JP2002351028A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide color photographic sensitive material excellent in color reproducibility and suitability to a light source and free of a change in photographic properties due to variation in processing. SOLUTION: The silver halide color photographic sensitive material has at least one blue-sensitive silver halide emulsion layer containing a yellow coupler, at least one green-sensitive silver halide emulsion layer containing a magenta coupler, at least one red-sensitive silver halide emulsion layer containing a cyan coupler and at least one non-photosensitive layer on a substrate, the sensitivity SR (580) of the red-sensitive silver halide emulsion layer at 580 nm has the relation of 0.25<=SR (max)-SR (580)<=0.9 to the sensitivity SR (max) of the layer at the maximum sensitivity wavelength and at least one of the silver halide emulsion layers or the non-photosensitive layer contains a compound (A) having at least 3 heteroatoms and increasing the photographic sensitivity of a photosensitive material when the material. contains the compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic material. More specifically, the present invention relates to a high-sensitivity silver halide color photographic material having excellent light source suitability.

[0002]

2. Description of the Related Art Hitherto, 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 light-sensitive material, by giving a development suppressing effect from a green-sensitive silver halide emulsion layer (hereinafter also referred to as a green-sensitive layer) to a red-sensitive silver halide emulsion layer (hereinafter also referred to as a red-sensitive layer). The color development of the red-sensitive layer in white exposure can be suppressed as compared with that in the case of red exposure. In the color negative paper system, the gradation is balanced so that, when exposed with white light, grayscale is reproduced on a color print. For this reason, the multilayer effect (interlayer effect; also referred to as an interlayer effect) gives a higher density cyan color development in red exposure than in gray exposure. As a result, it is possible to reproduce red with higher saturation with suppressed cyan color development on the print. Similarly, the effect of suppressing the development from the red-sensitive layer to the green-sensitive layer gives green reproduction with a high degree of saturation.

When the saturation of the primary colors of red, green and blue is increased by using these methods, there is a disadvantage that the hue of yellow to cyanish green is not faithful.
The technology described in US Pat. This technique is based on a blue-sensitive silver halide emulsion layer containing at least one yellow color coupler (hereinafter also referred to as a blue-sensitive layer), a green-sensitive layer containing a magenta color coupler, a silver halide emulsion layer containing a magenta color coupler, In a color light-sensitive material having a red-sensitive silver halide emulsion layer containing a cyan color coupler, the center of gravity wavelength (λ _G ) of the spectral sensitivity distribution of the green-sensitive silver halide emulsion layer is 520 nm <λ _G ≦ 580 nm,
In addition, the center-of-gravity wavelength (λ _-R ) of the spectral sensitivity distribution of the magnitude of the multilayer effect that all the red-sensitive silver halide emulsion layers containing the cyan coupler receive from other silver halide emulsion layers in the range of 500 nm to 600 nm. 500 nm <λ- _R ≦ 5
A silver halide color photosensitive material characterized in that it has a thickness of 60 nm and a λ _G -λ- _R of 5 nm or more, preferably 10 nm or more, in order to achieve vivid and faithful color reproduction. is there. The silver halide color photographic light-sensitive material obtained here is also excellent in light source suitability, and can reproduce natural colors even when photographed under a fluorescent lamp indoors.

However, in the silver halide color photographic material obtained here, it is necessary to newly provide a layer which gives a multilayer effect to the red photosensitive layer, and the sharpness is deteriorated due to an increase in the film thickness. It was easy. If a high-sensitivity silver halide color photographic light-sensitive material is to be obtained, the film thickness is further increased, so that commercialization has been difficult. Therefore, general amateur users who use single-use cameras and compact cameras rarely enjoy the benefits.

Japanese Patent Application Laid-Open No. 62-160449 discloses that the light source suitability is improved by a silver halide color photographic light-sensitive material having a specified spectral sensitivity and the size of the layering effect. Not enough levels had been reached.

A photosensitive material for further improving the suitability for a light source is described in JP-A-11-305396. However, although the photosensitive material described in JP-A-11-305396 sufficiently satisfies the suitability for the light source, it is desired to improve the photographic property due to a large change in photographic properties due to fluctuations in development processing. On the other hand, Japanese Patent Application Laid-Open No. 2000-194085 discloses a means for improving the sensitivity using a specific compound, but does not suggest that the compound can improve the processing fluctuation.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color photographic light-sensitive material which is excellent in color reproducibility and light source suitability, and has improved photographic properties due to processing fluctuations.

[0008]

The object of the present invention is achieved by a silver halide color photographic light-sensitive material having the following constitution and a photographic product incorporating the same. That is, (1) a blue-sensitive silver halide emulsion layer containing at least one yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a red-sensitive halide containing a cyan coupler on a support. Having a silver emulsion layer and a non-light-sensitive layer;
In a silver halide color photographic material, the sensitivity S _R (580) at nm has the following relationship with the sensitivity S _R (max) at the maximum sensitivity wavelength of the layer: 0.25 ≦ S _R (max) − S _R (580) ≦
0.9 A silver halide color photographic light-sensitive material, characterized in that at least one silver halide emulsion layer or non-light-sensitive layer contains the following compound (A). Compound (A): a compound having at least three heteroatoms and having an increased photographic sensitivity of the light-sensitive material as compared to a case where the compound is not contained.

(2) The center-of-gravity sensitivity wavelength (λ _-R ) of the spectral sensitivity distribution of the multilayer effect that the above-mentioned red-sensitive silver halide emulsion layer (all when there are a plurality of layers) is received from another layer in the range of 500 nm to 600 nm. Is 500 nm <λ- _R ≦ 560 nm
And the center-of-gravity wavelength (λ _G ) of the spectral sensitivity distribution of the green-sensitive silver halide emulsion layer (if there is more than one),
Is 520 nm <λ _G ≦ 580 nm, and λ _G −
The silver halide color photographic light-sensitive material according to (1), wherein λ- _R ≧ 5 nm.

(3) The compound (A) is 1,3,4,6-
The silver halide color photographic material according to (1) or (2), which is a tetraazaindene compound.

(4) The silver halide color photographic material as described in any one of (1) to (3) above, wherein the specific sensitivity is 640 or more.

Is achieved by:

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The specific sensitivity in the present invention is determined by the method described in JP-A-63-236035. This measuring method is based on JIS K 7614-198.
1 in that development processing is completed within 30 minutes to 6 hours after exposure for sensitometry, and development processing is performed by the method described in Example 1 of the present application. Others are substantially the same as those described in JIS.

Further, when the red-sensitive silver halide emulsion layer is 500
The center of gravity wavelength λ of the wavelength distribution of the magnitude of the multilayer effect received from other silver halide emulsion layers in the range of nm to 600 nm.
_-R is determined as follows. First, uniform exposure is performed using a red filter that transmits a specific wavelength or more or an interference filter that transmits only a specific wavelength so that a red-sensitive layer that emits cyan at a wavelength of 600 nm or more is exposed and other layers are not exposed. To uniformly cover the cyan sensitive red-sensitive layer to an appropriate value. Next, when a spectral exposure is applied, the blue-sensitive layer and the green-sensitive layer act on the above-mentioned fogged red-sensitive layer emulsion by a layering effect of development suppression to give a reversal image. (Refer to FIG. 1A) By this inverted image, the spectral sensitivity distribution S as the inverted photosensitive material is obtained.
_-R (λ) is calculated. (S _-R (λ) for a specific wavelength λ
Is obtained as a relative point from the point a shown in FIG. 1A. Calculate the center-of-gravity wavelength (λ- _R ) of the multilayer effect by the following equation (L).

Equation (L)

(Equation 1)

S _G (λ) is a spectral sensitivity distribution curve of the green sensitive layer, and a relative value of S _G (λ) at a specific wavelength λ is obtained from point b shown in FIG. 1B.

Hereinafter, the present invention will be described in more detail.
FIG. 2 shows the spectral energy distribution of a white fluorescent lamp. The white fluorescent lamp produces white light by superimposing broad light emission in a yellow region around 570 nm and sharp blue light emission around 430 nm. In a color negative film, an object under a fluorescent lamp is often reproduced in a green tint because the long wavelength end of the spectral sensitivity of the green photosensitive layer is set to a long wave, so that the white fluorescent lamp emits light near 570 nm. And the short-wave end of the spectral sensitivity of the red-sensitive layer is set to a long-wave, which makes it difficult to sense this light emission. If the spectral sensitivity of the green photosensitive layer is set to the short wavelength while the red photosensitive layer is set to the short wavelength, the suitability of the fluorescent lamp is improved, but the adverse effect of lowering the chroma of the green occurs. At the same time, the long wavelength side of the green photosensitive layer acts as a filter in the red photosensitive layer, so that the amount of light reaching the red photosensitive layer decreases and the sensitivity becomes low. If the wavelength of the green photosensitive layer is shortened in order to improve the low sensitivity, the chroma of green is further reduced, and the green is unpractical. As described above, it is difficult to satisfy the three requirements of sensitivity, green color saturation, and suitability for fluorescent light, and it is difficult to realize these in a high-sensitivity color photographic light-sensitive material in which deterioration of graininess is hardly allowed.

For example, a scene in which a main subject is illuminated with a strobe light and a fluorescent light is illuminated in the background is often seen.
When shooting with low-sensitivity film, the background is underexposed and the background is dark, but by using a high-sensitivity film, it is possible to capture the background. In recent years, color negative films of ISO400 have come into common use, but in the above-mentioned scenes, there are quite a few cases in which the background illuminated by fluorescent lights is reproduced in green. The light-sensitive material disclosed in JP-A-62-160449 has a low emulsion sensitivity, and the background cannot be sufficiently darkened under the above-mentioned use conditions, so that the effect cannot be exhibited.

After repeated studies to overcome the above problems, the spectral sensitivities S _R (58) of the red and green photosensitive layers were determined.
0), it was found that S _G (580) was preferable when it was in the following range. Here, S _G (580) and S _R (580) are defined by the logarithmic value of the reciprocal of the amount of exposure necessary to obtain the minimum density of magenta and cyan at each wavelength plus 0.5 density. Is done. S _G (max) and S _R (ma
x) is defined by the logarithm of the reciprocal of the exposure amount that gives the maximum density of magenta and cyan colors, respectively. Further, it is preferable that the spectral sensitivity does not change from an underexposed portion to an overexposed portion. _{0.25 ≦ S R (max) -S} R (580) ≦ 0.9 0.4 ≦ S G (max) -S G (580) ≦ 1.1.

The wavelength at which the red photosensitive layer has the highest sensitivity is from 610 nm to 640 nm, and preferably 620 nm.
nm to 635 nm. Further, it is desirable that the sensitivity S _R (650) of the red photosensitive layer at 650 nm has the following relationship.

S _R (650) ≦ S _R (max) −0.7 Here, the definition of sensitivity is the same as the above definition.

The wavelength at which the green photosensitive layer has the highest sensitivity is from 520 nm to 580 nm, preferably 540 nm.
nm to 565 nm. It is desirable that the sensitivity S _G (525) of the green photosensitive layer at 525 nm has the following relationship. _{0.1 ≦ S G (max) -S} G (525) ≦ 0.3.

As a means for improving color reproducibility, it is preferable to use an interlayer suppression effect. In particular, the center-of-gravity sensitivity wavelength (λ _G ) of the spectral sensitivity distribution of the green-sensitive silver halide emulsion layer
520 nm <λ _G ≦ 580 nm, and the center-of-gravity wavelength (λ ₋₎ of the spectral sensitivity distribution of the magnitude of the multilayer effect that the red-sensitive silver halide emulsion layer receives from other silver halide emulsion layers in the range of 500 nm to 600 nm. _R ) is 500 nm <λ _−R
<560 nm, and λ _G −λ _−R is 5 nm or more,
Preferably it is 10 nm or more.

In order to provide the above-mentioned layering effect on the red-sensitive layer in a specific wavelength region, it is preferable to provide a layering effect donor layer containing silver halide grains which have been separately spectrally sensitized. In order to realize the spectral sensitivity of the present invention, the multilayer sensitivity wavelength of the multilayer effect donor layer is 510 nm to 540 n.
m.

When S _-B (λ) is obtained in the same manner as in the above-described procedure for obtaining S _-R (λ), the overlay effect given by the donor layer needs to satisfy the following expression (2). .

Equation (2)

(Equation 2)

As a material giving the layering effect, a compound which reacts with an oxidation product of a developing agent obtained by development to release a development inhibitor or a precursor thereof is used. For example, D
An IR (development inhibitor releasing type) coupler, a DIR-hydroquinone, a coupler releasing DIR-hydroquinone or a precursor thereof, and the like are used. In the case of a development inhibitor having a large diffusivity, the development suppression effect can be obtained regardless of where the donor layer is located in the multilayer structure, but the development suppression effect in an unintended direction also occurs, so this is corrected. Color the donor layer (e.g., to the same color as the layer affected by the undesired development inhibitor).
Is preferred. In order to obtain the spectral sensitivity of the present invention, magenta color development is preferred.

The silver halide grains used in the layer giving the layering effect to the red-sensitive layer are not particularly limited in size and shape, for example, so-called tabular grains having a high aspect ratio and monodispersed emulsions having a uniform grain size. Silver iodobromide grains having a layered structure of iodine are preferably used.
In order to enlarge the exposure latitude, it is preferable to mix two or more emulsions having different grain sizes.

The donor layer which gives the layer effect to the red-sensitive layer may be provided at any position on the support, but is provided closer to the support than the blue-sensitive layer and farther from the support than the red-sensitive layer. Is preferred. Further, it is more preferable that it is closer to the support than the yellow filter layer.

It is more preferable that the support is closer to the support than the green-sensitive layer and farther from the support than the red-sensitive layer, and it is most preferable that the green-sensitive layer be located adjacent to the support closer to the support. In this case, “adjacent” means that no intermediate layer or the like is interposed. The layer giving the multilayer effect to the red-sensitive layer may be composed of a plurality of layers. In that case, their positions may be adjacent to or separated from each other.

Next, the compound of the present invention (compound (A)) having at least three heteroatoms will be described. The compound (A) of the present invention may be used in any of a silver halide photosensitive layer and a non-photosensitive layer in a photosensitive material, but is preferably used in a silver halide photosensitive layer. When the photosensitive layer is divided into a plurality of layers having different sensitivities, it may be used for a layer having any sensitivity, but is preferably used for a layer having high sensitivity.

The method of adding the compound (A) to the light-sensitive material is not particularly limited, but includes a method of emulsifying and dispersing the compound (A) with a coupler, a high-boiling organic solvent and the like, a method of solid dispersion, and a method of dissolving in an organic solvent such as methanol to prepare a coating solution. There are a method of adding the compound and a method of adding the compound during the preparation of the silver halide emulsion.

A method of introducing the compound (A) as it is into the light-sensitive material is also preferable, but a compound which reacts with an oxidized developing agent to release a residue of a compound having at least three heteroatoms is introduced into the light-sensitive material. Is preferred, and the compound is also included in the scope of compound (A).

[0034] There is no particular limitation on the addition amount of the compound (A), preferably from 0.1 to 1000 mg / m ^2, more preferably ^{1~500mg / m 2, 5~100g / m} 2 is particularly preferred. When used in a light-sensitive silver halide emulsion layer, 1 mole per mole of silver in the same layer
× 10 ^{- 4} are preferably to 1 × 10 ^{-1 mol, 1 × 10 -3 ~1 × 10} -2 mol and more preferably.

The following are examples of the compound (A) of the present invention, but are not limited thereto.

[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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The silver halide grains contained in the donor layer having the multilayer effect are preferably spectrally sensitized by a compound represented by the following formula (I).

[0043]

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In the formula (I), Z ₁₁ represents an atom group necessary for forming a benzene ring, and at least one atom of these atom groups may be substituted with an alkyl group, an alkoxy group or an aryloxy group. The benzene ring formed by Z ₁₁ is preferably substituted with an alkyl group at the 6-position. Here, the alkyl group in which Z ₁₁ is substituted is, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a t-butyl group, an n-butyl group, an n-octyl group, an n-decyl group, an n-hexadecyl group , Cyclopentyl group, cyclohexyl group, etc., and preferably a methyl group and an ethyl group.

The alkoxy group is, for example, a methoxy group, an ethoxy group, a propoxy group, a methylenedioxy group and the like, and is preferably a methoxy group. The aryloxy group is a phenoxy group, a 4-methylphenoxy group, a 4-chlorophenoxy group or the like, and is preferably a phenoxy group.

Z ₁₂ represents an atomic group necessary for forming a benzoxazole nucleus, and these may have a substituent. Z ₁₂ preferably represents a benzoxazole nucleus substituted with a halogen atom, an alkyl group, an alkoxy group, an alkylthio group or an aryl group at the 5-position. Here, the halogen atom substituted with the benzoxazole nucleus is, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom,
Preferred are a bromine atom and a chlorine atom.

The alkyl group may have a substituent, for example, methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-butyl group, n-octyl group,
It is an n-decyl group, an n-hexadecyl group, a cyclopentyl group, a cyclohexyl group, a trifluoromethyl group or a hydroxyethyl group, preferably a trifluoromethyl group.

The alkoxy group is, for example, a methoxy group, an ethoxy group, a propoxy group, a methylenedioxy group and the like, and is preferably a methoxy group. The alkylthio group is a methylthio group, an ethylthio group, a propylthio group, or the like, and is preferably a methylthio group. The aryl group represents a phenyl group, a pentafluorophenyl group, a 4-chlorophenyl group, a 3-sulfophenyl group, a 4-methylphenyl group or the like, and is preferably a phenyl group.

In the general formula (I), R ₁₁ and R _{12 each} have 1 carbon atom.
8 or less unsubstituted alkyl groups (eg, methyl, ethyl, propyl, butyl, pentyl, octyl, decyl, dodecyl, octadecyl) or substituted alkyl groups ｛substituents such as carboxy group, sulfo group, cyano group, halogen atom ( For example, fluorine, chlorine, and bromine.), A hydroxy group, an alkoxycarbonyl group having 8 or less carbon atoms (eg, methoxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl), an alkanesulfonylaminocarbonyl group having 8 or less carbon atoms, and 8 or less carbon atoms An acylaminosulfonyl group, an alkoxy group having 8 or less carbon atoms (eg, methoxy, ethoxy, benzyloxy, phenethyloxy), an alkylthio group having 8 or less carbon atoms (eg, methylthio, ethylthio, methylthioethylthioethyl),
An aryloxy group having 20 or less carbon atoms (for example, phenoxy, p-tolyloxy, 1-naphthoxy, 2-naphthoxy), an acyloxy group having 3 or less carbon atoms (for example, acetyloxy, propionyloxy), and an acyl group having 8 or less carbon atoms (for example, Acetyl, propionyl, benzoyl), carbamoyl group (eg, carbamoyl, N, N-dimethylcarbamoyl, morpholinocarbonyl, piperidinocarbonyl), sulfamoyl group (eg, sulfamoyl,
N, N-dimethylsulfamoyl, morpholinosulfonyl, piperidinosulfonyl), C18 substituted with an aryl group having 20 or less carbon atoms (eg, phenyl, 4-chlorophenyl, 4-methylphenyl, α-naphthyl) The following alkyl groups｝ are mentioned.

Preferably, an unsubstituted alkyl group (eg, a methyl group, an ethyl group, an n-propyl group, an n-butyl group,
-Pentyl group, n-hexyl group), carboxyalkyl group (for example, 2-carboxyethyl group, carboxymethyl group), sulfoalkyl group (for example, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, 3-
Sulfobutyl group).

More preferred as the alkyl group represented by R ₁₁ and R ₁₂ are a sulfoethyl group, a sulfopropol group, a sulfobutyl group, a carboxymethyl group and a carboxyethyl group.

In the general formula (I), X ₁₁ represents a charge balancing counter ion. The ion that cancels the charge in the molecule is selected from an anion and a cation. The anion is an inorganic or organic acid anion (e.g., p-toluenesulfonate,
-Nitrobenzenesulfonate, methanesulfonate,
Represents methylsulfate, ethylsulfate, perchlorate, etc.), halogen ions (eg, chloride, bromide, iodide, etc.). Cations include inorganic and organic ones, specifically, hydrogen ions, alkali metal ions, (eg, lithium, sodium, potassium,
Ions such as cesium), alkaline earth metal ions (eg, ions such as magnesium, calcium, strontium), ammonium ions, organic ammonium, triethanolammonium, and pyridinium). m represents 0 or 1, and m is 0 when an internal salt is formed.

Further, it is preferable to mix a sensitizing dye represented by the following general formula (II) in the donor layer having the multilayer effect.

Formula (II)

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The nucleus formed by Z ₃₁ and Z ₃₂ includes a thiazole nucleus and a thiazole nucleus (for example, thiazole,
4-methylthiazole, 4-phenylthiazole, 4,
5-dimethylthiazole, 4,5-diphenylthiazole, 3,4-dihydronaphtho [4,5-a] thiazole, a benzothiazole nucleus (for example, benzothiazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6 -Chlorobenzothiazole, 5-nitrobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole,
5-bromobenzothiazole, 6-bromobenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-ethoxybenzothiazole, 5-ethoxycarbonylbenzothiazole, 5 -Phenoxybenzothiazole, 5-carboxybenzothiazole, 5-acetylbenzothiazole, 5-acetoxybenzothiazole, 5-phenethylbenzothiazole, 5-fluorobenzothiazole, 5-trifluoromethylbenzothiazole, 5-chloro-6-methyl Benzothiazole, 5,6-dimethylbenzothiazole,
5,6-dimethoxybenzothiazole, 5,6-methylenedioxybenzothiazole, 5-hydroxy-6-methylbenzothiazole, tetrahydrobenzothiazole, 4-phenylbenzothiazole, 5,6-bismethylthiobenzothiazole), naphthothiazole Nuclei (for example, naphtho [2,1-d] thiazole, naphtho [1,2
-D] thiazole, naphtho [2,3-d] thiazole,
5-methoxynaphtho [1,2-d] thiazole, 7-ethoxynaphtho [2,1-d] thiazole, 8-methoxynaphtho [2,1-d] thiazole, 5-methoxynaphtho [2,3-d] Thiazole), 8-methylthionaphtho [2,1-d] thiazole｝, thiazoline nucleus (for example,
Thiazoline, 4-methylthiazoline, 4-nitrothiazoline), oxazole nucleus ｛oxazole nucleus (for example, oxazole, 4-methyloxazole, 4-nitrooxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole), benzoxazole nucleus (for example, benzoxazole, 5-chlorobenzoxazole, 5
-Methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-nitrobenzoxazole, 5-trifluoromethylbenzoxazole, 5-hydroxybenzoxazole, 5 -Carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-nitrobenzoxazole, 6-methoxybenzoxazole, 6-hydroxybenzoxazole,
5,6-dimethylbenzoxazole, 4,6-dimethylbenzothiazole, 5-ethoxybenzoxazole, 5-acetylbenzoxazole, naphthooxazole nucleus (for example, naphtho [2,1-d] oxazole, naphtho [1,2 -D] oxazole, naphtho [2,
3-d] oxazole, 5-nitronaphtho [2,1-
d] oxazole)}, oxazoline nucleus (for example, 4,
4-dimethyloxazoline), selenazole nucleus selenazole nucleus (for example, 4-methyl selenazole, 4-nitro selenazole, 4-phenyl selenazole), benzo selenazole nucleus (for example, benzo selenazole, 5-chlorobenzo selenazole) , 5-nitrobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 6-nitrobenzoselenazole,
5-chloro-6-nitrobenzoselenazole, 5,6-
Dimethyl benzo selenazole), naphtho selenazole nucleus (for example, naphtho [2,1-d] selenazole, naphtho [1,2-d] selenazole)}, selenazoline nucleus (for example, selenazoline, 4-methyl selenazoline), tellurazole Nuclear ｛tellurazole nucleus (eg, tellurazole,
4-methyltellurazole, 4-phenyltellurazole), benzotellurazole nucleus (for example, benzotellurazole, 5-chlorobenzotellurazole, 5-methylbenzotellurazole, 5,6-dimethylbenzotellurazole, 6-methoxy) Benzotellurazole), naphthotellurazole nucleus (for example, naphtho [2,1-d] tellurazole, naphtho [1,2-d] tellurazole)}, tellurazoline nucleus (for example, tellurazoline, 4-methyltellurazoline), 3, 3-dialkylindolenine nucleus (eg, 3,
3-dimethylindolenine, 3,3-diethylindolenine, 3,3-dimethyl-5-cyanoindolenine,
3,3-dimethyl-6-nitroindolenine, 3,3-
Dimethyl-5-nitroindolenine, 3,3-dimethyl-5-methoxyindolenine, 3,3,5-trimethylindolenine, 3,3-dimethyl-5-chloroindolenine), imidazole nucleus and indazole nucleus (for example, , 1
-Alkylimidazole, 1-alkyl-4-phenylimidazole, 1-arylimidazole), benzimidazole nucleus (for example, 1-alkylbenzimidazole, 1-alkyl-5-chlorobenzimidazole, 1
-Alkyl-5,6-dichlorobenzimidazole, 1
-Alkyl-5-methoxybenzimidazole, 1-alkyl-5-cyanobenzimidazole, 1-alkyl-5-fluorobenzimidazole, 1-alkyl-5
-Trifluoromethylbenzimidazole, 1-alkyl-6-chloro-5-cyanobenzimidazole, 1-
Alkyl-6-chloro-5-trifluoromethylbenzimidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-arylbenzimidazole, 1-aryl-
5-chlorobenzimidazole, 1-aryl-5,6
-Dichlorobenzimidazole, 1-aryl-5-methoxybenzimidazole, 1-aryl-5-cyanobenzimidazole), naphthoimidazole nucleus (for example, 1-alkylnaphtho [1,2-d] imidazole,
-Arylnaphtho [1,2-d] imidazole), the alkyl group having 1 to 8 carbon atoms, for example, an unsubstituted alkyl group such as methyl, ethyl, propyl, isopropyl, butyl and the like, and a hydroxyalkyl group (for example, , 2-
Hydroxyethyl, 3-hydroxypropyl) is preferred. Particularly preferred are a methyl group and an ethyl group.

The aforementioned aryl groups represent phenyl, halogen (for example, chloro) substituted phenyl, alkyl (for example, methyl) substituted phenyl, and alkoxy (for example, methoxy) substituted phenyl. ｝, Pyridine nucleus (for example, 2-pyridine, 4-pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine), quinoline nucleus ｛quinoline nucleus (for example, 2-quinoline, 3-methyl-2-pyridine) Quinoline, 5-ethyl-2-quinoline, 6-methyl-2-quinoline, 6-
Nitro-2-quinoline, 8-fluoro-2-quinoline,
6-methoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, 4-quinoline, 6
-Ethoxy-4-quinoline, 6-nitro-4-quinoline, 8-chloro-4-quinoline, 8-fluoro-4-quinoline, 8-methyl-4-quinoline, 8-methoxy-4
-Quinoline, 6-methyl-4-quinoline, 6-methoxy-4-quinoline, 6-chloro-4-quinoline, 5,6-
Dimethyl-4-quinoline), isoquinoline nucleus (for example,
6-nitro-1-isoquinoline, 3,4-dihydro-1
-Isoquinoline, 6-nitro-3-isoquinoline)},
Imidazo [4,5-b] quinoxaline nucleus (for example, 1,
3-diethylimidazo [4,5-b] quinoxalin, 6
-Chloro-1,3-diallylimidazo [4,5-b] quinoxaline), oxadiazole nucleus, thiadiazole nucleus, tetrazole nucleus and pyrimidine nucleus.

The nucleus formed by Z ₃₁ and Z ₃₂ is preferably a benzoxazole nucleus.

R ₃₁ and R ₃₂ have the same meanings as R ₁₁ and R ₁₂ in formula (I), and are preferably a sulfoethyl group, a sulfopropyl group, a sulfobutyl group, a carboxymethyl group and a carboxyethyl group.

R ₃₃ is a hydrogen atom or a substituted or unsubstituted alkyl group (eg, methyl, ethyl, propyl, butyl, hydroxyethyl, trifluoromethyl, 2-chloroethyl, chloromethyl, methoxymethyl, 2-methoxyethyl, benzyl ), An unsubstituted or substituted aryl group (eg, phenyl, o-carboxyphenyl, p-tolyl, m-tolyl). R ₃₃ is preferably a hydrogen atom, a methyl group or an ethyl group. X ₃₁ and p have the same meanings as X ₁₁ and m in formula (I), respectively.

The compounds represented by the general formulas (I) and (II) are described in FM Hamer, "Heterocyclic Compounds-Cyanine Soybeans and Relatated Compounds".
unds-Cyanine Dyes and Related Compounds, John Wiley & Sons, Inc.-New York, London, 1964, by DM Sturmer, Heterocyclic.・ Compounds-Special Topics in Heterocyclic Chemistry
ompounds-Special topics in heterocyclic chemistr
y) ", Chapter 18, Section 14, pp. 482-515, John Wiley & Sons
s), New York, London (1977),
"Rodd's Chemistry of Carbon Compounds", (2
Vol. IV, part B, 1977), Chapter 15, pages 369-422; (2nd Ed. vol. IV, part B, 1985), Chapter 15, pages 267-296. , Elsbayer Science Public Company, Inc. (Elsv
ier Science Publishing Company Inc.), New York, and the like.

Specific examples of the compound represented by formula (I) are shown below, but the scope of the present invention is not limited thereto.

[0062]

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[0063]

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[0064]

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[0065]

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The amount of the dye represented by the general formula (I) is from 4 × 10 ^-6 to 2 × 10 ^-2 per mol of silver halide as an actual addition amount.
Although it can be used in moles, 5 × 10 ^{−5 to} 5 × 10 ⁻³
Molar is more preferred. The dye may be added to the emulsion at any stage in the preparation of the emulsion which has been known to be useful.

The dye of the general formula (II) is more preferably used in the range of 0.5 mol% to 50 mol% of the amount of the dye of the general formula (I). More preferably, 5 mol% to 3 mol%
0 mol%.

Hereinafter, specific examples of the compound represented by formula (II) of the present invention will be shown, but the scope of the present invention is not limited thereto.

[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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[0079]

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The present invention can be applied to various color light-sensitive materials. In addition, the present invention generally has a large number of emulsion layers and other hydrophilic colloid layers and kinds of additives constituting the photosensitive material as compared with black and white, and therefore the thickness of the photosensitive material is increased, and an oil-soluble additive is used. It is effective for color light-sensitive materials in which the decolorizing properties of the dye tend to be reduced due to the large content.

As a material giving the layering effect, a compound which reacts with an oxidation product of a developing agent obtained by development to release a development inhibitor or a precursor thereof is used. For example, DIR
(Development inhibitor releasing type) Couplers, couplers which release DIR-hydroquinone, DIR-hydroquinone or a precursor thereof are used. As a method of using these compounds, it is preferable to use them in the highest sensitivity layer, but they may be used in the middle and low sensitivity layers. Further, it may be used for the highest-sensitivity layer of any of the blue-sensitive layer, green-sensitive layer and red-sensitive layer, but is more preferably used for the blue-sensitive layer. The amount used depends on the performance required of the light-sensitive material, but is from 1 × 10 ^-5 to 1 × 10 per mol of silver halide in the layer to be added.
^Although it is in the range of ^-1 mol, it is preferably 5 × 10 ^-3 mol or more.

The photographic product with a built-in photosensitive material provided with an exposure function according to the present invention has a photographic lens such as a monocular lens or an aspherical lens and an exposure mechanism such as a shutter mechanism.
It is a packaging unit having a storage room (film roll chamber) in which a color photographic light-sensitive material is wound and stored directly or in a storage device. It is preferable to store the photosensitive material directly in the storage chamber. The photosensitive material may be placed in a cartridge or a cartridge.

The photographic lens used in the present invention may have a variable aperture or a fixed aperture. However, in order to handle a photographic product with a built-in photosensitive material easily and easily, It is preferable to have a fixed aperture. The aperture value (F value) is preferably 8 or more and 16 or less, and more preferably 10 or more and 14 or less.

The shutter speed may be variable or fixed, but is preferably fixed as with the aperture. Preferably 1/50 sec to 1/250 sec, more preferably 1/8
0 second to 1/160 second.

In the present invention, 1 g of gelatin is added to at least one of the silver halide light-sensitive layer and the non-light-sensitive layer constituting the light-sensitive material.
On the other hand, it may be 4.0 × 10 ⁻³ g or more and 8.0 × 10 ⁻² g or less, more preferably 6 × 10 ⁻³ g or more and 4.0 × 10 ⁻² g or less, 12 × 10 ⁻³ g or more and 3.0
More preferably, it is not more than × 10 ^-2 g.

Further, the total content of calcium contained in the light-sensitive material is 4.0 × 10 ⁻³ g or more and 8.0 × 10 ⁻² g or less per g of gelatin with respect to all gelatin contained in the light-sensitive material. Is preferably 6 × 10 ⁻³ g or more and 4.0 × 1
More preferably, it is 0 ^-2 g or less. If the calcium content is less than this, the effect on storage stability is small,
An amount exceeding this amount is not preferable because it causes adverse effects such as softening of gradation.

Here, the calcium content is represented by the mass converted to calcium atoms for all compounds containing calcium such as calcium ions and calcium salts.
The calcium can be determined by, for example, ICP emission spectroscopy.

The calcium-added layer may be a light-sensitive layer, a non-light-sensitive layer, or both layers, but is preferably used for the light-sensitive layer. Note that calcium in the support is not included.

Any method can be used for the addition. For example, it can be added at the time of preparing a coating solution as an aqueous solution of calcium nitrate or the like, and can also be added at the time of preparing a silver halide emulsion. When it is added during the preparation of the silver halide emulsion, it can be added at any position from before the formation of the grains to the end of the preparation of the silver halide, but is preferably added after the addition of the dye. It is more preferable to add the dye after the dye is added and before the chemical sensitization is started.

The light-sensitive material of the present invention may have at least one light-sensitive layer provided on a support. 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. It is. The photosensitive layer is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light, and in a multilayer silver halide color photographic material, the arrangement of the unit photosensitive layers is generally A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are provided in this order from the support side. 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. A non-photosensitive layer may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer. These may contain a coupler, a DIR compound, a color mixing inhibitor and the like described below. As described in DE 1,121,470 or GB 923,045, a plurality of silver halide emulsion layers constituting each unit light-sensitive layer are formed by sequentially exposing two layers of a high-speed emulsion layer and a low-speed emulsion layer toward a support. It is preferable to arrange them so that the degree is low. Also, JP-A-57-112751, 62-200350, 62-206
As described in 541 and 62-206543, a low-speed emulsion layer may be provided on the side farther from the support, and a high-speed emulsion layer may be provided on the side closer to the support.

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

Further, as described in JP-B-55-34932, the blue-sensitive layer / GH / RH
They can also be arranged in the order of / GL / RL. JP-A-56-2
As described in 5738 and 62-63936, the layers may be arranged in the order of blue-sensitive layer / GL / RL / GH / RH from the side farthest from the support.

Further, as described in JP-B-49-15495, the upper layer is a silver halide emulsion layer having the highest sensitivity, the middle layer is a silver halide emulsion layer having a lower sensitivity, and the lower layer is a further layer. An example is an arrangement in which a silver halide emulsion layer having a low sensitivity is arranged and three layers having different sensitivities are sequentially reduced in sensitivity toward a support. Even when such a three-layer structure having different photosensitivity is used,
As described in JP-A-59-202464, in the same color-sensitive layer, the layers may be arranged in the order of medium-speed emulsion layer / high-speed emulsion layer / low-speed emulsion layer from the side away from the support.

In addition, a high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or a low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer may be arranged in this order. The arrangement may be changed as described above even in the case of four or more layers.

Preferred silver halides for use in the present invention are silver iodobromide, silver iodochloride, or silver iodochlorobromide containing up to about 30 mole percent 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 include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystalline forms such as spherical and plate-like,
It may have a crystal defect such as a twin plane or a composite form thereof. The silver halide may be fine grains having a grain size of about 0.2 μm or less or large grains having a projected area diameter of about 10 μm, and may be a polydisperse emulsion or a monodisperse emulsion.

The silver halide photographic emulsion usable in the present invention is, for example, Research Disclosure (hereinafter referred to as RD).
No. 17643 (December 1978), pp. 22-23, "I. Emulsion preparation and types", and No. 18716 (November 1979), 648, No. 307105 (1989
Nov., pp. 863-865, and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chimie et.
Phisique Photographiques, Paul Montel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (G.
F. Duffin, Photographic Emulsion Chemistry, Focal P
ress, 1966), "Manufacture and coating of photographic emulsions" by Zerikman et al., Published by Focal Press (VL Zelikman, et a
l., Making and Coating Photographic Emulsion, Foca
l Press, 164).

US 3,574,628, US 3,655,394 and GB 1,4
Monodisperse emulsions described in 13,748 are also preferred. Tabular grains having an aspect ratio of about 3 or more are particularly preferable and can be used in the present invention. Tabular grains are described by Gatoff, Photographic Science and Engineerin.
g), Vol. 14, pp. 248-257 (1970); US 4,434,226,
4,414,310, 4,433,048, 4,439,520 and GB
It can be easily prepared by the method described in 2,112,157.

The crystal structure may be uniform, the inside and the outside may be composed of different halogen compositions, or may have a layered structure. Silver halides having different compositions may be joined by epitaxial joining, or may be joined to a compound other than silver halide, such as, for example, silver rhodanate or lead oxide. Also, a mixture of particles of various crystal forms may be used.

The above emulsion preferably has dislocations. In particular, tabular grains preferably have dislocations in the fringe. As a method for introducing dislocation, a method of forming a high silver iodide layer by adding an aqueous solution of an alkali iodide or the like, a method of adding AgI fine particles, and a method described in JP-A-5-3234
87 and the like can be used.

The above emulsion may be 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 inside a grain, or a type having a latent image on both the surface and the inside. Type emulsion. Among the internal latent image types, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used.
-133542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, and 5 to 40 nm.
20 nm is particularly preferred.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. Additives used in such a process are RD No. 17643 and RD No. 187.
16 and No. 307105, and the relevant portions are summarized in the table below.

The light-sensitive material of the present invention comprises a light-sensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more emulsions differing in at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer.

The silver halide grains having a fogged surface described in US Pat. No. 4,082,553, US Pat. No. 4,626,498, JP-A-59-214852.
It is preferable to apply the silver halide grains and colloidal silver having the inside of the grains described in (1) to the light-sensitive silver halide emulsion layer and / or the substantially light-insensitive hydrophilic colloid layer. The term "silver halide particles having a fogged interior or surface" refers to silver halide grains that can be uniformly (non-imagewise) developed regardless of unexposed portions and exposed portions of the photosensitive material. , Its preparation method is described in US Pat.
It is described in 214852. The silver halide forming the internal nucleus of the core / shell type silver halide grain having the inside of the grain fogged may have a different halogen composition. 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. The average grain size of these fogged silver halide grains is 0.01 to 0.75 μm, particularly 0.05
~ 0.6 μm is preferred. The grains may be regular grains or polydisperse emulsions, but may be monodisperse (at least 95% of the mass or number of silver halide grains has a grain size within ± 40% of the average grain size). Is preferable.

In the present invention, it is preferable to use non-light-sensitive 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 has an average grain size (average value of the circle equivalent diameter of the projected area).
It is preferably from 0.01 to 0.5 μm, more preferably from 0.02 to 0.2 μm.

The fine silver halide grains can be prepared in the same manner as for ordinary light-sensitive silver halide. The surface of the silver halide grains does not need to be optically sensitized, and no spectral sensitization is required. However, before adding this to the coating solution, a triazole-based, azaindene-based,
It is preferable to add a known stabilizer such as a benzothiazolium-based or mercapto-based compound or a zinc compound. Colloidal silver can be contained in the layer containing fine silver halide grains. The coated silver amount of the light-sensitive material of the present invention is preferably 8.0 g / m ² or less.

The photographic additives which can be used in the present invention are also described in RD, and the relevant portions are shown in the following table. Type of additive RD17643 RD18716 RD307105 Chemical sensitizer page 23, page 648, right column, page 866 2. 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23 to 24, page 648, right column 866 to 868 Super sensitizer, page 649, right column Brightener page 24 page 647 page right column page 868 5. 5. Light absorbers, pages 25 to 26, page 649, right column, page 873 Filters, page 650, left column, dyes, ultraviolet absorbers Binder page 26 page 651 left column pages 873 to 874 7. 7. Plasticizer, page 27 page 650, right column, page 876 Lubricant Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876 Surfactant 9. Static 27 pages 650 page right column 876-877 Inhibitors 10. Matting agents 878-879.

Various dye-forming couplers can be used in the light-sensitive material of the present invention, and the following couplers are particularly preferable. Yellow couplers: couplers represented by formulas (I) and (II) in EP 502,424A; couplers represented by formulas (1) and (2) in EP 513,496A (especially Y-28 on page 18); EP 568,037A Claim 1
A coupler represented by the general formula (I) in column 1, lines 45 to 55 of US 5,066,576; a coupler represented by the general formula (I) in paragraph 0008 of JP-A-4-274425; Couplers described in claim 1 on page 40 of EP 498,381 A1 (especially D-35 on page 18); Couplers of the formula (Y) on page 4 of EP 447,969 A1 (especially Y-1 (page 17), Y -54 (p. 41)); US
Couplers represented by formulas (II) to (IV) in columns 7, 36 to 58 of column 4,476,219 (particularly II-17, 19 (column 17), II-24 (column 19)).

Magenta coupler; JP-A-3-39737 (L-57 (1
L-68 (lower right of page 12), L-77 (lower right of page 13); EP 456,
257 (A-4) -63 (p. 134), (A-4) -73, -75 (p. 139);
EP486,965 M-4, -6 (page 26), M-7 (page 27); EP 571,959A
M-45 (page 19); JP-A-5-204106 (M-1) (page 6); JP-A-4-204106
M-22 of paragraph 0237 of 362631.

Cyan coupler: CX-1, described in JP-A-4-04843
3,4,5,11,12,14,15 (pages 14 to 16); JP-A 4-43345 C-
7,10 (p. 35), 34, 35 (p. 37), (I-1), (I-17) (pp. 42-43);
A coupler represented by the general formula (Ia) or (Ib) according to claim 1 of JP-A-6-67385.

Polymer coupler: P-1, described in JP-A-2-44345
P-5 (page 11).

Examples of couplers in which the color forming dye has an appropriate diffusibility include US Pat. No. 4,366,237, GB 2,125,570, EP 96,873B,
Those described in DE 3,234,533 are preferred. Couplers for correcting unnecessary absorption of color-forming dyes are yellow colored cyan couplers represented by the formulas (CI), (CII), (CIII), and (CIV) described on page 5 of EP 456,257A1 (especially on page 84). YC-86), the EP
Yellow colored magenta coupler ExM-7 (202
), EX-1 (page 249), EX-7 (page 251), US 4,833,069
Magenta colored cyan coupler CC-9 (column
8), CC-13 (column 10), (2) of US 4,837,136 (column 8),
Colorless masking couplers of formula (A) in claim 1 of WO 92/11575 (especially the exemplified compounds on pages 36 to 45) are preferred.

Examples of compounds (including couplers) which react with oxidized developing agents to release photographically useful compound residues include the following. Development inhibitor releasing compound:
Compounds of the formulas (I), (II), (III) and (IV) described on page 11 of EP 378,236A1 (especially T-101 (page 30), T-104 (page 31), T-11
3 (page 36), T-131 (page 45), T-144 (page 51), T-158 (page 58)), EP43
Compounds represented by the formula (I) described on page 7 of 6,938A2 (particularly D-49 (page 51)), compounds represented by the formula (1) of EP 568,037A (particularly (23) (page 11)), Compounds of the formulas (I), (II) and (III) described on pages 5 to 6 of EP 440,195 A2 (especially on page 29)
I- (1)); Bleaching accelerator releasing compounds: compounds represented by the formulas (I) and (I ′) on page 5 of EP 310,125A2 (especially (60) and (6) on page 1)
1)) and a compound represented by formula (I) of claim 1 of JP-A-6-59411 (particularly (7) (page 7)); Ligand releasing compound: US
A compound represented by LIG-X described in claim 1 of 4,555,478 (especially a compound on line 21 to 41 of column 12); a leuco dye-releasing compound: compound 1 of column 3 to 8 of US 4,749,641
~ 6; Fluorescent dye releasing compound: Claim 4, C of US 4,774,181
Compound represented by OUP-DYE (especially compounds 1 to 11 in columns 7 to 10); Development accelerator or fogging agent releasing compound: US
4,656,123, the compounds represented by the formulas (1), (2), and (3) in column 3 (particularly, (I-22) in column 25) and EP 450,637A2
ExZK-2, p. 75, lines 36-38; a compound which releases a group which becomes a pigment only upon leaving: Formula of claim 1 of US 4,857,447
Compounds represented by (I) (especially, Y-1 to Y- of columns 25 to 36)
19).

As the additives other than the coupler, the following are preferable. Oil-soluble organic compound dispersion medium: P-3,5,1 of JP-A-62-215272
6,19,25,30,42,49,54,55,66,81,85,86,93 (140-144
Page); Latex for impregnation of oil-soluble organic compounds: US 4,199,
Latex according to No. 363; oxidized developing agent scavenger: a compound represented by the formula (I) in columns 2, 54 to 62 of US Pat. No. 4,978,606 (especially I-, (1), (2), (6), (12 ) (Column 4 ~
5), US Pat. No. 4,923,787, columns 5 to 10 of formula (particularly compound 1 (column 3); stain inhibitor: EP 298321A 4
Formulas (I) to (III) on page 30-33, especially I-47, 72, III-1, 27 (24
-48 pages); Anti-fading agent: A-6, 7, 20, 21, 23, 2 of EP 298321A
4,25,26,30,37,40,42,48,63,90,92,94,164 (pp.69-118),
US 5,122,444 columns 25-38 II-1 to III-23, especially III-
10, EP 471347A, pages 8-12, I-1 to III-4, especially II-2, US
5,139,931 columns 32-40 A-1 to 48, especially A-39,42;
Materials that reduce the amount of the coloring enhancer or color-mixing inhibitor used: EP 411324A, pages 1 to 24, I-1 to II-15, especially I-46; Formalin scavenger: EP 477932A, pages 24 to 29, SCV-
1-28, especially SCV-8; Hardener: JP-A 1-214845, p. 17
Formula (VII) of columns 13 to 23 of H-1,4,6,8,14, US 4,618,573
~ (XII) represented by the compound (H-1 ~ 54), JP-A-2-214852
Compounds (H-1 to 76) represented by the formula (6) on the lower right of page 8
H-14, compounds described in claim 1 of US Pat. No. 3,325,287; development inhibitor precursors: P-24, 37, 39 (6) of JP-A-62-168139.
77); compounds as claimed in claim 1 of US 5,019,492,
28, 29, especially in column 7; preservatives, fungicides: US 4,923,790
Columns 3 to 15 of I-1 to III-43, especially II-1,9,10,18, III
-25; Stabilizer, antifoggant: column 6, US 4,923,793
~ 16 I-1 ~ (14), especially I-1,60, (2), (13), US 4,952,48
Compounds 1 to 65, especially 36 in columns 25 to 32 of 3, Chemical sensitizer: triphenylphosphine selenide, JP-A-5-4032
Compound 50 of No. 4; Dye: a-1 on pages 15 to 18 of JP-A-3-156450
~ B-20, especially a-1,12,18,27,35,36, b-5, V-1 on page 27 ~ 29
~ 23, especially V-1, EP 445627A, FI-1 ~ F-II on pages 33 ~ 55
-43, especially III-11, F-II-8, III- on pages 17 to 28 of EP 457153A
1 to 36, especially III-1,3, Dye-1 of 8 to 26 of WO 88/04794
Compound 1 on page 6-11 of EP 319999A
-22, especially compound 1, EP 519306A, compounds D-1 to 87 represented by formulas (1) to (3) (pages 3 to 28), US Pat.
Compounds 1 to 22 represented by (I) (columns 3 to 10), US4,9
Compounds (1) to (31) represented by the formula (I) of 23,788 (columns 2 to 9); UV absorbers: compounds (18b) to (18r) represented by the formula (1) of JP-A-46-3335 , 101-427 (pp. 6-9), EP 520
Compounds (3) to (66) represented by the formula (I) of 938A (10 to 44
Page) and the compounds HBT-1 to 10 (14
Page), EP 521823A, compounds (1) to (3)
1) (columns 2-9).

The present invention can be applied to various color light-sensitive materials such as color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films and color reversal papers. In addition, 2-26,315 and 3,
Suitable for the film unit with lens described in -39784.

Suitable supports that can be used in the present invention include, for example, the aforementioned RD. No. 17643, page 28, RD. No. 18716, page 647, right column to page 648, left column, and RD. It is described in.

The specific photographic sensitivity in the present invention is described in
It is determined by the method described in 3-23635. This measuring method is based on JIS K 7614-1981.
The differences are that the development processing is completed within 30 minutes or more and 6 hours after exposure for sensitometry, and that the development processing is based on the Fujicolor standard processing recipe CN-16. Others are substantially the same as the measurement method described in JIS.

In the light-sensitive material of the present invention, the thickness from the light-sensitive silver halide layer closest to the support to the surface of the light-sensitive material is preferably 24 μm or less, more preferably 22 μm or less. Further, the film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. T _1/2 is the time required for the film thickness to reach 1/2 when the saturated film thickness is 90% of the maximum swollen film thickness reached when the color developing solution is processed at 30 ° C. for 3 minutes 15 seconds. Is defined. Film thickness is 25 ° C and relative humidity 55%
T _1/2 means the film thickness measured under humidity control (2 days), and T _1/2 is the value of A. Green et al.'S Photographic Science and Engineering (Photogr.Sci.En).
g.), Vol. 19, pp. 2,124-129, can be measured by using a serometer (swelling meter) of the type described. T
_{The 1/2} can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling ratio is preferably from 150 to 400%. The swelling ratio can be calculated from the maximum swelling film thickness under the conditions described above by the following formula: (maximum swelling film thickness-film thickness) / film thickness.

In the light-sensitive material of the present invention, a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 to 20 μm is preferably provided on the side opposite to the side having the emulsion layer. In this back layer, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder,
It is preferable to include a plasticizer, a lubricant, a coating aid, and a surfactant. The swelling ratio of the back layer is preferably from 150 to 500%.

The light-sensitive material of the present invention is obtained by using the above-mentioned RD.
No. 18716, No. 18716, 651 left column to right column, and N
o. 307105, pages 880 to 881.

Next, the processing solution for a color negative film used in the present invention will be described. The color developing solution used in the present invention is described in JP-A-4-121739, page 9, upper right column, line 1 to
The compounds described in page 11, lower left column, line 4, can be used. Particularly, color developing agents for rapid processing include 2-methyl-4- [N-ethyl-N- (2-hydroxyethyl) amino] aniline and 2-methyl-4- [N
-Ethyl-N- (3-hydroxypropyl) amino] aniline and 2-methyl-4- [N-ethyl-N- (4-hydroxybutyl) amino] aniline are preferred.

These color developing agents are used per liter of color developing solution (hereinafter, liter is also referred to as “L”).
It is preferably used in the range of 0.01 to 0.08 mol, particularly preferably 0.015 to 0.06 mol, more preferably 0.02 to 0.05 mol. In addition, the replenisher of the color developing solution includes
It is preferable to contain a color developing agent of 1.1 to 3 times this concentration, particularly preferably 1.3 to 2.5 times.

As a preservative of the color developing solution, hydroxylamine can be used widely. However, when higher preservation is required, substitution with an alkyl group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, or the like is required. A hydroxylamine derivative having a group is preferable, and specifically, N, N-di (sulfoethyl) hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, N, N-di (carboxyethyl) Hydroxylamines are preferred. Among the above, N, N-di (sulfoethyl) hydroxylamine is particularly preferred. These may be used in combination with hydroxylamine, but it is preferable to use one or more of them instead of hydroxylamine.

The preservative is preferably used in the range of 0.02 to 0.2 mol per liter, particularly preferably 0.03 to 0.15 mol, more preferably 0.04 to 0.1 mol. As in the case of the color developing agent, the replenisher preferably contains a preservative at a concentration of 1.1 to 3 times the concentration of the mother liquor (processing tank solution).

In the color developing solution, a sulfite is used as an anti-tarring agent for the oxide of the color developing agent. The sulfite is preferably used in the range of 0.01 to 0.05 mol per liter, and particularly preferably in the range of 0.02 to 0.04 mol. In the replenisher, it is preferable to use the replenisher at a concentration 1.1 to 3 times the above.

The pH of the color developer is preferably in the range of 9.8 to 11.0, particularly preferably 10.0 to 10.5, and the replenisher is set to a higher value in the range of 0.1 to 1.0 from these values. Preferably. In order to stably maintain such a pH, a known buffer such as carbonate, phosphate, sulfosalicylate, and borate is used.

The replenishment amount of the color developing solution is 80 to 1300 ml per m ² of the light-sensitive material (hereinafter, milliliter means “mL”).
Also described as. ) Is preferred, but from the viewpoint of reducing the environmental pollution load, a smaller amount is more preferred, and specifically 80 to 60
0 mL, more preferably 80-400 mL.

The bromide ion concentration in the color developing solution is usually from 0.01 to 0.06 mol per liter. However, fog is suppressed while maintaining sensitivity, discrimination is improved, and graininess is improved. From the purpose, per 1L
It is preferably set to 0.015 to 0.03 mol. When the bromide ion concentration is set in such a range, the replenisher may contain bromide ions calculated by the following formula. However, when C becomes negative, it is preferred that the replenisher does not contain bromide ions.

C = A−W / V C: Bromide ion concentration in the color developing replenisher (mol / L) A: Target bromide ion concentration in the color developing solution (mol / L) W: 1 m ² exposure Amount (mol) of bromide ions eluted from the light-sensitive material into the color developer when the material is color-developed. V: Replenishment amount (L) of the color-developing replenisher for 1 m ² of the light-sensitive material.

When the replenishment rate is reduced or when the bromide ion concentration is set to a high value, 1-phenyl-3-pyrazolidone or 1-phenyl-
Pyrazolidones represented by 2-methyl-2-hydroxymethyl-3-pyrazolidone and 3,6-dithia-1,8
It is also preferable to use a development accelerator such as a thioether compound represented by octanediol.

Compounds and processing conditions described in JP-A-4-125558, page 4, lower left column, line 16 to page 7, lower left column, line 6 can be applied to the processing solution having bleaching ability in the present invention. . The bleaching agent preferably has an oxidation-reduction potential of 150 mV or more, and specific examples thereof include JP-A-5-72694 and JP-A-5-73331.
The compounds described in No. 2 are preferable, and 1,3-diaminopropanetetraacetic acid, particularly, a ferric complex salt of the compound of the specific example 1 on page 7 of JP-A-5-73312 is preferable.

In order to improve the biodegradability of the bleaching agent, JP-A-4-251845, JP-A-4-268552, EP588,289, and 591,
934, a compound ferric complex salt described in JP-A-6-208213 is preferably used as a bleaching agent. The concentration of these bleaching agents is preferably 0.05 to 0.3 mol per liter of a solution having bleaching ability.
It is preferred to design with a mole to 0.15 mole. When the solution having bleaching ability is a bleaching solution, 0.2 mol / L is used.
Preferably, it contains 1 mol of bromide, especially 0.3 mol.
It is preferable to contain 0.80.8 mol.

The replenisher of the solution having the bleaching ability basically contains the concentration of each component calculated by the following formula. Thereby, the concentration in the mother liquor can be kept constant. C _R = C _T × (V ₁ + V ₂ ) / V ₁ + C _P C _R : Concentration of component in replenisher C _T : Concentration of component in mother liquor (processing tank liquid) C _P : Consumed during processing the concentration of component V _1: amount of replenisher having bleaching ability for the light-sensitive material of 1m _² (mL) V ^2: amount carried from previous bath by the photographic material of 1 m ² (m
L).

In addition, the bleaching solution preferably contains a pH buffer, particularly preferably a dicarboxylic acid having a low odor, such as succinic acid, maleic acid, malonic acid, glutaric acid, and adipic acid. Also, JP-A-53-9
It is also preferred to use the known bleaching accelerators described in US Pat. No. 5,630, RD No. 17129, US Pat. The bleaching solution is preferably replenished with 50 to 1000 mL of bleach replenisher per m ² of the light-sensitive material, particularly preferably 80 to 500 mL, more preferably 100 to 300 mL. Further, it is preferable to perform aeration on the bleaching solution.

The processing solution having a fixing ability is described in
The compounds and processing conditions described on page 7, lower left column, line 10 to page 8, lower right column, line 19 of 4-125558 can be applied. In particular, in order to improve the fixing speed and the preservability, the compounds represented by the general formulas (I) and (II) of JP-A-6-301169 are contained alone or in combination in a processing solution having a fixing ability. Is preferred. In addition to p-toluenesulfinic acid salts, it is also possible to use the sulfinic acid described in JP-A-1-2224762.
It is preferable from the viewpoint of improvement in preservation.

It is preferable to use ammonium as a cation in the solution having the bleaching ability or the solution having the fixing ability from the viewpoint of improving the desilvering property. However, from the viewpoint of reducing environmental pollution, ammonium is reduced or reduced to zero. Is more preferred. In the bleaching, bleach-fixing and fixing steps, JP-A-1-30
It is particularly preferred to carry out jet stirring as described in 9059. The replenishment amount of the replenisher in the bleach-fixing or fixing process is
100 to 1000 mL per 1 m ^{2 of} photosensitive material, preferably 150 to 1000 mL
700700 mL, particularly preferably 200-600 mL.

In the bleach-fixing and fixing steps, it is preferable to install various silver recovery devices in-line or off-line to recover silver. By installing in-line, the processing can be carried out with a reduced silver concentration in the solution, so that the replenishment amount can be reduced. It is also preferable to recover silver off-line and reuse the remaining liquid as a replenisher.

The bleach-fixing step and the fixing step can be constituted by a plurality of processing tanks, and it is preferable that each tank is cascaded to form a multistage countercurrent system. From the balance with the size of the developing machine, a two-tank cascade configuration is generally efficient, and the ratio of the processing time in the former tank and the latter tank is preferably in the range of 0.5: 1 to 1: 0.5. In particular, the range of 0.8: 1 to 1: 0.8 is preferable.

It is preferable that a free chelating agent not forming a metal complex is present in the bleach-fixing solution or the fixing solution from the viewpoint of improvement of preservation. These chelating agents are described in connection with the bleaching solution. Preferably, a biodegradable chelating agent is used.

Regarding the washing and stabilizing steps, the contents described in JP-A-4-125558, page 12, lower right column, line 6 to page 13, right lower column, line 16 can be preferably applied. In particular,
EP 504,609 instead of formaldehyde
Azolylmethylamines described in 519,190 and JP-A-4-36
From the viewpoint of preserving the working environment, it is preferable to use the N-methylolazoles described in 2943, or to dimerize the magenta coupler to obtain a surfactant-free liquid containing no image stabilizer such as formaldehyde. . In order to reduce the adhesion of dust to the magnetic recording layer applied to the photosensitive material, a stabilizing solution described in JP-A-6-289559 can be preferably used.

The amount of washing and replenishment of the stabilizing solution can be adjusted according to the photosensitive material 1
80 to 1000 mL per m ² is preferable, and particularly 100 to 500 mL, and more preferably 150 to 300 mL, is a preferable range in terms of both securing a washing or stabilizing function and reducing waste liquid for environmental protection. In the treatment performed with such a replenishing amount, thiabendazole, 1, 1
2-benzoisothiazoline-3-one, 5-chloro-2-
It is preferable to use a known fungicide such as methylisothiazolin-3-one, an antibiotic such as gentamicin, or water deionized with an ion exchange resin.
It is more effective to use a combination of deionized water and a bactericide or antibiotic.

Further, the liquid in the washing or stabilizing liquid tank is
JP-A-3-46652, 3-53246, -355542, 3-121448,
It is also preferable to reduce the replenishment amount by performing the reverse osmosis membrane treatment described in the above-mentioned 3-126030, and in this case, the reverse osmosis membrane is preferably a low pressure reverse osmosis membrane.

In the process of the present invention, it is particularly preferable to carry out the correction of the evaporation of the processing solution disclosed in the Invention Association's published technical report, Official Technical Publication No. 94-4992. In particular, a method of performing correction using temperature and humidity information of a developing machine installation environment based on (Equation 1) on page 2 is preferable. The water used for evaporation correction is preferably collected from a replenishment tank for washing,
In that case, it is preferable to use deionized water as the washing replenishing water.

As the treating agent used in the present invention, those described in page 3, right column, line 15 to page 4, left column, line 32 of the above-mentioned published technical report are preferable. In addition, as a developing machine used for this,
The film processor described on page 22, right column, lines 22 to 28 is preferred.

Specific examples of preferred processing agents, automatic developing machines, and evaporation correction systems for carrying out the present invention are described in the above-mentioned published technical report, from page 5, right column, line 11 to page 7, right column, last line. Have been.

The supply form of the treating agent used in the present invention is as follows.
It may be in any form, such as a liquid preparation in the form of a liquid used or a concentrated form, or granules, powders, tablets, pastes, and emulsions. As an example of such a treating agent, JP-A-63-1
7453 discloses a liquid agent contained in a container having low oxygen permeability,
19655, 4-230748, vacuum-packed powders or granules, 4-221951, granules containing a water-soluble polymer,
JP-A-51-61837 and JP-A-6-102628 describe tablets and JP-A-57-5
Discloses a paste-like treating agent, which can be preferably used, but from the viewpoint of simplicity at the time of use,
It is preferable to use a liquid that has been prepared in advance in a concentration for use.

The containers for storing these treating agents are made of polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, nylon, etc., alone or as a composite material. These are selected according to the required level of oxygen permeability. For an easily oxidizable liquid such as a color developing solution, a material having low oxygen permeability is preferable, and specifically, a polyethylene terephthalate or a composite material of polyethylene and nylon is preferable. These materials have a thickness of 500 to 1500 μm and are used for containers, and preferably have an oxygen permeability of 20 mL / m ² · 24 hrs · atm or less.

Next, the processing solution for a color reversal film used in the present invention will be described. For the processing for the color reversal film, see page 6, line 5 to page 10, line 5 and page 15, line 8 to page 24, 2 of the publicly known technique No. 6 (April 1, 1991) issued by Aztec Co., Ltd. Each row is described in detail, and any of the contents can be preferably applied.

In processing a color reversal film, an image stabilizer is contained in a conditioning bath or a final bath. Such image stabilizers include, in addition to formalin, sodium formaldehyde sodium bisulfite and N-methylolazole, and from the viewpoint of working environment, sodium formaldehyde sodium bisulfite or N-methylolazole is preferable, and N-methylol is preferred. As the azoles, N-methyloltriazole is particularly preferred. Further, the contents relating to the color developing solution, the bleaching solution, the fixing solution, the washing water and the like described in the processing of the color negative film can be preferably applied to the processing of the color reversal film. Preferred processing agents for color reversal films containing the above contents include E-6 processing agent manufactured by Eastman Kodak Company and Fuji Photo Film Co., Ltd.
CR-56 treating agent.

Next, the magnetic recording layer used in the present invention will be described. The magnetic recording layer used in the present invention is obtained by coating a support with an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder. Magnetic particles used in the present invention include ferromagnetic iron oxide such as γFe ₂ O _3, Co deposited γFe ₂ O _3, Co coated magnetite, Co containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy Hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite, etc. can be used. Co deposited γFe ₂ O ₃
Co-coated ferromagnetic iron oxide such as The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape and the like.
Preferably at least 20 m ² / g in S _BET is the specific surface area, and particularly preferably equal to or greater than 30 m ² / g.

The saturation magnetization (σs) of the ferromagnetic material is preferably
3.0 × 10 ^{4 to} 3.0 × 10 ⁵ A / m, particularly preferably 4.0 × 10 5
^{It is 4 to} 2.5 × 10 ⁵ A / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, the surface of the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent as described in JP-A-6-161032. Also JP-A-4-59911
No. 5,816,52 can also be used.

The binder used for the magnetic particles may be a thermoplastic resin, a thermosetting resin, a radiation-curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, or a natural material described in JP-A-4-219569. Combinations (cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The Tg of the above resin is -40 ° C to 300 ° C, and the weight average molecular weight is
It is between 2,000 and 1,000,000. Examples thereof include vinyl copolymers, cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins, and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. As the isocyanate-based crosslinking agent, tolylene diisocyanate,
Isocyanates such as 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, and the reaction products of these isocyanates with polyalcohols (for example, the reaction product of 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane) ), And polyisocyanates formed by condensation of these isocyanates, and the like, which are described in, for example, JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic material in the binder, a kneader, a pin type mill, an annular type mill and the like are preferably used, as in the method described in JP-A-6-35092. Dispersants described in JP-A-5-088283 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm,
More preferably, it is 0.3 μm to 3 μm. The mass ratio between the magnetic particles and the binder is preferably 0.5: 100 to 60: 100, and more preferably 1: 100 to 30: 100. The coating amount of the magnetic particles is 0.005 to 3 g / m ² , preferably 0.01 to ² g / m ² , and more preferably 0.02 to 0.5 g / m ² . The transmission yellow density of the magnetic recording layer is preferably 0.01 to 0.50, and 0.03 to 0.20.
Is more preferable, and 0.04 to 0.15 is particularly preferable. The magnetic recording layer can be provided on the entire back surface of the photographic support by coating or printing, or in a stripe shape. Methods for applying the magnetic recording layer include air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray,
Dip, bar, extrusion, etc. are available,
The coating liquid described in JP-A-5-341436 is preferred.

In the magnetic recording layer, lubricity improvement, curl control,
It may have functions such as antistatic, antiadhesion, and head polishing, or may provide another functional layer to provide these functions. At least one of the particles has a Mohs hardness of 5 or more. The abrasives of the above non-spherical inorganic particles are preferred. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. For photosensitive materials having a magnetic recording layer, see US Pat.
5,229,259, 5,215,874 and EP 466,130.

Next, the polyester support preferably used in the present invention will be described. For details including photosensitive materials, treatments, cartridges and examples described later, refer to Published Technical Report, Official Technique No. 94-6023 (Invention Association; 1994.15.). The polyester used in the present invention is formed by using diol and aromatic dicarboxylic acid as essential components. As aromatic dicarboxylic acids, 2,6-, 1,5-, 1,4-, and 2,7-naphthalenedicarboxylic acid, and terephthalic acid are used. Acids, isophthalic acid, phthalic acid, and diols include diethylene glycol, triethylene glycol, cyclohexane dimethanol, bisphenol A, and bisphenol. Examples of the polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene-2,
6-naphthalate. The average molecular weight range is about 5,000
Or 200,000. The Tg of the polyester of the present invention is 50
° C or higher, and more preferably 90 ° C or higher.

Next, the polyester support has a winding habit.
The heat treatment temperature should be 40 ° C or higher and lower than Tg to reduce
More preferably, the heat treatment is performed at Tg-20 ° C. or higher and lower than Tg.
The heat treatment may be performed at a constant temperature within this temperature range,
The heat treatment may be performed while cooling. This heat treatment time is 0.
1 hour or more and 1500 hours or less, more preferably 0.5 hour or more
Less than 200 hours. The heat treatment of the support is performed in roll form.
Or may be carried out while being transported in web form.
Good. The surface is made uneven (for example, SnO_TwoAnd Sb_TwoO _FiveEtc.
(Apply conductive inorganic fine particles.)
No. Also, knurling is applied to the end and only the end is raised slightly
Innovative measures such as preventing the cut edge from appearing on the core
It is desirable. These heat treatments are performed on the surface after forming the support.
After treatment, after coating the back layer (antistatic agent, slip agent, etc.)
It may be carried out at any stage after the application. Preferred
Is after the application of the antistatic agent.

An ultraviolet absorber may be incorporated in this polyester. In order to prevent light piping, the purpose can be achieved by kneading a commercially available dye or pigment for polyester, such as Diaresin manufactured by Mitsubishi Kasei or Kayaset manufactured by Nippon Kayaku.

Next, in the present invention, it is preferable to perform a surface treatment in order to bond the support and the light-sensitive material constituting layer. Chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
Surface activation treatments such as laser treatment, mixed acid treatment, ozone oxidation treatment and the like can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.

Next, the undercoating method will be described. It may be a single layer or two or more layers. As a binder for the undercoat layer,
Starting from copolymers starting from monomers selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride, etc., polyethylene imine, epoxy resin, grafting Gelatin, nitrocellulose and gelatin are included.
Compounds that swell the support include resorcinol and p-chlorophenol. In the undercoat layer, as a gelatin hardener, chromium salt (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6) are used.
-Hydroxy-S-triazine), epichlorohydrin resin, active vinyl sulfone compound and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm) may be contained as a matting agent.

In the present invention, an antistatic agent is preferably used. As those antistatic agents, carboxylic acid and carboxylate, polymers including sulfonate,
Examples include cationic polymers and ionic surfactant compounds.

The most preferred antistatic agent is Zn.
O, TiO_Two, SnO_Two, Al_TwoO_Three, In_TwoO_Three, SiO _Two, MgO, BaO, Mo
O_Three, V_TwoO_FiveAt least one type of volume resistivity selected from
Ten⁷Ωcm or less, more preferably 10^FiveGrains that are Ω · cm or less
0.001 to 1.0 μm crystalline metal oxide or
Fine particles of these composite oxides (Sb, P, B, In, S, Si, C, etc.),
Furthermore, sol-like metal oxides or composite oxides thereof
Particles.

The content in the light-sensitive material is 5 to 500 mg / m^TwoBut
Preferably particularly preferably 10 to 350 mg / m ^TwoIt is. Conductive
Ratio of the amount of the crystalline oxide or its composite oxide to the binder
Is preferably 1/300 to 100/1, more preferably 1/100 to 100
/ 5.

The light-sensitive material of the present invention preferably has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.
It is 25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball having a diameter of 5 mm was conveyed at 60 cm / min (25
° C, 60% RH). In this evaluation, even when the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level.

Examples of the slipping agent usable in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes such as polydimethylsiloxane, polydiethyl Siloxane, polystyrylmethylsiloxane, polymethylphenylsiloxane, or the like can be used. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable.

The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be on either the emulsion side or the back side, but is particularly preferably added to the outermost layer on the emulsion side.
The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, and the particle size distribution is preferably narrower, and the average particle size is 0.9 to 1.1 μm.
It is preferable that 90% or more of the total number of particles be contained during the doubling. It is also preferable to simultaneously add fine particles having a size of 0.8 μm or less in order to enhance the matting property. For example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm)), Polystyrene particles (0.25 μm) and colloidal silica (0.03 μm).

Next, the film cartridge used in the present invention will be described. The main material of the patrone used in the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the patrone of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonionic, anionic, cationic and betaine surfactants or polymers can be preferably used. These antistatic patrones are described in JP-A 1-312537 and JP-A 1-312538. Particularly, the resistance at 25 ° C. and 25% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded in order to impart light shielding properties. The size of the patrone may be the same as the current 135 size, and the size reduction of the camera requires the current 135 size 25 mm cartridge diameter to be 22 mm.
The following is also effective. The volume of the patrone case is preferably 30 cm ³ or less, more preferably 25 cm ³ or less. The mass of the plastic used for the patrone and the patrone case is preferably 5 g to 15 g.

Further, a patrone used in the present invention to feed a film by rotating a spool may be used. Further, a structure may be employed in which the leading end of the film is housed in the patrone main body, and the leading end of the film is sent out from the port portion of the patrone by rotating the spool shaft in the film sending direction. These are disclosed in US Pat. Nos. 4,834,306 and 5,226,613. The photographic film used in the present invention may be a so-called raw film before development or a photographic film that has been subjected to development processing. Also, raw film and developed photographic film may be stored in the same new patrone,
A different patrone may be used.

The color photographic light-sensitive material of the present invention is also suitable as a negative film for an advanced photo system (hereinafter referred to as an AP system), and NEXIA A manufactured by Fuji Photo Film Co., Ltd. (hereinafter referred to as Fuji Film). NEXIA
Films processed into the AP system format like F, NEXIA H (in order, ISO 200/100/400) and stored in a special cartridge. These AP system cartridge films are used by loading them into an AP system camera such as the EPION series (e.g., EPION 300Z) manufactured by Fujifilm. Further, the color photographic light-sensitive material of the present invention is also suitable for a film with a lens such as a super color slim made by Fujifilm.

The film photographed by the above is printed in the mini-lab system through the following steps. (1) Reception (exposed cartridge film received from customer) (2) Detaching process (transfer film from cartridge to intermediate cartridge for developing process) (3) Film development (4) Retouching process (developed negative (Return the film to the original cartridge.) (5) Print (continuous automatic printing of C / H / P 3 type prints and index prints on color paper (preferably SUPER FA8 made by FUJIFILM)) (6) Verification and shipment (The cartridge and index print are collated by ID number and shipped together with the print.)

These systems include Fujifilm Minilab Champion Super FA-298 / FA-278 / FA-258 / F
A-238 and Fujifilm Digital Lab System Frontier are preferred. FP922AL / FP562B / FP562B, AL / FP362B / FP as a minilab champion film processor
362B, AL, and the recommended treatment chemicals are Fujicolor Justit CN-16L and CN-16Q. As a printer processor, PP3008AR / PP3008A / PP1828AR / PP1828A / PP12
58AR / PP1258A / PP728AR / PP728A, and the recommended treatment chemicals are Fujicolor Justit CP-47L and CP-40FAII. In Frontier System, Scanner & Image Processor SP-1000 and Laser Printer & Paper Processor LP-1000P or Laser Printer LP
-1000W is used. The detacher used in the detaching step and the reattacher used in the rear attaching step are preferably DT200 / DT100 and AT200 / AT100 of Fujifilm, respectively.

The AP system can also be enjoyed by a photo joy system centered on Fujifilm's Aladdin 1000 digital image workstation. For example, Aladdin 1000 can be directly loaded with a developed AP system cartridge film, or negative, positive, and print image information can be transferred to a 35mm film scanner FE.
The digital image data obtained by inputting using the -550 or PE-550 flat head scanner can be easily processed and edited. The data are stored in a digital color printer NC-550AL using a light fixing type thermal color printing system and a pictograph 3000 using a laser exposure thermal development transfer system.
Or as prints by existing laboratory equipment through a film recorder. The Aladdin 1000 can also output digital information directly to a floppy (registered trademark) disk or Zip disk, or to a CD-R via a CD writer.

On the other hand, at home, the developed AP system cartridge film is transferred to a Fujifilm photo player AP.
You can enjoy photos on TV just by loading it in -1,
By loading it onto a Fujifilm AS-1 photo scanner, image information can be continuously and rapidly captured on a personal computer. To input a film, print or three-dimensional object to a personal computer, use Fujifilm PhotoVision FV-10 / FV
-5 is available. Furthermore, image information recorded on a floppy disk, Zip disk, CD-R, or hard disk can be variously processed and enjoyed on a personal computer using Fujifilm's application software Photo Factory. In order to output high-quality prints from a personal computer, a digital color printer NC-2 / NC-2D manufactured by Fujifilm of a light fixing type thermal color print system is suitable.

In order to store the developed AP system cartridge film, the Fuji Color Pocket Album AP-5 POP L, AP-1 POP L, AP-1 POP KG or the cartridge file 16 is preferable.

[0174]

Examples of the present invention will be described below. However, the present invention is not limited to this embodiment.

Example 1 The support used in this example was produced by the following method. 1) First layer and undercoat layer For a polyethylene naphthalate support having a thickness of 90 μm, a treatment atmosphere pressure of 2.66 × 10
Pa, H ₂ O partial pressure of 75% in the atmosphere gas, a discharge frequency 3
0 kHz, output 2500 W, processing intensity 0.5 kV ・ A ・
A glow discharge treatment was performed at a rate of min / m ² . On this support,
For the first layer, a coating solution having the following composition was used.
The coating was performed at a coating amount of 5 mL / m ² by using the bar coating method described in Japanese Patent Application Laid-Open No. H10-163,036.

Conductive fine particle dispersion (SnO ₂ / Sb ₂ O ₅ particle concentration 50 parts by mass 10% aqueous dispersion. Secondary aggregate having a primary particle diameter of 0.005 μm and an average particle diameter of 0.05 μm) Gelatin 0.5 parts by mass Water 49 parts by mass Polyglycerol polyglycidyl ether 0.16 parts by mass Poly (degree of polymerization 20) oxyethylene 0.1 parts by mass Sorbitan monolaurate.

Further, after the first layer was applied, it was wound around a stainless steel core having a diameter of 20 cm, heated at 110 ° C. (Tg of the PEN support: 119 ° C.) for 48 hours, heat-treated, and annealed. Thereafter, a coating solution having the following composition was applied to the side opposite to the first layer side as an undercoat layer for the emulsion at a coating amount of 10 mL / m ² using a bar coating method.

Gelatin 1.01 part by weight Salicylic acid 0.30 part by weight Resorcin 0.40 part by weight Poly (degree of polymerization 10) oxyethylene nonylphenyl ether 0.11 part by weight Water 3.53 parts by weight Methanol 84.57 parts by weight n -Propanol 10.08 parts by weight.

Further, a second layer and a third layer described later are sequentially coated on the first layer, and finally, a color negative photosensitive material having a composition described later is overlaid on the opposite side to form a silver halide emulsion layer. A transparent magnetic recording medium was manufactured.

2) Second layer (transparent magnetic recording layer) Dispersion of magnetic material Co-coated γ-Fe ₂ O ₃ magnetic material (average major axis length: 0.25 μm)
m, S _BET : 39 m ² / g, Hc: 6.56 × 10 ⁴ A /
m, σs: 77.1 Am ² / kg, σr: 37.4 Am ²
/ Kg) 1100 parts by mass, water 220 parts by mass and 165 parts by mass of a silane coupling agent [3- (poly (degree of polymerization 10) oxyethynyl) oxypropyl trimethoxysilane] are added and kneaded well in an open kneader for 3 hours. did. The coarsely dispersed viscous liquid was dried at 70 ° C. for 24 hours to remove water, and then heat-treated at 110 ° C. for 1 hour to produce surface-treated magnetic particles.

Further, the mixture was kneaded again in the open kneader for 4 hours according to the following formulation. The above-mentioned surface-treated magnetic particles 855 g Diacetyl cellulose 25.3 g Methyl ethyl ketone 136.3 g Cyclohexanone 136.3 g Further, the mixture was finely dispersed at 2,000 rpm for 4 hours by a sand mill (1/4 G sand mill) according to the following formulation. As the media, 1 mmφ glass beads were used. The kneading liquid 45 g Diacetyl cellulose 23.7 g Methyl ethyl ketone 127.7 g Cyclohexanone 127.7 g.

Further, a magnetic substance-containing intermediate liquid was prepared according to the following formulation. Preparation of Magnetic Substance-Containing Intermediate Solution 674 g of the above magnetic substance fine dispersion liquid 24280 g (solid content: 4.34%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) cyclohexanone 46 g And stirred to produce a “magnetic substance-containing intermediate liquid”.

An α-alumina abrasive dispersion of the present invention was prepared according to the following formulation. (A) Sumicorundum AA-1.5 (average primary particle size 1.5 μm, specific surface area 1.3 m ² / g).

Preparation of Particle Dispersion Liquid Sumicorundum AA-1.5 152 g Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicone Co., Ltd.) 0.48 g Diacetyl cellulose solution 227.52 g (solid content 4.5%, solvent: methyl ethyl ketone / Cyclohexanone = 1/1) A sand mill (1/1 /
(4G sand mill) at 800 rpm for 4 hours. The media used was zirconia beads of 1 mmφ.

(B) Colloidal silica particle dispersion (fine particles) "MEK-ST" manufactured by Nissan Chemical Industries, Ltd. was used. This is a dispersion liquid of colloidal silica having an average primary particle diameter of 0.015 μm using methyl ethyl ketone as a dispersion medium,
The solids content is 30%.

Preparation of Coating Solution for Second Layer The above magnetic substance-containing intermediate solution 19053 g Diacetyl cellulose solution 264 g (solid content: 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) Colloidal silica dispersion “MEK-ST” [Dispersion b] 128 g (solid content 30%) AA-1.5 dispersion [dispersion a] 12 g Millionate MR-400 (manufactured by Nippon Polyurethane Industries, Ltd.) Diluent 203 g (solid content 20%, dilution) solvent: at methylethylketone / cyclohexanone = 1/1) Methyl ethyl ketone 170 g cyclohexanone 170 g the above mixed and stirred coating solution of a wire bar, was applied so that the coating amount of 29.3 mL / m ^2. 11 for drying
Performed at 0 ° C. The thickness of the dried magnetic layer is 1.0 μm.
m.

3) Third Layer (High Fatty Acid Ester Slip Agent-Containing Layer) Preparation of Dispersion Stock Solution of Slip Agent The following solution A was heated and dissolved at 100 ° C., added to Solution A, and dispersed with a high-pressure homogenizer. Was prepared. Solution A The following compound 399 parts by mass C ₆ H ₁₃ CH (OH) (CH ₂ ) ₁₀ COOC ₅₀ H _{101 The following} compound 171 parts by mass n-C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H cyclohexanone 830 parts by mass Liquid Cyclohexanone 8600 parts by mass.

Preparation of Spherical Inorganic Particle Dispersion A spherical inorganic particle dispersion [c1] was prepared according to the following formulation. Isopropyl alcohol 93.54 parts by mass Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicone) Compound 1-1: (CH ₃ O) ₃ Si— (CH ₂ ) ₃ —NH ₂ ) 5.53 parts by mass Compound 12 .93 parts by mass

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Seahoster KEP50 88.00 parts by mass (amorphous spherical silica, average particle size 0.5 μm, manufactured by Nippon Shokubai Co., Ltd.).

After stirring for 10 minutes with the above formulation, the following is further added. 252.93 parts by mass of diacetone alcohol While cooling the above liquid with ice and stirring, an ultrasonic homogenizer “SONIFIER450 (BRANSON CORPORATION)
)) For 3 hours to obtain a spherical inorganic particle dispersion c1.
Was completed.

Preparation of Spherical Organic Polymer Particle Dispersion A spherical organic polymer particle dispersion [c2] was prepared according to the following formulation. XC99-A8808 (manufactured by Toshiba Silicone Co., Ltd., spherical crosslinked polysiloxane particles, average particle size 0.9 μm) 60 parts by mass methyl ethyl ketone 120 parts by mass cyclohexanone 120 parts by mass (solid content 20%, solvent: methyl ethyl ketone / cyclohexanone = 1 / 1) While cooling with ice and stirring, ultrasonic homogenizer “SONI”
Using FIER450 (manufactured by BRANSON), the dispersion was performed for 2 hours to complete a spherical organic polymer particle dispersion c2.

Preparation of Third Layer Coating Solution The following was added to 542 g of the above-mentioned slip agent dispersion stock solution to prepare a third layer coating solution.

Diacetone alcohol 5950 g Cyclohexanone 176 g Ethyl acetate 1700 g The above-mentioned Seahosta KEP50 dispersion [c1] 53.1 g The above-mentioned spherical organic polymer particle dispersion [c2] 300 g FC431 2.65 g (3M Co., Ltd.) BYK310 5.3 g (manufactured by BYK Chemi Japan KK, solid content 25%). The third layer coating solution was applied on the second layer at a coating amount of 10.35 mL / m ² , dried at 110 ° C., and further dried at 97 ° C. for 3 minutes.

4) Coating of Photosensitive Layer Next, on the opposite side of the back layer obtained above, each layer having the following composition was applied in a multi-layer manner to prepare a color negative film sample 101. (Composition of photosensitive layer) The number corresponding to each component indicates the coating amount expressed in units of g / m ² , and the silver halide indicates the coating amount in terms of silver.

(Sample 101) First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.122 0.07 μm Silver Iodobromide Emulsion Silver 0.01 Gelatin 0.919 ExM-1 0.066 ExC-1 0.002 ExC-3 0.002 Cpd-2 0.001 F-8 0.001 HBS-1 0.050 HBS-2 0.002.

Second Layer (Second Antihalation Layer) Black Colloidal Silver Silver 0.055 Gelatin 0.425 ExF-1 0.002 F-8 0.001 Solid Disperse Dye ExF-7 0.120 HBS-1 074.

Third layer (intermediate layer) ExC-2 0.050 Cpd-1 0.090 Polyethyl acrylate latex 0.200 HBS-1 0.100 Gelatin 0.700.

Fourth layer (low-sensitivity red-sensitive emulsion layer) Em-D silver 0.500 Em-C silver 0.347 ExC-1 0.188 ExC-2 0.011 ExC-3 0.075 ExC-40 .121 ExC-5 0.010 ExC-6 0.007 ExC-8 0.050 ExC-9 0.020 Cpd-2 0.025 Cpd-4 0.025 Cpd-7 0.015 UV-2 0.047 UV-3 0.086 UV-4 0.018 HBS-1 0.245 HBS-5 0.038 Gelatin 0.994.

Fifth Layer (Medium Speed Red Sensitive Emulsion Layer) Em-B Silver 0.480 Em-C Silver 0.460 ExC-1 0.154 ExC-2 0.068 ExC-3 0.018 ExC-40 .103 ExC-5 0.023 ExC-6 0.010 ExC-8 0.016 ExC-9 0.005 Cpd-2 0.036 Cpd-4 0.028 Cpd-7 0.020 HBS-1 0.129 Gelatin 0.882.

Sixth layer (high-sensitivity red-sensitive emulsion layer) Em-A silver 1.100 ExC-1 0.250 ExC-3 0.035 ExC-6 0.029 ExC-8 0.110 ExC-9 020 Cpd-2 0.064 Cpd-4 0.077 Cpd-7 0.030 HBS-1 0.329 HBS-2 0.120 Gelatin 1.245.

Seventh layer (intermediate layer) Cpd-1 0.094 Cpd-6 0.369 Solid disperse dye ExF-4 0.030 HBS-1 0.049 Polyethyl acrylate latex 0.088 Gelatin 0.886.

Eighth Layer (Layer that Gives Layering Effect to Red Sensitive Layer) Em-J Silver 0.170 Em-K Silver 0.173 Cpd-4 0.030 ExM-2 0.120 ExM-3 0.016 ExM -4 0.026 ExY-1 0.016 ExY-4 0.036 ExC-7 0.026 HBS-1 0.218 HBS-3 0.003 HBS-5 0.030 Gelatin 0.610.

Ninth layer (low-sensitivity green-sensitive emulsion layer) Em-H silver 0.329 Em-G silver 0.333 Em-I silver 0.088 ExM-2 0.378 ExM-3 0.047 ExY-1 0.017 ExC-7 0.007 HBS-1 0.098 HBS-3 0.010 HBS-4 0.077 HBS-5 0.548 Cpd-5 0.010 Cpd-7 0.020 Gelatin 1.470.

Tenth Layer (Medium Speed Green Sensitive Emulsion Layer) Em-F Silver 0.457 ExM-2 0.032 ExM-3 0.029 ExM-4 0.029 ExY-3 0.007 ExC-6 010 ExC-7 0.012 ExC-8 0.010 HBS-1 0.065 HBS-3 0.002 HBS-4 0.020 HBS-5 0.020 Cpd-5 0.004 Cpd-7 0.010 Gelatin 0.446.

Eleventh layer (high-sensitivity green-sensitive emulsion layer) Em-E silver 0.794 ExC-6 0.002 ExC-8 0.010 ExM-1 0.013 ExM-2 0.011 ExM-3 0. 035 ExM-4 0.020 ExY-3 0.003 Cpd-3 0.004 Cpd-4 0.007 Cpd-5 0.010 Cpd-7 0.020 HBS-1 0.148 HBS-3 0.003 HBS -4 0.020 HBS-5 0.037 polyethyl acrylate latex 0.099 gelatin 0.939.

Twelfth layer (yellow filter layer) Cpd-1 0.094 Solid disperse dye ExF-2 0.070 Solid disperse dye ExF-5 0.010 Oil-soluble dye ExF-6 0.010 HBS-1 0.049 Gelatin 0.630.

13th layer (low-sensitivity blue-sensitive emulsion layer) Em-O silver 0.112 Em-M silver 0.320 Em-N silver 0.240 ExC-1 0.027 ExC-7 0.013 ExY-1 0.002 ExY-2 0.890 ExY-4 0.058 Cpd-2 0.100 Cpd-3 0.004 HBS-1 0.222 HBS-5 0.074 Gelatin 1.553.

Fourteenth layer (high-sensitivity blue-sensitive emulsion layer) Em-L silver 0.725 ExY-2 0.201 ExY-4 0.068 Cpd-2 0.075 Cpd-3 0.001 Cpd-7 030 HBS-1 0.124 gelatin 0.678.

Fifteenth layer (first protective layer) 0.07 μm silver iodobromide emulsion Silver 0.301 UV-1 0.211 UV-2 0.132 UV-3 0.198 UV-4 0.026 F -11 0.009 S-1 0.086 HBS-1 0.175 HBS-4 0.050 gelatin 1.984.

Sixteenth layer (second protective layer) H-1 0.400 B-1 (diameter 1.7 μm) 0.050 B-2 (diameter 1.7 μm) 0.150 B-3 0.050 S- 10.20 Gelatin 0.750.

Further, in order to improve the storability, processability, pressure resistance, fungicidal / antibacterial properties, antistatic properties and coatability of each layer, W-1 to W-6, B-4 to B -6, F
-1 to F-18, and lead salts, platinum salts, iridium salts, and rhodium salts.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 of the twelfth layer was dispersed by the following method. ExF-2 wet cake (containing 17.6% by weight of water) 2.800 kg Sodium octylphenyldiethoxymethanesulfonate (31% by weight aqueous solution) 0.376 kg F-15 (7% aqueous solution) 0.011 kg water 4 0.020 kg Total 7.210 kg (adjusted to pH = 7.2 with NaOH).

After the slurry having the above composition was roughly dispersed by stirring with a dissolver, using an agitator mill LMK-4,
Circumferential speed 10m / s, discharge rate 0.6kg / min, 0.3m
The dispersion was dispersed until the absorbance ratio of the dispersion became 0.29 at a filling rate of zirconia beads of m diameter of 80% to obtain a solid fine particle dispersion. The average particle size of the fine dye particles was 0.29 μm.

Similarly, ExF-4 and ExF-7
Was obtained. The average particle size of the fine dye particles was 0.28 μm and 0.49 μm, respectively. ExF-5
Was dispersed by a microprecipitation dispersion method described in Example 1 of European Patent No. 549,489A. The average particle size was 0.06 μm.

[0215]

[Table 1]

In Table 1, Emulsions A to C were added with optimal amounts of spectral sensitizing dyes 1 to 3 and optimally sensitized with gold, sulfur and selenium. Emulsions EG are spectral sensitizing dyes 4-6
In an optimal amount, and are optimally sensitized to gold, sulfur, and selenium. Emulsion J was optimally added with spectral sensitizing dyes 7 and 8 and optimally sensitized with gold, sulfur and selenium. Emulsion L was added with an optimal amount of spectral sensitizing dyes 9 to 11,
Optimally gold, sulfur and selenium sensitized. Emulsion O is optimally gold sensitized and sulfur sensitized with optimal addition of spectral sensitizing dyes 10-12. Emulsions D, H, I, K,
For M and N, the spectral sensitizing dyes shown in Table 2 were added in optimal amounts, and gold sensitization, sulfur sensitization, and selenium sensitization were optimally performed.

[0219]

[Table 2] The sensitizing dyes described in Table 2 are shown below.

[0218]

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[0219]

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[0220]

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[0221]

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[0222]

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[0223]

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[0224]

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[0225]

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[0226]

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[0227]

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[0228]

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[0229]

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[0230]

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The preparation of tabular grains is described in JP-A-1-1584.
According to the example described in No. 26, low molecular weight gelatin is used. Emulsions A to K contain optimum amounts of Ir and Fe. Emulsions L to O were reduction sensitized during grain preparation. When a high-pressure electron microscope is used for tabular grains, see JP-A-3-2.
Dislocation lines as described in No. 37450 are observed. Emulsions A to C and J were subjected to dislocation introduction using an iodide ion releasing agent in accordance with the examples described in JP-A-6-11782. Emulsion E was subjected to dislocation introduction using silver iodide fine particles prepared immediately before addition in a separate chamber having a magnetic coupling induction type stirrer described in JP-A-10-43570. The compounds used for each layer are shown below.

[0232]

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[0233]

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[0234]

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[0235]

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[0236]

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[0237]

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[0238]

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[0239]

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[0240]

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[0241]

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The above-mentioned silver halide color photographic light-sensitive material was used as sample 101. Sample 101 was exposed for 1/100 second through a gelatin filter SC-39 manufactured by FUJIFILM Corporation and a continuous wedge.

(Preparation of Samples 102 to 104) Sample 101
In the sixth, eleventh, and fourteenth layers, a compound represented by HET-3 was added at 4 × 10 ⁻³ mol / mol A with respect to Ag in the addition layer.
g was added. Further, samples having the spectral sensitivities shown in Table 3 were prepared by appropriately changing the MIX ratio of the sensitizing dye of the emulsion used in Sample 101.

(Preparation of Sample 105) With respect to the sample of Sample 104, the eighth layer was removed, and the emulsion amounts and coupler amounts of the ninth to eleventh layers were adjusted. Sample 105 was prepared in the same manner.

(Samples 106 to 118) HET-3 entering the sixth layer, the eleventh layer, and the fourteenth layer with respect to the sample 104 was HET-5, HET-15, HET-8, and HET-
16, HET-19, HET-27, HET-36, H
ET-39, HET-40, HET-44, HET-4
5, HET-46 and HET-47 were equimolarly changed to obtain samples 106 to 118. Further, samples having the spectral sensitivities shown in Table 3 were prepared by appropriately changing the MIX ratio of the sensitizing dye in the emulsion.

The color reproduction and suitability for a fluorescent lamp were evaluated by the following methods. (Appropriate for fluorescent light) After shooting the subject with natural light from one side and white fluorescent light from the other side, evaluate the change in color under fluorescent light as a pudding so that gray balance can be achieved with natural light. did.

(Color Reproducibility) The green of natural trees was photographed, and the fidelity was evaluated as a pudding so that a gray balance could be obtained.

Evaluation of processing stability was performed as follows. Sample 1 shows the range of sensitivity variation when the amount of 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate in the color developing solution was changed by ± 10%.
It was expressed as a relative value to 01. The smaller the value is, the smaller the processing fluctuation is, and thus, the more preferable.

The treatment was carried out in the following manner. (Processing method) Process Processing time Processing temperature Color development 3 minutes 15 seconds 38 ° C Bleaching 3 minutes 00 seconds 38 ° C water washing 30 seconds 24 ° C Settling 3 minutes 00 seconds 38 ° C water washing (1) 30 seconds 24 ° C water washing (2) 30 seconds 24 ° C Stability 30 seconds 38 ° C Drying 4 minutes 20 seconds 55 ° C.

Next, the composition of the processing solution will be described. (Color developing solution) (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 5 mg hydroxylamine sulfate 2.4 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 Add water and add 1.0 L pH (to potassium hydroxide and sulfuric acid) Adjusted) 10.05.

(Bleach) (unit g) Sodium ferric ethylenediaminetetraacetate trihydrate 100.0 Disodium ethylenediaminetetraacetate 10.0 3-Mercapto-1,2,4-triazole 0.03 Ammonium bromide 140.0 Ammonium nitrate 30.0 Ammonia water (27%) 6.5 mL Water was added to 1.0 L pH (adjusted with ammonia water and nitric acid) 6.0.

(Fixing solution) (Unit: g) Disodium ethylenediaminetetraacetate 0.5 Ammonium sulfite 20.0 Aqueous ammonium thiosulfate (700 g / L) 295.0 mL Acetic acid (90%) 3.3 Add water 0 L pH (adjusted with aqueous ammonia and nitric acid) 6.7.

(Stabilizing Solution) (Unit g) p-nonylphenoxypolyglycidol (glycidol average polymerization degree 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 Chemical HEC SP-2000) 1,2-benzoisothiazolin-3-one 0.05 1.0 L pH 8.5.

As a result of performing the above-mentioned development processing, samples 101 to 101
109 was ISO800. The RL sensitivity was expressed as a relative sensitivity, with Sample 101 as 100.

[0255]

[Table 3]

As described above, it is apparent that the sensitivity of the present invention is high, the processing stability is excellent, and the suitability for fluorescent lamps and the color reproducibility are also excellent.

Example 2 (Preparation of Sample 201) When emulsions A to O of Example 1 were subjected to the treatment of Example 1 by appropriately changing the grain size of silver halide, Sample 201 having an ISO sensitivity of 420 was obtained. Created.

(Preparation of Sample 202) Sixth Sample 201
The compound represented by HET-3 was added to the layer, the eleventh layer, and the fourteenth layer in an amount of 4.0 × 10 ⁻³ mol / mol Ag with respect to Ag in the added layer.
Was added to prepare Sample 202.

The same evaluation as in Example 1 was performed, and the results shown in Table 4 were obtained. The RL sensitivity was expressed as relative sensitivity with the sample (201) as 100.

[0260]

[Table 4]

From the results in Tables 3 and 4, it can be seen that the effect of the present invention was more pronounced for the high-sensitivity photographic materials.

[Brief description of the drawings]

FIG. 1A is a graph for _obtaining a spectral sensitivity distribution S _−R (λ). FIG. 1B is a graph for obtaining S _G (λ).

FIG. 2 is a graph showing a spectral energy distribution of a white fluorescent lamp.

Claims (4)

[Claims] 1. A blue-sensitive silver halide emulsion layer containing at least one yellow coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and a red-sensitive halide containing a cyan coupler on a support. Having a silver emulsion layer and a light-insensitive layer, wherein the red-sensitive silver halide emulsion layer has a sensitivity S _R (580) at 580 nm,
In a silver halide color photographic material having the following relationship with the sensitivity S _R (max) at the maximum sensitivity wavelength of the layer, 0.25 ≦ S _R (max) −S _R (580) ≦
0.9 A silver halide color photographic light-sensitive material, characterized in that at least one silver halide emulsion layer or non-light-sensitive layer contains the following compound (A). Compound (A): a compound having at least three heteroatoms and having an increased photographic sensitivity of the light-sensitive material as compared to a case where the compound is not contained. 2. The center-of-gravity sensitivity wavelength (λ _−R ) of the spectral sensitivity distribution of the multilayer effect that the above-mentioned red-sensitive silver halide emulsion layer (if there are a plurality of layers) is received from another layer in the range of 500 nm to 600 nm. , 500 nm <λ- _R ≦ 560 nm, and the center-of-gravity wavelength (λ _G ) of the spectral sensitivity distribution of the green-sensitive silver halide emulsion layer (if there is more than one) is 5
20 nm <λ _G ≦ 580 nm, and λ _G −λ _−R ≧
2. The silver halide color photographic material according to claim 1, wherein the thickness is 5 nm. 3. The compound according to claim 1, wherein the compound (A) is a 1,3,4,6-tetraazaindene compound.
Or the silver halide color photographic light-sensitive material according to item 2. 4. The silver halide color photographic material according to claim 1, wherein the specific sensitivity is 640 or more.