JPH0667386A - Silver halide color photographic sensitive material and treating method - Google Patents

Abstract

PURPOSE:To obtain such a color photographic sensitive material that has excellent color reproducibility and excellent color image rigidity of magenta images even when formaldehyde in a treating liquid is removed and shows little change in the photographic property against changes in pH of a color developer, and to provide its treating method. CONSTITUTION:A green-sensitive layer of this photosensitive material contains a substantially colorless magenta dye-forming coupler selected from compds. expressed by formulae I and II, and further, contains an emulsion containing silver halide particles having projections of silver halide on the surface of silver halide base particles. In formula, R1 is an aryl group which may be substituted, X1, X2 are each hydrogen atom, a halogen atom, or an alkyl group, X3, X4, X5 are each a substituent necessary to give 0.9 or a higher Hammett's substitution const sigma, and L is a group which can be released by the reaction with an oxidant of an aromatic primary amine color developing agent.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material.

[0002]

2. Description of the Related Art Recently, in color photographic light-sensitive materials,
To meet the needs of users, increase the sensitivity of photosensitive materials,
Higher image quality is being promoted. Among these, in terms of high image quality, mainly improvement of color reproducibility, improvement of sharpness and improvement of graininess are extremely important in discussing the performance of the light-sensitive material. Furthermore, recently, in addition to these, various performances such as improvement of color image fastness, quality assurance against processing liquid fluctuation, and consideration for environmental protection have been attracting much attention. Regarding the color image fastness, it is widely known that formaldehyde is contained in the final bath of the development processing step of the color photographic material in order to improve the fastness of the magenta image. Much research has already been done on the role of formaldehyde, for example PW Vittum, F. et al.
C. Duennebier and J. Am. Chem. Soc. 72.1536 (1950) describe that pyrazolone couplers react with azomethine dyes to cause fading of the dyes. On the other hand, RWGHun
t, "The Reproduction of Color", 2nd Eddition, J. Wil
In ey and Sons., Inc., New York, P306 (1967), formaldehyde was added to the stabilizing bath to prevent the unreacted coupler from reacting with the dye and fading. There is a statement to prevent the reaction of. Also, The
Journal of Photographic Science 36, 64 (1988) also has a similar description. As described above, formaldehyde plays a large role in image fastness, but formaldehyde has a problem in environmental protection, and it is strongly demanded to remove it from a photographic processing solution.

[0003] Several techniques have been known in the past that do not deteriorate form fastness by not performing formaldehyde treatment in the developing process. As an example of this, JP-A-60-9
No. 8435 describes that when a 2-equivalent pyrazolone coupler is used, color image fastness is not impaired even if formaldehyde is not substantially contained. Further, JP-A-62-5
No. 4261 describes that even in pyrazoloazole type couplers, the use of 2-equivalent type couplers does not impair the color image fastness even if formaldehyde is removed from the stabilizing bath. U.S. Pat. No. 3,127,269, Japanese Patent Publication No. 40
No. 6035 describes a 4-equivalent pyrazolone type magenta coupler having an anilino substituent, and the use of this coupler eliminates the need for stabilizing treatment with formaldehyde. JP-B Nos. 53-33846 and 55-29
No. 420 and No. 55-31460. However, when using the above couplers in photographic materials,
The 2-equivalent coupler had a problem that the graininess was deteriorated, and the anilino-type pyrazolone magenta coupler had a problem that red was tinged with vermilion in color reproduction. The latter is a problem that a known 4-equivalent anilino type magenta coupler has a shorter wavelength than that of a magenta coupler having an acylamino group as a substituent which has been used in a conventional photographic material. As described above, the anilino type pyrazolone magenta coupler is required to have a longer wavelength of hue, and is disclosed in Japanese Examined Patent Publication No. 55-30615.
No. 6 presents compounds having a structure similar to the magenta coupler of the present invention. However, the present inventors have found that the use of the above-mentioned coupler causes deterioration of pH dependency in color development, and a solution has been required.

[0004]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is, firstly, to provide excellent color image fastness of a magenta image even when formaldehyde contained in a processing solution is removed. Thirdly, to provide a color photographic light-sensitive material excellent in color reproducibility and a processing method in which the change in photographic property is small against fluctuation.

[0005]

It has been found that the above-mentioned objects can be achieved by the following means for processing silver halide color photographic light-sensitive materials and processing methods. That is, (1) in a silver halide color photographic light-sensitive material having one or more blue-sensitive emulsion layers, green-sensitive emulsion layers, and red-sensitive emulsions each on a support, the following general formula (M) is contained in the green-sensitive layers. And a substantially colorless magenta dye-forming coupler selected from compounds represented by (N), and at least one of the green-sensitive emulsion layers has a silver halide emulsion containing halogen on the surface of silver halide host grains. A silver halide color photographic light-sensitive material, which is an emulsion containing silver halide grains having silver halide protrusions. (2) A method for processing a silver halide color photographic light-sensitive material, which comprises processing the silver halide color photographic light-sensitive material described in the above item (1) with a color developer having a pH of 11.0 or higher. (3) In a silver halide color photographic light-sensitive material having a green-sensitive emulsion layer composed of two or more emulsion layers having different sensitivities on a support, the following general formula (M) is added to at least the highest sensitivity layer of the green-sensitive layer. The silver halide color photographic light-sensitive material as described in the above item (1), which contains a substantially colorless magenta dye-forming coupler selected from the compounds represented by and (N).

[0006]

[Chemical 2]

In the formula, R ₁ represents an optionally substituted aryl group, X ₁ and X ₂ each represent a hydrogen atom, a halogen atom and an alkyl group, and X ₃ , X ₄ and X ₅ represent each Hammett Represents a substituent necessary for the total sum of the substituent constant σ values to be 0.9 or more. L represents a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine color developing agent. The couplers represented by the formulas (M) and (N) of the present invention are substantially colorless when the coupler has no chromophore and leaves the colored coupler, the fluorescent dye-releasing coupler or the dye precursor group. It means that a coupler used for the purpose of correcting unnecessary absorption of a color forming dye, such as a coupler having a group, is not included in the coupler of the present invention.

In the present invention, R ₁ , X ₁ , X ₂ , X ₃ , X ₄ and X _{5 in the} compound represented by the general formula (M) are used.
Will be described in detail, but before that, the Hammett's substituent constant will be briefly described. Hammett's rule is used to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. The rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants obtained by the Hammett's rule include σ _p values and σ _m values, and these values can be found in many general textbooks. A. Dean
Edited by "Lange's Handbook of Ch
"emission" 12th edition, 1979 (McGraw
-Hill) and "The Area of Chemistry" special edition, No. 122, 96-
Details on page 103, 1979 (Nankodo). In the present invention, each substituent is represented by Hammett's substituent constants σ _p and σ _m
Limited or explained by the above, which can be found in the above mentioned books. It does not mean that the value known in the literature is limited only to a certain substituent, and it also includes the substituent that will be included in the range when the value is unknown even in the literature when measured based on Hammett's rule. Needless to say. In the future, the σ _p and σ _m values will have this meaning.

However, σ _p and σ _m found in books, documents, etc.
Even if the values are the same, it may be found that the values differ depending on the literature. In the present invention, in order to avoid confusion caused by this, X ₃ , based on the values in the tables listed in “Chemical Region”, special issue, No. 122, pp. It is defined as calculating the sum of the σ values of X ₄ and X ₅ . Here, the σ _m value is used for X ₃ and X ₄ , and the σ _p value is used for X ₅ .

Next, R ₁ will be described in detail. R ₁ is an optionally substituted aryl group, more specifically, an optionally substituted aryl group having 6 to 46 carbon atoms, and the substituent is linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. It is an organic substituent or a halogen atom, a hydroxyl group, a nitro group, or a cyano group.

More specifically, R ₁ is an optionally substituted aryl group having 6 to 46 carbon atoms, such as an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group or an amino group. , Acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, acylamino group, alkylamino group , Anilino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, sulfonamide group, aryloxycarbonylamino group, imide group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfonyl group, sulfinyl group , It may be substituted with a zo group, a phosphonyl group, an azolyl group, a fluorine atom, a chlorine atom or a bromine atom, and examples thereof include phenyl, 2-chlorophenyl, 2-methoxyphenyl, 2-chloro-5-tetradecanamidophenyl, 2-chloro. -5- (3-octadecenyl-1-
Succinimido) phenyl, 2-chloro-5-octadecylsulfonamidophenyl, 5-hexadecanoamidophenyl, 2-chloro-5- [2- (4-hydroxy-
3-tert-butylphenoxy) tetradecanamidophenyl].

Preferred R ₁ -NH- groups in the formula (M) are represented by the following formulas (Ma), (Mb) and (Mc). Formula (Ma)

[0013]

[Chemical 3]

In the formula, R ₂ represents an alkyl group, an aryl group or a heterocyclic group, and more specifically, R ₂ is an alkyl group (a linear, branched or cyclic alkyl group having 1 to 23 carbon atoms, which is an alkenyl group). Group, alkynyl group, aryl group, hydroxyl group, nitro group, cyano group, halogen atom or other oxygen atom, nitrogen atom, sulfur atom or carbon atom which may be substituted with a substituent, for example, heptyl, nonyl, undecyl , Tridecyl, heptadecyl, 2-ethylhexyl, 2-hexyldecyl, 4-
Hexylcyclohexyl, 3-pentadecylcyclohexyl, norbornyl, 7 / 7-dialkyl-norbornyl, 2-pentadecyl, 7 / 7-dialkylnorbornyl, 1- (2,4-di-t-pentylphenoxy) propyl, 3- (2,4-di-t-pentylphenoxy) propyl, an aryl group (an aryl group having 6 to 38 carbon atoms, which is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group, a halogen). May be substituted with a substituent linked with an atom or other oxygen atom, nitrogen atom, sulfur atom or carbon atom, for example, phenyl, naphthyl, p-methoxyphenyl), heterocyclic group (oxygen atom having 1 to 5 carbon atoms) , A 5- or 6-membered aromatic or aliphatic ring containing at least one nitrogen atom or sulfur atom Type number and elemental hetero atoms constituting the ring A heterocycle may be a plurality, even one, also these hetero ring group further having a carbon number 1 to 1
6 may be substituted with an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a hydroxyl group, a nitro group, a cyano group, a halogen atom or other substituents linked by an oxygen atom, a nitrogen atom, a sulfur atom or a carbon atom. For example, 2-furyl, 2-thienyl, 2-pyrimidinyl,
2-benzotriazolyl, imidazolyl, pyrazolyl)
Represents R ₂ is preferably an alkyl group.

Y and A are each a hydrogen atom alkyl group (eg methyl, tert-butyl, octyl, dodecyl), an aryl group (eg phenyl group, tolyl group), an alkoxy group (eg methoxy, octoxy), an aryloxy group (eg. Phenoxy, p-tert-butylphenoxy, naphthoxy), alkylthio groups (eg methylthio, octylthio), arylthio groups (eg phenylthio), amino groups (eg amino, methylamino,
Dimethylamino, anilino), an amide group (eg acetamide, butyramide, methanesulfonamide, diacylamide), a halogen atom (fluorine, chlorine, bromine), a hydroxyl group, a cyano group or a nitro group.

Y and A may be the same or different. m represents an integer of 0 to 3. m is preferably 0 or 1, and most preferably 0. Y is preferably a hydrogen atom,
A halogen atom, particularly preferably a hydrogen atom or a chlorine atom, and particularly preferably a chlorine atom. Formula (Mb)

[0017]

[Chemical 4]

In the formula, R ₃ represents an alkyl group, and more specifically, R ₃ represents a linear or branched alkyl group having 1 to 32 carbon atoms or a cyclic alkyl group (for example, cyclohexyl and terpenyl), wherein the above alkyl is The group is a halogen atom, a nitro group, a hydroxyl group, a carboxyl group, an amino group (for example, amino, alkylamino, dialkylamino, anilino, N-alkylanilino), an aryl group, a carboxyester group (for example, carboalkoxy,
Carboallyloxy), amide group (eg acetamide, butyramide, ethyl sulfonamide, N-methylbenzamide, N-propylbenzamide, 4-ter
t-butylbenzamide, diacylamide), carbamyl group (for example, carbamyl, N-octadecylcarbamyl, N, N-dihexylcarbamyl, N-methyl-N-).
Phenylcarbamyl, 3-pentadecylphenylcarbamyl), sulfamyl group (eg N-propylsulfamyl, N-tolylsulfamyl), alkoxy group (eg ethoxy, octadecoxy), aryloxy group (eg phenoxy, tolyloxy, Naphthyloxy), sulfonic acid group, sulfonyl group (for example, methylsulfonyl,
Octadecyl sulfonyl, ethoxy sulfonyl, deoxy sulfonyl, phenyl sulfonyl, tolyl sulfophenyl, phenoxy sulfonyl).

Y, A and m are synonymous with those shown in the formula (Ma), including their preference. Formula (Mc)

[0020]

[Chemical 5]

In the formula, R ₄ and R ₅ each represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and more specifically, R ₄ and R ₅ each represent a hydrogen atom or a carbon atom number of 1 to 1.
32 linear or branched alkyl groups, cyclic alkyl groups (eg cyclohexyl, terpenyl, norbornyl), aryl groups (eg phenyl, naphthyl), heterocyclic groups (eg benzimidazolyl, benzthiazolyl) or morpholine, piperidine etc. Represents a group of non-metal atoms necessary for forming a heterocycle with such N-atoms. Here, the above-mentioned alkyl group, aryl group, heterocyclic group and the like include halogen atom, nitro group, hydroxyl group, carboxyl group, amino group (for example, amino, alkylamino, dialkylamino, anilino, N-alkylanilino), Aryl group, carboxyester group (eg, carboalkoxy, carboallyloxy), amide group (eg, acetamide, butylamide, ethylsulfonamide, N-methylbenzamide, N-propylbenzamide, 4-tert-butylbenzamide, diacylamide), carbamyl Group (eg carbamyl, N-octadecylcarbamyl, N, N-dihexylcarbamyl, N-methyl-N-phenylcarbamyl, 3-pentadecylphenylcarbamyl), sulfamyl group (eg N-propylsulfamyl) N- tolyl sulfamyl), an alkoxy group (e.g. ethoxy, Okutadekokishi), an aryloxy group (e.g., phenoxy, tolyloxy, naphthyloxy), a sulfonic acid group, a sulfonyl group (e.g., methylsulfonyl, octadecylsulfonylamino,
(Ethoxysulfonyl, Decoxysulfonyl, Phenylphonyl, Tolylsulfophenyl, Phenoxysulfonyl)
May be replaced with.

Y, A and m are synonymous with those shown in the formula (Ma) including their preference. R in formula (Ma)
₂ CONH- _{group, R 4 (R 5) NSO} 2 in the formula R ₃ OCO- groups and wherein in (Mb) (Mc) - substitution position relative to the benzene ring of the group is described in the formula -NH- It is preferably not in the ortho position with respect to the group, and more preferably not in the ortho position of Y described in each formula.

Of the substituents represented by formulas (Ma), (Mb) and (Mc), those represented by formula (Ma) are most preferred.

X ₁ and X ₂ may be the same or different and each represents a hydrogen atom, a halogen atom or an alkyl group. More specifically, X ₁ and X ₂ are a hydrogen atom, a halogen atom (for example, a fluorine atom or a chlorine atom), an alkyl group (a straight chain, branched chain or cyclic alkyl group having 1 to 8 carbon atoms) and are exemplified by R ₁ . It may be substituted with a substituent such as methyl, ethyl, 2-hydroxyethyl, isopropyl).

It is preferable that _one of X ₁ and X ₂ is a hydrogen atom, the other is a halogen atom, and it is more preferable that both are a halogen atom.
Among the halogen atoms, fluorine atom and chlorine atom are preferable, and chlorine atom is particularly preferable.

X ₃ , X ₄ and X ₅ are substituents necessary for the total sum of the Hammett's substituent constant σ values to be 0.9 or more, and more specifically X ₃ , X ₄ and X ₅ Is a hydrogen atom and a substituent exemplified below, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group,
Hydroxyl group, carboxyl 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 oxy group, azo group, acyloxy group, carbamoyloxy group, silyl group, silyloxy group, aryloxycarbonylamino group, imide group, heterocyclic thio group, sulfinyl group, phosphonyl group , Aryloxycarbonyl group, and acyl group, the Hammett σ of each substituent
It is selected so that the sum of the values is 0.9 or more. Further, the total sum is preferably 1.0 or more.

Among those exemplified above, X ₃ , X ₄ and X ₅ are hydrogen atom, halogen atom, alkyl group (particularly trifluoromethyl group), cyano group, nitro group, carbamoyl group, sulfamoyl group, sulfonyl group, It is preferable to select an alkoxycarbonyl group so that the sum of its σ values is 0.9 or more. Furthermore, the total sum of the σ values is preferably 1.0 or more, more preferably 1.1 or more.

Table 1 shows preferred combinations of X ₃ , X ₄ and X ₅ and the sum of the σ values at that time.

[0029]

[Table 1]

In Table 1, the combination No. 1, 3, 4, 5,
Those of 7, 8, 10, 15, 16, 21, and 25 are particularly preferable, and among them, the combination No. 1,7,15,21,25
It is most preferable to select X ₃ , X ₄ and X ₅ as follows.

The compound represented by formula (N) of the present invention will be described in detail below. In the formula, R ₁ , X ₁ ,
X ₂ , X ₃ , X ₄ and X ₅ have the same meanings as shown in formula (M).

L represents a hydrogen atom or a coupling-off group, and the coupling-off group will be described in detail below.
For example, halogen atom, alkoxy group, aryloxy group, acyloxy group, sulfonyloxy group, amide group,
An alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an alkyl, an aryl group is a heterocyclic thio group, an imide group, a 5-membered or 6-membered nitrogen-containing heterocyclic group, an arylazo group, and these groups are further represented by R ₁ It may be substituted with a group allowed as a substituent. More specifically, the coupling-off group represented by L is a silver halide (eg, fluorine atom, chlorine atom, bromine atom), an alkoxy group (eg, dodecyloxy, dodecyloxycarbonylmethoxy, methoxycarbamoylmethoxy, carboxypropyloxy, methane). Sulfonyloxy), an aryloxy group (for example, 4-methylphenoxy, 4-tert-butylphenoxy, 4-methoxyphenoxy, 4-methanesulfonylphenoxy, 4-
(4-benzyloxyphenylsulfonyl) phenoxy), acyloxy group (eg acetoxy, tetradecanoyloxy, benzoyloxy), sulfonyloxy group (eg methanesulfonyloxy, toluenesulfonyloxy), amide group (eg dichloroacetylamino, methanesulfonyl) Amino, triphenylphosphonamide), alkoxycarbonyloxy group (eg ethoxycarbonyloxy, benzyloxycarbonyloxy), aryloxycarbonyloxy group (eg phenoxycarbonyloxy, 2,4,6-trimethylphenoxycarbonyl), alkyl, aryl or Heterocyclic thio groups (eg dodecylthio, benzylthio, 1-
Carboxydodecylthio, phenylthio, 2-butoxy-5-tert-octylfetylthio, 2,5-dioctyloxyphenylthio, 2- (2-ethoxyethoxy) -5-tert-octylphenylthio, 2-pivaloylamino. Phenylthio, tetrazolylthio), imide groups (eg succinimide, hydantoinyl, 2,4
-Dioxooxazolidin-3-yl, 3-benzyl-
4-ethoxyhydantoin-1-yl), 5-membered or 6-membered nitrogen-containing heterocyclic group (for example, 1-pyrazolyl, 1-
Benzotriazole, 5-chloro-1,2,4-triazol-1-yl, 1,2-dihydro-2-oxo-1
-Pyridyl) and the like. In addition to these, L may take the form of a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom. Further, L may contain a photographically useful group such as a development inhibitor or a development accelerator. Preferably, L is a hydrogen atom, an alkyl, aryl or heterocyclic thio group, or a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom.

Specific examples of magenta couplers represented by formulas (M) and (N) are shown below, but the compounds are not limited thereto.

[0034]

[Chemical 6]

[0035]

[Chemical 7]

[0036]

[Chemical 8]

[0037]

[Chemical 9]

[0038]

[Chemical 10]

[0039]

[Chemical 11]

[0040]

[Chemical 12]

[0041]

[Chemical 13]

[0042]

[Chemical 14]

[0043]

[Chemical 15]

[0044]

[Chemical 16]

[0045]

[Chemical 17]

[0046]

[Chemical 18]

[0047]

[Chemical 19]

[0048]

[Chemical 20]

[0049]

[Chemical 21]

The magenta couplers represented by the formulas (M) and (N) can be synthesized by known methods described in, for example, JP-A-49-111631 and US Pat. No. 3,615,506. (Synthesis example) According to the following formula, the exemplary compound of the present invention (M-1
0) was synthesized.

[0051]

[Chemical formula 22]

(Synthesis of Compound (b)) Compound (a) 20
1 g (7.30 × 10 ⁻¹ mol) of 1,3-dimethyl-
2-Imidazolidone (1 liter) was added, and 84.1 g (1.68 mol) of hydrazine monohydrate was added over 1 hour while stirring with ice cooling.
) Was added dropwise. After stirring for 2 hours as it was, the reaction system was poured into 10 liters of water, filtered, and the residue was washed with acetonitrile to obtain 180 g of compound (b) (yield 91%). (Synthesis of Compound (d)) 155 g (5.7) of Compound (b)
1.9 liters of DMI was added to 2 × 10 ⁻¹ mol), 109 g (5.72 × 10 ⁻¹ mol) of compound (c) was added with stirring at room temperature, and the stirring was continued for 10 hours. When 3 liters of ethyl acetate was added to the reaction system and washed with water, the compound (d) was precipitated as crystals. Therefore, it was filtered. Distilled off. Methanol was added to the obtained crystals of the compound (d), the mixture was filtered, and 153 g (yield 64.8%) of the compound (d) was obtained by combining with the previously obtained fraction. (Synthesis of Compound (e)) 153 g (3.7) of Compound (d)
Ethanol (1.5 liters) was added to 0 × 10 ^-1 mol) and 28% sodium methylate 74.4 ml (3.
70 × 10 ⁻¹ mol) was added dropwise over 1 hour and 30 minutes, and stirring was continued for 6 hours. Next, add 22 ml of acetic acid to the reaction system.
After the addition of the above, the reaction system was poured into 1.5 liters of water, and the obtained crystals were filtered to obtain 84.8 g of compound (e) (yield: 62).
%) Was obtained. (Synthesis of Compound (g)) 43.9 g (1.
To 20 × 10 ⁻¹ mol), 44 ml of m-cresol, 24.8 g of compound (f) (1.43 × 10 ⁻¹ mol) and 2.33 ml of methanesulfonic acid (3.59 × 10 ⁻¹ mol) were added, and 1
The mixture was heated and stirred at 50 ° C. under a nitrogen atmosphere for 5 hours. Thereafter, methanol was added to the reaction system and the mixture was allowed to cool to room temperature, and the obtained crystals were filtered to give 19.3 g of compound (g) (yield 35
%) Was obtained. (Synthesis of Compound (h)) 21.8 g of reduced iron (3.91 ×)
2.09 g (3.91 of ammonium chloride) per 10 ^-1 mol)
X10 ^-2 mol), acetic acid 2.24 ml (3.91 x 10 ^-2 mo)
l) and 56 ml of water were added, and the mixture was heated under reflux with stirring for 15 minutes, 280 ml of isopropanol was added, and the mixture was further heated under reflux with stirring for 1 hour 45 minutes. Compound (g) 19.3g (3.
91 × 10 ^-2 mol) was added, and the mixture was heated under reflux with stirring for 2 hours, 100 ml of tetrahydrofuran was added, and the mixture was further heated under reflux with stirring for 1 hour. After that, the reaction solution was filtered using Celite as a filter aid, the solvent was distilled off from the filtrate under reduced pressure, ethyl acetate was added to the residue, and the mixture was washed with saturated brine, dried with sodium sulfate, and ethyl acetate was distilled off under reduced pressure. And compound (h) 9.10g
(Yield 49%) was obtained. (Synthesis of Exemplified Compound (M-10)) Compound (h) 9.1
0 g (1.96 × 10 ^-2 mol) of ethyl acetate 91 ml,
18.2 ml of N, N-dimethylacetamide was added, and the mixture was slowly stirred with stirring at room temperature to give myristyl chloride 5.3.
4 ml (1.96 × 10 ^-2 mol) followed by pyridine 1.5
9 ml (1.96 × 10 ^-2 mol) was added dropwise and stirring was continued for 3 hours. Next, 20 ml of ammonia water was added, and the mixture was stirred as it was for 1 hour, then 200 ml of ethyl acetate was added, and water,
The extract was washed with saturated saline and dried over sodium sulfate, and then ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography, and recrystallized from ethanol to obtain 4.3 g (yield 33%) of Exemplified compound (M1-10). The physical property values are shown below. Melting point: 155-157 ° C. ¹ H-NMR (DMSO-d ₆ ): δ = 0.86 (t,
3H), 1.1 to 1.4 (m, 20H), 1.4 to 1.
6 (m, 2H), 2.20 (t, 2H), 3.96
(S, 2H), 7.2-7.4 (m, 2H), 8.13
(D, 2H), 8.87 (s, 1H), 9.85 (s,
1H).

Exemplified compounds M-14 and M-37 were synthesized by the same synthetic method as for Exemplified compound M-10. The physical property values are shown below. Exemplified compound M-14 Melting point: 192-194 ° C. (recrystallized from ethanol) ¹ H-NMR (DMSO-d ₆ ): δ = 0.86 (t,
3H), 1.1 to 1.4 (m, 22H), 1.5 to 1.
7 (m, 2H), 2.27 (t, 2H), 3.90
(S, 2H), 7.0-7.2 (m, 2H), 7.33
(Dt, 1H), 7.64 (s, 1H), 9.66
(S, 1H), 9.80 (s, 1H). Exemplified compound M-37 Melting point: 210-213 ° C. (recrystallized from ethanol) ¹ H-NMR (DMSO-d ₆ ): δ = 0.85 (t,
3H), 1.1 to 1.4 (m, 20H), 1.5 to 1.
6 (m, 2H), 2.27 (t, 2H), 3.86
(S, 2H), 7.21 (dd, 1H), 7.82
(D, 1H), 7.96 (s, 1H), 8.58 (d,
1H), 8.79 (s, 1H), 9.91 (s, 1
H).

The addition layer of the magenta coupler represented by the formulas (M) and (N) can be added to the non-photosensitive intermediate layer adjacent to the green-sensitive layer in addition to the green-sensitive layer.

As the magenta coupler of the present invention, it is more preferable to use one represented by the formula (M).

Of course, the couplers of the formulas (M) and (N) can be used alone, but in these, Y in the formulas (Ma), (Mb) and (Mc) is a halogen atom. In specific couplers, the following formula (M
It is preferably used by mixing with a magenta coupler represented by d). Formula (Md)

[0057]

[Chemical formula 23]

In the formula, R ₁ , X ₁ and X ₂ have the same meanings as described above. X ₃ , X ₄ , and X ₅ have a sum of Hammett's substituent constant σ values of less than 1.1, preferably 0.5.
Represents a substituent necessary to be less than 0.3, more preferably less than 0.3.

R ₁ , X ₁ and X ₂ have the same meanings as described above including their preference, but it is particularly preferable that Y is a chlorine atom or a fluorine atom when mixed with the coupler of the present invention. It is more preferably a chlorine atom. L has the same meaning as L in the formula (N).

Specific examples of the magenta coupler represented by the formula (Md) are shown below, but the magenta coupler is not limited to these examples.

[0061]

[Chemical formula 24]

[0062]

[Chemical 25]

[0063]

[Chemical formula 26]

The couplers represented by the formulas (M) and (N) of the present invention may be used not only in the highest sensitivity layer of the green-sensitive layers but also in other lower emulsion layers. It can also be used for all of the layers. Formula (M) and amount of the coupler represented by (N) are all photosensitive material 1 m ² per 0.01Mmol～1mmol, preferably 0.
A range of 1 mmol to 0.5 mmol is common. The couplers represented by formulas (M) and (N) of the present invention may be used as a mixture of two or more kinds, or may be used in combination with other known couplers. The couplers represented by the formulas (M) and (N) of the present invention are the total amount of couplers in the same layer.
It is preferably 20 mol% or more, and more preferably 35 mol% or more. Next, the silver halide emulsion having silver halide protrusions on the surface of the silver halide base grains used in the present invention will be described. The above emulsion can be prepared according to the methods described in JP-A-63-244030, JP-A-63-264739 and EP0498302. That is, it can be prepared by forming base particles and chemically sensitizing them to form protrusions.

The silver halide protrusions can be formed at a high potential of +110 mV or higher. The projections have a projected area diameter of 0.15 μm or less and can store 10 to 10000 projections / μm ² . Here, the projected area diameter is represented by the diameter of a circle having the same area as the projected area of the projection from above. The halogen compositions of the base and the protrusions may be different,
The protrusions have higher solubility in the developer than the base silver halide. The combination of the mother / protrusion halogen composition is
Bromide / chloride or bromide / chlorobromide or chlorobromide / chloride or chloroiodide / chloride or chloroiodide / chlorobromide or bromoiodide / chloride or bromoiodide / bromide or bromoiodide / chloroiodo It may also be iodide or iodide / chloride or iodide / bromide or iodide / chlorobromide or iodide / chloroiodide or iodide / bromoiodide or iodide / chlorobromoiodide. The shape of the matrix may be an octahedron, a tetradecahedron, a cube, or a flat plate.

When the matrix contains iodide, it may be uniformly distributed at 18 mol% or less. At least 25% by weight of the total silver halide emulsion of the emulsion of the present invention preferably has at least 0.1% of the surface area of the base material covered with protrusions.

The outline of emulsion preparation is as follows. First, the base particles can be prepared by a method such as an acidic method, a neutral method, an ammonia method, etc., and a method of reacting a soluble silver salt with a soluble halogen salt can be selected from a one-sided mixing method, a simultaneous mixing method, a combination thereof and the like. .

As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is, a control double jet method can be used. A triple jet method (for example, a soluble silver salt, a soluble bromine salt and a soluble iodine salt) in which soluble halogen salts having different compositions are independently added can be used as another form of the simultaneous mixing method. Ammonia when preparing the base particles,
A silver halide solvent such as a rhodan salt, thiourea, thioether, or amine may be selected and used. The halogen composition of the base particles is preferably uniform. Whether the halogen composition of individual grains is uniform depends on the method of X-ray diffraction and EP.
It can be determined by the MA method. When the halogen composition of the base particles is more uniform, the diffraction width of X-ray diffraction is narrowed to give a sharp peak.

The size distribution of the base particles may be narrow or wide, but one preferable base particle is a monodisperse emulsion having a narrow size distribution (variation coefficient of 20% or less). The size of the base particles is preferably such that the average projected area diameter is 0.5 μm or more. 0.
It is more preferable to use particles of 7 μm or more, especially 1.0 μm or more. The (111) plane of the host particle is 50% of the total particle surface.
The above particles are preferable. More preferably 75% or more
It is a grain of the (111) plane. The shape of the base grains is preferably tabular grains having a high ratio of projected area diameter to grain thickness (aspect ratio) (for example, an aspect ratio of 5 to 20), but tetrahedral grains, octahedral grains and irregularly shaped twin grains (111 ) If the surface is 50% or more, it can be used as a mother particle.

The tabular grains as the mother grains are described in Gutoff, Photographic Science and Enginee.
ring), Vol. 14, pp. 248-257 (1970); U.S. Pat. Nos. 4,434,226 and 4,414,310.
No. 4,433,048, No. 4,439,520 and British Patent No. 2,112,157, JP-A-58-
It can be easily prepared by the method described in No. 127921. Also, tetrahedrons, octahedrons or irregularly shaped twinned grains are described in "The Logic of Photographic Process", 4th edition, by THM James (THJames "The The
ory of the Photographic Process 4th ed. Macmillan)
It can be easily prepared by referring to the description in Chapter 3 (pp. 88 to 104).

The surface ratio of the (111) plane in the base particles can be determined by the Kubelka-Munk dye adsorption method. For example, this method is described in Journal of Imaging Science 29,165-171 (1985).
As shown in Fig. 1, the (111) face or (100) face is adsorbed preferentially, and the association state of the dye on the (111) face and the association state of the dye on the (100) face are spectroscopically determined. The (111) plane ratio can be determined by selecting spectrally different dyes, adding such dyes to the emulsion, and examining the spectral spectrum with respect to the amount of dye added in detail. In the present invention, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt may be present together in the process of forming the base particles or physically aging. The water washing step for desalting may be carried out at any stage, but it is preferably carried out before forming the protrusions, that is, after forming the base particles or after chemical sensitization.

The base particles of the present invention are chemically sensitized before forming protrusions. Chemical sensitization by James (TH James)
Written by The Theory of Photographic Process, 4th Edition, published by Macmillan, 1977 (TH James,
The Theory of the Photogtaphic Process, 4th ed, M
acmillan, 1977) using active gelatin as described on pages 67-76, and Research Disclosure, Vol. 120, April 1974, 1200.
8; Research Disclosure, Volume 34, 1975
June, 13452, U.S. Pat. No. 2,642,361
No. 3,297,446, No. 3,772,031
Issue No. 3,857,711 Issue No. 3,901,714
No. 4,266,018, and 3,904,4.
15, and pAg 5-10, pH 5-8 and temperature 3 as described in GB 1,315,755.
Sulfur, selenium, tellurium, gold, platinum at 0-80 ° C,
It can be carried out using palladium, iridium or a combination of plural sensitizers. The optimum chemical sensitization is
Sulfur-containing compounds or hypo- or thiourea compounds described in U.S. Pat. Nos. 3,857,711, 4,266,018 and 4,054,457 in the presence of a gold compound and a thiocyanate compound. , A rhodanine-based compound or the like in the presence of a sulfur-containing compound. It is also possible to carry out chemical sensitization in the presence of a chemical sensitization aid. As the chemical sensitization aid used, compounds such as azaindene, azapyridazine, and azapyrimidine which are known to suppress fog and increase sensitivity in the process of chemical sensitization are used. Examples of chemical sensitization aid modifiers are described in US Pat.
1,038, 3,411,914, 3,55
No. 4,757, JP-A-58-126526 and the above-mentioned Duffin "Photographic Emulsion Chemistry", pages 138-143. In addition to, or as an alternative to chemical sensitization, US Pat. Nos. 3,891,446 and 3,984,24
It can be reduction sensitized with, for example, hydrogen as described in US Pat. No. 2,518,698.
No. 2,743,182 and No. 2,743,18
As described in No. 3, using reducing agents such as stannous chloride, thiourea dioxide, polyamines, and low pAg.
Reduction sensitization can be achieved by (eg less than 5) and / or high pH (eg greater than 8) treatment. U.S. Pat. Nos. 3,917,485 and 3,966,47.
The chemical sensitization method described in No. 6 can also improve the color sensitization.

Further, JP-A-61-3134 and 61-3
The sensitizing method using an oxidizing agent described in JP-A No. 136 can also be applied.

The projections are preferably prepared by adding a water-soluble silver salt and a water-soluble halogen salt corresponding to the projection composition. The addition rate of water-soluble silver at this time is preferably as high as possible within the range where re-nucleation is not generated. The silver potential is at least +110 mV or more, preferably +12, although it depends on the halogen composition of the protrusion and / or the temperature and / or the additives coexisting during the preparation.
It is necessary to prepare at a high silver potential of 0 mV or higher, more preferably +130 mV or higher. Further, the temperature during the preparation of the protrusions is preferably lower, but it is 80 ° C. or lower, preferably 70 ° C. or lower, and more preferably 65 ° C. or lower, although it depends on other conditions during the preparation.

The presence of an additive serving as a silver halide solvent during the preparation of the protrusions is not preferable, but the additives may be used within a range in which the base grains and the protrusions are not mixed with each other more than necessary.

The structure of the silver halide grain of the present invention comprises a chemically sensitized base grain portion and a protrusion portion. When the present invention is used as a method for producing a negative emulsion, preferred forms of the sensitized nuclei and the protrusions on the base grains formed by chemical sensitization are as follows.

One is a form in which the position where a sensitized nucleus is formed as a result of chemical sensitization on the base grain and the position where a protrusion is formed are different. Yet another is a form in which the sensitized nuclei on the grain matrix are covered with protrusions that are easily dissolved during development.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. Although aminophenol compounds are also useful as the color developing agent, p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-.
N, N-diethylanilide, 3-methyl-4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-
Examples thereof include N-ethyl-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, especially 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline sulfate is preferred. Two or more of these compounds can be used in combination depending on the purpose. The color developer is a developing agent such as a pH buffering agent such as an alkali metal carbonate, borate or phosphate, chloride salt, bromide salt, iodide salt, benzimidazole, benzothiazole or mercapto compound. It is common to include an inhibitor or an antifoggant. If necessary, hydroxylamine, diethylhydroxylamine, sulfite, N, N-
Hydrazines such as biscarboxymethylhydrazine,
Various preservatives such as phenylsemicarbazides, triethanolamine, catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dyes Forming couplers, competing couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, aminopolysulfonic acids, alkylphosphonic acids,
Various chelating agents represented by phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitriloacetic acid,
Diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,
N, N-trimethylphosphonic acid, ethylenediamine-
Representative examples are N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

The color developer of the present invention has a pH of 11.0 to 1.
3.0 is preferable and 11.5 to 12.5 is more preferable.

The light-sensitive material of the present invention may have at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive silver halide emulsion layer provided on a support. There is no particular limitation on the number and order of layers of the silver halide emulsion layer and the non-photosensitive layer, but it is preferable that the green-sensitive layer be two layers.
It is more preferable that the number of layers is three. A typical example is
A silver halide photographic light-sensitive material having at least one light-sensitive layer composed of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. Is a unit photosensitive layer having color sensitivity to any of blue light, green light, and red light.In a multilayer silver halide color photographic light-sensitive material, the unit photosensitive layers are generally arranged in order from the support side. The red-sensitive layer, the green-sensitive layer and the blue-sensitive layer are installed in this order. However, the order of installation may be reversed depending on the purpose, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layers. Non-photosensitive layers such as various intermediate layers may be provided between the above-described silver halide photosensitive layers and as the uppermost layer and the lowermost layer. The intermediate layer includes JP-A Nos. 61-43748, 59-113438, 59-113440 and 59-113440.
The couplers and DIR compounds as described in JP-A-61-20037 and JP-A-61-20038 may be contained, and a color mixing inhibitor may be contained as is commonly used. The plural silver halide emulsion layers constituting each unit light-sensitive layer are preferably composed of two layers of high-sensitivity emulsion layer and low-sensitivity emulsion layer as described in West German Patent No. 1,121,470 or British Patent No. 923,045. be able to. Usually, it is preferable to arrange so that the photosensitivity becomes lower toward the support,
A non-photosensitive layer may be provided between each halogen emulsion layer. In addition, JP-A-57-112751, 62-200350
No. 62-206541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side farther from the support, and a high-sensitivity emulsion layer may be provided on the side closer to the support.

As a specific example, from the side farthest from the support,
Low sensitivity blue photosensitive layer (BL) / High sensitivity blue photosensitive layer (BH) / High sensitivity green photosensitive layer (GH) / Low sensitivity green photosensitive layer (GL) / High sensitivity red photosensitive layer (RH) / Low sensitivity red photosensitive layer (RL) order, or BH / BL / GL / GH / RH / RL order, or BH / BL / GH /
It can be installed in the order of GL / RL / RH. In addition,
As described in JP-A-55-34932, the blue-sensitive layer / GH / RH / GL / RL may be arranged in this order from the side farthest from the support. In addition, JP-A-56-25738 and 62-63
As described in Japanese Patent No. 936, the blue-sensitive layer / GL / RL / GH / RH may be arranged in this order 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 more sensitive than the middle layer. An example is an arrangement in which a silver halide emulsion layer having a low degree of sensitivity is arranged, and the layer is composed of three layers having different sensitivities in which the sensitivities are gradually lowered toward the support. Even when it is composed of three layers having different sensitivities, as described in JP-A-59-202464, a medium-sensitivity emulsion from the side remote from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers may be arranged in this order. In addition, they may be arranged in the order of high-speed emulsion layer / low-speed emulsion layer / medium-speed emulsion layer, or low-speed emulsion layer / medium-speed emulsion layer / high-speed emulsion layer. Also, 4
In the case of more than one layer, the arrangement may be changed as described above.

In order to improve color reproducibility, US Pat.
No. 663,271, No. 4,705,744, No. 4,707,436, and JP-A Nos. 62-160448 and 63-89850.
It is preferable to arrange a donor layer (CL) having a multilayer effect, which has a spectral sensitivity distribution different from that of the main photosensitive layer such as BL, GL, or RL, adjacent to or in proximity to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each light-sensitive material. The preferable silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention other than the silver halide grains having protrusions of the present invention will be described below. The silver halide grains are silver iodobromide, silver iodochloride, or silver iodochlorobromide containing less than about 30 mol% 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 a photographic emulsion are those having regular crystals such as cubes, octahedra and tetradecahedrons, those having irregular crystal shapes such as spheres and plates, twin planes, etc. It may have a crystal defect of, or a composite form thereof. The grain size of silver halide may be fine grains of about 0.2 micron or less, or large grains having a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion. The silver halide photographic emulsion which can be used in the present invention is, for example, Research Disclosure (RD) No. 17643 (1).
December 978), pages 22-23, "I. Emulsion prep
aration and types) ”, and No. 18716 (November 1979)
Mon), p. 648, ibid. 307105 (Nov. 1989), 863-865.
Page, and "Graphics and Chemistry of Photography" by Graphide, published by Paul Montel (P.Glafkides, Chemie et Phisique Phot
ographique, PaulMontel, 1967), "Photoemulsion Chemistry" by Duffin, published by Focal Press (GF Duffin, Photog
raphic Emulsion Chemistry (Focal Press, 1966)), "Production and Coating of Photographic Emulsions" by Zelikmann et al., published by Focal Press (VL Zelikman et al., Making and Coating).
It can be prepared using the method described in Photographic Emulsion, Focal Press, 1964) and the like. U.S. Patents 3,574,628 and 3,655,394 and British Patent 1,4
Monodisperse emulsions described in No. 13,748 are also preferable.

Further, tabular grains having an aspect ratio of about 3 or more can be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and E.
14: 248-257 (1970); U.S. Pat. Nos. 4,434,226, 4,414,310, 4,433,048,
It can be easily prepared by the method described in U.S. Pat. No. 4,439,520 and British Patent No. 2,112,157. The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure,
Further, silver halides having different compositions may be joined by epitaxial joining, and, for example, silver rhodan,
It may be bonded to a compound other than silver halide such as lead oxide. Also, a mixture of particles having various crystal forms may be used. The above emulsion may be either a surface latent image type which forms a latent image mainly on the surface, an internal latent image type which is formed inside the grain, or a type which has a latent image on both the surface and the inside.
It must be a negative emulsion. Among the internal latent image type emulsions, core / shell type internal latent image type emulsions described in JP-A-63-264740 may be used. The method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on development processing and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm. As the silver halide emulsion, those which are physically ripened, chemically ripened and spectrally sensitized are usually used. Additives used in such processes are Research Disclosure N
No. 17643, No. 18716, and No. 307105, and the relevant parts are summarized in the table below.

The light-sensitive material of the present invention comprises a photosensitive silver halide emulsion having a grain size, a grain size distribution, a halogen composition,
Two or more kinds of emulsions having at least one characteristic of grain shape and sensitivity can be mixed and used in the same layer. U.S. Pat.No. 4,082,553 described above, the surface of which is covered with silver halide grains, U.S. Pat.No. 4,626,498, and JP-A-59-214852. It can be preferably used for a photosensitive silver halide emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. The fogged silver halide grain inside or on the surface is a silver halide grain that enables uniform (non-imagewise) development regardless of the unexposed area and exposed area of the light-sensitive material. . A method for preparing a silver halide grain whose inside or surface is fogged is described in US Pat. No. 4,626,4.
98, JP-A-59-214852. The silver halide forming the inner nucleus of a core / shell type silver halide grain having a fogged grain inside may have the same halogen composition or different halogen compositions. As the silver halide having the inside or surface of the grain fogged,
Any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide can be used. The grain size of these fogged silver halide grains is not particularly limited, but the average grain size is preferably 0.01 to 0.75 μm, particularly preferably 0.05 to 0.6 μm. The particle shape is not particularly limited,
Regular grains may be used, or a polydisperse emulsion may be used.
Monodispersion (wherein at least 95% of the weight or number of silver halide grains has a grain size within ± 40% of the average grain size) is preferred. In the present invention, it is preferable to use non-photosensitive fine grain silver halide. The non-photosensitive fine grain silver halide is a fine grain of silver halide which is not exposed to light during imagewise exposure for obtaining a dye image and is not substantially developed in the development process, and it is preferable that it is 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, if necessary. Preferably silver iodide is 0.5
~ 10 mol% is contained. Fine grain silver halide has an average grain size (average diameter of circles equivalent to the projected area) of 0.01
.About.0.5 .mu.m is preferable, and 0.02 to 0.2 .mu.m is more preferable. The fine grain silver halide can be prepared by a method similar to that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grain does not need to be chemically sensitized nor spectral sensitization. However, prior to adding this to the coating liquid, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, mercapto-based compound or zinc compound in advance. Colloidal silver can be preferably contained in this fine grain silver halide grain-containing layer. Coated silver amount of the light-sensitive material of the present invention is preferably 6.0 g / m ² or less, 4.5 g / m ² or less is most preferred. Known photographic additives that can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table.

Types of Additives RD17643 RD18716 RD307105 1. Chemical sensitizer, page 23, page 648, right column, page 866 2. Sensitivity enhancer, page 648, right column 3. Spectral sensitizer, pages 23-24, page 648, right column 866- Page 868 Supersensitizer to page 649 Right column 4. Brightener page 24 647 page to the right column 868 page 5. Fogging prevention page 24 to 25 page 649 to the right column 868 to 870 agent, stabilizer 6. Light absorber , Pages 25 to 26, page 649, right column, page 873, filter, page 650, left column, dyes, ultraviolet absorbers, stain 7. stain, page 25, right column, page 650, left column, page 872, inhibitor, right column 8. dye image, page 25, page 650, left Column Page 872 Stabilizer 9. Hardener 26 Page 651 Left column 874-875 10. Binder 26 Page 651 Left column 873-874 11. Plasticizer, Page 27 650 Right column 876 Lubricant 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876, surface active agent, 13. Static, page 27, page 650, right column, pages 876 to 877, inhibitor 14. matting agent, pages 878 to 879

The light-sensitive material of the present invention can be incorporated into US Pat. No. 4,740,4
54, No. 4,788,132, JP-A-62-18539, JP-A-1-
It is preferable to contain the mercapto compound described in No. 283551. A compound which, in the light-sensitive material of the present invention, releases a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof as described in JP-A 1-106052, irrespective of the amount of developed silver produced by development processing. Is preferably contained. In the light-sensitive material of the present invention, a dye dispersed by the method described in International Publication WO88 / 04794 or JP-A-1-502912 or
EP 317,308A, U.S. Pat.No. 4,420,555, JP 1-2593
It is preferable to include the dye described in No. 58. Various color couplers can be used in the light-sensitive material of the present invention. Specific examples thereof include Research Disclosure Nos. 17643, VII-CG, and No. 307105, VII.
-C-G. Examples of yellow couplers include U.S. Pat.Nos. 3,933,501, 4,022,620, 4,326,024, and 4,401,752.
No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent Nos. 1,425,020, No. 1,476,760, and U.S. Patent No. 3,97.
Those described in 3,968, 4,314,023, 4,511,649, European Patent 249,473A and the like are preferable.

As the magenta coupler which can be used in combination with the magenta coupler of the present invention, 5-pyrazolone type and pyrazoloazole type compounds are preferable, and US Pat. No. 4,310,619 is preferred.
No. 4,351,897, European Patent No. 73,636, US Patent No. 3,061,432, No. 3,725,067, Research Disclosure No. 24220 (June 1984), Japanese Patent Laid-Open No. 60-335.
52, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, 61-72238, 60-35730.
No. 55-118034, No. 60-185951, U.S. Pat.
Those described in 0,630, 4,540,654, 4,556,630, WO 88/04795 and the like are particularly preferable. Examples of cyan couplers include phenol-based and naphthol-based couplers, and U.S. Pat. Nos. 4,052,212 and 4,1
No. 46,396, No. 4,228,233, No. 4,296,200, No. 4
2,369,929, 2,801,171, 2,772,162,
No. 2,895,826, No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121,365A, No. 249,
453A, U.S. Pat.Nos. 3,446,622, 4,333,999,
No. 4,775,616, No. 4,451,559, No. 4,427,767
No. 4,690,889, 4,254,212, 4,29
Those described in 6,199, JP-A 61-42658 and the like are preferable. Furthermore, JP-A-64-553, JP-A-64-554, and JP-A-64-555
No., a pyrazoloazole coupler described in the same 64-556,
The imidazole couplers described in U.S. Pat. No. 4,818,672 can also be used. Typical examples of polymerized dye-forming couplers are disclosed in U.S. Pat.
4,080,211, 4,367,282, 4,409,320,
No. 4,576,910, British Patent 2,102,137, European Patent No.
No. 341,188A, etc. Examples of couplers in which the color forming dye has an appropriate diffusibility include U.S. Pat.
No., British Patent No. 2,125,570, European Patent No. 96,570,
Those described in West German Patent (Publication) No. 3,234,533 are preferable.

Compounds releasing a photographically useful residue upon coupling are also preferably used in the present invention.
DIR couplers that release development inhibitors are described in RD 176 above.
43, VII-F and No. 307105, and patents described in VII-F, JP-A-57-151944, 57-154234, and 60-
184248, 63-37346, 63-37350, U.S. Pat.
Those described in 48,962 and 4,782,012 are preferable. The bleaching accelerator releasing couplers described in RD No. 11449, 24241, JP-A-61-201247 and the like are effective for shortening the time of the processing step having a bleaching ability, and in particular, the tabular halogenated compound described above. The effect is great when it is added to a light-sensitive material using silver particles. Examples of couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Nos. 2,097,140 and 2,131,188, and JP-A-59-157638.
Nos. 59 and 170840 are preferable. Further, JP-A-60-107029, JP-A-60-252340 and JP-A-1-44940.
Also preferred are compounds capable of releasing a fogging agent, a development accelerator, a silver halide solvent and the like by a redox reaction with an oxidized product of a developing agent described in JP-A No. 1-45687.

Other compounds that can be used in the light-sensitive material of the present invention include competitive couplers described in US Pat. No. 4,130,427 and US Pat. Nos. 4,283,472 and 4,3.
38,393, 4,310,618 and the like, multi-equivalent couplers, DIR redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds described in JP-A-60-185950 and JP-A-62-24252. Alternatively, DIR redox-releasing redox compounds, couplers that release dyes that undergo color restoration after withdrawal described in European Patents 173,302A and 313,308A, ligand-releasing couplers described in U.S. Pat. -75747 couplers releasing leuco dyes, U.S. Pat.
Examples thereof include couplers that release the fluorescent dye described in No. 181.

The coupler used in the present invention can be introduced into the photographic material by various known dispersion methods. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Specific examples of the high-boiling-point organic solvent having a boiling point of 175 ° C. or higher at atmospheric pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis phthalate. (2,4-di-t-amylphenyl) phthalate, bis (2,4-di-t-amylphenyl)
Isophthalate, bis (1,1-diethylpropyl) phthalate, etc.), phosphoric acid or phosphonic acid esters (triphenyl phosphate, tricresyl phosphate,
2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di
-2-Ethylhexyl phenylphosphonate, etc., Benzoic acid esters (2-ethylhexyl benzoate, dodecyl benzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), Amides (N, N-diethyldodecane amide, N, N-diethyllauryl) Amides, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) sebacate, dioctylazese) Rate, glycerol tributyrate, isostearyl lactate,
Trioctyl citrate, etc., aniline derivatives (N, N-
Dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.) and the like. The auxiliary solvent has a boiling point of about 30 ° C or higher, preferably 50 ° C.
Organic solvents above 160 ° C can be used. Typical examples are ethyl acetate, butyl acetate, ethyl propionate,
Methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide and the like can be mentioned. The steps and effects of the latex dispersion method and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363, West German Patent Application (OLS) Nos. 2,541,274 and 2,541,230.

In the color light-sensitive material of the present invention, phenethyl alcohol, JP-A-63-257747 and JP-A-62-272248,
And 1,2-benzisothiazolin-3-one described in JP-A-1-80941, n-butyl p-hydroxybenzoate,
It is preferable to add various preservatives or antifungal agents such as phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol, and 2- (4-thiazolyl) benzimidazole. Suitable supports that can be used in the present invention are described, for example, in RD. No. 17643, page 28, No. 18716, page 647, right column to page 648, left column, and No. 307105, page 879. In the light-sensitive material of the present invention, the total thickness of all hydrophilic colloid layers on the emulsion layer side is preferably 28 μm or less, more preferably 23 μm or less, further preferably 18 μm or less, and particularly preferably 16 μm or less. The film swelling speed T _1/2 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness is 25 ° C and 55% relative humidity (2 days)
The film swelling speed T _1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering by A. Green et al.
(Photogr.Sci.Eng.), Vol. 19, No. 2, p. 124-129. A swellometer of the type described can be used for the measurement, and T _1/2 is 30 in a color developer. The saturated film thickness is defined as 90% of the maximum swollen film thickness reached when the film is treated at ℃ for 3 minutes and 15 seconds, and is defined as the time required to reach 1/2 of the saturated film thickness.
The film swelling speed T _1/2 can be adjusted by adding a film hardening agent to gelatin as a binder or changing aging conditions after coating. The swelling rate is 1
50 to 400% is preferable. The swelling rate is calculated from the maximum swollen film thickness under the conditions described above by the formula: (maximum swollen film thickness-film thickness)
/ Can be calculated according to the film thickness. The light-sensitive material of the present invention has a total dry film thickness of 2 μm to 20 on the side opposite to the side having the emulsion layer.
It is preferable to provide a hydrophilic colloid layer (referred to as a back layer) having a thickness of μm. This back layer preferably contains the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, surface active agent and the like. The swelling ratio of this back layer is preferably 150 to 500%.

The color developing solution used for the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N diethylaniline and 3-methyl. -4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl -β-methoxyethylaniline, 4-amino-3-methyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N-
(3-Hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (2-hydroxypropyl) aniline, 4-
Amino-3-ethyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-propyl-N- (3-
Hydroxypropyl) aniline, 4-amino-3-propyl
-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-methyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-ethyl-N -(4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl
-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl-N, N-bis (4-hydroxybutyl) aniline, 4-amino-3-methyl-N, N-bis (5-
Hydroxypentyl) aniline, 4-amino-3-methyl-N
-(5-hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethoxy-N, Examples thereof include N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, especially 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl)
Aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline and their hydrochlorides, p-toluenesulphonates or sulphates are preferred. Two or more of these compounds can be used in combination depending on the purpose. The color developing solution is a developing agent such as a pH buffering agent such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, benzimidazoles, benzothiazoles or a mercapto compound. It is common to include an inhibitor or an antifoggant. Also, if necessary,
Hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catechol sulfonic acids,
Organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, 1-phenyl-3-
Auxiliary developing agents such as pyrazolidone, viscosity imparting agents, aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, various chelating agents represented by phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, Diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-
Hydroxyethylidene-1,1-diphosphonic acid, nitrilo-
N, N, N-trimethylenephosphonic acid, ethylenediamine-N,
N, N, N- tetramethylenephosphonic acid, ethylenediamine-
Di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples.

Processing solutions and processing steps for the color reversal light-sensitive material of the present invention other than the color developing solution will be described below. Among the processing steps of the color reversal light-sensitive material of the present invention, the steps from black development to color development are as follows. 1) Black-white development-water washing-reversal-color development 2) Black-white development-water washing-light reversal-color development 3) Black-white development-water washing-color development Steps 1) to 3) are all performed in US Pat.
In place of the rinse process described in No. 04,616, it is possible to simplify the process and reduce waste liquid. Next, the steps after color development will be described. 4) Color development-adjustment-bleaching-fixing-washing-stable 5) Color development-washing-bleaching-fixing-washing-stable 6) Color development-adjusting-bleaching-washing-fixing-washing-stable 7) Color development-washing -Bleaching-washing-fixing-washing-stable 8) color development-bleaching-fixing-washing-stable 9) color development-bleaching-bleach-fixing-washing-stable 10) color development-bleaching-bleach-fixing-washing-stable 11) Color development-bleaching-washing-fixing-washing-stable 12) Color development-adjusting-bleaching fixing-washing-stable 13) Color development-washing-bleaching fixing-washing-stable 14) Color development-bleaching fixing-washing- Stable 15) Color development-fixing-bleach-fixing-washing-stable 4) to 15), the washing step immediately before the stabilizing step may be eliminated, or conversely the final stabilizing step is not performed. May be. Any one of the above steps 1) to 3) and any one of steps 4) to 15) are connected to form a color reversal step.

Next, the processing liquid in the color reversal processing step of the present invention will be described. Known developing agents can be used in the black and white developing solution used in the present invention. Examples of developing agents include dihydroxybenzenes (for example, hydroquinone) and 3-pyrazolidones (for example, 1-phenyl-).
3-pyrazolidone), aminophenols (eg N
-Methyl-p-aminophenol), 1-phenyl-3
-Pyrazolines, ascorbic acid and US Pat.
The heterocyclic compounds such as 1,2,3,4-tetrahydroquinoline ring and indrene ring described in No. 67,872 can be used alone or in combination. In the black and white developer used in the present invention, other preservatives (eg, sulfite, bisulfite, etc.), buffers (eg, carbonate, boric acid, borate, alkanolamine), alkaline agents (eg, Hydroxides, carbonates), dissolving tablets (eg polyethylene glycols, their esters), pH adjusters (eg organic acids such as acetic acid),
A sensitizer (for example, a quaternary ammonium salt), a development accelerator,
A surfactant, a defoaming agent, a film hardening agent, a viscosity imparting agent, etc. can be contained. The black-and-white developing solution used in the present invention needs to contain a compound acting as a silver halide solvent, and a sulfite salt added as the above preservative usually serves its function. Specific examples of the sulfite and other silver halide solvents that can be used include KSCN and NaSC.
N, K ₂ SO ₃ , Na ₂ SO ₃ , K ₂ S ₂ O ₅ , Na ₂ S ₂ O
₅ , K ₂ S ₂ O ₃ , Na ₂ S ₂ O _{3 and the} like can be mentioned. The pH value of the developer thus adjusted is selected to an extent sufficient to provide the desired density and contrast, but is in the range of about 8.5 to about 11.5. In order to perform a sensitizing process using such a black-and-white developing solution, it is usually necessary to extend the time up to about 3 times that of the standard process. At this time, if the processing temperature is raised, the extension time for the sensitization processing can be shortened.

The pH of these black and white developers is generally 9-12. The replenishing amount of the color developing solution and the black and white developing solution of the present invention depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per 1 m 2 of the light-sensitive material, and the bromide ion concentration in the replenishing solution can be reduced. It is possible to make it less than 500 ml by setting it. When the replenishment amount is reduced, it is preferable to prevent the liquid evaporation and air oxidation by reducing the contact area of the treatment tank with the air. The contact area between the photographic processing liquid and air in the processing tank is
It can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between treatment liquid and air (cm ² )] ÷ [volume of treatment liquid (cm ³ )] The above aperture ratio is preferably 0.1 or less, and more preferably 0.001 to 0.05. Is. As a method of reducing the aperture ratio in this way, in addition to providing a cover such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033 is disclosed. The slit development processing method described in 63-216050 can be mentioned. Reducing the aperture ratio is not limited to both the color development and black and white development steps, but also the subsequent steps such as bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing with water, and stabilization. Further, the amount of replenishment can be reduced by using a means for suppressing the accumulation of bromide ions in the developing solution. The reversal bath used after black and white development may contain a known fogging agent. That is, stannous ion-organic phosphoric acid complex salt (US Pat. No. 3,617,282), stannous ion organic phosphonocarboxylic acid complex salt (Japanese Patent Publication No. 56-32616), stannous ion-
Aminopolycarboxylic acid complex salt (US Pat. No. 1,209,0
50), stannous ion complex salts, borohydride compounds (US Pat. No. 2,984,567),
Heterocyclic amine borane compounds (UK Patent No. 1,011,0
No. 00 specification) and the like, and the like. The fogging bath (reversal bath) has a wide pH range from the acidic side to the alkaline side, and has a pH of 2 to 12, preferably 2.5 to 10, and particularly preferably 3 to 9.
A light reversal process by re-exposure may be performed instead of the reversal bath, and the reversal step may be omitted by adding the fogging agent to the color developing solution. The silver halide color photographic light-sensitive material of the present invention is bleached or bleach-fixed after color development. These treatments may be carried out immediately after color development without passing through other treatment steps,
In order to prevent unnecessary post-development, air fogging, and to reduce the amount of color developing solution brought into the desilvering process, and in the sensitizing material such as sensitizing dyes and dyes contained in photographic light-sensitive materials and photographic light-sensitive materials. In order to wash out the impregnated color developing agent and render it harmless, it may be subjected to a bleaching treatment or a bleach-fixing treatment after a processing step such as stopping, adjusting and washing with water after the color developing treatment.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process), or may be performed individually. Further, in order to speed up the processing, a processing method of bleach-fixing processing after bleaching processing may be used. Further, treatment with two continuous bleach-fixing baths, fixing treatment before the bleach-fixing treatment, or bleaching treatment after the bleach-fixing treatment can be optionally carried out according to the purpose. As the bleaching agent, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. As a typical bleaching agent, an organic complex salt of iron (III),
For example, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, and other aminopolycarboxylic acids, or complex salts such as citric acid, tartaric acid, and malic acid. Etc. can be used. Among them, ethylenediaminetetraacetic acid iron (III) complex salt and 1,3-diaminopropanetetraacetic acid iron (III)
II) Complex salts and other aminopolycarboxylic acid iron (III) complex salts are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Further, the aminopolycarboxylic acid iron (III) complex salt is particularly useful in both the bleaching solution and the bleach-fixing solution. The pH of the bleaching solution or the bleach-fixing solution using these aminopolycarboxylic acid iron (III) complex salts is usually 4.0 to 8, but a lower pH can be used for speeding up the processing. Bleach,
If necessary, a bleaching accelerator can be used in the bleach-fixing solution and the prebath thereof. Specific examples of useful bleach accelerators are described in the following specification: US Pat. No. 3,89
3,858, West German Patents 1,290,812, 2,059,988,
JP-A-53-32736, 53-57831, 53-37418, 53
-72623, 53-95630, 53-95631, 53-104232
No. 53, No. 124424, No. 53-141623, No. 53-28426,
Research Disclosure No.17129 (July 1978)
Compounds having a mercapto group or a disulfide group described in JP-A No. 50-140129; JP-B Nos. 45-8506, 52-20832, and 53.
-32735, thiourea derivatives described in U.S. Pat. No. 3,706,561; West German Patent 1,127,715, iodide salts described in JP-A-58-16,235; West German Patents 966,410, 2,748,430.
Compounds described in Japanese Patent Publication No. 45-883
Polyamine compounds described in No. 6; Others JP-A-49-40,943
No. 49-59,644 No. 53-94,927 No. 54-35,727
Nos. 55-26,506 and 58-163,940; bromide ions and the like can be used. Among them, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large accelerating effect, and the compounds described in US Pat. No. 3,893,858, West German Patent 1,290,812 and JP-A-53-95,630 are particularly preferred. Further, the compounds described in US Pat. No. 4,552,834 are also preferable. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color light-sensitive material for photography. In addition to the above compounds, the bleaching solution and the bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pKa) of 2 to 5, and specifically acetic acid, propionic acid, hydroxyacetic acid and the like are preferable.

Examples of the fixing agent used in the fixing solution and the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas and a large amount of iodide salts. Use of thiosulfates Are generally used, and ammonium thiosulfate is most widely used. Further, the combined use of thiosulfate and thiocyanate, thioether compounds, thiourea and the like is also preferable. As a preservative for the fixing solution and the bleach-fixing solution, sulfites, bisulfites, carbonyl bisulfite adducts or sulfinic acid compounds described in EP 294769A are preferable. Further, various aminopolycarboxylic acids and organic phosphonic acids are preferably added to the fixing solution and the bleach-fixing solution for the purpose of stabilizing the solution. The total time of the desilvering process is preferably as short as possible in the range where desilvering failure does not occur. The preferred time is 1 to 3 minutes, more preferably 1 to 2 minutes. The treatment temperature is 25 ° C to 50 ° C, preferably 35 ° C to
45 ° C. In the preferable temperature range, the desilvering rate is improved, and the stain generation after the processing is effectively prevented. In the desilvering process, it is preferable that the stirring is as strong as possible. As a specific method for strengthening stirring, a method of impinging a jet of a processing solution on the emulsion surface of the light-sensitive material described in JP-A-62-183460, or stirring using a rotating means of JP-A-62-183461 Method to increase the effect, further moving the photosensitive material while the emulsion surface is in contact with the wiper blade provided in the solution to further improve the stirring effect by making the emulsion surface turbulent, circulation of the entire processing solution There is a method of increasing the flow rate. Such a stirring improving means is effective in any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate. Further, the above-mentioned stirring improving means is more effective when a bleaching accelerator is used, and it is possible to remarkably increase the accelerating effect and eliminate the fixing inhibiting action of the bleaching accelerator. Automatic developing machines used in the light-sensitive material of the present invention are disclosed in JP-A-60-191257, JP-A-60-191258 and JP-A-60-1912.
It is preferable to have a photosensitive material conveying means described in No. 59. As described in the above-mentioned JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

The silver halide color photographic light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering treatment. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions. It can be set in a wide range.
Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture a
nd Television Engineers, Volume 64, P. 248-253 (May 1955 issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, such a problem is solved as a solution.
The method of reducing calcium ion and magnesium ion described in 62-288,838 can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8,542, chlorine-based bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc., Hiroshi Horiguchi "Chemistry of antifungal agents" (1986) Sankyo Publishing Co., Ltd., Hygiene Engineering Society, "Microbial sterilization, sterilization, and antifungal technology"
(1982) The sterilizing agent described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by Japan Society of Industrial Technology and Antifungal can also be used. The pH of the washing water in the processing of the light-sensitive material of the present invention is 4
It is -9, preferably 5-8. The washing water temperature and washing time can be variously set depending on the characteristics of the photosensitive material, the application, etc.
Generally, 15 seconds to 45 degrees Celsius for 20 seconds to 10 minutes, preferably 25 to 40 degrees Celsius
The range from 30 seconds to 5 minutes is selected with. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, all known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used. Further, there is a case where further stabilizing treatment is carried out after the water washing treatment, and an example thereof is a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath of a color light-sensitive material for photographing. be able to. Examples of dye stabilizers include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts, but it is preferable not to use formalin. Various chelating agents and antifungal agents can also be added to this stabilizing bath. The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor or the like, when each processing solution described above is concentrated by evaporation, it is preferable to add water to correct the concentration.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and accelerating the processing. For incorporation, it is preferable to use various precursors of color developing agents. For example U.S. Pat.
42,597 Indoaniline compounds, 3,342,5
99, Research Disclosure 14,850 and 1
Examples thereof include Schiff base type compounds described in 5,159, aldol compounds described in 13,924, metal salt complexes described in US Pat. No. 3,719,492, and urethane compounds described in JP-A-53-135628. The silver halide color light-sensitive material of the present invention may contain various 1-phenyl-3-pyrazolidones in order to accelerate color development, if necessary.
Typical compounds are JP-A-56-64339, JP-A-57-144547,
And No. 58-115438, etc. The various treatment liquids in the present invention are used at 10 ° C to 50 ° C. Normally, a temperature of 33 ° C to 38 ° C is standard, but a higher temperature accelerates the processing to shorten the processing time, and a lower temperature lowers the image quality to improve the stability of the processing liquid. be able to.

[0101]

EXAMPLES The present invention will now be specifically described with reference to examples, but the invention is not limited thereto.

Example 1 Preparation of Sample 101 Sample 101 was prepared by preparing a multilayer color light-sensitive material having the following compositions on a cellulose triacetate film support having a thickness of 127 μ and having an undercoat. The numbers represent the amount added per m ² . The effect of the added compound is not limited to the described use.

First layer: antihalation layer Black colloidal silver 0.20 g Gelatin 1.9 g UV absorber U-1 0.1 g UV absorber U-3 0.04 g UV absorber U-4 0.1 g High boiling organic solvent Oil-1 0.1 g Microcrystalline solid dispersion of dye E-1 0.1 g

Second layer: intermediate layer Gelatin 0.40 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg Compound Cpd-K 3 mg High boiling organic solvent Oil-3 0.1 g Dye D-4 0.4 mg

Third Layer: Intermediate Layer Finely grained silver iodobromide emulsion on the surface and inside (average grain size 0.06 μm, variation coefficient 18%, AgI content 1 mol%) silver amount 0.05 g gelatin 0.4 g

Fourth Layer: Low Sensitivity Red Sensitive Emulsion Layer Emulsion A Silver amount 0.1 g Emulsion B Silver amount 0.4 g Gelatin 0.8 g Coupler C-1 0.15 g Coupler C-2 0.05 g Coupler C -3 0.05 g Coupler C-9 0.05 g Compound Cpd-C 10 mg High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g

Fifth layer: Medium-speed red-sensitive emulsion layer Emulsion B Silver amount 0.2 g Emulsion C Silver amount 0.3 g Gelatin 0.8 g Coupler C-1 0.2 g Coupler C-2 0.05 g Coupler C-3 0.2 g High boiling point organic solvent Oil-2 0.1 g Additive P-1 0.1 g

Sixth layer: High-sensitivity red-sensitive emulsion layer Emulsion D Silver amount 0.4 g Gelatin 1.1 g Coupler C-1 0.3 g Coupler C-2 0.1 g Coupler C-3 0.7 g Additive P-1 0.1 g

Seventh Layer: Intermediate Layer Gelatin 0.6 g Additive M-1 0.3 g Color mixing inhibitor Cpd-1 2.6 mg UV absorber U-1 0.01 g UV absorber U-2 0. 002 g UV absorber U-5 0.01 g Dye D-1 0.02 g Dye D-5 0.02 g Compound Cpd-C 5 mg Compound Cpd-J 5 mg Compound Cpd-K 5 mg High boiling point organic solvent Oil-1 0.02 g

Eighth layer: intermediate layer Silver iodobromide emulsion with fogged surface and inside (average grain size 0.06 μm, variation coefficient 16%, AgI content 0.3 mol%) silver amount 0.02 g gelatin 1. 0 g additive P-1 0.2 g color mixing inhibitor Cpd-1 0.1 g

Ninth layer: low-sensitivity green-sensitive emulsion layer Emulsion E Silver amount 0.1 g Emulsion F Silver amount 0.2 g Emulsion G Silver amount 0.2 g Gelatin 0.5 Coupler C-7 0.30 g Coupler C -8 0.10 g Compound Cpd-B 0.03 g Compound Cpd-C 10 mg Compound Cpd-D 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-L 0 .05 g High-boiling point organic solvent Oil-1 0.1 g High-boiling point organic solvent Oil-2 0.1 g

Layer 10: Medium-speed green-sensitive emulsion layer Emulsion G Silver amount 0.3 g Emulsion H Silver amount 0.1 g Gelatin 0.6 g Coupler C-7 0.40 g Coupler C-8 0.05 g Compound Cpd -B 0.03g Compound Cpd-D 0.02g Compound Cpd-E 0.02g Compound Cpd-F 0.05g Compound Cpd-G 0.05g Compound Cpd-L 0.05g High boiling point organic solvent Oil-2 0.01g

Eleventh layer: High-sensitivity green-sensitive emulsion layer Emulsion H Silver amount 0.5 g Gelatin 1.0 g Coupler C-7 0.55 g Compound Cpd-B 0.08 g Compound Cpd-C 5 mg Compound Cpd-D 0 0.02 g Compound Cpd-E 0.02 g Compound Cpd-F 0.02 g Compound Cpd-G 0.02 g Compound Cpd-J 5 mg Compound Cpd-K 5 mg Compound Cpd-L 0.05 g High boiling point organic solvent Oil-1 0.02 g High boiling organic solvent Oil-2 0.02 g

Twelfth layer: intermediate layer Gelatin 0.6 g

Thirteenth layer: Yellow filter layer Yellow colloidal silver Silver amount 0.07 g Gelatin 1.1 g Color mixing inhibitor Cpd-A 0.01 g High boiling point organic solvent Oil-1 0.01 g Dye E-2 microcrystalline solid Dispersion 0.05g

Fourteenth layer: Intermediate layer Gelatin 0.6 g

Fifteenth layer: low-sensitivity blue-sensitive emulsion layer Emulsion J Silver amount 0.2 g Emulsion K Silver amount 0.3 g Emulsion L Silver amount 0.1 g Gelatin 0.8 g Coupler C-5 0.2 g Coupler C-6 0.1 g Coupler C-10 0.4 g

Sixteenth layer: Medium sensitivity blue-sensitive emulsion layer Emulsion L Silver amount 0.1 g Emulsion M Silver amount 0.4 g Gelatin 0.9 g Coupler C-5 0.1 g Coupler C-6 0.1 g Coupler C-10 0.6 g

Seventeenth layer: High-sensitivity blue-sensitive emulsion layer Emulsion N Silver amount 0.4 g Gelatin 1.2 g Coupler C-5 0.1 g Coupler C-6 0.1 g Coupler C-10 0.6 g High boiling organic solvent Oil-2 0.1 g

Eighteenth layer: First protective layer Gelatin 0.7 g UV absorber U-1 0.2 g UV absorber U-2 0.05 g UV absorber U-5 0.3 g Formalin scavenger Cpd-H 0.4 g Dye D-1 0.1 g Dye D-2 0.05 g Dye D-3 0.1 g

19th layer: 2nd protective layer Colloidal silver Silver amount 0.1 mg Fine grain silver iodobromide emulsion (average particle size 0.06 μm, AgI content 1 mol%) Silver amount 0.1 g Gelatin 0.4 g

20th layer: third protective layer Gelatin 0.4 g Polymethylmethacrylate (average particle size 1.5 μ) 0.1 g Methyl methacrylate / acrylic acid 4: 6 copolymer (average particle size 1. 5 μ) 0.1 g Silicone oil 0.03 g Surfactant W-1 3.0 mg Surfactant W-2 0.03 g

In addition to the above composition, additives F-1 to F-8 were added to all emulsion layers. In addition to the above composition, gelatin hardener H-1 and coating and emulsifying surfactants W-3, W-4, W-5 and W-6 were added to each layer. Furthermore, phenol, 1,2-benzisothiazolin-3-one, 2-phenoxyethanol, phenethyl alcohol, and p-benzoic acid butyl ester were added as antiseptic and antifungal agents.

(Preparation of Emulsion) Among the emulsions used in Sample 101, emulsions A to C, E to G, J to L and N can be prepared by a known production method. Emulsion D,
The manufacturing method of H and M will be described. Potassium bromide, potassium iodide and gelatin were added and dissolved, and a silver nitrate solution and a mixed solution of potassium bromide and potassium iodide were added by a double jet method to the solution kept at 75 ° C. with stirring. Following this, a silver nitrate solution and a potassium bromide solution were further added by the double jet method.

After the addition was completed, the temperature was lowered to 35 ° C., the soluble salts were removed by the sedimentation method, the temperature was again adjusted to 40 ° C., 60 g of gelatin was added and dissolved, and the pH was adjusted to 6.8 to prepare a mother grain emulsion. The base particles thus obtained were tabular and had an average diameter of 1.7 μm and a thickness of 0.15 μm.

Then, using hypo and chloroauric acid, 50
Emulsion 1 was prepared by chemical sensitization at 40 ° C. for 40 minutes. Emulsion 1 90
200 ml of water was added to 0 g (corresponding to 70 g of AgNO ₃ ) and kept at 45 ° C. by adding the aqueous solution of silver nitrate (corresponding to 7 g of AgNO ₃ ) and the aqueous solution of sodium chloride by the double jet method while keeping the silver potential at +160 mV. Emulsion 2 was prepared by forming protrusions on the surface. The number of protrusions of Emulsion 2 was 110 / μm ² .

A sensitizing dye was added as shown in Table 2 using Emulsion 1 by a known method to prepare Emulsion H. Similarly, Emulsion 2 was used to prepare Emulsions D and M.

The silver iodobromide emulsion used for Sample 101 is as follows. Equivalent sphere Emulsion name Grain characteristics Average grain size Coefficient of variation AgI content (μm) (%) (%) A Monodisperse tetradecahedral grain 0.28 16 3.7 B Monodisperse cubic internal latent image grain 0.30 10 3.3 C monodisperse tabular grains, 0.38 18 5.0 average aspect ratio 4.0 D average grains, average aspect ratio 11.3 0.55 15 2.0 E E monodisperse cubic grains 0.20 17 4.0 F Monodisperse cubic particles 0.23 16 4.0 G Monodisperse cubic internal latent image type particles 0.28 11 3.5 H Average particles, 0.55 15 2.0 Average aspect ratio 11.3 J Monodisperse tetrahedral grains 0.30 18 4.0 K Monodisperse tabular grains, 0.45 17 4.0 Average aspect ratio 7.0 L Monodisperse cubic internal latent image type grains 0.46 14 3.5 M Tabular grains Particles, 0.55 15 2.0 average Aspect ratio 11.3 N tabular grains 1.00 33 1.3 Average aspect ratio 12.0

[0129]

[Table 2]

[0130]

[Table 3]

[0131]

[Chemical 27]

[0132]

[Chemical 28]

[0133]

[Chemical 29]

[0134]

[Chemical 30]

[0135]

[Chemical 31]

[0136]

[Chemical 32]

[0137]

[Chemical 33]

[0138]

[Chemical 34]

[0139]

[Chemical 35]

[0140]

[Chemical 36]

[0141]

[Chemical 37]

[0142]

[Chemical 38]

[0143]

[Chemical Formula 39]

[0144]

[Chemical 40]

(Samples 102 to 120) No. 9 of Sample 101
Magenta couplers C-7 and C- added to layers 11 to 11
In place of 8, the compounds of the present invention shown in Table 4 were added by substituting 1 times the total number of moles of the coupler, and added.
For Nos. 2 and 103, the magenta couplers were replaced with Md-1 and M-10, respectively, as shown in Table 4. Further, instead of Emulsion H of the 10th and 11th layers of Sample 101, an equivalent amount of silver amount was substituted for Emulsion I of the present invention shown below, and the magenta coupler was replaced as shown in Table 4. Is the same as sample 101, and samples 104-1
19 was created. Also, an octahedral emulsion 3 having protrusions was prepared in accordance with the emulsion B of Example 8 described in European Patent No. 0498302, and the emulsion H of the sample 101 was replaced with the emulsion 3 to prepare the sample 120. The silver iodobromide emulsion used for Samples 102 and 103 is the same as that for Sample 101. Emulsion I was prepared using Emulsion 2 and spectral sensitization was performed in the same manner as Emulsion H. Average particle size, coefficient of variation, A
The gI content is the same as that of Emulsion H.

[0146]

[Table 4]

The samples 101 to 120 prepared in this manner were processed into a 35 mm size patrone form and photographed for practical use. As a subject, a color checker manufactured by Macbeth Co. was used, and the following development processing was performed. A plurality of evaluators evaluated the color reproducibility of the obtained practical sample in five stages with the sample 101 as a control. Then, the average value of these evaluation values was used as a value representing color reproducibility. The obtained sample 101
After cutting ~ 120 into strips, gradation exposure was performed through an optical wedge, development was performed in the following development processing step, and density was measured to obtain a characteristic curve. At this time, in order to evaluate the color image fastness, a processing step in which the formalin precursor was removed from the preparation liquid was prepared to prepare a preparation liquid B. A preparation liquid containing a usual formaldehyde bisulfite addition product is referred to as preparation liquid A. After measuring the density of the characteristic curve, it was stored for 7 days under the condition of 70 ° C. and 70% relative humidity to evaluate the image storability of a magenta color image. The evaluation was performed by obtaining the change rate (%) after storage with respect to the initial density of magenta of 2.0. Next, in order to evaluate the processing dependence, the pH value of the color developing solution was set to 11.8 in the following development processing steps (designated as color developing solution A), and 1
What was prepared in 1.7 (designated as color developer B) was prepared. After passing through each color-developing processing solution and developing, the density was measured. In the obtained characteristic curve, the common numerical value of the exposure amount for each pH value at the point where the magenta density due to green light was 0.4 was read, and the range of change was taken as the evaluation value of pH dependence. The results obtained are summarized in Table 5.

[0148]

[Table 5]

The development processing steps are shown below. Treatment process time Temperature First development 6 minutes 38 ° C Water wash 2 minutes 38 ° C Inversion 2 minutes 38 ° C Color development 6 minutes 38 ° C adjustment 2 minutes 38 ° C Bleach 6 minutes 38 ° C Settling 4 minutes 38 ° C Water wash 4 minutes 38 ℃ Stability 1 minute 25 ℃

The composition of each processing liquid was as follows. [First developer] Nitrilo-N, N, N-trimethylenephosphonic acid / 5 sodium salt 1.5 g Diethylenetriamine pentaacetic acid / 5 sodium salt 2.0 g Sodium sulfite 30 g Hydroquinone / potassium monosulfonate 20 g Potassium carbonate 15 g Bicarbonate Sodium 12g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1.5g Potassium bromide 2.5g Potassium thiocyanate 1.2g Potassium iodide 2.0mg Diethylene glycol 13g Water was added to 1000 ml pH 9. 60 pH was adjusted with hydrochloric acid or potassium hydroxide.

[Inversion Liquid] Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 3.0 g stannous chloride dihydrate 1.0 g p-aminophenol 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 hydrochloric acid or sodium hydroxide.

[Color Developer A] Nitrilo-N, N, N-trimethylenephosphonic acid-5 sodium salt 2.0 g sodium sulfite 7.0 g phosphoric acid trisodium dodecahydrate 36 g potassium bromide 1.0 g iodide Potassium 90 mg Sodium hydroxide 3.0 g Citrazinic acid 1.5 g N-Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 11 g 3,6- Dithiaoctane-1,8-diol 1.0 g Water was added to 1000 ml pH 11.80 pH was adjusted with hydrochloric acid or potassium hydroxide. [Color Developer B] The color developer A was adjusted in the same manner except that the pH of the color developer A was adjusted to 11.70.

[Preparation liquid A] Ethylenediamine tetraacetic acid / disodium salt / dihydrate 8.0 g Sodium sulfite 12 g 1-Thioglycerol 0.4 g Sodium formaldehyde bisulfite adduct 30 g Water was added to 1000 ml pH 6.20 pH Was adjusted with hydrochloric acid or sodium hydroxide. [Preparation Solution B] Preparation was carried out in the same manner except that the formaldehyde sodium bisulfite adduct was removed from Preparation Solution B. [Bleaching solution] Ethylenediamine tetraacetic acid / disodium salt / dihydrate 2.0 g Ethylenediamine tetraacetic acid / Fe (III) / ammonium / dihydrate 120 g Potassium bromide 100 g Ammonium nitrate 10 g Water was added to 1000 ml pH 5.70 pH Was adjusted with hydrochloric acid or sodium hydroxide.

[Fixing Solution] Ammonium thiosulfate 80 g Sodium sulfite 5.0 g Sodium bisulfite 5.0 g Water was added to 1000 ml pH 6.60 The pH was adjusted with hydrochloric acid or aqueous ammonia.

[Stabilizer] Benzisothiazolin-3-one 0.02 g Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 g Water was added to 1000 ml pH 7.0.

From the results of Samples 103 and 106 in Table 5, it is clear that the combined use of the emulsion of the present invention and the magenta coupler of the present invention has a remarkable effect of improving the processing dependence. Further, from the results of Samples 107 and 108, it is understood that the use of the magenta coupler of the present invention in the high-sensitivity emulsion layer has a greater effect on the processing dependence than the use of only the low-sensitivity layer. Also, from Sample 119, coupler M-3
The effect of improving the process variation when using 4 is relatively small,
When the sum of Hammett's substituent constant σ values of X ₃ , X ₄ , and X ₅ in the formulas (M) and (N) of the magenta coupler of the present invention is 1.0 or more, the effect on processing stability is greater. It is clear. For color reproducibility, see Sample 11
From the results of 5 to 118, a more remarkable effect can be expected by mixing and using the conventional anilino type magenta coupler. With respect to color image fastness, excellent results independent of formalin could be obtained.

[0157]

As described above in detail, the silver halide color photographic light-sensitive material of the present invention is
The change in photographic property is small, and the effect is remarkable in color reproducibility and color image fastness.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 27, 1993

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

In the present invention, R ₁ , X ₁ , X ₂ , X ₃ , X ₄ and X _{5 in the} compound represented by the general formula (M) are used.
Will be described in detail, but before that, the Hammett's substituent constant will be briefly described. Hammett's rule is used to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. The rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants obtained by the Hammett's rule include σ _p values and σ _m values, and these values can be found in many general textbooks. A. Dean
Edited by "Lange's Handbook of Ch
"emission" 12th edition, 1979 (McGraw
-Hill) and "The Area of Chemistry" special edition, No. 122, 96-
Details on page 103, 1979 (Nankodo). In the present invention, each substituent is represented by Hammett's substituent constants σ _p and σ _m
Although it is limited or explained by this, this does not mean that the value found in the above-mentioned book is limited only to a substituent having a known value in the literature, and even if the value is unknown in the literature, Hammett's rule is applied. It goes without saying that it also includes a substituent that would be included in the range when measured based on the above. In the future, the σ _p and σ _m values will have this meaning.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

More specifically, R ₁ is an optionally substituted aryl group having 6 to 46 carbon atoms, such as an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, a carboxy group or an amino group. , Acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, alkoxy group, aryloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, aryloxycarbonylamino group, acylamino group, alkylamino group , Anilino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, sulfonamide group, aryloxycarbonylamino group, imide group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfonyl group, sulfinyl group , It may be substituted with a zo group, a phosphonyl group, an azolyl group, a fluorine atom, a chlorine atom or a bromine atom, and examples thereof include phenyl, 2-chlorophenyl, 2-methoxyphenyl, 2-chloro-5-tetradecanamidophenyl and 2-chloro. -5- (3-octadecenyl-1
-Succinimido) phenyl, 2-chloro-5-octadecylsulfonamidophenyl, 5-hexadecanoamidophenyl, 2-chloro-5- [2- (4-hydroxy-3-tert-butylphenoxy) tetradecanoamidophenyl].

[Procedure 3]

[Document name to be amended] Statement

[Name of item to be corrected] 0015

[Correction method] Change

[Correction content]

Y and A are each a hydrogen atom, an alkyl group (eg methyl, tert-butyl, octyl, dodecyl), an aryl group (eg phenyl group, tolyl group), an alkoxy group (eg methoxy, octoxy), an aryloxy group ( For example, phenoxy, p-tert-butylphenoxy, naphthoxy), alkylthio group (eg methylthio, octylthio), arylthio group (eg phenylthio), amino group (eg amino, methylamino,
Dimethylamino, anilino), an amide group (eg acetamide, butyramide, methanesulfonamide, diacylamide), a halogen atom (fluorine, chlorine, bromine), a hydroxyl group, a cyano group or a nitro group.

[Procedure amendment 4]

[Document name to be amended] Statement

[Name of item to be corrected] 0032

[Correction method] Change

[Correction content]

L represents a coupling-off group, and the coupling-off group will be described in detail. For example, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a sulfonyloxy group, an amide group, an alkoxycarbonyloxy group, an aryloxycarbonyl group. Oxy group, alkyl, aryl, or heterocyclic thio group, imido group,
It is a 5- or 6-membered nitrogen-containing heterocyclic group or an arylazo group, and these groups may be further substituted with a group acceptable as a substituent for R ₁ . More specifically, the coupling-off group represented by L is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom), an alkoxy group (eg, dodecyloxy, dodecyloxycarbonylmethoxy, methoxycarbamoylmethoxy, carboxypropyloxy, methanesulfonyl). Oxy), an aryloxy group (for example, 4-methylphenoxy, 4-tert-butylphenoxy, 4-methoxyphenoxy, 4-methanesulfonylphenoxy, 4- (4-benzyloxyphenylsulfonyl) phenoxy), an acyloxy group (for example, acetoxy, Tetradecanoyloxy, benzoyloxy), sulfonyloxy group (eg methanesulfonyloxy, toluenesulfonyloxy), amide group (eg dichloroacetylamino, methanesulfonyloxy) Roh,
Triphenylphosphonamide), an alkoxycarbonyloxy group (eg ethoxycarbonyloxy, benzyloxycarbonyloxy), an aryloxycarbonyloxy group (eg phenoxycarbonyloxy, 2,
4,6-trimethylphenoxycarbonyl), alkyl, aryl or heterocyclic thio groups (eg dodecylthio, benzylthio, 1-carboxydodecylthio, phenylthio, 2-butoxy-5-tert-octylphenethylthio, 2,5-dioctyloxyphenyl) Thio,
2- (2-ethoxyethoxy) -5-tert-octylphenylthio, 2-pivaloylaminophenylthio,
Tetrazolylthio), imide group (for example, succinimide, hydantoinyl, 2,4-dioxooxazolidin-3-yl, 3-benzyl-4-ethoxyhydantoin-1-yl), 5-membered or 6-membered nitrogen-containing heterocyclic group (For example, 1-pyrazolyl, 1-benzotriazole, 5
-Chloro-1,2,4-triazol-1-yl, 1,
2-dihydro-2-oxo-1-pyridyl) and the like. In addition to these, L may take the form of a bis-type coupler obtained by condensing a 4-equivalent coupler with an aldehyde or a ketone as a leaving group bonded via a carbon atom.
Further, L may contain a photographically useful group such as a development inhibitor or a development accelerator. Preferably, L is a hydrogen atom, an alkyl, aryl or heterocyclic thio group, or a 5- or 6-membered nitrogen-containing heterocyclic group bonded to the coupling active position with a nitrogen atom.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Name of item to be corrected] 0045

[Correction method] Change

[Correction content]

[0045]

[Chemical 17]

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction content]

[0046]

[Chemical 18]

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0052

[Correction method] Change

[Correction content]

(Synthesis of Compound (b)) Compound (a) 20
1 g (7.30 × 10 ⁻¹ mol) of 1,3-dimethyl-
2-Imidazolidone (1 liter) was added, and 84.1 g (1.68 mol) of hydrazine monohydrate was added over 1 hour while stirring with ice cooling.
) Was added dropwise. After stirring for 2 hours as it was, the reaction system was poured into 10 liters of water, filtered, and the residue was washed with acetonitrile to obtain 180 g of compound (b) (yield 91%). (Synthesis of Compound (d)) 155 g (5.7) of Compound (b)
1.9 liters of DMI was added to 2 × 10 ⁻¹ mol), 109 g (5.72 × 10 ⁻¹ mol) of compound (c) was added with stirring at room temperature, and the stirring was continued for 10 hours. When 3 liters of ethyl acetate was added to the reaction system and washed with water, the compound (d) was precipitated as crystals. Therefore, it was filtered. Distilled off. Methanol was added to the obtained crystals of the compound (d), the mixture was filtered, and 153 g (yield 64.8%) of the compound (d) was obtained by combining with the previously obtained fraction. (Synthesis of Compound (e)) 153 g (3.7) of Compound (d)
Ethanol (1.5 liters) was added to 0 × 10 ^-1 mol) and 28% sodium methylate 74.4 ml (3.
70 × 10 ⁻¹ mol) was added dropwise over 1 hour and 30 minutes, and stirring was continued for 6 hours. Next, add 22 ml of acetic acid to the reaction system.
After the addition of the above, the reaction system was poured into 1.5 liters of water, and the obtained crystals were filtered to obtain 84.8 g of compound (e) (yield: 62).
%) Was obtained. (Synthesis of Compound (g)) 43.9 g (1.
To 20 × 10 ⁻¹ mol), 44 ml of m-cresol, 24.8 g of compound (f) (1.43 × 10 ⁻¹ mol) and 2.33 ml of methanesulfonic acid (3.59 × 10 ⁻¹ mol) were added, and 1
The mixture was heated and stirred at 50 ° C. under a nitrogen atmosphere for 5 hours. Thereafter, methanol was added to the reaction system and the mixture was allowed to cool to room temperature, and the obtained crystals were filtered to give 19.3 g of compound (g) (yield 35
%) Was obtained. (Synthesis of Compound (h)) 21.8 g of reduced iron (3.91 ×)
2.09 g (3.91 of ammonium chloride) per 10 ^-1 mol)
X10 ^-2 mol), acetic acid 2.24 ml (3.91 x 10 ^-2 mo)
l) and 56 ml of water were added, and the mixture was heated under reflux with stirring for 15 minutes, 280 ml of isopropanol was added, and the mixture was further heated under reflux with stirring for 1 hour 45 minutes. Compound (g) 19.3g (3.
91 × 10 ^-2 mol) was added, and the mixture was heated under reflux with stirring for 2 hours, 100 ml of tetrahydrofuran was added, and the mixture was further heated under reflux with stirring for 1 hour. Then, the reaction solution was filtered using Celite as a filter aid, the solvent was distilled off from the filtrate under reduced pressure, ethyl acetate was added to the residue, and the mixture was washed with saturated brine, dried over sodium sulfate, and ethyl acetate was distilled off under reduced pressure. Thus, 9.10 g (yield 49%) of compound (h) was obtained. (Synthesis of Exemplified Compound (M-10)) Compound (h) 9.1
0 g (1.96 × 10 ^-2 mol) of ethyl acetate 91 ml,
18.2 ml of N, N-dimethylacetamide was added, and the mixture was slowly stirred with stirring at room temperature to give myristyl chloride 5.3.
4 ml (1.96 × 10 ^-2 mol) followed by pyridine 1.5
9 ml (1.96 × 10 ^-2 mol) was added dropwise and stirring was continued for 3 hours. Next, 20 ml of ammonia water was added, and the mixture was stirred as it was for 1 hour, then 200 ml of ethyl acetate was added, and water,
The extract was washed with saturated saline and dried over sodium sulfate, and then ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography, and recrystallized from ethanol to obtain 4.3 g (yield 33%) of Exemplified compound (M1-10). The physical property values are shown below. Melting point: 155-157 ° C. ¹ H-NMR (DMSO-d ₆ ): δ = 0.86 (t,
3H), 1.1 to 1.4 (m, 20H), 1.4 to 1.
6 (m, 2H), 2.20 (t, 2H), 3.96
(S, 2H), 7.2-7.4 (m, 2H), 8.13
(D, 2H), 8.87 (s, 1H), 9.85 (s,
1H).

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0132

[Correction method] Change

[Correction content]

[0132]

[Chemical 28]

[Procedure Amendment 9]

[Document name to be amended] Statement

[Name of item to be corrected] 0133

[Correction method] Change

[Correction content]

[0133]

[Chemical 29]

[Procedure Amendment 10]

[Document name to be amended] Statement

[Name of item to be corrected] 0146

[Correction method] Change

[Correction content]

[0146]

[Table 4]

Claims (3)

[Claims] 1. A silver halide color photographic light-sensitive material having one or more blue-sensitive emulsion layers, green-sensitive emulsion layers, and red-sensitive emulsions each on a support, wherein the green-sensitive layers have the following general formula (M). And a substantially colorless magenta dye-forming coupler selected from the compounds represented by (N), and at least one silver halide emulsion of the green-sensitive emulsion layer contains halogen on the surface of silver halide host grains. A silver halide color photographic light-sensitive material, which is an emulsion containing silver halide grains having silver halide protrusions. [Chemical 1] In the formula, R ₁ represents an optionally substituted aryl group, X ₁ and X ₂ each represent a hydrogen atom, a halogen atom, and an alkyl group, and X ₃ , X ₄ , and X ₅ represent Hammett's substituents. It represents a substituent necessary for the sum of constant σ values to be 0.9 or more. L represents a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine color developing agent. 2. A method for processing a silver halide color photographic light-sensitive material, which comprises processing the silver halide color photographic light-sensitive material according to claim 1 with a color developing solution having a pH of 11.0 or higher. 3. A silver halide color photographic light-sensitive material having a green-sensitive emulsion layer consisting of two or more emulsion layers having different sensitivities on a support, and the highest sensitivity layer of the green-sensitive layer is represented by the following general formula (M). The silver halide color photographic light-sensitive material according to claim 1, which contains at least one substantially colorless magenta dye-forming coupler selected from the compounds represented by and (N).