coating film.
A ^0-4 mole amount was added to each of the second and fourth layers. An evaluation test similar to that of Example 1 was performed on the obtained sample. Here, ΔY is shown as a relative value when the value of the sample 101 of Example 1 is set to 100. Table 7 shows the results.

Table 7 shows the excellent effects of the present invention. That is, in a sample in which the amount of gelatin applied does not satisfy the requirements of the present invention, the value of DmB / DmA is relatively low, which is not preferable for rapid processing (samples 317 to 320). The sample is improved in this respect. However, when only the amount of gelatin applied is reduced without reducing the calcium content, the surface condition deteriorates when the dye represented by the general formula (I), which is preferable for the dye remaining, is used (samples 302 to 307). . This deterioration of the surface condition is improved in the samples in which the amount of calcium applied satisfies the requirements of the present invention (samples 313 to 316), and the surface condition is further improved particularly when an emulsion having a silver iodide-containing phase is used (sample). 314-31
6). On the other hand, the storage fogging that is worsened by reducing the amount of calcium applied can be reduced by selecting the coating pH (sample 308 with respect to sample 309), and the antioxidant represented by the general formula (II) is used in combination. This almost eliminates the problem of storage cover (samples 311 to 313 for sample 308). This effect is more remarkable when an emulsion having a silver iodide-containing phase is used (samples 315 and 316 with respect to sample 314).

[0214]

[Table 7]

Example 4 Each of the samples prepared in Examples 1 and 2 was subjected to scanning exposure with laser light of three colors B, G, and R using the following exposure apparatus, and developed. It was confirmed that all of these samples had high rapid processing properties and were excellent as photosensitive materials for scanning exposure.

(Exposure apparatus) The light source is a semiconductor laser Ga.
A YAG solid-state laser (oscillation wavelength: 946 nm) using AlAs (oscillation wavelength: 808.5 nm) as an excitation light source is wavelength-converted by an SHG crystal of LiNbO ₃ having an inversion domain structure, and 473 nm, and a semiconductor laser GaAlAs (oscillation wavelength). ; 808.5 nm) as an excitation light source using a YVO ₄ solid-state laser (oscillation wavelength: 1064 n).
m) is the SHG of LiNbO ₃ having an inverted domain structure
532 nm extracted by wavelength conversion by a crystal and Al
GaInP (oscillation wavelength: 680 nm: type No. LN9R20 manufactured by Matsushita Electric Industrial Co., Ltd.) was used. The laser light of each of the three colors is intensity-modulated by the AOM, moved in a direction perpendicular to the scanning direction by a polygon mirror, and can be sequentially scanned and exposed on color photographic paper. Fluctuations in light intensity due to the temperature of the semiconductor laser are suppressed by using a Peltier element to keep the temperature constant. The scanning exposure is 600 dpi, and the light beam diameter measuring device [118
OGP / Beam Scan Co., Ltd. (USA)], the B, G, and R were 65 μm (a circular beam having a difference of 1% or less in the main scanning direction diameter / sub-scanning direction diameter). T).

Example 5 An evaluation test similar to that of Examples 1, 2 and 4 was performed on a sample prepared in the same manner as in Example 1 or Example 2 except that the support was changed as follows. Where
The sample of the present invention is excellent in all of the characteristics. Even in the silver halide photographic light-sensitive material of the present invention using a transmissive support, white background contamination and surface failure are prevented, rapid processing is excellent, and scanning is further improved. It was confirmed that the composition can be suitably used in exposure.

(Support) Polyethylene terephthalate (thickness: 180 μm) (on the surface opposite to the emulsion layer, gelatin (6.2 g / m ² ) and the following dye-1, dye-2 and dye-3 (0.07 g / m2 ^each ) m ² , 0.04 g / m ² ,
0.095 g / m ² ). )

[0219]

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[0220]

According to the silver halide color photographic light-sensitive material of the present invention, a specific spectral sensitizing dye is used, and the amount of a hydrophilic binder and the amount of calcium are reduced to predetermined ranges.
It has excellent properties such as excellent rapid processing property, little residual spectral sensitizing dye after processing, and prevention of planar failure due to aggregation of spectral sensitizing dye. Further, in the light-sensitive material of the present invention in which the coating pH is in a specific range, in addition to prevention of white background contamination and surface failure, deterioration of storage fogging can be suppressed without using an additive.
Further, the light-sensitive material of the present invention using a compound having a molecular weight of 330 or less or a compound represented by the general formula (II) as an antioxidant is excellent in rapid processing property, has little white background contamination and surface failure, and suffers from fogging due to storage. It has an excellent effect that the rise is reduced. According to the image forming method of the present invention using this silver halide color photographic light-sensitive material, rapid processing is possible, and in imagewise exposure, any of surface exposure and scanning exposure can be suitably applied. Ultra-rapid processing is possible, especially with 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.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03C 1/34 G03C 1/34 7/392 7/392 A 7/407 7/407

Claims (7)

[Claims] 1. The method according to claim 1, wherein the support has at least three different color sensitivities.
Silver halide color copying with two silver halide emulsion layers
In a true light-sensitive material, at least the silver halide emulsion layer is required.
The silver halide emulsion in one layer is represented by the following general formula (I).
Silver chloride containing at least one of the spectral sensitizing dyes
A silver halide emulsion having a ratio of 95 mol% or more, and
Silver halide color photographic materials
The amount of hydrophilic binder is 3.0 g / m^Two6.0 g / m or more^Two
Below, the amount of calcium is 6.0 mg / m^TwoMust be
And a silver halide color photographic material. Embedded image(Where Z₁And Z_TwoAre independently sulfur atoms and selenium atoms
Represents a child or an oxygen atom. V₁And V_TwoIs a monovalent substitution
Represents a group. Where V₁And V_TwoIs not an aromatic group,
Further, two or more adjacent groups are fused with each other to form a condensed ring.
Never. R ₁, R_TwoEach independently represents an alkyl group
Then M₁Represents a charge-balancing counter ion. m₁Is the molecular charge
Represents a number of 0 or more necessary to neutralize₁and
n_TwoRepresents an integer of 0 to 4. ) 2. The coating comprising a photographic constituent layer has a pH of 4.0.
2. A silver halide color photographic light-sensitive material according to claim 1, wherein 3. The silver halide color photographic material according to claim 1, further comprising an antioxidant having a molecular weight of 330 or less. 4. The silver halide color photographic material according to claim 3, wherein the antioxidant is represented by the following general formula (II). Embedded image (In the formula, Z ₁₁ represents an atom group necessary for completing a carbocyclic or heterocyclic ring, and may be further substituted with a substituent.) 5. A silver halide emulsion having a silver chloride content of 95 mol% or more is used in an amount of 0.01 to 1 mol per mol of the silver halide.
5. The silver halide color photographic light-sensitive material according to claim 1, wherein the material contains mol% of silver iodide. 6. An image forming method in which a silver halide color photographic light-sensitive material is scanned and exposed with a light beam modulated based on image information and then developed, wherein the silver halide color photographic light-sensitive material is used. A color image forming method, comprising the silver halide color photographic light-sensitive material according to any one of the above. 7. A color image forming method, comprising processing the silver halide color photographic light-sensitive material according to claim 1 for a color development time of 20 seconds or less.