JPH07117727B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

The present invention relates to a method for processing a silver halide color photographic light-sensitive material, more specifically, an improved development inhibitor releasing compound (hereinafter abbreviated as DIR compound). Of a silver halide color photographic light-sensitive material having improved sharpness and color reproducibility.

(Prior Art) With the spread of small-sized cameras (for example, 110 cameras) in recent years, the image quality expanded from a small-sized screen is
It is becoming more and more demanded that the image quality is the same as that of an image enlarged from a 35 mm size screen. In order to satisfy such requirements, it is necessary to develop a silver halide color photographic light-sensitive material having both graininess and sharpness so that the print image quality is not deteriorated even when the enlargement ratio is increased.

Conventionally, various methods for increasing the sharpness of an image are known, but it is widely known that a great effect can be obtained by increasing the edge effect and reducing light scattering in a photographic light-sensitive material. . Among these, the edge effect utilizes the concentration gradient of the development-inhibiting substance present during development. In this case, the development inhibitor is
For example, iodo ions, brom ions or oxidation products of developing agents that are released when silver halide is developed in a developing solution can be mentioned. Further, this edge effect uses the compounds described in U.S. Pat.Nos. 3,227,554, 3,615,506, 3,617,291 and 3,701,783, or the DIR compounds and DIR couplers described in JP-B-55-34933. It is also known that this can be increased by doing. Further, JP-A-62-166334 and JP-A-63-3734
Further improved DIR compounds and DIs described in No. 6
It is also known that the effect can be further enhanced by using an R coupler.

However, even when using the above DIR couplers and the like, a large amount of DIR couplers must be used when a strong edge effect is required, which inevitably greatly suppresses development. However, since there is no choice but to lower the maximum density and the sensitivity of the obtained image, the amount of DIR coupler used is naturally limited, and the edge effect of the above DIR couplers and the like must be acknowledged. There was a drawback. If the coating amount of silver is increased to solve such a drawback, not only will the product cost rise, but also the MTF curve in the high spatial frequency region will decrease due to increased light scattering by silver halide, Not only the DIR coupler added layer, but also the lower layer sharpness is deteriorated. (For the MTF curve, see “The Theor” by Mies.
y of Photographic Process ", 3rd Edition, published by Macmillan, Inc.).

Japanese Patent Laid-Open No. 59-131934 has developed a DIR compound capable of improving the above-mentioned drawbacks and keeping the maximum density of an image constant and particularly enhancing the edge effect. The present invention provides a light-sensitive material capable of increasing the sharpness at the time of development. However, the present invention contains a development-inhibitor-releasing compound capable of reacting with an oxidation product of a developing agent to release a development-inhibiting substance during color development. And a silver halide color photographic light-sensitive material.

Further, JP-A-61-173248 relates to the improvement of the above invention, and when a DIR coupler is used, the MTF value in the low frequency region generally increases, and as a result, the psychological sharpness increases. However, the image sharpness and the layering effect were still not sufficient, and further, the MTF value in the low frequency region was improved.

Further, in JP-A-62-166334, an improved DIR compound was provided to try to improve the sharpness and color reproducibility by controlling the dry film thickness of the emulsion layer.

Most recently, the improved DIR compounds described in JP-A-63-37346, JP-A-63-254453 and U.S. Pat.No. 4,782,012 have a sharper sharpness than the conventional DIR compounds. There is a statement that it will improve.

On the other hand, as a technique for improving graininess, it is possible to use a monodisperse silver halide emulsion, for example, JP-A-58-14829,
No. 58-28743, No. 58-100846, etc.
There are drawbacks such as a narrow exposure latitude and poor graininess in a high exposure amount region. Further, the color reproducibility was not good when only the monodisperse emulsion was used.

In order to improve these drawbacks, a combination of a monodisperse emulsion and a DIR compound which releases a diffusible development inhibitor is disclosed in JP-A-58-10.
No. 0847 proposed that the color reproducibility was improved to some extent and the sharpness was also improved. Further, a combination of a monodisperse emulsion having a high silver iodobromide content inside a silver halide grain and a DIR compound having a certain degree of development inhibition is used in combination with JP-A-60-2325.
No. 44 and JP-A-63-24237, the graininess and sharpness have been improved successively.

In order to improve sharpness, color reproducibility and graininess,
For example, U.S. Patent Nos. 3,227,554, 3,701,783, and
It is known to add a DIR compound via a timing group described in 3,703,375, 4,052,213, 4,138,258, 4,146,396 and 4,421,845 to a light-sensitive material. Furthermore, for the purpose of improving the photographic performance, JP-A-60-185950 and JP-A-57-56 are used.
The compounds described in 837 and the like have been proposed.
However, the improvement effect by only these compounds is still insufficient.

Also, from the demand of simplifying the processing method, there is a strong demand for a method that requires a small amount of replenishment of the processing solution in the development processing step by the replenishing method.

In the continuous development processing, the replenishing amount of the developing solution is somewhat different depending on the kind of the light-sensitive material to be processed, but in the case of silver halide color photographic light-sensitive material for photographing, it is usually 13 per 1 m ^2.
It is about 00 to 1100 ml.

From the viewpoints described above, the reduction of the replenishment amount is desired, but the reduction of the replenishment amount deteriorates the photographic characteristics, so that the reduction is generally very difficult.

On the other hand, in order to meet the demand for environmental protection, various color developing solution recycling methods have been tried in the color development processing step.

For example, Journal of Applied Photographic Engineering (J.Appl.Phot.Eng.), 5 , 208
(1979); Monthly Lab, 15 , 113 (1979); SMPTE Journal (SMPTE.J). 88 , 165 (1979); J.Appl.Phot.Eng.,
5 , 32 (1974); SMPTE.J., 88 , 168 (1979); JP-A-52-
No. 143018; No. 52-146236; No. 53-149331; No. 54-9629
No .; J.Appl.Phot.Eng., 5 , 216 (1979) and the like.

In addition, generally, when the replenishment amount is reduced, the eluate from the silver halide photographic light-sensitive material becomes relatively large (for example,
Halogen ions produced by decomposition of silver halide),
There is a problem of reduced sensitivity.

With respect to the problem of decreased sensitivity, attempts have been made to increase the processing temperature to prevent the sensitivity from decreasing and to reduce the amount of replenishment.

For example, Hunt's color paper treatment agent CP-LR
Treatment agent (Specifically, Photographic Bulletin No. 4 (Photographic Bulletin No. 4 issued by Hunt)
9) Page 6 of the Color Print Chemistries (Col
or Print Chemistries)], and the methods described in Proceedings of the Photographic Society of Japan, A-7 "Low Replenishment of Color Paper Processing" (1980) and the like. The former processing agent reduces the replenishment amount of the color developing solution to 1/2 to 2/3.

However, since these are processing agents for color paper, they cannot be immediately applied to color photographic light-sensitive materials for photography because of problems in photographic characteristics such as sensitivity, gradation and color reproduction.

In the processing of color negative film, the above-mentioned Hunt's processing agent (published by Hunt, described in Photographik Bretein No.55) has a low replenishment formula of 754 ml per 1 m ^2, but the processing is stable. In terms of sex, it is not enough.

This is a DI that is often used to improve the layering effect and sharpness, which is a problem peculiar to color photographic light-sensitive materials for photography.
It is speculated that this is because the development inhibitor that has come off after R (development inhibitor-releasing type) carapu is subjected to the coupling reaction and flows out and accumulates in the developer.

In particular, in the DIR compound described in JP-A-63-37346, by having a plurality of timing groups, it is possible to increase the diffusion distance of the withdrawal development inhibitor precursor, and enhance the interlayer effect and edge effect. When the low replenishment amount processing as described above is carried out, it has become clear that there is a big problem that the separation inhibitor accumulates in the developing solution and the photographic performance is changed.

JP-A-62-148951 discloses a combination of a DIR coupler having a group that undergoes decomposition in a developing solution and a low replenishment treatment in order to maintain stable photographic performance, and image quality such as graininess and sharpness. However, the DIR coupler described in JP-A-63-37346 needs to be further improved in terms of decomposition time.

Further, the use of DIR compounds described in JP-A-63-24237 and JP-A-63-254453 and U.S. Pat.No. 4,782,012 shows the above-mentioned image quality improving effect and photographic performance in a low replenishing amount processing of a color developing solution. There is no description and it cannot be guessed.

(Problems to be Solved by the Invention) Accordingly, the first object of the present invention is to stabilize a photosensitive material containing an improved DIR compound, even when color development processing is performed with a reduced replenisher amount of the color developing solution. Another object of the present invention is to provide a processing method which provides an image quality excellent in photographic performance, sharpness and color reproducibility. A second object of the present invention is to reduce the pollution of the treatment and provide an inexpensive treatment.

(Means for Solving the Problem) As a result of various studies, the present inventor was able to achieve the above object by the method described below.

That is, in a method in which a silver halide color photographic light-sensitive material having at least one light-sensitive core / shell type silver halide emulsion layer on a support is subjected to imagewise exposure and then a treatment including a color development step is carried out. Silver color photographic light-sensitive material
The silver halide emulsion layer or its adjacent layer contains at least one compound represented by the following general formula [I], and in the color developing step, replenishment of a color developing solution of 500 ml or less per 1 m ^{2 of the} light-sensitive material is carried out. This can be achieved by a method of processing a silver halide color photographic light-sensitive material, which comprises replenishing the solution and performing color development processing.

General formula (I) In the formula, A reacts with an oxidized product of a developing agent to produce — (L) _n —X—Y—
Represents a group capable of cleaving the group represented by COOR, L is after cleaving from A Represents a group capable of cleaving the group represented by, n represents 0 or 1, and X represents Represents a divalent linking group having 10 or less carbon atoms or a mere bond, and R represents an aliphatic group having 1 to 6 carbon atoms or a heterocyclic group. Here, Z ₁ represents a group of non-metal atoms required to form a heterocycle with carbon atoms and nitrogen atoms, Z ₂ represents a group of non-metal atoms required to form a heterocycle with nitrogen atoms, and * indicates A- (L) _n and ** mark represent the position to bond with Y-COOR.

Next, the compound represented by formula (I) will be described in detail.

In the general formula (I), A specifically represents a coupler residue or a redox group.

Examples of the coupler residue represented by A include a yellow coupler residue (for example, an open-chain ketomethylene type coupler residue such as acylacetanilide and malondianilide), a magenta coupler residue (for example, 5-pyrazolone type, pyrazolotriazole type or pyrazole group). Coupler residue such as zoleimidazole type), cyan coupler residue (eg phenol type, naphthol type or European Patent Publication No. 249,45)
No. 3 coupler group such as imidazole type) and a colorless coupler residue (for example, indanone type or acetophenone type coupler residue). Also, U.S. Patent Nos. 4,315,070, 4,183,752, 4,174,
969, 3,961,959, 4,171,223, JP-A-63-2612
It may be a heterocyclic coupler residue described in No. 62, No. 52-82423 or No. 51-104825.

When A represents a redox group, the redox group is a group that can be cross-oxidized by an oxidized product of a developing agent, and examples thereof include hydroquinones, catechols, pyrogallols, 1,4
-Naphthohydroquinones, 1,2-naphthohydroquinones, sulfonamide phenols, hydrazides or sulfonamide naphthols. Specific examples of these groups include, for example, JP-A Nos. 61-230135 and 62-251746.
No. 61-278,852, U.S. Pat.Nos. 3,364,022, 3,37
No. 9,529, No. 3,639,417, No. 4,684,604 or J.Org.C
hem., 29 , 588 (1964).

Examples of the group represented by L in the general formula (I) include the following.

(1) Group Utilizing Cleavage Reaction of Hemiacetal For example, a group described in US Pat. No. 4,146,396 and JP-A-60-249148 and 60-249149 and represented by the following general formula. Here, the * mark represents the position of bonding with A of the compound represented by the general formula [I], and the ** mark represents XY-COOR.
Represents the position to combine with.

General formula (T-1) In the formula, W is an oxygen atom, a sulfur atom or Represents a group, R ₁₁ and R ₁₂ represent a hydrogen atom or a substituent, R ₁₃ represents a substituent, and t represents 1 or 2. When t is 2, two Represents the same or different. R ₁₁ and R ₁₂
Is a substituent and typical examples of R ₁₃ are R ₁₅
Group, R ₁₅ CO- group, R ₁₅ SO ₂ - group, Is mentioned. Here, R ₁₅ represents an aliphatic group, an aromatic group or a heterocyclic group, and R ₁₆ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. The case where each of R ₁₁ , R ₁₂ and R ₁₃ represents a divalent group and is linked to form a cyclic structure is also included. Specific examples of the group represented by formula (T-1) include the following groups.

(2) Group that causes cleavage reaction utilizing intramolecular nucleophilic substitution reaction For example, a timing group described in US Pat. No. 4,248,962 can be mentioned. It can be represented by the following general formula.

General formula (T-2) * -Nu-Link-E-** In the formula, Nu represents a nucleophilic group, an oxygen atom or a sulfur atom is an example of a nucleophilic species, E represents an electrophilic group, Nu A group that can be more nucleophilically attacked to cleave the bond with **
nk represents a linking group that sterically links Nu and E so that they can undergo an intramolecular nucleophilic substitution reaction. General formula (T-
Specific examples of the group represented by 2) are as follows.

(3) A group that causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system.

For example, U.S. Pat. Nos. 4,409,323 and 4,421,845, JP-A-57
-188035, 58-98728, 58-209736, 58-20973
No. 7, No. 58-209738, etc., the following general formula (T-
It is a group represented by 3).

General formula (T-3) In the formula, *, **, W, R ₁₁ , R ₁₂ and t are (T-
It has the same meaning as described in 1). However,
R ₁₁ and R ₁₂ may bond to each other to form a benzene ring or a heterocyclic ring. Specific examples include the following groups.

(4) A group that utilizes a cleavage reaction due to hydrolysis of an ester.

For example, the following groups are the connecting groups described in West German Published Patent No. 2,626,315. In the formula, asterisks and asterisks have the same meanings as described for the general formula (T-1).

General formula (T-4) General formula (T-5) (5) A group that utilizes an imino ketal cleavage reaction.

For example, it is a linking group described in US Pat. No. 4,546,073 and is a group represented by the following general formula.

General formula (T-6) In the formula, *, **, and W have the same meanings as described in formula (T-1), and R ₁₄ has the same meaning as R ₁₃ . Specific examples of the group represented by formula (T-6) include the following groups.

When X in the general formula (I) represents a group represented by the following general formula (D-1), the general formula (D-1) Z ₁ is preferably, represents a non-metallic atomic group necessary for forming a thickness which may be a heterocyclic ring fused ring optionally substituted 5- to 7-membered ring together with -C = N-. Examples of such heterocycles include pyrazole, triazole, tetrazole, imidazole, pyrrole, oxazole, thiazole, oxadiazole, thiadiazole, benzimidazole, pyridine, pyrimidine or indazole. Particularly preferred among these are tetrazole, 1,3,4-thiadiazole, 1,3,4-oxadiazole and 1,2,4-triazole.

When X in the general formula (I) represents a group represented by the following general formula (D-2), the general formula (D-2) Z ₂ preferably represents a 5- to 7-membered optionally substituted heterocycle together with a nitrogen atom. Examples of such heterocycles include imidazole, 1,2,4-triazole, 1,2,3-
Triazole, pyrazole, pyrrole, imidazoline-
Examples include 2-thione, oxazoline-2-thione, 1,2,4-triazoline-3-thione, and 1,3,4-thiadiazoline-2-thione. Particularly preferred among these are 1,2,4-triazole, 1,2,3-triazole and pyrazole.

When the heterocycles represented by the general formulas (D-1) and (D-2) have a substituent at a substitutable position other than A- (L) _n and Y-COOR, examples thereof include an aliphatic group. (1 to 10 carbon atoms, eg methyl, ethyl), halogen atom (eg chloro, fluorine, bromine), heterocyclic group (1 carbon atom
To 5, a 3- to 6-membered ring selected from an oxygen atom, a sulfur atom or a nitrogen atom as a hetero atom, for example, a furyl group, a thienyl group, an imidazolyl group), a nitro group, a cyano group, an aromatic group (having 6 to 10 carbon atoms). Examples thereof include phenyl), an amino group, an alkylthio group (having 1 to 10 carbon atoms, such as methylthio and ethylthio), or an acylamino group (having 2 to 10 carbon atoms, such as acetamide and benzamide).

The divalent group represented by Y in the general formula (I) is preferably an ether bond, a thioether bond or -NHCO.
_{-, - SO 2 -, -} CO-, or -NHSO ₂ - represents a divalent linking group or a single bond of those aliphatic group or aromatic including a linking group containing a hetero atom such as indicated by. Particularly preferable Y here is an aliphatic group which may contain an ether bond or a thioether bond. For example methylene, ethylene, propylene, -SCH _2- , _{-CH 2 O-CH 2 -,} - SCH 2 CH 2 - or -CH ₂ SCH ₂ - group.

The group represented by R in formula (I) is preferably an aliphatic group having 1 to 6 carbon atoms, which may be substituted. Examples of the substituent include those listed above as the substituent that the heterocyclic group represented by (D-1) may have.

The compounds of the present invention are disclosed, for example, in JP-A Nos. 63-261262 and 63-25.
4453, US Pat. No. 4782012, or US Pat. No. 4,477,563.

(Compound example) The compound represented by the general formula [I] of the present invention is preferably added and used in the light-sensitive silver halide emulsion layer or its adjacent layer in the light-sensitive material, and the addition amount is from 1 × 10 ⁻⁶ to
1 × 10 ⁻³ mol / m ² , preferably 3 × 10 ^{−6 to} 5 × 10
^-4 mol / m ² , more preferably 1 × 10 ^-5 to 2 × 10 ^-4 mol /
m ² .

The photosensitive core / shell type silver halide emulsion in the present invention is a silver halide grain having substantially no fog nuclei inside the grain and is composed of two or more layers having different silver iodide contents. It is preferable that the layer having the highest content of silver iodide has a grain structure other than the outermost surface layer (shell portion). A grain in which the innermost layer (core portion) has the highest silver iodide content is more preferable.

The innermost layer (core portion) having the highest silver iodide content may have a silver iodide content of 6 to 45 (solid solution limit) mol%, preferably 10 to 45 mol%. It is more preferably 15 to 40 mol%. The silver iodide content of the shell portion is preferably less than 6 mol%, more preferably 4 mol% or less. The proportion of the shell portion of the core / shell type silver halide grains is preferably 10 to 80% by volume, more preferably 15 to 70%, and particularly preferably 20 to 60%.

The ratio of the core portion is preferably 10 to 80% of the total particles, and more preferably 20 to 50%.

In the present invention, the difference in content between the core portion having a high silver iodide content and the shell portion having a low content in the silver halide grains may have a sharp boundary, and the boundary is not necessarily clear and is continuous. It may change. Further, an intermediate layer having an intermediate silver iodide content between the core portion and the shell portion is preferably used between the core portion and the shell portion, and an intermediate layer and a shell portion having a lower silver iodide content portion than the core portion are preferably used. Even those having a grain structure in which the silver iodide content in the intermediate layer and the silver iodide content in the shell portion are slightly different but are high in the shell portion are also used.

In the case of core / shell type halogenated grains having the above-mentioned intermediate layer, the volume of the intermediate layer is 5 to 60% of the whole grains, and further,
20-55% is preferable.

The silver iodide content difference between the shell and the intermediate layer and the intermediate layer and the core is preferably 2 mol% or more, and the silver iodide content difference between the core and the shell is preferably 6 mol% or more.

In the present invention, the core / shell type silver halide emulsion is preferably composed of silver iodobromide, and the average silver iodide content is preferably 2 to 30 mol%, more preferably 4 to 20 mol%.
Is. Further, silver chloride may be contained within a range that does not impair the effects of the present invention.

The core / shell type silver halide emulsion of the present invention can be prepared by a known method disclosed in, for example, JP-A-59-177535, JP-A-60-138538 and JP-A-60-258536. When a core / shell type silver halide emulsion is grown starting from seed (nucleus) grains as in the method disclosed in JP-A-60-138538 and described in Examples, a halogen different from the core is formed in the center of the grain. It is possible to have a compositional domain.

In such a case, the halogen composition of the seed (nucleus) grains may be any composition such as silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide, silver chloride, etc. Silver content is 10
A mol% or less of silver iodobromide or silver bromide is preferable. Also,
The ratio of the seed (nucleus) emulsion to the total silver halide is% by volume.
30% or less is preferable, and 10% or less is particularly preferable.

The distribution state of silver iodide in the above core / shell type silver halide grains can be detected by various physical measurement methods. An example of applying the X-ray diffraction method to silver halide grains is the article by H. Hirschyu, Journal of Photographic Scienc.
e) It is described in pp. 129 et seq. of Volume 10 (1962).
When the lattice constant is determined by the halogen composition, a diffraction peak occurs at a diffraction angle satisfying the Bragg condition (2d sin θ = nλ).

The method for measuring X-ray diffraction is described in detail in Basic Analytical Chemistry Course 24, "X-ray Analysis" (Kyoritsu Shuppan), "Guide to X-ray Diffraction" (Rigaku Denki Co., Ltd.) and the like. The standard measurement method is to use Cu as a target, and use the Kβ ray of Cu as a radiation source (tube voltage 40 KV, tube current 60 mA) to obtain the diffraction curve of the (220) plane of silver halide. To increase the resolution of the measuring instrument, the width of slits (divergent slits, light receiving slits, etc.), the time constant of the device, the scanning speed of the goniometer,
It is necessary to properly select the recording speed and confirm the measurement accuracy using a standard sample such as silicon.

For example, when the emulsion grains have two distinct layered structures, a diffraction maximum due to silver halide in the high iodine layer and a diffraction maximum due to silver halide in the low iodine layer appear and two peaks appear in the diffraction curve.

A method of decomposing a diffraction curve composed of two diffraction components is well known, and is described in, for example, Experimental Physics Course 11 Lattice Defects (Kyoritsu Shuppan).

It is also useful to assume that the curve is a function such as a Gaussian function or Lorentz function, and to analyze it using a curve analyzer manufactured by Du Pont.

Even in the case of an emulsion in which two kinds of grains having different halogen compositions which do not have clear layered structures coexist, two peaks appear in the X-ray diffraction.

In order to determine whether the silver halide emulsion is an emulsion having a layered structure or an emulsion in which two kinds of silver halide grains as described above coexist, in addition to the X-ray diffraction method, the EPMA method (El
ectron-Probe Micro Analyzer method).

In this method, a sample in which emulsion grains are well dispersed so that they do not come into contact with each other is prepared, and an electron beam is irradiated. Elemental analysis of extremely small parts can be performed by X-ray analysis by electron beam excitation.

By this method, the halogen composition of each grain can be determined by obtaining the characteristic X-ray intensities of silver and iodine emitted from each grain.

If the halogen composition of at least 50 grains is confirmed by the EPMA method, it can be judged whether or not the emulsion has a layered structure.

The emulsion having a layered structure preferably has a more uniform iodine content between grains.

When the distribution of iodine content between particles was measured by the EPMA method, the relative standard deviation was 50% or less, further 35% or less, especially 20%.
% Or less is preferable.

The core / shell type silver halide emulsion used in the present invention may be either a polydisperse emulsion or a monodisperse emulsion, but a monodisperse emulsion is more preferable.

The monodisperse emulsion according to the present invention is an emulsion having a grain size distribution with a variation coefficient S / relating to the grain size of silver halide grains being 0.25 or less. Here, the average particle size and S are standard deviations related to the particle size. That is, the grain size of each emulsion grain is ri
And when the number is ni, the average particle size is And its standard deviation S is Is defined as

The term "individual grain size" as used in the present invention refers to a silver halide emulsion as described in "The Theory of the Photographic Process" by TH James et al.
e Theory of the Photographic Process) Third Edition 36 ~
With a projected area equivalent diameter equivalent to the projected area when micro-photographed by a method well known in the industry (usually electron microscope photography) as described in p. 43, published by Macmillan (1966) is there. Here, the projected equivalent diameter of a silver halide grain is defined by the diameter of a circle equal to the projected area of a silver halide grain as shown in the above-mentioned book. Therefore, even when the silver halide grains have a shape other than spherical (eg, cubic, octahedral, tetradecahedral, tabular, potato-like), the average grain size and its deviation S can be obtained as described above. is there.

The variation coefficient relating to the grain size of the silver halide grains is 0.25 or less, preferably 0.20 or less, more preferably 0.15 or less.

The size of the core / shell type silver halide grain of the present invention is not particularly limited, but is preferably 0.1 μm to 2.5 μm, more preferably 0.3 μm to 2 μm, and particularly preferably 0.4 μm to 1.5 μm.

The core / shell type silver halide grains of the present invention may have a regular crystal form (normal grain) such as a hexahedron, an octahedron, a dodecahedron, and a tetradecahedron. It may have an irregular crystal form such as a sphere, a sphere, a string, a plate, or the like. Moreover, although it may be a mixture thereof, it is preferably normal crystal grains.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is, in addition to the above-mentioned core / shell type monodisperse silver halide, containing about 30 mol% or less of silver iodide, iodobromide. It is silver, silver iodochloride, or silver iodochlorobromide. Particularly preferred is silver iodobromide containing from about 2 mol% to about 25 mol% silver iodide.

Silver halide grains in photographic emulsions have regular crystals such as cubes, octahedra and tetradecahedrons, grains having irregular crystal forms such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof.

The grain size of silver halide may be fine grains of about 0.2 μm or less, or large grains having a projected area diameter of up to about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD), No. 17643 (1978.
December), pp. 22-23, "I. Emulsion preparati
on and types) ”, and No. 18716 (November 1979),
648, Graphide, "Physics and Chemistry of Photography", published by Paul Montel (P.Glafkides, Chemic et Phisique Photogr
aphique Paul Montel, 1967), “Photoemulsion Chemistry” by Duffin, published by Forcal Press (GFDuffin, Photographi
c Emulsion Chemistry (Focal Press, 1966)), "Production and Coating of Photographic Emulsions" by Zelikmann et al., VLZelikman et al. Making and Coating Photog.
It can be prepared using the method described in raphic Emulsion, Focal Press, 1964).

Monodisperse emulsions described in US Pat. Nos. 3,574,628 and 3,655,394 and British Patent 1,413,748 are also preferable.

Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineerin.
g), Vol. 14, pp. 248-257 (1970); U.S. Pat. No. 4,43.
4,226, 4,414,310, 4,433,048, 4,439,520
It can be easily prepared by the method described in Japanese Patent No. 2,112,157 and the like.

The crystal structure may have a uniform halogen composition, but it is preferable that the crystal structure has a core / shell structure having different halogen compositions inside and outside, and may have a layered structure, or an epitaxial junction. Therefore, silver halides having different compositions may be bonded, or may be bonded to a compound other than silver halide such as silver rhodanide and lead oxide.

Also, a mixture of particles having various crystal forms may be used.

The silver halide emulsion is usually one which has been physically ripened, chemically ripened and spectrally sensitized. Additives used in such processes are Research Disclosure No.176.
43 and No. 18716, and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above-mentioned two Lederch Disc closures, and the relevant portions are shown in the following table.

Various color couplers can be used in the present invention, specific examples of which are described in the patents described in Research Disclosure (RD) No. 17643, VII-CG.

Yellow couplers include, for example, U.S. Pat.
No. 1, No. 4,022,620, No. 4,326,024, No. 4,401,7
Those described in No. 52, Japanese Examined Patent Publication No. 58-10739, British Patent Nos. 1,425,020, 1,476,760 and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. No. 4,310,61
9, No. 4,351,897, European Patent No. 73,636, U.S. Patent No. 3,061,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984), JP-A-60-33552.
Issue, Research Disclosure No. 24230 (6 June 1984)
JP-A-60-43659, U.S. Pat. Nos. 4,500,630 and 4,540,654 are particularly preferable.

Examples of cyan couplers include phenol type and naphthol type couplers, and U.S. Pat. No. 4,052,212;
4,146,396, 4,228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162,
No. 2,895,826, No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent 121,365A, U.S. Patent No. 3,4.
46,622, 4,333,999, 4,451,559, 4,
Those described in 427,767, EP 161,626A and the like are preferable.

Colored couplers for correcting unwanted absorption of color forming dyes are Research Disclosure No. 17643 VII-
Section G, U.S. Patent No. 4,163,670, Japanese Patent Publication No. 57-39413, U.S. Patent Nos. 4,004,929, 4,138,258, British Patent No. 1,
Those described in No. 146,368 are preferable.

As the coupler in which the color forming dye has an appropriate diffusibility, those described in U.S. Pat. No. 4,366,237, British Patent 2,125,570, European Patent 96,570 and West German Patent (Publication) 3,234,533 are preferable.

Typical examples of polymerized dye-forming couplers are U.S. Pat.Nos. 3,451,820, 4,080,211 and 4,367,282.
No. 2,102,173 and the like.

Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors have the general formula [I] described above.
In addition to the compounds represented by the above-mentioned, RD17643, the patents described in the paragraphs VII to F, JP-A-57-151944 and 57-154234.
No. 60-184248 and US Pat. No. 4,248,962 may be used in combination.

Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,13.
Those described in 1,188, JP-A-59-157638 and JP-A-59-170840 are preferable.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat.No. 4,130,427, multi-equivalent couplers described in U.S. Pat.Nos. 4,283,472, 4,338,393, and 4,310,618. , JP-A-60-18
5950, DIR redox compounds or DIR coupler-releasing couplers or DIR coupler-releasing couplers or redox described in JP-A-62-24252, couplers for releasing dyes that undergo color restoration after separation described in European Patent 173,302A, RDN
No. 11449, No. 24241, the bleaching accelerator releasing coupler described in JP-A-61-2201247 and the like, and the ligand releasing coupler described in US Pat. No. 4,553,477 and the like.

In the present invention, it is preferable to use the following compounds together with the above-mentioned coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler.

That is, the compound (F) that chemically bonds with the aromatic amine-based developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound and / or the fragrance remaining after the color development processing. The use of the compound (G), which forms a chemically inactive and substantially colorless compound by chemically bonding with an oxidant of a group amine color developing agent, simultaneously or solely, for example, in storage after processing. It is preferable in order to prevent stains and other side effects due to the formation of a coloring dye due to the reaction of the coupler with the color developing agent remaining in the film or its oxidant.

The compound (F) preferably has a second-order reaction rate constant k ₂ with p-anisidine (in trioctyl phosphate at 80 ° C.) of 1.0 l / mol · sec to 1 × 10 ₋₅ l / mol · sec. A compound that reacts within a range. The second-order reaction rate constant can be measured by the method described in JP-A-63-158545.

When k ₂ is larger than this range, the compound itself becomes unstable and may react with gelatin or water to decompose. On the other hand, if k ₂ is smaller than this range, the reaction with the remaining aromatic amine-based developing agent is slow, and as a result, the side effect of the remaining aromatic amine-based developing agent, which is the object of the present invention, may not be prevented. .

More preferable compound (F) can be represented by the following general formula (FI) or (FII).

General formula (FI) R ₁ − (A) _n −X General formula (FII) In the formula, R ₁ and R ₂ each represent an aliphatic group, an aromatic group, or a heterocyclic group. n represents 1 or 0. A represents a group which reacts with an aromatic amine type developing agent to form a chemical bond, and X represents a group which reacts with an aromatic amine type developing agent and leaves. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group or a sulfonyl group, and Y accelerates the addition of the aromatic amine developing agent to the compound of the general formula (FII). Represents the group Here, R ₁ and X, Y and R ₂ or B may be bonded to each other to form a cyclic structure.

Among the methods of chemically bonding with the residual aromatic amine-based developing agent, representative ones are substitution reaction and addition reaction.

Specific examples of the compounds represented by formulas (FI) and (FII) are described in JP-A-63-158545, JP-A-62-283338, and Japanese Patent Application No. 62-158338.
-158342 and Japanese Patent Application No. 63-18439 are preferred.

On the other hand, a more preferred compound (G) that chemically bonds with the oxidation product of the aromatic amine-based developing agent remaining after color development processing to form a chemically inactive and colorless compound is represented by the following general formula (GI ).

General formula (GI) RZ In formula, R represents an aliphatic group, an aromatic group, or a heterocyclic group. Z represents a nucleophilic group or a group that decomposes in the light-sensitive material to release a nucleophilic group. In the compound represented by the general formula (GI), Z is Pearson's nucleophilic ⁿ CH ₃ I value (RG Pearson, et
al., J. Am. Chem. Soc., 90 , 319 (1968)) is 5 or more, or a group derived therefrom is preferable.

Regarding specific examples of the compound represented by the general formula (GI), European Published Patent No. 255722, JP-A Nos. 62-143048 and 62-2291 are disclosed.
No. 45, Japanese Patent Application No. 63-18439, No. 63-136724, No. 62-214681
Nos. 62-158342 and the like are preferable.

Further, details of the combination with the compound (G) and the compound (F) are described in Japanese Patent Application No. 63-18439.

Compound (F) and / or compound (G) may be contained in any of the layers constituting the light-sensitive material. It is preferable to coexist in a layer containing a coupler. In particular, it is preferably used together with a pyrazoloazole coupler.

Compound (F) and / or compound (G) is coupler 1
1 × 10 ⁻² to 10 mol, preferably 2 × 10 ⁻² to ² per mol
It is a mole.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods.

Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027.

Specific examples of the high-boiling-point organic solvent having a boiling point of 175 ° C. or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis phthalate. (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), esters of phosphoric acid or phosphonic acid ( Trifuel phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di- Two
-Ethylhexylphenylphosphonate, etc.), Benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), Amides (N, N-diethyldodecaneamide, N, N-diethyllaurylamide) , N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-
Amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2) -Butoxy-5-tert
-Octylaniline, etc.), hydrocarbons (paraffin,
Dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C.
Above, preferably an organic solvent of 50 ℃ or more and about 160 ℃ or less can be used, as a typical example, ethyl acetate, butyl acetate,
Examples include ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like.

The steps of the latex dispersion method, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

The present invention can be applied to various color light-sensitive materials. In particular, it is preferably applied to a color negative film for general use or movies.

Suitable supports that can be used in the present invention include, for example, the aforementioned R
Page 28 of D.No.17643 and page 647 of the same No.18716 From right column 6
See page 48, left column.

The light-sensitive material of the present invention may have at least one silver halide emulsion layer of a blue color-sensitive layer, a green color-sensitive layer and a red color-sensitive layer provided on a support. There is no particular limitation on the number of layers of the emulsion layer and the non-photosensitive layer and the layer order. As a typical example, a silver halide photographic light-sensitive material having on a support at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. And the photosensitive layer is blue light, green light,
And a unit photosensitive layer having a color sensitivity to any of red light, and in a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layer is generally arranged in order from the support side.
The red color-sensitive layer, the green color-sensitive layer and the blue color-sensitive layer are arranged in this order. However, even if the above installation order is reversed depending on the purpose,
Alternatively, the installation order may be such that different color-sensitive layers are sandwiched between the same color-sensitive layers.

A non-photosensitive layer such as various intermediate layers may be provided between the silver halide photosensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A Nos. 61-43748, 59-113438 and 5
9-113440, No. 61-20037, No. 61-20038 may contain a coupler, a DIR compound, etc. as described in the specification, a mixing inhibitor and an ultraviolet absorber as commonly used May be included.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer,
As described in West German Patent No. 1,121,470 or British Patent No. 923,045, a two-layer structure of a high sensitivity emulsion layer and a low sensitivity emulsion layer can be preferably used. In general, it is preferable to arrange the layers so that the sensitivities are gradually decreased toward the support, and a non-photosensitive layer may be provided between the halogen emulsion layers. Further, JP-A-57-112751 and 62-2003.
No. 5, No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support. .

As a specific example, from the side farthest from the support, low-sensitivity blue photosensitive layer (BL) / high-sensitivity blue photosensitive layer (BH) / high-sensitivity green photosensitive layer (GH) / low-sensitivity green photosensitive layer (GL) / High-sensitivity red photosensitive layer (RH) / Low-sensitivity red photosensitive layer (RL), or BH / BL / GL
It can be installed in the order of / GH / RH / RL or BH / BL / GH / GL / RL / RH.

Further, as described in JP-B-55-34932, blue-sensitive layers / GH / RH / GL / RL can be arranged in this order from the fastest side of the support. In addition, JP-A-56-25738 and 62-6
As described in 3936, the blue-sensitive layer / GL / RL / GH / RH may be arranged in this order from the fastest side of the support.

Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is more sensitive than the middle layer. A silver halide emulsion layer with a low degree of sensitivities is arranged, and the sensitivities are gradually reduced toward the support.
An example is an array composed of layers. Even in the case of being composed of three layers having different sensitivities as described above, JP-A-59-20246
As described in No. 4, the medium-speed emulsion layer / high-speed emulsion layer / low-speed emulsion layer may be arranged in this order from the side distant from the support in the same color-sensitive layer.

As described above, various layer configurations and arrangements can be selected according to the purpose of each sensitive material.

Next, the processing of the present invention will be described in detail.

A color light-sensitive material for photographing, such as a color negative film, is usually replenished with about 1200 ml of color developing replenisher per 1 m ^{2 of} film during color developing. In fact, at such a replenishing amount, a problematic change in the processing performance is unlikely to occur even under a considerably small amount of processing and a condition in which the processing amount varies. However, when the replenishment amount is reduced to 700 ml or less, the above problem is significantly increased. Such changes in performance are caused by a gradation increase in fog density due to evaporative concentration of the developer and an increase in fog density, a gradation decrease due to oxidation of the color developing agent and a decrease in fog density, and a change in processing amount. Change in performance such as sensitivity, gradation, etc. due to the increase or decrease in fog density, increase or decrease in fog density, and accumulation of the development inhibitor released from the DIR compound in the developer due to increase or decrease in bromine ion concentration. Are involved in each other and have an extremely complicated appearance. However, no solution has been found for this problem.

The present inventors have surprisingly found that the above-mentioned problems are caused by using the DIR compound represented by the above-mentioned general formula [I] in a light-sensitive material with a core / shell type monodispersed silver halide. Significantly improved per 1 m ^{2 of} light-sensitive material
It has been found that stable processing results can be obtained in continuous color development processing with a replenisher amount of color developing solution of 700 ml or less.

The color developing agents used in the color developing solution and the color developing replenisher are aromatic primary amine compounds and include known compounds widely used in various color photographic processes. However, in the present invention, preferred color developing agents are (1) 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate (2) 4- (N-ethyl-N-β- Methanesulfonamidoethylamino) -2-methylaniline sulfate (3) 4- (N-ethyl-N-β-methoxyethylamino) -2-methylaniline-p-toluenesulfonate (4) 4- (N , N-Diethylamino) -2-methylaniline hydrochloride (5) 4- (N-ethyl-N-dodecylamino) -2
-Methylaniline sulfate (6) N, N-dialkyl-p-phenylenediamine type color developing agent such as N, N-diethyl-p-phenylenediamine hydrochloride. These compounds are contained in the color developer at 0.00
5-0.05 mol / l is added, but preferably 0.01-
The range is 0.04 mol / l, particularly preferably 0.015-0.03 mol / l. Further, in the color developing replenisher, it is preferable to add it so as to have a higher concentration than the above concentration. Specifically,
How high the concentration should be depends on the setting of the replenishing amount, but it is generally added in the range of 1.05-2.0 times, more than 1.2-1.8 times that of the color developing solution (mother solution).

The above color developing agents may be used alone or in combination according to the purpose. Preferred examples of the combined use include (1) and (2), (1) and (3), (2) and (3) of the above color developing agents.

In the present invention, the bromine ion concentration of the color developing solution is 0.005-
It is preferably in the range of 0.02 mol / l, but for this purpose, it is preferable to keep the bromide content of the replenisher at 0.005 mol / l or less. Generally, as the replenishing amount is reduced, the bromide content in the replenishing liquid should be set lower. Particularly, in the present invention, it is preferable that the replenishing liquid does not contain bromide in order to greatly reduce the replenishing amount. .

Examples of the bromide include potassium bromide, sodium bromide, lithium bromide, hydrobromic acid and the like.

Color developing solutions and color developing replenishers include hydroxylamine, diethylhydroxylamine, triethanolamine, compounds described in West German Patent (OLS) 2622950, compounds described in Japanese Patent Application No. 61-265149, and sulfurous acid. Preservatives such as salts and bisulfite are used.

Further, various chelating agents are added for the purpose of softening water and hiding the metal, but in the present invention, at least one compound represented by the following general formulas (A), (B) and (C) is particularly used. It is preferable to contain it.

General formula (A) General formula (B) General formula (C) In the formula, n represents 1 or 2, R represents a lower alkyl group, M may be the same or different, and represent a hydrogen atom, an alkali metal atom, or ammonium.

R is preferably a methyl group or an ethyl group, and M is preferably a hydrogen atom or a sodium atom. The above compounds have an effect of suppressing changes in gradation and fog density particularly in the low replenishment processing of color light-sensitive materials.

Therefore, the present invention provides a color developing solution and a color developing replenishing solution,
At least one of the compounds of the general formulas (A), (B) and (C)
By including the seed, it is more effectively carried out.

Particularly, it is more preferable to use one or more compounds represented by (A) and (B) or (A) and (C), respectively.

Specific examples of the compounds represented by formulas (A), (B) and (C) are shown below.

The compound of the general formula (A) is used as a color developer and its replenisher.
It is added in the range of 0.0005-0.02 mol / l, preferably 0.001
-0.01 mol / l is added. The compounds of the general formulas (B) and (C) are also 0.002-0.1 mol / l, preferably 0.005-0.1 mol / l.
It is added in the range of 0.05 mol / l.

When the compounds of the general formulas (A) and (B) or (A) and (C) are used in combination, the compound of (A) is 2 to 20 times the molar ratio of the compound of (B) or (C), The amount is preferably set to 3 to 15 times, more preferably 3 to 10 times.

Among the above specific examples, (A-1) and (B-1),
It is preferable to use (A-1) and (C-1) together.

In the color developer used in the present invention, in addition to the above compounds, a pH buffering agent such as an alkali metal carbonate, borate or phosphate; iodide, benzimidazoles, benzothiazoles, mercapto compounds Development inhibitors or antifoggants; organic solvents such as diethylene glycol; development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium, amines, thiocyanates; nucleating agents such as sodium borohydride; Auxiliary developing agents such as 1-phenyl-3-pyrazolidone; tackifiers; also general formulas (A), (B),
In addition to the compounds represented by (C), ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, Research Disclosure
Various chelating agents such as organic phosphonic acids described in 18170 (May 1979) can be used alone or in combination.

In the present invention, the pH value of the color developer and its replenisher are
It is usually 9 or more, preferably 9.5-12, particularly preferably
It is 9.5-11.0. In the above range, the replenisher for the color developer is preferably set to a value higher by about 0.05-0.3.

Further, the temperature in the color development processing is carried out at 30-45 ° C., but it is preferably higher temperature in order to achieve a broader range of low replenishing processing, and in the present invention, 35-45 ° C., particularly 38-45 ° C.
It is preferably carried out at 42 ° C.

The present invention can be carried out by either an automatic processor or a manual process, but it is preferably carried out by an automatic processor. In the processing of the automatic developing machine, the number of color developing solution tanks may be one or plural, but using a plurality of tanks and using a multi-stage forward replenishment system in which the tanks are replenished in the foremost tank and sequentially flowed into the succeeding tank, the replenishment is further reduced. be able to. Further, the contact area between the developer and the air in the tank is preferably as small as possible. Specifically, a floating lid, a seal with a liquid having a high boiling point and a smaller specific gravity than the developer, described in JP-A-63-131138 The use of a shielding means such as a tank structure having a narrowed opening has a further effect on the present invention.

Further, as a means for enhancing the effect of the present invention, it is preferable to supplement water according to the amount of evaporation in order to correct the evaporation and concentration of the developer. The water to be replenished is preferably deionized water that has been subjected to ion exchange treatment or deionized water that has been subjected to treatment such as reverse osmosis or distillation.

The color developing solution and the color developing replenishing solution are prepared by sequentially adding and dissolving the above-mentioned chemicals in a fixed amount of water, and the deionized water is preferably used as the preparation water.

In the present invention, the light-sensitive material after color development is processed with a bleaching solution or a bleach-fixing solution. As the bleaching agent used in these, a complex salt of ferric ion and a chelating agent such as aminopolycarboxylic acid, polycarboxylic acid, aminopolyphosphonic acid is generally used. Examples of preferable chelating agents used as complex salts with these ferric ions include (1) ethylenediaminetetraacetic acid (2) diethylenetriaminepentaacetic acid (3) cyclohexanedimianetetraacetic acid (4) 1,3-diaminopropanetetraacetic acid (5) Nitrilotriacetic acid (6) Iminodiacetic acid (7) Glycol ether diamine tetraacetic acid and the like can be mentioned, but the invention is not limited thereto.

The ferric ion complex salt may be used in the form of a complex salt.
Iron salts, such as ferric sulfate, ferric chloride, ferric sulfate, ferric ammonium sulfate, ferric phosphate, etc., and chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc. May be used to form a ferric ion complex salt in a solution. When used in the form of a complex salt, one type of complex salt may be used, or two or more types of complex salt may be used. On the other hand, when a complex salt is formed in a solution using a ferric salt and a chelating agent, one or more ferric salts may be used. Furthermore, one or more chelating agents may be used. Further, in any case, the chelating agent may be used in an amount more than that for forming the ferric ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complex is preferable, and the addition amount thereof is 0.1 to 1 mol / mol in the bleaching solution of the color photographic light-sensitive material for photographing such as color negative film.
l, preferably 0.2 to 0.4 mol / l, and in the bleach-fixing solution 0.05 to 0.5 mol / l, preferably 0.1 to 0.3.
Mol / l. Further, in a bleaching solution or a bleach-fixing solution for a color photographic light-sensitive material for printing such as color paper,
The amount is 0.03 to 0.3 mol / l, preferably 0.05 to 0.2 mol / l.

Further, a bleaching accelerator can be used in the bleaching solution or the bleach-fixing solution, if necessary. As a specific example of a useful bleaching accelerator, a compound having a mercapto group or a disulfide group is preferable from the viewpoint of a large accelerating effect, and particularly, U.S. Pat.No. 3,893,858, West German Patent 1,290,812, JP-A-53-9.
The compounds described in 5630 are preferred.

In addition, the bleaching solution or bleach-fixing solution of the present invention contains bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride) or iodide (eg, iodide). Ammonium) rehalogenating agents can be included. If necessary, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid,
Add one or more types of inorganic acids, organic acids and their alkali metal or ammonium salts having pH buffering ability such as phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc., or corrosion inhibitors such as ammonium nitrate, guanidine, etc. can do.

The above bleaching solution is usually used in a pH range of 4 to 7,
It is preferably 4.5 to 6.5, particularly preferably 5 to 6.3.
The pH of the bleach-fixing solution is 4 to 9, preferably 5 to 8, and particularly preferably 5.5 to 7.5. If the pH is higher than the above range, defective bleaching is likely to occur, and if the pH is low, defective coloring of the cyan dye is likely to occur.

The fixing agent used in the bleach-fixing solution of the present invention or the fixing solution used after treatment with the bleaching solution is a known fixing agent, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; sodium thiocyanate, ammonium thiocyanate. A thiocyanate salt such as; a thioether compound such as ethylenebisthioglycolic acid, 3,6-dithia-1,8-octanediol, and a water-soluble silver halide solubilizer such as thioureas; Two or more kinds can be mixed and used. In addition, JP-A-51-155354
It is also possible to use a special bleach-fixing solution containing a combination of the fixing agent described in JP-A No. 1994-0415 and a large amount of a halide such as potassium iodide. In the present invention, it is preferable to use thiosulfate, particularly ammonium thiosulfate.

The amount of the fixing agent per 1 is preferably 0.3 to 2 moles, particularly 0.8 to 1.5 moles in the processing of color photographic light-sensitive materials for photographing, and in the processing of color photographic light-sensitive materials for printing.
It is in the range of 0.5 to 1 mol.

The pH range of the fixing solution in the present invention is preferably 4 to 9, and particularly preferably 5 to 8. When it is lower than this range, the deterioration of the liquid is remarkable, and when the pH is higher than this range, ammonia is easily volatilized from the ammonium salt contained or stain is easily generated.

To adjust the pH, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, bicarbonate, ammonia, caustic potash, caustic soda, sodium carbonate, potassium carbonate and the like can be added as necessary.

The bleach-fixing solution and the fixing solution used in the present invention are sulfites (eg sodium sulfite, potassium sulfite,
Sulfite ion such as ammonium sulfite, etc.), bisulfite (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite), metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.) Contains a release compound. These compounds are converted to sulfite ion and the drug is 0.02-0.50 mol / l.
It is preferable to contain 0.04 to 0.40.
Mol / l.

As a preservative, it is common to add sulfite, but in addition, ascorbic acid, carbonyl bisulfite adduct,
Alternatively, a carbonyl compound or the like may be added.

Further, a buffering agent, a fluorescent whitening agent, a chelating agent, an antifungal agent, etc. may be added as required.

As described above, the light-sensitive material after color development is processed with a bleaching solution, a bleach-fixing solution, and a fixing solution. If the pH of these processing solutions after color development is 6 or more, the squeegee of the automatic developing machine to be used is If it is bad, yellow fog may occur, but the present invention has an advantage of alleviating such a problem.

That is, the present invention is preferably carried out when processing in a processing solution having a pH of 6 or more after color development.

After the fixing step or the bleach-fixing step, it is common to carry out a treatment step such as washing and stabilizing, and only a washing step is carried out, or conversely, only a stabilizing step is provided without providing a substantial washing step. A simple treatment method can also be used.

The water washing step removes processing liquid components adhering to or occluded in the color light-sensitive material, or unnecessary components in the color light-sensitive material, thereby improving the image storability and film physical properties after processing. Acts to hold.

On the other hand, the stabilizing step is a step of improving the storability of an image to a level that cannot be obtained by washing with water.

The washing process may be carried out in one tank, but in most cases it is 2
It is carried out by a multi-stage countercurrent washing method of more than a tank. The amount of water in the washing step can be arbitrarily set according to the type and purpose of the color light-sensitive material. For example, Journal of Motion Picture and Television Engineering 64: 248-253 (May 1955) Issue) "Water Flowrates in Immersion Worthing of the
Motion Picture Film “Water Flow Rates in Immersion-Washing of Motion Pi
cture Film, written by SR Goldwasser).

When reducing the amount of washing water, the generation of bacteria and mold becomes a problem, but as a countermeasure against this, it is preferable to use the washing water with reduced calcium and magnesium described in JP-A-62-288838. In addition, bactericides and antifungal agents,
For example, Journal of Antibacterial and Anfunningal Ages (J.Antibact.Antif
ug.Agents) vol. 11, No. 5, P207-223 (1983) and Hiroshi Horiguchi, "Compounds described in" Chemistry of Antibacterial and Antifungal Chemistry ") can be added. A chelating agent such as ethylenediaminetetraacetic acid or diethylenetriaminepentaacetic acid may be added as a water softener.

When saving the amount of washing water, the amount of water used is usually 100 ml to 2000 ml per 1 m ^{2 of the} color light-sensitive material, but particularly preferably 200 ml to 1000 ml in terms of achieving both color image stability and water saving effect. .

The pH in the washing step is usually in the range of 5-9. In addition, various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, various buffers for adjusting the membrane pH after treatment (for example, borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, Dicarboxylic acid, polycarboxylic acid and the like are used in combination), a chelating agent similar to that which can be added to washing water, a bactericidal agent, and a fluorescent whitening agent can be added depending on other uses, ammonium chloride, ammonium sulfite, Various ammonium salts such as ammonium sulfate and ammonium thiosulfate can be added.

The pH of the stabilizing bath is usually 3 to 8, but a low pH range of 3 to 5 may be particularly preferably used depending on the type of sensitive material and the purpose of use.

(Examples) Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited to these.

Example 1 Preparation of Emulsion Controlled by double-jet method, the average grain size was 0.4 μm and 0.6 μm in the presence of ammonia when the content of silver iodide was 12 mol%.
An octahedral emulsion having m and a coefficient of variation of 0.10 and 0.18 was prepared and designated as core emulsion a and b.

These core emulsions a and b were washed with water and desalted, then mixed in various proportions to form core particles, and pure silver bromide was shelled until the amount of silver in the core and that of the shell were equal. Was prepared. After desalting in the usual way, sodium thiosulfate,
Chloroauric acid was added and the mixture was aged at 60 ° C. for 70 minutes and chemically sensitized. Emulsion A prepared here had an average particle size of 0.77 μm and a coefficient of variation of 0.25; Emulsion B had an average particle size of 0.78 μm and a coefficient of variation of 0.17; Emulsion C had an average particle size of 0.77 μm and a coefficient of variation of 0.12.

Further, the same core grains as in Emulsion B were subjected to shelling containing silver iodide (2 mol%) in an amount such that the silver amounts in the core part and the shell part were equal, to prepare tetradecahedral grains. Since the silver iodide content of shell is high and the gradation is softened, emulsions having almost the same gradation as the emulsions A to C were prepared by adjusting the amount of chemical sensitizer and the chemical ripening time. This is Emulsion D. This emulsion D had an average grain size of 0.78 μm and a coefficient of variation of 0.17. These emulsions A to
Using D, a multilayer color photographic light-sensitive material shown below was prepared.

On a subbed cellulose triacetate film support,
Each layer having the composition shown below was coated in multiple layers to prepare Sample 01, which is a multilayer color light-sensitive material.

(Photosensitive layer composition) Numbers corresponding to each component are g / m Shows the amount applied in units
For silver halide, the coating amount in terms of silver is shown.
However, a sensitizing dye and a compound represented by the general formula [I] of the present invention
The compound is based on 1 mol of silver halide in the same layer
The coating amount is shown in mol.

(Sample 01) First layer (antihalation layer) Black colloidal silver 0.18 Gelatin 0.40 Second layer (intermediate layer) 2,5-di-t-pentadecylhydroquinone 0.18 EX-1 0.07 EX-3 0.02 EX-12 0.002 U-1 0.06 U-2 0.08 U-3 0.10 HBS-1 0.10 HBS-2 0.02 Gelatin 1.04 Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (6 mol% silver iodide, average grain size 0.80) μ) silver 0.
50 Sensitizing dye I 6.9 × 10 ^-5 Sensitizing dye II 1.8 × 10 ^-5 Sensitizing dye III 3.1 × 10 ^-4 EX-2 0.335 Compound of the present invention (11) 5.0 × 10 ^-3 HBS-1 0.060 Gelatin 0.87 4th layer (2nd red-sensitive emulsion layer) Silver iodobromide emulsion (5 mol% silver iodide, average grain size 0.85μ) Silver 1.
0 Sensitizing dye I 5.1 × 10 ⁻⁵ Sensitizing dye II 1.4 × 10 ⁻⁵ Sensitizing dye III 2.3 × 10 ⁻⁴ EX-2 0.400 EX-3 0.050 Compound (11) of the present invention 4.0 × 10 ⁻³ HBS− 1 0.060 Gelatin 1.30 Fifth layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 10 mol%, average grain size 1.5 μ) Silver 1.6
0 Sensitizing dye I 5.4 × 10 ^-5 Sensitizing dye II 1.4 × 10 ^-5 Sensitizing dye III 2.4 × 10 ^-4 EX-3 0.010 EX-4 0.080 EX-2 0.097 HBS-1 0.22 HBS-2 0.10 Gelatin 1.63 Sixth layer (intermediate layer) EX-5 0.040 HBS-1 0.020 Gelatin 0.80 Seventh layer (first green emulsion layer) Silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.77 μ) Silver 0.
30 Sensitizing dye V 3.0 × 10 ^-5 Sensitizing dye VI 1.0 × 10 ^-4 Sensitizing dye VII 3.8 × 10 ^-4 EX-6 0.260 EX-1 0.021 EX-7 0.030 EX-8 0.025 HBS-1 0.100 HBS- 3 0.010 Gelatin 0.63 Eighth layer (second green-sensitive emulsion layer) Silver iodobromide emulsion (6 mol% silver iodide, average grain size 0.77μ) Silver 0.
45 Sensitizing dye V 2.1 × 10 ^-5 Sensitizing dye VI 7.0 × 10 ^-5 Sensitizing dye VII 2.6 × 10 ^-4 EX-6 0.094 EX-8 0.018 EX-7 0.026 HBS-1 0.160 HBS-3 0.008 Gelatin 0.50 9th layer (3rd green emulsion layer) Silver iodobromide emulsion (10 mol% silver iodide, average grain size 1.5μ) Silver 1.2
Sensitizing dye V 3.5 × 10 ^-5 Sensitizing dye VI 8.0 × 10 ^-5 Sensitizing dye VII 3.0 × 10 ^-4 EX-13 0.015 EX-11 0.100 EX-1 0.025 HBS-1 0.25 HBS-2 0.10 Gelatin 1.54 10 layers (yellow filter layer) yellow colloidal silver 0.05 EX-5 0.08 HBS-1 0.03 gelatin 0.95 11th layer (first blue-sensitive emulsion layer) silver iodobromide emulsion (6 mol% silver iodide, average grain size 0.60) μ) silver 0.
22 Sensitizing dye VIII 3.5 × 10 ^-4 EX-9 0.721 EX-8 0.042 HBS-1 0.28 Gelatin 1.10 12th layer (2nd blue-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 10 mol%, average grain Diameter 1.0μ) Silver 0.4
5 Sensitizing dye VIII 2.1 × 10 ^-4 EX-9 0.154 HBS-1 0.05 Gelatin 0.78 13th layer (3rd blue-sensitive emulsion layer) Silver iodobromide emulsion (10 mol% silver iodide, average grain size 1.8μ) Silver 0.7
7 Sensitizing dye VIII 2.2 × 10 ^-4 EX-9 0.20 HBS-1 0.07 Gelatin 0.69 14th layer (1st protective layer) Silver iodobromide emulsion (1 mol% silver iodide, average grain size 0.07μ) Silver 0 .
5 U-4 0.11 U-5 0.17 HBS-1 0.05 Gelatin 1.00 15th layer (2nd protective layer) Polymethyl acrylate particles (diameter about 1.5 μm) 0.54 S-1 0.20 Gelatin 1.20 In addition to the above components in each layer , Gelatin hardening agent H-1 and a surfactant were added.

HBS-1 tricresyl phosphate HBS-2 di-n-butyl phthalate (Preparation of Samples 02 to 04) Next, the silver iodobromide emulsion A of the seventh and eighth layers of Sample 01 above
Samples 02 to 04 were prepared by replacing Emulsions B to D described above in the same amount with no change.

(Preparation of Samples 05 to 08) EX-8 used in the seventh and eighth layers of Samples 01 to 04 was replaced with the compound (2) represented by the general formula [I] of the present invention in an equimolar amount, Samples in the same way without changing others
05-08 were made.

(Preparation of Sample 09) Sample 09 was prepared in the same manner as in Sample 01, except that the emulsion used in the photosensitive layer of Sample 01 was changed as shown in Table 1 below and the others were not changed. At this time, the coated silver amount of each layer was exactly the same as that of Sample 01, and each was an iodobromide emulsion. However, in order to adjust sensitivity and gradation in the same manner, the chemical ripening time and the addition amount of the chemical sensitizer were changed, and the fine adjustment was performed by the addition amount of the sensitizing dye and the addition amount of the chemical sensitizer.

(Preparation of Sample 10) The silver iodobromide emulsions of the seventh layer and the eighth layer of Sample 09 have a spherical equivalent diameter of 0.
Sample 10 was prepared in the same manner as above, using an emulsion of plate-like grains in which silver iodide was uniformly distributed, prepared so as to have a variation coefficient of 0.17 at 75 μm.

(Preparation of Samples 11 and 12) The seventh and eighth layers of Samples 05 and 06 were replaced with the emulsions used for the seventh and eighth layers of Samples 09 and 10, and otherwise the sample 11 was prepared in the same manner. And 12 were produced.

(Preparation of Sample 13) Using the silver iodobromide emulsion B of the 7th and 8th layers of Sample 02,
The EX-8 used in the same 7th and 8th layers is disclosed in JP-A-60
No. 232544 was replaced with the compound (D-10) in an equimolar amount, and Sample 13 was prepared in exactly the same manner as Sample 02.

Compounds described in JP-A-60-232544 (D-10) (Preparation of Sample 14) Similar to Sample 13, EX-8 used in the seventh and eighth layers of Sample 02 was equimolar to the compound (95) described in JP-A-63-24237. Sample 14 was prepared in the same manner as sample 02 except for the amount replacement.

JP-A-63-24237 Compounds (95) The samples 01 to 14 produced as described above were cut into a width of 35 mm and used as the test sample in the following experiment.

First, these samples were subjected to wet exposure (color temperature of light source: 4800 ° K), and each was subjected to processing by an automatic processor in the steps described below.

In the above table, the replenishing amount is per 1 m ² of the light-sensitive material.

Next, the above-mentioned 35 mm-width-cut sample 01 is put in a camera, exposed to light, and then replenished with processing Nos. 1 to 4 shown in Table 2 so that the replenisher amount of the color developing solution becomes 5 l per day. However, the processing was continuously carried out by an automatic developing and developing machine until the cumulative amount of replenisher reached 20 l (twice the capacity of the color developing tank).

The composition of the treatment liquid used is described below.

(Washing liquid) Mother liquor and replenisher common Tap water mixed with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-400) Water was passed through a bed-type column to treat calcium and magnesium ions at a concentration of 3 mg / l or less, and then 20 mg / l sodium diisocyanurate dichloride and sodium sulfate were added.

The pH of this solution was in the range 6.5-7.5.

When the cumulative replenishing amount of the replenisher for the color developing solution reached 20 liters, the wafer was exposed to the same conditions as described above and processed. The resulting color image was subjected to density measurement to obtain respective characteristic curves.

The above experiment was carried out for each of the samples 02 to 14, and the characteristic curve was obtained in the same manner.

Sensitivity and gradation were examined as the photographic process variation between before and after the continuous process in Sample Nos. 1 to 4 of Samples 01 to 14.

The sensitivity is the exposure value (log that gives a density of (minimum density + 0.2) (log
The difference (ΔS) before and after the start of the continuous processing of E) was calculated.

For gradation, read the density of the exposure value obtained by adding 1.5 as the logarithm of the exposure value from the exposure value (logE) that gives the density of (minimum density +0.2), and from that value (minimum density +0.2) The value obtained by subtracting the value of was obtained before and after the continuous processing was started, and the difference (ΔG) was calculated.

Table 3 shows the results of variations in these photographic characteristic values due to continuous processing, which were obtained for a magenta color image.

From the results of Table 3 above, the sample 05 satisfying the constitutional requirements of the present invention
It is clear that when the replenishing amount of the color developing solution is processed with a low replenishing amount of Nos. To 08, the sensitivity and gradation are less changed than those of the other comparative samples, and stable processing can be performed. Even if the sample satisfies the constitutional requirements of the present invention, sample 06
As is clear from comparison between 08 and 08, in the case of core / shell emulsion, the halogen composition (ioto content) of the core and shell
It can also be seen that it is preferable that the iodine content in the shell part is small and the difference in iodine content from the core part is large.

Example 2 The following experiment was performed using Samples 01 to 14 prepared in Example 1.

The layering effect was examined as a measure of color reproducibility. For the measurement of the multilayer effect, see “The Theory of t” by TH James.
he Photographic Process "(4th Edition, Macmillan
Company) The procedure described below was performed by the method described in Chapter 18, EP 532 to 534.

First, each sample is exposed to a uniform blue light, and then B
The sample exposed by adjusting the exposure amount so that the density becomes 1.5 was further subjected to imagewise (wet) exposure with green light, and then the development processing shown below was performed to give a magenta color as shown in FIG. An image characteristic curve (1) and a yellow color image density curve (2) were obtained. Here, when the green photosensitive emulsion layer is developed from the unexposed area (point A) to the exposed area (point B), the density curve of the blue photosensitive emulsion layer uniformly exposed is G → B. 2 shows the degree of inhibition (ΔD _B ) that the blue photosensitive emulsion layer receives in response to the development of the green photosensitive emulsion layer of No. 1 of FIG.
That is, in FIG. 1, the curve 1 represents the characteristic curve of the magenta color image of the green light-sensitive emulsion layer, and the curve 2 represents the yellow image density of the blue light-sensitive emulsion layer by uniform exposure to blue light. Point A represents the minimum density (fog) part of the magenta image, and point B represents the exposure amount part that gives a magenta density of 2.0.

Same as yellow density (D _a = 1.5) at unexposed area A point B
Density difference of yellow density (D _b ) at the point (ΔD _B = D _a −
It was represented by D _b ) and used as a scale of color reproducibility.

The above method was carried out for Samples 01 to 14. The results are shown in Table 4.
Shown in.

Then, the MTF value was measured as a measure of sharpness. Measured by Mies, The Theory of Photographic Process, 3
rd Edition, Matsukumilan Co., Ltd. The measurement is described in Chapter 21, C4, P609-641 of the above-mentioned literature.
It was carried out according to the method described in.

The results are also shown in Table 4.

Processing method Until the cumulative replenishment amount of color developer reaches twice the tank capacity by using an automatic processor, separately FUJIFILM and Super HR
-100 exposed parts were processed before processing the samples of this experiment.

Next, the composition of the treatment liquid will be described.

(Washing liquid) Common for mother liquor and replenishing liquid Tap water mixed with H type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-400) Water was passed through the bed-type column to treat calcium and magnesium ions at a concentration of 3 mg / L or less, and then 20 mg / L of sodium isocyanurate dichloride and 1.5 g / L of sodium sulfate were added.
The pH of this solution was in the range 6.5-7.5.

From the results in Table 4, when the same emulsions were used and the same emulsions of Samples 05 to 08 using the compound represented by the general formula [I] of the present invention and Samples 01 to 04 of the comparative compound were compared, It is clear that the compound represented by the general formula [I] is excellent. Further, when comparing the sample 06 of the present invention with the samples 13 and 14 using the comparative compound, the sample 06 also using the compound represented by the general formula [I] of the present invention is superior in both ΔD _B and MTF values. It can be seen that excellent color reproducibility and sharpness are exhibited. Further, the use of the core / shell emulsion which is a constituent of the present invention is apparent from the comparison of Samples 05 and 06 with Samples 11 and 12 and Samples 01 and 02 with Samples 09 and 10.
The superiority of the shell type emulsion is also due to the fact that the compound represented by the general formula [I] and the core /
It is clear that the use of the shell type emulsion shows the greatest effect of improving the color reproducibility and sharpness.

Example 3 Using Samples 01 to 14 produced in Example 1, the same experiment as in Example 1 was carried out except that the treatment steps and treatment liquid compositions were changed as shown below.

In the above table, the replenishing amount is per 1 m ² of the light-sensitive material.

The composition of the treatment liquid used is described below.

(Bleaching solution) Common for mother liquor and replenisher (unit: g) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 120.
0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol Ammonia water (27%) 15.0 ml Water added 1.0 l pH 6.3 (bleach-fixing solution) Mother liquor and replenisher common (unit: g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 50.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 240.0 ml Ammonia water (27%) 6.0 ml Water is added to 1.0 l pH 7.2 (Washing liquid) Mother liquor and replenishing liquid Common tap water is H type strong acid cation exchange resin (Rohm and Haas Company) Made Amberlite IR-120B) and OH type anion exchange resin (Amberlite IR-400) are passed through a mixed bed type column to treat calcium and magnesium ions at a concentration of 3 mg / l or less. Sodium isocyanurate dichloride 20 mg / l and sodium sulphate 1.5 g / l were added.

The pH of this solution was in the range 6.5-7.5.

(Stabilizer) Mother liquor and replenisher common (unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1.0 l pH 5.0-8.0 Replenisher for color development is 1200, 700, 500 and 300 ml / sensitive material 1
The variation in photographic performance, sensitivity and gradation after continuous color development processing at m ² is exactly the same as the result obtained in Example 1, and variation in photographic performance of Samples 05 to 08 satisfying the constituent requirements of the invention. Was confirmed to be small and exhibit excellent performance.

Example 4 On a subbed cellulose triacetate film support,
Sample 21, which is a multi-layer color light-sensitive material having the following composition, was prepared.

(Composition of photosensitive layer) The coating amount of silver halide and colloidal silver is silver.
The amount represented in units of g / m ^2, also couplers, moles per 1 mol of silver halide in the same layer for the amount for the additives and gelatin represented in units of g / m ^2, also the sensitizing dye Indicated by. The symbols indicating additives have the following meanings. However, when there are multiple utilities, one of them is listed as a representative.

UV: UV absorber, Solv: High boiling organic solvent, ExF: Dye, Ex
S: Sensitizing dye, ExC: Cyan coupler, ExM: Magenta coupler, ExY: Yellow coupler, Cpd: Additive first layer (antihalation layer) Black colloidal silver 0.15 Gelatin 2.9 UV-1 0.03 UV-2 0.06 UV-3 0.07 Solv-2 0.08 ExF-1 0.01 ExF-2 0.01 Second layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent spherical diameter 0.4)
[mu] m, spherical coefficient of variation of 37% equivalent diameter, the plate-like particles, diameter / thickness ratio 3.0) coating silver amount 0.4 Gelatin ^{0.8 ExS-1 2.3 × 10 -4} ExS-2 1.4 × 10 -4 ExS-5 2.3 × 10 - ⁴ ExS-7 8.0 × 10 ^-6 ExC-1 0.17 ExC-2 0.03 ExC-3 0.13 Third layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio 2: 1 inside) High
AgI type, sphere equivalent diameter 0.65 μm, variation coefficient of sphere equivalent diameter 20%,
Plate-like grains, diameter / thickness ratio 2.0) Coating silver amount 0.65 Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent spherical diameter 0.4)
[mu] m, spherical coefficient of variation of 37% equivalent diameter, the plate-like particles, diameter / thickness ratio 3.0) coating silver amount 0.1 Gelatin ^{1.0 ExS-1 2 × 10 -4} ExS-2 1.2 × 10 -4 ExS-5 2 × 10 - ⁴ ExS-7 7 × 10 ^-6 ExC-1 0.31 ExC-2 0.01 ExC-3 0.06 4th layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio 2: 1 inside) High
AgI type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 20%, plate-like particles, diameter / thickness ratio 2.5) Coating silver amount 0.9 Gelatin 0.8 ExS-1 1.6 × 10 ^-4 ExS-2 1.6 × 10 ^-4 ExS-5 1.6 × 10 ^-4 ExS-7 6 × 10 ^-4 ExC-1 0.07 ExC-4 0.05 Solv-1 0.07 Solv-2 0.20 Cpd-7 4.6 × 10 ^-4 Fifth layer (intermediate layer) Gelatin 0.6 UV -4 0.03 UV-5 0.04 Cpd-1 0.1 Polyethyl acrylate latex 0.08 Solv-1 0.05 6th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent spherical diameter 0.4)
[mu] m, spherical coefficient of variation of 37% equivalent diameter, the plate-like particles, diameter / thickness ratio 2.0) coating silver amount 0.18 Gelatin ^{0.4 ExS-3 2 × 10 -4} ExS-4 7 × 10 -4 ExS-5 1 × 10 - ⁴ ExM-5 0.11 ExM-7 0.03 ExY-8 0.01 Solv-1 0.09 Solv-4 0.01 7th layer (medium speed green emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, surface with core-shell ratio of 1: 1) High
AgI type, equivalent sphere diameter 0.5 μm, coefficient of variation of equivalent sphere diameter 20%, plate-shaped particles, diameter / thickness ratio 4.0) Coating silver amount 0.27 Gelatin 0.6 ExS-3 2 × 10 ^-4 ExS-4 7 × 10 ^-4 ExS-5 1 × 10 ^-4 ExM-5 0.17 ExM-7 0.04 ExY-8 0.02 Solv-1 0.14 Solv-4 0.02 Eighth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 8.7 mol%, Multi-layered grains having a silver content ratio of 3: 4: 2, AgI content from the inside of 24 mol, 0 mol, 3 mol%,
Equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter / thickness ratio 1.6) Coating silver amount 0.7 Gelatin 0.8 ExS-4 5.2 × 10 ^-4 ExS-5 1 × 10 ^-4 ExS-8 0.3 × 10 ^-4 ExM-5 0.1 ExM-6 0.03 ExY-8 0.02 ExC-1 0.02 ExC-4 0.01 Solv-1 0.25 Solv-2 0.06 Solv-4 0.01 Cpd-7 1 × 10 ^-4 9th layer (intermediate Layer) Gelatin 0.6 Cpd-1 0.04 Polyethyl acrylate latex 0.12 Solv-1 0.02 10th layer (donor layer of multi-layer effect for red-sensitive layer) Silver iodobromide emulsion (AgI 6 mol%, core-shell ratio of 2: 1)
AgI type, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 20%, plate-like grain, diameter / thickness ratio 2.0) Coating silver amount 0.68 Silver iodobromide emulsion (AgI 4 mol%, uniform AgI type, equivalent sphere diameter) 0.4
μm, variation coefficient of equivalent sphere diameter 37%, plate-like particles, diameter / thickness ratio 3.0) Coating silver amount 0.19 Gelatin 1.0 ExS-3 6 × 10 ^-4 ExM-10 0.19 Solv-1 0.20 11th layer (yellow filter layer) ) Yellow colloidal silver 0.06 Gelatin 0.8 Cpd-2 0.13 Solv-1 0.13 Cpd-1 0.07 Cpd-6 0.002 H-1 0.13 12th layer (low sensitivity blue emulsion layer) Silver iodobromide emulsion (AgI 4.5 mol%, uniform) AgI type, sphere equivalent diameter 0.
7 μm, coefficient of variation of equivalent sphere diameter 15%, plate-like grain, diameter / thickness ratio 7.0) Coating silver amount 0.3 Silver iodobromide emulsion (AgI 3 mol%, uniform AgI type, equivalent sphere diameter 0.3)
μm, variation coefficient of spherical equivalent diameter 30%, plate-like particles, diameter / thickness ratio 7.0) Coating silver amount 0.15 Gelatin 1.8 ExS-6 9 × 10 ^-4 ExC-1 0.06 ExC-4 0.03 ExY-9 0.14 ExY-11 0.89 Solv-1 0.42 13th layer (intermediate layer) Gelatin 0.7 ExY-12 0.20 Solv-1 0.34 14th layer (high-sensitivity blue emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, sphere) Equivalent diameter
1.0 μm, coefficient of variation of equivalent sphere diameter 20%, multiple twinned plate-like particles, diameter / thickness ratio 2.0) Coating silver amount 0.5 Gelatin 0.5 ExS-6 1 × 10 ^-4 ExY-9 0.01 ExY-11 0.20 ExC-1 0.02 Solv-1 0.10 Fifteenth layer (first protective layer) Fine grain silver iodobromide emulsion (AgI 2 mol%, uniform AgI type, sphere equivalent diameter 0.07 μm) Silver coating amount 0.12 Gelatin 0.9 UV-4 0.11 UV-5 0.16 Solv-5 0.02 H-1 0.13 Cpd-5 0.10 Polyethyl acrylate latex 0.09 16th layer (2nd protective layer) Fine grain silver iodobromide emulsion (AgI 2 mol%, uniform AgI type, equivalent spherical diameter 0.07 μm) Coated silver Amount 0.36 Gelatin 0.55 Polymethylmethacrylate particles (diameter 1.5 μm) 0.2 H-1 0.17 In addition to the above components in each layer, emulsion stabilizer Cpd-3
(0.07 g / m ² ) and the surfactant Cpd-4 (0.03 g / m ² ) were added as coating aids.

Solv-1 Tricresyl Phosphate Solv-2 Dibutyl Phthalate Solv-5 Trihexyl Phosphate Following sample 21, the following sample was prepared.

(Preparation of Samples 22 to 24) ExC-2 in the second and third layers of Sample 21 is equimolar to the compounds (9), (11) and (23) represented by the general formula [I] of the present invention, respectively. A sample was prepared in the same manner as in Sample 21, except that the amount was replaced.

(Preparation of Samples 25 to 28) The ExY-8 of the sixth layer, the seventh layer and the eighth layer of Sample 21 were replaced by the compounds (6), (15), which are represented by the general formula [I] of the present invention,
Samples were prepared in the same manner as in Sample 21, except that (16) and (19) were replaced with equimolar amounts.

(Preparation of Samples 29 to 32) ExY-9 of the twelfth layer and the fourteenth layer of Sample 21 was replaced with the compounds (2), (3), (7) and (18) represented by the general formula [I] of the present invention. Samples were prepared in the same manner as in Sample 21, except that the same molar amount was substituted for each.

(Preparation of Samples 33 and 34) In Sample 21, the compound (9) represented by the general formula [I] of the present invention was used in the second and third layers, and the same compound (6) was used in the sixth, seventh and eighth layers. Samples 33 were prepared by substituting (2) with equimolar amounts in the 12th and 14th layers, and subsequently, the compound (11) represented by the general formula [I] of the present invention was added to the 6th and 6th layers, Sample 34 was prepared by substituting (5) for the 7th and 8th layers and substituting (3) for the 12th and 14th layers in the same manner.

The samples 21 to 34 produced as described above were cut into a width of 35 mm and used as test samples in the following experiment.

These samples were exposed under the exposure conditions shown in Example 1, and processed in the same manner with the same processing steps and processing solution compositions as in Example 1, and a color development processing was performed in which the amount of replenisher for color development was changed. The variation of photographic characteristics in continuous processing was investigated with respect to sensitivity and gradation.

Variation in sensitivity and gradation in each continuous processing, ΔS and ΔG
Is the same as the method described in Example 1, except that
Compare and compare the cyan color image of sample 21 for 22-24, 33 and 34, the magenta image of sample 21 for samples 25-28, 33 and 34 and the yellow image of sample 21 for samples 29-34. It was used as a sample. The results are shown in Table 6.

From the results shown in Table 6, when the compound represented by the general formula [I] of the present invention was used, any of the samples was subjected to continuous treatment of Treatment 3 to Treatment 4 in which the replenisher amount for color development was reduced. However, the processing stability was excellent, and it was clear that there was little variation in photographic performance, sensitivity and gradation.

Example 5 The samples 21 to 34 prepared in Example 4 were used to carry out the color reproducibility evaluation described in Example 2.

That is, for samples 21 to 24, 33, and 34, first, uniform green light exposure is applied to each sample, the exposure amount is adjusted so that the G concentration is 1.5, and then red light is applied. After imagewise exposure, the development process shown below was carried out to obtain a characteristic curve and a density curve according to the figure, and from these data, the degree of suppression of R → G received by the green photosensitive emulsion layer (ΔD _G ) Was asked.

Next, for Samples 21, 25 to 28 and 34, a uniform exposure of red light and an imagewise exposure of green light were applied, and the degree of suppression of G → R received by the red photosensitive emulsion layer (ΔD _R ).
I asked.

Further, for Samples 21 and 29 to 32, uniform exposure of green light was performed, and imagewise exposure of blue light was further applied to obtain the degree of suppression (ΔD _G ) of B → G received by the green photosensitive emulsion layer. The reproducibility was evaluated. The results are shown in Tables 7-9.

Processing method Separately, using an automatic processor, the cumulative replenishment amount of the color developing solution becomes twice the tank capacity. FUJIFILM and Super HR-1
A sample of this experiment was processed after processing 00 exposed.

Next, the composition of the treatment liquid will be described.

(Bleach-fixing solution) Common for mother liquor and replenisher (Unit: g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 90.0 Ethylenediaminetetraacetic acid disodium salt 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 260.0 ml Acetic acid (98%) 5.0 ml Bleaching accelerator 0.01 mol 1.0L pH 6.0 (washing solution) with water added Common for mother liquor and replenisher Tap water is H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite). Water is passed through a mixed bed column packed with IR-400) to treat calcium and magnesium ions at a concentration of 3 mg / L or less, and then 20 mg / L of sodium diisocyanurate dichloride and 0.15 g / L of sodium sulfate are added. did.

The pH of this solution is in the range 6.5-7.5.

(Stabilizer) Mother liquor and replenisher common (unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Add water 1.0 L pH 5.0-8.0 Further, as a measure of the sharpness, the MTF value was determined in the same manner as in Example 2. The results are shown in Tables 7-9.

From the results of Tables 7 to 9 described above, the use of the compound represented by the general formula [I] of the present invention shows an excellent improving effect on color reproducibility and sharpness, and further improves image quality. It is clearly a sensitive material.

Furthermore, with respect to color reproducibility, ΔD _{B from} G to B was also examined, but as in Tables 7 to 9, the use of the compound represented by the general formula [I] of the present invention (Samples 29 to 34) was Comparative Sample 21. It was confirmed that it was clearly improved compared to.

Example 6 Using Samples 21 to 34 produced in Example 4, the storage stability of the photosensitive material over time was evaluated under the conditions described below.

(1) 45 ° C., 80% RH, 3 days (2) 50 ° C., no humidity adjustment, 3 days (3) 5 ° C. (refrigerated storage) The exposure described in Example 1 was applied, and the treatment described in Example 5 was applied. A color image was obtained by performing processing with a color developing solution that was accumulated and replenished in an amount twice the tank capacity for color developing depending on the process and composition of the processing solution. These densities were measured to determine their photographic characteristic values, sensitivity and gradation. These characteristic values were determined according to the method described in Example 1. The evaluation was based on (3) and the difference was calculated. The results are shown in Tables 10-12.

The results in Tables 10 to 12 above show that the use of the compound represented by the general formula [I] of the present invention is stable in the raw storage stability of the light-sensitive material,
It is clear that it exhibits excellent performance with little variation.

Next, samples 21 to 34 were also used, and the following experiments were conducted to evaluate the storage stability of latent images after exposure of these samples.

To examine the latent image storage stability, the above samples were exposed under the conditions described in Example 1 and stored under the following conditions.

(1) 40 ° C, 70% RH, 7 days (2) 50 ° C, (no humidity adjustment), 7 days (3) 0 ° C, 7 days Perform the samples (1) to (3) stored under the above conditions Processing was carried out using the color development which was continuously processed in the same manner as the raw storability of the above-mentioned photosensitive material with the processing step and processing solution composition described in Example 5. The density of the obtained color image was measured, and the sensitivity was determined as its photographic characteristic value. The sensitivity was evaluated according to Example 1, and the latent image storage stability was evaluated based on (3), and the difference (ΔS) was determined. The results are shown in Tables 13-15.

The results of the latent image storage stability shown in Tables 13 to 15 show that Samples 22 to 34 using the general formula [I] of the present invention are similar to the comparative Sample 21 in the latent image storage property of the photosensitive material. It is clear that the compound also exhibits excellent performance in storage stability.

[Brief description of drawings]

FIG. 1 shows a characteristic curve. Curve (1) represents the characteristic curve of the magenta image of the green light sensitive layer, curve (2) represents the yellow image density of the blue light sensitive emulsion layer upon uniform exposure to blue light and line (3).
Represents the theoretical straight line of curve (2). Point A represents the minimum density (fog) part of the magenta image, and point B represents the exposure amount part that gives a magenta density of 2.0.

Claims (1)

[Claims] 1. A photosensitive core comprising at least one layer on a support.
In a method of imagewise exposing a silver halide color photographic light-sensitive material having a shell type silver halide emulsion layer, and then performing a process including a color developing step, the silver halide color photographic light-sensitive material is a silver halide emulsion layer or In its adjacent layers,
It contains at least one compound represented by the following general formula [I], and the color development step is carried out at 500 m / m ^{2 of the} light-sensitive material.
A method of processing a silver halide color photographic light-sensitive material, which comprises replenishing a color developer replenishing solution of the following or less and performing color development processing. General formula [I] In the formula, A reacts with an oxidized product of a developing agent to produce — (L) _n —X—Y—
Represents a group capable of cleaving the group represented by COOR, L is after cleaving from A Represents a group capable of cleaving the group represented by, n represents 0 or 1, and X represents Represents a divalent linking group having 10 or less carbon atoms or a mere bond, and R represents an aliphatic group having 1 to 6 carbon atoms or a heterocyclic group. Here, Z ₁ represents a group of non-metal atoms required to form a heterocycle with carbon atoms and nitrogen atoms, Z ₂ represents a group of non-metal atoms required to form a heterocycle with nitrogen atoms, and * indicates A- (L) _n and ** mark represent the position to bond with Y-COOR.