JPH0727190B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Detailed Description of the Invention

 The present invention relates to a silver halide color photographic light-sensitive material, and
Specifically, a silver halide emulsion consisting essentially of silver chloride
Halogen with layers to form a fast and stable dye image
The present invention relates to a method of processing a silver halide color photographic light-sensitive material. [Prior Art and its Problems] Dye images using ordinary silver halide color photographic light-sensitive materials
In the method for forming a film, after the imagewise exposure, the oxidized P-
Phenylenediamine color developing agents and dye image forming caps
To form a dye image. using this method
Is usually applied to the color reproduction method by the subtractive color method, and the red, green,
Cyan, magenta, and yellow for blue and blue
Of each dye image is formed on each photosensitive layer. Near
Year, during the development process, when forming such a dye image
High temperature development processing and processing steps are saved
Abbreviation is commonly done. Above all,
To shorten development processing time by high temperature development processing
Is very important to increase the developing speed in color development
Is. Development speed in color development is affected by two aspects
Receive. One is a silver halide color photographic light-sensitive material.
Yes, the other one is a color developer. In the former, especially, the grains of the photosensitive silver halide emulsion used
The shape, size, and composition of the child greatly affect the development speed
In the latter case, the conditions of the color developer, especially the development
It is sensitive to the type of inhibitor, especially silver chloride grains.
It turns out that it shows a remarkably high developing speed under certain conditions.
There is. A silver halide catalyst in which the silver halide consists essentially of silver chloride.
In the case of large photographic light-sensitive materials, it is
In order to prevent
Bromide such as thorium
Salt), instead of sodium chloride, potassium chloride, etc.
And certain organic development inhibitors such as adenyl
, Guanine, benzimidazole, benzotriazol
5-membered, 6-membered or condensed nitrogen-containing compounds such as
Uses heterocyclic compounds to maintain good photographic performance.
And an extremely high developing speed can be obtained. Water soluble, among others
Chloride or adenine is a particularly preferred development inhibitor.
It Therefore, silver halide grains consisting essentially of silver chloride
Silver halide color having silver halide emulsion layer containing
Photographic material (hereinafter referred to as silver chloride color photographic material) is water.
Contains soluble chloride or adenine as a development inhibitor,
And color development containing a P-phenylenediamine color developing agent
When processed with a developer, it is significantly more visible than conventional color development.
Image time can be shortened, which leads to rapid development processing.
Downsizing of automatic processor and reduction of developing replenisher
Going to, there is great practical value such as reduction of pollution load. On the other hand, silver halide color photographic light-sensitive by high speed and rapid processing
In forming a dye image of a material, for example during photographic processing
Obtained by changing the concentration, pH, temperature, etc. of the color developing agent
Photographic performance of color photographic light-sensitive materials (fogging, sensitivity, gradation
Etc.) and it is impossible to obtain a photographic image of constant quality.
It's difficult. Therefore, a large amount of color photographic light-sensitive material
A color lab that processes in
Therefore, the concentration of the above-mentioned eluted compounds, pH,
That the replenishment rate must be strictly controlled
It is annoying. In this regard, silver chloride color photographic light-sensitive materials
Even when processing with a color developer containing
The development speed is extremely high while maintaining good photographic performance.
Although it is possible to obtain the degree, on the other hand, the developing unit
Satisfactory photographic performance against changes in product, pH, temperature, etc.
There was room for improvement because it was not possible to obtain a photographic image. The inventors of the present invention applied for stabilization of such photographic performance.
(JP-A-59-232342), a specific organic development suppression
By carrying out color development processing in the coexistence of a denaturant and adenine
It was found that the stabilization of the treatment was significantly achieved. However, in recent years, silver halide photographic light-sensitive materials have been processed.
In order to reduce the pollution load as much as possible,
Benzyl alcohol, which is a color improver from the color developer
There is a particularly strong demand for the removal. Following the invention of the prior application, the present inventor
Good photographic properties even when benzyl alcohol is removed
As a result of repeated research on how to obtain stable Noh
It can be seen that clear processing alone does not provide sufficient stabilization.
It was. [Object of the Invention] Therefore, the present invention has been made in view of the above circumstances.
The purpose is to produce a dye image from a silver chloride color photographic light-sensitive material.
When the image is formed, benzyl alcohol
Even when the image is removed, the fogging, sensitivity, gradation, etc.
Provides good photographic performance and gives extremely high development speed
Dye image formation that can be obtained is always stable,
The present invention relates to a method for processing a halogen color silver halide photographic light-sensitive material. [Structure of the Invention] The object of the present invention is to prevent at least one layer of diffusion resistance on a support.
Having a silver halide emulsion layer containing a functional coupler,
At least one of the silver halide emulsion layers is silver chloride
Contains silver chlorobromide grains having a content of 80 to 99 mol%,
Furthermore, 20 to 1 mol% of silver bromide constituting the silver chlorobromide grains
Chlorobromide in which silver is localized in silver halide crystals
A silver halide color photographic light-sensitive material containing grains is
Processing with a color developer that contains substantially no alcohol.
Silver halide color photographic light-sensitive material characterized by
It is achieved by the method of processing the charge. [Specific Configuration of the Invention] The configuration of the present invention will be described in more detail below. Used in the silver halide color photographic light-sensitive material of the present invention
The photosensitive silver halide emulsion contains 80 mol% or more of silver chloride and 99 mol.
% Silver chlorobromide emulsions are preferred, especially silver chloride.
A silver chlorobromide emulsion containing 90 mol% or more and 98 mol% or less
It is preferable that the silver halide composition other than the silver chloride composition has an odor.
It must be silver halide. And takes 80 mol%
The silver halide grains having the above silver chloride composition are
In a silver halide emulsion layer containing silver genide grains
80% by weight or more of all silver halide grains
It is preferable that it is
Good The silver chloride composition of the present invention is 80 mol% or more and 99 mol% or less.
The content of silver halide grains contained is 20 to 1 mol%.
The silver bromide composition is localized in the silver halide grains.
Need to be present. The term "localization" as used herein means that the silver halide emulsion is treated with X-rays.
At least 70 mol% or more is preferable when analyzed by the diffraction method
Or a set of silver halides having a silver bromide composition of 90 mol% or more
The peak corresponding to the composition is clearly separated from the peak of the silver chloride composition.
It refers to a silver halide emulsion obtained separately. Such silver bromide grains in which silver bromide is localized are
Silver halide grains in which silver and silver chloride have a layered structure, and
Silver bromide grains are epitaxially bonded to silver chloride grains
It indicates a silver halide grain having Such silver halide grains are disclosed, for example, in JP-A-59-162540.
Method formed by Japanese Patent Publication No. 60-136,735, etc.
Can be formed in accordance with the following. The silver bromide localized portion of the present invention is in one silver halide grain.
In, two or more may be included. The silver halide emulsion of the present invention comprises a noble metal ion inside the grain.
If the exposure seconds during exposure change
It is particularly preferable in order to prevent the change in gradation. Precious metal salt
Is preferably iridium salt, rhodium salt, or gold salt.
The dium salt is preferred. The amount of these precious metal salts added is halo.
10 per mol of silver genide^-9~Ten^-FiveGood mole, 10^-8~Ten^-6
Molar is preferred. The silver halide emulsion of the present invention is transparent in an unchemically sensitized state.
Silver coverage on support 2g / m²While chemically sensitized
Coated silver halide emulsion under the same conditions and exposed to white light
Then, the maximum density when treated with the surface developer A below ▲ D^s
_u▼ (Unchemically sensitized emulsion) and ▲ D^s _s▼ (chemically sensitized emulsion)
▲ D^s _u▼ ＜ ▲ D^s _s▼ × 0.5, preferably ▲ D^s _u▼ ＜ ▲ D^s _s▼
× 0.3, while each sample was exposed to white light and
After bleaching with a bleaching solution (BL), process with the following internal developer B
Maximum concentration when ▲ Dⁱ _s▼ ＜ ▲ Dⁱ _u▼ × 0.5, preferably
▲ Dⁱ _s▼ ＜ ▲ Dⁱ _u▼ Chemically sensitized to be 0.2
It is necessary, moreover, ▲ D above^s _s▼ and ▲ Dⁱ _u▼ is ▲ D^s _s▼ ＞ ▲ D
ⁱ _u▼ is preferable. Developer A, development conditions 20 ° C for 4 minutesDeveloper B, development conditions 4 minutes at 20 ℃Bleaching solution (BL) Bleaching condition 20 ° C for 8 secondsSilver halide grains used in the silver halide emulsion of the present invention
Children can be obtained by the acidic method, the neutral method, or the ammonia method.
You can use the one that has been used. The particles may be grown at one time
Alternatively, seed particles may be formed and then grown. Seed particles
Even though the method of coming and the method of growing are different,
Good. A silver halide emulsion has the same halide and silver ions.
Even if mixed occasionally, in the liquid in which one exists, the other
May be mixed, but the critical growth rate of silver halide crystals
Taking into account the fact that the silver halide ion and silver ion are mixed
Sequential and simultaneous addition while controlling the internal pH and pAg
It is preferable to generate the particles by adjusting the particle size distribution.
Good Also, after growth, the conversion method is used to
Changing the gen composition also impairs the effects of the present invention.
It is possible within the range. In this case, the odor that should be added later
The compound ion is usually 5 mol% or less with respect to the total silver halide.
The lower limit is preferably 3 mol% or less. The silver halide emulsion of the present invention may be prepared as needed at the time of its production.
Then, using a silver halide solvent, the grains of silver halide grains
Child size, particle shape, particle size distribution and particle growth
You can control the speed. As the silver halide solvent, ammonia, thioether
Thiourea derivatives such as thiol, thiourea, and 4-substituted thiourea
Mention may be made of imidazole derivatives. To thioether
Regarding this, U.S. Patent Nos. 3,271,157 and 3,790,387,
You can refer to the same number 3,574,628. The amount of solvent used is not
10 of liquid^-3~ 1.0% by weight, especially 10^-2~Ten^-1Wt% is preferred
Yes. In the case of ammonia, it can be selected arbitrarily. Silver halide grains used in the silver halide emulsion of the present invention
Offspring are regular crystals such as cubes, octahedra and tetradecahedrons
It may have a shape, or an irregular shape such as a sphere or a plate.
It may have a crystalline form. In these particles,
Any ratio of {100} plane to {111} plane can be used.
It Also, it may have a composite form of these crystal forms,
Particles of various crystal forms may be mixed. The average grain size of the silver halide grains of the present invention (grain size
Represents the diameter of a circle with an area equal to the projected area) is 3μ
m or less is preferable, but 1 μm or less is particularly preferable.
And most preferably 0.8 μm or less. The silver halide emulsion of the present invention can be prepared by a conventional method.
It is necessary to chemically sensitize the grains. That is, sulfur sensitization
Method, selenium sensitization method, reduction sensitization method, gold and other precious metal compounds
Precious metal sensitization method using materials alone or in combination
However, at least a sulfur sensitizer may be used.
Particularly preferred. Suitable chemical sensitization methods include, for example, British Patent No. 618,061.
No. 1,1,315,755, 1,396,696, Japanese Patent Publication No.44-15748
U.S. Pat.Nos. 1,574,944, 1,623,499, 1,673,
No. 522, No. 2,278, 947, No. 2,399,083, No. 2,410,689
No., No. 2,419,974, No. 2,448,060, No. 2,487,850,
2,518,698, 2,521,926, 2,642,361, 2,6
94,637, 2,728,668, 2,739,060, 2,743,18
No. 2, No. 2,743,183, No. 2,983,609, No. 2,983,610,
3,021,215, 3,026,203, 3,297,446, 3,2
No. 97, 447, No. 3,361,564, No. 3,411,914, No. 3,554,7
No. 57, No. 3,565,631, No. 3,565,633, No. 3,591, 385
No., No. 3,656,955, No. 3,761,267, No. 3,772,031,
3,857,711, 3,891,446, 3,901,714, 3,9
04,415, 3,930,867, 3,984,249, 4,054,
No. 457, No. 4,067,740, Research Disclosure
(Research Disclosure) 12008, 13452, 13654
Issue, T.H. James "The Theory of the Photo"
Graphic Process "(T.H.James; The Theory of
the Photographic Process.) (4th Ed. Macmillan. 197
7) Using chemical sensitizers and sensitization methods described in pp 67-76 etc.
It is preferable to sensitize. The silver halide emulsion of the present invention is a sensitized color in the photographic industry.
Light in a desired wavelength range using a dye known as
Can be sensitized. The sensitizing dye may be used alone,
You may use it in combination of 2 or more type. With sensitizing dye
A dye that does not have a spectral sensitizing effect by itself, or visible
A compound that does not substantially absorb light,
The emulsion may contain a supersensitizer that enhances the sensitizing effect.
Yes. Furthermore, these sensitizing dyes have their original spectral sensitizing effect.
In addition to the purpose, it can be used for the purpose of gradation adjustment and development adjustment.
I can do it. As the sensitizing dye, a cyanine dye, a merocyanine dye,
Complex cyanine dye, complex merocyanine dye, holopolar
-Cyanine dye, hemicyanine dye, steryl dye and
And hemioxanol dyes are used. Particularly useful dyes are cyanine dyes, merocyanine dyes,
And a complex merocyanine dye. To these pigments
Is commonly used in cyanine dyes as a basic heterocyclic nucleus.
Any of the nuclei used can be applied. That is, the pyrroline nucleus,
Xazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazol
Le nucleus, thiazole nucleus, selenazole nucleus, imidazole
Nuclei, tetrazole nuclei, pyridine nuclei and alicyclic rings on these nuclei
Formulas Nuclei fused with hydrocarbon rings: and aromatic coals in these nuclei
Nucleus fused with hydrogen ring, ie, indolenine nucleus, benz
Indolenine nucleus, indole nucleus, benzoxazole
Nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphth
Tothiazole nucleus, benzoselenazole nucleus, benzimidazole
Examples are sol nucleus and quinoline nucleus. These nuclei are carbon
It may be substituted on the atom. Keto for merocyanine dyes or complex merocyanine dyes
As a nucleus having a methylene structure, pyrazolin-5-one
Nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,
4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodani
Nuclei, thiobarbituric acid nuclei, etc.
It can be applied. Sensitizing colors used in useful blue-sensitive silver halide emulsion layers
For example, West German Patent 929,080, US Patent 2,23
1,658, 2,493,748, 2,503,776, 2,519,001
No., No. 2,912,329, No. 3,656,959, No. 3,672,897,
No. 3,694,217, No. 4,025,349, No. 4,046,572, United Kingdom
Patents 1,242,588, Japanese Patent Publication Nos. 44-14030, 52-24844
And the like. Also green light
As a useful sensitizing dye used in a photosensitive silver halide emulsion
Are, for example, U.S. Patents 1,939,201, 2,072,908, and 2,
739,149, 2,945,763, British Patent 505,979, etc.
Cyanine dye, merocyanine dye or
Is a typical example of complex cyanine dyes.
You can Furthermore, when used in red-sensitive silver halide emulsions
Examples of useful sensitizing dyes include, for example, U.S. Pat.
No. 4, No. 2,270,378, No. 2,442,710, No. 2,454,629,
Cyanine dyes such as those described in No. 2,776,280,
Typical examples are merocyanine dyes and complex cyanine dyes.
Can be listed as Furthermore, US Patent 2,
213,995, 2,493,748, 2,519,001, West German patent 9
Cyanine dyes such as those described in No. 29,080, Meloshi
Anine dye or complex cyanine dye with green-sensitive halogen
It should be used advantageously for silver halide emulsions or red light-sensitive halogen emulsions.
You can These sensitizing dyes may be used alone or in combination with each other.
You may use a combination. Special combination of sensitizing dyes
In addition, it is often used for the purpose of supersensitization. Typical example
Is Japanese Patent Publication No. 43-4932, No. 43-4933, No. 43-4936,
44-32753, 45-25831, 45-26474, 46
-11627, 46-18107, 47-8741, 47-1111
No. 4, No. 47-25379, No. 47-37443, No. 48-28293,
48-38406, 48-38407, 48-38408, 48
-41203, 48-41204, 49-6207, 50-4066
No. 2, No. 53-12375, No. 54-34535, No. 55-1569,
JP-A-50-33220, JP-A-50-33828, JP-A-50-38526,
51-107127, 51-115820, 51-135528,
51-151527, 52-23931, 52-51932, 52-
104916, 52-104917, 52-109925, 52-11
0618, 54-80118, 56-25728, 57-1483
No. 58-10753, No. 58-91445, No. 58-153926,
59-114533, 59-116645, 59-116647, US
National Patent Nos. 2,688,545, 2,977,229, 3,397,060
No., No. 3,506,443, No. 3,578,447, No. 3,672,898,
No. 3,679,428, No. 3,769,301, No. 3,814,609, No. 3,8
No. 37,862. Used with sensitizing dyes, it has a self-sensitizing effect.
Pigments or substances that do not substantially absorb visible light
Examples of the substance exhibiting supersensitization include aromatic compounds.
Organic acid formaldehyde condensate (see, for example, US Pat.
No. 7,510), cadmium salt, azaindene
Compounds, aminostilbenes substituted with nitrogen-containing heterocyclic groups
Compounds (for example, US Pat. Nos. 2,933,390 and 3,635,721)
Those listed in the issue). U.S. Pat.No. 3,615,613
No., No. 3,615,641, No. 3,617,295, No. 3,635,721
The combinations described are particularly useful. The silver halide emulsion of the present invention includes a light-sensitive material manufacturing process,
Preventing or copying fog during storage or photo processing
Chemical aging during chemical aging for the purpose of keeping the true performance stable
Halogen at the end of maturation and / or after the completion of chemical maturation
By the time the silver halide emulsion is applied, it prevents fog in the photographic industry.
Addition of compounds known as inhibitors or stabilizers
You can Antifoggants and stabilizers include U.S. Patent No. 2,713,541
Pen described in No. 2, No. 2,743,180, No. 2,743, 181
Tazaindenes, U.S. Patent Nos. 2,716,062 and 2,444,607
No. 2, No. 2,444,605, No. 2,756,147, No. 2,835,581,
No. 2,852,375, Research Disclosure (Resea
rch Disclosure) Tetrazainde described in No. 14851
, Triazai described in US Pat. No. 2,772,164
And the polymers described in JP-A-57-211142
Azaindenes such as azaindenes; US Patent No. 2,
131,038, 3,342,596, 3,954,478
Thiazolium salt, described in U.S. Pat.No. 3,148,067
Pyrylium salts, and those described in Japanese Patent Publication No. 5040665
Quaternary onium salts such as phosphononium salts; US Pat. No. 2,40
3,927, 3,266,897, 3,708,303, JP-A-55-1
35835, 59-71047 described mercaptotetra
Sols, mercaptotriazoles, mercaptodia
Sols, merca described in US Pat. No. 2,824,001
Putothiazoles, described in U.S. Patent No. 3,397,987
Mercaptobenzthiazoles, mercaptobenzii
Midazoles, the compounds described in U.S. Pat.No. 2,843,491.
Rucaptooxadiazoles, U.S. Pat.No. 3,364,028
Such as mercaptothiadiazoles described in No.
Put-substituted heterocyclic compounds; US Pat. No. 3,236,652,
Catechols described in JP-B-43-10256, JP-B-5
Resorcinols described in 6-44413, and Japanese Patent Publication No. 43-
Polyhydroxyl compounds such as gallic acid esters described in 4133
Cybenzenes; TE described in West German Patent No. 1,189,380
Trasols, compounds described in U.S. Pat.No. 3,157,509
Reazoles, compounds described in U.S. Pat.No. 2,704,721
Nzentriazoles, described in US Pat. No. 3,287,135
Urazoles described in U.S. Patent No. 3,106,467.
Pyrazoles described in US Pat. No. 2,271,229
Indazoles, and those described in JP-A-59-90844.
Azoles such as polymerized benztriazoles
Pyrimidines described in US Pat. No. 3,161,515, rice
3-Pyrazolidone described in Japanese Patent No. 2,751,297
And polymers described in US Pat. No. 3,021,213
Heterocycles such as polypyrrolidone or polyvinylpyrrolidones
Compounds; JP-A Nos. 54-130929, 59-137945, and 14
0445, British Patent 1,356,142, U.S. Patent 3,575,6
Various inhibitor prescriptions described in No. 99, No. 3,649,267, etc.
Curser; Sulf as described in US Pat. No. 3,047,393
Phosphoric acid, sulfonic acid derivatives; US Pat. No. 2,566,263
No. 2, No. 2,839,405, No. 2,488,709, No. 2,728,663
There are listed inorganic salts and the like. The binder (or protective co-coat) of the silver halide emulsion of the present invention is
It is advantageous to use seratin as the Lloyd)
However, gelatin derivatives, grafts of gelatin and other polymers
Polymers, other proteins, sugar derivatives, cellulose derivatives
Conductive, synthetic hydrophilic polymer such as homopolymer or copolymer
Hydrophilic colloids of quality etc. can also be used. Gelatin can be lime-treated gelatin or acid-treated gelatin.
Bulletin of Society of Science
Of Photography of Japan (Bull.Soc.S
ci.Phot.Japan) No.16, page 30 (1966)
Enzyme-treated gelatin may be used.
Water decomposition products and enzymatic decomposition products can also be used. gelatin
Examples of the derivative include gelatin such as acid halide and acid anhydride.
Products, isocyanates, bromoacetic acid, alkanesaltone
, Vinyl sulfonamides, maleimide compounds
Species, polyalkyleonoxides, epoxy compounds, etc.
Those obtained by reacting various compounds are used. So
Examples of U.S. Pat.Nos. 2,614,928, 3,132,945,
3,186,846, 3,312,553, British patent 861,414,
1,033,189, 1,005,784, Japanese Patent Publication No. 42-26845, etc.
It is described in. Proteins include albumin, casein, and cellulose
Derivatives include hydroxyethyl cellulose and carboxy.
Cimethyl cellulose, cellulose sulfate,
Sodium alginate and starch derivatives are preferred sugar derivatives.
Good As the graft polymer of the above gelatin and other polymers,
Acrylic acid, methacrylic acid and their essence on gelatin
Derivatives of telluride, amide, acrylonitrile, styrene
Single or homopolymer of vinyl monomers such as
What grafted the coalescence can be used. thing
In addition, some polymers that are compatible with gelatin, such as
Acrylic acid, acrylamide, methacrylamide, hydr
Graph with polymers such as Roxyalkylmethacrylate
Topopolymers are preferred. Examples of these are U.S. Pat.
No. 3,625, No. 2,831,767, No. 2,956,884, etc.
Has been. A typical synthetic hydrophilic polymer is polyvinyl alcohol.
Polyvinyl alcohol partial acetal, poly-N-
Vinylpyrrolidone, polyacrylic acid, polymethacryl
Acid, polyacrylamide, polyvinyl imidazole,
It may be a single or copolymer such as ribinylpyrazole.
For example, West German patent application (OLS) 2,312,708, US patent
No. 3,620,751, No. 3,879,205, Japanese Patent Publication No. 437561
It is the one described. Photographic emulsion of a light-sensitive material using the silver halide emulsion of the present invention
Layers, other hydrophilic colloid layers, binder (or
(Curing protective colloid) Hardener that crosslinks molecules to increase film strength
Can be hardened by using one kind or two or more kinds.
it can. Hardener does not need to be added to the processing liquid.
The photosensitive material can be added to the extent that it can be hardened.
However, it is also possible to add a hardening agent to the processing liquid. Hardeners include aldehyde-based and aziridine-based (eg
PB Report, 19,921, U.S. Patent No. 2,950,197,
No. 2,964,404, No. 2,983,611, No. 3,271,175,
, Japanese Patent Publication No. 46-40898 and Japanese Patent Application Laid-Open No. 50-91315.
Those described in each publication), isoxazole-based (eg,
Those described in US Pat. No. 331,609), epoxy
Systems (e.g., U.S. Patent No. 3,047,394, West German Patent No. 1,085,
No. 663, each specification of British Patent No. 1,033,518, Japanese Patent Publication No. 48-
35495), vinyl sulfone type (example
For example, PB Report 19,920, West German Patent No. 1,100,942,
2,337,412, 2,545,722, 2,635,518, 2,74
2,308, 2,749,260, British Patent No. 1,251,091,
Japanese Patent Application Nos. 45-54236 and 48-110996, U.S. Pat.
44, No. 3,490,911 in each specification),
Crylroyl type (for example, Japanese Patent Application No. 48-27949, US patent
(Described in each specification of No. 3,640,720), Carbo
Diimide type (for example, US Pat. Nos. 2,938,892 and 4,04
No. 3,818, No. 4,061,499, Japanese Patent Publication No. 46-38715
Gazette, those described in the specification of Japanese Patent Application No. 49-15095),
Riazine type (for example, West German Patent Nos. 2,410,973 and 2,55
3,915, U.S. Pat.No. 3,325,287, JP-A-52
-12722), polymer type (for example, English
National Patent No. 822,061, U.S. Patent No. 3,623,878, No. 3,396,
Nos. 029 and 3,226,234, JP-B-47-18578
No., No. 18579, No. 47-48896)
Other maleimide type, acetylene type, methanesulfonic acid
Ester-based and (N-methylol-based) hardeners are used alone.
Or can be used in combination. With useful combination technology
For example, West German Patent Nos. 2,447,587, 2,505,746, and
2,514,245, U.S. Pat.Nos. 4,047,957 and 3,832,181
Nos. 3,840,370 and JP-A-48-43319,
50-63062, 52-127329, and Japanese Patent Publication 48-32464.
The combinations described in the publication can be mentioned. When the color development processing is performed using the silver halide emulsion of the present invention
Synthetic aromatic primary amine developers (eg p-phenylene diene
Oxidation of amine derivatives and aminophenol derivatives)
A pigment-forming agent that forms a pigment through a coupling reaction with the body
A puller is used. The dye-forming coupler is an emulsion of each
The dye that absorbs the light in the light-sensitive spectrum of the emulsion layer
Normally selected to be formed, blue-sensitive milk
Yellow dye-forming coupler in the agent layer, in the green-sensitive emulsion layer
Is a magenta dye-forming coupler, while the red-sensitive emulsion layer is a cyan
Dye forming couplers are used. However for the purpose
Depending on the combination, the silver halide may be used in a different way.
You may make a color photographic light-sensitive material. These dye-forming couplers are called ballast groups in the molecule.
Has a group with 8 or more carbon atoms that makes the coupler non-diffusing
Is desirable. Also, these dye-forming couplers are
4 molecules of silver ions are reduced to form child pigments.
2 molecules of silver ion, even if they are 4 equivalence
It is only necessary to reduce the dimer, and it may be either of two dimerities. color
Coupling with the oxidant of the developing agent in the element-forming coupler
Depending on development accelerator, bleaching accelerator, developer, halogenated
Silver solvent, toning agent, hardening agent, fogging agent, antifoggant, chemical
Photographically useful as sensitizers, spectral sensitizers, and sensitizers
It is possible to include compounds that release various fragments.
Wear. With the effect of color correction on these dye-forming couplers
Colored coupler, or development suppression with development
DI that releases agents to improve image sharpness and image graininess
An R coupler may be used in combination. At this time, the DIR coupler
The dye formed from the coupler is used in the same emulsion layer
Is a family of dyes formed from dye-forming couplers
Preferred, but different if turbidity is not noticeable
It may be one that forms a type of dye. Replaced with DIR coupler
Therefore, with the coupler or in combination with the oxidant of the developing agent.
Coupling reaction produces a colorless compound and at the same time
DIR compounds that release development inhibitors may be used. The DIR couplers and DIR compounds used are
When the inhibitor is directly bonded to the position
Is coupled to the coupling position via
Intramolecular nucleophilic reactions within the group that is released by
Bound so that the inhibitor is released by the child transfer reaction etc.
Things (Timing DIR coupler and Timing DIR combination
(Referred to as a thing) is included. In addition, the inhibitor also diffuses after withdrawal
What is not so diffused with those of
They can be used alone or in combination. Aromatic
Coupling reaction with the oxidant of primary amine developer
However, a colorless coupler that does not form a dye is a dye-forming coupler.
It can also be used in combination with. Yellow dye-forming couplers include various acylacetates.
Toanilide type couplers can be preferably used.
Of these, benzoylacetanilides and pivalo
Ilacetanilide compounds are advantageous. Yellow that can be used
Specific examples of color couplers are described in British Patent No. 1,077,874, Japanese Patent Publication
45-40757, JP-A 47-1031, 47-26133, and
48-94432, 50-87650, 51-3631 and 52-11
5219, 54-99433, 54-133329, 56-30127
U.S. Pat.Nos. 2,875,057, 3,253,924, 3,265,
No. 506, No. 3,408, 194, No. 3,551,155, No. 3,551,156
No., No. 3,664,841, No. 3,725,072, No. 3,730,722,
3,891,445, 3,900,483, 3,929,484, 3,9
33,500, 3,973,968, 3,990,896, 4,012,25
No. 9, No. 4,022,620, No. 4,029,508, No. 4,057,432,
4,106,942, 4,133,958, 4,269,936, 4,2
86,053, 4,304,845, 4,314,023, 4,336,32
No. 7, No. 4,356,258, No. 4,386,155, No. 4,401,752, etc.
It is described in. As a magenta dye forming coupler, a 5-pyrazolone type coupler is used.
Puller, pyrazolobenzimidazole coupler, pyra
Zoroazole coupler, open-chain acylacetonitrile coupler
A coupler can be preferably used. Can be used to advantage
Specific examples of magenta couplers are Japanese Patent Application No. 58-164882,
58-167326, 58-206321, 58-214863,
58-217339, 59-24653, JP-B-406031, 4
0-6035, 45-40757, 47-27411, 49-378
54, JP-A-50-13041, 51-26541, 51-3764
No. 6, No. 51-105820, No. 52-42121, No. 53-123129
No. 53-125835, No. 53-129035, No. 54-48540
No. 56-29236, No. 56-75648, No. 57-17950,
57-35858, 57-146251, 59-99437, United Kingdom
Patents 1,252,418, U.S. Patents 2,600,788, 3,00
5,712, 3,062,653, 3,127,269, 3,214,437
No., No. 3,253,924, No. 3,311,476, No. 3,419,391,
3,519,429, 3,558,319, 3,582,322, 3,6
15,506, 3,658,544, 3,705,896, 3,725,06
No. 7, No. 3,758,309, No. 3,823,156, No. 3,834,908,
3,891,445, 3,907,571, 3,926,631, 3,9
28,044, 3,935,015, 3,960,571, 4,076,53
No. 3, No. 4,133,686, No. 4,237,217, No. 4,241,168,
No. 4,264,723, No. 4,301,235, No. 4,310,623, etc.
It is listed. Cyan dye forming couplers include naphthol couplers
, A phenol coupler can be preferably used.
It Examples of cyan couplers that can be used advantageously are British patents.
No. 1,038,331, No. 1,543,040, Japanese Patent Publication No. 48-36894,
JP-A-48-59838, JP-A-50-137137, JP-A-51-146828
No. 53-105226, No. 54-115230, No. 56-29235
No. 56-104333, No. 56-126833, No. 57-133650
No. 57-155538, No. 57-204545, No. 58-118643
No. 59-31953, 59-31954, 59-59656,
59-124341, 59-166956, U.S. Pat.No. 2,369,92
No. 9, No. 2,423,730, No. 2,434,272, No. 2,474,293,
2,698,794, 2,772,162, 2,801,171, 2,8
95,826, 3,253,924, 3,311,476, 3,458,31
No. 5, No. 3,476,563, No. 3,591,383, No. 3,737,316,
No. 3,758,308, No. 3,767,411, No. 3,790,384, No. 3,8
80,661, 3,926,634, 4,004,929, 4,009,03
No. 5, No. 4,012,258, No. 4,052,212, No. 4,124,396,
4,134,766, 4,138,258, 4,146,396, 4,1
49,886, 4,178,183, 4,205,990, 4,254,21
No. 2, No. 4,264,722, No. 4,288,532, No. 4,296,199,
4,296,200, 4,299,914, 4,333,999, 4,3
34,011, 4,386,155, 4,401,752, 4,427,76
No. 7 etc. Silver halide photograph containing the silver halide emulsion of the present invention
In the light-sensitive material, various photographic additives other than the above compounds are added.
Agents can be added. As such an example, for example, an ultraviolet absorber (for example, benzo
Phenone compounds, benzotriazole compounds, etc.),
Development accelerator (for example, 1-aryl-3-pyrazolidone type)
Compounds, etc., surfactants (eg alkylnaphthalene)
Ruphonate, alkyl succinate sulfonate,
Itaconic acid salts, polyalkylene oxide compounds
Etc.), water-soluble anti-irradiation dyes (for example, azo-based dyes)
Compounds, styryl compounds, oxonol compounds,
Nsulaquinone compounds and triphenylmethane compounds
Etc.), film property improving agents (eg glycerin, polyalkyle)
Glycol, polymer latex, solid or liquid paraffin
Fins, etc., anti-turbidity agent (diffusion-resistant hydroquinone type)
Compounds, etc., dye image stabilizers (eg hydroquinone
Conductor, gallic acid derivative, phenolic compound, hydroxy
Cycloman compounds, polyalkylpiperidine compounds
Substance, aromatic amine compound, etc.), water-soluble or oil-soluble
Fluorescent whitening agents, ground color tone regulators (oil-soluble coloring dyes, etc.)
It Dye formation without the need for adsorption on the silver halide crystal surface
Coupler, colored coupler, DIR coupler, DIR combination
Objects, image stabilizers, antifoggants, UV absorbers, fluorescent
Among the whitening agents, hydrophobic compounds are solid dispersion method, LATEC
Dispersion method, oil-in-water emulsion dispersion method, etc.
This is the chemistry of hydrophobic compounds such as couplers.
It can be appropriately selected depending on the structure and the like. Oil-in-water type
The emulsion dispersion method disperses hydrophobic additives such as couplers.
Various methods can be applied, usually high boiling point of about 150 ℃ or higher.
Low boiling point and / or water-soluble as required for organic solvent
Dissolves in combination with an organic solvent, giving hydrophilicity such as gelatin aqueous solution.
Stirrer and homogenizer using a surfactant in a hydrophilic binder
Nizer, colloid mill, flowgit mixer, supersonic
After emulsifying and dispersing with a dispersing device such as a wave device,
It may be added to the hydrophilic colloid layer. Dispersion
Include a process to remove low boiling organic solvent at the same time as dispersion
Good. The ratio of high boiling organic solvent to low boiling organic solvent is 1: 0.1 to 1: 5
It is preferably 0, more preferably 1: 1 to 1:20. As a high-boiling point oil agent, it does not react with the oxidant of the developing agent.
Nole derivative, phthalic acid alkyl ester, phosphoric acid
Steal, citrate, benzoate, alk
Lamide, fatty acid ester, trimesic acid ester, etc.
An organic solvent having a boiling point of 150 ° C or higher is used. As the high boiling point organic solvent that can be used, US Patent
No. 2,322,027, No. 2,533,514, No. 2,835, 579, No. 3,
287,134, 2,353,262, 2,852,383, 3,554,7
Issue 55, Issue 3,676,137, Issue 3,676,142, Issue 3,700,454
No., No. 3,748,141, No. 3,779,765, No. 3,837,863,
British Patents 958,441, 1,222,753, OLS 2,538,889,
JP-A-47-1031, 49-90523, 50-23823, and
51-26037, 51-27921, 51-27922, 51-2
No. 6035, No. 51-26036, No. 50-62632, No. 53-1520
No. 53-1521, No. 53-15127, No. 54-119921,
54-119922, 55-25057, 55-36869, 56
-19049, 56-81836, Japanese Patent Publication No. 48-29060, etc.
It is listed. Low boiling point that can be used with or instead of high boiling point solvents
Dots or water-soluble organic solvents are described in U.S. Pat.
Listed in No. 2,949,360, etc.
It Ethylene is a low-boiling, substantially water-insoluble organic solvent.
Lu acetate, propyl acetate, butyl acetate
, Butanol, chloroform, carbon tetrachloride, nitrogen
Tan, nitroethane, benzene, etc.
As the machine solvent, acetone, methyl isobutyl ketone,
β-ethoxyethyl acetate, methoxyglycol
Cate, methanol, ethanol, acetonitrile,
Dioxane, dimethylformamide, dimethyl sulfoxide
Side, hexamethylphosphoramide, diethylene glycol
Cole monophenyl ether, phenoxyethanol, etc.
Is given as an example. A surfactant can be used as a dispersion aid, for example,
Alkylbenzene sulfonate, alkylnaphthalene
Ruphonate, alkyl sulfonate, alkyl sulfate
Tells, alkyl phosphates, sulfosuccinates
Steals and sulfoalkyl polyoxyethylene al
Anionic surface active agents such as kill phenyl ether
Agent, steroidal savonine, alkylene oxide derivative
Nonionic interfaces such as body and glycidol derivatives
Activators, amino acids, aminoalkyl sulfonic acids, and
And amphoteric surfactants such as alkyl betaines, and
And cation-based interfaces such as quaternary ammonium salts
Preference is given to using activators. Of these interfacial bulking agents
Specific examples are "Surfactant Handbook" (Industrial Books, 1966),
"Emulsifier / Emulsifier Research / Technical Data" (General Science)
Company, 1978). As the latex dispersion method, for example, U.S. Pat.
No. 3, No. 4,214,047, No. 4,203,716, No. 4,247,627,
JP-A-49-74538, 51-59942, 51-59943,
The method described in JP-A-54-32552 is preferable. Using the silver halide color photographic light-sensitive material of the present invention, color
-When developing, color development process, bleaching process
A fixing process step, a washing process step if necessary, and /
Alternatively, a stabilization treatment process is performed, but a treatment using a bleaching solution is performed.
1-bath bleach-fix instead of processing process
You can also use the solution to perform the bleach-fixing process,
One bath capable of color development, bleaching and fixing in one bath
Perform a monobath processing process using a developing bleach-fixing solution.
I can do it. In combination with these treatment steps, the pre-dural treatment step,
Performs neutralization process, stop-fixing process, post-hardening process, etc.
May be. Instead of the color development process in these processes
Color developing agent or its precursor in the material
Activator solution is included in the development process.
You may carry out a civet treatment process, or for monobass treatment
Instead, the activator processing and bleaching / fixing processing are performed at the same time.
You may. A typical process is shown among these processes. (This
These treatments are the final process, such as washing process and stabilization process.
One of the treatment process, washing process and stabilization process
To do. (1) Color development processing step-bleaching processing step-fixing processing step (2) Color development processing step-bleach fixing processing step (3) Pre-hardening processing step-neutralization processing step-color development processing step
Process-stop fixing process-washing process-bleaching process-
Fixing process-Washing process-Post-hardening process (4) Color development process-Washing process-Supplementary color development
Treatment step-Stop treatment step-Bleach treatment step-Fixing treatment step (5) Monobath treatment step (6) Activator treatment step-Bleaching fixing treatment step (7) Activator treatment step-Bleaching treatment step-Fixing treatment
Processing step The silver halide color photographic light-sensitive material of the present invention is processed below.
For the processing step (2) that is preferably used when
Will be described in detail. As the color developing agent used in the color developing solution, fragrance
Group primary amine compounds, especially P-phenylenediamine compounds
Are typical, and preferred examples include N, N-di
Ethyl-P-phenylenediamine hydrochloride, N-ethyl-
P-phenylenediamine hydrochloride, N, N-dimethyl-P-
Phenylenediamine hydrochloride, 2-amino-5- (N-E
Cyl-N-dodecylamino) -toluene, N-ethyl-
N- (β-methanesulfonamidoethyl) -3-methyl
-4-Aminoaniline sulfate, N-ethyl-N-β-hi
Droxyethylaminoaniline, 4-amino-N- (2
-Methoxyethyl) -N-ethyl-3-methylaniline
-P-toluenesulfonate, N, N-diethyl-3-me
Cyl-4-aminoaniline, N-ethyl-N- (β-hi
Droxyethyl) -3-methyl-4-aminoaniline, etc.
Can be mentioned. These color developing agents are
Or two or more kinds may be used in combination.
1 or 2 or more color developing agents and other black and white developing agents,
For example, hydroquinone, 1-phenyl-3-pyrazolid
In combination with N-methyl-P-aminophenols
You may use. This color developing agent is the silver chloride color of the present invention.
-It may be contained in the photographic light-sensitive material. In this case,
The amount of color developing agent added is not included in the silver chloride color photographic light-sensitive material.
0.2 mol to 2 mol per mol of silver halide
Range, preferably in the range of 0.4 to 0.7 mol
It The silver halide color photographic light-sensitive material of the present invention is subjected to color development processing.
In particular, when the above-mentioned compound is used as a color developing agent,
In particular, N-ethyl-N- (β-methanesulfonamide
Ethyl) -3-methyl-4-aminoaniline sulfate
Is preferred. In addition to the above color developing solution, for example, a hydroxide may be used as the color developing solution.
Sodium, potassium hydroxide, sodium carbonate, 3rd
Sodium phosphate, potassium carbonate, potassium hydrogen carbonate, etc.
Alkaline agent, N, N-diethylhydroxylamine, tri
Ethanolamine, diethanolamine, glucose, etc.
Preservative, methanol, ethanol, butanol, ethi
Organic solvents such as len glycol and diethylene glycol,
Development control of citrazinic acid and polyethylene glycol
Agents and optical brighteners, heavy metal ion masking agents, development accelerators, etc.
If necessary, various photographic additives known in the photographic field may be used.
It can be contained once. The silver chloride color photographic light-sensitive material of the present invention contains a water-soluble bromide.
Color developer containing no or very small amount
To be developed. When it contains an excess of water-soluble bromide,
The development speed of silver chloride color photographic light-sensitive materials was drastically reduced.
Therefore, the object of the present invention cannot be achieved. Color development
The bromide ion concentration in the liquid is converted to potassium bromide,
About 0.1 g or less per color developing solution, preferably 0.05
It is less than or equal to g. In the color developer, a water-soluble chloride is used as a development modifier.
The effect of the present invention is particularly remarkable when using.
The water-soluble chloride used is converted to potassium chloride to develop color.
Use in the range of 0.5 to 5 g, preferably 1 to 3 g per developer.
To be The color developer is further described in JP-A-58-95,345.
The organic development inhibitor described above is used within a range not impairing the present invention.
You can Preferably adenine and guanine
It is used in the range of 0 to 0.02 g / l in a color developer. The pH of the developer of the present invention is 9.5 or higher, preferably 13 or higher.
Below. By increasing the pH of the developing solution
It is known that the halo of the present invention
Even if the pH is less than 11
However, sufficient rapid developability can be obtained. The temperature of the color developing solution is 15 to 45 ° C, preferably 20 to 40 ° C.
Done. Bleach-fix processing that is performed after color development processing
As the bleaching agent used at this time, metal complex salts of organic acids are preferred.
In addition, the presence of aminopolycarboxylic acid or oxalic acid, citric acid, etc.
Coordination of metal ions such as iron, cobalt and copper with mechanical acid
Is. In order to form such metal complex salts of organic acids
The most preferred organic acid used is polycarboxylic acid.
An acid is mentioned. These polycarboxylic acids or amino
Licarboxylic acid may be an alkali metal salt or ammonium salt.
May be a water-soluble amine salt. As specific examples of these
The following can be cited as examples. [1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N- (β-oxyethyl)-
N, N²， N²-Triacetic acid [4] propylenediaminetetraacetic acid [5] nitrilotriacetic acid [6] cyclohexanediaminetetraacetic acid [7] iminodiacetic acid [8] dihydroxyethylglycine citric acid (or tartar
acid)

[9] Ethyletherdiaminetetraacetic acid [10] Glycoletherdiaminetetraacetic acid [11] Ethylenediaminetetrapropionic acid [12] Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra (trimethylammonium) Salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] Ethylenediamine-N- (β-oxyethyl)-
N, N ^2, N ² - triacetic acid sodium salt [18] propylenediaminetetraacetic sodium tetraacetate [19] nitrilotriacetic acid sodium salt [20] cyclohexanediaminetetraacetic sodium tetraacetate These bleaching agents 5~450g / l, more preferably 20-250g
Use with / l. 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, a bleach-fixing solution having a composition containing a small amount of an ethylenediaminetetraacetic acid iron (III) complex bleach and a halide such as ammonium bromide other than the above silver halide fixing agent, or conversely, a halide such as ammonium bromide. A bleach-fix solution composed of a large amount of iron, and further ethylenediaminetetraacetate iron (II
I) A special bleach-fixing solution having a composition composed of a complex salt bleaching agent and a large amount of a halide such as ammonium bromide can also be used. As the halide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may be used in addition to ammonium bromide. it can. The silver halide fixing agent contained in the bleach-fixing solution is a compound which forms a water-soluble complex salt by reacting with silver halide as used in ordinary fixing processing, for example, potassium thiosulfate, sodium thiosulfate, thiol. Typical examples thereof include thiosulfates such as ammonium sulfate, potassium thiocyanate, sodium thiocyanate, thiocyanates such as ammonium thiocyanate, thiourea and thioether. These fixing agents are used in an amount in the range of 5 g / l or more so that they can be dissolved, but generally 70 g to 250 g / l are used. The bleach-fix solution contains boric acid, borax, sodium hydroxide,
Various pH treating agents such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide can be contained alone or in combination of two or more kinds. Furthermore, various fluorescent whitening agents, antifoaming agents or surfactants may be contained. In addition, preservatives such as bisulfite adducts of hydroxylamine, hydrazine, and aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohol and nitrates, organic agents such as methanol, dimethylsulfamide, dimethylsulfoxide, etc. A solvent and the like can be contained as appropriate. The bleach-fixing solution used in the present invention includes JP-B-46-280, JP-B-45-8506, JP-B-46-556, and Belgian Patent No. 770,910.
No. 5, Japanese Patent Publication No. 45-8836, No. 53-9854, JP-A-54-7163
Various bleaching accelerators described in No. 4 and No. 49-42349 can be added. The bleach-fix solution is used at a pH of 4.0 or higher, but it is generally
Used at pH 5.0 to pH 9.5, preferably pH 6.0 to pH
Used below 8.5, further stated the most preferred pH is 6.5
Processed above 8.5. The processing temperature is 80 ° C. or lower, which is lower than the processing temperature of the color developing tank by 3 ° C. or higher, preferably 5 ° C. or higher, but is preferably 55 ° C. or lower to suppress evaporation and the like. The bleach-fixing time is within 90 seconds, preferably within 60 seconds. It is necessary to remove unnecessary processing chemicals by washing the color light-sensitive material subjected to color development and bleach-fixing treatment with water, but instead of washing with water, JP-A-58-14834, 58-105145 and 58-58
-134634 and 58-18631 and Japanese Patent Application Nos. 58-2709 and 59-89288 may be subjected to water washing alternative stabilization treatment. When processing is carried out while continuously replenishing the color developing, bleach-fixing and stabilizing solution of the present invention, the replenishing rate of each replenishing solution is 100 to 1000 ml / m ² of the color light-sensitive material, preferably 150 ml.
~ 500 ml. Specific examples of the present invention will be described below, but embodiments of the present invention are not limited to these. Reference Example 1 A 2 mol% silver nitrate aqueous solution and a 2 mol% sodium chloride aqueous solution were added to a 6% gelatin aqueous solution at 40 ° C. while maintaining pAg = 4.2 over 20 minutes to give a 0.36 μm cubic monodispersed chloride emulsion. Got This silver chloride emulsion was further added with an aqueous solution of silver nitrate and sodium chloride, respectively, while maintaining pAg = 4.8, to obtain 0.61 μm.
To obtain a silver chloride emulsion of (Em-1). On the other hand, to this silver chloride emulsion, 0.1 mol of silver nitrate aqueous solution and 0.1 mol of potassium bromide aqueous solution were added over 2 minutes (pAg =
6.2) and a silver chlorobromide emulsion having a silver bromide composition of 0.5 mol% was prepared. (Em-2) The addition time of the aqueous solution of potassium bromide and the aqueous solution of silver nitrate was further extended with respect to Em-2 to prepare four types of silver halide emulsions having the following silver bromide compositions. Em-3 silver bromide composition 1.5 mol% Em-4 〃 5 mol% Em-5 〃 12 mol% Each of the obtained silver halide emulsions was treated with sodium thiosulfate as a chemical sensitizer to reach the maximum sensitivity. After the sensitization, spectral sensitization was performed with the following blue sensitizing colorant (BSD-1). Further, as a stabilizer, 4-hydroxy-
1-g of 6-methyl-1,3,3a, 7-tetrazaindene (stabilizer) was added per mol of silver halide. The halogen composition of the obtained silver halide emulsion was analyzed by the X-ray diffraction method, and the following results were obtained. It has a peak only at the position where the composition of Em-1 AgCl is 100%. There is a peak at the position of 100% Em-2 AgCl composition. Almost no peak is detected at the position of 100% AgBr composition. Em-3 has a peak at the position of AgCl composition 100% and AgB
A slight peak is observed at the position of 90 mol% r composition. Em-4 has a peak at the position of 100 mol% AgCl composition, AgB
It has a peak at the position of r composition of 98 mol%. Em-5 has a peak at the position of 99 mol% AgCl composition,
It has a peak at the position of 99 mol% of the composition. Further, a silver halide emulsion in which a stabilizer and BSD-1 were added in the same manner as above, though not chemically sensitized, was also prepared. The obtained 18 kinds of samples were coated on a transparent film base so as to have a silver coverage of 2.0 g / m ² , exposed to a wedge of white light, and then subjected to internal development and surface development described in the above specification. Table 1 shows D _max (maximum density) of the obtained sample during internal development and surface development. In addition, the maximum density is (D _min + + in the characteristic curve obtained as a result of surface development treatment by subjecting the silver halide emulsion subjected to surface chemical sensitization to optical wedge exposure.
When the exposure amount that gives an optical density of D _max ) / 2 is E1 / 2,
The densities at the exposure amounts where logE = logE1 / 2 + 1.5 are shown as the respective maximum densities. On the other hand, the following samples 1 to 5 were prepared using each of the chemically sensitized silver halide emulsions. That is, 170 g / m ² of polyethylene support on one side of the paper support, polyethylene on the other side of 11% by weight of anatase titanium dioxide on a support laminated polyethylene, titanium dioxide containing polyethylene was subjected to corona standing, The respective layers are sequentially coated. The addition amount is shown in 1 m ² unless otherwise specified. Layer 1 ... 0.7 g dissolved in 1.2 g of gelatin, 0.28 g (in terms of silver, the same below) of the above blue-sensitive silver chlorobromide emulsion, and 0.50 g of di-2-ethylhexyl phthalate (hereinafter abbreviated as DOP).
A layer containing 8 g of yellow coupler (Y-1), 0.35 g of the following image stabilizer STB-1 and 0.04 g of color stain inhibitor HQ-1. Layer 2 ... Intermediate layer containing 0.7 g gelatine, 15 mg anti-irradiation dye (AI-1), 10 mg (AI-2) and 0.05 g DOP with 0.05 g HQ-1 dissolved. Layer 3: 1.25 g gelatin, 0.22 g green light-sensitive silver chlorobromide emulsion (Note-1, AgBr10 mol%, average particle size 0.40 μm) 0.30 g D
Magenta coupler (M-1) of 0.45g dissolved in OP 0.0g
Light stabilizer STB = 2, 0.15g light stabilizer STB-2 and 0.01g
HQ-1 containing layers. Layer 4 ... 1.25 g gelatin, 0.08 g HQ-1 and 0.4 g UV absorber (UV-1) and 0.2 g (UV-2) dissolved 0.35 g
Intermediate layer containing DOP. Layer 5: 1.4 g of gelatin, 0.20 g of red-sensitive silver chlorobromide emulsion (Note-2, AgBr5 mol%, average particle size 0.65 μm), 0.20 g
0.25g cyan coupler (C-1) dissolved in DOP, 0.25
g cyan coupler (C-2), 0.15 g STB-1 and 0.0
Layer containing 1 g of HQ-1. Layer 6 ... 0.30 g dissolved in 1.0 g gelatin and 0.20 g DOP
UV-1 and a layer containing 0.05 g of polyvinylpyrrolidone. Layer 7 ... A layer containing 0.5 g of gelatin. As a hardener, 2,4-dichloro-6-hydroxy-s
Sodium triazine was added to the above layer and to layer 4 the reactants of (tetrakisvinylsulfonylmethyl) methane and sodium taurine 4: 1 (molar ratio) were added just prior to coating, respectively. (Note-1) Green-sensitive silver chlorobromide emulsion 3.5 × 10 5 sodium thiosulfate per mol of silver halide
Chemical sensitization was carried out by adding ^-5 mol and optically sensitized with a green sensitizing (GSD-1) dye. 4-hydroxy- as a stabilizer
1.2 g of 6-methyl-1,3,3a, 7-tetrazaindene compound was added per mol of silver halide. (Note-2) Red-sensitive silver chlorobromide emulsion sodium thiosulfate 3.5 × 10 5 per mol of silver halide
^-3 mol was added for chemical sensitization, red sensitizing dye (RSD-
Optical sensitization was performed according to 1). As a stabilizer, 1.2 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene compound was added per mol of silver halide. Note Separately silver nitrate aqueous solution and the E _m -1~5, a mixed aqueous solution of potassium bromide and potassium chloride (molar ratio 5:95) 42
It was adjusted by simultaneous mixing at ℃ and pAg = 6.2. A silver chlorobromide emulsion (average particle size: 0.64 μm) containing 95 mol% silver chloride was prepared.
(E _m -6) As a result of X-ray diffraction, this product had a peak at 95 mol% of silver chloride. This was subjected to E _m 1 to 5 at the same time as chemical sensitization and spectral sensitization was used as the blue-sensitive emulsion at the same time. After subjecting the obtained samples 1 to 6 to optical wedge exposure, they were processed according to the following processing steps. [Processing step] Color development 35 ℃ 30 seconds, 40 seconds, 50 seconds, 60 seconds Bleach fixing 35 ℃ 50 seconds Water washing 30-34 ℃ 90 seconds Dry 50-70 ℃ 60 seconds Color developing solution and bleach-fixing solution used The composition of is as follows. (Per 1) The density of the obtained sample was measured with blue monochromatic light, and the sensitivity and the gradation were obtained from the obtained characteristic curve. Table of results
2 shows. (30, 40, 50, and 60 in the table indicate development time.) In the table, the sensitivities are represented by relative sensitivities, where the sensitivity of Sample 1 at a developing time of 60 seconds is 100, and the gradation is represented by a slope of reflection density of 0.5 to 1.5. From the results shown in Table 2, in the case of silver halide emulsion Em-1 containing 100% of silver chloride, the sensitivity and the gradation change were extremely high with respect to the change of the development time, and Em-5 having a high silver bromide ratio was developed. The deterioration of sex is remarkable. Furthermore, lead bromide composition is not localized
In Em-6, as in Em-1, the change in gradation is particularly remarkable as the developing time changes. On the other hand, in Samples 2 to 5 of the present invention, changes in sensitivity and gradation are small with respect to changes in development time. Example 1 Using Samples 1 to 6 used in Reference Example 1, Reference Example 1 was repeated except that benzyl alcohol in the color developer was removed. The results are shown in Table-3. The results shown in Table 3 show that the effect of the present invention is particularly great when benzyl alcohol in the color developing solution is removed.

Claims (1)

[Claims] 1. A support has at least one silver halide emulsion layer containing a diffusion-resistant coupler, and at least one of the silver halide emulsion layers has a silver chloride content of at least one.
A chloroodor containing 80 to 99 mol% of silver chlorobromide grains, and 20 to 1 mol% of silver bromide constituting the silver chlorobromide grains is localized in silver halide crystals. A method of processing a silver halide color photographic light-sensitive material, which comprises processing a silver halide color photographic light-sensitive material containing silver halide grains with a color developing solution containing substantially no benzyl alcohol.