JPH0625859B2 - Silver halide color photographic light-sensitive material having a novel layer structure - Google Patents

Description

The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material excellent in sharpness and graininess.

[Conventional technology]

In recent years, the image quality of silver halide color photographic light-sensitive materials (hereinafter referred to as "color light-sensitive materials") has been remarkably improved, but the sharpness and graininess are still insufficient. Particularly in stretch printing of a negative type color film in a small format (110 film, disc film, etc.), the image sharpness and granularity significantly lower the level of the printed image. This is because the graininess and sharpness of the negative film have not reached the level to withstand high-magnification printing.

Conventionally, various techniques for improving granularity and sharpness are known.

As a technique for improving the graininess, it is known to provide an intermediate layer between the high sensitivity emulsion layer and the low sensitivity emulsion layer. Tokusho
53-7230, a technique in which an intermediate-speed silver halide layer containing a DIR compound which reacts with an oxidant of a color developing agent to release a development inhibitor is provided as an intermediate layer, JP-A-57-57230.
-155539 describes a technique of providing a non-photosensitive intermediate layer containing a coupler that develops the same hue as the high-speed emulsion layer and has a slower coupling speed than the high-speed emulsion layer, as an intermediate layer. . However, the technique of providing these intermediate layers has many drawbacks such that not only the improvement of graininess is insufficient, but also the provision of the intermediate layer increases the film thickness and deteriorates the sharpness. On the other hand, it has been known in recent years to improve the graininess by using a coupler having a high color developing property.
For example, an attempt is made to improve green graininess by using a pyrazolotriazole-based magenta coupler in the green-sensitive layer. However, even with this coupler, due to the diffusion of the oxidant of the main agent from the adjacent layer during color development,
The present inventors have found that the original performance is impaired. This is largely due to the currently known arrangement of the color-sensitive layer. As a technique for improving sharpness, there are a method using a so-called DIR coupler and a method using an unsharp mask. Among them, the method using the unsharp mask may cause deterioration of sensitivity and deterioration of graininess, and is practically limited. Many methods using DIR couplers are known, and as useful DIR couplers, JP-B-55-34933, JP-A-57-93344, U.S. Patents 3,227,554, 3,615,506 and 3,617,291.
There are compounds described in No. However DIR
When the edge effect is emphasized by using a coupler, the MTF is improved in the low frequency region, but the MTF improvement in the high frequency region necessary for a high magnification cannot be expected, and the sensitivity and the density are lowered, which is not preferable. With side effects. Diffusive D
If a DIR coupler that exerts a so-called long-distance action effect such as IR and timing DIR is used, the decrease in sensitivity and density can be reduced, but the MTF improvement region shifts to the lower frequency side, and sharpness at high magnification is improved. I can't expect much improvement.

On the other hand, as a technique for preventing light scattering, a coloring substance addition method,
Thin film forming methods and the like are known. The latter has a great effect of reducing the amount of coated silver, but since it reduces the number of coloring points, it deteriorates the graininess. In addition, gelatin in the coating liquid, coupler,
Although there is a reduction in the amount of coupler solvent and the like, all of them have limitations because they lead to lower coating properties and color density.

[Object of the Invention]

It is an object of the present invention to provide a silver halide color photographic light-sensitive material having sharply improved sharpness and excellent graininess.

[Structure of Invention]

The present inventors, as a result of various studies to achieve the above object,
In order to improve graininess and sharpness at the same time, a pyrazolotriazole-based magenta coupler having a specific structure is used,
And it has been found that this can be achieved by changing the arrangement of the color-sensitive layers known so far as follows.

That is, the above-mentioned object of the present invention has two or more silver halide emulsion layers having different color sensitivities on a support, and at least one of the emulsion layers has two different sensitivity. In the silver halide color photographic light-sensitive material, the emulsion layer having a color sensitivity consisting of at least one of two silver halide emulsion layers having different sensitivities is the layer closer to the support than the layer farther from the support. At least one of the layers having higher sensitivity and color sensitivity contains a pyrazolotriazole-based magenta coupler represented by the following general formula [I] or [II]. And a silver halide color photographic light-sensitive material.

Hereinafter, the present invention will be described more specifically.

In the present invention, a pyrazolotriazole-based magenta color represented by the general formula [I] or [II] is used,
It has recently been known that this coupler has a high color-forming property and therefore can be formed into a thin film. Therefore, this coupler is useful in terms of graininess and sharpness. In general, it is effective to reduce the film thickness in order to increase the sharpness, but with conventional couplers, there is a limit to thinning due to a decrease in color density.

In the present invention, when the film thickness when dried is measured at 23 ° C. and 55% humidity, the total dry film thickness of all hydrophilic colloid layers on the emulsion layer side (hereinafter referred to as the emulsion surface thickness). The upper and lower limits are the silver halide emulsion contained, oil agents such as couplers,
There is a preferred range depending on the constitution of additives and binders such as gelatin. That is, the preferable thickness of the emulsion surface is 5 μm to 20 μm, more preferably 10 μm to 1
It is 8 μm. Further, the distance from the outermost surface of the emulsion surface to the lower end of the emulsion layer closest to the support is preferably 14 μm or less, and the color sensitivity is different from that of the emulsion layer, and the emulsion layer next to the support is at the lower end of the emulsion layer. Is preferably 10 μm or less.

The thickness of the layer containing the pyrazolotriazole-based magenta coupler represented by the general formula [I] or [II] is
It is preferably 0.5 μm to 5 μm per layer.

Next, the pyrazolotriazole type magenta couplers represented by the following general formulas [I] and [II] used in the present invention will be described. Preferred examples of the pyrazolotriazole-based magenta couplers represented by the general formulas [I] and [II] are listed below.

General formula (I) General formula (II) In the present invention, the pyrazolotriazole magenta coupler can be used in an amount of 1 × 10 ⁻³ to 1 mol, preferably 1 × 10 ⁻² to 8 × 10 ⁻¹ mol per mol of silver halide.

In the above formulas [I] and [II], R ₁ R ₂ represents an alkyl, aryl or hetero ring, and the alkyl, aryl or hetero ring may be bonded via an oxygen atom, a nitrogen atom or a sulfur atom. Further, the above-mentioned alkyl, aryl and heterocycle may be bonded to each other via a bonding group shown below. That is, acylamino, carbamoyl, sulfonamide, sulfamoylcarbonyl, carbonyloxy, oxycarbonyl, ureido, thioureido, thioamide, sulfone,
Sulfonyloxy.

The groups represented by R ₁ and R ₂ are linear or branched alkyl groups having 1 to 20 carbon atoms (for example, methyl, ethyl, propyl,
i-propyl, sec-butyl, n-butyl, t-butyl, n-octyl, t-octyl, dodecyl, octadecyl and the like). These groups may further have a substituent (for example, a halogen atom, nitro, cyano, alkoxy, aryl, oxy, amino, acylamino, carbamoyl, sulfonamide, sulfamoyl, imide, alkylthio, arylthio, aryl, alkoxycarbonyl, acyl). Specifically, chloromethyl, brommethyl, trichloromethyl, β-nitroethyl, δ-cyanobutyl, methoxymethyl, ethoxyethyl, phenoxyethyl, N-methylaminoethyl, dimethylaminobutyl, acetaminoethyl, benzoylamino, propyl, ethyl. Carbamoylethyl, methanesulfonamidoethyl, ethylthioethyl, p-methoxyphenylthiomethyl, phenylmethyl, p-chlorophenylmethyl,
Naphthylethyl, ethoxycarbonylethyl, acetylethyl, etc.).

Further, the aryl group represents a phenyl group or a naphthyl group and may have the substituent shown in the section of the alkyl group.

The heterocycle represents a 5-membered or 6-membered ring having at least one of a nitrogen atom, an oxygen atom and a sulfur atom, and may or may not have aromaticity. For example, pyridyl, quinolyl, pyrrolyl, morpholyl, furanyl, tetrahydrofuranyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, oxazolyl, imidazolyl, thiadiazolyl and the like. Moreover, these may have the substituent shown in the item of the alkyl group.

Examples of the alkyl, aryl, or hetero ring represented by R ₁ or R ₂ which is bonded via the above-mentioned bonding group or nitrogen atom, oxygen atom, or sulfur atom include Etc. Where R ₂ ′ is alkyl, aryl,
Represents a heterocycle, and R ₂ ″ and R ₂ represent a hydrogen atom, alkyl, aryl or heterocycle.

When the heterocyclic group is a → pyrazolotriazolyl-based compound, it forms a bis-type → pyrazolo → triazole-based compound, which is, of course, a magenta coupler included in the present invention.

Next, specific examples of R ₁ R ₂ represented by the above general formula are shown.

CH ₃ − C ₂ H ₅ − (n) C ₃ H ₇ − (n) C ₈ H ₁₇ − (n) C ₁₅ H ₃₁ − (t) C ₄ H ₉ − (t) C ₅ H ₁₁ − (t) C ₈ H ₁₇ − −C ₁₇ H ₃₅ −CH ₂ CH ₂ CH ₂ OC ₁₂ H ₂₅ −CH ₂ CH ₂ CONHC ₁₄ H ₂₉ − OC ₁₂ H ₂₅ -S-C ₁₆ H ₃₃ -CONHC ₁₄ H ₂₉ -NHSO ₂ C ₁₆ H ₃₃ -SO ₂ NHC ₁₆ H ₃₃ -COC ₁₁ H ₂₃ -OCOC ₁₅ H ₃₁ Z represents a hydrogen atom or a group that is released when a dye is formed by coupling with an oxidized product of an aromatic primary amine color developing agent.

Specifically, for example, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an arylthio group, an alkylthio group, (Z ₂ is a nitrogen atom together with a carbon atom, an oxygen atom, a nitrogen atom,
It represents a group of atoms required to form a 5- or 6-membered ring with an atom selected from sulfur atoms. ) Specific examples are given below.

Halogen atom: chlorine, bromine, fluorine Alkoxy group: ethoxy group, benzyloxy group, methoxyethylcarbamoylmethoxy group, tetradecylcarbamoylmethoxy group, etc.Aryloxy group: phenoxy group, 4-methoxyphenoxy group, 4-nitrophenoxy group, etc. Acyloxy Group: acetoxy group, myristoyloxy group, benzoyloxy group, etc. Arylthio group: phenylthio group, 2-butoxy-5-
Octylphenylthio group, 2,5-dihexyloxyphenylthio group, etc. Alkylthio group: methylthio group, octylthio group, hexadecylthio group, benzylthio group, 2- (diethylamino) ethylthio group, ethoxycarbonylmethylthio group,
Ethoxyethylthio group, phenoxyethylthio group, etc. Pyrazolyl group, imidazolyl group, triazolyl group, tetrazolyl group, etc. For example, Etc.

1 Two Three Four 5 6 7 8 9 Ten 11 12 13 14 15 16 17 18 19 20 twenty one twenty two twenty three twenty four twenty five 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 one two Three 124 125 126 127 128 129 130 131 132 133 134 135 136 137 138 139 140 141 142 143 144 145 146 147 148 149 150 151 152 153 154 155 156 157 158 159 160 161 162 163 164 165 166 167 168 169 170 171 172 173 174 175 176 177 178 179 180 181 182 183 184 185 186 187 188 189 190 191 192 193 194 195 196 197 In the present invention, at least one of the emulsion layers having color sensitivity is composed of two silver halide emulsion layers having different sensitivities, but such a color sensitive emulsion layer can be arbitrarily selected.

For example, a layer containing the magenta coupler of the present invention can be selected.

Only one of the two or more color-sensitive layers may have two layers as described above, or a plurality of layers may have two layers, and the structure thereof is arbitrary.

In the present invention, at least one of the emulsion layers having a color sensitivity composed of two silver halide emulsion layers having different sensitivities has a higher sensitivity than a layer far from a layer close to the support. It is a thing.

For example, a typical color photographic light-sensitive material is preferably formed by sequentially forming a red-sensitive layer, a green-sensitive layer and a blue-sensitive layer from a support, and at least one of the respective color-sensitive layers is used for sensitivity. The color photographic light-sensitive material of the present invention comprising two different layers, and at least one of the two color-sensitive layers thus formed is structured so that the support has a higher sensitivity layer. Can be For example, the red-sensitive layer can be composed of two layers, a high-sensitivity layer and a low-sensitivity layer, and the red-sensitive layer can be configured so that the one closer to the support becomes the high-sensitivity layer. This is one of the preferred embodiments of the present invention. In this case, a green-sensitive layer is provided on the side farther from the support than the red-sensitive layer, and the green-sensitive layer also has two layers,
Positioning the low-sensitivity layer of the green-sensitive layer closer to the support,
Each of the low-sensitivity layers of the red-sensitive layer and the green-sensitive layer can be arranged adjacent to each other (the intermediate layer may be interposed). Alternatively, also for the green-sensitive layer, one closer to the support can be the high-sensitivity layer. Further, focusing on the green-sensitive layer, one closer to the support can be the high-sensitivity layer, which is also a preferred embodiment of the present invention. The same applies to the blue-sensitive layer.

In the practice of the present invention, the same color-sensitive layer may be a single layer, but preferably 2 to 3 layers. Too many layers may affect the sharpness in terms of film thickness.

Specific examples of preferable layer constitutions include BS as a support, RH and RL for high-sensitivity and low-sensitivity red-sensitive layers, and GH and GL for high-sensitivity and low-sensitivity green-sensitive layers, and high-sensitivity and low-sensitivity When each of the blue-sensitive layers is BH, BL, IL is an intermediate layer, YC is a yellow filter layer, and Pro is a protective layer, B is sequentially provided from the support.
S, IL, RH, PL, IL, GL, GH, YC, B
It is possible to have a layered structure of L, BH, and Pro. This is a red-sensitive layer and a green-sensitive layer, the one closer to the support being the high-sensitivity layer. Similarly, BS, IL, R
H, RL, IL, GH, GL, YC, BL, BH, Pr
It may have a layered structure of o. This is a red-sensitive layer and a green-sensitive layer, the one closer to the support being the high-sensitivity layer. Furthermore, BS, IL, RH, RL, IL, GH,
A layer structure of GL, YC, BL, BH, Pro can be used. This is a green-sensitive layer in which the side closer to the support is the high-sensitivity layer. As a modification, RL and RH
It is possible to adopt a configuration in which an IL is further provided between and. Also, BS, RH, IL, RL, IL, GH, YC, B,
A YC layer structure can be used, where B is one blue-sensitive layer, that is, in this layer structure example, the blue-sensitive layer is one layer.

In addition, the present invention can be embodied as various layer configurations by appropriately recombining the above layer configurations.

In the light-sensitive material of the present invention, the difference in sensitivity between the high-sensitivity emulsion layer and the low-sensitivity emulsion layer is preferably 0.3 to 2.0 log E.

In the light-sensitive material of the present invention, the color-sensitive layer containing the dye image-forming coupler has a plurality of halogens having substantially the same color sensitivity and at least one of the color-sensitive layers having different sensitivities. It only has to have a silver halide emulsion layer. Here, "substantially the same color sensitivity" means, for example, in the wavelength range of any of the blue range, the green range and the red range in the spectral wavelength range in which a general color multilayer photosensitive material can be exposed. When the photosensitive layer has photosensitivity, the photosensitive layers are considered to have substantially the same color sensitivities even when the photosensitive zones are slightly different from each other in a certain wavelength range.

In addition, it is preferable that the photosensitive layers having the same color sensitivity are adjacent to each other without the photosensitive layers having different color sensitivities.

In addition, it is preferable that such a non-photosensitive intermediate layer contains a scavenger substance or the like that reacts with the oxidized product of the developing agent to deactivate it.

As the composition of silver halide in each emulsion layer, any composition can be used as described later. Silver iodobromide or silver bromide is preferable, but silver chlorobromide, silver chloroiodobromide or the like may be used.

Regarding the grain size of silver halide grains in the emulsion layer, the average grain size of silver halide grains in each high-sensitivity layer is 0.4 to 3.0.
μ, particularly 0.7 to 2.5 μ is preferable.

On the other hand, the average grain size of silver halide grains in each low-sensitivity layer is preferably 0.2 to 1.5 µ, and particularly preferably 0.2 to 1.0 µ.

Such silver halide grains, even if monodisperse,
Although it may be polydispersity, monodispersity is preferable from the viewpoint of improving graininess and sharpness.

The method for producing the emulsion layer having each of these color sensitivities is not limited, and various arbitrary methods can be applied, for example, known methods can be adopted. As the protective colloid to be used, any one such as gelatin may be used.

The silver coating amount of each emulsion layer is preferably about 4 to 40 mg / dm ² .

When the blue-sensitive layer is provided, it is preferable that the particles contained in the blue-sensitive layer have a small particle size of 0.3 to 0.5 μm in order to control light scattering.

The grain size of the silver halide grains described above is defined as the length of one side of a cube having the same volume as the silver halide grains.

In the present invention, the silver halide emulsion used may be either polydisperse emulsion or monodisperse emulsion. However, as described above, it is preferable to use a monodispersant. The light scattering properties can be controlled by using a monodisperse emulsion.

That is, the silver halide emulsion used in the present invention is preferably a monodisperse emulsion having a variation coefficient of grain size distribution of 20% or less, more preferably 15% or less. This coefficient of variation is Is a measure of monodispersity.

The film thickness of the light-sensitive material of the present invention is preferably 18 μm or less in dry film thickness.

Regarding the film thickness of each layer, by taking an enlarged image of the cross section of the dried sample with a scanning electron microscope and measuring the film thickness of each layer,
I can know.

The upper and lower limits of the total dry film thickness of all hydrophilic colloid layers on the side having the emulsion layer (hereinafter referred to as the film thickness on the emulsion side) are the silver halide emulsion contained, oil agents such as couplers, additives, gelatin. There is a preferable range depending on the volume occupied by the binder and the like. That is, the preferable thickness of the emulsion surface is 5 μm to 20 μm.
m, and more preferably 10 μm to 18 μm. Further, the distance from the outermost surface of the emulsion surface to the lower end of the emulsion layer closest to the support is preferably 14 μm or less, and the color sensitivity is different from that of the emulsion layer, and the emulsion layer next to the support has a lower end of 10 μm.
m or less is preferable.

In the present invention, silver halide grains having any grain structure can be used. For example, core / shell type silver halide grains can be preferably used. An example of this is a grain structure composed of two or more layers having different silver iodide contents. When grains having such a structure are used, silver iodobromide in which the layer having the highest silver iodide content (called the core) is other than the outermost surface layer (called the shell) is preferable. The inner layer (core) having the highest silver iodide content preferably has a silver iodide content of 6 to 40 mol%, more preferably 8 to 40 mol%.
It is 30 mol%, more preferably 10 to 20%. The silver iodide content of the outermost surface layer is preferably 0.5 to 6 mol%, more preferably 0.5 to 4.0 mol%.

The ratio of the shell portion of the core / shell type silver halide grains is preferably 10 to 80%, more preferably 15 to
70%, more preferably 20 to 60%.

The ratio of the core portion is 10 to 80 of the whole particle.
% Is preferable, and 20 to 50% is more preferable.

In the present invention, when a grain structure as described above is used, the difference in content between the core portion having a high silver iodide content and the shell portion having a low content of silver halide grains has a sharp boundary. However, the boundary may be continuously changing, which is not necessarily clear. Further, those having an intermediate layer having a silver iodide content intermediate between the core portion and the shell portion between the core and the shell are also preferably used. When the core / shell type silver halide grain having such an intermediate layer is used, the volume of the intermediate layer is preferably 5 to 60%, and more preferably 20 to 55% of the whole grain.

The difference in silver iodide content between the shell and the intermediate layer and between the intermediate layer and the core is preferably 3 mol% or more, and the difference in silver iodide content between the shell and the core is preferably 6 mol% or more.

When the core / shell type silver halide grains are used in the present invention, the average silver iodide content is preferably 4 to 20 mol%, more preferably 5 to 15 mol%. Further, silver chloride may be contained within a range that does not impair the effects of the present invention.

Such a core / shell type emulsion is disclosed in JP-A-59-177.
535, ibid. 60-138538, ibid. 59-52238,
60-143331, 60-35726 and 60
It can be manufactured by a known method disclosed in, for example, JP-A-258536.

When a core / shell type silver halide emulsion is grown starting from seed grains as in the method described in the examples, it may have a halogen composition region different from the core in the grain center part. It is possible. In such a case, the halogen composition of the seed grains may be any composition such as silver bromide, silver iodobromide, silver chloroiodobromide, silver chlorobromide, and silver chloride. Is 10 mol% or less, and silver iodobromide or silver bromide is preferable. The proportion of the total silver halide in the seed emulsion is preferably 50% or less, particularly preferably 10% or less.

The distribution state of silver iodide in the above-mentioned core / shell type silver halide grains can be detected by various physical measurement methods, and is described, for example, in the proceedings of the 56th Annual Meeting of the Photographic Society of Japan. The luminescence can be measured by measuring the luminescence at a low temperature or by an X-ray diffraction method.

When the core / shell type silver halide grain is used in the present invention, it may be a regular crystal such as a cube, a tetrahedron or an octahedron, may be composed of twins, or may be a mixture thereof. Normal crystals are preferred.

Next, in the practice of the present invention, a benzoyl-type coupler can be preferably used, which can be used as a yellow dye image-forming coupler when a blue-sensitive layer is provided to embody the present invention. As the benzoyl type coupler, a coupler represented by the following general formula [Y] can be preferably used.

General formula [Y] In the formula, R ¹ , R ² and R ³ may be the same or different,
Hydrogen atom, halogen atom (for example, each atom of fluorine, chlorine, bromine, etc.), alkyl group (for example, methyl, ethyl, etc.)
Allyl, dodecyl, etc. groups, aryl groups (eg, phenyl, naphthyl groups, etc.), alkoxy groups (eg, methoxy, ethoxy, dodecyloxy groups, etc.), acylamino groups (eg, acetamide, α (p-dodecyloxy). Phenoxy) butanamide and the like), carbamoyl group (eg, carmoyl, N, N-dimethylcarbamoyl,
N-δ- (2.4-di-tert-amylphenoxy) butylcarbamoyl and other groups), alkoxycarbonyl group (eg ethoxycarbonyl, dodecyloxycarbonyl, α)
(Dodecyloxycarbonyl) ethoxycarbonyl, etc.), sulfonamide group (eg, methanesulfonamide, p-dodecyloxybenzenesulfonamide, N-)
Each group such as benzyldodecanesulfonamide) or a sulfamoyl group (eg, sulfamoyl, N-methylsulfamoyl, N-δ- (2.4-di-tert-amylphenoxy) butylsulfamoyl, N, N-diethylsulfa) Each group such as moyle) is represented.

R ⁴ , R ⁵ , R ⁶ and R ⁷ may be the same or different,
Respectively hydrogen atom, alkyl group (eg methyl, ethyl, te
rt-butyl etc.), alkoxy group (eg methoxy, ethoxy, propoxy, octoxy etc.), aryloxy group (eg phenoxymethylphenoxy etc.), acylamino group (eg acetamide, α-
(2.4-di-tert-amylphenoxy) butanamide or the like) or a sulfonamide group (eg, methanesulfonamide, p-dodecylbenzenesulfonamide, N-benzyldodecanesulfonamide or the like).

W is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), alkyl group (eg, methyl, ethyl, tert-butyl group, etc.), alkoxy group (eg, methoxy, ethoxy, propoxy, octoxy, etc.) Group), an aryloxy group (eg, phenoxy, methylphenoxy, etc.), or a dialkylamino group (eg, dimethylamino, N-butyl-N-octylamino, etc.).

X represents a hydrogen atom or a removable group. A preferred group as the removable group is represented by the general formula [Y '].

General formula [Y '] Y represents a non-metal atomic group necessary for forming a 5- or 6-membered ring. (The formed cyclic compound is, for example, 2,5-dioxo-imidazoline, 2,5-pyrrolidinedione, 1,3
-Isoindoledione, 2,3,5-trioxo-imidazolidine, 2,5-dioxo-triazolidine,
2,4-oxazolidinedione, 2,4-thiazolidinedione, 2 (1H) -pyridone, 2 (1H) -pyrimidone, 2 (1H) -pyrazone, 5 (1H) -imidazolone, 5 (1H) -triazolone, 2 (1H) -pyrimidone, 2-pyrazolone (5), 2-isothiazolone (5), 2
(1H) -quinoxazolone, 4 (3H) -pyrimidone, 2-benzoxazolone, 4-isoxazolone
(5), 3-Fluorone (2), 4-imidazolone (2), 3-pyrazolone, 2-tetrazolone (5), 3-tetrazolone (5)
Represents each derivative such as. ) Specific examples of the yellow coupler represented by the general formula [Y] are shown below.

[Y-1] [Y-2] [Y-3] [Y-4] [Y-5] [Y-6] [Y-7] [Y-8] [Y-9] [Y-10] [Y-11] [Y-12] [Y-13] [Y-14] [Y-15] For the silver halide emulsion, any silver halide such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloroiodobromide and silver chloride can be used. However, silver bromide, silver iodobromide, and silver chloroiodobromide are particularly preferable.

The silver halide grains used in the silver halide emulsion may be those obtained by any of the acidic method, the neutral method and the ammonia method. The grains may be grown at one time, or may be grown after forming seed grains. The method of forming seed particles and the method of growing seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed at the same time, or the other may be mixed in a liquid containing either one. Alternatively, it may be produced by sequentially adding halide ions and silver ions simultaneously while controlling the pH and pAg in the mixing vessel while considering the critical growth rate of silver halide crystals. By this method, silver halide grains having a regular crystal form and a substantially uniform grain size can be obtained. The conversion may be used at any step in the formation of AgX to change the halogen composition of the grains.

A known silver halide solvent such as ammonia, thioether or thiourea can be present during the growth of silver halide grains.

The silver halide grains include cadmium salt, zinc salt, lead salt, thallium salt, iridium salt (including complex salt), rhodium salt (including complex salt) and iron salt (in the process of forming grains and / or growing grains). By adding a metal ion using at least one selected from the group consisting of complex salts), these metal elements can be contained inside the particles and / or on the surface of the particles, and by placing in a suitable reducing atmosphere, Reduction sensitization nuclei can be imparted to the inside of the grain and / or the surface of the grain.

In the silver halide emulsion, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or may be contained. When removing the salts, Research Disclosure (hereinafter R)
(Abbreviated as D)) No. 17643, Item II.

The silver halide grain may be one having a uniform silver halide composition distribution within the grain, or may be a core / shell grain having a different silver halide composition between the inside of the grain and the surface layer.

The silver halide grain may be a grain in which a latent image is mainly formed on the surface, or may be a grain in which a latent image is mainly formed inside the grain.

The silver halide grain may have a regular crystal form such as a cube, an octahedron or a tetradecahedron, or may have an irregular crystal form such as a sphere or a plate. In these grains, any ratio of {100} plane to {111} plane can be used. Further, it may have a composite form of these crystal forms, and particles of various crystal forms may be mixed.

The size of silver halide grains may be 0.05 to 30 .mu.m, preferably 0.1 to 20 .mu.m.

The silver halide emulsion may have any grain size distribution. An emulsion having a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion having a narrow grain size distribution (referred to as a monodisperse emulsion. The monodisperse emulsion referred to here is the standard deviation of the grain size distribution. The value when divided by the average particle size is 0.02 or less, where the particle size is in accordance with the above definition), or may be a mixture of several kinds. Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used.

As the silver halide emulsion, two or more kinds of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion can be chemically sensitized by a conventional method. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
A noble metal sensitization method using gold and other noble metal compounds can be used alone or in combination.

The silver halide emulsion can be optically sensitized to a desired wavelength range by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dyes may be used alone or in combination of two or more. A dye that does not have a spectral sensitizing action by itself with a sensitizing dye, or a compound that does not substantially absorb visible light, and that contains a supersensitizer that enhances the sensitizing action of the sensitizing dye in the emulsion. Good.

As the sensitizing dye, a cyanine dye, a merocyanine dye,
Complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, steryl dyes and hemioxanol dyes are used.

Particularly useful dyes are cyanine dyes, merocyanine dyes,
And a complex merocyanine dye.

Silver halide emulsion, during the manufacturing process of the light-sensitive material, during storage,
Alternatively, for the purpose of preventing fogging during photographic processing or maintaining stable photographic performance, during chemical ripening, at the end of chemical ripening, and / or after the end of chemical ripening, before coating a silver halide emulsion, Compounds known in the art as antifoggants or stabilizers can be added.

Binder (or protective colloid) for silver halide emulsion
As for, it is advantageous to use gelatin, but synthetic hydrophilic polymer substances such as gelatin derivatives, gelatin and other high molecular weight graft polymers, other proteins, sugar derivatives, cellulose derivatives, and single or copolymers. Hydrophilic colloids such as can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the silver halide emulsion of the present invention include one or more hardeners that crosslink binder (or protective colloid) molecules to enhance film strength. By using it, a dura mater can be obtained. The hardener can be added in an amount such that the photosensitive material can be hardened to the extent that it is not necessary to add the hardener to the processing liquid, but it is also possible to add the hardener to the processing liquid.

For example, aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives) 2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5- Triacryloyl-hexahydro-s-triazine, 1,
3-vinylsulfonyl-2-propanol, etc., active halogen compounds (2,4-dichloro-6-hydroxy-)
s-triazine etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid etc.) and the like can be used alone or in combination.

A plasticizer may be added to the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material for the purpose of increasing flexibility. Preferred plasticizers are RD17643, Section XII, A
The compound described in 1.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material may contain a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability.

For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or these and acrylic acid, A polymer having a monomer component of a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid and the like can be used.

In the color development processing, the emulsion layer of the light-sensitive material forms a dye by a coupling reaction with an oxidant of an aromatic primary amine developer (eg, p-phenylenediamine derivative, aminophenol derivative). A coupler is used. The dye-forming couplers are usually selected so that a dye that absorbs the light of the light-sensitive spectrum of the emulsion layer is formed for each emulsion layer. A magenta dye forming coupler is used in the sensitive emulsion layer and a cyan dye forming coupler is used in the red sensitive emulsion layer. However, a silver halide color photographic light-sensitive material may be prepared by a method different from the above combination depending on the purpose.

It is desirable that these dye-forming couplers have a group called a ballast group, which has a carbon number of 8 or more, which makes the coupler non-diffusible. Also, these dye-forming couplers need only reduce 4 molecules of silver ions in order to form 1 molecule of dye, but even if they are 4 equivalence, they need only reduce 2 molecules of silver ions. Either of two equivalence may be used. The dye-forming coupler has a color-correcting effect and is coupled with a colored coupler and an oxidation product of a developing agent to develop a development inhibitor, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent. , Hardeners, antifoggants, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizing compounds that release photographically useful fragments. Of these, couplers that release development inhibitors with development and improve image sharpness and image graininess are DIR.
Called a coupler. Instead of the DIR coupler, a DIR compound which releases a development inhibitor at the same time as producing a colorless compound by coupling reaction with an oxidized product of a developing agent may be used.

The DIR coupler and the DIR compound used are those in which the inhibitor is directly bonded to the coupling position and those in which the inhibitor is 2
Those linked to the coupling position via a valent group so that the inhibitor is released by an intramolecular nucleophilic reaction in the group that has left due to the coupling reaction or an intramolecular electron transfer reaction ( Timing DIR couplers, and timing DIR compounds). Further, as the inhibitor, one that is diffusible after withdrawal and one that is not so diffusible can be used alone or in combination depending on the application. A colorless coupler (also referred to as a competing coupler) which undergoes a coupling reaction with an oxidized product of an aromatic primary amine developer but does not form a dye can also be used in combination with the dye-forming coupler.

As the yellow dye-forming coupler, a known acylacetanilide type coupler can be preferably used.
Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous. Specific examples of yellow color forming couplers that can be used include, for example, U.S. Pat.
No. 7, No. 3,265,506, No. 3,408,194, No. 3,551,1
No. 55, No. 3,582,322, No. 3,725,072, No. 3,891,
No. 445, West German patent 1,547,868, West German application published 2,219,91
No. 7, No. 2,261,361, No. 2,414,006, British Patent No.
1,425,020, JP-B-51-10783, JP-A-47-26133, 4
8-73147, 50-5034, 50-87650, 50-123342
50, 130442, 51-21827, 51-102636, 51-102636
52-82424, 52-115219, 58-95346, etc.

As the cyan dye forming coupler, a phenol or naphthol type coupler is generally used. Specific examples of cyan color couplers that can be used include, for example, U.S. Pat.
No. 730, No. 2,474,293, No. 2,801,171, No. 2,89
5,826, 3,476,563, 3,737,326, 3,7
58,308, 3,893,044, JP-A-47-37425
No. 50, No. 50-10135, No. 50-25228, No. 50-112038, No. 5
The couplers described in JP-A Nos. 0-117422 and 50-130441 and the couplers described in JP-A-58-98731 are preferable.

Dye-forming couplers, colored couplers, DIR couplers, DIRs that do not need to be adsorbed on the silver halide crystal surface
Compounds, image stabilizers, antifoggants, UV absorbers,
Among the fluorescent whitening agents, various methods such as solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method can be used for the hydrophobic compound, which is the chemical structure of the hydrophobic compound such as coupler. It can be appropriately selected according to the above. As the oil-in-water emulsion dispersion method, a conventionally known method of dispersing a hydrophobic additive such as a coupler can be applied, and usually has a boiling point of about 150 ° C.
A low boiling point and / or a water-soluble organic solvent may be used in combination with the above high-boiling point organic solvent, if necessary, and a surfactant is used in a hydrophilic binder such as an aqueous gelatin solution with a stirrer, a homogenizer, It may be added to the target hydrophilic colloid liquid after emulsifying and dispersing using a dispersing means such as a colloid mill, a flow jet mixer, an ultrasonic device. A step of removing the low boiling point organic solvent may be added at the same time as the dispersion liquid or the dispersion.

Organic solvents with a boiling point of 150 ° C or higher such as phenol derivatives, phthalic acid alkyl esters, phosphoric acid esters, citric acid esters, benzoic acid esters, alkylamides, fatty acid esters and trimesic acid esters that do not react with the oxidized product of the developing agent as a high boiling point solvent. A solvent is used.

Low-boiling or water-soluble organic solvents can be used with or instead of high-boiling solvents. As a low boiling point substantially water-insoluble organic solvent, ethyl acetate, propyl acetate, butyl acetate, butanol, chloroform,
There are carbon tetrachloride, nitromethane, nitroethane, benzene, etc.

Dye-forming couplers, DIR couplers, color couplers, DIR compounds, image stabilizers, color antifoggants, UV absorbers, fluorescent brighteners, etc. are alkaline when they have an acid group such as carboxylic acid or sulfonic acid. It can also be introduced into the hydrophilic colloid as an aqueous solution.

Dissolving a hydrophobic compound in a solvent having a low boiling point solvent alone or in combination with a high boiling point solvent, as a dispersion aid when dispersed in water using mechanical or ultrasonic waves, an anionic surfactant, a nonionic surfactant, Cationic and amphoteric surfactants can be used.

Between the emulsion layers of the light-sensitive material (the same color-sensitive layers and / or different color-sensitive layers), the oxidant of the developing agent or the electron transfer agent migrates to cause color turbidity or deterioration of sharpness,
An antifoggant can be used to prevent the graininess from being noticeable.

The color antifoggant may be contained in the emulsion layer itself,
An intermediate layer may be provided between adjacent emulsion layers and contained in the intermediate layer.

An image stabilizer that prevents deterioration of a dye image can be used in the light-sensitive material. Compounds which can be preferably used are those described in Item VII, J of RD17643.

The hydrophilic colloid layers such as the protective layer and the intermediate layer of the photosensitive material may contain an ultraviolet absorber in order to prevent fogging due to discharge caused by charging of the photosensitive material due to friction and the like and to prevent deterioration of the image by ultraviolet rays. Good.

A formalin scavenger can be used in the light-sensitive material in order to prevent deterioration of the magenta dye-forming coupler and the like due to formalin during storage of the light-sensitive material.

When the hydrophilic colloid layer of the light-sensitive material contains a dye, an ultraviolet absorber or the like, they may be mordanted with a mordant such as a cationic polymer.

To the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material, compounds such as a development accelerator and a development retarder which change the developability and a bleaching accelerator can be added. The compound which can be preferably used as the development accelerator is RD1764.
No. 3, Item XXI, B to D, and the development retarder is the compound, No. 17643, Item XXI, Item E. A black and white developing agent and / or its precursor may be used for the purpose of accelerating the development and other purposes.

The emulsion layer of the photographic light-sensitive material contains polyalkylene oxide or its derivative such as ether, ester, amine, thioether compound, thiomorpholine, quaternary ammonium compound, urethane derivative for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may include a urea derivative, an imidazole derivative and the like.

A fluorescent whitening agent can be used in the light-sensitive material for the purpose of emphasizing the whiteness of the white background and making the coloring of the white background inconspicuous. The compound which can be preferably used as the fluorescent brightening agent is described in the item V of RD17643.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an irradiation prevention layer. In these layers and / or in the emulsion layers, dyes which may be bleached or bleached from the light-sensitive material during the development process may be incorporated. Examples of such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes, and azo dyes.

A matting agent may be added to the silver halide emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material for the purpose of reducing the gloss of the light-sensitive material, improving writing properties, preventing sticking of the light-sensitive materials to each other, and the like. Any matting agent may be used, for example, silicon dioxide, titanium dioxide, magnesium dioxide, aluminum dioxide, barium sulfate,
Examples thereof include calcium carbonate, acrylic acid and methacrylic acid polymers and their esters, polyvinyl resins, polycarbonates, styrene polymers and their copolymers. The matting agent preferably has a particle size of 0.05 μ to 10 μ. The amount to be added is preferably 1 to 300 mg / m ² .

A lubricant may be added to the light-sensitive material to reduce sliding friction.

An antistatic agent for the purpose of antistatic can be added to the light-sensitive material. The antistatic agent may be used in the antistatic layer on the side of the support on which the emulsion is not laminated, and a protective colloid layer other than the emulsion layer on the side on which the emulsion layer is laminated to the emulsion layer and / or the support. May be used for. Antistatic agents preferably used are the compounds described in RDI17643 XIII.

For the photographic emulsion layer and / or other hydrophilic colloid layer of the light-sensitive material, coating property is improved, antistatic property, slipperiness is improved, emulsion dispersion, adhesion prevention, photographic properties (development promotion, hardening, sensitization, etc.)
Various surfactants can be used for the purpose of improvement.

The support used in the light-sensitive material of the present invention includes an α-olefin polymer (for example, polyethylene, polypropylene,
Flexible reflection support such as paper laminated with ethylene / butene copolymer), synthetic paper, etc., semi-synthetic or synthetic polymer such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene phthalate, polycarbonate, polyamide, etc. And a flexible support in which a reflective layer is provided on these films, glass, metal, pottery, and the like.

The photosensitive material is subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the surface of the support as necessary, and then directly or on the surface of the support, antistatic property, dimensional stability, abrasion resistance, hardness, It may be applied via one or more subbing layers to improve antihalation properties, friction properties, and / or other properties.

At the time of applying the light-sensitive material, a thickener may be used to improve the coatability. For a hardener such as a hardening agent, which has a high reactivity and causes gelation before coating when it is added to the coating solution in advance, it is preferable to mix it just before coating with a static mixer or the like. preferable.

As the coating method, extrusion coating and curtain coating, which can simultaneously coat two or more layers, are particularly useful, but basket coating is also used depending on the purpose. Further, the coating speed can be arbitrarily selected.

The surfactant is not particularly limited, and examples thereof include natural surfactants such as saponin, nonionic surfactants such as alkylene oxide-based, glycerin-based, and dalicidol-based, higher alkylamines, quaternary ammonium salts, pyridine and others. Heterocycles, cation surfactants such as phosphonium or sulfonium, carboxylic acids, sulfonic acids,
Anionic surfactants containing an acidic group such as phosphoric acid, sulfuric acid ester, phosphoric acid ester, etc., and amphoteric surfactants such as sulfuric acid or phosphoric acid ester of amino acids, aminosulfonic acids, aminoalcohol may be added. Further, it is also possible to use a fluorine-based surfactant for the same purpose.

To obtain a dye image using the light-sensitive material of the present invention, after exposure,
Perform color photo processing. Color processing includes a color development processing step, a bleaching processing step, a fixing processing step, a water washing processing step and a stabilization processing step if necessary, but instead of a processing step using a bleaching solution and a processing step using a fixing solution. In addition, the bleach-fixing treatment step can be carried out using the 1-bath bleach-fixing solution, and the mono-bath processing step using the 1-bath development bleach-fixing solution capable of performing color development, bleaching and fixing in a single bath. You can also do

In combination with these treatment steps, a pre-hardening treatment step, a neutralizing step thereof, a stop fixing treatment step, a post-hardening treatment step and the like may be performed. In these processes, instead of the color development processing step, a color developing agent or its precursor may be contained in the material and the development processing may be performed by an activator solution. Can be applied. Typical processing is shown below among these processings. (These steps include any one of a washing step, a washing step and a stabilizing step as the final step.) ・ Color development processing step-bleaching step-fixing step-Color development processing step-bleach-fixing step Process-Pre-hardening process-Color development process-Stop fixing process-Water washing process-Bleaching process-Fixing process-Water washing process-Post-hardening process-Color development process-Water washing process-Supplement Color development processing step-stop processing step-bleaching processing step-fixing processing step-activator-processing step-bleach fixing processing step-activator-processing step-bleaching processing step-fixing processing step-monobath processing step The processing temperature is usually Although it is selected in the range of 10 ° C to 65 ° C,
The temperature may exceed 65 ° C. Preferably from 25 ° C
Treated at 45 ° C.

The color developing solution generally comprises an alkaline aqueous solution containing a color developing agent. The color developing agent is an aromatic primary amine color developing agent, and includes aminophenol-based and p-phenylenediamine-based derivatives. These color developing agents can be used as salts of organic acids and inorganic acids, for example, salt acid, sulfate, p-toluenesulfonate, sulfite, oxalate, benzenesulfonate and the like. it can.

These compounds generally account for about 0.1 for Color Developer 1.
It is used at a concentration of -30 g, more preferably at a concentration of about 1-15 g for color developer 1. If the amount added is less than 0.1 g, sufficient color density cannot be obtained.

Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, 5-amino-
2-oxy-toluene, 2-amino-3-oxy-toluene, 2-oxy-3-amino-1,4-dimethyl-benzene and the like are included.

Particularly useful primary aromatic amine color developing agents are N, N-
A dialkyl-p-phenylenediamine compound,
The alkyl and phenyl groups may or may not be substituted. Among them, examples of particularly useful compounds include N, N-dimethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N, N-dimethyl-p-phenylenediamine hydrochloride, and 2-amino-. 5- (N-ethyl-N-dodecylamino) -toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylamino Aniline, 4-amino-3-methyl-N, N-diethylaniline, 4-amino-N- (2-methoxyethyl) -N-
Examples thereof include ethyl-3-methylaniline-p-toluenesulfonate.

The color developing agents may be used alone or in combination of two or more kinds. Furthermore, the color developing agent may be incorporated in a color photographic material. In this case, the silver halide color photographic light-sensitive material can be treated with an alkali solution (activator solution) instead of the color developing solution, and the bleach-fixing process is carried out immediately after the alkali solution treatment.

The color developing solution used in the present invention may contain an alkaline agent usually used in a developing solution, such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, sodium carbonate, potassium carbonate, sodium sulfate, sodium metaborate or borax. And various additives such as benzyl alcohol, alkali metal halides such as potassium bromide or potassium chloride, or development modifiers such as citrazinic acid, and preservatives such as hydroxylamine or sulfite. You may. Further, various antifoaming agents and surfactants, and an organic solvent such as methanol, dimethylformamide or dimethylsulfoxide, etc. may be appropriately contained.

The pH of the color developer used in the present invention is usually 7 or more, preferably about 9 to 13.

In the color developer used in the present invention, if necessary, diethylhydroxyamine, tetronic acid, tetronimide, 2-anilineethanol, dihydroxyacetone, secondary aromatic alcohol, hydroxamic acid, bentose or hexose may be used as an antioxidant. , Pyrogallol-1,
It may contain 3-dimethyl ether or the like.

In the color developing solution used in the present invention, various chelating agents can be used together as a sequestering agent. For example, as the chelating agent, an amine polycarboxylic acid such as ethylenediaminetetraacetic acid or diethylenetriaminopentaacetic acid, 1
-Organophosphonic acid such as hydroxyethylidene-1,1'-diphosphonic acid, aminopolyphosphonic acid such as aminotri (methylenephosphonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acid such as citric acid or gluconic acid, 2-phosphonobutane, 1 , 2,4-tricarboxylic acid and other phosphonocarboxylic acids, tripolyphosphoric acid, hexametaphosphoric acid and other polyphosphoric acids, and polyhydroxy compounds.

The bleaching process may be performed simultaneously with the fixing process as described above, or may be performed individually. As the bleaching agent, a metal complex salt of an organic acid is used, and for example, an organic acid such as polycarboxylic acid, aminopolycarboxylic acid or oxalic acid, citric acid, etc., in which metal ions such as iron, cobalt and copper are coordinated is used. . Among the above-mentioned organic acids, the most preferable organic acid is polycarboxylic acid or aminopolycarboxylic acid. Specific examples of these include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid,
Ethylenediamine-N- (β-oxyethyl) -N,
N'-N'-triacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid, dihydroxyethylglycine citric acid (or tartaric acid), ethyletherdiaminetetraacetic acid, glycoletherdiaminetetraacetic acid, ethylenediaminetetraacetic acid Propionic acid, phenylenediamine tetraacetic acid, etc. can be mentioned. These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. 5 to 450 g of these bleaches
/, More preferably 20 to 250 g /.

As the bleaching solution, in addition to the bleaching agent as described above, a solution having a composition containing sulfite as a preservative is applied if necessary. Further, a bleaching solution having a composition containing an ethylenediaminetetraacetate iron (III) complex salt bleaching agent and adding a large amount of a halide such as ammonium bromide may be used. As the halide, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. may be used. it can.

The bleaching solution used in the present invention, JP-A-46-280, JP-B-45-8506, 46-566, Belgium Patent 770,910,
Various bleaching accelerators described in JP-B-45-8836, JP-B-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

The bleaching solution is used at a pH of 2.0 or higher, but generally 4.0 to 9.
Used in 5, preferably used in 4.5-8.0, most preferably 5.0-7.0.

The fixer may have a commonly used composition. As the fixing agent, a compound which reacts with silver halide to form a water-soluble complex salt as used in a usual fixing process, for example, thiosulfate such as calcium thiosulfate, sodium thiosulfate and ammonium thiosulfate, potassium thiocyanate. Typical examples thereof include thiocyanates such as sodium thiocyanate and ammonium thiocyanate, thiourea and thioether. These fixing agents are used in an amount of 5 g / or more, which can be dissolved, but generally 70 to 250 g /. A part of the fixing agent can be contained in the bleaching tank, and conversely, a part of the bleaching agent can be contained in the fixing tank.

The bleaching solution and / or the fixing solution have various pH buffers such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide. The agents can be contained alone or in combination of two or more. Furthermore, various fluorescent whitening agents, antifoaming agents or surfactants may be contained. Further, hydroxylamine, hydrazine, preservatives such as bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids or stabilizers such as nitroalcohol, nitrates, hardeners such as water-soluble aluminum salts, An organic solvent such as methanol, dimethylsulfamide, dimethylsulfoxide or the like may be appropriately contained.

The pH of the fixer used is 3.0 or higher, but generally 4.5 to 1
0, preferably 5 to 9.5, and most preferably 6 to 9.

Examples of the bleaching agent used in the bleach-fixing solution include the metal complex salts of organic acids described in the bleaching treatment step, and preferable compounds and concentrations in the processing solution are the same as in the bleaching treatment step.

As the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the above-mentioned bleaching agent and, if necessary, a sulfite as a preservative is applied. Further, a bleach-fixing solution having a composition in which a small amount of an ethylenediaminetetraacetate iron (III) complex salt bleaching agent and the above-mentioned silver halide fixing agent and a halide such as ammonium bromide are added, or conversely, a halide such as ammonium bromide is used. A bleach-fix solution consisting of a large amount of added composition, and further ethylenediaminetetraacetic acid iron (II
I) A special bleach-fixing solution having a composition comprising a combination of a complex salt bleaching agent and a large amount of a halide such as ammonium bromide can also be used. As the halide,
In addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like can be used.

Examples of the silver halide fixing agent that can be contained in the bleach-fixing solution include the stabilizers described in the fixing processing step. The concentration of the fixing agent and the pH buffering agent and other additives that can be contained in the bleach-fixing solution are the same as those in the fixing processing step.

The pH of the bleach-fix solution is 4.0 or higher, but it is generally 5.0.
~ 9.5, preferably 6.0-8.5, most preferably 6.5-8.5.

〔Example〕

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

In all of the following examples, the addition amount in the silver halide photographic light-sensitive material is per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver.

A multilayer color photographic element sample A was prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support.

Sample-A (Comparative) First layer: Antihalation layer (HC-1) Gelatin layer containing black colloidal silver.

Second layer: intermediate layer (IL) A gelatin layer containing an emulsified dispersion of 2,5-di-t-octylhydroquinone.

Third layer: low-sensitivity red-sensitive silver halide emulsion layer (RL-1) Average grain size () 0.38 μm, monodispersed emulsion of AgBrI containing 6 mol% of AgI (emulsion I) ... Silver coating amount 1.8 g / m ² Sensitizing dye I: 6 × 10 ^-5 mol per mol of silver Sensitizing dye II: 1.0 × 10 ^-5 mol per mol of silver Cyan coupler (C-1): relative to 1 mol of silver 0.06 moles Colored cyan coupler (CC-1) ... 0.003 moles per 1 mole of silver DIR compound (D-1) ... 0.0035 moles per 1 mole of silver Fourth layer; high-sensitivity red-sensitive silver halide emulsion Layer (RH-1) Average particle size () 0.75 μm, AgBrI containing 7.0 mol% AgI Monodisperse emulsion (Emulsion II) ... Silver coating amount 1.3 g / m ² Sensitizing dye I ... 1 mol silver 0.02 mol colored cyan coupler with respect to 3 × 10 ^-5 mol sensitizing dye II ...... 1 mol of silver relative to 1.0 × 10 ^-5 mol cyan coupler (C-1) ...... silver mole for -(CC-1) ... 0.0015 mol per mol of silver DIR compound (D-1) ... 0.001 mol per mol of silver Fifth layer; Intermediate layer (IL) Same as the second layer, gelatin layer .

Sixth layer; low-sensitivity green-sensitive silver halide emulsion layer (GL-1) Emulsion-I ... Coating amount of silver 1.5 g / m ² Sensitizing dye III: 2.5 × 10 ^-5 mol increase per mol of silver Dye IV: 1.2 × 10 ^-5 mol / mol silver Magenta coupler (EM-I): 0.050 mol / mol silver Colored magenta coupler (CM-1): 1 mol silver 0.009 mol DIR compound (D-1) ... 0.0040 mol per 1 mol of silver Seventh layer; high-sensitivity green-sensitive silver halide emulsion layer (GH-1) Emulsion-II ... Coating silver amount 1.4 g / m ² Sensitizing dye III: 1.5 × 10 ^-5 mol / mol of silver Sensitizing dye IV 1.0 × 10 ^-5 mol / mol of silver Magenta coupler (EM-1): 0.020 / mol of silver Molar colored magenta coupler (CM-1) ... 0.002 mol per mol of silver DIR compound (D-1) ... 0.0010 mol per mol of silver Eighth layer: yellow Iruta layer (YC-1) Gelatin layer containing an emulsified dispersion of yellow colloidal silver and 2,5-di -t- octylhydroquinone.

Ninth layer: low-sensitivity blue-sensitive silver halide emulsion layer (BL-1) Monodisperse emulsion (Emulsion III) consisting of AgBrI with an average grain size of 0.40 μm and AgI 6 mol% ... Silver coating amount 0.9 g / m ² sensitization Dye V: 1.3 × 10 ^-5 mol per mol of silver Yellow coupler (EY-1): 0.29 mol per mol of silver 10th layer: High-sensitivity blue-sensitive emulsion layer (BH-1) Average grain Monodisperse emulsion consisting of AgBrI containing 0.8 μm in diameter and 15 mol% AgI (Emulsion IV) ... Silver coating amount 0.5 g / m ² Sensitizing dye V …… 1.0 × 10 ⁻⁵ mol per 1 mol silver Yellow coupler (EY -1) ... 0.08 mol per mol of silver DIR compound (D-1) ... 0.0015 mol per mol of silver 11th layer; first protective layer (Pro-1) silver iodobromide (1 mol of AgI) % Average particle diameter 0.07 μm) Silver coating amount 0.5 g / m ² UV absorber (gelatin layer containing UV-1 and UV-2).

12th layer: 2nd protective layer (Pro-2) A gelatin layer containing polymethylmethacrylate particles (diameter 1.5 μm) and formalin scavenger (HS-1).

In addition to the above composition, each layer contains a gelatin hardening agent (H-
1) and a surfactant were added.

The compounds contained in each layer of Sample 1 are as follows.

Sensitizing dye I; Anhydro 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) thiacarbocyanine hydroxide Sensitizing dye II; Anhydro 9-ethyl-3,3'- The- (3-
Sulfopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide Sensitizing dye III; Anhydro 5,5'-diphenyl-9-ethyl-3,3'-di- (3-sulfopropyl) Oxacarbocyanine hydroxide Sensitizing dye IV; Anhydro 9-ethyl-3,3'-di- (3-
Sulfopropyl) -5,6,5 ', 6'-dibenzooxacarbocyanine hydroxide Sensitizing dye V; Anhydro 3,3'-di- (3-sulfopropyl) -4,5-benzo-5'-methoxy Thiacyanin C-1 CC-1 D-1 EM-1 CM-1 EY-1 UV-1 UV-2 HS-1 H-1 Sample A thus prepared was replaced with a magenta coupler and a yellow coupler as shown in Table-1, and the respective photosensitive layers were combined as shown in Table 2 below to prepare Samples B to I. The film thickness of each of the samples A to I was 18 μm.

It should be noted that, in Table 1, the column of Y coupler shows the above.
EY-1 and Y numbers of those exemplified as the above-mentioned preferable benzoyl type couplers, which are described in the column of M couplers are those of the above EM-1 (comparative coupler) and the above-mentioned pyrazolotriazole system of the present invention. It is an exemplary compound number of the coupler.

Furthermore, as Sample J (invention), Sample H was prepared by changing the silver halide emulsion of each color-sensitive layer to polydispersity. However, this average particle diameter approximated that of the comparative sample (A). The coefficient of variation was set to 40.

Each of the sample Nos. A to I thus prepared was subjected to wedge exposure using white light and then subjected to the following development processing.

Treatment process (38 ℃) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Washing 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying The composition of the treatment solution used in each processing step is as follows. Is the street.

(Color developer) 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) -aniline ・ sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine ・ 1/2 sulfate 2.0 g anhydrous potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Add water to make 1.

<Bleach> Ethylenediaminetetraacetic acid iron ammonium salt 100.g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0m Water is added to adjust the pH to 6.0 using ammonia water.

<Fixing solution> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 and pH is adjusted to 6.0 using acetic acid.

<Stabilizer> Formalin (37% aqueous solution) 1.5m Conidax (Konishi Rokusha Kogyo Co., Ltd.) 7.5m Add water to make 1.

The sharpness (MTF) and RMS of each of the obtained samples were measured using white light (W). The results are shown in Table-3.

The sharpness improving effect is due to the MTF (Modulation Tra
nsfer Function) was obtained and indicated as a relative value of MTF at 40 lines / mm (Sample No. 1 is 100).

The RMS value (indicating the graininess) is indicated by 1000 times the standard deviation of the fluctuation of the density value which occurs when the density of the minimum density + 1.2 is scanned by a microdecitometer having an opening scanning area of 250 μm ² .

As is clear from Table 3, the sample of the present invention has improved RMS value and MTF value as compared with the comparative sample. That is, comparing the sample A, which is a comparative sample, with the samples B to J of the present invention, it can be seen that the sample of the present invention is superior. Further, it can be seen that particularly, for Samples G to I, a remarkable improvement effect is observed.

The effect of the present invention is also seen in Sample J using the polydisperse emulsion.

〔The invention's effect〕

As described above, according to the present invention, a silver halide color photographic light-sensitive material excellent in both sharpness and graininess can be obtained.

Claims (1)

[Claims] 1. A halogenated product comprising two or more silver halide emulsion layers having different color sensitivities on a support, and at least one of the emulsion layers is composed of two silver halide emulsion layers having different sensitivities. In a silver color photographic light-sensitive material, an emulsion layer having a color sensitivity consisting of at least one two silver halide emulsion layers having different sensitivities has a sensitivity closer to a layer closer to the support than to a layer distant from the support. A novel layer characterized in that at least one layer having high color sensitivity and containing a pyrazolotriazole-based magenta coupler represented by the following general formula [I] or [II]: Composition silver halide color photographic light-sensitive material. General formula [I] General formula (II) However, in the above general formula, R ₁ and R ₂ each represent an alkyl, aryl, or heterocyclic group which may be bonded via a bonding group and which may have a substituent. Z represents a hydrogen atom or a group that is released when a dye is formed by coupling with an oxidized product of an aromatic primary amine color developing agent.