JPH05181241A - Method for forming color image - Google Patents

Abstract

PURPOSE:To provide a silver halide photographic sensitive material capable of ultrarapid processing and small in fluctuation of photographic performances in successive processing. CONSTITUTION:The silver halide photographic sensitive material containing a silver halide emulsion as high in silver chloride content as 95-99.9mol% is processed with a color developing solution containing substantially no benzyl alcohol, and this method is characterized by containing in at least one of the emulsion layers or other photographic constituent layers a compound represented by formula I, and controlling the color development time to <=25sec, and the total processing time to <=2min, and setting the chlorine ion concentration in the color developing solution to 3X10<-2>-l.5X10<-1>mol/l. In formula I, A1 is a group for releasing a group of formula II; A2 is a group for releasing a group of formula III: each of Time1 and Time2 is a timing group; and BA is a bleach promoter or its precursor; k is 0, 1, or 2; and each of m and n is 0 or 1.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color image forming method. More particularly, it relates to a color image forming method using a silver halide photographic light-sensitive material capable of ultra-rapid processing and having little fluctuation in photographic performance in continuous processing.

[0002]

BACKGROUND OF THE INVENTION Generally, in order to obtain a color image by processing a light-sensitive material which has been imagewise exposed, metallic silver produced is desilvered after a color development step, and then washed with water or stabilized with a substitute for washing. Processing steps are provided.

However, such a light-sensitive material is subjected to running processing by an automatic developing machine provided at each developing station. However, it is required to develop the image within the same day and return it to the user.Recently, it is even required to return it within a few hours from the reception desk, and further rapid development of rapid processing technology is urgently needed. It is peeling.

Further, there is a strong demand for the development of an ultra-rapid processing in which the total processing time is within 1 minute. If the processing time is shortened because the ultra-rapid processing is performed, defective desilvering occurs in the bleach-fixing step, which is a problem. On the other hand, it is known that the desilvering property is improved by containing a bleaching accelerator (hereinafter abbreviated as BAR compound) in the silver halide photographic light-sensitive material. However, when a silver halide photographic light-sensitive material containing a BAR compound is subjected to ultra-rapid continuous processing, fluctuations in photographic performance (particularly gradation) occur, which is a problem.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a color image forming method using a silver halide photographic light-sensitive material capable of ultra-rapid processing and having little fluctuation in photographic performance in continuous processing.

[0006]

As a result of intensive studies, the present inventors have found that the object of the present invention is to provide a silver halide photographic light-sensitive material having at least one high chloride silver halide emulsion layer on a support with an aromatic group. After processing with a color developing solution containing a primary amine color developing agent and containing substantially no benzyl alcohol,
In the method of forming a color image by bleach-fixing and washing with water, the high chloride silver halide emulsion layer contains silver halide emulsion grains in which 95 to 99.9 mol% is silver chloride. Containing at least one layer of the compound of the general formula [A] in the layer or another photographic constituent layer, the color development time is 25 seconds or less, and the color development processing time, the bleach-fix processing time and the water washing processing time are According to the color image forming method, the total processing steps are within 2 minutes in total, and the chlorine ion concentration in the color developing solution is 3 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / liter. The inventors have found that they have been achieved and have completed the present invention.

[0007]

[Chemical 3]

In the formula, A ₁ represents a group which releases a group represented by the general formula [A-1] by a reaction with an oxidized product of a developing agent, and A ₂ represents a group which reacts with an oxidized product of a developing agent. Represents a group releasing a group represented by the general formula [A-2], and
₁ and Time ₂ represent a timing group, BA represents a bleach accelerator or its precursor, k represents 0, 1, or 2, and m and n represent 0 or 1.

[0009]

[Chemical 4]

The present invention will be described in more detail below. The silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is characterized by containing silver chloride in an amount of 95 to 99.9 mol%, but is substantially free of silver iodide. Silver is preferred. Silver chloride content is 97-99.9 mol%
Is more preferable. When the amount of development or the replenishment amount of the color developing solution is reduced in a shorter time, it is more preferably 99.5 to 99.9 mol%.

The silver halide grains according to the present invention may have any shape. One preferred example is
It is a cube having a (100) plane as a crystal surface. US Pat. Nos. 4,183,756 and 4,225,66.
6, JP-A-55-26589, JP-B-55-427.
No. 37, The Journal of Photographic Science (J. Photogr. Sci.) 21,
39 (1973) and other methods,
Particles having a shape such as an octahedron, a tetradecahedron, and a dodecahedron can be prepared and used. Further, grains having twin planes may be used.

The silver halide grain according to the present invention may be a grain having a single shape or a mixture of grains having various shapes. The grain size of the silver halide grains according to the present invention is not particularly limited, but it is preferably 0.
1 to 0.2 μm, more preferably 0.2 to 1.0 μm
The range is.

The above particle size can be measured by various methods commonly used in the art. A typical method is Loveland's “Particle Size Analysis Method” (ASMTM Symposium on Light.
Microcopy, pp. 94-122, 1955) or
The method described in "Theory of Photographic Process, 3rd Edition" (Co-authored by Mies and James, Chapter 2, published by Macmillan, 1966) can be mentioned.

This particle size can be measured using the projected area of the particle or a diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be fairly accurately expressed as a diameter or projected area. The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse. Preferably, the coefficient of variation is 0.
The number of monodispersed silver halide grains is 22 or less, more preferably 0.15 or less. Here, the coefficient of variation is a coefficient indicating the breadth of the particle size distribution and is defined by the following equation. Coefficient of variation = S / R (where S is the standard deviation of the particle size distribution, and R is the average particle size.)

The term "grain size" as used herein means the diameter of spherical silver halide grains, and the diameter of a cubic image or a shape other than spherical grains when the projected image is converted into a circular image of the same area. Represents. As a device and method for preparing a silver halide emulsion, various methods known in the art can be used.

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

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

Further, JP-A-57-92523 and 57-57
-92524, etc., an apparatus for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition apparatus arranged in a reaction mother liquor, water-soluble silver described in German Published Patent 2,921,164, etc. Apparatus for adding salt and water-soluble halide salt aqueous solution with continuously changing concentration, Japanese Patent Publication No. 56-
An apparatus for forming grains while keeping the distance between silver halide grains constant by taking out the reaction mother liquor from the reactor described in No. 501776 and concentrating it by ultrafiltration may be used.

Further, if necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added during the formation of silver halide grains or after the completion of grain formation.

A known method can be used for reduction sensitizing the silver halide emulsion according to the present invention. For example,
It is also possible to use a method of adding various reducing agents,
A method of aging under conditions of high silver ion concentration or a method of aging under conditions of high pH can be used.

As the reducing agent used for reduction sensitization of the silver halide emulsion according to the present invention, stannous chloride of stannous chloride,
Examples thereof include boranes such as tri-t-butylamine borane, sodium sulfite, sulfites such as potassium sulfite, reductones such as ascorbic acid, and thiourea dioxide. Among these, thiourea dioxide, ascorbic acid and its derivatives, and sulfite can be preferably used. Compared with the case where reduction sensitization is performed by controlling the silver ion concentration and pH during ripening, the method using a reducing agent as described above is excellent in reproducibility and is preferable.

These reducing agents are dissolved in a solvent such as water or alcohol and added to a silver halide emulsion for ripening, or added at the time of forming silver halide grains to reduce and increase at the same time as grain formation. You may feel. The amount of these reducing agents to be added needs to be adjusted according to the pH of the silver halide emulsion, the silver ion concentration, etc., but generally 10 ^-7 to 10 ^-2 mol per mol of the silver halide emulsion. Is preferred.

After the reduction sensitization, a small amount of an oxidizing agent may be used to modify the reduction sensitizing nucleus or deactivate the remaining reducing agent. Examples of compounds used for such purposes include:
Examples thereof include potassium hexacyanoferrate (III), bromosuccinimide, p-quinone, potassium perchlorate, and hydrogen peroxide solution.

The silver halide emulsion according to the present invention can be reduction sensitized and can be used in combination with a sensitizing method using a gold compound and a sensitizing method using a chalcogen sensitizer. As the chalcogen sensitizer applied to the silver halide emulsion according to the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer and the like can be used, and the sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamidothiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine and the like.

As the gold sensitizer applied to the silver halide emulsion according to the present invention, various gold complexes other than chloroauric acid, gold sulfide, gold thiosulfate and the like can be added. Examples of the ligand compound used include dimethylrhodnin, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of the gold compound used varies depending on the type of silver halide emulsion, the type of compound used, ripening conditions, etc.
It is preferably 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁸ mol per mol. More preferably 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸
It is a mole.

The silver halide emulsion according to the present invention is intended to prevent fog that occurs during the process of preparing a silver halide photographic light-sensitive material, reduce performance fluctuation during storage, and prevent fog that occurs during development. Known antifoggants and stabilizers can be used.

As an example of the compound which can be used for such a purpose, there can be mentioned the compound represented by the general formula (II) described in JP-A-2-146036, page 7, lower column, and specific examples thereof are given. The compounds include (IIa-1) to (IIa-8) and (IIb-) described on page 8 of the publication.
1)-(IIb-7) compounds, 1- (3-methoxyphenyl) -5-mercaptotetrazole and the like can be mentioned.

These compounds can be added in steps such as the step of preparing silver halide emulsion grains, the step of chemical sensitization, the end of the chemical sensitization step and the step of preparing a coating solution depending on the purpose. When chemical sensitization is performed in the presence of these compounds, 1 × 10 ⁻⁵ mol to 5 × 10 ⁵ mol per mol of silver halide.
It is preferably used in an amount of about ^-4 mol.

[0029] When added to the end of the chemical sensitization, the amount of 1 × 10 ^-6 mol to 5 × 10 ^-2 mol per mol of silver halide is preferred, 1 × 10 ^-5 mol to 5 × 10 ^{- 3} mol is more preferred. When it is added to the silver halide emulsion layer in the coating solution preparation step, the amount is 1 per mol of silver halide.
The amount is preferably in the range of × 10 ^-6 mol to 1 × 10 ^-1 mol.
It is more preferably x10 ^-5 mol to 1 x 10 ^-2 mol. When it is added to a layer other than the silver halide emulsion layer, the amount in the coating solution coating is preferably about 1 × 10 ⁻⁹ mol to 1 × 10 ⁻³ mol.

When the silver halide photographic light-sensitive material of the present invention is used as a color photographic light-sensitive material, a combination of a yellow coupler, a magenta coupler and a cyan coupler is used to spectrally sensitize a specific region of a wavelength range of 400 to 900 nm. A layer containing a silver halide emulsion. The silver halide emulsion contains one kind or a combination of two or more kinds of sensitizing dyes.

Any known compound can be used as the spectral sensitizing dye used in the silver halide emulsion according to the present invention, and as the blue-sensitive sensitizing dye, Japanese Patent Application No. 2-5 is used.
BS-1 to 108 described in No. 1124, pages 108 to 109
8 can be preferably used alone or in combination. As the green sensitizing dye, GS-1 to 5 described on page 110 of the same specification are preferably used. Examples of the red sensitizing dye include RS-described on pages 111 to 112 of the same specification.
1-8 are preferably used.

When the silver halide photographic light-sensitive material according to the present invention is exposed by a printer using a semiconductor laser, it is necessary to use a sensitizing dye having infrared sensitivity, which is an infrared-sensitive sensitizing dye. As for Japanese Patent Application No. 3-7361
The dyes of IRS-1 to 11 described in No. 9 specification, pages 12 to 14 are preferably used. Further, it is preferable to use the supersensitizers SS-1 to SS-9 described on pages 14 to 15 of the same specification in combination with these dyes.

When the silver halide photographic light-sensitive material according to the present invention is exposed by using a laser, it is advantageous to use an exposure device using a semiconductor laser in terms of downsizing of the device. In scanning exposure, the exposure time per pixel corresponds to the exposure time actually received by the silver halide emulsion, but the exposure time per pixel is the exposure time of the light flux in the case of scanning exposure with laser light. In the spatial variation of the intensity, the outer edge of the light flux is defined as the point where the light intensity becomes 1/2 of the maximum value, and the line that is parallel to the scanning line and that passes through the point where the light intensity is maximum intersects the outer edge of the light flux. When the distance between two points is the diameter of the light beam, the (light beam diameter) / (scanning speed) can be considered as the exposure time per pixel.

The relationship between the exposure time and the color density tends to become complicated as the exposure time per pixel becomes shorter, and the present invention is particularly effective when an apparatus having a short exposure time per pixel is used. ..

A laser printer device that is considered to be applicable to such a system is, for example, Japanese Patent Laid-Open No. 55-55.
-4071, 59-10662, 63-197.
947, JP-A-2-74942, and JP-A-2-23658.
No. 3, Japanese Patent Publication No. 56-14963, No. 56-40822.
No., European Wide Area Patent 77410, Technical Report of the Electronics and Communications Division, Volume 80, No. 244, and Movie Television Technical Journal, 1984.
/ 6 (382), pages 34 to 36, and the like.

In the silver halide photographic light-sensitive material of the present invention, dyes having absorption in various wavelength regions can be used for the purpose of preventing irradiation and halation. For this purpose, any of the known compounds can be used, and particularly as the dye having absorption in the visible region, the dyes of AI-1 to 11 described in Japanese Patent Application No. 2-51124, pages 117 to 118. As the infrared absorbing dye, compounds represented by the general formulas (I), (II), and (III) described in JP-A 1-280750, page 2, lower left column have preferable spectral characteristics. However, there is no influence on the photographic characteristics of the silver halide photographic emulsion and there is no contamination due to residual color, which is preferable. Specific examples of preferable compounds include Exemplified Compounds (1) to (45) listed on page 3, lower left column to page 5, lower left column.

The silver halide photographic light-sensitive material according to the present invention is characterized in that at least one of the silver halide emulsion layers or other photographic constituent layers contains the compound of the above-mentioned general formula [A]. In the general formula [A], A ₁ specifically represents a coupler residue or a reducing agent residue. The coupler residue represented by A ₁ includes a yellow, magenta and cyan color forming coupler residue and a residue that forms a substantially colorless compound.

Typical examples of the yellow coupler residue are US Pat. Nos. 2,298,443 and 2,407,2.
No. 10, No. 2,875, 057, No. 3, 048, 19
No. 4, No. 3,265,506, No. 3,447,928
No. and Farb Kupler Aineliteratul Vergicht Agfa Mitting (B and II)
(Farbkuplepleine Liteatur
Bersiecht Agfa Mitteilung
(B and II)) 112-126 (1961)
Year) etc. Of these, acylacetanilides such as benzoylacetanilide and pivaloylacetanilide are preferable.

Typical examples of the magenta coupler residue are US Pat. Nos. 2,369,489 and 2,343,7.
03, 2,311,182, 2,600,78
No. 8, No. 2,908,573, No. 3,062,653
Nos. 3,152,896, 3,519,429
No. 3,725,067, No. 4,540,654
No. 59-162548, and the aforementioned Agfa.
Mitteilung (B and II) 126-
156 (1961) and the like. Of these, pyrazolone or pyrazoloazole (eg, pyrazoloimidazole, pyrazolotriazole, etc.) is preferable.

Typical examples of the cyan coupler residue are US Pat. Nos. 2,367,531 and 2,423,7.
No. 30, No. 2,474,293, No. 2,772,16
No. 2, No. 2,395,826, No. 3,002,836
Issue 3,034,892, Issue 3,041,236
No. 4,666,999, and the aforementioned Agfa.
Mitteilung (B and II) 156-1
P. 75 (1961). Of these, phenols or naphthols are preferable.

Representative coupler residues that form substantially colorless products are described, for example, in British Patent 861,1.
38, U.S. Pat. Nos. 3,632,345 and 3,92.
8,041, 3,958,993 and 3,96
1, 959, etc. Of these, cyclic carbonyl compounds are preferred.

Examples of the bleaching accelerator residue represented by BA in the general formula [A] include, for example, JP-A-49-42349.
No. 53, No. 53-94927, No. 53-95630, No. 53-141623, No. 55-26506, Japanese Patent Publication No. 45-8506, No. 49-26586, No. 53-9.
854, U.S. Pat. Nos. 3,893,858 and 4,55.
The bleach-accelerating residues described in 2,834 and British Patent 1,138,842 are mentioned.

BA is more preferably the following general formula [BA-
1] and [BA-2].

[0044]

[Chemical 5]

In the formula, R ₂₀ , R ₂₂ , R ₂₃ and R ₂₄ are linear or branched alkylene groups having 1 to 8 carbon atoms, cycloalkylene groups having 3 to 12 carbon atoms, and 6 carbon atoms. ~
10 arylene group or heterocyclic group having 1 to 10 carbon atoms (for example, pyrazole, imidazole, triazole, tetrazole, oxazole, thiazole, pyrrole, indole, benzimidazole, benzoxazole, benzthiazole, tetraazaindene, isoxazole, Isothiazole, pyridine, aziridine,
A group derived from piperidine, morpholine, piperazine, oxazoline or the like), R ₂₁ and R ₂₅ each represent a hydrophilic substituent, preferably a π substituent constant of 0.5 or less, more preferably a negative value. It is a substituent.

The π-substituent constant is the constant, constant for correlation, analysis in chemistry and biology (Sub).
situation Constants for Co
relation Analysis in Che
mystery and Biology), C.I. C. Hansch and A. Leo
Written by Jhon Wiley 197
It is a value calculated for X ₃ by the method described in 1997. Z ₄ is -O-, -S-, -OCO-, -OSO ₂
-, -SO-,

[0047]

[Chemical 6]

(R ₂₆ represents an alkyl group) a represents an integer of 0 to 2, and b represents 0 or 1. R ₂₀ , R ₂₂ ,
R ₂₃ and R ₂₄ are preferably alkylene groups, and R ₂₁ is preferably a carboxyl group, a sulfo group, a hydroxy group or an amino group.

When A ₁ represents a reducing agent residue, the reducing agent residue is preferably the theory of photographic processes (The Theor).
y of Photographic Procedures
s) A compound having a reducing agent nucleus according to the Kendall rule or the Pelz rule published by the fourth edition Macmillan Co. (1977), for example, hydroquinone, naphthohydroquinone, catechol, pyrogallol, gallic acid, p- Examples thereof include derivative residues such as phenylenediamine and ascorbic acid. A ₁ is preferably a coupler residue or a hydrazine derivative residue, more preferably a coupler residue.

In the general formula [A], Time ₁ , Tim
The timing group represented by e ₂ is conveniently used for the purpose of adjusting the coupling activity, the release rate, the diffusivity and the like. Typical timing groups include the following known timing groups. (1) A group that causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system. For example, JP-A-56-114946,
The groups described in Nos. 57-154234, 62-86361, 62-87958 and the like.

(2) A group which causes a cleavage reaction by utilizing an intramolecular nucleophilic substitution reaction. For example, US Pat. No. 4,248,962
And the groups described in JP-A-57-56837. (3) A group that utilizes the cleavage reaction of hemiacetal. For example, U.S. Pat. No. 4,146,396, JP-A-60-249148.
And the groups described in No. 60-249194.

In the general formula [A], the group represented by A ₂ is specifically a group which becomes a coupler or a reducing agent residue after being cleaved from the group represented by the general formula [A-3]. In the case of a phenol type coupler, for example, a group serving as a coupler is an oxygen atom excluding a hydrogen atom of a hydroxyl group, which is bonded to a group represented by the general formula [A-3], and is released therefrom. Only then can it become a phenol-type coupler capable of coupling with an oxidized product of a developing agent. The coupling position has a group represented by the general formula [A-2].

[0053]

[Chemical 7]

The group serving as a reducing agent residue is preferably a group represented by the general formula [A0].

[0055]

[Chemical 8]

The group represented by the general formula [A-3] is bonded with P, P and Q each independently represent an oxygen atom or a substituted or unsubstituted imino group, and n and V are W and W respectively.
At least one of the above represents a methine group having a group represented by the general formula [A-3] as a substituent, V and W other than that represent a substituted or unsubstituted methine group or a nitrogen atom, and r is It represents an integer of 1 to 3, and R represents a hydrogen atom or a group that can be removed by an alkali.

(X = Y) n preferably represents a benzene ring. A ₂ is preferably a reducing agent residue, more preferably a gallic acid derivative residue. k is preferably 0 or 1, m and n are preferably 0, and most preferably k, m and n are both 0.

Examples of the BAR compound used in the present invention include those disclosed in JP-A-61-201247 and JP-A-55-250.
No. 56, No. 55-29805, No. 60-50533.
No. 61, No. 61-28947, No. 62-56963, No. 62-173463, No. 62-247363, No. 6
3-70854, 63-106748, 121
No. 843, No. 63-121844, No. 63-1218.
No. 45, No. 63-214752, No. 63-25445.
No. 2, 64-21159, JP-A-1-201657.
No. 1-207747, No. 1-209447, No. 1-214847, No. 1-231049 and the like.

The addition amount of the BAR compound used in the present invention to the light-sensitive material is 1 × 10 ³ per 1 m ² of the light-sensitive material.
^-7 mol to 1 x 10 ^-1 mol is preferable, and 1 x 10 ^-6 mol to 5 x 10 ^-2 mol is particularly preferable. The BAR compound used in the present invention can be added to all layers of the light-sensitive material and may be used in two or more layers. Further, it is preferably added to the photosensitive emulsion layer. Specific examples of BA are shown below, but the compound used in the present invention is not limited thereto.

[0060]

[Chemical 9]

Specific examples of the BAR compound of the present invention are shown below, but the compounds of the present invention are not limited to these.

[0062]

[Chemical 10]

[0063]

[Chemical 11]

[0064]

[Chemical 12]

[0065]

[Chemical 13]

The coupler used in the silver halide photographic light-sensitive material according to the present invention forms a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm through a coupling reaction with an oxidant of a color developing agent. Any compound that can be used can be used, but as a particularly typical example, a yellow coupler having a spectral absorption maximum wavelength in a wavelength range of 350 to 500 nm, a wavelength range of 500 to 60
A magenta coupler having a spectral absorption maximum wavelength at 0 nm,
The one known as a cyan coupler having a spectral absorption maximum wavelength in the wavelength range of 600 to 750 nm is typical.

The yellow coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention is a coupler represented by the general formula (Y-I) described on page 8 of Japanese Patent Application No. 2-234208. Can be mentioned. Specific compounds are described in YC-1 on pages 9 to 11 of the specification.
To those listed as YC-9. Among them, YC-described on page 11 of the same specification.
8 and YC-9 are preferable because they can reproduce a preferable yellow color.

As the magenta coupler which can be preferably used in the silver halide photographic light-sensitive material according to the present invention, the general formula (M-I) and the general formula (M) described in Japanese Patent Application No. 2-234208, page 12 can be used. A coupler represented by -II) may be mentioned.

Specific compounds include those described as MC-1 to MC-11 on pages 13 to 16 of the same specification. Among them, MC-8 to MC-11 described on pages 15 to 16 of the same specification are preferable because they are excellent in reproduction of colors ranging from blue to purple and red and are also excellent in detail descriptive power.

Cyan couplers that can be preferably used in the silver halide photographic light-sensitive material of the present invention include:
Examples thereof include couplers represented by the general formula (C-I) and the general formula (C-II) described on page 17 of Japanese Patent Application No. 2-234208. Specific compounds are described in the same specification 1
Examples thereof include those described as CC-1 to CC-9 on pages 8 to 21.

In the case of the oil-in-water type emulsion dispersion method used for adding the coupler used in the silver halide photographic light-sensitive material of the present invention, it is usually used in a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher. If necessary, a low-boiling point and / or water-soluble organic solvent is also used in combination to dissolve, and a surfactant is emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution.

As the dispersing means, a stirrer, homogenizer, colloid mill, flow jet mixer, ultrasonic disperser or the like can be used. After the dispersion or at the same time as the dispersion, a step of removing the low boiling point organic solvent may be added.
As the high boiling point organic solvent that can be used for dissolving and dispersing the coupler, phthalic acid esters such as dioctyl phthalate and phosphoric acid esters such as tricresyl phosphate are preferably used.

In place of the method using a high-boiling point organic solvent, the coupler and the water-insoluble and organic-solvent-soluble polymer compound are dissolved in a low-boiling point and / or water-soluble organic solvent, if necessary, to prepare a gelatin aqueous solution or the like. A method of emulsifying and dispersing by using various dispersing means using a surfactant in a hydrophilic binder can also be used. The water-insoluble organic solvent-soluble polymer used at this time is poly (Nt
-Butylacrylamide) and the like.

For the purpose of shifting the absorption wavelength of the color forming dye, the compound (d-11) described on page 33 of Japanese Patent Application No. 2-234208 and the compound (A'-1) described on page 35 of the specification. And other compounds can be used. Also,
Besides, the fluorescent dye-releasing compounds described in US Pat. No. 4,774,187 can also be used.

The coating amount of the coupler is not particularly limited as long as a sufficiently high concentration can be obtained, but it is preferably 1 × 10 ^{−3 to} 5 mol, and more preferably 1 mol per mol of silver halide. It is used in a range of × 10 ^-2 to 1 mol.

In the silver halide photographic light-sensitive material of the present invention, it is advantageous to use gelatin as a binder, but if necessary, other gelatin, gelatin derivatives, graft polymers of gelatin and other polymers, gelatin. Other than the above, hydrophilic colloids such as proteins, sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymer substances such as single or copolymers can be used.

As the reflective support according to the present invention, any material may be used, including white pigment-containing polyethylene coated paper, baryta paper, vinyl chloride sheet, white pigment-containing polypropylene, polyethylene terephthalate support and the like. Can be used. Above all, a support having a polyolefin resin layer containing a white pigment on its surface is preferable.

As the white pigment used in the reflective support according to the present invention, inorganic and / or organic white pigments can be used, and preferably inorganic white pigments are used. For example, alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, finely divided silicic acid, silicas such as synthetic silicates, calcium silicate, alumina, alumina hydrate, oxidation Examples thereof include titanium, zinc oxide, talc and clay. The white pigment is preferably barium sulfate or titanium oxide.

The amount of the white pigment contained in the waterproof resin layer on the surface of the reflective support according to the present invention is preferably 10% by weight or more as the content in the waterproof resin layer,
Further, the content is preferably 13% by weight or more, and more preferably 15% by weight or more.

The dispersity of the white pigment in the water resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, and more preferably 0.10 or less as the coefficient of variation described in the above publication. Is more preferable.

In the silver halide photographic light-sensitive material according to the present invention, the support surface is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, and then directly or undercoat layer (adhesiveness of the support surface, Applied through one or more undercoat layers for improving antistatic property, dimensional stability, abrasion resistance, hardness, antihalation property, friction property and / or other property) Good.

When coating a photographic light-sensitive material using a silver halide emulsion, a thickener may be used in order to improve coatability. As the coating method, extrusion coating and curtain coating, which can simultaneously coat two or more layers, are particularly useful.

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

CD-1) N, N-diethyl-p-phenylenediamine CD-2) 2-amino-5-diethylaminotoluene CD-3) 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4) 4- (N-ethyl-N- (β-hydroxyethyl) amino) aniline CD-5) 2-methyl-4- (N-ethyl-N- (β-
Hydroxyethyl) amino) aniline CD-6) 4-amino-3-methyl-N- (β- (methanesulfonamido) ethyl) -aniline CD-7) N- (2-amino-5-diethylaminophenylethyl) methane Sulfonamide CD-8) N, N-dimethyl-p-phenylenediamine CD-9) 4-amino-3-methyl-N-ethyl-N-
Methoxyethylaniline CD-10) 4-amino-3-methyl-N-ethyl-N
-(Β-Ethoxyethyl) aniline CD-11) 4-amino-3-methyl-N-ethyl-N
-(Β-Butoxyethyl) aniline

In the case of the image forming method used in the present invention, the compound represented by the following general formula (CD-1) is more preferably used from the viewpoint of development processing for a short time.

[0086]

In the formula (CD-1), R is a linear or branched alkylene group having 3 carbon atoms, and m and n are each 1
Is an integer of ~ 4, HA represents an inorganic or organic acid,
For example, it represents hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, or the like. These color developing agents are
American Chemical Society Volume 73, 3100
It can be easily synthesized by the method described in (1951). Specific examples of the compound represented by formula (CD-1) are shown below.

[0088]

[Chemical 15]

[0089]

[Chemical 16]

The color developing agent according to the present invention is usually used in the range of 1 × 10 ^-2 to 2 × 10 ^-1 mol per liter of the developing solution, and from the viewpoint of rapid processing, 1 is added per 1 liter of the color developing solution. It is preferably used in the range of 0.5 × 10 ^{-2 to} 2 × 10 ^-1 mol. The color developing agent used in the image forming method of the present invention may be used alone or in combination with other known p-phenylenediamine derivatives.

In the image forming method of the present invention, (CD-5), (CD-6) and (CD-9) are preferable as the compound used in combination with the compound represented by the general formula [A]. These p-phenylenediamine derivatives are
It is generally used in the form of salt such as sulfate, hydrochloride, sulfite, nitrate and p-toluenesulfonate.

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

In the present invention, the color developing solution contains chlorine ions in an amount of 3.4 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / liter. Preferably, 3.4 × 10 ^{-2 to} 1.5
It is × 10 ^-1 mol / liter. Chloride ion is 3.4 ×
When it is less than 10 ^-2 , the photographic performance varies greatly when a photographic material containing a BAR compound is continuously processed, which is not preferable for suppressing fog. Also 1.5 × 10 ^-1 mol /
When it is more than 1 liter, the development is delayed and the maximum density is lowered.

In the present invention, the color developing solution preferably contains bromine ions in an amount of 3.0 × 10 ^{−5 to} 1.0 × 10 ⁻³ mol / liter. More preferably 5.0
It is × 10 ^{-5 to} 5 × 10 ^-4 mol / liter. If the bromine ion is less than 3.0 × 10 ^-5 , fog cannot be sufficiently prevented, and if it is more than 1.0 × 10 ^-3 mol / liter, the development is delayed and the maximum density is lowered, which is preferable. Absent.

Here, chlorine ions and bromine ions may be added directly to the developing solution, or may be eluted from the light-sensitive material into the developing solution during the development processing. When added directly to the color developer, sodium chloride,
Examples thereof include potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, cadmium chloride and the like, among which sodium chloride and potassium chloride are preferable. Further, it may be supplied from an optical brightener added to the developing solution.

As the bromine ion supplying substance, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, nickel bromide, magnesium bromide, manganese bromide,
Calcium bromide, cadmium bromide, cerium bromide, thallium bromide and the like can be mentioned. Among them, preferable ones are
Sodium bromide and potassium bromide. When it is 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.

Further, if necessary, a development accelerator can be used. Examples of the development accelerator include various pyridinium compounds represented by US Pat. Nos. 2,648,604, 3,671,247 and JP-B-44-9503, other cationic compounds, and phenosafranine. Cationic dyes, neutral salts such as thallium nitrate, US Pat. Nos. 2,533,990 and 2,531,8
No. 32, No. 2,950,970, No. 2,577,12
Nonionic compounds such as polyethylene glycol and its derivatives, and polythioethers described in JP-B No. 7-9 and JP-B-44-9504, organic solvents, organic amines, ethanolamine, ethylenediamine, diethanolamine, triethanol described in JP-B-44-9509 Includes amines and the like.

Further, phenethyl alcohol described in US Pat. No. 2,304,925, and other acetylene glycol, methyl ethyl ketone, cyclohexanone,
Pyridine, ammonia, hydrazine, thioethers,
Examples thereof include amines. Further, in the color developer according to the present invention, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other Japanese Patent Publication No. 47-3.
The compounds described in Japanese Patent Nos. 3378 and 44-9509 can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developing agent may be used together with the developing agent. Examples of these auxiliary developers include N-methyl-p-aminephenol sulfate, phenidone, N, N'-diethyl-p-aminophenol hydrochloride, N, N, N ', N'-tetramethyl- P-phenylenediamine hydrochloride and the like are known, and the addition amount thereof is usually 0.01 to 1.0 g per liter of the developing solution.
Used. In addition to these, competing couplers, fogging agents, development inhibitor-releasing couplers (so-called DIR couplers), development inhibitor-releasing compounds and the like can be added as required.

Furthermore, various additives such as other stain preventing agents, sludge preventing agents, and multi-layer effect accelerators can be used. Each component of the above color developing solution can be prepared by sequentially adding and stirring to a fixed amount of water. In this case, the component having a low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. Further, more generally, a color developing solution according to the present invention is prepared by adding a plurality of components, each of which can coexist stably, in a concentrated aqueous solution or in a solid state prepared in advance in a small container into water and stirring. Can also be prepared.

In the present invention, the above-mentioned color developing solution can be used in an arbitrary pH range, but from the viewpoint of rapid processing, the pH of the color developing solution is 9.
It is preferably 5 to 13.0, and more preferably used in the pH range of 9.8 to 12.0. The processing temperature for color development according to the present invention is preferably 35 ° C. or higher and 70 ° C. It is preferable that the temperature is higher because the treatment can be performed for a shorter time, but it is preferable that the temperature is not so high in view of the stability of the treatment liquid, and it is preferable that the treatment is performed at 37 ° C or higher and 60 ° C or lower.

The color development time is conventionally about 3 minutes and 30 seconds, but in the present invention, it is within 25 seconds.
Further, it is preferable to carry out in the range of 20 seconds to 3 seconds. The processing steps substantially consist of a color development step, a bleach-fixing step, and a water washing step (including a stabilization treatment as an alternative to water washing), but steps may be added or have the same meaning as long as the effects of the present invention are not impaired. Can be replaced with For example, the bleach-fixing step can be separated into a bleaching step and a fixing step, or the bleaching step can be performed before the bleach-fixing step. The processing steps used in the image forming method of the present invention include:
It is preferable to provide a bleach-fixing step immediately after the color developing step.

The bleaching agent that can be used in the bleach-fixing solution used in the image forming method of the present invention is not limited, but is preferably a metal complex salt of an organic acid. The complex salt is obtained by coordinating a polycarboxylic acid, an aminopolycarboxylic acid, or an organic acid such as oxalic acid or citric acid with a metal ion such as iron, cobalt or copper. The most preferred organic acid used to form such a metal complex salt of an organic acid includes
Mention may be made of polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific examples of these compounds are described in JP-A-1.
Compounds [2] to [20] described in JP-A-205262, pages 58 to 59 can be mentioned. These bleaching agents are used in an amount of 5 to 450 g, preferably 20 to 250 g, per liter of the bleach-fixing solution. As the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied.

Further, iron (III) ethylenediaminetetraacetate
A bleach-fixing solution having a composition in which a large amount of a halide such as ammonium bromide is added in addition to the acid bleaching agent and the silver halide fixing agent, and further ethylenediaminetetraacetic acid iron (I
II) A special bleach-fixing solution having a composition comprising a combination of an acid bleaching agent and a large amount of a halide such as ammonium can be used. As the halide,
In addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like can be used.

The silver halide fixing agent contained in the bleach-fixing solution is a compound which reacts with silver halide as used in ordinary fixing processing to form a water-soluble complex salt, for example, potassium thiosulfate or sodium thiosulfate. Typical examples thereof include thiosulfates such as ammonium thiosulfate, potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiocyanate, thiourea and thioether. These fixing agents are used in an amount of 5 g or more per liter of the bleach-fixing solution in a range where they can be dissolved, but generally 70 to 250 g is used.

The bleach-fixing solution contains various pH values such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide.
The buffer may be contained alone or in combination of two or more kinds. Further, various fluorescent whitening agents, antifoaming agents or surfactants may be contained.

Further, hydroxylamine, hydrazine,
Preservatives such as bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids or stabilizers such as nitroalcohol and nitrate, organic solvents such as methanol, dimethyl sulfonamide, dimethyl sulfoxide, etc. You can

The bleach-fixing solution according to the present invention is described in JP-A-46 / 46.
-280, Japanese Patent Publication No. 458506, 46-556.
No., Belgian Patent No. 770910, Japanese Patent Publication No. 45-883
Various bleaching accelerators described in JP-A Nos. 6-53, 53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

The bleach-fixing paint is used at a pH of 4.0 or higher, but is generally used in the range of 4.0 to 9.5.
It is preferably used at a pH of 4.5 to 8.5. Most preferably, it is used in the pH range of 5.0 to 8.5. The treatment is performed at a temperature of 80 ° C. or lower, preferably 55 ° C. or lower, while suppressing evaporation and the like. The processing time for bleach-fixing is preferably 3 to 45 seconds, more preferably 5 to 30 seconds.

In the developing treatment according to the present invention, washing with water is carried out subsequent to the color developing and bleach-fixing steps. A preferred embodiment of the washing treatment will be described below. As the compound preferably used in the washing solution, a chelating agent having a chelate stabilization constant for iron ions of 8 or more is preferable.

Here, the chelate stabilization constant is defined as L. G.
Sillen, A .; E. Martell, "Stab
ility Constants of Metali
on Complexes ”, The Chemical
Society, London (1964) and S.S. C
haberek, A .; E. Martell, "Org
anic Sequestering Agent
s ", Wiley (1959), etc., and generally known constants.

Examples of chelating agents having a chelate stability constant of 8 or more for iron ions, which are preferably used in the washing solution, include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. Be done. The iron ion means ferric ion.

The chelate stability constant with ferric ion is 8
Specific examples of the above-mentioned chelating agent include compounds described in JP-A-1-205162, page 63, line 15 to page 64, line 17. The amount of the chelating agent used is preferably 0.01 to 50 g, and more preferably 0.05 to 20 g, per liter of the washing solution.

Further, as a compound to be added to the washing solution, an ammonium compound is mentioned as a particularly preferable compound. These are supplied by ammonium salts of various inorganic compounds, and specific examples thereof include compounds described in JP-A-1-205162, page 65, line 5 to page 66, line 11. The amount of the ammonium compound added is preferably 1.0 × 10 ⁻⁵ mol or more, more preferably 0.001 to 5.0 mol, and further preferably 0.002 to 1.0 mol, per liter of the washing liquid. It is in the molar range.

Further, it is desirable that the washing liquid contains sulfite in an amount within the range where bacteria are not generated.
The sulfite to be contained in the washing solution may be any one such as an organic substance or an inorganic substance as long as it releases a sulfite ion, but is preferably an inorganic salt, and preferable specific compounds include sodium sulfite, potassium sulfite and ammonium sulfite. , Ammonium bisulfite, potassium bisulfite,
Examples thereof include sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite and hydrosulfite, cartaraldehyde bis sodium bisulfite, succinic aldehyde bis sodium bisulfite and the like.

It is preferable that at least 1.0 × 10 ^-5 mol of the sulfite is added to 1 liter of the washing solution.
More preferably, it is 5 × 10 ^{−5 to} 1.0 × 10 ⁻¹ mol. It may be added directly to the washing solution, but it is preferably added to the washing replenisher. The washing liquid used in the present invention preferably contains a fungicide,
This makes it possible to prevent sulfidation and improve image storability.

Examples of the fungicide which can be used in the washing liquid according to the present invention include sorbic acid, benzoic acid compounds, phenol compounds, thiazole compounds, pyridine compounds, guadinine compounds, morpholine compounds, quaternary compounds. Phosphonium compounds, ammonium compounds, urea compounds, isoxazole compounds, propanolamine compounds, sulfamide compounds, pyronone compounds and amino compounds.

Specific compounds are described in JP-A 1-20
Compounds described in JP-A No. 5162, page 68, line 10 to page 72, line 16 are mentioned. Among these compounds, particularly preferably used compounds are thiazole compounds, sulfamide compounds and pyronone compounds. The amount of the antifungal agent added to the washing liquid is 0.001 to 1 liter of the washing liquid.
It is preferably used in the range of 30 g, and more preferably in the range of 0.003 to 5 g.

The washing liquid according to the present invention preferably contains a metal compound in combination with a chelating agent. Examples of such metal compounds include Ba, Ca, Ce, Co, In and L.
a, Mn, Ni, Bi, Pb, Sn, Ti, Zr, M
Examples thereof include compounds of g, Al and Sr. These metal compounds can be supplied as an inorganic or organic salt such as a halide salt, a sulfate salt, a carbonate salt, a phosphate salt or an acetate salt, a hydroxide or a water-soluble chelate compound. The addition amount of these compounds is 1.0 × 10 1 liter of the washing liquid.
^{-4 to} 1.0 x 10 ^-1 mol is preferable and 4.0 x 10 ^-4 to
2.0 × 10 ^-2 mol is more preferable.

In addition to the above, a compound having an aldehyde group may be used as the one contained in the washing solution according to the present invention. Specific compounds include, for example, JP-A-1-20516.
The Exemplified Compound 1 to Exemplified Compound 32 described on pages 73 to 75 of Japanese Patent Publication No. 2 can be mentioned. The compound having an aldehyde group is 0.1 to 50 g per 1 liter of washing water.
It is preferable to use it in the range of 0.5 to 10 g.
It is preferably used in the range of.

Further, ion-exchanged water treated with an ion-exchange resin may be used for the washing solution according to the present invention. The pH of the washing solution applicable to the present invention is in the range of 5.5 to 10.0. As the pH adjuster applicable to the present invention, any of generally known alkali agents and acid agents can be used.

The treatment temperature of the water washing treatment is preferably 15 ° C to 60 ° C, more preferably 20 ° C to 45 ° C. Also,
The washing time is preferably 5 to 60 seconds, more preferably 5 to 50 seconds. When the water washing treatment is performed in a plurality of tanks, it is preferable that the earlier tank is treated in a shorter time and the latter tank is treated in a longer time. The processing time of the back tank is especially 20
It is preferable that the treatments are sequentially performed with treatment times increasing by 50% to 50%.

When the multi-tank counter flow current system is used as the method for supplying the washing liquid in the washing treatment step according to the present invention, it is preferable that the washing liquid is supplied to the post-bath and allowed to overflow into the pre-bath. Of course, it can also be processed in a single tank. As a method of adding the compound, various methods such as adding as a concentrated solution to the washing tank, or adding the above compound and other additives to the washing solution supplied to the washing tank, and using this as a washing replenisher Is used.

The amount of washing water in the washing step according to the present invention is preferably 0.1 to 50 times, particularly preferably 0.5 to 30 times, the amount carried in the pre-bath (usually bleach-fixing solution or fixing solution) per unit area of the light-sensitive material. preferable. The washing tank in the washing treatment according to the present invention is preferably 1 to 5 tanks, and more preferably 1 to 3 tanks.

As a developing processing apparatus for the silver halide photographic light-sensitive material used in the image forming method of the present invention, any known apparatus may be used. Specifically, it may be a roller transport type in which the photosensitive material is conveyed by sandwiching it between rollers arranged in a processing tank, or an endless belt method in which the photosensitive material is fixed and conveyed in a belt, The processing tank is formed in a slit shape, the processing solution is supplied to the processing tank and the photosensitive material is conveyed, the spray method for spraying the processing solution, and the web method by contact with the carrier impregnated with the processing solution A method using a viscous treatment liquid can also be used.

In the image forming method of the present invention, the time from exposure to development may be any time, but a shorter time is preferable in order to shorten the overall processing time. Further, the silver halide photographic light-sensitive material according to the present invention is advantageous because the change in image density is small even when the time from exposure to development is 30 seconds or less and a high quality image can be stably obtained. Can be used for.

[0128]

The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 A paper support was prepared by laminating high density polyethylene on both sides of a paper pulp weighing 180 g / m ² . However, on the side on which the emulsion layer was coated, a molten polyethylene containing 15% by weight of surface-treated anatase type titanium oxide dispersed therein was laminated to prepare a reflective support. On this reflective support, each layer having the following constitution was coated to prepare a multilayer silver halide photographic light-sensitive material, 101. The coating solution was prepared as follows.

First layer coating solution 26.7 g of yellow coupler (Y-1), 10.0 g of dye image stabilizer (ST-1), dye image stabilizer (ST
-2) 6.67 g, additive (HQ-1) 0.67 g and high boiling point organic solvent (DNP) 6.67 g to ethyl acetate 6
0 ml was added and dissolved, and this solution was added with 10% containing 9.5 ml of 15% surfactant (SU-1).
220 ml of an aqueous gelatin solution was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion liquid. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.68 g of silver) prepared under the following conditions to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Further, as a hardening agent, (H-1) was added to the second and fourth layers, and (H-2) was added to the seventh layer. As the coating aid, surfactants (SU-2), (SU-3)
Was added to adjust the surface tension. The layer structure is as follows.

[0132]

[Table 1]

[0133]

[Table 2]

[0134]

[Chemical 17]

[0135]

[Chemical 18]

[0136]

[Chemical 19]

[0137]

[Chemical 20]

[0138]

[Chemical 21]

[Method for preparing blue-sensitive silver halide emulsion] 4
In 1000 ml of a 2% gelatin aqueous solution kept at 0 ° C., the following (solution A) and (solution B) were pAg = 6.5, p
Simultaneously added over 30 minutes while controlling H = 3.0, and the following (solution C) and (solution D) were added to pAg = 7.3, pH =
Simultaneous addition was carried out over 180 minutes while controlling at 5.5. The pAg at this time was controlled by the method described in JP-A-59-45437, and the pH was controlled by using an aqueous solution of sulfuric acid or sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.07 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g Potassium bromide 2. Add 10 g water to 600 ml (solution D) Silver nitrate 300 g Add water to 600 ml

After the addition is completed, Demol N manufactured by Kao Atlas Co., Ltd.
Of 5% aqueous solution of magnesium sulfate and 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous solution of gelatin to have an average particle size of 0.85 μm, coefficient of variation (S / R) = 0.07, silver chloride content. 99.0 mol% monodisperse cubic emulsion EMP-1
Got The emulsion EMP-1 was chemically ripened at 50 ° C. for 90 minutes using the following compound to obtain a blue-sensitive silver halide emulsion (Em-B1).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye BS-1 4 × 10 ⁻⁴ mol / mol AgX Sensitizing dye BS-2 1 × 10 ^-4 mol / mol AgX

[Preparation Method of Green-Sensitive Silver Halide Emulsion]
(A solution) and (B solution) addition time and (C solution) and (D solution)
In the same manner as EMP-1 except that the addition time of
Average particle size 0.43 μm, coefficient of variation (S / R) = 0.0
7. Monodisperse cubic emulsion E having a silver chloride content of 99.0 mol%
MP-2 was obtained. EMP-2 was chemically ripened at 55 ° C. for 120 minutes using the following compound to obtain a green-sensitive halogenated emulsion (Em-G1).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX Stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye GS-1 4 × 10 ⁻⁴ mol / mol AgX

[Preparation Method of Red-Sensitive Silver Halide Emulsion]
(A solution) and (B solution) addition time and (C solution) and (D solution)
The average particle size is 0.50 μm and the coefficient of variation (S / R) = 0.0 in the same manner as in EMP-1 except that the addition time is changed.
8. Monodisperse cubic emulsion E having a silver chloride content of 99.0 mol%
MP-3 was obtained. EMP-3 was chemically ripened at 60 ° C. for 90 minutes using the following compound to obtain a red-sensitive silver halide emulsion (Em-R1).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX Sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX

[0147]

[Chemical formula 22]

[0148]

[Chemical formula 23]

Here, in the preparation of the sample 101, the first
Samples 102-106 prepared by substituting an equimolar amount of BAR-1 for the yellow coupler of the layer and varying the potassium chloride and potassium bromide in the color developer as shown in Table 3.
And a magenta color forming coupler of the third layer with an equimolar BA
Sample 1 prepared by substituting R-4 and changing potassium chloride and potassium bromide in the color developing solution as shown in Table 3.
Nos. 07 to 111 were prepared by further replacing the cyan color coupler of the fifth layer with an equimolar amount of BAR-9, and changed potassium chloride and potassium bromide in the color developing solution as shown in Tables 3 and 4. 112-116 were produced.

After subjecting these samples to wedge exposure according to a conventional method, continuous processing was carried out according to the following processing steps until replenishment of three times the tank capacity of the color developing solution.

[Processing Step A] Processing Step Temperature Time Replenishment Amount Color development 35.0 ± 0.3 ° C. 20 seconds 80 ml / m ² Bleach-fixing 35.0 ± 0.5 ° C. 20 seconds 120 ml / m ² Washing with water 30-34 ° C. 60 seconds 150 ml / m ² dry 60-80 ° C. 30 seconds The composition of the developing solution is shown below.

[Color developer tank liquid] Pure water 800 ml Triethylenediamine 2 g Diethylene glycol 10 g Potassium bromide Table 3, Table 4 Potassium chloride Table 3, Table 4 Potassium sulfite 0.25 g N-ethyl-N- (β-methanesulfone Amidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g N, N-diethylhydroxylamine 6.8 g triethanolamine 10.0 g Diethylenetriaminepentaacetic acid sodium salt 2.0 g Optical brightener (4,4 ′) -Diaminostilbene sulfonic acid derivative) 2.0 g Potassium carbonate 30 g Water is added to adjust the total amount to 1 liter, and pH is adjusted to 10.10.

[Color developer replenisher] Pure water 800 ml Triethylenediamine 3 g Diethylene glycol 10 g Potassium sulfite 0.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 10 0.0 g N, N-diethylhydroxylamine 6.0 g Triethanolamine 10.0 g Diethylenetriamine pentaacetic acid sodium salt 2.0 g Optical brightener (4,4′-diaminostilbene sulfonic acid derivative) 2.5 g Potassium carbonate 30 g Water In addition, the total amount is adjusted to 1 liter, and the pH is adjusted to 10.60.

[Bleach-fixing solution tank solution and replenishing solution] Diethylenetriamine pentaacetate ammonium ferric dihydrate 65 g Diethylenetriamine pentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 5-Amino-1,3,4-thiadiazole-2 -Thiol 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 millitorr Water is added to bring the total volume to 1 liter, and the pH is adjusted to 6.5 with potassium carbonate or glacial acetic acid.

[Washing liquid tank liquid and replenishing liquid] Orthophenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-Methyl-4-isothiazolin-3-one 0.02 g diethylene 1.0g fluorescent brightener (Tinopal SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g BiCl ₃ (45% aqueous _{solution) 0.65g MgSO 4 · 7H 2 O} 0.2g PVP ( Polyvinylpyrrolidone) 1.0 g Ammonia water (25% ammonium hydroxide aqueous solution) 2.5 g Nitriloacetic acid trisodium salt 1.5 g Water is added to bring the total volume to 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or ammonia water. To do.

The obtained samples were evaluated by the methods shown below.

[Evaluation of Fog Resistance] Density (D
min) was measured by reflection with 310TF of X-Light Co. and evaluated. The smaller the value of Dmin, the better the fog resistance.

[Evaluation of Maximum Density] Maximum reflection density (Dam
x) was measured using a PDA-65 densitometer (manufactured by Konica Corporation). The larger the value of Damx, the better the resistance to ultra-rapid processing.

[Evaluation of Processing Stability] The gradation variation before and after the continuous processing (the gradation is defined as the average gradient between the density curve 0.3 and the density curve 0.75) was evaluated as Δγ. ..
The smaller the value of Δγ, the better the processing stability.

The results are shown in Tables 3 and 4 below.
As is clear from the results of Tables 3 and 4, the sample No. containing no BAR compound was used. It can be seen that 101 is insufficient in desilvering property when subjected to ultra-rapid processing. Further, samples 104, 105 of the silver halide photographic light-sensitive material according to the present invention,
106, 109, 110, 111, 114, 115, 1
16 and comparative samples 102, 103, 107, 108, 11
Comparing Nos. 2 and 113, even if a BAR compound is used, a sufficient maximum density can be obtained in the ultra-rapid processing, there is no increase in fog, there is little gradation variation in continuous processing, and excellent desilvering properties are obtained. You can see that

[0161]

[Table 3]

[0162]

[Table 4]

As is clear from the results of Tables 3 and 4,
Sample No. containing no BAR compound. It can be seen that 101 is insufficient in desilvering property when subjected to ultra-rapid processing. Further, Sample 10 of the silver halide photographic light-sensitive material according to the present invention
4, 105, 106, 109, 110, 111, 11
4, 115, 116 and comparative samples 102, 103, 10
Comparing Nos. 7, 108, 112, and 113, even when the BAR compound was used, a sufficient maximum density was obtained in the ultra-rapid processing, there was no increase in fog, there were few gradation fluctuations in continuous processing, and desilvering was performed. It turns out that it is also excellent in sex.

Example 2 In the preparation of the color developing solution of Example 1, the color developing agent was N-ethyl-N- (β-metalsulfonamidoethyl).
-3-Methyl-4-aminoaniline sulfate (Exemplary compound (CD-6)) from equimolar Exemplified compound (1-2),
(CD-5), (CD-9), and exemplary compound (1-
A color developer was prepared in the same manner except that the mixture of 2) and (CD-6) was replaced with an equal amount of the mixture, and evaluated in the same manner as in Example 1. As a result, the effect of the present invention was obtained with any color developing agent.

[0165]

EFFECTS OF THE INVENTION The silver halide photographic light-sensitive material according to the present invention is capable of ultra-rapid processing and can produce color prints with little fluctuation in photographic performance during continuous processing.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having at least one high chloride silver halide emulsion layer on a support,
In the method for forming a color image by processing with a color developing solution containing an aromatic primary amine color developing agent and containing substantially no benzyl alcohol, followed by bleach-fixing and washing with water to form a color image. The silver halide emulsion layer contains silver halide emulsion grains consisting of 95 to 99.9 mol% of silver chloride. At least one of the silver halide emulsion grains and the other photographic constituent layers contains the compound of the general formula [A]. And the color development time is 25 seconds or less, the total processing steps of the color development processing time, the bleach-fix processing time and the water washing processing time are within 2 minutes in total, and chlorine ion in the color development processing solution is contained. A color image forming method, wherein the density is 3 × 10 ^{-2 to} 1.5 × 10 ^-1 mol / liter. [Chemical 1] In the formula, A ₁ represents a group which releases a group represented by the general formula [A-1] by a reaction with an oxidized product of a developing agent, and A ₂ represents a group represented by a general formula by a reaction with an oxidized product of a developing agent. It represents a group that releases a group represented by [A-2], and is represented by Time ₁ and Time.
₂ represents a timing group, BA represents a bleaching accelerator or a precursor thereof, k represents 0, 1, or 2, m and n
Represents 0 or 1. [Chemical 2]