JPH09197635A - Photographic material for halogenated silver color photograph - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the photosensitive material, which has high saturation and the excellent color reproducibility and the excellent graduation reproducibility and of which deterioration with a lapse of time at the time of leaving it after the photographing is balanced so as to realize the stabilized finish, by including the specified compound in photograph structural layers. SOLUTION: A compound selected from a formula is included in one layer of the photograph structural layers. In the formula, Ra1 means alkyl group, alkenyl group and aryl group, and Ra2 means hydrogen atom or a group expressed with Ra1 , Ra1 and Ra2 can be connected to each other so as to form a ring formed of 5-7 members, but a S-triazine ring is never formed by them. Maximum values γRP, γGP, γBP of the degree of gradation of monochrome exposure at a wavelength, which gives the peak sensitivty of each halogenated silver emulsion layer, satisfy 0.80<γRP<1.4, 0.80<γGP<1.6, 0.65<γBP<1.3, and degree of gradation γR, γG, γB of exposure by a standard white color light source satisfy 0.35<γRP<0.65, 0.35<γGP<0.65, 0.35<γBP<0.65.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a color photographic light-sensitive material. More particularly, it relates to a silver halide color photographic light-sensitive material having high saturation, excellent color reproducibility and gradation reproducibility, and having improved storability of unused light-sensitive materials and latent image storability after storage.

[0002]

2. Description of the Related Art Conventionally, it has been known to utilize an interlayer suppression effect as a means for improving color reproducibility in a color photographic light-sensitive material. In the case of a color negative photosensitive material, by giving a development suppressing effect from the green-sensitive layer to the red-sensitive layer, the color development of the red-sensitive layer in white exposure can be suppressed more than that in the case of red exposure. Since the color negative paper system is balanced in gradation so that it is reproduced on a color print as gray when exposed with white light, the above-mentioned layering effect is higher in red exposure than in gray exposure. As a result, it is possible to reproduce red with higher saturation with suppressed cyan color on a print. Similarly, the effect of suppressing development from the red-sensitive layer to the green-sensitive layer gives green reproduction with a high degree of saturation.

As a method for enhancing the interlayer effect, a method is known in which iodide ions released from the silver halide emulsion during development are used. That is, this is a method in which the silver iodide content of the layer giving the multilayer effect is increased and the silver iodide content of the receiving layer is reduced. Another method for enhancing the interlayer effect is disclosed in Japanese Patent Laid-Open No.
As disclosed in JP-A-2537, a coupler which reacts with an oxidation product of a developing agent in a para-phenylenediamine color developing solution to release a development inhibitor is added to the interlayer effect imparting layer. Another method to increase the inter-layer effect is called auto masking, which is effective for colorless couplers.
This is a method in which a colored coupler is added to mask unnecessary absorption of a coloring dye of a colorless coupler. In the method using a colored coupler, masking can be provided more than masking unnecessary absorption of a colorless coupler by increasing the amount of addition, and an effect similar to the multilayer effect can be obtained.

Further, Japanese Patent Application Laid-Open No. 01-182847 describes a technique for delicately reproducing skin color, in particular, continuity of highlight and shadow hues of human face, and accurate depiction of skin color of white, black and yellow races. Has been. However,
When a light-sensitive material excellent in color reproducibility and gradation reproducibility is produced by using the above technique, a new problem has occurred. In particular, it has been found that when the inter-layer suppressing effect is increased, the latent image storability of the light-sensitive material, that is, the photographic property when left to stand after development after photographing is significantly increased.

The change in photographic property due to storage of a latent image is caused by a change in development progress (ease of development) due to rearrangement of fine silver nuclei in silver halide grains due to the action of oxygen and heat during photography. It has become clear from recent research. In particular, in the light-sensitive material with increased interlayer suppression related to the present invention, the gradation is designed substantially in the shallow area of silver development, and the effect of the change in susceptibility to development as described above is reflected more sensitively. It is presumed that this is because it will happen.

Further, in a light-sensitive material with increased inter-layer suppression, when one layer changes due to latent image storage, the other layer changes in reverse. This amplifies the change in the gradation balance of B, G and R, which has a fatal adverse effect on the color reproducibility. The use of hydroxylamine derivatives in photographic light-sensitive layers is described, for example, in U.S. Pat. Nos. 4,339,515 and 4,330,606. However, all of these improve the storability of color images produced by the coupling reaction between the coupler and the oxidized form of the developing agent, and the photographic materials can be stored in various environments for a long period of time between the production of the photosensitive material and the development and development. It did not solve the problem of being placed.

Further, in order to improve the storage stability of the light-sensitive material, compounds having an S-triazine ring are known.
For example, JP-A-59-162546 discloses that the storage stability of a latent image is improved by using it in combination with a compound having an active vinyl group, and JP-A-59-97134 discloses a tabular silver halide grain. It is disclosed that the fog is reduced when used in combination with the emulsion consisting of. However, even with the above-mentioned technique using the S-triazine (1,3,5-triazine) ring, the storability of the light-sensitive material with time, particularly the photographic property (especially the sensitivity) when stored under high temperature and high humidity, varies greatly, and the shooting It was not possible to solve the problem that the latent image regressed when the photosensitive material was stored later.

[0008]

DISCLOSURE OF THE INVENTION The present invention has a high saturation, is excellent in color reproducibility and gradation reproducibility, and is capable of achieving a well-balanced improvement in deterioration over time when left after photographing to realize a stable finish. An object is to provide a silver halide color photographic light-sensitive material that can be used.

[0009]

The above object can be achieved by the following. That is, the present invention is (1) a color photographic material having at least one red-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer, and at least one blue-sensitive silver halide emulsion layer on a support. General formula (AI), (AI)
I) or (A-III), and the maximum gradation value γ _R ^p , γ _G in monochromatic exposure of a wavelength which gives a peak sensitivity of each silver halide emulsion layer.
^p and γ _B ^p are 0.80 <γ _R ^p <1.4 0.80 <γ _G ^p <1.6 0.65 <γ _B ^p <1.3, and the gradation degree in standard white light source exposure γ _R , γ
_A silver halide color photograph characterized in that _G and γ _B are 0.35 <γ _R ^p <0.65 0.35 <γ _G ^p <0.65 0.35 <γ _B ^p <0.75 Photosensitive material.

[0010]

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In the general formula (AI), R _a1 is an alkyl group, an alkenyl group, an aryl group, an acyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryl group. It represents an oxycarbonyl group, and R _a2 represents a hydrogen atom or a group represented by R _a1 . However, when R _a1 is an alkyl group, an alkenyl group or an aryl group, R _a2 is an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group,
A carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. R _a1
And R _a2 may combine with each other to form a 5- to 7-membered ring, provided that they do not form an S-triazine ring.

In the general formula (A-II), X represents a heterocyclic group excluding the S-triazine ring, and R _b1 represents an alkyl group, an alkenyl group or an aryl group. X and R _b1
May combine with each other to form a 5- to 7-membered ring, provided that they do not form an S-triazine ring. In the general formula (A-III), Y represents a nonmetallic atom group necessary for forming a 5-membered ring together with -N = C-. Y represents a group of non-metal atoms necessary for forming a 6-membered ring together with -N = C- group, and the terminal of Y bonded to the carbon atom of -N = C- group is -N (R _c1 ). -, -C (R _c2 ) (R
_c3 )-, -C ( _Rc4 ) =, a group selected from -O- and -S- (bonded to the carbon atom of -N = C- on the left side of each group). However, it does not form an S-triazine ring. R _{c1 to} R _c4 each represent a hydrogen atom or a substituent. (2) Magnitude of stacking effect defined in the text IE (X /
Y) is 0.15 <IE (R / G) <0.50 0.15 <IE (G / R) <0.50 0.15 <IE (G / B) <0.50 0 <IE (R The silver halide color photographic light-sensitive material according to claim 1, wherein /B)/IE(G/B)<1.0.

IE (X / Y) represents the magnitude of the stacking effect from Y to X. This effect is most preferable in the structure of JP-A-61-34541, that is, a structure having a donor layer having a multilayer effect, but it has been confirmed that the same effect can be obtained even in a normal layer structure. γ _R ^P , γ _G ^P , γ _B
The more preferable range of ^P is as follows.

0.90 <γ _R ^P <1.3 0.90 <γ _G ^P <1.5 0.65 <γ _B ^P <1.2 Further preferred ranges of γ _R , γ _G and γ _B are It is as follows. 0.4 <γ _R <0.65 0.4 <γ _G <0.65 0.4 <γ _B <0.75 In a silver halide color negative film, it is necessary to have a wide exposure latitude. Since it is not preferable that the color reproducibility changes depending on the type, it is desirable that the spectral sensitivity distributions of the same color-developing layer match. Due to the absorption of the diffusion-resistant dye, the colored coupler, etc., the spectral sensitivity distribution may slightly differ. Therefore, there is a case where the gradation changes depending on the wavelength. There are also cases where the spectral sensitivity distribution is intentionally changed. For example, if the high-sensitivity emulsion layer of the red-sensitive layer is set to have a longer wavelength than the spectral sensitivity distribution of the low-sensitivity emulsion layer, the whole red-sensitive layer has a soft gradation on the long-wave side and a hard gradation on the short-wave side. In this case, if the layer that greatly contributes to the color density is a low-sensitivity layer, the gradation at the peak wavelength of the low-sensitivity emulsion greatly contributes to color reproducibility.

The wavelength giving the peak sensitivity is defined as follows. The wavelength giving the peak sensitivity of the red-sensitive silver halide emulsion layer has a sensitivity in the range of 550 nm to 700 nm, and is coupled with an oxidized product of a developing agent,
The maximum wavelength of the spectral sensitivity distribution given by the reciprocal of the exposure dose that gives a (constant Kaburi density) of a silver halide emulsion layer containing a color coupler that develops cyan is fog +0.4, 0.6, 0. The arithmetic mean is shown instead of 8 and 1.0.

Similarly, the wavelength giving the peak sensitivity of the green-sensitive silver halide emulsion layer has a sensitivity in the range of 480 nm to 620 nm, and is coupled with an oxidized product of a developing agent,
The maximum wavelength of the spectral sensitivity distribution given by the reciprocal of the exposure amount that gives (fog + constant density) of a silver halide emulsion layer containing a color coupler that develops magenta, the density is fog + 0.4, 0.6, It represents the average obtained by changing it to 0.8 and 1.0.

Similarly, the wavelength giving the peak sensitivity of the blue-sensitive silver halide emulsion layer has a sensitivity in the range of 400 nm to 520 nm, and is coupled with an oxidized product of a developing agent,
Fog of a silver halide emulsion layer containing a color coupler that develops yellow + the wavelength at which the maximum spectral sensitivity distribution given by the reciprocal of the sensitization amount gives a density of fog-0.4, 0.6, 0. The average is obtained by changing the values to 8 and 1.0.

An example of the wavelength obtained by the above method is shown in FIG. The gradient at the wavelength giving the peak sensitivity in the present invention is obtained as follows. The test photosensitive material was subjected to wedge exposure using a metal deposition interference filter (MIF-W type manufactured by Nippon Vacuum Optical Co., Ltd.) having a peak wavelength obtained by the above-described method, and after specified development processing, it was performed as shown in FIG. The densities were measured through red, green, and blue filters having the absorption characteristics shown, and the horizontal axis represents the logarithm of the exposure amount and the vertical axis represents the density.
The values giving the densities of 6, 0.8 and 1.0 were plotted, these points were approximated by a straight line by the method of least squares, and tan θ was γ _R ^P of this sensitive material with respect to the angle θ from the horizontal axis. γ _G ^P , γ _B
^P.

Similarly, the gradation of a standard white light source is obtained as follows. First, if the standard white light source is a delight type sensitive material, the
The test light-sensitive material was subjected to wedge exposure with a light source having an energy distribution of 500 ° K, and after specified development processing, the densities were measured through red, green, and blue filters having absorption characteristics shown in FIG. On the graph in which the horizontal axis is the logarithm of and the vertical axis is the density, fog +0.4, 0.6, 0.
The values giving the densities of 8 and 1.0 are plotted, these points are approximated by a straight line by the method of least squares, and tan θ is γ _R , γ _G , γ _B of this sensitive material with respect to the angle θ from the horizontal axis. And

The silver halide color photographic material of the present invention comprises
In the case of a color negative film, any commercially available color paper for printing can be used. The preferred gradation of color paper is about 2.7 ± 0.1 in colorimetric density. (For the color measurement density, see page 387, "Basics of Photographic Engineering", Silver Salt Photography, edited by the Photographic Society of Japan).

If the average gradient of the color paper is multiplied by α for some reason in the future, the gradient in the present invention may be set as follows. That is, the gradation degree in monochromatic exposure of the wavelength giving each peak sensitivity is 0.80 / α <γ _R ^P <1.4 / α 0.80 / α <γ _G ^P <1.6 / α 0.65 / α <Γ _B ^P <1.3 / α, the gradation in standard white light source exposure is 0.35 / α <γ _R <0.65 / α 0.35 / α <γ _G <0.65 / α 0. 35 / α <γ _B <0.75 / α.

Further, as a preferable range of γ _R ^P , γ _G ^P and γ _B ^P , 0.90 / α <γ _R ^P <1.3 / α 0.90 / α <γ _G ^P <1.5 / Α 0.65 / α <γ _B ^P <1.2 / α γ _R , γ _G , γ _B is preferably 0.4 / α <γ _R <0.65 / α 0.4 / α <Γ _G <0.65 / α 0.4 / α <γ _B <0.75 / α.

The present invention provides a red,
It has succeeded in enhancing the color reproduction and tone reproduction by setting a certain limit on the gradation of green and blue sensitive silver halide emulsion layers and the gradation for white light.
It is essentially different from the technique disclosed in JP-A-160449, in which the spectral sensitivity and the magnitude of the layering effect are regulated to obtain an effect on color reproduction.

That is, even if any combination of the spectral sensitivity and the layering effect is adopted, the gradations of the red, green and blue sensitive silver halide emulsion layers for the specific spectrum light of the present invention and those for white light do not satisfy the limitation. In some cases, good results cannot be obtained. This will be apparent in the examples. The present invention relates to a light-sensitive material having a high gradation when not receiving an interlayer suppression effect from another layer and a low gradation when receiving the interlayer suppression effect. Preferably, it is excellent. Therefore, it is preferable to use double-structure particles or multi-structure particles having high quantum sensitivity. For the same reason, it is preferable to use tabular grains having a high color sensitization rate.

It is preferable to use an emulsion having the same amount of coated silver and a high gradation, for reasons of cost, improvement of desilvering speed in processing, and improvement of image sharpness due to reduction of optical scattering.
Therefore, the silver halide grains used in the present invention preferably contain silver iodide in an amount of 15 mol% or less on average,
It is preferably 10 mol% or less, more preferably 8 mol% or less.

When silver halide containing 8 mol% or more of silver iodide is used in any of the layers of the present invention, for the same reason,
The silver iodide content on the surface is 6 mol% or less, more preferably 4 mol% or less.
Mol% or less. Next, means for controlling the multilayer effect used in the present invention will be described. In general, the so-called multilayer effect means that when the same layer is irradiated with the same amount of light, the other color-sensitive layer is suppressed or masked when it is developed. In the present specification, this is focused on the contrary to the positive multilayer effect because the development of the layer which is focused when the other color-sensitive layer is developed is promoted or the color turbidity of the color development of the other layer is caused. The case where the color density of a layer seems to increase is called a negative layering effect.

In order to give a positive multilayer effect, a masking technique using a colored coupler as described in US Pat.
And a method using a DIR compound having a large multi-layer effect as described in JP-A-54-145135. A method of incorporating a DIR compound in the non-photosensitive layer as described in JP-A-64-143745.

A method for successfully selecting the properties of a DIR compound, as described in JP-A-62-54255. As described in JP-A-58-100847, there is a method in which the emulsion is monodispersed to reduce the adsorption of the inhibitor by the fine grain emulsion. Further, in the green-sensitive silver halide emulsion layer, Japanese Patent Laid-Open No.
When the pyrazolotriazole magenta coupler described in 1-022324 is used, there is no secondary absorption of yellow, and therefore, the effect of superimposing on the substantially blue sensitive layer can be increased. When the 5-amide naphthol type cyan coupler described in JP-A-61-153460 is used for the red-sensitive layer, the sub-absorption of magenta is small, so that the effect of superimposing on the green-sensitive layer can be increased.

In the present invention, the means for increasing the gradation degree γ ^p at the wavelength giving the peak sensitivity will be specifically described, but the present invention is not limited to this method. The simplest method is to increase the coating amount of silver halide or coupler. In addition, there are methods for improving the developability of silver halide, such as reducing the silver iodide content, which greatly suppresses development, or including silver chloride, which has a high development speed. Similarly, there is a method of reducing the coating amount of the development inhibitor releasing compound (DIR compound).

The above method increases not only γ ^p but also γ by white light exposure. Therefore, means for suppressing the value of γ in the present invention is required. The method is listed below. 1. Reduce the amount of couplers that have absorption at the same wavelength as the color of the emulsion layer to be suppressed. 2. Strengthen auto masking with colored couplers.

3. The inter-layer development suppressing effect is increased. The diffusive DIR compound used in the present invention is effective even if it is contained in only one of the blue-sensitive layer, the green-sensitive layer and the blue-sensitive layer, but it is contained in two or more layers to obtain better color reproduction. It is preferable. In addition, if a leaving group is released due to a substantial coupling reaction with an oxidized color developing agent diffused from another layer during color development, it does not contain silver halide by itself or exhibit color sensitivity. You may make it contain in the layer which does not have.

It is also possible that a certain color-sensitive layer is divided into two or more layers, one or more layers of which contain the diffusible DIR compound and the other layers do not contain. At this time, the sensitivities of the plurality of layers may be different from each other, such as a so-called high-sensitivity layer and a low-sensitivity layer, and the color sensitivities may not be completely the same. Further, in order to arbitrarily change the degree of the interlayer suppression effect, the iodine content of the emulsion may be appropriately changed, or a method of adding a colored coupler to mask unnecessary absorption of the color forming dye may be used. Alternatively, a method may be used in which a coloring dye is intentionally mixed to increase color turbidity and cancel the interlayer suppression effect.

Next, the general formula (A-
The compounds represented by I) to (A-III) will be described in more detail. In these formulas, the alkyl group is a linear, branched, or cyclic alkyl group, which may have a substituent. The magnitude IE (X / Y) of the stacking effect is determined by the following method.

A metallized interference filter having a peak sensitivity of color sensitivity Y (Nissha Optical Co., Ltd., M
FIG. 1 shows a characteristic curve obtained by performing a wedge exposure using an IF-W type) and performing the development processing described in the examples. Color sensitivity Y
IE (X / Y) is the decrease in the density of the color sensitivity X that decreases from the sensitivity point (logarithm of the exposure amount that gives the density of fog + 0.2) to high exposure by 1.0 log E.

In the general formula (AI), R _a1 is an alkyl group (preferably an alkyl group having 1 to 36 carbon atoms such as methyl, ethyl, i-propyl, cyclopropyl, butyl, isobutyl, cyclohexyl, t-octyl). , Decyl, dodecyl, hexadecyl, benzyl), an alkenyl group (preferably an alkenyl group having 2 to 36 carbon atoms such as allyl, 2-butenyl, isopropenyl, oleyl, vinyl), an aryl group (preferably having 6 to 40 carbon atoms).
Is an aryl group such as phenyl and naphthyl, an acyl group (preferably an acyl group having 2 to 36 carbon atoms such as acetyl, benzoyl, pivaloyl, α- (2,4-di-te).
rt-amylphenoxy) butyryl, (3-cyclohexen-1-yl) -carbonyl, myristoyl, stearoyl, naphthoyl, m-pentadecylbenzoyl,
(5-norbornen-2-yl) carbonyl, isonicotinoyl), an alkyl or arylsulfonyl group (preferably an alkyl or arylsulfonyl group having 1 to 36 carbon atoms, such as methanesulfonyl, octanesulfonyl,
Benzenesulfonyl, toluenesulfonyl), alkyl or arylsulfinyl group (preferably having 1 to 4 carbon atoms).
An alkyl or arylsulfinyl group of 0 such as methanesulfinyl and benzenesulfinyl), a carbamoyl group (including an N-substituted carbamoyl group, preferably a carbamoyl group having 1 to 40 carbon atoms such as N-ethylcarbamoyl, N-phenylcarbamoyl, N, N-dimethylcarbamoyl, N-butyl-N-phenylcarbamoyl), a sulfamoyl group (including an N-substituted sulfamoyl group, preferably a sulfamoyl group having 1 to 40 carbon atoms such as N-methylsulfamoyl, N, N-diethylsulfamoyl, N-phenylsulfamoyl, N-cyclohexyl-N-phenylsulfamoyl, N-ethyl-N-dodecylsulfamoyl), alkoxycarbonyl group (preferably alkoxy having 2 to 36 carbon atoms) For example, a carbonyl group Alkoxycarbonyl, cyclohexyloxycarbonyl, benzyloxycarbonyl, isoamyl oxycarbonyl, hexadecyl oxycarbonyl)
Alternatively, it represents an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 40 carbon atoms, such as phenoxycarbonyl or naphthoxycarbonyl).
R _a2 represents a hydrogen atom or the group represented by R _a1 above.

In the general formula (A-II), the heterocyclic group of X is a 5- to 7-membered S-triazine ring (1 having a nitrogen atom, a sulfur atom, an oxygen atom or a phosphorus atom as a ring-constituting atom). , 3,5-triazine ring), and the bonding position of the hetero ring (position of monovalent group) is preferably a carbon atom, for example 1,2,4-triazine-3-. Yl, pyridin-2-yl, pyrazinyl, pyrimidinyl, purinyl, quinolyl,
Imidazolyl, 1,2,4-triazol-3-yl,
Represents benzimidazol-2-yl, thienyl, furyl, imidazolidinyl, pyrrolinyl, tetrahydrofuryl, morpholinyl, phosphinolin-2-yl. R
_a1 is an alkyl group for R _a1 in the general formula (AI),
It has the same meaning as an alkenyl group or an aryl group.

In the general formula (A-III), Y is -N
A non-metal atomic group necessary for forming a 5-membered ring with ═C— (for example, the ring group formed is imidazolyl, benzimidazolyl, 1,3-thiazol-2-yl, 2-imidazolin-2-yl, purinyl). 3H-indole-2-
Il). Y is a group of non-metal atoms necessary for forming a 6-membered ring together with -N = C- group, and-
The end of Y bonded to the carbon atom of the N = C- group is -N.
(R _c1 )-, -C (R _c2 ) (R _c3 )-, -C (R _c4 ).
Represents a group selected from =, -O-, and -S- (bonded to the carbon atom of -N = C- on the left side of each group). However,
It does not form an S-triazine (1,3,5-triazine) ring. R _{c1 to} R _c4 may be the same or different,
Represents a hydrogen atom or a substituent (eg, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylamino group, an arylamino group, and a halogen atom). Here, the alkyl group, the alkenyl group, and the aryl group are represented by the general formula (A-
It has the same meaning as the alkyl group, alkenyl group or aryl group in R _a1 of I), and the alkoxy group, the alkylthio group, the alkyl group of the alkylamino group, and the aryl group of the aryloxy group, the arylthio group and the arylamino group are also general. It has the same meaning as described for R _a1 in formula (AI). The halogen atom represents, for example, chlorine, bromine or fluorine atom.

Examples of the 6-membered ring group formed by Y include quinolyl, isoquinolyl, phthalazinyl, quinoxalinyl and 6H-1,2,5-thiadiazin-6-yl. In formula (AI) or (A-II), R _a1 and R _a2 , and X and R _b1 may be bonded to each other to form a 5- to 7-membered ring, for example, a succinimide ring, a phthalimide ring, a triazole ring. , Urazole ring, hydantoin ring and 2-oxo-4-oxazolidinone ring. However, the S-triazine ring is excluded.

Each group of the compounds represented by formulas (A-I) to (A-III) may be further substituted with a substituent. Examples of the substituents are an alkyl group, an alkenyl group, an aryl group, Heterocyclic group, hydroxy group, alkoxy group, aryloxy group, alkylthio group, arylthio group, amino group, acylamino group, sulfonamide group, alkylamino group, arylamino group, carbamoyl group, sulfamoyl group, sulfo group, carboxyl group,
Examples thereof include a halogen atom, a cyano group, a nitro group, a sulfonyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group and a hydroxyamino group.

In the general formula (AI), R _a2 is a hydrogen atom, an alkyl group, an alkenyl group or an aryl group, and R _a1 is an acyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group or a carbamoyl group. , Sulfamoyl group, alkoxycarbonyl group,
It is preferably an aryloxycarbonyl group, more preferably R _a2 is an alkyl group or an alkenyl group, and R _a1 is an acyl group, an alkyl or arylsulfonyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, or aryloxy. A compound that is a carbonyl group. Most preferably, R _a2 is an alkyl group and R _a1 is an acyl group.

In the general formula (A-II), R _a1 is preferably an alkyl group or an alkenyl group, more preferably an alkyl group. On the other hand, the general formula (A-II) is preferably represented by the following general formula (A-II-1).

[0042]

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[0043] In formula (A-II-1), R b1 represents R _b1 in formula (A-II), X ₁ is -C = N-
Represents a non-metal atomic group necessary for forming a 5- to 6-membered ring together. Among the compounds represented by formula (A-II-1), it is more preferable that X ₁ forms a 5- or 6-membered heteroaromatic ring. However, it does not form an S-triazine ring.

Of the compounds represented by the general formula (A-III), it is preferable that Y is a group of non-metal atoms necessary for forming a 5-membered ring, which is bonded to the carbon atom of the -N = C- group. It is more preferable that the terminal atom of Y is a nitrogen atom. However, it does not form an S-triazine ring. Y
Most preferably forms an imidazoline ring. This imidazoline ring may be condensed with a benzene ring.

Among the compounds represented by the general formulas (AI) to (A-III), the general formulas (AI) and (A-II) are shown.
Those represented by are preferred, and those represented by general formula (AI) are more preferred. Specific examples of the compounds represented by formulas (AI) to (A-III) of the present invention are shown below, but the present invention is not limited thereto.

[0046]

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[0047]

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[0048]

[Chemical 6]

[0049]

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[0050]

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These compounds and the above-mentioned general formula (AI)
Correspondence with ~ (A-III) is as follows. General formula (AI): A-1 to A-9, A-11 to A-1
8, A-33 to A-55. General formula (A-II): A-10, A-20, A-30.

General formula (A-III): A-19, A-2
1-A-29, A-31, A-32. These compounds of the invention are described in J. Org. Chem. ,
27,4054 ('62), J. Amer. Chem.
Soc. , 73, 2981 ('51), Japanese Patent Publication Sho 49-1
It can be easily synthesized by the method described in 0692 or the like or a method analogous thereto.

In the present invention, general formulas (AI) to (A
The compound represented by -III) is added by emulsification dispersion even if it is dissolved in a water-soluble solvent such as methanol, ethanol, dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or a mixed solvent thereof. You may. Further, they may be added in advance during the preparation of the emulsion.

In the present invention, the general formulas (A-I) to (A
Two or more of the compounds represented by formula (III) may be used in combination. The coating amount of the compounds (A-1) to (A-III) is 0.01 to 200 / mg / m ² per one photographic constituent layer.
Is preferred. 0.1-100 mg / m < ² > is more preferable, and 1-50 mg / m < ² > is still more preferable.

These compounds are used in at least one of the photographic constituent layers, but the same compound may be used in a plurality of layers, or different compounds may be used in each layer. Further, the photographic constituent layers are a photosensitive layer and a non-photosensitive layer, and the non-photosensitive layer includes, for example, an intermediate layer, a colloidal silver-containing yellow filter layer, an AH layer and a protective layer.

In the present invention, general formulas (AI) to
The compound represented by (A-III) has the general formula (I) above.
Is most preferably used in the same layer containing a silver halide emulsion spectrally sensitized by a compound represented by the following formula. In this case, excellent color reproducibility, high photographic sensitivity are given, and the aging of the light-sensitive material, especially It is possible to suppress variations in photographic properties such as increase in fog and decrease in sensitivity when aged under high temperature and high humidity, and to prevent latent image from degrading after taking a light-sensitive material and to improve storage stability.

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

Non-photosensitive layers such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer includes, for example, JP-A-61-2374.
No. 8, No. 59-113438, No. 59-113440
No. 61-20037, No. 61-20038, a coupler as described in the specification, a DIR compound may be contained, and a color mixing inhibitor may be contained as is usually used.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. A two-layer structure of a sensitivity emulsion layer can be preferably used. In general, it is preferable that the layers are arranged so that the photosensitivity is gradually decreased toward the support, and a non-photosensitive layer may be provided between each silver halide layer. JP-A-57-112751, JP-A-62-20035
No. 0, 62-206541, 62-206543
As described in Japanese Patent Application Laid-Open No. H10-284, a low-speed emulsion layer may be provided on the side remote from the support, and a high-speed emulsion layer may be provided on the side near the support.

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

Further, as described in JP-B-55-34932, the layers can be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. JP-A-56-25738 and JP-A-62-639.
As described in the specification of JP-A No. 36, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

As described in JP-B-49-15495, a silver halide emulsion layer having the highest photosensitivity in the upper layer, a silver halide emulsion layer having a lower photosensitivity in the middle layer, and a lower layer than the middle layer. Another example is an arrangement in which a silver halide emulsion layer having a lower photosensitivity is arranged and three layers having different sensitivities are sequentially lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order. In addition, the layers may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer.
The arrangement may be changed as described above even in the case of four or more layers.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, 4,707,436 and JP-A-62-160448 are used.
And BL and G described in the specification of JP-A-63-89850.
It is preferable to dispose a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as L and RL, adjacent to or in proximity to the main photosensitive layer.

As described above, various layer structures and arrangements can be selected according to the purpose of each photosensitive material.
Preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mol% to about 10 mol% silver iodide.

The silver halide grains in the photographic emulsion have regular crystals such as cubes, octahedra and tetradecahedrons, and irregular crystal forms such as spheres and plates.
It may have a crystal defect such as a twin plane or a composite form thereof. The grain size of silver halide is about 0.2 μm
The following fine particles or large-sized particles having a projected area diameter of about 10 μm may be used, and a polydisperse emulsion or a monodisperse emulsion may be used.

The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) N.
o. 17643 (December 1978), pp. 22-23,
"I. Emulsion preparation
ion and types) ", and No. 18 of the same.
716 (November 1979), p.648, ibid. 30
7105 (Nov. 1989), pages 863-865, and Graphide, "Physics and Chemistry of Photography," published by Paul Montel, P. Glafkides, Chemieet.
Physique Photographique, P
aul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duff).
in, Photographic Emulsion
Chemistry (Focal Press, 196
6)), "Production and Coating of Photographic Emulsions" by Zelikmann et al., Published by Focal Press (VL Zelikman et.
al. , Making and Coating Ph
autographic Emulsion, Focal
Press, 1964) and the like.

US Pat. Nos. 3,574,628 and 3,
655,394 and British Patent 1,413,748.
Monodisperse emulsions described in Nos. 1 and 2 are also preferred. Tabular grains having an aspect ratio of about 3 or more can also be used in the present invention. Tabular grains are described in Photographic Science and Engineering by Gatov (Gut).
off, Photographic Science
and Engineering), Vol. 14, 248
257 (1970); U.S. Patent No. 4,434,2.
No. 26, No. 4,414,310, No. 4,433,04
8 and 4,439,520 and British Patent 2,1
It can be easily prepared by the method described in JP-A No. 12,157 or the like.

The crystal structure may be uniform, may have different halogen compositions inside and outside, may have a layered structure, and silver halides having different compositions may be bonded by epitaxial bonding. May be
Further, it may be bonded to a compound other than silver halide such as, for example, silver rhodan or lead oxide. Also, a mixture of particles of various crystal forms may be used.

The above-mentioned emulsion may be either a surface latent image type in which a latent image is mainly formed on the surface, an internal latent image type in which a latent image is formed, or a type having a latent image on both the surface and the inside. Must be a type of emulsion. Of the internal latent image type, the core / core described in JP-A-63-264740 is used.
It may be a shell type internal latent image type emulsion. The preparation method of this core / shell type internal latent image type emulsion is described in JP-A-59-13.
No. 3542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additive used in such a process is Research Disclosure No. 17643, the same No. 18716 and the same No. 307105, and the corresponding portions are summarized in the table below. In the light-sensitive material of the present invention, two or more types of emulsions having at least one characteristic different from each other in the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used.

The fogged silver halide grains described in US Pat. No. 4,082,553 and the fogged grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are fogged. The prepared silver halide grains and colloidal silver can be preferably used in the photosensitive silver halide emulsion layer and / or the substantially non-photosensitive hydrophilic colloid layer.
The term "silver halide particles having a fogged inside or surface thereof" means silver halide grains which can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. . A method for preparing silver halide grains having the inside or the surface of the grains fogged is described in U.S. Pat. No. 4,626,498 and JP-A-59-214852.

The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged, any of silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide can be used. There is no particular limitation on the grain size of these fogged silver halide grains, but the average grain size is 0.01 to 0.7.
5 μm, particularly preferably 0.05 to 0.6 μm, is preferred. Also,
The grain shape is not particularly limited, and may be regular grains or polydispersed emulsions, but may be monodispersed (at least 95% of the weight or the number of silver halide grains is within ± 40% of the average grain size). Having a particle size of 1).

In the present invention, it is preferable to use a non-photosensitive fine grain silver halide. Non-photosensitive fine grain silver halide is silver halide fine grains that are not exposed during imagewise exposure to obtain a dye image and are not substantially developed in the developing process, and are preferably not fogged in advance. . The fine grain silver halide has a silver bromide content of 0 to 100 mol%, and may contain silver chloride and / or silver iodide as needed. Preferably, it contains 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average diameter of circles corresponding to the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be chemically sensitized, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in the layer containing fine silver halide grains.

The amount of silver coated on the light-sensitive material of the present invention was 6.0 g.
/ M ² or less is preferable, and 4.5 g / m ² or less is most preferable. Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table. Type of additive RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity increasing agent, page 648, right column 3. Spectral sensitizer, pages 23-24, page 648, right column 866-868, super sensitizer ~ page 649, right column Brightener page 24 page 647 right column page 868 5. Fogging prevention 24 to 25 pages 649 right column 868 to 870 Agents and stabilizers 6. 6. Light absorbers, pages 25 to 26, page 649, right column, page 873, filter dyes, 頁 650, left column, ultraviolet absorbers. Stain prevention page 25 right column page 650 page left column page 872 inhibitor to right column 8. Dye image safety Page 25 Page 650 Left column Page 872 Fixed agent 9. 10. Hardener page 26 page 651 left column pages 874-875 Binder page 26 page 651 left column pages 873 to 874 11. Plasticizers and lubricants Page 27 Page 650 Right column Page 876 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876 Surfactant 13. Static 27 pages 650 right column 876-877 Inhibitors 14. Matting agent pp. 878-879 Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, it is immobilized by reacting with formaldehyde described in US Pat. Nos. 4,411,987 and 4,435,503. It is preferable to add a compound capable of being added to the light-sensitive material.

The light-sensitive material of the present invention can be prepared according to US Pat.
0,454, 4,788,132, JP-A-62
It is preferable to include a mercapto compound described in JP-A-18539 and JP-A-1-283551. Compounds which release a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof irrespective of the amount of developed silver produced by the development processing described in JP-A-1-106052. Is preferably contained.

The light-sensitive material of the present invention includes the international publication WO88.
No. 04794, and dyes or EP317,308A dispersed by the method described in JP-A-1-502912.
No. 4,420,555, JP-A-1-259
No. 358 is preferably contained. Various color couplers can be used in the present invention,
A specific example is Research Disclosure N mentioned above.
o. Nos. 17643, VII-CG and No. 17643; 30
7105, VII-C-G.

Examples of yellow couplers include US Pat. Nos. 3,933,501 and 4,022,620.
No. 4,326,024 and 4,401,75
No. 2, No. 4,248,961, Japanese Patent Publication No. 58-107
No. 39, British Patent Nos. 1,425,020 and 1,4
No. 76,760; U.S. Pat. Nos. 3,973,968; 4,314,023; 4,511,649;
Those described in European Patent No. 249,473A and the like are preferable.

As the magenta coupler, 5-pyrazolone compounds and pyrazoloazole compounds are preferable, and US Pat. Nos. 4,310,619 and 4,351,897 are preferred.
No. 3,073,636; U.S. Pat.
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984
), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and JP-A-60-72238.
-35730, 55-118034, 60-1
No. 85951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, and WO88 / 04795 are particularly preferable.

Examples of the cyan coupler include phenol type and naphthol type couplers.
No. 52,212, No. 4,146,396, No. 4,
Nos. 228,233, 4,296,200, 2,369,929, 2,801,171, 2,772,162, 2,895,826,
No. 3,772,002 and No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent Nos. 121,365A and 249,453A, U.S. Patent Nos. 3,446,622 and 4,333,999.
No. 4,775,616, No. 4,451,55
No. 9, No. 4,427,767, No. 4,690, 8
No. 89, No. 4,254,212, No. 4,296,
199 and JP-A-61-42658 are preferred. Further, JP-A-64-553 and JP-A-64-5
Nos. 54, 64-555 and 64-556, and pyrazoloazole couplers described in U.S. Pat.
No. 8,672 can also be used.

Typical examples of polymerized dye-forming couplers are shown in US Pat. Nos. 3,451,820 and 4,084.
No. 0,211, No. 4,367,282, No. 4,4
09,320, 4,576,910, British Patent 2,102,137, and European Patent 341,188A. Examples of couplers in which the color forming dye has an appropriate diffusibility include U.S. Pat. No. 4,366,237, British Patent 2,125,570, and European Patent 96,57.
No. 0 and West German Patent (Publication) No. 3,234,533 are preferred.

Colored couplers for correcting unwanted absorption of color forming dyes are available from Research Disclosure N.
o. 17643, page VII-G, ibid. 307105
No. VII-G, U.S. Pat. No. 4,163,670, JP-B-57-39413, U.S. Pat. No. 4,004,92.
No. 9, No. 4,138,258, British Patent No. 1,14
No. 6,368 is preferred. In addition, a coupler described in U.S. Pat. No. 4,774,181 for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling, or reacting with a developing agent described in U.S. Pat. No. 4,777,120. It is also preferable to use a coupler having a dye precursor group capable of forming a dye as a leaving group.

Compounds that release a photographically useful residue upon coupling are also preferably used in the present invention.
The DIR coupler releasing the development inhibitor is the RD1 described above.
No. 7643, VII-F and No. 307105, V
Patents described in section II-F, JP-A-57-15194
No. 4, No. 57-154234, No. 60-184248
And JP-A-63-37346 and JP-A-63-37350, and U.S. Pat. Nos. 4,248,962 and 4,782,012 are preferred.

R. D. No. 11449, 2424
1. The bleaching accelerator releasing couplers described in JP-A-61-201247 and the like are effective for shortening the processing time having a bleaching ability. When added to the material, the effect is great. As a coupler which releases a nucleating agent or a development accelerator in an image-like manner during development, British Patent No. 2,097,1
No. 40, No. 2,131,188, JP-A-59-15
Those described in 7638 and 59-170840 are preferable. Also, Japanese Patent Application Laid-Open Nos.
No. 252340, JP-A-1-44940, 1-45
The compounds described in No. 687, which release a fogging agent, a development accelerator, and a silver halide solvent by a redox reaction with an oxidized product of a developing agent are also preferable.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat.
No. 427, etc .; U.S. Pat.
No. 3,472, No. 4,338,393, No. 4,3
Multiequivalent couplers described in JP-A No. 10,618, etc., JP-A-60
-185950, JP-A-62-24252, DIR redox compound releasing coupler, DIR coupler releasing coupler, DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent Nos. 173,302A, 313, 313. No. 308A, a coupler that releases a dye that recolors after separation, a ligand-releasing coupler described in U.S. Pat. No. 4,555,477, and a leuco dye-releasing coupler described in JP-A-63-75747. Examples thereof include couplers that release fluorescent dyes described in Japanese Patent No. 4,774,181.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling solvents used in the oil-in-water dispersion method are described in US Pat.
No. 027, etc. Specific examples of the high-boiling point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure, which is used in the oil-in-water dispersion method, include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, Screw (2,4
-Di-t-amylphenyl) phthalate, bis (2,4
-Di-t-amylphenyl) isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl) Phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenylphosphonate, etc., benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p -Hydroxybenzoate, etc.), amides (N, N-diethyldodecane amide, 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) and hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or more, preferably 50 ° C. or more and about 160 ° C. or less can be used, and typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, Examples include ethoxyethyl acetate and dimethylformamide.

The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,3.
No. 63, West German Patent Application (OLS) No. 2,541,274
And No. 2,541,230. In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-1722.
No. 48 and JP-A-1-80941.
-Benzisothiazolin-3-one, n-butyl p-
Hydroxybenzoate, phenol, 4-chloro-
It is preferable to add various preservatives or fungicides such as 3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers.
Suitable supports that can be used in the present invention include, for example, the aforementioned R
D. No. No. 17643, page 28; No. 18716, from the right column on page 647 to the left column on page 648; 307
105, page 879.

In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, and 18 μm or less.
m or less, more preferably 16 μm or less.
Further, the film swelling speed T _1/2 is preferably 30 seconds or less, and more preferably 20 seconds or less. The film thickness means a film thickness measured at 25 ° C. and a relative humidity of 55% (2 days), and the film swelling speed T
_1/2 can be measured according to techniques known in the art. For example, A. Gr.
een) et al. in Photographic Science and Engineering (Photogr. Sci. E).
ng. ), Vol. 19, No. 2, can be measured by using a type of Swellometer described (swelling meter) pp 124-129, T _1/2 is 30 ° C. with a color developing solution, and treated for 3 minutes 15 seconds 90% of the maximum swollen film thickness that reaches at time is the saturated film thickness,
It is defined as the time required to reach 1/2 of the saturated film thickness.

The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing the aging condition after coating. The swelling ratio is preferably from 150 to 400%. The swelling rate can be calculated from the maximum swollen film thickness under the above-described conditions according to the formula: (maximum swollen film thickness-film thickness) / film thickness. The light-sensitive material of the present invention preferably has a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. In this back layer, the above-mentioned light absorber, filter dye, ultraviolet absorber,
It is preferable to include an antistatic agent, a hardener, a binder, a plasticizer, a lubricant, a coating aid, a surfactant, and the like. The swelling ratio of the back layer is preferably from 150 to 500%.

The color photographic light-sensitive material according to the present invention has the RD. No. No. 17643, pages 28 to 29;
No. 18716, page 651, left column to right column; 30
The development can be carried out by a usual method described on pages 880 to 881 of No. 7105. The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine color developing agent. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N-diethylaniline and 3- Methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-
N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline, 4-amino-3-methyl-N-methyl-N-
(3-Hydroxypropyl) aniline, 4-amino-3
-Methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-ethyl-N-ethyl-
N- (2-hydroxypropyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-propyl-N- (3-hydroxy Propyl) aniline, 4-amino-3-propyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-
Methyl-N- (4-hydroxybutyl) aniline, 4-
Amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl-N- (4-hydroxybutyl) aniline, 4-
Amino-3-ethyl-N-ethyl-N- (3-hydroxy-2-methylpropyl) aniline, 4-amino-3-
Methyl-N, N-bis (4-hydroxybutyl) aniline, 4-amino-3-methyl-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-methyl-
N- (5-hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-
Ethyl-N- (4-hydroxybutyl) aniline, 4-
Amino-3-ethoxy-N, N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N-
(4-hydroxybutyl) aniline, and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Among these, especially 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline,
4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-
N-ethyl-N- (4-hydroxybutyl) aniline,
And their hydrochlorides, p-toluenesulfonates or sulfates are preferred. These compounds can be used in combination of two or more depending on the purpose.

The color developer contains a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole compound, a benzothiazole compound or a mercapto compound. It is common to include such a development inhibitor or an antifoggant. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, catecholsulfonic acid, ethylene glycol, Organic solvents such as diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting Agents, aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, various chelating agents represented by phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cycloalkyl Hexane diamine tetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene--
1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N
-Tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as typical examples.

When the reversal process is carried out, the black and white development is usually carried out before the color development. In this black-and-white developing solution, a known black-and-white developing agent such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol is used alone. Or in combination. The color developing solution and the black-and-white developing solution generally have a pH of 9 to 12. The replenishment amount of these developers depends on the color photographic light-sensitive material to be processed, but is generally 3 L or less per 1 m 2 of the light-sensitive material, and is 500 ml or less by reducing the bromide ion concentration in the replenisher. You can also When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air.

The contact area between the photographic processing liquid and the air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷
[Volume of Treatment Liquid (cm ³ )] The aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. As a method of reducing the aperture ratio in this manner, in addition to providing a shield such as a floating lid on the surface of the photographic processing solution in the processing tank, Japanese Patent Application Laid-Open No.
No. 033, a method using a movable lid,
And a slit developing method described in JP-A-216050. Reducing the aperture ratio is not only in both the color development and black-and-white development steps, but also in the subsequent steps,
For example, it is preferably applied in all steps such as bleaching, bleach-fixing, fixing, washing with water, and stabilization. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The color development processing time is usually set between 2 and 5 minutes, but the processing time can be further shortened by using a high temperature and high pH and using a high concentration of the color developing agent. it can. The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Furthermore, processing in two successive bleach-fixing baths, fixing before bleach-fixing,
Alternatively, bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Iron (III) as a typical bleaching agent
An organic complex salt of, for example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, and the like, aminopolycarboxylic acids such as citric acid, Complex salts such as tartaric acid and malic acid can be used. Among these, iron (III) complex salts of aminopolycarboxylic acid such as iron (III) complex salt of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate are preferable from the viewpoint of rapid treatment and prevention of environmental pollution. . Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in a bleaching solution and a bleach-fixing solution. The pH of a bleaching solution or a bleach-fixing solution using these iron (III) aminopolycarboxylic acid complex salts is usually 4.0 to 8, but it is also possible to process at a lower pH for speeding up the processing.

If necessary, a bleaching accelerator can be used in the bleaching solution, the bleach-fixing solution and their pre-bath.
Specific examples of useful bleaching accelerators are described in the following specifications; US Pat. No. 3,893,858, West German Patents 1,290,812, 2,059,988, JP No. 53-32736, No. 53-57831, No. 53
No. 37418, No. 53-72623, No. 53-95
No. 630, No. 53-95731, No. 53-10423
No. 2, No. 53-124424, No. 53-141623
No. 53-28426, Research Disclosure No. Compounds having a mercapto group or a disulfide group described in No. 17129 (July, 1978);
Thiazolidine derivatives described in JP-A-50-140129; JP-B-45-8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5
No. 61; thiourea derivative; West German Patent No. 1,12
7,715; JP-A-58-16235; West German Patent Nos. 966,410 and 2,748,
No. 430; polyamine compounds described in JP-B-45-8836; and JP-A-49-40,943; JP-A-49-59,644; JP-A-53-94,927; 54-35,727, 5
Compounds described in Nos. 5-26,506 and 58-163,940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and in particular, US Pat.
No. 858, West German Patent No. 1,290,812,
Compounds described in 3-95,630 are preferred. Furthermore,
The compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material.
These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, specifically acetic acid,
Propionic acid, hydroxyacetic acid and the like are preferred. The fixer used in the fixer and the bleach-fixer is thiosulfate,
Thiocyanates, thioether compounds, thioureas,
Although a large amount of iodide salt and the like can be mentioned, thiosulfate is generally used, and ammonium thiosulfate is most widely used. It is also preferable to use a thiosulfate solution in combination with a thiocyanate, a thioether-based compound, or thiourea. As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, a carbonyl bisulfite adduct, or a sulfinic acid compound described in EP-A-294769A is preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixer or the bleach-fixer contains a compound having a pKa of 6.0 to 9.0 for pH adjustment, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, 2- It is preferable to add 0.1 to 10 mol / L of imidazoles such as methylimidazole. The total time of the desilvering step is preferably shorter as long as the desilvering failure does not occur. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. Further, the processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In a preferred temperature range, the desilvering speed is improved,
In addition, the occurrence of stain after processing is effectively prevented.

In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method of strengthening the stirring, a method described in JP-A-62-183460, in which a jet of a processing solution is made to impinge on the emulsion surface of a photosensitive material, or a method using a rotating means described in JP-A-62-183461, is used. A method of increasing the effect, a method of moving the photosensitive material while bringing the wiper blade provided in the solution into contact with the emulsion surface, and increasing the stirring effect by turbulently flowing the emulsion surface, and circulating the entire processing solution. There is a method of increasing the flow rate. Such stirring improving means include a bleaching solution, a bleach-fixing solution,
It is effective in any of the fixing solutions. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator.

The automatic developing machine used for the light-sensitive material of the present invention is described in JP-A-60-191257 and JP-A-60-19125.
No. 8, No. 60-191259. JP-A-60-1
As described in JP-A-91257, such a transporting means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to a desilvering solution, washing with water and / or a stabilizing step. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set widely.
Among them, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent method is described in Journal of the Society.
y of Motion Picture and T
elevation Engineers, Vol. 64,
p. 248-253 (May, 1955).

According to the multistage countercurrent method described in the above-mentioned document,
Although the amount of washing water can be greatly reduced, the increase in the residence time of the water in the tank causes a problem that bacteria proliferate and generated floating substances adhere to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, a method for reducing calcium ions and magnesium ions described in JP-A-62-28838 can be used very effectively. Also, Japanese Unexamined Patent Publication No.
No. 8,542, isothiazolone compounds, siabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and other bend triazoles, etc. Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing, edited by Hygiene Technology Society, "Microbial sterilization, sterilization, and antifungal technology"
The fungicide described in "Encyclopedia of Bactericidal and Fungicides" (ed. 1986), edited by the Japan Society of Bacteria and Fungi.

The pH of washing water in the processing of the light-sensitive material of the present invention is 4 to 9, preferably 5 to 8. The washing temperature and washing time can also be variously set depending on the characteristics of the photosensitive material, the application, etc., but are generally in the range of 15 to 45 ° C for 20 seconds to 10 minutes, preferably in the range of 25 to 40 ° C for 30 seconds to 5 minutes. Selected. Further, the light-sensitive material of the present invention can be processed directly with a stabilizing solution instead of the above-mentioned washing. In such a stabilizing process, JP-A-57-8543 and JP-A-58-8543 are used.
All known methods described in JP-A Nos. 14834 and 60-220345 can be used.

In some cases, a stabilization treatment may be performed after the water washing treatment. For example, a stabilization treatment containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photography, may be used. Baths can be mentioned. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts. Various chelating agents and fungicides can also be added to this stabilizing bath.

The overflow solution accompanying the washing with water and / or the replenishment of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic developing machine or the like, when each of the above processing solutions is concentrated by evaporation,
It is preferable to correct the concentration by adding water.

In the silver halide color light-sensitive material of the present invention, a color developing agent may be incorporated for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, U.S. Pat.
No. 342,597, indoaniline compounds, and No. 3,342,599, Research Disclosure No. 14, 850 and the same No. 15,159, Schiff base compounds, aldol compounds described in JP-A-13,924, metal salt complexes described in U.S. Pat. No. 3,719,492, and urethane-based compounds described in JP-A-53-135628. be able to.

The silver halide color light-sensitive material of the present invention comprises:
If necessary, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339 and JP-A-57-14.
Nos. 4547 and 58-115438. Various treatment liquids in the present invention are 10 ° C to 50 ° C.
Used in Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature promotes the processing and shortens the processing time, and a lower temperature achieves an improvement in the image quality and an improvement in the stability of the processing solution. be able to.

The silver halide color photographic light-sensitive material of the present invention is more likely to exert the effect when applied to a film unit with a lens described in JP-B-2-32615, JP-B-3-39784 and the like. It is valid.

[0109]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photographic material composed of each layer having the following composition, was prepared. The amount coated amount (Composition of photosensitive layer) is represented in units of g / m ² of silver for silver halide and colloidal silver, also couplers, the amount for the additives and gelatin, expressed in units of g / m ^2, The sensitizing dyes are shown in terms of moles per mole of silver halide in the same layer. The symbols indicating the additives have the following meanings. However, when there is more than one utility, only one of them is listed as a representative.

UV: UV absorber, Solv: High boiling organic solvent, ExF: Dye, ExS: Sensitizing dye, ExC: Cyan coupler, ExM: Magenta coupler, ExY: Yellow coupler, Cpd: Additive first layer (halation) Prevention layer) Black colloidal silver 0.22 Gelatin 1.80 UV-1 3.0x10 ^-2 UV-2 6.0x10 ^-2 UV-3 7.0x10 ^-2 ExF-1 1.2x 10 ^-2 ExF-2 4.0 x 10 ^-2 ExF-3 5.0 x 10 ^-2 ExM-3 0.13 ExC-7 9.4 x 10 ^-2 Cpd-5 1.0 x 10 ^-2 Solv -1 0.16 Solv-2 0.10 Second layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion A Coating amount of silver 0.21 Silver iodobromide emulsion B Coating amount of silver 0.35 Gelatin 1.53 ExS-1 6.5 × 10 ⁻⁴ ExS-2 3.6 × 10 ⁻⁴ ExS -5 6.2 × 10 ^-4 ExS-7 4.1 × 10 ^-6 ExC-1 1.7 × 10 ^-1 ExC-4 8.0 × 10 ^-2 ExC-5 1.1 × 10 ^-1 ExC −6 3.7 × 10 ⁻² ExC-7 3.7 × 10 ⁻² ExC-9 5.0 × 10 ⁻³ Cpd-4 6.7 × 10 ⁻² Solv-1 0.13 Third layer (middle) Sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion C Coating amount 0.81 Gelatin 1.00 ExS-1 4.3 × 10 ⁻⁴ ExS-2 2.4 × 10 ⁻⁴ ExS-5 4.1 × 10 ^-4 ExS-7 4.3x10 ^-6 ExC-1 1.0x10 ^-1 ExC-4 3.7x10 ^-2 ExC-5 7.2x10 ^-2 ExC-6 3.2x10 ^-2 ExC-7 2.6x10 ^-2 ExC-9 1.2x10 ^-2 Cpd-4 2.8x10 ^-2 Solv-1 0.08 Fourth layer (high-sensitivity red-sensitive emulsion layer) Iodine Silver bromide emulsion D Coating amount of silver 0.95 Latin 0.80 ExS-1 3.6 × 10 ⁻⁴ ExS-2 2.0 × 10 ⁻⁴ ExS-5 3.4 × 10 ⁻⁴ ExS-7 1.4 × 10 ⁻⁵ ExC-1 7.0 × 10 ^-2 ExC-4 2.2 × 10 ^-2 ExC-7 1.2 × 10 ^-2 ExC-8 1.0 × 10 ^-2 ExC-9 2.3 × 10 ^-2 Cpd-4 3.2 × 10 ^-3 Solv-1 0.10 Solv-2 0.06 Fifth layer (intermediate layer) Gelatin 0.92 Cpd-1 0.12 Cpd-8 4.0 × 10 ^-3 Polyethyl acrylate latex 4.1 × 10 ^-2 Solv-1 6.0 × 10 ^-2 6th layer (low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion A coating amount of silver 0.09 Silver iodobromide emulsion E coating amount of silver 0.13 Gelatin ^{0.73 ExS-4 1.28 × 10 -5} ExS-5 2.1 × 10 -4 ExS-8 1.2 × 10 -4 ExM-1 0.22 ExM- ^{9.7 × 10 -2 ExY-1 1.3} × 10 -2 Solv-1 0.27 Solv-3 7.0 × 10 -3 Seventh Layer (medium-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion B Coating silver amount 0.15 Silver iodobromide emulsion F Coating silver amount 0.10 Gelatin 0.30 ExS-4 8.5 × 10 ⁻⁴ ExS-5 1.4 × 10 ⁻⁴ ExS-8 8.3 × 10 ^{-5 ExM-1 6.5 × 10 -2} ExM-7 2.9 × 10 -2 ExY-1 1.1 × 10 -2 Solv-1 0.076 Solv-3 1.8 × 10 -2 8 Layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion D Coating amount 0.72 Gelatin 0.72 ExS-4 7.1 × 10 ⁻⁴ ExS-5 1.4 × 10 ⁻⁴ ExS-8 4. 6 × 10 ⁻⁵ ExM-1 4.8 × 10 ⁻² ExM-3 1.8 × 10 ⁻² ExM-8 5.0 × 10 ⁻³ ExY-1 4.0 × 10 ⁻² ExC-1 9. 0 x 10 ^-3 ExC-4 1.2x10 ^-3 Cpd-6 2.0x10 ^-3 Solv-1 0.12 9th layer (intermediate layer) Gelatin 0.66 Cpd-1 2.0x10 ^-2 polyethyl acrylate Latex 1.4 × 10 ^-2 Solv-1 1.0 × 10 ^-2 10th layer (donor layer of multi-layer effect for red-sensitive layer) Silver iodobromide emulsion A Coating amount of silver 0.10 Silver iodobromide emulsion G Amount of coated silver 0.55 Silver iodobromide emulsion H Amount of coated silver 0.18 Gelatin 1.55 ExS-3 8.5 × 10 ^-4 ExS-4 1.5 × 10 ^-4 ExM-2 0.24 Solv- 1 0.67 11th layer (yellow filter layer) Yellow colloidal silver 9.2 × 10 ^-2 gelatin 0.83 Cpd-1 0.14 Cpd-5 1.0 × 10 ^-3 Solv-1 0.070 12th layer Layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion I Coating amount of silver 0.23 Gelatin 0 ^{89 ExS-6 9.0 × 10 -4} ExY-6 8.5 × 10 -2 ExY-2 5.5 × 10 -3 ExY-3 0.32 ExC-1 5.3 × 10 -2 ExC-9 3.5 × 10 ^-2 Solv-1 0.18 13th layer (medium-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J Coating silver amount 0.33 Silver iodobromide emulsion K Coating silver amount 0.15 Gelatin 2 .49 ExS-6 9.0 × 10 ⁻⁴ ExY-6 3.9 × 10 ⁻² ExY-4 0.26 ExY-3 0.89 ExC-10 0.18 ExC-9 3.9 × 10 ⁻² Solv-1 0.51 14th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Coating amount 0.20 Gelatin 0.28 ExS-6 6.3 × 10 ⁻⁴ ExY-3 8.0 × ^{10 -2 ExY-4 2.4 × 10} -2 Solv-1 4.3 × 10 -2 15th layer (first protective layer) fine iodobromide emulsion M silver coverage .60 Gelatin 1.14 UV-4 0.11 UV-5 0.18 Cpd-3 0.10 Solv-1 2.0 × 10 -2 polyethyl acrylate latex 9.0 × 10 ^-2 16th layer (first 2 Protective layer) Gelatin 0.76 B-1 (diameter 2.0 μm) 8.0 × 10 ^-2 B-2 (diameter 2.0 μm) 8.0 × 10 ^-2 B-3 2.0 × 10 ^-2 W-5 2.0 × 10 ^-2 H-1 0.34 In addition to the above, 1,2-benzisothiazolin-3-one (average 2% for gelatin) was added to the sample thus prepared.
00 ppm), n-butyl-p-hydroxybenzoate (about 1,000 ppm), and 2-phenoxyethanol (about 10,000 ppm). Further, W-1 may be suitably added to each layer in order to improve the storability, processability, pressure resistance, fungicide / antibacterial properties, antistatic properties and coatability.
To W-6, B-1 to B-6, F-1 to F-16 and iron salts, lead salts, gold salts, platinum salts, iridium salts and rhodium salts.

[0111]

[Table 1] In Table 1, (1) Emulsions H to L were subjected to reduction sensitization during the preparation of grains using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938. (2) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426. (3) Using a high voltage electron microscope, dislocation lines as described in JP-A-3-237450 can be observed in the tabular grains. (4) Emulsions A to L are B.I. H. Carroll, Pho
graphical Science and Eng
Inering, 24, 265 (1980), iridium is contained inside the particles.

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[0124]

[Chemical 21]

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Preparation of Sample 102 A sample was prepared by making the following changes to the sample 101. -The ExC-9 of the second layer, the third layer, and the fourth layer are respectively 5.
0x10^-3→ 2.5 × 10^-3, 1.2 x 10^-2→ 0.6
× 10^-22.3 × 10^-2→ 1.5 × 10^-2Reduced to
Was. -ExY-1 of the sixth layer, the seventh layer, and the eighth layer are 1.
3 x 10^-2→ 0.7 × 10^-2, 1.1 x 10^-2→ 0.6
× 10^-24.0 x 10^-2→ 2.5 × 10^-2Reduced to
Was.・ Reduced ExM-2 of 10th layer from 0.22 to 0.15
Was. -The 12th layer ExY-6 and ExY-2 are each 8.5.
× 10^-2→ 5.0 × 10 ^-25.5 x 10^-3→ 3.5 ×
10^-3Reduced to. -ExY-6 and ExY-4 of the 13th layer are 3.9, respectively.
× 10^-2→ 2.5 × 10 ^-2, Reduced from 0.23 to 0.18
did. -The 14th layer of ExY-4 is 2.4 x 10^-2→ 1.8 × 1
0^-2Reduced to. Preparation of Sample 103 As shown in Table 2 with respect to Sample 102, the general formula (AI) was used.
Was added. Preparation of Samples 104 to 106 As shown in Table 2 with respect to Sample 101, the general formula (AI) was used.
Was added.

Samples 101 to 106 were processed into product forms,
Black-white, white-white, yellow-skinned skin, hair, and Macbeth Color Rendition Chart were photographed under different lighting, the following color processing was performed, and the results were printed appropriately on Fuji Color Paper and the evaluation results are shown in Table-2. It was

[Table 2]

[Table 3]

The latent image storability was evaluated as follows. White light (color temperature of light source 4800
The exposure was given through a sensitometric wedge at (K). After the exposure, the film was stored at 50 ° C. and 60% relative humidity for 14 days, and then the following color development processing was carried out to measure cyan density, magenta density and yellow density, and from the characteristic curve, a density of minimum density + 2.0 was given. The logarithm of the reciprocal of the exposure dose was obtained.

The difference between this value and the value of those processed within 1 hour after exposure was calculated, and this value (ΔS) was used as a representative value of the change with time when the photosensitive material was stored after photography. This value (ΔS) is 0
The closer to, the smaller the change with time and the more preferable. After exposing the color photographic light-sensitive material as described above, it was processed by the method described below. (Treatment method) Step Treatment time Treatment temperature Color development 3 minutes 15 seconds 38 ° C Bleach 3 minutes 00 seconds 38 ° C Water wash 30 seconds 24 ° C settling 3 minutes 00 seconds 38 ° C Water wash (1) 30 seconds 24 ° C Water wash (2) 30 seconds 24 ° C Stability 30 seconds 38 ° C Drying 4 minutes 20 seconds 55 ° C Next, the composition of the treatment liquid is described. (Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1. 5 mg Hydroxylamine sulfate 2.4 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 Water was added to 1.0 liter pH (potassium hydroxide and sulfuric acid 10.05 (bleaching solution) (unit g) ethylenediaminetetraacetic acid sodium ferric trihydrate 100.0 ethylenediaminetetraacetic acid disodium salt 10.0 3-mercapto-1,2,4-triazole 03 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 ml Add water 1.0 liter pH (adjusted with ammonia water and nitric acid) 6.0 (fixing solution) (unit g) ethylenediaminetetraacetic acid disodium salt 0.5 ammonium sulfite 20.0 ammonium thiosulfate aqueous solution (700 g / liter) 295.0 Milliliter acetic acid (90%) 3.3 Water was added to 1.0 liter pH (adjusted with ammonia water and acetic acid) 6.7 (stabilizing solution) (unit: g) p-nonylphenoxypolyglycidol (Glycidol average degree of polymerization 10 ) 0.2 ethylenediaminetetraacetic acid 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 hydroxyacetic acid 0.02 hydroxyethylcellulose 0 .1 (Daicel Chemistry HEC SP-2000) 1,2-Benzisothiazoline 3-on 0.05 Water added 1.0 liter pH 8.5 As shown in Table 2, the light-sensitive materials 104 to 105 of the present invention are excellent in skin color reproduction, and have a photographic property when left after photographing. It is clear that the variation of is significantly improved and is preferable. Example 2 Instead of the support of Example 1, a support, an undercoat layer and a back layer were prepared as in the following 1) to 3), and a sample coated with a light-sensitive material was used. Results were obtained. 1) Support The support used in this example was prepared by the following method.

Polyethylene-2,6-naphthalate poly
100 parts by weight and Tinuvin as a UV absorber
 P. 326 (Ciba-Geigy, Inc.
2 parts by weight, and after melting at 300 ° C., T
Extruded from the die and longitudinally stretched 3.3 times at 140 ℃
No, followed by transverse stretching of 3.3 times at 130 ° C and further
Then, heat set at 250 ° C for 6 seconds to obtain a PEN with a thickness of 90 μm.
I got a film. This PEN film is dyed in blue
, Magenta dye and yellow dye (public technical report: public technique number
No. 94-6023, I-1, I-4, I-6, I
-24, I-26, I-27, II-5) is added in an appropriate amount.
did. Furthermore, it is wrapped around a stainless steel core with a diameter of 20 cm.
And give a heat history of 110 ° C for 48 hours,
It was made a difficult support. 2) Coating of undercoat layer The above-mentioned support has corona discharge treatment and UV discharge treatment on both sides thereof.
And then glow discharge treatment, and then apply a zero to each surface.
Latin 0.1g / m^Two, Sodium α-sulfodi-2-d
Chilhexyl succinate 0.01 g / m^Two,salicylic
Acid 0.04g / m^Two, P-chlorophenol 0.2 g /
m^Two, (CH_Two= CHSO_TwoCH_TwoCH _TwoNHCO)_Two
CH_Two0.012 g / m^Two, Polyamide-Epichlorhi
Drin polycondensate 0.02 g / m^TwoApply the undercoat liquid
(10 cc / m^Two, Using a bar coater), stretching the undercoat layer
It was installed on the high temperature side. Drying was performed at 115 ° C. for 6 minutes
(All the rollers and conveyors in the drying zone are 115 ° C.
Has become). 3) Coating of back layer The following set of back layers is provided on one surface of the above-mentioned support after undercoating.
An antistatic layer, a magnetic recording layer and a sliding layer were applied. 3-1) Application of antistatic layer Tin oxide-antimony oxide composite having an average particle size of 0.005 μm
The specific resistance of the compound is 5Ω · cm, which is a dispersion of fine particle powder (secondary
Aggregated particle diameter of about 0.08μm) 0.2g / m ^Two, Zera
Chin 0.05g / m^Two, (CH_Two= CHSO_TwoCH_TwoC
H_TwoNHCO) _TwoCH_Two0.02 g / m^Two, Poly (polymerization
10) Oxyethylene-p-nonylphenol 0.0
05g / m^TwoAnd resorcin. 3-2) Coating of magnetic recording layer 3-Poly (degree of polymerization 15) oxyethylene-propyloxy
Coated with citrimethoxysilane (15% by weight)
Cobalt-γ-iron oxide (specific surface area 43m^Two/ G, long axis
0.14 μm, uniaxial 0.03 μm, saturation magnetization 89 emu
/ G, Fe⁺²/ Fe⁺³= 6/94, aluminum oxide oxide on the surface
Treated with silicon oxide at 2% by weight of iron oxide) 0.06
g / m^TwoDiacetyl cellulose 1.2 g / m^Two(Oxidation
Dispersion of iron was carried out with an open kneader and a sand mill.
C) as a curing agent_TwoH_FiveC (CH_TwoOCONH-C
₆H_Three(CH_Three) NCO)_Three0.3 g / m^TwoWith a solvent
Acetone, methyl ethyl ketone, cyclohexano
Coating with a bar coater using dibutyl phthalate
Then, a magnetic recording layer having a thickness of 1.2 μm was obtained. As a slip agent
C₆H ₁₃CH (OH) C_TenH₂₀COOC₄₀H₈₁50 g /
m^Two, Silica particles (1.0 μm) as a matting agent and 3-
Poly (degree of polymerization 15) oxyethylene-propyl oxyto
Polishing treated with Limethoxysilane (15% by weight)
Aluminum oxide (0.20 μm and 1.0 μm)
50 mg / m each^TwoAnd 10 mg / g
Was added. Drying was carried out at 115 ° C for 6 minutes (drying zone
All rollers and conveyors are 115 ° C). X-light
D of magnetic recording layer with (blue filter) ^BIncreased color density
Addition is about 0.1, and the saturation magnetization moment of the magnetic recording layer
Is 4.2 emu / g, coercive force 7.3 × 10^FourA / m, corner
The form ratio was 65%. 3-3) Preparation of sliding layer Diacetyl cellulose (25 mg / m^Two), C₆H₁₃C
H (OH) C_TenH₂₀COOC₄₀H₈₁(6 mg / m^Two),
Polydimethylsiloxane (B-3) 1.5 mg / m^TwoTo
Applied. This mixture is xylene / propylene.
105 ° C in glycol monomethyl ether (1/1)
Melted at room temperature to produce propylene monomethyl ether (10
Double volume) to make dispersion, and then disperse in acetone
(Average particle diameter of 0.01 μm) and then added. Drying
Performed at 115 ° C for 6 minutes
All devices are 115 ° C). The sliding layer has a dynamic friction coefficient of 0.1
0 (5 mmφ stainless hard ball, load 100 g, speed
6 cm / min), static friction coefficient 0.08 (clip method),
The dynamic friction coefficient between the emulsion surface and the sliding layer, which will be described later, is also 0.15.
It had excellent characteristics. Example 3 Instead of the A-50 used in the sample 104 of Example 1,
Compounds A-10 and A-2 of general formulas (A-II) and (A-III)
0, A-23, A-25, A-32 for equimolar amounts
Prepared samples were prepared. All samples were the same as in Example 1.
The latent image storability was improved and favorable results were obtained.

[0133]

According to the present invention, a color photograph having high saturation, excellent color reproducibility and gradation reproducibility, and excellent storability of an unused light-sensitive material and latent image storability after storage. A photosensitive material is obtained.

[Brief description of drawings]

FIG. 1 shows a method for determining the magnitude of a stacking effect. FIG. 1 shows the layering effect from color sensitivity Y to color sensitivity X. From the sensitivity point of the color sensitivity Y (logarithm of the exposure amount giving the density of fog + 0.2) to the high exposure by 1.0 log E, the density reduction of the color sensitivity X is reduced to IE (X / Y).
And

FIG. 2 shows a spectral sensitivity distribution curve used when determining a wavelength giving a peak sensitivity. Each curve in FIG. 2 shows the exposure wavelength dependence of the reciprocal of the exposure dose which gives a density of fog +0.4, 0.6, 0.8, and 1.9, respectively. From this figure, the wavelength having the peak sensitivity was read from each curve (marked with ◯), and the averaged value was taken as the wavelength giving the peak sensitivity.

FIG. 3 shows the absorption characteristics of a density measuring filter used when obtaining a gradation. In the figure, (a),
The blue, green, and red filters have transmittance peaks in (b) and (c), respectively.

Claims (2)

[Claims] 1. A red-sensitive silver halide emulsion layer on a support,
A color photographic material having a photographic constituent layer containing at least one green-sensitive silver halide emulsion layer and at least one blue-sensitive silver halide emulsion layer, wherein at least one of the photographic constituent layers is provided.
The layer has the general formula (AI), (A-II), or (A-II)
The maximum gradation value γ _R ^p , γ _G ^p , γ by monochromatic exposure of a wavelength containing a compound selected from I) and giving a peak sensitivity of a red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer.
_B ^p is 0.80 <γ _R ^p <1.4 0.80 <γ _G ^p <1.6 0.65 <γ _B ^p <1.3, and the gradation degree γ _R by standard white light source exposure,
A silver halide color photographic light-sensitive material characterized in that γ _G and γ _B are 0.35 <γ _R <0.65 0.35 <γ _G <0.65 0.35 <γ _B <0.75. . Embedded image In the general formula (AI), _Ra1 represents an alkyl group, an alkenyl group, an aryl group, an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group,
A carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group;
_a2 represents a hydrogen atom or a group represented by R _a1 . However,
When R _a1 is an alkyl group, an alkenyl group or an aryl group, R _a2 is an acyl group, an alkyl or arylsulfonyl group, an alkyl or arylsulfinyl group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or an aryloxycarbonyl group. R _a1 and R _a2 may combine with each other to form a 5- to 7-membered ring, provided that S
-Does not form a triazine ring. General formula (A-I
In I), X represents a heterocyclic group excluding the S-triazine ring, and R _b1 represents an alkyl group, an alkenyl group or an aryl group. X and R _b1 may combine with each other to form a 5- to 7-membered ring, provided that they do not form an S-triazine ring. In the general formula (A-III), Y is-.
It represents a group of non-metal atoms necessary for forming a 5-membered ring with N = C-. Y represents a group of non-metal atoms necessary for forming a 6-membered ring together with -N = C- group, and -N
The terminal of Y bonded to the carbon atom of the ═C-group is —N (R _c1 ).
-, -C ( _Rc2 ) ( _Rc3 )-, -C ( _Rc4 ) =, _-O
-, A group selected from -S- (-N = on the left side of each group)
(Bonded to the carbon atom of C-). However, it does not form an S-triazine ring. R _{c1 to} R _c4 each represent a hydrogen atom or a substituent. 2. The magnitude I of the stacking effect as defined in the text.
E (X / Y) is 0.15 <IE (R / G) <0.50 0.15 <IE (G / R) <0.50 0.15 <IE (G / B) <0.50 0 The silver halide color photographic light-sensitive material according to claim 1, wherein <IE (R / B) / IE (G / B) <1.0.