JPH04234759A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the color photosensitive material for photography capable of being rapid process with particularly excellent graininess and processing stability concerning the development processing method for the color photosensitive material suitable for rapid processing. CONSTITUTION:This method has a stage for subjecting the silver halide color photographic sensitive material which has respectively at least one layer of red sensitive, green sensitive and blue sensitive silver halide emulsion layers on a transparent base and has >=5mol% average silver chloride content of these silver halide emulsion layers to color development processing in the presence of a color developing agent after exposing. The gamma R, gamma G and gamma B of the red sensitive layers, green sensitive layers and blue sensitive layers after the above-mentioned color development are respectively in a 0.2 to 1.0 range in the development processing method for the silver halide color photographic sensitive material having >=80% developing silver forming range in the max. color development density region.

Description

[Detailed description of the invention]

0001

[Field of Industrial Application] The present invention relates to a method for processing silver halide color photographic light-sensitive materials suitable for rapid processing, and particularly for developing color light-sensitive materials for photographic use that are excellent in graininess and processing stability and capable of rapid processing. This relates to a processing method.

0002

BACKGROUND OF THE INVENTION In the field of photographic color light-sensitive materials and their processing techniques, light-sensitive materials using silver halide emulsions containing mainly silver chloride and their processing systems have become known. The present inventors discovered that the above-mentioned system has a developed silver production rate (silver development rate) of 80% or more in the maximum color density region and excellent processing stability, and have completed the present invention. It is something.

However, in recent years, in the field of silver halide color photographic materials, ISO-1600 to ISO-320
There is a need for higher image quality due to advances in ultra-high sensitivity as typified by 0, and small formats as typified by disc film. Therefore, the requirements for silver halide color light-sensitive materials are becoming increasingly strict, and even higher standards are being made for a wide range of photographic performance such as high sensitivity, excellent graininess, high sharpness, low fog, and a wide exposure range. There is.

[0004]Currently, the so-called negative-positive method, in which color photographs are taken with a color negative film and then stretched onto color paper and printed in color, is widely used.

One of the reasons for this is that color negative film has a very wide exposure latitude, has a low probability of failure during photographing, and allows even general users without specialized knowledge to easily take color photographs. Color negative film, unlike color reversal film and color paper, is a photosensitive material that requires strict control of gradation over a wider exposure range, and if this gradation is poor, the color reproducibility and tone reproduction of dye images will deteriorate. As a result, the quality deteriorates and the color tone becomes distorted when printed.

Furthermore, the dyes used in color photographic light-sensitive materials differ from the block-type dyes that are ideal in the subtractive color method, that is, those that are sensitive only to a specific wavelength range, and have considerable asymmetric absorption in other regions of the spectrum. Therefore, even if it is exposed to light that you do not want it to absorb, it will absorb some of the light, so it cannot reproduce colors satisfactorily as it is. For this reason, for example, in color negative films, masking using colored couplers is performed to correct this asymmetric absorption, thereby achieving good color reproducibility.

Furthermore, negative spectral sensitivity correction is performed based on the subtractive color principle of the three primary colors and the characteristics of the human eye, and an interimage effect is used to emphasize pure colors.

Conventionally, it has been well known to use a DIR compound that releases a development inhibitor as an image quality improving agent for improving the gradation, sharpness, graininess, color reproducibility, etc. of color images.

Furthermore, in addition to techniques for improving image characteristics using DIR compounds, it is also possible to improve image quality by incorporating silver iodide into silver halide grains and utilizing the development suppressing effect of iodide ions released during development. Techniques for adjusting gradation are also well known.

[0010]Also, although photographic negative films using silver iodobromide emulsions take full advantage of the advantages of silver iodide, such as high sensitivity and interlayer multilayer effects, they are difficult to develop due to the silver iodide content. This makes it difficult to shorten the term.

That is, the iodide ions accumulated in the desilvering solution have the fatal disadvantage of significantly retarding the bleaching and fixing of silver, thereby impeding speedy processing and low replenishment.

[0012] As described above, these conventional techniques have the disadvantage that they generally act to suppress the silver development reaction, and in the case of silver iodide, they also control the sulfur sensitization reaction during chemical ripening. .

[0013] This results in a negative effect from the viewpoint of short-time processing suitability, so-called rapid processing performance, of color development, which has become rapidly popular in recent years.

On the other hand, emulsions with a high silver chloride content are advantageous in that they shorten the development and bleach-fixing processes. However, silver chloride emulsions tend to have high contrast and tend to have poor graininess and color reproducibility.

Furthermore, starting with color negative film,
The gradations of various color photographic materials are extremely susceptible to changes in development processing conditions, and deterioration of color reproduction, tone reproducibility, etc. is recognized as a particularly important problem.

JP-A No. 60-156059 discloses that silver halide grains having substantially no photosensitivity are contained between two emulsion layers having different photosensitivity for the purpose of improving the progress of development of a color photographic light-sensitive material. A layered technique has been proposed, and in JP-A No. 60-128429, a technique is proposed in which non-photosensitive silver halide grains are contained in the outer layer of the photosensitive silver halide emulsion layer furthest from the support. discloses a technique for reducing the effects of process variability.

However, these conventional techniques are also insufficient and have not yet been able to sufficiently improve the processing stability, and there has been a strong desire to solve this problem as well as the above-mentioned problem of inhibiting development processing.

Although color light-sensitive materials using silver halide emulsions containing silver chloride are excellent in rapid development processing, they have poor graininess and are generally not used as color light-sensitive materials for photography.

[0019]

OBJECTS OF THE INVENTION The object of the present invention is to provide silver halide color that can be stably obtained without processing fluctuations by rapidly processing color images with excellent graininess using a silver halide emulsion containing silver chloride. An object of the present invention is to provide a method for developing photographic materials.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As a result of extensive studies, the present inventors have found that the object of the present invention can be achieved as follows.

[0021] The development processing method of the present invention which achieves the above object comprises at least one layer of red-sensitive, red-sensitive and
After exposure, a silver halide color photographic light-sensitive material having green-sensitive and blue-sensitive silver halide emulsion layers and having an average silver chloride content of 5 mol % or more in the silver halide emulsion layer is exposed to light in the presence of a color developing agent. In a method for developing a silver halide color photographic material, which comprises a step of color development and a development silver production rate of 80% or more in the maximum color density region, a red-sensitive layer, a green-sensitive layer after the color development; , gamma R of the blue-sensitive layer,
This was achieved by a method for processing a silver halide color photographic material, characterized in that gamma G and gamma B are each in the range of 0.2 to 1.0.

The present invention will be explained in detail below.

The silver halide color photographic light-sensitive material of the present invention has a plurality of light-sensitive silver halide emulsion layers on a support, and plurality refers to the presence of two or more layers consisting of emulsions having different photographic properties. say. For example, one example is a plurality of layers having different color sensitivities such as red sensitivity, green sensitivity, blue sensitivity, etc., and another example is a high sensitivity layer, a medium sensitivity layer, and a low sensitivity layer. Refers to a plurality of layers having substantially the same color sensitivity but different photographic sensitivities. The term "substantially the same color sensitivity" as used herein means that the spectral sensitivity characteristics are not necessarily the same, for example, in terms of blue sensitivity, green sensitivity, and red sensitivity.

The preferable maximum spectral sensitivity wavelength of each layer is, for example, 570 to 650 nm for the blue-sensitive layer and 520 nm for the green-sensitive layer.
~580 nm, and the red-sensitive layer is between 570 and 650 nm.

A particularly preferred layer structure in the present invention is a layer structure in which a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer are coated, each having one to three layers having different sensitivities. It is suitable for color photosensitive materials having such a layer structure.

In the present invention, the dry film thickness of the entire photographic constituent layer is preferably 30 μm or less, but in order to most effectively exhibit processing stability and rapid processing suitability, the above dry film thickness is It is particularly preferable that the thickness be 10 to 25 μm.

The silver halide grains according to the present invention contain 5 mol % or more of silver chloride. The silver chloride content is preferably 50 mol% or more, particularly preferably 80 mol%.
That's all.

The constituent elements other than silver chloride are preferably silver bromide or silver iodide, and the silver halide emulsion includes silver chlorobromide, silver chloride, and silver chloroiodobromide.

When the silver halide emulsion of the present invention is composed of solid solution crystals such as silver chlorobromide or silver chloroiodobromide, silver bromide or silver iodide is localized in a specific region of the silver halide grain crystals. Preferably.

When the silver halide emulsion of the present invention is silver chlorobromide, it is preferable that the silver bromide is localized at or near the apex of the silver halide crystals. Such silver halide emulsions are prepared by adsorbing a sensitizing dye or inhibitor onto silver chloride or silver chlorobromide grain crystals, and then ripening by adding fine silver bromide grains, or by adding a water-soluble bromide solution to the silver halide emulsion. It can be obtained by adding halogen and replacing with halogen.

Further, when the silver halide emulsion is silver chloroiodobromide, it is preferable that the silver iodide is localized inside the grains.

A silver halide emulsion in which silver iodide is localized inside the grains can be obtained by depositing silver chloride or silver chlorobromide on a core containing silver iodide. For depositing silver chloride or silver chlorobromide, known silver halide crystal growth methods such as the double jet method and the Ostwald ripening method can be used.

The core preferably has a silver iodide content of 10 mol% or more, more preferably 15 to 40 mol%.
It is.

The core is preferably silver iodobromide. The above silver halide emulsion was disclosed in Japanese Patent Application Laid-Open No. 64-69
No. 41, No. 64-26839 and JP-A-1-1218
It can be made by the method described in No. 48 and No. 1-138550.

When the silver halide grains according to the present invention contain silver iodide, the content in the whole grains is 20 mol %.
The following is preferable, 12 mol% or less is more preferable, and 0 to 5 mol% is particularly preferable.

The silver halide grains according to the present invention may be normal crystals such as cubic, tetradecahedral or octahedral, or twin crystals such as tabular, but octahedral or tabular grains are particularly preferred. The shape of the crystals can be controlled by appropriately selecting pAg, pH, etc. during mixing. In addition, octahedral or tabular particles are disclosed in, for example, JP-A-58-1193.
No. 5, No. 58-11936, No. 58-11937,
As seen in Japanese Patent Publications No. 58-108528, No. 62-163046, No. 63-41845, and No. 63-212932, crystallization occurs in the presence of a sensitizing dye or inhibitor adsorbable to silver halide grains. It can be obtained by growing.

The silver halide grains according to the present invention preferably have an average grain size of 0.05 to 10 μm, more preferably 0.1 to 5 μm, particularly preferably 0.2 to 3 μm.

The silver halide grains according to the present invention may be mixed with other silver halide grains to the extent that the effects of the present invention are not impaired. At this time, it is preferable that the silver halide grains according to the present invention account for 30% or more by weight, more preferably 50% or more, particularly preferably 80% or more.

The localization of halogen within the silver halide grains is
This can be confirmed by examining a section of silver halide grains dispersed in a resin using a line diffraction method or an X-ray microanalysis method.

The silver halide emulsion according to the present invention is preferably monodisperse.

In the present invention, monodispersity means that the weight of silver halide contained within a grain size range of ±20% around the average grain size d is 70% or more of the total weight of silver halide. , preferably 80% or more, more preferably 90% or more.

Here, the average particle size d is defined as the particle size d1 when the product n1 x d13 of the frequency n1 of particles having the particle size d1 and d13 is maximum. (3 significant figures,
(The smallest digit number is rounded to the nearest 4.) The particle size referred to here is the diameter when the projected image of the particle is converted into a circular image with the same area.

The particle size can be determined by, for example, dispersing the particles on a flat sample stage so that they do not overlap, and photographing the particles with an electron microscope at a magnification of 10,000 to 50,000 times, and then measuring the particle diameter on the print or the diameter at the time of projection. It can be obtained by actually measuring the area. (The number of grains to be measured shall be 1,000 or more indiscriminately.) The particularly preferred highly monodisperse emulsion of the present invention is defined by grain size standard deviation/average grain size x 100 = breadth of distribution (%). The width of the distribution is 20% or less, more preferably 15% or less.

[0044] The particle size measurement method here follows the measurement method described above, and the average particle size is the arithmetic mean.

Average grain size=Σd1 n1 /Σn1 The feature of the present invention is that a color light-sensitive material using the above-mentioned silver halide emulsion can be rapidly processed and quality with excellent graininess can be stably obtained even with processing fluctuations. It is in. The present inventors have discovered that it is important to control the efficiency of the coupling reaction between the oxidation product of the developing agent and the coupler in the color development process as a factor affecting graininess. In particular, the silver halide emulsion used in the present invention has a high silver development speed,
The coupling between the oxidation product of the developing agent and the coupler during the color development process tends to increase the reaction efficiency;
It has been found that by controlling and lowering the ratio of the dye density produced to the amount of developed silver produced without changing the silver development speed, excellent graininess can be obtained stably against processing fluctuations.

In the color photosensitive material according to the present invention, the development silver production rate (development utilization rate) of photosensitive silver halide in the maximum color development density region is 80% or more. By using this development utilization rate range that is close to substantially complete development, extremely excellent processing stability can be obtained.

In the present invention, the maximum color density region is defined as:
This refers to the lowest exposure amount region that provides the highest density in the characteristic curve when sensitometry is performed with an exposure of 1/50 second.

In the present invention, the development silver production rate is determined by exposure,
After color development and post-fixing treatment, the amount of developed silver is determined using fluorescent X-rays, and can be determined from the ratio to the amount of coated silver.

Next, gamma referred to in the present invention will be explained in detail. Gamma (γ) generally represents the slope of a straight line on the characteristic curve of a photographic light-sensitive material, and is a measure of the condition of the light-sensitive material.

Gamma in the present invention refers to the slope of a straight line connecting the exposure amount that gives a density of 0.3 from the minimum density to the density obtained by the exposure amount of the rear area log=1.0.

[0051] The gamma of each layer in which the effects of the present invention are more easily exhibited in the present invention is as follows: red-sensitive layer γR: preferably 0.4 to 0.9, more preferably 0.4 to 0.8;
Green-sensitive layer γG: preferably 0.5 to 1.0, more preferably 0.5 to 0.9, blue-sensitive layer γB: preferably 0.
It is preferably 0.55 to 0.95, more preferably 5 to 1.0.

Further, in the present invention, in order to obtain a wide exposure latitude, low gamma, and interlayer effect, a compound or its precursor (precursor) capable of reacting with the oxidation product of the developing agent and scavenging the oxide is used. It is preferable to use a compound that can release .

[0053] These compounds are compounds that cause a coupling reaction with the oxidized developing agent imagewise during development by being contained in the layer that provides an interlayer effect, or compounds that undergo a redox reaction with the oxidized developing agent. It has the function of suppressing pigment formation in its own layer by releasing and reacting with the oxidized developing agent produced as a result of development in its own layer. This lowers the gamma of the own layer, and the compounds that scavenge these oxidized developing agents have the effect of diffusing to other layers and suppressing color reactions in other layers, in addition to their effects in the own layer. have.

Due to this effect, for example, when these compounds are added to the magenta layer, when magenta develops, the color development of the cyan dye in the cyan layer can be suppressed in proportion to the magenta dye concentration in the magenta layer. It is thought that this suppresses the absorption of red, for example, which the magenta dye has in areas other than the original green region, and performs a masking effect. Among them, it is preferable to use the magenta layer as a layer that gives an interlayer effect and apply an interimage effect from the magenta layer to other layers for color reproduction in the red to purple range, and is particularly effective in forming highly pure red. .

It is also preferable to use the cyan layer as a layer that provides an interlayer effect. For example, applying an interimage from the cyan layer to the magenta layer in the same way is particularly effective in reproducing blue-based colors. Similarly, by increasing the degree of diffusion of the compound that scavenges the released oxidized developing agent, interimage is applied from the cyan layer to the yellow layer, and vice versa. The present invention can be used in various ways.

It is also possible to use iodine-containing silver halide emulsions, DIR couplers, etc. as materials that produce interlayer effects, but these release development inhibitors and therefore delay the overall development. This goes against the request for faster processing. Therefore, it is difficult to use the photosensitive material of the present invention, which requires rapid processing. In addition, for these multilayer photosensitive materials that require rapid processing, it is difficult to stop the development of each layer in a well-balanced manner, so masking by releasing these development inhibitors may require some ingenuity when applied to such photosensitive materials. be.

In the present invention, the compound capable of reacting with the oxidation product of the developing agent to scavenge the oxide or the compound capable of releasing its precursor (hereinafter referred to as "DSR compound") preferably has the general formula [ DSR-I].

[0058]

[Chemical formula 1]

In the above general formula [DSR-I], Co
UP is caused by reaction with oxidized color developing agent.

0060
]

[Case 2]

represents a coupler residue capable of releasing Tim
e is S after Time-Sc is released from Coup.
Sc represents a timing group capable of releasing c, and Sc represents a timing group capable of scavenging the oxidized color developing agent by a redox reaction or a coupling reaction after being released from the Coup or Time-Sc. It represents a scavenger or its precursor, and l represents 0 or 1.

To further specifically explain the compound represented by the general formula [DSR-I], the coupler residue represented by Coup is generally a yellow coupler residue, a magenta coupler residue, a cyan coupler residue, or A coupler residue that does not substantially produce an image-forming coloring dye, and preferably has the following general formulas [DSR-Ia] to [DSR-Ih]
It is a coupler residue represented by

[0063]

[Chemical formula 3]

In the above general formula [DSR-Ia], R
1 represents an alkyl group, an aryl group, or an arylamino group, and R2 represents an aryl group or an alkyl group.

In the above general formula [DSR-Ib], R
3 represents an alkyl group or an aryl group, and R4 represents an alkyl group, an acylamino group, an arylamino group, an arylureido group, or an alkylureido group.

In the above general formula [DSR-Ic], R
4 has the same meaning as R4 in general formula [DSR-Ib],
R5 represents an acylamino group, a sulfonamide group, an alkyl group, an alkoxy group, or a halogen atom.

[DSR-Id] and [DS
R-Ie], R7 is an alkyl group, an aryl group, an acylamino group, an arylamino group, an alkoxy group,
Represents an aryl ureido group, an alkyl ureido group, and R6
represents an alkyl group or an aryl group.

In the above general formula [DSR-If], R
9 represents an acylamino group, carbamoyl group, or arylureido group, and R8 represents a halogen atom, an alkyl group, an alkoxy group, an acylamino group, or a sulfonamide group.

In the above general formula [DSR-Ig], R
9 has the same meaning as the general formula [DSR-If], and R10 represents an amino group, an acid amide group, a sulfonamide group, or a hydroxyl group.

In the above general formula [DSR-Ih], R
11 is a nitro group, an acylamino group, a succinimide group,
Represents a sulfonamide group, an alkoxy group, an alkyl group, a halogen atom, and a cyano group.

In the above general formula, l in [DSR-Ic] is 0 to 3, [DSR-If] and [DS
n in R-Ih] is 0 to 2, [DSR-Ig]
m represents an integer from 0 to 1, and when l and n are 2 or more, each of R5, R8 and R11 may be the same or different.

Each of the above groups includes those having a substituent,
Preferred substituents include halogen atoms, nitro groups, cyano groups, sulfonamide groups, hydroxyl groups, carboxyl groups, alkyl groups, alkoxy groups, carbonyloxy groups, acylamino groups, aryl groups, as well as so-called bis couplers and polymers. Examples include those containing a coupler portion that constitutes a coupler.

The lipophilicity exhibited by R1 to R11 in the above general formula can be arbitrarily selected depending on the purpose. In the case of conventional image-forming couplers, the total number of carbon atoms in R1 to R10 is preferably 10 to 60, more preferably 15 to 30. In addition, in the case where the dye produced by color development can be appropriately moved in the photosensitive material, the R1 to R10
The total number of carbon atoms is preferably 15 or less.

Couplers that do not substantially form image-forming coloring dyes include those that do not generate coloring dyes, so-called run-off dye-forming couplers in which coloring dyes flow out from the light-sensitive material into the processing solution, and couplers that do not generate coloring dyes. This refers to so-called bleaching dye-forming couplers that are bleached by reacting with other components and do not leave a color image after development.In the case of run-off dye-forming couplers, the total number of carbon atoms in R1 to R10 is The number is preferably 15 or less, and it is further preferable that R1 to R10 have at least one carboxyl group, arylsulfonamide group, or alkylsulfonamide group as a substituent.

In the general formula [DSR-I], Ti
The timing group represented by me preferably has the following general formula [DSR-Ii], [DSR-Ij] or [DSR-
Ik].

[0076]

[C5]

In the formula, B represents an atomic group necessary to complete the benzene ring or naphthalene ring, and Y represents -O-, -S
-or

[0078]

[C6]

Co of the general formula [DSR-I]
Binds to the active site of up (coupling component). R12
, R13 and R14 represent a hydrogen atom, an alkyl group or an aryl group. the above

[0080]

[C7]

[0081] is substituted at the ortho or para position with respect to Y, and the other is S of the general formula [DSR-I]
It is connected to c.

[0082]

[Chemical formula 8]

In the formula, Y, R12, and R13 each have the same meaning as in the above general formula [DSR-Ii], and R15 is a hydrogen atom,
Represents an alkyl group, aryl group, acyl group, sulfonyl group, alkoxycarbonyl group or heterocyclic residue, R16
represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, an alkoxy group, an amino group, an acid amide group, a sulfonamide group, a carboxyl group, an alkoxycarbonyl group, a carbamoyl group, or a cyano group.

Further, the timing group represented by the above general formula [DSR-Ij] is similar to the above general formula [DSR-Ii], where Y is a Coup (coupling component) of the above general formula [DSR-I]. At the active point of

[0085]

[Chemical formula 9]

[0086] is bonded to Sc.

Next, as a Time group that releases Sc by an intramolecular nucleophilic substitution reaction, there is a group represented by the following general formula [DSR-Ik].

General formula [DSR-Ik] -Nu-D-E- In the formula, Nu represents a nucleophilic group having an electron-rich oxygen, sulfur or nitrogen atom. I]
It binds to the active site of the Coup (coupling component). E represents an electrophilic group having an electron-poor carbonyl group, thiocarbonyl group, phosphinyl group, or thiophosphinyl group. This electrophilic group E is bonded to the heteroatom of Sc, and D is sterically related to Nu and E, and after Nu is released from Coup (coupling component), a 3-membered ring to a 7-membered ring is formed. Represents a linking group capable of breaking intramolecular nucleophilic substitution by a reaction involving the formation of a ring and thereby releasing Sc.

Furthermore, the scavenger of the oxidized color developing agent represented by Sc (if Sc is a precursor, the scavenger produced from the precursor) is of the redox type and the coupling type.

In the general formula [DSR-I], when Sc scavenges the oxidized color developing agent by a redox reaction, the Sc is a group capable of reducing the oxidized color developing agent, for example, Angew. ．． Chem.
Int. Ed. , 17 875-886 (1978)
, The Theory of the Photo
graphic Process 4th edition (Mac
illan 1977) Chapter 11, JP-A-59-524
Reducing agents described in No. 7 and the like are preferred, and Sc may be a precursor that can release these reducing agents during development. Specifically, -OH group, -NHSO2R group,

[0091]

[Chemical formula 10]

(In the formula, R and R' are hydrogen atoms, alkyl,
Represents a cycloalkyl, alkenyl, or aryl group. ) is preferable, and an aryl group or a heterocyclic group having at least two of them is preferable, an aryl group is especially preferable, and a phenyl group is more preferable. The lipophilicity of Sc is expressed by the above general formula [DSR-Ia]
Like the couplers represented by [DSR-Ih], they can be arbitrarily selected depending on the purpose, but in order to maximize the effects of the present invention, the total number of carbon atoms in Sc is 6 to 50, preferably 6 to 50. 6-30, more preferably 6-20.

When Sc scavenges the oxidized color developing agent through a coupling reaction, the Sc
can be a variety of coupler residues, but is preferably a coupler residue that does not substantially form an image-forming color dye, and is a coupler residue that does not substantially form an image-forming color dye, and is similar to the aforementioned efflux dye-forming couplers, bleachable dye-forming couplers, and reactive active sites. A Weiss coupler or the like that has a non-leaving substituent and does not form a dye can be used.

Specific compounds represented by the above general formula [DSR-I] include, for example, those described in British Patent No. 1,546,837, JP-A-52-150631, and JP-A-57-111.
No. 536, No. 57-111537, No. 57-1386
No. 36, No. 60-185950, No. 60-20394
No. 3, No. 60-213944, No. 60-214358
No. 61-53643, No. 61-84646, No. 61-86751, No. 61-102646, No. 61
-102647, 61-107245, 61-
No. 113060, No. 61-231553, No. 61-2
No. 33741, No. 61-236550, No. 61-23
No. 6551, No. 61-238057, No. 61-240
No. 240, No. 61-249052, No. 62-8163
No. 8, No. 62-205346, No. 62-287249
There are some that are listed in the No. 1 gazette, etc.

A redox type scavenger can be preferably used as Sc, and in this case, the color developing agent can be reused by reducing the oxidized product of the color developing agent.

Next, DSR compounds represented by the above general formula [DSR-I] will be illustrated, but the present invention is not limited to the exemplified compounds below.

[0097]

[Chemical formula 11]

[0098]

[Chemical formula 12]

0099

[Chemical formula 13]

[0100]

[Chemical formula 14]

[0101]

[Chemical formula 15]

[0102]

[Chemical formula 16]

[0103]

[Chemical formula 17]

[0104]

[Chemical formula 18]

[0105]

[Chemical formula 19]

[0106]

[C20]

[0107]

[C21]

[0108]

[C22]

[0109]

[C23]

[0110]

[C24]

The DSR compound of the present invention can be added to a light-sensitive silver halide emulsion layer and/or a non-light-sensitive photographic constituent layer, but it is preferably added to a light-sensitive silver halide emulsion layer.

Two or more DSR compounds of the present invention can be contained in the same layer. Also, the same DSR compound may be included in two or more different layers.

These DSR compounds are generally used in an amount of preferably 2.times.10@-4 to 5.times.10@-1 mol, more preferably 1.times.10@-3 to 1.times.10@-1 mol, per mol of silver in the emulsion layer.

In order to incorporate these DSR compounds into the silver halide emulsion according to the present invention or into the coating solution for other photographic constituent layers, if the DSR compound is alkali-soluble, it may be added as an alkaline solution. If it is oil-soluble, for example, U.S. Pat. No. 2,322,027
No. 2,801,170, No. 2,801,17
No. 1, No. 2,272,191 and No. 2,304,
It is preferable to dissolve the DSR compound in a high boiling point solvent, optionally in combination with a low boiling point solvent, and to disperse the DSR compound in the form of fine particles and add it to the silver halide emulsion according to the method described in each specification of No. 940.

[0115] The above DSR compound is disclosed in Japanese Patent Application Laid-Open No. 57-13
No. 8638, No. 57-155537, No. 57-171
No. 334, No. 58-111941, No. 61-5364
No. 3, No. 61-84646, No. 61-86751,
It can be synthesized by the method described in 61-102646, 61-102647, 61-107245, 61-113060, etc.

In the light-sensitive emulsion layer, the compound or its precursor that undergoes a coupling reaction or redox reaction with the oxidized developing agent released from the DSR compound of the present invention in accordance with the density of the image during development is It suppresses the pigment formation reaction (coupling reaction) depending on the concentration, producing so-called intra-image effects such as improving image sharpness.
On the other hand, in other layers into which it has diffused, two types of image effects occur, such as a masking effect that inhibits the pigment-forming reaction in that layer in accordance with the density of the image in the diffusion source layer. It is possible to obtain

As the support for the silver halide photographic light-sensitive material in the present invention, transparent cellulose acetate film, polyethylene terephthalate film, etc. having a thickness of 10 to 200 μm may be used.

The light-sensitive silver halide emulsion used in the light-sensitive material of the present invention can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye.

Antifoggants, stabilizers and the like can be added to the photosensitive silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened, and can also contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

A coupler is used in the light-sensitive silver halide emulsion layer of the light-sensitive material for color photography.

Furthermore, by coupling with a colored coupler having the effect of color correction, a competitive coupler, and an oxidized form of a developing agent, the developer, silver halide solvent, toning agent, hardening agent, antifoggant, chemical Compounds that release photographically useful fragments such as sensitizers, spectral sensitizers and desensitizers can be used.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.

A formalin scavenger, a fluorescent whitening agent, a matting agent, a lubricant, an image stabilizer, a surfactant, a color fog preventive agent, a development accelerator, a development retardant, a bleach accelerator, etc. can be added to the photosensitive material.

The photosensitive material of the present invention is particularly useful as a negative photosensitive material.

To obtain a dye image using the light-sensitive material of the present invention, commonly known color photographic processing can be performed after exposure.

[0127] The color developing agent used in the color developer according to the present invention is preferably an aromatic primary amine type, and in particular p
-Phenylenediamine color developing agents are preferred.

These color developing agents are preferably used in a concentration of 0.1 to 30 g, more preferably 1 to 15 g, per liter of color developer.

To obtain a dye image using the light-sensitive material according to the present invention, color photographic processing is performed after exposure. Color photographic processing generally includes a color development process, a bleaching process, a fixing process, a water washing process, and, if necessary, a stabilizing process. Alternatively, a one-bath bleach-fixing solution can be used to perform the bleach-fixing process, or a one-bath developing, bleach-fixing solution can be used to perform color development, bleaching, and fixing in one bath. A monobath treatment process can also be performed. Also,
In place of the water washing treatment step, a water washing alternative stabilization treatment can also be performed.

[0130] In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these processes, instead of the color development processing step, a color developing agent or its precursor may be contained in the light-sensitive material, and an activator processing step may be performed in which the development processing is performed using an activator solution. Beta processing can be applied. Among these processes, typical processes are shown below. (These treatments are performed as a final step, either a water washing process, a water washing process and a stabilization process, or a water washing alternative stabilization process or stabilization process.) Color development process - Bleaching process - Fixing Processing process/Color development process - Bleach-fixing process/Pre-hardening process - Color development process - Stop-fixing process - Washing process - Bleach process - Fixing process - Washing process - Post-hardening process - Color development process - Water washing process - Supplementary color development process - Stop process - Bleach process - Fixing process - Activator process - Bleach-fixing process - Activator process - Bleaching process - Fixing process - Monobath processing process - Pre-treatment - Color development process - Bleaching process - Fixing process In addition, in place of the "Water wash process" in the above typical processing steps, "Water substitute stabilization treatment" may be replaced with "Water substitute stabilization treatment". Stabilization treatment may also be performed.

[0131] The treatment temperature is usually selected in the range of 10°C to 65°C, but it may also be at a temperature exceeding 65°C. Preferably, the treatment is carried out at 25°C to 45°C.

[0132] The color developing solution contains an alkaline agent commonly used in developing solutions, such as sodium hydroxide, potassium hydroxide,
ammonium hydroxide, sodium carbonate, potassium carbonate,
It may contain sodium sulfate, sodium metaborate, borax, etc., and may further contain various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, or development regulators such as citradinic acid. , hydroxylamine or sulfite may be contained as a preservative. Furthermore, various antifoaming agents and surfactants, as well as organic solvents such as methanol, dimethylformamide or dimethyl sulfoxide, etc. can be appropriately contained.

[0133] The pH of the color developing solution is usually 7 or more, preferably about 9-13.

[0134] The color developing solution used in the present invention may also contain diethylhydroxyamine, tetronic acid, tetronimide, 2-anilinoethanol, dihydroxyacetone, aromatic secondary alcohol, etc. as antioxidants, if necessary.
Hydroxamic acid, pentose or hexose, pyrogallol-1,3-dimethyl ether, etc. may be contained.

[0135] In the color developing solution, various chelating agents can be used in combination as metal ion sequestering agents. For example, as the chelating agent, amine polycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-
Organic phosphonic acids such as hydroxyethylidene-1,1'-diphosphonic acid, aminopolyphosphonic acids such as aminotri(methylenephosphonic acid) or ethylenediaminetetraphosphonic acid, oxycarboxylic acids such as citric acid or gluconic acid, 2-phosphonobutane-1, Examples include phosphonocarboxylic acids such as 2,4-tricarboxylic acid, polyphosphoric acids such as tripolyphosphoric acid or hexametaphosphoric acid, and polyhydroxy compounds.

The bleaching process may be carried out simultaneously with the fixing process as described above, or may be carried out separately. As the bleaching agent, preferably a metal complex salt of an organic acid is used, for example, an organic acid such as polycarboxylic acid, aminopolycarboxylic acid, oxalic acid, citric acid, etc., coordinated with metal ions such as iron, cobalt, copper, etc. is used. Among the above organic acids, the most preferred organic acids include polycarboxylic acids and aminopolycarboxylic acids. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(β-oxyethyl)-N,N',N'-triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, and iminodiacetic acid. , dihydroxyethylglycine citric acid (or tartaric acid), ethyl ether diamine tetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediaminetetrapropionic acid, phenylenediaminetetraacetic acid, and the like.

These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

[0138] These bleaching agents are preferably used in an amount of 5 to 450 g.
/l, more preferably 20 to 250 g/l.

In addition to the above bleaching agents, the bleaching solution may contain a sulfite salt as a preservative, if necessary. Further, the bleaching solution may be a solution containing an ethylenediaminetetraacetate iron(III) complex salt bleaching agent and a large amount of a halide such as ammonium bromide. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can.

[0140] Bleaching solutions include JP-A No. 46-280, JP-A-45-8506, JP-A-46-556, Belgian Patent No. 770,910, JP-A-45-8836, JP-A-53.
-9854, JP-A-54-71634 and JP-A-49-
Various bleaching accelerators such as those described in No. 42349 can be added.

[0141] The pH of the bleaching solution used is 2.0 or higher, generally 4.0 to 9.5, preferably 4.0 to 9.5.
5 to 8.0, most preferably 5.0 to 7.0
It is.

[0142] As the fixer, one having a commonly used composition can be used. As a fixing agent, compounds that react with silver halide to form water-soluble complex salts, such as those used in ordinary fixing processes, such as thiosulfates such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, and potassium thiocyanate are used. , sodium thiocyanate,
Typical examples include thiocyanates such as ammonium thiocyanate, thioureas, thioethers, and the like. These fixing agents are used in an amount of 5 g/l or more within a soluble range, but are generally used in an amount of 70 to 250 g/l. Incidentally, a part of the fixing agent can be contained in the bleaching solution, or conversely, a part of the bleaching agent can also be contained in the fixing solution.

[0143] The bleaching solution and the fixing solution include boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, ammonium hydroxide, etc. with various pH values. Buffers can be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydrokylamine, hydrazine, bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitro alcohols and nitrates, hardening agents such as water-soluble aluminum salts, Organic solvents such as methanol, dimethylsulfamide, dimethylsulfoxide, etc. can be appropriately contained.

[0144] The fixer is used at a pH of 3.0 or higher, but
Generally used is 4.5 to 10, preferably 5 to 9.
5, most preferably 6-9.

Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of organic acids described in the above bleaching process, and the preferred compounds and concentrations in the processing solution are also the same as in the above bleaching process.

The bleach-fixing solution contains a silver halide fixing agent in addition to the above-mentioned bleaching agent, and if necessary, a solution containing sulfite as a preservative is applied. In addition, a bleach-fix solution consisting of an ethylenediaminetetraacetic acid iron (III) complex salt bleach and a small amount of a halide such as ammonium bromide in addition to the above-mentioned silver halide fixing agent, or conversely, a halogen such as ammonium bromide may be used. A special bleach-fixing solution having a composition containing a large amount of chemical compounds can also be used. As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can.

Examples of the silver halide fixing agent that can be included in the bleach-fixing solution include the fixing agents described in the above fixing treatment step. The concentration of the fixing agent and the pH buffering agent and other additives that can be contained in the bleach-fixing solution are the same as in the above-mentioned fixing step.

[0148] The pH of the bleach-fix solution is used at 4.0 or higher, generally 5.0 to 9.5, preferably 6.0 to 8.5, most preferably 6.5. ~8
．． It is 5.

[0149] Regarding the stabilizing liquid, there are stabilizing liquids used after washing with water, stabilizing liquids used in place of washing, and stabilizing liquids conventionally used in color negative photosensitive materials. may be used without any particular restrictions.

In the silver halide color photographic light-sensitive material used in the present invention, the silver halide emulsion is
What is described in Disclosure No. 308119 (hereinafter abbreviated as RD308119) can be used. The table below shows the locations. [item]
[RD308119 page] Iodine tissue
993
I-A manufacturing method
Section 993I-A and 9
94 E-term crystal habit Normal crystal habit
9
93 I-A term twin crystal

〃Epitaxial

〃Halogen composition uniform

993 Section I-B
not uniform
〃Halogen conversion
994 I-C Section 〃 Substitution
〃Metal content

994 I-D term monodisperse

995 I-F term solvent addition
〃Latent image formation position Surface
995 I-G term
internal

〃Applicable sensitive material negative
995
I-H section Positive (including internal fog particles)〃Used by mixing emulsion
995 I-J section desalination

995 II-
Section A In the present invention, the silver halide emulsion is subjected to physical ripening,
Use those that have been chemically ripened and spectrally sensitized. Additives used in such processes are listed in Research Disclosure No. 17643, No. 18716 and no. 3
08119 (hereinafter referred to as RD17643 and RD18, respectively)
716 and RD308119).

[0151] The descriptions are shown in the table below. [Item] [RD308119 page]
[RD 17643] [RD 1871
6] Chemical sensitizer 996 Section III-A
23
648 Spectral sensitizer 996 IV-A-A,
B, C, D, H, H, I, J items 23-24
648-9 Supersensitizer 996 IV-A-
E, J sections 23-24
648-9 Antifoggant 998 VI
24-25
649 Stabilizer 998 V
I 24
~25 649 Known photographic additives that can be used in the present invention are also described in the above Research Disclosure. The relevant entries are shown in the table below. [Item] [RD308119 page] [RD 17643] [RD 1871
6] Color clouding prevention agent 1002 Section VII-I 25
650 Dye image stabilizer 1001 VII-J
Section 25 Brightener
998V
24 Ultraviolet absorber 1003 VI
II C, XIII Section C 25-26 Light absorber 1003 VIII
25-26 light scattering agent
1003 VIII Filter Dye
1003 VIII 2
5-26 binder 1003 IX
26
651 Static inhibitor 1006 X
III 27
650 hardener
1004 x 2
6 651 Plasticizer
1006 XII
27 650 Lubricant 1006 XII
27
650 Activator/Coating Aid 1005 XI
26-27 65
0 Matting agent 1007 X VI
Developer (contained in photosensitive material) 1011 XX-B
Section: Various couplers can be used in the photosensitive material used in the present invention, and specific examples thereof are described in the above Research Disclosure. The relevant entries are shown in the table below. [Item] [
RD308119 page] [RD 17643] [
RD 18716] Yellow coupler
1001 Section VII-D
VII C-G Section Magenta Coupler
1001 Section VII-D
VII C-G Cyan coupler
1001 VII-F Section VII C-G Section DIR Coupler 1001 VI
I-F term VII F term
BAR coupler 10
02 Section VII-F Other useful residue-releasing couplers
1001 Section VII-F alkali soluble coupler
1001 Section VII-E The additives used in the present invention can be added by the dispersion method described in RD308119 XIV.

[0152] In the present invention, the above-mentioned RD17643
28 pages, RD1871664 pages 7-8 and RD3
The supports described in No. 0819 XIX can be used.

The photosensitive material of the present invention includes the above-mentioned RD3081.
Auxiliary layers such as filter layers and intermediate layers as described in Section 19 VII-K may be provided.

[0154] The photosensitive material of the present invention is the above-mentioned RD30811.
9 Various layer configurations such as normal layer, reverse layer, and unit configuration described in Section VII-K can be adopted.

The present invention can be applied to color photosensitive materials having various transparent supports, such as color negative films for general use or movies, color reversal films for slides or television, and color positive films.

Other than the above, the photosensitive material of the present invention has the following:
Above mentioned RD17643 pages 28-29, RD18716
647 and RD308119, XVII.

[0157]

Effects of the Invention According to the present invention, a silver halide emulsion containing silver chloride can be used to quickly process a color image with excellent graininess and to stably obtain a color image without processing fluctuation. A method for developing a color photographic material can be provided.

[0158]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

(Preparation of EM-1) Silver chlorobromide emulsion EM-1
was adjusted as follows.

2% gelatin aqueous solution kept at 40°C 10
The following (solution A) and (solution B) were added in 00ml at pAg=6.
6. Simultaneously added over 30 minutes while controlling pH = 2.0, and further added the following (solution C) and (solution D) to pAg = 7.3, p
They were simultaneously added over 180 minutes while controlling H=5.8.

[0161] At this time, the control of pAg is described in Japanese Patent Application Laid-Open No. 59-4
The method described in No. 5437 was used to control the pH using an aqueous solution of sulfuric acid or sodium hydroxide. (Liquid A) Sodium chloride

1.03g potassium bromide

Add 0.006g water


50ml (solution B) silver nitrate

Add 3g water

5
0ml (Liquid C) Sodium chloride

103.0g potassium bromide

Add 0.63g water

60
0ml (Liquid D) Silver nitrate

Add 300g water

600ml
After the addition, desalination was performed using a 5% aqueous solution of Demol N manufactured by Kao Atlas Co., Ltd. and a 20% aqueous solution of magnesium sulfate, and then mixed with an aqueous gelatin solution to obtain an average particle size of 0.70μ.
m, coefficient of variation of particle size distribution 7%, silver chloride content 99.7
A monodisperse cubic emulsion EM-1 with mol % was obtained.

[0162] Also, the halide compositions of liquids A and C were arbitrarily changed according to the method for preparing EM-1, and liquids C and D were
EM-2 to 4, EM-8, and EM-10 listed in Table 1 were prepared by arbitrarily changing the pAg, pH, mixing time, and amount added when adding the liquid. (Creation of EM-5 and EM-6) JP-A-58-11193
No. 5, No. 58-111936, No. 58-111937
No. 58-108528, No. 62-163046, No. 63-41845, No. 63-212932, No. 63-25643, No. 63-281149, JP-A No. 1-72142, etc. By method EM-
A monodispersed octahedral emulsion EM-5 having the same halogen composition, grain size distribution, and average grain size as Example 1 and having an octahedral final grain shape was obtained. In addition, by the method shown in the above-mentioned publications, etc.,
Same halogen composition as EM-1, average particle size (diameter corresponding to average imaging area circle) of 1.05 μm and thickness of 0.21 μm
A hexagonal tabular emulsion EM-6 having an aspect ratio of 5 was obtained. (Preparation of EM-7) A silver iodobromide phase with an iodine content of 35 mol% was created inside the grains by the method described in Japanese Patent Application No. 2-23336, and the preparation method was similar to that of EM-1. The layer has a silver chlorobromide phase on the shell side, an average grain size of 0.70 μm, a coefficient of variation of grain size distribution of 7%, a silver bromide content of 15 mol%, and a silver iodide content of 5 mol%. A dispersed cubic emulsion EM-7 was obtained. (Creation of EM-11 to EM-14) JP-A-61-246
No. 740, No. 61-275741, No. 61-2868
By the method shown in Publication No. 45, the coefficient of variation of the silver halide composition, final shape, and grain size distribution shown in Table 1 was 10%.
Monodispersed emulsions EM-11 to EM-14 were obtained. (Creation of EM-9) JP-A No. 64-28640, No. 64
-6941, JP-A-1-102453, JP-A-1-24
By the method disclosed in Publication No. 3057, silver bromide was localized at or near the corners of cubic silver chloride grains as host grains, with an average grain size of 0.70 μm, a coefficient of variation of grain size distribution of 7%, and bromide. A monodisperse cubic emulsion EM-9 with a silver content of 20 mol % was obtained.

[0163]

[Table 1]

Example 1 In all the following examples, the amount added in the silver halide photographic material is expressed in grams per m2 unless otherwise specified. In addition, silver halide and colloidal silver are shown in terms of silver. Sensitizing dyes are expressed in moles per mole of silver.

[0165] Sample No. 1 was formed on a triacetylcellulose support by a layer having the composition shown below. 101
was created. Sample No. 101 First layer: Emulsion layer Emulsion EM-1 was mixed with sensitizing dyes (S-1), (S-2), (
S-3), optimally chemically sensitized using sodium thiosulfate, chloroauric acid and ammonium thiocyanate, and coated with 6.0 x 10-2 mol of cyan coupler (C-1) added per mol of silver. It was applied so that the amount of silver was 2.50 g/m2. 2nd layer; protective layer gelatin layer coating amount 2.0 g/m2 In addition to the above composition, gelatin hardening agent H-3 and coating aids (Su-3) and (Su-4) were added as appropriate to each layer. .

Next, sample No. 101, the first layer E
An emulsion as shown in Table 2 was used instead of M-1, and an emulsion as shown in Table 2 was used instead of cyan coupler (C-1).
) and DSR compound at different ratios to produce sample No. 2 shown in Table 2. 101 to 126 were produced.

[0167]

[C25]

[0168]

[C26]

[0169]

[Table 2]

[0170] Furthermore, sample No. Each of the silver halide emulsions EM-1, EM-5 to EM-10, and EM-12 used in Nos. 101 to 126 was chemically processed optimally using the same sensitizing dye and sensitizer as EM-1. Sensitized. The thus prepared sample was subjected to sensitometric wedge exposure using white light at an exposure dose of 50 CMS, and then the following development treatments A, B, and C were performed.

Sensitometric density measurements were performed using red light on each sample obtained from each treatment. The obtained γ values are shown in Table 3.

[0172] Graininess was also evaluated by RMS value. (For RMS graininess, see T.H. James, ed.
“The Theory of the Ph.
otographic process” 4th edition
Described in Chapter 21. ) To measure the RMS value, measure the lowest red density (called fog) + 0.3 red density part of the so-called characteristic curve obtained by sensitometry using Sakura Microdensitometer Model PDM-5 Type AR (Konica Corporation aperture scanning area of 1800
μm2 (slit width 10μm, slit length 180μm)
was measured, and the standard deviation of fluctuations in concentration values was determined for 1000 or more concentration measurement samples, and expressed as a relative value when the value of each treatment of sample (101) was taken as 100. The above results are shown in Table 3.

[0173] The amount of developed silver in the highest color density region was determined by performing stepwise wedge exposure, measuring the amount of residual silver using fluorescent X-rays through the steps of Processing A, Processing B, and Processing C, and further degrading. The silver density was measured and the molar ratio of silver used for color development was calculated. Processing A Processing step (38℃) Color development 2 minutes 10 seconds bleaching
White 6 minutes 30 seconds water
Wash for 3 minutes and 15 seconds
Arrive 6 minutes 30 seconds Wednesday
Washing 3 minutes 15 seconds stabilization 1 minute 30 seconds drying
The composition of the processing liquid used in each drying process is as follows.

<Color developer> 4-amino-3-methyl-N-ethyl-N-(β-
Hydroxyethyl) aniline sulfate

4.75g anhydrous sodium sulfite
4.2
5g Hydroxylamine 1/2 sulfate
2.
0g anhydrous potassium carbonate

37.5g Sodium Bromide

1.3g Nitriloacetic acid trisodium salt (monohydrate)
2.5g potassium hydroxide

1.0g
Add water to make 1 liter. (pH=10.1)
<Bleach solution> Ethylenediaminetetraacetic acid iron ammonium salt
100g ethylenediaminetetraacetic acid diammonium salt
10.0g ammonium bromide
150.0g
glacial acetic acid

Add 10 ml of water to make 1 liter, and adjust the pH to 6.0 using aqueous ammonia.

<Fixer> Ammonium thiosulfate
17
5.0g Anhydrous sodium sulfite

8.5g Sodium metasulfite

Add 2.3 g of water to make 1 liter, and adjust the pH to 6.0 using acetic acid.

<Stabilizing solution> Formalin (37% aqueous solution)
1
．． 5ml Konidax (manufactured by Konica)

Add 7.5 ml water to make 1 liter.

At the same time, a dye image was obtained by processing the following Process B in the same manner as Process A except that only the color development step and the color developer were changed as described below. Treatment B Treatment process Temperature
Color development 60 seconds 40℃
<Color developer> 4-amino-3-methyl-N-(β-hydroxyethyl)aniline sulfate

11
．． 1g anhydrous sodium sulfite

4.25g Hydroxylamine 1/2 sulfate
2.0g anhydrous potassium carbonate

30.0g Sodium Bromide

1.3g
Nitrilo trisulfate trisodium salt (monohydrate)
Add 2.5g water to make 1 liter. (pH=10.2) Treatment C Treatment process Temperature
Time color development 38.0±0.3℃
45 seconds bleach fixing 35.0±0.5℃
Stabilized for 45 seconds 30-34℃
Dry for 90 seconds 60~
80℃ 60 seconds Color developer Pure water

800ml triethanolamine
10g N
,N-diethylhydroxylamine
5g
potassium bromide

0.02g potassium chloride

2g potassium sulfite
0
．． 3g 1-hydroxyethylidene-1,1-diphosphonic acid 1.0g ethylenediaminetetraacetic acid
1.0
g Catechol-3,5-diphosphonate disodium 1.0 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate

9g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative)
1.0g potassium carbonate

Add 27 g of water to bring the total volume to 1 liter, and adjust the pH to 10.10.

Bleach-fix solution Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid
3
g Ammonium thiosulfate (70% aqueous solution)
100ml
Ammonium sulfite (40% aqueous solution)
27.5ml
Add water to bring the total volume to 1 liter, and adjust the pH to 5.7 with potassium carbonate or glacial acetic acid.

Stabilizing liquid 5-chloro-2-methyl-4-isothiazoline-3
-one 1.0g ethylene glycol
1.0g 1
-Hydroxyethylidene-1,1-diphosphonic acid
2.0g ethylenediaminetetraacetic acid
1.0g ammonium hydroxide (20% aqueous solution)
3.0g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.5g Add water to make a total volume of 1 liter, and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide.

[0180]

[Table 3]

[0181] As can be seen from Table 3 above, sample No. 1 according to the present invention. 109-114, No. 117-1
It is clear that Sample No. 22 is superior to the comparative examples in terms of RMS graininess as well.

Example 2 Sample No. prepared in Example 1. The γ variation rate was examined in the same manner as in Example 1, except that 109 to 124 and development treatment (B) were used, and the color development time was changed to 40 seconds and 90 seconds in the development treatment (B). The results obtained are shown in Table 4.

The γ fluctuation rate refers to the ratio of γ when the color development time is 90 seconds to γ when the color development time is 40 seconds. It is expressed as a relative γ variation rate when the γ variation rate of 109 is taken as 100%.

[0184]

[Table 4]

[0185] From Table 4 above, it is clear that the samples according to the present invention exhibit very small performance fluctuations with respect to changes in development processing time.

Example 3 Sample No. used in Example 1. 1
01, No. No. 109 was exposed to white light in the same manner as in Example 1, and in Process D described below, only the color development time was processed according to the description in Table 5. As in Example 1, the γ value, RMS value (relative value), and molar ratio (%) used for color development in the maximum color density region were determined. The results obtained are shown in Table 5. Treatment D Treatment process Temperature
Time color development 35.0±0.3℃
Table-4 Bleach-fixing 35.0±0.5℃
Stabilized for 45 seconds 30-34℃
Dry for 90 seconds 60~
80℃ 60 seconds Color developer Pure water

800ml triethanolamine
10g N
,N-diethylhydroxylamine
5g
potassium bromide

0.02g potassium chloride

2g potassium sulfite
0
．． 3g 1-hydroxyethylidene-1,1-diphosphonic acid 1.0g ethylenediaminetetraacetic acid
1.0
g Catechol-3,5-diphosphonate disodium 1.0 g N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate

4.5g Fluorescent brightener (4
, 4'-diaminostilbendisulfonic acid derivative) 1.
0g potassium carbonate

Add 27 g of water to bring the total volume to 1 liter, and adjust the pH to 10.10. Bleach-fix solution Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid
3
g Ammonium thiosulfate (70% aqueous solution)
100ml
Ammonium sulfite (40% aqueous solution)
27.5ml
Add water to bring the total volume to 1 liter, and adjust the pH to 5.7 with potassium carbonate or glacial acetic acid. Stabilizing liquid 5-chloro-2-methyl-4-isothiazoline-3
-one 1.0g ethylene glycol
1.0g 1
-Hydroxyethylidene-1,1-diphosphonic acid
2.0g ethylenediaminetetraacetic acid
1.0g ammonium hydroxide (20% aqueous solution)
3.0g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.5g Add water to make a total volume of 1 liter, and adjust the pH to 7.0 with sulfuric acid or potassium hydroxide.

[0187]

[Table 5]

As is clear from the results in Table 5, the molar ratio utilized for color development of the photosensitive silver halide emulsion in the maximum color density region is 80 mol% or more, and γ
It can be seen that good graininess can be obtained when is within the range of 0.2 to 1.0.

Example 4 On a triacetyl cellulose film support, each layer having the composition shown below was sequentially formed from the support side to obtain multilayer color photographic material No. 201 was created. 1st layer; antihalation layer (HC) black colloidal silver
0.15
Ultraviolet absorber (UV-1)
0.2
0 Colored cyan coupler (CC-1) 0.02
High boiling point solvent (Oil-1
)
0.20 〃
(Oil-2)
0.20
gelatin
1.6
2nd layer; intermediate layer (IL-1) gelatin
1.3
3rd layer; low sensitivity red-sensitive emulsion layer (R-L) EM-2

0.4 EM-4

0.3 Sensitizing dye (S-1)
3.2×10-4 (mol/silver 1 mol)
〃 (S-2)
3.2×10-4 (mol/silver 1 mol)
〃 (S-3)
0.2 x 10-4 (mol/silver 1 mol)
Cyan coupler (C-1)
0.50
〃 (C-2)
0.13
Colored cyan coupler (CC-1) 0.07
High boiling point solvent (Oil-1)
0
．． 55 Gelatin

1.0
4th layer; high sensitivity red-sensitive emulsion layer (R-H) EM
-1
0.9
Sensitizing dye (S-1)
1.7×10-4 (mol/
1 mole of silver) (S-2)
1.6×10-4 (mol/1 mol of silver) (S-3)
0.1×10-4 (mol/silver 1
Mol) Cyan coupler (C-2)
0.23
Colored cyan coupler (CC-1
) 0.03
High boiling point solvent (Oil-1)
0.25
gelatin

1.0 5th
Layer: Intermediate layer (IL-2) Gelatin
0.8
6th layer; low-sensitivity green-sensitive emulsion layer (GL) EM-2

0.6 EM-4

0.2 Sensitizing dye (S-4)
6.7 x 10-4 (mol/1 mol of silver)
〃 (S-5)
0.8 x 10-4 (mol/1 mol of silver)
Magenta coupler (M-1)
0.17
〃 (M-2)
0.43
Colored magenta coupler (CM-1) 0.10
High boiling point solvent (Oil-2)
0.
70 Gelatin

1.0
7th layer; high-sensitivity green-sensitive emulsion layer (GH) EM-
1
0.9
Sensitizing dye (S-6)
1.1×10-4 (mol/1 mol of silver) (S-7)
2.0×10-4 (mol/silver 1
mole) 〃 (S-8)
0.3 x 10-4 (mol/silver 1 mol) Magenta coupler (M-1)
0.03
〃 (M-
2) 0
．． 13 Colored magenta coupler (CM-1)
0.04 High boiling point solvent (Oil
-2)
0.35 Gelatin

1.0
8th layer; yellow filter layer (YC)
yellow colloidal silver
0.1
Additive (HS-1)

0.07 (H
S-2)
0.07
〃 (SC-1)
0.12
High boiling point solvent (Oil-2)
0.1
5 Gelatin

1.0
9th layer; low-speed blue-sensitive emulsion layer (BL) EM-2

0.25
EM-4

0.25 Sensitizing dye (
S-9) 5.8
×10-4 (mol/1 mole of silver) Yellow coupler (
Y-1)
0.60 〃
(Y-2)
0.32
High boiling point solvent (Oil-2)
0.18
gelatin

1.3 10th layer; High sensitivity blue sensitive emulsion layer (B-H) EM-3

0.5
Sensitizing dye (S-10)
3.0×10-4 (mol/1 mole of silver)
〃 (S-11)
1.2×10-4 (mol/1 mol of silver) Yellow coupler (Y-1)
0.18
〃 (Y-2)
0.10 High boiling point solvent (Oil-2)
0.05 gelatin

1.0 11th layer; 1st protective layer (PRO
-1) Fine grain silver chloride (average grain size 0.06 μm)
0.3
Ultraviolet absorber (UV-1)
0.07
〃 (UV-2)
0.
1 Additive (HS-1
)
0.2
〃 (HS-2)
0.1
High boiling point solvent (Oil-1)
0.07
〃 (O
il-3)
0.07 Gelatin
0.8
12th layer; 2nd protective layer (PRO-2) Alkali-soluble matting agent (average particle size 2 μm)
0.13 Polymethyl methacrylate (average particle size 3 μm) 0.02 Gelatin

0.5 In addition to the above composition, each layer also contains coating aid SU-2 and dispersion aid SU-2.
1. Hardeners H-1 and H-2 and dyes AI-1 and AI-2 were added as appropriate.

[0190]

[C27]

[0191]

[C28]

[0192]

[C29]

[0193]

[C30]

[0194]

[Chemical formula 31]

[0195]

[C32]

[0196]

[Chemical formula 33]

Next, sample No. For 201, the third layer,
The emulsions shown in Table 6 were used instead of the emulsions used in the 4th, 6th, 7th, 9th, and 10th layers, and the couplers listed in Table 6 were used in place of the couplers in each photosensitive emulsion layer. Sample No. 1 was prepared by changing the ratio of the coupler and DSR compound instead of the coupler as shown in FIG. 201 to 204 were produced.

Next, exposure was carried out in the same manner as in Example 1 except that red light was used, and in Process A, the color development time was carried out according to the description in Table 7.

Next, as in Example 1 and Example 2, the γ value and γ
The fluctuation rate, RMS value (relative value), and molar ratio (%) used for color development in the maximum color density region were determined. The results obtained are shown in Table 7.

[0200]

[Table 6]

[0201]

[Table 7]

As is clear from the results in Table 7, the molar ratio utilized for color development of the photosensitive silver halide emulsion in the maximum color density region is 80 mol% or more, and γ is 0.2 to 1. It can be seen that within the range of .0, good graininess can be obtained and the processing stability is also excellent.

Example 5 Sample No. used in Example 4. 203, No. 204 was exposed using blue light and green light, and the same processing as in Example 4 was performed, and the RMS value and γ value were determined for the obtained blue density and green density in the same manner as in Example 4. , Similarly, the molar ratio (%) utilized for color development in each maximum color density region
), it was found that if the molar ratio was 80 mol% or more, the γ value,
Results similar to those of Example 4 were obtained in terms of both good graininess and processing stability.

Claims (1)

[Claims] 1. A transparent support having at least one red-sensitive, green-sensitive, and blue-sensitive silver halide emulsion layer, respectively;
The silver halide color photographic light-sensitive material in which the silver halide emulsion layer has an average silver chloride content of 5 mol % or more is subjected to color development treatment in the presence of a color developing agent after exposure. In a method for developing a silver halide color photographic light-sensitive material having a developed silver production rate of 80% or more, gamma R, gamma G, and gamma B of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer after color development are respectively A method for processing a silver halide color photographic material, characterized in that the silver halide color is in the range of 0.2 to 1.0.