JP2001109114A - Silver halide color photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide color photosensitive material having improved color reproducibility and sharpness as well as improved suitability to development for high emulsion speed. SOLUTION: The silver halide color photographic sensitive material includes one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer and one red-sensitive silver halide emulsion layer on the substrate, has a photosensitive emulsion layer containing 1st photosensitive silver halide particles having 0.15 to <2.00 μm equivalent spherical average diameter (ϕ) and 2nd silver halide particles having 0.02 to <0.40 μm ϕ which is <1/3 of that of the 1st particles and having substantially no sensitivity and contains a compound of formula I (where M is H, a metal atom or a blocking group, G1 is a group of nonmetallic atoms required to form an N-containing heterocycle, L is H or a substituent, Y is a substituent, X is H or a substituent combined to constituent C of G1 when the N-containing heterocycle containing G1 is, e.g. thiazole, (m) is 0 or 1 and (n) is an integer of 0-6 in the photosensitive layer and/or a non-photosensitive layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material, particularly to a silver halide color photographic material, and more particularly to a silver halide color reversal photographic material.

[0002]

2. Description of the Related Art In a color reversal image forming method, in order to compensate for insufficient exposure of a color photographic light-sensitive material, sensitivity is adjusted by extending a black-and-white development time in a color reversal processing step. "Sensitization processing"
is called.

Conventionally, various attempts have been made to improve the sensitization processability. For example, Japanese Patent Application Laid-Open No. Sho 59-21485
No. 2, No. 60-170849, No. 60-170850
No., No. 60-170851, No. 60-170852
Nos. 60-170853 and 63-193147 disclose a method for improving sensitization processability by a color reversal photosensitive material using a silver halide emulsion having a fog nucleus inside silver halide grains. .

EP-A-0547983 A1 (Japanese Patent Application Laid-Open No. 5-257243) discloses an improvement in sensitization processing by a color reversal photosensitive material containing colloidal silver in an intermediate layer combined with a silver halide emulsion layer. A method is disclosed.

[0005] However, these methods are based on the premise that fog is increased, so that there is a problem that the maximum density of a color image is greatly reduced when sensitization processing is performed.

[0006] In order to solve this problem, the photosensitive emulsion layer is mixed with fine silver halide grains having higher solubility than the photosensitive emulsion, thereby improving the maximum density of the color reversal image while increasing the sensitivity of the foot. A method for obtaining a high-contrast image is disclosed in Japanese Patent Publication No. 7-11551.
Although this patent does not disclose application to sensitization processing, it does provide a solution to the problem of increasing the sensitivity of the foot and maintaining the maximum density in a color reversal photosensitive material.

[0007] However, this method also has some problems. Japanese Patent Publication No. 7-11551 does not disclose the practice with a multilayer color film, and when the present inventors attempted to apply the technique to a multilayer color film, it was found that there were the following problems. The first problem is that when the photosensitive emulsion is used in combination with fine grain silver halide having higher solubility than the photosensitive emulsion, the sharpness is deteriorated. The second problem is that the saturation is reduced. there were.

In recent years, the demand for color reproduction of color photographic light-sensitive materials has become more and more severe, and the hue of the subject has been faithfully determined.
Moreover, it is desired to reproduce vividly. To obtain more vivid color reproduction, US Pat. No. 2,521,9
No. 08, the so-called multilayer (inter-image) effect has been used.

In a color reversal photographic light-sensitive material, it is known that the layering effect can be obtained also by adding a compound having a property of inhibiting development in the first development to the light-sensitive material. It is also effective to include a development inhibitor as a precursor in the light-sensitive material and make it function at the time of development processing. For example, JP-A-2-21127 and JP-A-2-2112.
8, No. 2-2129, or U.S. Pat.
DIR hydroquinone disclosed in No. 29.

The present inventors have found a method of first using a compound having a property of accelerating physical development to solve the problems of improving sensitivity during sensitization processing, maintaining the maximum density, and improving color saturation. As another solution, fine silver halide grains are mixed in the above-mentioned photosensitive emulsion layer to increase the foot sensitivity of a color reversal image and to maximize the sensitivity. While keeping the concentration, the development of a development inhibitor and DIR hydroquinone to improve the color saturation and sharpness was studied diligently.
The result was that the sensitivity of the color reversal image was reduced, or the color saturation and sharpness were not improved.
In other words, prior to the present invention, the method of mixing fine silver halide grains in the photosensitive emulsion layer had a bad effect of lowering the chroma and sharpness and was still difficult to employ.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide color light-sensitive material, in particular a color reversal photographic light-sensitive material, which has improved suitability for sensitized development processing and also improved color reproducibility and sharpness. It is.

[0012]

As a result of intensive studies by the present inventors, the objects of the present invention have been achieved by the following constitutions.

(1) At least one each on the support
In a silver halide color photographic material containing a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer, the sphere-equivalent average particle size is 0.15 μm to 2.00 μm. The first photosensitive silver halide grains having a diameter of less than 0.02 μm and an equivalent spherical diameter of less than 0.02 μm.
Photosensitivity containing both less than 40 [mu] m and substantially insensitive second silver halide grains having a sphere-equivalent average particle diameter of less than 1/3 with respect to the first photosensitive silver halide grains. It has at least one emulsion layer, and has at least one photosensitive layer and / or non-photosensitive layer represented by the following general formula (I)
A silver halide color photographic light-sensitive material comprising at least one compound represented by the formula:

[0014]

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In the formula, M is a hydrogen atom, a metal atom, or a block group having a property that an MS bond is cleaved in a developing step (however, a property of coupling with an oxidized aromatic primary amine color developer) G ¹ represents a group of non-metallic atoms necessary to form a nitrogen-containing heterocyclic ring selected from thiazole, oxazole, imidazole, triazole, and oxadiazole;
Represents a divalent group substituted on a carbon atom constituting G ¹ ,
m represents 0 or 1, n represents an integer of 0 or more and 6 or less, X represents a nitrogen-containing heterocyclic ring containing G ¹ as a thiazole,
When it is oxazole or imidazole, it represents a hydrogen atom or a substituent bonded to a carbon atom constituting G ¹ . Y is _{-OH, -OR 1, -CN, -COOR} 1, -C
OR ₁ , -CONH ₂ , -CONHR ₁ , -CONR
₁ represents a substituent selected from R ₂ , -NHCOR ₁ , -COOH, an amino group and a heterocyclic group, wherein R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group or alkenyl having 1 to 8 carbon atoms. Represents a group, which may have a substituent, and R ₁ and R ₂ may be bonded to each other to form a ring. However, when the nitrogen-containing heterocyclic ring containing G ¹ is thiazole, Y is not —COOH.

(2) The silver halide according to (1), wherein the compound represented by the formula (I) is a compound represented by the following formula (II) or (III): Color photographic light-sensitive material.

[0017]

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Wherein Z ¹ is —NH ₂ , —NHR ₁ , —NR ₁
R ₂ represents —OR ₁ , and n, X, M, R ₁ and R ₂ have the same meanings as those in formula (I).

(3) The silver halide color photographic material as described in (1), wherein the compound represented by the formula (I) is further represented by the following formula (IV).

[0020]

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Where Z^TwoIs -OH, -OR₁, -CN,-
COR₁, -COOR₁, -CONH _Two, -CONHR₁,
-CONR₁R_Two, -NR₁R_TwoTable shows the substituents selected from
Then R ₁, R_TwoHas the same meaning as in general formula (I)
You.

(4) The silver halide color photographic light-sensitive material according to any one of (1) to (3), wherein M is a block group defined by the general formula (I).

(5) A silver halide color photographic light-sensitive material having a blue-sensitive unit, a green-sensitive unit, and a red-sensitive unit comprising two or more photosensitive emulsion layers having different sensitivities on a support. (1) to (1) characterized by having at least one photosensitive unit comprising at least two photosensitive emulsion layers containing both the prescribed first photosensitive silver halide grains and the prescribed second photosensitive silver halide grains. 5) The silver halide color photographic light-sensitive material according to any one of the above 5).

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The compound represented by formula (I) of the present invention will be described.

In the formula, M represents a hydrogen atom, a metal atom, or a blocking group other than a coupler having a property that the MS bond is cleaved in the developing step. When M is a metal atom and the compound of the general formula (I) is a metal salt, preferred as M are sodium, potassium, lithium, calcium, magnesium and silver.

When the compound is a block group, the following general formula (B)
Groups represented by -1) to (B-13) are preferred.

[0027]

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[0028]

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In the formula, R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ each represent a hydrogen atom or a substituent, and EWG represents an electron-withdrawing group. A ₁ and A _{2 each} represent a hydrogen atom or a protecting group that can be removed in a developing solution.

The substituents represented by R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ include a halogen atom, an alkyl group, an aryl group,
Heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, amino group, alkoxy group, aryloxy group, acylamino group, alkylamino group, anilino group,
Ureido group, sulfamoylamino group, alkylthio group, arylthio group, alkoxycarbonylamino group,
Sulfonamide group, carbamoyl group, sulfamoyl group, sulfonyl group, alkoxycarbonyl group, heterocyclic group oxy group, azo group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, imino group, heterocyclic thio group, Sulfinyl group, phosphonyl group, aryloxycarbonyl group, acyl group,
An azolyl group may be mentioned, and these may have a substituent.

More specific examples of the substituent include a halogen atom (for example, a chlorine atom and a bromine atom), an alkyl group (for example, a linear or branched alkyl group having 1 to 32 carbon atoms,
Aralkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, specifically, for example, methyl, ethyl, propyl, isopropyl, t-butyl,
Tridecyl, 2-methanesulfonylethyl, 3- (3-
Pentadecylphenoxy) propyl, 3- {4-} 2-
[4- (4-hydroxyphenylsulfonyl) phenoxy] dodecaneamide {phenyl} propyl, 2-ethoxytridecyl, trifluoromethyl, cyclopentyl,
3- (2,4-di-t-amylphenoxy) propyl), an aryl group (for example, phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl, 4-tetradecanamidophenyl), a heterocyclic ring (Eg 2-furyl,
2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group, amino group, alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2-dodecylethoxy, 2-methanesulfonyl) Ethoxy), an aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t
-Butylphenoxy, 3-nitrophenoxy, 3-t-
Butyloxycarbamoylphenoxy, 3-methoxycarbamoylphenoxy), acylamino group (for example, acetamido, benzamido, tetradecaneamido, 2-
(2,4-di-t-amylphenoxy) butanamide,
4- (3-t-butyl-4-hydroxyphenoxy) butanamide, 2- {4- (4-hydroxyphenylsulfonyl) phenoxy} decanamide, alkylamino group (for example, methylamino, butylamino, dodecylamino, diethylamino, methyl Butylamino), anilino group (for example, phenylamino, 2-chloroanilino, 2-
Chloro-5-tetradecaneaminoanilino, 2-chloro-5-dodecyloxycarbonylanilino, N-acetylanilino, 2-chloro-5- {α- (3-t-butyl-4-hydroxyphenoxy) dodecaneamide @Anilino), ureido groups (eg, phenylureido, methylureide, N, N-dibutylureido), sulfamoylamino (eg, N, N-dipropylsulfamoylamino, N-methyl-N-decylsulfamoylamino) ,
Alkylthio groups (eg, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio, 3- (4-t-butylphenoxy) propylthio), arylthio groups (eg, phenylthio, 2-butoxy-5-t) -Octylphenylthio,
3-pentadecylphenylthio, 2-carboxyphenylthio, 4-tetradecanamidophenylthio), alkoxycarbonylamino group (for example, methoxycarbonylamino, tetradecyloxycarbonylamino), sulfonamide group (for example, methanesulfonamide, hexadecanesulfonamide) , Benzenesulfonamide, p-toluenesulfonamide, octadecanesulfonamide,
2-methyloxy-5-t-butylbenzenesulfonamide), carbamoyl group (for example, N-ethylcarbamoyl, N, N-dibutylcarbamoyl, N- (2-dodecyloxyethyl) carbamoyl, N-methyl-N-dodecylcarbamoyl , N- {3- (2,4-di-t-amylphenoxy) propyl} carbamoyl), a sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N- (2-dodecyloxy) Ethyl) sulfamoyl, N-ethyl-N-dodecylsulfamoyl, N, N-diethylsulfamoyl), sulfonyl group (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group (eg, methoxycarbonyl, Butyloxycarboni , Dodecyloxycarbonyl, octadecyloxycarbonyl), a heterocyclic oxy group (e.g., 1-phenyl-5-oxy, 2-tetrahydropyranyloxy), azo group (e.g. phenylazo,
4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo), acyloxy group (eg, acetoxy), carbamoyloxy group (eg, N-methylcarbamoyloxy, N-phenylcarbamoyloxy) ), A silyloxy group (eg, trimethylsilyloxy, dibutylmethylsilyloxy), an aryloxycarbonylamino group (eg, phenoxycarbonylamino), an imide group (eg, N-succinimide, N-phthalimide, 3-octadecenylsuccinimide), a heterocyclic ring Thio groups (eg, 2-benzothiazolylthio, 2,4-di-phenoxy-1,
3,5-triazole-6-thio, 2-pyridylthio), a sulfinyl group (for example, dodecanesulfinyl,
3-pentadecylphenylsulfinyl, 3-phenoxypropylsulfinyl), phosphonyl group (for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (for example, phenoxycarbonyl), acyl group (for example, acetyl, 3-phenylpropanoyl, benzoyl, 4-dodecyloxybenzoyl), azolyl groups (for example, imidazolyl, pyrazolyl, 3-chloro-pyrazol-1-yl, triazole).

The electron-withdrawing group represented by EWG is an electron-withdrawing group having a Hammett's substituent constant σp value (hereinafter simply referred to as σp value) of 0.20 to 1.0. Preferably, it is an electron-withdrawing group having a σp value of 0.30 or more and 0.8 or less. Hammett's rule is used to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives,
An empirical rule proposed by LP Hammett in 2005, which is widely accepted today. The substituent constants determined by the Hammett's rule include a σp value and a σm value,
Although these values are described in many general books, for example, "Lange's Handbook of Chemistry" edited by JA Dean
Twelveth Edition, 1979 (Mc Graw-Hill) and "Chemical Area Special Edition", No. 122, pp. 96-103, 1979 (Nankodo), Chemical Reviews, 91, 165-195.
Page, 1991. The present invention does not mean that the literature-known values described in these publications are limited to only certain substituents, and that the values are not included in the range when measured based on the Hammett rule even if the literature is unknown. It is of course included as far as possible.

Specific examples of the electron-withdrawing group having a σp value of 0.20 or more and 1.0 or less include an acyl group, an acyloxy group, a carbamoyl group, an aliphatic oxycarbonyl group, an aryloxycarbonyl group, a cyano group, and a nitro group. Group, dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group An alkyl group substituted with at least two or more halogen atoms,
An alkoxy group substituted with at least two or more halogen atoms, an aryloxy group substituted with at least two or more halogen atoms, an alkylamino group substituted with at least two or more halogen atoms, at least two or more halogen atoms An alkylthio group substituted with an atom, σp0.
An aryl group substituted with 20 or more other electron-withdrawing groups,
Examples include a heterocyclic group, a chlorine atom, a bromine atom, an azo group, or a selenocyanate group. Among these substituents, the group capable of further having a substituent may further have the substituent described above.

Of these, in (B-2), an acyl group, a carbamoyl group, an aliphatic oxycarbonyl group,
In the case of an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, a sulfamoyl group, or (B-10), it was substituted with another electron-withdrawing group having a σp of 0.20 or more. Aryl groups (more preferably substituted with at least one nitro group) are preferred.

When A ₁ and A ₂ are protective groups that can be removed in a developing solution, examples thereof include an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. A ₁ and A ₂ are preferably hydrogen atoms.

In the general formulas (B-1) to (B-13), * represents a site bonded to S in the general formula (I), but a timing group (the general formulas (B-1) to (B-13) After being released from the blocking group represented by the formula, a group capable of releasing the compound of the general formula (I) by electron transfer and nucleophilic substitution (hydrolysis or nucleophilic substitution with another nucleophile). And may be bonded to S via

Of these, general formulas (B-5) and (B-
6), (B-7), (B-8), (B-9), (B-1)
0) and (B-13) are preferred, and particularly (B-7) and (B-13)
-9) is preferred.

More preferred examples of the block group represented by formula (B-7) or (B-9) include the following formulas (B-7-II) and (B-9-II). .

[0039]

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In the formula (B-7-II), J represents -O-, -S
-, -NHCO-, -NHCOO-, -NHCONH
-, - NHCOCO -, - NHSO 2 -, - CO -, -
CONH-, represents a divalent group selected from -COO-,
R ₈ represents an alkyl group or an aryl group, and may have a substituent. Examples of the substituent include those described later in the section of X.

In particular, when J is -S-, -NHCO-, -NHC
OO-, -NHCONH-, and R ₈
Is preferably an alkyl group or an aryl group containing an alkyl chain having 6 to 30 carbon atoms.

In the formula (B-9-II), R ₉ represents a substituent, k represents an integer of 0 to 5, and when k is 2 or more, even if a plurality of R ₉ are the same, they are different. May be. R ₉
Examples of the above include those described later in the section of X.

Next, L will be described.

L represents a divalent group substituted on a carbon atom of the nitrogen-containing heterocyclic ring containing G ¹ . An example of L is-
O-, -S-, -NR-, -CO-, -COO-, -O
_{CO -, - SO 2 -,} - CONR -, - NRCO -, -
OCONR-, -NRCOO-, -NRCONR-,-
_{SO 2 NR -, - NRSO 2} -, - CONRSO 2 -, -
SO ₂ NRCO— and an arylene group (for example, p-phenylene). Here, R represents a hydrogen atom, an alkyl group, or an aryl group.

Of these, -O-, -S-, -NR-,
-CONR-, -NRCO-, and -NRCONR- are preferred, and -O-, -S-, and -NR- are particularly preferred.

N represents an integer of 0 or more and 6 or less, preferably 1 or more and 4 or less.

M represents 0 or 1, and is preferably 0.

The substituent represented by X will be described in detail.

X represents a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom or a bromine atom), an alkyl group (having 1 carbon atom).
6 to 6 linear, branched or cyclic alkyl groups;
Methyl, ethyl, propyl, isopropyl, t-butyl, 2-methanesulfonylethyl, 2-methoxyethyl, trifluoromethyl, cyclohexyl), heterocyclic group (for example, 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl) ), A hydroxyl group, a carboxyl group, an amino group (for example, dimethylamino, ethylamino, diethylamino, dihydroxyethylamino, morpholino, pyrrolidino, piperidino), an alkoxy group (for example, methoxy, ethoxy, 2-methoxyethoxy,
2-methanesulfonylethoxy), an aryloxy group (for example, phenoxy, 2-methylphenoxy, 4-t-
Butylphenoxy, 3-t-butyloxycarbamoylphenoxy, 3-methoxycarbamoylphenoxy),
Acylamino groups (eg acetamido, benzamido,
4- (3-t-butyl-4-hydroxyphenoxy) butanamide), anilino group (for example, phenylamino,
-Chloroanilino), ureido groups (eg phenylureido, methylureide, N, N-dibutylureide),
Alkylthio groups (eg, methylthio, octylthio, tetradecylthio, 2-phenoxyethylthio, 3-phenoxypropylthio), arylthio groups (eg, phenylthio, 2-butoxy-5-t-octylphenylthio, 3-pentadecylphenylthio, 2-carboxyphenylthio), a carbamoyl group (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), a carbamoyloxy group (eg, N-methylcarbamoyloxy,
N-phenylcarbamoyloxy), a sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl, N, N-diethylsulfamoyl), a sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, p-toluenesulfonamide), sulfonyl group (eg, methanesulfonyl, octanesulfonyl, benzenesulfonyl, toluenesulfonyl), alkoxycarbonyl group (eg, methoxycarbonyl, butyloxycarbonyl), acyloxy group (eg, acetoxy), phosphonyl group (eg, phenoxyphospho) Nyl, octyloxyphosphonyl, phenylphosphonyl), acyl group (eg, acetyl, 3-phenylpropanoyl, benzoyl), sulfo group, ammonium salt (eg, trimethylan Niumukurorido, triethylammonium bromide, methyl morpholino chloride) and the like.

Among these, X is preferably a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkylthio group, or an arylthio group, particularly a hydrogen atom, a halogen atom, an alkyl group having 3 or less carbon atoms,
Alkoxy groups and alkylthio groups are preferred.

Y is -OH, -OR ₁ , -CN, -COO
_{R 1, -COR 1, -CONH 2} , -CONHR 1, -CO
NR ₁ R ₂ represents a substituent selected from —NHCOR ₁ , —COOH, an amino group, and a heterocyclic group, and R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms in total. , An alkenyl group, and R ₁ and R ₂ may combine with each other to form a saturated or unsaturated carbocyclic or heterocyclic ring. As R ₁ and R ₂ , an alkyl group having 1 to 4 carbon atoms (for example, methyl, ethyl, n-propyl, i
-Propyl, n-butyl, i-butyl) are preferred.

Preferred examples of the compound represented by the general formula (I) include the following general formulas (II) and (III).

[0053]

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In the formula, M, X and n have the same meanings as described in the formula (I), and those described in the description of the formula (I) are preferable.

Z¹Is -NH_Two, -NHR₁, -NR₁R_Two,
-OR₁And R₁, R_TwoIs defined by the general formula (I)
Synonymous, those described in the description of formula (I) are preferred.
No. Z ₁Particularly, -NH_Two, -NHR₁, -NR₁R
_TwoIs preferred.

Among the compounds represented by formula (II) or (III), particularly preferred are compounds represented by formula (II), wherein X is a hydrogen atom, n is 1 and Z ¹ is NH ₂ , NHCH ₃ or NHC.
_{2 H 5, NHC 3 H 7} , is of the NHC ₄ H _9.

Among the compounds represented by the general formula (I), another preferred compound is the general formula (IV).

[0058]

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Where Z^TwoIs -OH, -OR₁, -CN, -C
OR₁, -COOR₁, -CONH_Two, -CONHR₁, −
CONR₁R_Two, -NR₁R_TwoRepresents a substituent selected from
R₁, R_TwoHas the same meaning as in formula (I). Of these, Z
^TwoAre -OH, -OR ₁, -CONH_Two, -CON
R₁, -CONR₁R_TwoIs preferred. R₁, R_TwoIs the general formula
It has the same meaning as defined in (I), and is described in general formula (I).
Are preferred.

Among the compounds represented by the general formula (IV), preferred are those wherein n is 1 to 3, Z ² is --OH, --OCH ₃ ,
_{-OC 2 H 5, -OC 3 H} 7, -CONH 2, -CONHC
H _3, -CONHC ₂ H _5, are those wherein -CONHC ₃ H _7.

Hereinafter, specific examples of the compound represented by formula (I) are shown, but the present invention is not limited to these specific examples.

[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[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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Specific examples of preferred compounds when M is a block group in the general formula (I) are shown below. In the present invention, it is preferred that M is a blocking group. The present invention is not limited to these specific examples.

[0080]

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[0081]

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[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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The compound represented by the general formula (I) of the present invention (hereinafter, also referred to as “the compound of the present invention”) may be added to any layer in the light-sensitive material, but is preferably a light-sensitive emulsion layer. It is preferable to add the compound to a non-photosensitive layer, preferably an intermediate layer, which is in contact with the photosensitive emulsion layer directly or via one intermediate layer.

The preferable addition amount of the compound of the present invention is 0.0
It is from 0.01 to 0.200 mmol / m ² , more preferably from 0.002 to 0.05 mmol / m ² . It is also preferable to use a plurality of compounds of the present invention in combination.

The compound of the present invention can be introduced into a silver halide color photographic light-sensitive material by dissolving it in water or an organic solvent miscible with water such as methanol, ethanol, isopropanol, butanol, dimethylformamide and dimethylacetamide. can do. In addition to these solvents, a pH adjuster or a surfactant may be used in combination.

As another method for introducing the compound of the present invention into a light-sensitive material, the compound may be dissolved in a high-boiling organic solvent and emulsified and dispersed using a surfactant, or may be added in a fine crystalline or amorphous solid state. It is also preferable to disperse and add.

In particular, when M is a block group, it is preferable to add by emulsifying and dispersing.

In the case of dissolving in a high boiling point organic solvent, another organic solvent (for example, ethyl acetate, butyl acetate, methanol, ethanol, isopropanol, methyl ethyl ketone, cyclohexanone, dimethylformamide, dimethylacetamide, etc.) is used for the purpose of assisting dissolution. You may use together.

The high-boiling organic solvent used in combination with the compound of the present invention may be any liquid or solid at room temperature, and may be any of phosphate esters (for example, tricresyl phosphate, triphenyl phosphate, phosphorus phosphate, etc.). Trihexyl acid, tricyclooctyl phosphate, tricyclopentyl phosphate, trioctyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tri-3-methyl phosphate
5-dimethylhexyl), phthalates (e.g., dibutyl phthalate, dicyclohexyl phthalate,
Di-2-ethylhexyl phthalate, dioctyl phthalate, dihexyl phthalate, etc., carbonamides (eg, N, N-diethyllauramide, N, N, -dimethylpalmitoylamide, N, N, -dimethyloleylamide) Are preferable, and phosphates are particularly preferable.

The high boiling point organic solvent used in combination with the compound of the present invention is 0.1 to 10 times by weight the compound of the present invention.
It is preferably used in a range of 0 times, particularly preferably 2 to 10 times. A plurality of high-boiling organic solvents may be used in combination, and for the purpose of improving the stability of the emulsified dispersion, compounds known in the photographic field other than the present invention (for example, ultraviolet absorbers, image-forming couplers, A color mixing inhibitor, a water-insoluble polymer, an anti-fading agent, etc.) may be emulsified and dispersed in the presence of the compound of the present invention.

Next, the first photosensitive silver halide grains and the second silver halide grains of the present invention will be described.

The first photosensitive silver halide grains of the present invention may be of any type as long as they have a sphere-equivalent average particle size of 0.15 μm or more and less than 2.00 μm, but are preferably silver bromide, silver iodobromide, It is preferred that it is composed of silver iodochlorobromide. In the present invention, silver iodide or silver iodochlorobromide preferably further contains 0.5 to 30 mol% of silver iodide, and particularly preferably contains 1 to 10 mol% of silver iodide. Other silver salts, such as silver rhodanate, silver sulfide, silver selenide, silver carbonate, silver phosphate,
Organic acid silver may be contained as separate grains or as part of silver halide grains.

The first photosensitive silver halide emulsion of the present invention preferably has a distribution or a structure with respect to the halogen composition in the grains. The typical one is Shoko 4
JP-A-3-13162, JP-A-61-215540, JP-A-60-222845, JP-A-60-143331
And a core-shell type or double structure type particle having a halogen composition in which the inside and the surface of the particle have different halogen compositions as disclosed in JP-A-61-75337. In addition to a simple structure, a triple structure as disclosed in Japanese Patent Application Laid-Open No. 60-222844, or a multilayer structure of more than that, or a different composition on the surface of a core-shell double structure particle Or a thin silver halide having the following formula:

In order to provide a structure inside the particle, not only the above-described wrapping structure but also a particle having a so-called bonding structure can be produced. These examples are disclosed in
-133540, JP-A-58-108526, European Patent No. 199,290A2, JP-B-58-24772.
And JP-A-59-16254.
The crystal to be bonded can be formed by bonding to the edge, corner, or face of the host crystal with a composition different from that of the host crystal. Such a junction crystal can be formed even if the host crystal is uniform in the halogen composition or has a core-shell structure.

In the case of grains such as silver iodobromide having these structures, it is a preferable embodiment that the core portion has a higher silver iodide content than the shell portion. Conversely, grains having a low silver iodide content in the core and a high shell are sometimes preferred.
Similarly, grains having a junction structure may be grains having a high silver iodide content in the host crystal and relatively low silver iodide content in the junction crystal, or vice versa. Further, the boundary portions having different halogen compositions of the grains having these structures may be clear boundaries or unclear boundaries. In addition, a configuration in which the composition is positively and continuously changed is also a preferable embodiment.

In the case of silver halide grains in which two or more silver halides are present as a mixed crystal or with a structure, it is important to control the halogen composition distribution between the grains. The method for measuring the halogen composition distribution between grains is described in JP-A-60-254032. Uniform halogen distribution between grains is a desirable property. In particular, a highly uniform emulsion having a coefficient of variation of 20% or less is preferable.
Another preferred form is an emulsion having a correlation between the grain size and the halogen composition. As an example, there is a correlation such that the iodine content is higher for larger size particles, while the iodine content is lower for smaller size particles. Depending on the purpose, an inverse correlation or a correlation with another halogen composition can be selected. For this purpose, it is preferable to mix two or more emulsions having different compositions.

The first photosensitive silver halide grain of the present invention can be a normal crystal having no twin planes, even if it is a normal crystal. 163, such as a single twin with one twin plane, a parallel multiple twin with two or more parallel twin planes, a non-parallel with two or more non-parallel twin planes It can be selected from multiple twins or the like depending on the purpose. An example of mixing particles having different shapes is disclosed in U.S. Pat. No. 4,865,964, but this method can be selected as necessary. In the case of a normal crystal, a cube consisting of (100) planes,
Octahedron consisting of (111) plane, Japanese Patent Publication No. 55-42737
And Japanese Patent Application Laid-Open No. 60-222842 (1).
10) A dodecahedral particle having a plane can be used.
Furthermore, Journal of Imaging Science Vol. 30 247
(Hll) plane particles represented by (211), (hhl) plane particles represented by (331), and (hk0) represented by (210) plane, as reported in page 1986.
Plane particles and (hkl) plane particles represented by the (321) plane also need to be devised in the preparation method, but they can be selected and used according to the purpose. A tetrahedral particle in which (100) plane and (111) plane coexist in one particle, a particle in which (100) plane and (110) plane coexist, or a particle in which (111) plane and (110) plane coexist, Particles in which two faces or many faces coexist can be selected and used according to the purpose.

The value obtained by dividing the circle-equivalent diameter of the projected area by the grain thickness is called an aspect ratio, and defines the shape of tabular grains. Tabular grains having an aspect ratio of greater than 1 can be used in the present invention. Tabular grains are described in Cleve, Photography Theory and Practice.
(1930)), p. 131; Gatofu, Photographic Science and Engineering (Gutoff, Ph.
otographic Science and Engineering), Vol. 14, 2
48-257 (1970); U.S. Pat.
4,226, 4,414,310, 4,43
No. 3,048, 4,439,520 and British Patent No. 2,112,157. When tabular grains are used, there are advantages such as an increase in covering power and an increase in the color sensitization efficiency of a sensitizing dye, and the like. U.S. Pat.
No. 26 describes this in detail. 8 of the total projected area of the grain
The average aspect ratio of 0% or more is desirably 1 or more and less than 100. It is more preferably 2 or more and less than 20 and particularly preferably 3 or more and less than 10. The shape of the tabular grains can be selected from triangles, hexagons, and circles. A regular hexagon having almost equal lengths of six sides as described in U.S. Pat. No. 4,797,354 is a preferred form.

Further, when monodisperse tabular grains having a narrow grain size distribution are used, more preferable results may be obtained. U.S. Pat. No. 4,797,354 and
No. -838 describes a method for producing monodisperse hexagonal tabular grains having a high tabularization ratio. Also, European Patent No. 514,
No. 742 describes a method for producing tabular grains having a coefficient of variation of the grain size distribution of less than 10% using a polyalkylene oxide block copolymer. It is preferable to use these tabular grains in the present invention. Further, particles having a high uniformity of thickness with a variation coefficient of the particle thickness of 30% or less are also preferable.

In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. It is preferable to select a particle containing no dislocation line, a particle containing several dislocations, or a particle containing many dislocations according to the purpose. It is also possible to select dislocations introduced linearly or distorted dislocations in a specific direction of the crystal orientation of the grains, or to introduce them all over the grains, or to introduce them only into a specific portion of the grains, for example. The dislocation can be introduced only in the fringe portion of the particle. The introduction of dislocation lines is preferable not only in the case of tabular grains, but also in the case of irregular grains typified by normal crystal grains or potato grains. Also in this case, it is a preferable embodiment to limit the particle to a specific portion such as a vertex or a ridge.

The grain size of the first photosensitive silver halide grain of the present invention can be determined by a circle equivalent diameter of a projected area using an electron microscope, a sphere equivalent diameter of a grain volume calculated from the projected area and the grain thickness, or a Coulter counter method. It can be evaluated by the volume equivalent sphere diameter.

As the first photosensitive silver halide emulsion of the present invention, a so-called polydisperse emulsion having a wide grain size distribution or a monodisperse emulsion having a narrow size distribution can be selected and used according to the purpose. In some cases, the variation coefficient of the projected area equivalent circle diameter of a particle or the sphere equivalent diameter of a volume is used as a scale representing the size distribution. When a monodispersed emulsion is used, it is preferable to use an emulsion having a size distribution with a coefficient of variation of 25% or less, more preferably 20% or less, and still more preferably 15% or less. In the present invention, the first photosensitive silver halide emulsion is preferably a monodisperse emulsion having a coefficient of variation of 20% or less.

The first photosensitive silver halide grain of the present invention is prepared by preparing at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization or noble metal sensitization and reduction sensitization for a silver halide emulsion. It can be applied in any of the steps. 2
It is preferred to combine more than one sensitization method. Various types of emulsions can be prepared depending on the step of chemical sensitization. There are a type in which a chemical sensitizing nucleus is embedded in the grain, a type in which the chemical sensitizing nucleus is embedded in a position shallow from the grain surface, and a type in which a chemical sensitizing nucleus is formed on the surface. In the emulsion of the present invention, the location of the chemical sensitization nucleus can be selected according to the purpose. Generally, the case where at least one type of chemical sensitization nucleus is formed near the surface is preferred.

It is preferable to use gold sensitization in combination with the first photosensitive silver halide emulsion of the present invention. The preferred amount of the gold sensitizer is 1 × 10 ^-4 to 1 × 1 per mol of silver halide.
^0-7 mol, more preferably 1 × 10 ^{-5 to} 5 ×.
10 ^-7 mol. The preferred range of the palladium compound is 1 × 10 ^-3 to 5 × 10 ^-7 mol per mol of silver halide. The preferred range of the thiocyan compound or the selenocyan compound is 5 × 10 5 per mol of silver halide.
^-2 to 1 × 10 ^-6 mol.

The preferred amount of sulfur sensitizer used for the first silver halide grains of the present invention is 1 × 10 ^-4 to 1 × 10 ^-7 mol per mol of silver halide, and more preferably, It is 1 × 10 ^{−5 to} 5 × 10 ⁻⁷ mol.

Selenium sensitization is a preferred sensitizing method for the first silver halide emulsion of the present invention. In the selenium sensitization, a known unstable selenium compound is used, and specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, N, N-diethylselenourea, etc.), selenoketone And selenium compounds such as selenoamides can be used. It may be preferable to use selenium sensitization in combination with sulfur sensitization and / or noble metal sensitization.

It is preferable that the first silver halide emulsion of the present invention is subjected to reduction sensitization during grain formation, after grain formation and before or during chemical sensitization, or after chemical sensitization.

Here, reduction sensitization is a method in which a reduction sensitizer is added to a silver halide emulsion, or a pAg1 called silver ripening.
7, a method of growing or ripening in a low pAg atmosphere, or a method of growing or ripening in a high pH atmosphere of pH 8-11 called high pH ripening. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method since the level of reduction sensitization can be finely adjusted.

As reduction sensitizers, stannous salts, ascorbic acid and its derivatives, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds and the like are known. For the reduction sensitization of the present invention, these known reduction sensitizers can be selected and used, and two or more compounds can be used in combination. Stannous chloride, thiourea dioxide, dimethylamine borane, ascorbic acid and derivatives thereof are preferred compounds as reduction sensitizers. Since the addition amount of the reduction sensitizer depends on the emulsion production conditions, it is necessary to select the addition amount, but an appropriate range is from 10 ^-7 to 10 ^-3 mol per mol of silver halide.

The sensitizing dye may be added to the emulsion at any stage in the preparation of the emulsion which has hitherto been known to be useful. Most commonly, it is performed after completion of chemical sensitization but before coating, but US Pat.
As described in JP-A Nos. 8,969 and 4,225,666, spectral sensitization can be carried out simultaneously with chemical sensitization by simultaneous addition with a chemical sensitizer.
It can be carried out prior to chemical sensitization as described in US Pat. No. 3,928, or can be added prior to completion of silver halide grain precipitation to start spectral sensitization. Furthermore, these compounds may be added separately as taught in U.S. Pat. No. 4,225,666, i.e., some of these compounds may be added prior to chemical sensitization and the remainder chemically sensitized. It is also possible to add the silver halide grains after the silver halide grains have been formed, and may be added at any time during the formation of silver halide grains, including the method disclosed in U.S. Pat. No. 4,183,756.

The amount of addition was 4 × / mol of silver halide.
The amount is preferably from 10 ^-6 to 8 × 10 ^-3 mol, and when the silver halide grain size is more preferably from 0.2 to 1.2 μmm, about 5 × 10 ^-5 to 2 × 10 ^-3 mol is more effective.

Next, the second silver halide grains of the present invention will be described.

The second silver halide grains of the present invention have a sphere-equivalent average particle size of 0.02 μm or more and less than 0.40 μm, and the size relationship with the first photosensitive silver halide grains is equivalent to a sphere. Any material that has substantially no photosensitivity with an average particle size of less than 1/3 may be used. The halogen composition of the second silver halide grains of the present invention is preferably silver bromide, silver iodide, or silver iodobromide. In the case of silver iodobromide, the silver iodide content is 1 to 20 mol%. It is preferred that

The size of the second silver halide grains of the present invention is preferably from 0.02 μm to less than 0.40 μm, and more preferably from 0.03 μm to less than 0.10 μm.

The second silver halide grains of the present invention have a sphere-equivalent average particle diameter of less than 1/3 of the size of the first photosensitive silver halide grains. 1 when the silver particles have a sphere equivalent average particle size of 0.40 μm or more.
Preferably, the size is / 4 or less.

The second silver halide grains of the present invention are substantially light-insensitive. In the present invention, the term "substantially light-insensitive" means that the developing property of the grains does not show a response to the exposure dose, or even if they have a response to the exposure dose, It means that the sensitivity is 1/100 or less. In particular, non-photosensitive particles whose developability does not respond to the exposure amount are preferable. Although the inside or surface of the second silver halide grains may be fogged in advance, non-photosensitive grains which are not fogged are particularly preferred.

Although the silver halide color photographic light-sensitive material of the present invention has at least one layer containing a first photosensitive silver halide emulsion and a second silver halide emulsion, it has a blue sensitivity (or a green sensitivity or a red sensitivity). If the unit is composed of two or more light-sensitive emulsion layers having different sensitivities, the plurality of light-sensitive emulsion layers in the same color-sensitive unit may be the first light-sensitive emulsion layer of the present invention.
It is more preferred that both the photosensitive silver halide emulsion and the second silver halide emulsion are contained. In this case, it is natural that the photosensitive silver halide emulsions of the low-speed layer and the high-speed layer may be different from each other. Silver halide grains and the first and second silver halide grains contained in the high-speed layer
Silver halide grains of each may be different,
It may be the same.

The second silver halide grains are preferably mixed with the first silver halide grains in a silver molar ratio of 3% to 50%, more preferably 5% to 25%.
Use in the following range.

The second silver halide grain of the present invention comprises a first silver halide grain.
May have the structure and the degree of dispersion of the halogen composition as described in the description of the photosensitive silver halide grains, and may be chemically sensitized in the same manner as described for the first photosensitive silver halide grains. Or a sensitizing dye. Further, the compound represented by the general formula (I) and other development inhibitors, development accelerators and stabilizers may be added.

The light-sensitive material of the present invention may have at least one blue-sensitive emulsion layer containing a yellow coupler, a green-sensitive emulsion layer containing a magenta coupler, and a red-sensitive emulsion layer containing a cyan coupler. Is preferably a unit structure composed of two or more photosensitive emulsion layers having different sensitivities, and more preferably each photosensitive layer is composed of 3 or more photosensitive emulsion layers.
It comprises at least two photosensitive emulsion layers. It is preferable that a non-color-forming intermediate layer is provided between the photosensitive layers having different color sensitivities, and the intermediate layer further comprises two or more non-color-forming layers,
It is also preferred that the non-photosensitive layer in direct contact with the lowest sensitivity emulsion layer in the photosensitive unit contains colloidal silver grains or silver halide grains whose surface or inside is fogged beforehand.

The layer containing the first photosensitive silver halide grains and the second silver halide grains of the present invention is preferably a layer containing an image forming coupler, but may be a non-color-forming layer.

In the present invention, when the photosensitive unit has a three-layer structure, 10 to 60% of the coating amount of the silver halide emulsion in the entire unit is used in the present invention.
10 to 50% for the medium speed layer, 30 to 70% for the low speed layer
Are preferably allocated. In the present invention, the lower the sensitivity of the layer, the higher the silver density (the value obtained by dividing the weight in terms of silver of the contained silver halide emulsion by the weight of gelatin of the layer), the better the result. Specifically, the silver density is 0.5
To 1.5 is preferred.

The light-sensitive material of the present invention may be subjected to any development processing. However, the effect of the present invention is remarkable when black-and-white development is performed, reversal processing is performed, and color development is performed. Preferably, reversal processing and color development are performed after black-and-white development in a processing solution containing sulfite ions and thiocyanate ions.

Regarding various techniques and inorganic and organic materials which can be used for the silver halide photographic emulsion of the present invention and the silver halide photographic light-sensitive material using the same, generally, Research Disclosure No. 308119 (19)
89 and 37038 (1995) can be used.

In addition to this, more specifically, for example,
The techniques and inorganic / organic materials which can be used for color photographic light-sensitive materials to which the silver halide photographic emulsion of the present invention can be applied are described in the following portions of European Patent 436,938A2 and the patents cited below. I have.

Item The present section 1) Layer structure Page 146, line 34 to page 147, line 25 2) Silver halide emulsion which can be used in combination page 147, line 26 to page 148, line 12 3) Yellow coupler, page 137, line 35 to page 146, line 33, page 149, lines 21 to 23 4) Magenta coupler, page 149, lines 24 to 28; EP 421,453A1 No. 3, page 25 to line 55 5) Cyan Coupler, page 149, lines 29 to 33; EP 432,804A2, page 3, line 28 to page 40, line 2 Item 6) Polymer coupler, page 149, lines 34 to 38; EP 113,334A2, page 113, line 39 to page 123, line 37 7) Colored coupler page 53, lines 42 to 137 Page 34, line 149, line 39 8 to 45: 8) Functional coupler: page 7, line 1 to page 53, line 41, page 149, line 46 to page 150, line 3; page 3 of EP 435,334 A2 Lines to page 29, line 50 9) Preservatives and fungicides page 150, lines 25 to 28 10) Formalin, page 149 lines 15 to 17 Scavenger 11) Others that can be used in combination page 153, 38 Lines 47 to 47: Additives of EP 421, 453A1, page 75, line 21 to page 84, line 56, page 27, line 40 to page 37, line 40 12) Dispersion method Page 150, lines 4 to 24 13) Support, page 150, lines 32 to 34 14) Film thickness and film properties Page 150, lines 35 to 49 15) Color development step, page 150, line 50 Line-page 151, line 47 16) Desilvering process page 151, line 48-page 152, line 53 17) Automatic development Machine, page 152, line 54 to page 153, line 2 18) Washing and stabilization step Page 153, lines 3 to 37.

[0132]

EXAMPLES (Example 1) Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto.

Preparation of Sample 101 A multilayer color light-sensitive material comprising the following layers was prepared on an undercoated cellulose triacetate film support having a thickness of 127 μm to prepare Sample 101. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the use described.

First layer: Antihalation layer Black colloidal silver 0.10 g Gelatin 2.00 g UV absorber U-1 0.20 g UV absorber U-3 0.040 g UV absorber U-4 0.15 g High boiling organic solvent Oil-1 0.10 g Dye amount D-4 1.0 mg Dye D-8 2.5 mg 0.10 g of a microcrystalline solid dispersion of dye E-1.

Second layer: Intermediate layer Gelatin 0.40 g Compound Cpd-K 0.10 g Ultraviolet absorber U-6 0.010 g High boiling organic solvent Oil-3 0.050 g High boiling organic solvent Oil-5 2.0 mg High boiling organic solvent Oil- 7 2.0 mg High boiling organic solvent Oil-8 5.0 mg Dye D-7 2.5 mg.

Third layer: Intermediate layer Yellow colloidal silver Silver amount 0.010 g Gelatin 0.40 g Compound Cpd-K 0.050 g High boiling organic solvent 0il-3 0.020 g.

Fourth layer: low-sensitivity red-sensitive emulsion layer Emulsion A silver amount 0.20 g Emulsion B silver amount 0.20 g Emulsion C silver amount 0.15 g gelatin 0.70 g Coupler C-1 0.10 g Coupler C-2 0.050 g Coupler C-3 0.050 g Coupler C-9 0.010 g Coupler C-11 0.050 g Compound Cpd-C 5.0 mg Compound Cpd-I 0.020 g High boiling organic solvent Oil-2 0.10 g Additive P-1 0.10 g.

Fifth layer: Medium-speed red-sensitive emulsion layer Emulsion C silver amount 0.25 g Emulsion D silver amount 0.25 g gelatin 0.70 g coupler C-1 0.15 g coupler C-2 0.050 g coupler C-3 0.020 g coupler C-11 0.070 g High boiling organic solvent Oil-2 0.10 g Additive P-1 0.10 g.

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion E silver amount 0.20 g Emulsion F silver amount 0.25 g gelatin 1.20 g Coupler C-1 0.10 g Coupler C-2 0.10 g Coupler C-3 0.50 g Coupler C-11 0.15 g High boiling organic solvent Oil-9 0.050 g High boiling organic solvent Oil-2 0.10 g Additive P-1 0.10 g.

Seventh layer: Intermediate layer Gelatin 0.60 g Additive P-2 0.30 g Compound Cpd-I 2.6 mg Dye D-5 0.020 g Dye D-6 0.010 g Compound Cpd-K 0.040 g Compound Cpd-M 3.0 mg Compound Cpd-N 2.5 mg High boiling organic solvent Oil-1 0.020 g High boiling organic solvent Oil-6 0.050 g.

Eighth layer: Intermediate layer Yellow colloidal silver Amount of silver 0.010 g Gelatin 0.60 g Additive P-2 0.05 g Compound Cpd-A 0.10 g Compound Cpd-K 0.10 g High boiling organic solvent Oil-6 0.10 g.

Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion G silver amount 0.25 g Emulsion H silver amount 0.30 g Emulsion I silver amount 0.25 g gelatin 0.80 g Coupler C-4 0.050 g Coupler C-7 0.10 g Coupler C-8 0.12 g Coupler C-12 0.050 g Compound Cpd-B 0.030 g Compound Cpd-D 0.020 g Compound Cpd-E 0.020 g Compound Cpd-G 2.5 mg Compound Cpd-F 0.040 g Compound Cpd-J 0.020 g High boiling organic solvent Oil- 1 0.10 g High boiling organic solvent Oil-2 0.10 g.

Tenth layer: Medium-sensitive green-sensitive emulsion layer Emulsion I Silver content 0.20 g Emulsion J Silver content 0.20 g Gelatin 0.60 g Coupler C-4 0.10 g Coupler C-7 0.050 g Coupler C-8 0.050 g Coupler C-12 0.030 g Compound Cpd-B 0.030 g Compound Cpd-D 0.020 g Compound Cpd-F 0.050 g Compound Cpd-G 2.0 mg High boiling organic solvent Oil-2 0.010 g.

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion K Silver content 0.55 g Gelatin 0.70 g Coupler C-4 0.25 g Coupler C-7 0.10 g Coupler C-8 0.050 g Coupler C-12 0.050 g Compound Cpd-B 0.080 g Compound Cpd-D 0.020 g Compound Cpd-F 0.040 g High boiling organic solvent Oil-1 0.020 g High boiling organic solvent Oil-2 0.020 g.

Twelfth layer: Intermediate layer Gelatin 0.30 g Compound Cpd-K 0.05 g High boiling organic solvent Oil-3 0.025 g High boiling organic solvent Oil-6 0.025 g.

13th layer: Yellow filter layer Yellow colloidal silver Amount of silver 5.0 mg Gelatin 1.00 g Compound Cpd-C 0.010 g Compound Cpd-K 0.050 g High-boiling organic solvent Oil-1 0.020 g Fine crystalline solid dispersion of dye E-2 0.030 g of a microcrystalline solid dispersion of dye E-3 0.020 g.

Fourteenth layer: Intermediate layer Gelatin 0.40 g.

Fifteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion L silver amount 0.20 g Emulsion M silver amount 0.20 g gelatin 0.80 g coupler C-5 0.20 g coupler C-6 0.10 g coupler C-10 0.10 g compound Cpd-I 0.010 g Compound Cpd-K 0.010 g.

Sixteenth layer: Medium-sensitivity blue-sensitive emulsion layer Emulsion N silver amount 0.20 g Emulsion O silver amount 0.20 g gelatin 0.90 g Coupler C-5 0.10 g Coupler C-6 0.10 g Coupler C-10 0.10 g Compound Cpd-L 2.0 mg High boiling organic solvent Oil-2 0.050 g.

17th layer: Highly sensitive blue-sensitive emulsion layer Emulsion O silver amount 0.20 g Emulsion P silver amount 0.25 g gelatin 1.20 g Coupler C-5 0.10 g Coupler C-6 0.10 g Coupler C-10 0.80 g High boiling organic solvent Oil-2 0.050 g Compound Cpd-B 0.25 g Compound Cpd-L 5.0 mg Compound Cpd-O 0.20 g.

Eighteenth layer: First protective layer Gelatin 0.70 g UV absorber U-1 0.20 g UV absorber U-2 0.050 g UV absorber U-5 0.30 g Compound Cpd-M 5.0 mg Compound Cpd-A 0.030 g Compound Cpd-H 0.20 g Dye D-1 0.10 g Dye D-2 0.050 g Dye D-3 0.07 g High boiling organic solvent Oil-3 0.10 g.

Nineteenth layer: Second protective layer Colloidal silver Silver content 0.10 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver content 0.10 g Gelatin 0.50 g.

20th layer: 3rd protective layer Gelatin 0.80 g Polymethyl methacrylate (average particle size 1.5 μm) 0.10 g Copolymer of methyl methacrylate and methacrylic acid (average particle size 1.5 μm) 0.10 g Silicone oil SO-1 0.030 g Surfactant W-1 3.0 mg Surfactant W-2 0.030 g Surfactant W-7 2.5 mg.

In addition, additives F-1 to F-8 were added to all the emulsion layers in addition to the above composition. Further, in addition to the above composition, gelatin hardener H-1 and surfactants W-3, W-4, W-5 and W-6 for coating and emulsification were added to each layer.

Further, phenol and 1,1 are used as antiseptic and antifungal agents.
2-Benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, p-benzoic acid butyl ester were added.

[0156]

[Table 1]

[0157]

[Table 2]

[0158]

[Table 3]

[0159]

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[0160]

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[0161]

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[0162]

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[0163]

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[0164]

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[0165]

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[0166]

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[0167]

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[0168]

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[0169]

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[0170]

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[0171]

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[0172]

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[0173]

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[0174]

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[0175]

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Preparation of Dispersion of Organic Solid Disperse Dye Dye E-1 was dispersed by the following method. That is, water and 200 g of Pluronic F88 (ethylene oxide-propylene oxide block copolymer) manufactured by BASF were added to 1430 g of a dye wet cake containing 30% of methanol, followed by stirring to obtain a slurry having a dye concentration of 6%. Next, 1700 mL of zirconia beads having an average particle size of 0.5 mm was charged into Ultra Viscomil (UVM-2) manufactured by Imex Co., Ltd., and the peripheral speed was about 10 m / sec and the discharge rate was 0.5
Milled for 8 hours at L / min. The beads were removed by filtration and diluted with water to a dye concentration of 3% by adding water.
Heated at ° C for 10 hours. The average particle size of the obtained fine dye particles was 0.60 μm, and the width of the particle size distribution (standard deviation of particle size × 100 / average particle size) was 18%.

Similarly, solid dispersions of dyes E-2 and E-3 were obtained. Average particle size 0.54μm and 0.56μm
Met.

Compounds and fine silver halide grains were added to Sample 101 as shown in Table 4 to prepare Samples 102 to 127.

Fine grain types of silver halide grains A, B,
C, D, E, and F are as follows.

A: silver bromide, sphere-equivalent mean particle size 0.06 μm, shape = cube B: silver iodobromide (silver iodide content 9%), sphere-equivalent mean particle size
08 μm, shape = cube C: silver iodobromide (silver iodide content: 3%)
D: silver bromide, sphere-equivalent average particle size 0.15 μm, shape = cube E: silver bromide, sphere-equivalent average particle size 0.20 μm, shape = cube F: Silver iodide, sphere equivalent average particle size 0.06 μm, shape = cube.

[0181]

[Table 4]

[0182]

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In this example, the following development processing was performed. In processing, sample 101 and Fujichrome RDP
II, RVP (Fuji Photo Film Co., Ltd.), Ektachrome E100S, EPR (Kodak)
A sample completely exposed to 0% white light was 2: 3: 1: 3:
It was used after passing through at a rate of 1 until the replenishment amount became three times the tank capacity.

Processing Step Time Temperature Tank capacity Replenishment amount First development 6 minutes 38 ° C 12L 2200mL / m ² First water wash 2 minutes 38 ° C 4L 7500mL / m ² Inversion 2 minutes 38 ° C 4L 1100mL / m ² Color development 6 minutes 38 ℃ 12L 2200mL / m ² before bleaching 2 min 38 ℃ 4L 1100mL / m ² bleaching 6 min 38 ℃ 12L 220mL / m ² Fixing 4 min 38 ℃ 8L 1100mL / m ² second water washing 4 minutes 38 ° C. 8L 7500 ml / m ² final rinse 1 min 25 ℃ 2L 1100mL / m ^2.

The composition of each processing solution was as follows.

[First developer] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid · pentasodium salt 1.5 g 1.5 g Diethylenetriaminepentaacetic acid · pentasodium salt 2.0 g 2.0 g Sodium sulfite 30 g 30 g Potassium hydroquinone monosulfonate 20 g 20 g Potassium carbonate 15 g 20 g Potassium bicarbonate 12 g 15 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5 g 2.0 g Potassium bromide 2.5 g 1.4 g Potassium thiocyanate 1.2 g 1.2 g Potassium iodide 2.0 mg-Diethylene glycol 13 g 15 g Water was added to the mixture, and the mixture was adjusted with sulfuric acid or potassium hydroxide.

[Reversing solution] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid tank solution • Same as 3.0 g of pentasodium salt 1.0 g of stannous chloride • dihydrate p-amino Phenol 0.1 g Sodium hydroxide 8 g Glacial acetic acid 15 mL Water was added to 1000 mL pH 6.00 The pH was adjusted with acetic acid or sodium hydroxide.

[Color developing solution] [Tank solution] [Replenisher] Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 2.0 g 2.0 g Sodium sulfite 7.0 g 7.0 g Trisodium phosphate / 12 hydrate 36 g 36 g Potassium bromide 1.0 g-Potassium iodide 90 mg-Sodium hydroxide 3.0 g 3.0 g Citrazinic acid 1.5 g 1.5 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4- Aminoaniline 3/2 sulfuric acid monohydrate 11 g 11 g 3,6-dithiaoctane-1,8-diol 1.0 g 1.0 g Add water 1000 mL 1000 mL pH 11.80 12.00 Adjust pH with sulfuric acid or potassium hydroxide did.

[Pre-bleaching] [Tank liquid] [Replenisher] Ethylenediaminetetraacetic acid disodium salt dihydrate 8.0 g 8.0 g Sodium sulfite 6.0 g 8.0 g 1-thioglycerol 0.4 g 0.4 g Sodium formaldehyde sodium bisulfite adduct 30 g 35 g Water was added and 1000 mL 1000 mL pH 6.30 6.10 pH was adjusted with acetic acid or sodium hydroxide.

[Bleaching solution] [Tank solution] [Replenisher] Ethylenediaminetetraacetic acid disodium salt dihydrate 2.0 g 4.0 g Ethylenediaminetetraacetic acid Fe (III) ammonium ammonium dihydrate 120 g 240 g Bromide Potassium 100 g 200 g Ammonium nitrate 10 g 20 g Water was added to 1000 mL 1000 mL pH 5.70 5.50 The pH was adjusted with nitric acid or sodium hydroxide.

[Fixing solution] [Tank solution] [Replenisher] Ammonium thiosulfate 80 g Same sodium sulfite 5.0 g ナ ト リ ウ ム Sodium bisulfite 5.0 g タ ン ク Water added to 1000 mL ｐＨ pH 6.60 pH adjusted with acetic acid or aqueous ammonia It was adjusted.

[Stabilizing solution] [Tank solution] [Replenishing solution] 1,2-benzisothiazolin-3-one 0.02 g 0.03 g polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 g 0.3 g polymalein Acid (average molecular weight 2,000) 0.1 g 0.15 g Water was added to make 1000 mL 1000 mL pH 7.0 7.0.

(Evaluation of Samples) (Measurement of Sensitized Developing Width) Samples 101 to 124 were exposed to white light having a color temperature of 4800 ° C. through a wedge of continuously changing density, and then subjected to the above development processing. Then, the densities of yellow, magenta and cyan were measured. At this time (at the first development time of 6 minutes), the sensitivity for giving a density of 1.0 for each color was measured and was determined as S (1.0) -6.

In the above developing process, the sensitivity for giving a density of 1.0 for each color was measured in the same manner except that the first developing time was changed to 11 minutes, and the sensitivity was determined as S (1.0) -11. The difference between (1.0) -6 and S (1.0) -11 was defined as the sensitized development width.

Based on the sensitized development width of the sample 101, the sensitivity (log
E) Increase / decrease of change was shown.

(Measurement of Maximum Density) The maximum density of each color of the processed sample (sample having a first development time of 11 minutes) prepared by measuring the sensitized development width was measured. On the basis of the value of the sample 101,
The increase / decrease of the maximum concentration was indicated.

(Measurement of Sharpness) Samples 101 to 127 were exposed to white light through an MTF pattern, developed similarly, and the MTF value was measured. The sharpness was compared at an MTF value of 20 cycles / mm. The values are shown as ratios with the value of sample 101 being 1.0. The higher the value, the higher the sharpness.

The sensitized development width, the maximum density, and the MTF ratio of the samples 108, 114, 116, and 127 were compared with the measured values of the magenta density and the measured values of the yellow density of the sample 122 with the values of the sample 101, respectively. The other values are indicated by the difference between the measured values of the cyan density.

(Evaluation of Saturation) Samples 101 to 127
After processing to a size of 0.2 cm × about 12.7 cm, a gray reference table is created with a film recorder (Solitaire 16D; manufactured by Management Graphics), and then yellow, magenta, and cyan pure colors (for example, yellow pure color is green light) And the signal intensity of the red light is 100
An image pattern was created in which the signal intensity of blue light was continuously changed from 0 to 100. Where signal strength 1
00 represents an exposure amount that gives each sample a yellow, magenta, and cyan density = 0.20). The obtained pure color image was measured for color turbidity. The sensory evaluation was compared with that of the sample 101, and the saturation was higher than １０１ = １０１, almost equal to Δ △, and the saturation was lower than 101 = ×.

The above is summarized in Table 5.

[0201]

[Table 5]

Compared to Sample 101, Samples 102 and 103, to which fine silver halide grains were added, had a wider sensitized development width and a higher maximum density, but the MTF was greatly deteriorated and the color turbidity was also worsened. On the other hand, when only a known development inhibitor or the compound of the present invention is added as in the case of the sample 104 or the sample 106, the MTF and the chroma are increased, but the maximum density is maintained while expanding the sensitized development width. Has not been achieved.

Further, 105, 107, 108, 10
9, 110, the effects of MTF and color turbidity were not improved when fine silver halide grains were used in combination with a known development inhibitor.

In contrast, for example, the sample 11 of the present invention
In the case of sample No. 1, while the sensitized development width was expanded, the maximum density was changed to sample 101
The value was higher than the above, and the MTF and chroma were also improved. Sample 112, in which a fine grain silver halide emulsion was added to both the low-speed layer and the high-speed layer in the red-sensitive unit and the compound of the present invention was used in combination, showed a particularly remarkable improvement in MTF, which was favorable.

In Samples 118 to 122, 126, and 127 in which the compound of the present invention was a compound in which M is a blocking group, the effect of improving MTF was particularly large, and favorable results were obtained.

Claims (5)

[Claims] An at least one blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer on a support,
And a silver halide color photographic light-sensitive material containing a red-sensitive silver halide emulsion layer, having an equivalent sphere equivalent particle diameter of 0.15.
First photosensitive silver halide grains having a diameter of 0.02 μm or more and less than 2.00 μm and a sphere-equivalent average particle diameter of 0.02 μm or more and 0.40 μm or less.
, A light-sensitive emulsion containing both substantially insensitive second silver halide grains having a sphere-equivalent average particle diameter of less than 1/3 with respect to the first photosensitive silver halide grains. A silver halide color having at least one layer, wherein at least one photosensitive layer and / or non-photosensitive layer contains at least one compound represented by the following general formula (I). Photosensitive material. Embedded image In the formula, M is a hydrogen atom, a metal atom, or a block group having a property that an MS bond is cleaved in a development processing step (however, a coupler residue having a property of coupling with an oxidized aromatic primary amine color developer). Not a group) and G ¹
Represents a nonmetallic atom group necessary for forming a nitrogen-containing heterocyclic ring selected from thiazole, oxazole, imidazole, triazole, and oxadiazole, and L represents a divalent group that is substituted with a carbon atom constituting G ^1. And m represents 0 or 1, n represents an integer of 0 or more and 6 or less, and X represents a nitrogen-containing heterocyclic ring containing G ¹ represented by thiazole, oxazole,
Or a hydrogen atom or a substituent bonded to a carbon atom constituting G ¹ when it is imidazole. Y is -O
_{H, -OR 1, -CN, -COOR} 1, -COR 1, -C
_{ONH 2, -CONHR 1, -CONR 1} R 2, -NHCO
R ₁ represents a substituent selected from —COOH, an amino group, and a heterocyclic group; R ₁ and R ₂ each independently represent a total carbon number of 1 to 8;
Represents a substituted or unsubstituted alkyl group or alkenyl group, which may have a substituent, and R ₁ and R ₂ may be bonded to each other to form a ring. However, when the nitrogen-containing heterocyclic ring containing G ¹ is thiazole, Y is -C
Not OOH. 2. The silver halide color according to claim 1, wherein the compound represented by the general formula (I) is a compound represented by the following general formula (II) or (III). Photosensitive material. Embedded image In the formula, Z ¹ represents —NH ₂ , —NHR ₁ , —NR ₁ R ₂ , —OR ₁
Wherein n, X, M, R ₁ and R ₂ have the same meanings as those in formula (I). 3. The compound represented by the general formula (I) further comprises:
Claims characterized by the following general formula (IV):
2. The silver halide color photographic light-sensitive material according to item 1. Embedded imageWhere Z^TwoIs -OH, -OR₁, -CN, -COR₁, −
COOR₁, -CONH _Two, -CONHR₁, -CONR₁
R_Two, -NR₁R_TwoRepresents a substituent selected from ₁, R_Two
Has the same meaning as in general formula (I). 4. The method according to claim 1, wherein M is a block group defined by the general formula (I).
6. The silver halide color photographic light-sensitive material according to the above item. 5. A silver halide color photographic light-sensitive material having a blue-sensitive unit, a green-sensitive unit, and a red-sensitive unit comprising two or more light-sensitive emulsion layers having different sensitivities on a support, as defined in claim 1. 6. A photosensitive unit comprising at least one photosensitive unit comprising at least two photosensitive emulsion layers containing both the first photosensitive silver halide grains and the second photosensitive silver halide grains.
The silver halide color photographic light-sensitive material according to any one of the above items.