JP2715343B2 - Silver halide color photographic materials - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more particularly, to a silver halide emulsion having a high silver iodide content and a development inhibitor which is a leaving group. The present invention relates to a silver halide color photographic light-sensitive material containing a DIR coupler which releases a development inhibitor which changes into a substance which does not affect photographic performance.

[0002]

2. Description of the Related Art In recent years, silver halide photographic materials, particularly color photographic materials for photography, have high sensitivity and granularity represented by ISO 400 sensitivity (Super HG-400) having high image quality equivalent to ISO sensitivity of 100. There is a demand for a photosensitive material having excellent sharpness and color reproducibility. As means for improving graininess, silver halide having a clear layered structure of silver halide containing 7 to 45 mol% of silver iodide in grains and having an average silver iodide content of 7 mol% or more is used. Particles are disclosed in
However, it has been recently proposed to combine these emulsion grains with a so-called DIR coupler which releases a development inhibitor in an image-wise manner, because the emulsion grains alone have problems in sharpness and color reproducibility. Kaiping 1
186938, 1-259359, 1-26
No. 9935 and No. 2-28637.
Certainly, these techniques have improved graininess, sharpness, and color reproducibility, but their achievement levels have been still unsatisfactory. Furthermore, when the photosensitive material described in the above patent is processed commonly used in commercial labs at present, that is, when the processing is continuously performed while replenishing the developing solution, the developing solution may have a low activation or a high activation. It turned out that there was.

On the other hand, hydrolysis-type DIRs devised so as to improve the sharpness and color reproducibility while not changing the activity of the above-mentioned developer are disclosed in JP-A-57-151944 and JP-A-58-205150. It is proposed in JP-A-1-280755 and U.S. Pat. No. 4,782,012. Certainly, DIR couplers and DIR compounds that release leaving groups of the type in which these development inhibitor moieties are hydrolyzed in the developer to substantially lose their development inhibitory properties will improve fluctuations in developer activity. However, the effect was still insufficient. In particular, when the development inhibitor is deactivated in the developer to release aryloxy ions, this is incorporated into the coupler oil droplets in the photosensitive material and changes the coupling activity of the coupler, resulting in fluctuations in photographic performance. It became clear that it was a factor. Further, a so-called timing type DIR coupler has problems in its compound stability and synthesis cost, and those which are separated from the coupler via sulfur as in U.S. Pat. No. 4,782,012 have low coupling activity, that is, Since the release rate of the development inhibitor is low, there is a problem that sufficient effect of improving color reproducibility and sharpness cannot be obtained.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
To provide a photosensitive material which simultaneously satisfies the sensitivity, granularity, sharpness, color reproducibility and storability of the photosensitive material.
The third object is to provide a light-sensitive material in which the photographic performance is very little fluctuated in a method of continuously processing while replenishing a developing solution. Third, the synthesis route is short, inexpensive, has excellent compound stability, and has a small cup length. An object of the present invention is to provide a photosensitive material containing a DIR coupler having high ring activity.

[0005]

These objects of the present invention have been attained by the following light-sensitive materials. A silver halide color photographic light-sensitive material having at least one light-sensitive emulsion layer on a support, comprising a DI represented by the following formula (I):
Silver iodobromide containing an R coupler and containing 7 to 45 mol% of silver iodide is present in the emulsion layer in a well-defined layered structure, and the silver iodide content in the whole grain is 4 mol. % Silver halide color photographic light-sensitive material, characterized by containing an emulsion containing more than 1% of chemically sensitized silver halide grains. General formula (I)

[0006]

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( Wherein, A represents a coupler residue, n represents 1 when A represents a phenol-type or naphthol-type coupler residue, and n represents 0 when A represents another coupler residue.) And R is an alkoxycarbonyl group
Or substituted with an N, N-disubstituted carbamoyl group,
Excluding these, it represents an alkyl group having 1 to 4 carbon atoms or a pyridyl group. )

A shown in the general formula (I) is described in detail below. For example, yellow coupler residues (for example, open-chain ketomethylene type), magenta coupler residues (5-pyrazolone type, pyrazoloimidazole type, pyrazolotriazole type, etc.),
Examples thereof include a cyan coupler residue (phenol type, naphthol type, etc.) and a non-colored coupler residue (indanone type, acetophenone type, etc.). Further, it may be a heterocyclic coupler residue described in U.S. Pat. Nos. 4,315,070, 4,183,752, 3,961,959 or 4,171,223. . Preferred examples of A include the following general formulas (Cp-1), (Cp-2),
(Cp-3), (Cp-4), (Cp-5), (Cp-
6), (Cp-7), (Cp-8), (Cp-9) or a coupler residue represented by (Cp-10). These couplers are preferable because of their high coupling speed.

[0009]

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[0010]

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In the above formula, derived from the coupling position
Free bond indicates the bond position of the coupling-off group.
I forgot. In the above formula, R₅₁, R₅₂, R₅₃, R₅₄, R₅₅, R
₅₆, R₅₇, R₅₈, R₅₉, R₆₀ , R₆₁, R₆₂Or R₆₃But
If it contains a diffusion-resistant group, it has a total carbon number of 8 to 4
0, preferably chosen to be between 10 and 30;
In other cases, the total number of carbon atoms is preferably 15 or less.
For bis, telomer or polymer couplers
Has one of the above substituents represents a divalent group,
Units are connected. In this case, the range of carbon number is regulated.
It may be outside the fixed range.

The following R₅₁~ R₆₃, B, d and e
Will be described in detail. R below₄₁Represents an aliphatic group or an aromatic group.
Or a heterocyclic group;₄₂Is an aromatic or heterocyclic group
And R₄₃, R₄₄And R₄₅Is a hydrogen atom, aliphatic
Represents a group, an aromatic group or a heterocyclic group. R₅₁Is R₄₁Same as
Means the same. b represents 0 or 1. R₅₂and
R₅₃Is R₄₂Has the same meaning as R₅₄Is R₄₁Same as
A group of meanings, R₄₁CON (R₄₃) Group, R₄₁N (R₄₃)-
Group, R₄₁SO_Two N (R₄₃) -Group, R₄₁S-group, R₄₃O-
Group, R₄₅N (R₄₃) -CON (R₄₅) -Group or N≡C
-Represents a group. R₅₅Is R₄₁ Represents a group having the same meaning as R
₅₆And R₅₇Is R₄₃A group having the same meaning as₄₁S-group,
R₄₃O-group, R₄₁CON (R₄₃) -Group, or R₄₁SO
_Two N (R₄₃)-Represents a group. R₅₈Is R₄₁Group of the same meaning as
Represents R₅₉Is R₄₁A group having the same meaning as₄₁ CON (R
₄₃) -Group, R₄₁OCON (R₄₃) -Group, R₄₁SO_Two N
(R₄₃) -Group, R₄₃N (R₄₄) CON (R₄₅) -Group, R
₄₁O-group, R₄₁An S-group, a halogen atom, or R₄₁N
(R₄₃)-Represents a group. d represents 0 to 3. d
Multiple Rs₅₉Are the same or different substituents
Represents a group. Also, each R₅₉Becomes a divalent group and is linked
An annular structure may be formed. To form a ring structure
Examples of divalent groups of

Embedded imageIs a typical example. Where f is 0 to 4
And g represents an integer of 0 to 2. R₆₀Is
R₄₁Represents a group having the same meaning as R₆₁Is R₄₁Same meaning as
Group, R₆₂Is R₄₁A group having the same meaning as₄₁An OCONH- group,
R₄₁SO_Two NH- group, R₄₃N (R₄₄) CON (R₄₅)-
Group, R₄₃N (R₄₄) SO_Two N (R₄₅) -Group, R₄₃O-
Group, R₄₁S-group, halogen atom or R₄₁N (R₄₃)-
Represents a group. R₆₃Is R₄₁A group having the same meaning as₄₃C
(R₄₄) ON (R₄₅) -Group, R₄₃N (R₄₄) A CO- group,
R₄₁SO_Two N (R₄₄) -Group, R₄₃N (R₄₄) SO_Two −
Group, R₄₁SO_Two -Group, R₄₃OCO- group, R₄₃O-SO_Two 
Group, halogen atom, nitro group, cyano group or R₄₃C
Represents an O-group. e represents an integer of 0 to 4. Multiple
R₆₂ Or R₆₃When each is the same or different
Represents something.

In the above, the aliphatic group has 1 to 3 carbon atoms.
2, preferably 1 to 22 saturated or unsaturated, linear or
Is a cyclic, linear or branched, substituted or unsubstituted aliphatic carbon
It is a hydride group. Representative examples include methyl and ethyl.
, Propyl, isopropyl, butyl, (t) -butyl
, (I) -butyl, (t) -amyl, hexyl, cyclo
Rohexyl, 2-ethylhexyl, octyl, 1,1,
3,3-tetramethylbutyl, decyl, dodecyl, hex
Sadecyl, or octadecyl. Aromatic group
Is a substituted or unsubstituted fluorocarbon having 6 to 20 carbon atoms.
Phenyl or substituted or unsubstituted naphthyl
You. A heterocyclic group is a group having 1 to 20 carbon atoms, preferably 1 to 7 carbon atoms.
Nitrogen, oxygen or sulfur as a complex atom
Substitution on a 3- to 8-membered ring selected from atoms, preferably
Alternatively, it is an unsubstituted heterocyclic group. Representative of heterocyclic groups
Examples are 2-pyridyl, 2-thienyl, 2-furyl,
1,3,4-thiadiazol-2-yl, 2,4-dio
Xo-1,3-imidazolidin-5-yl, 1,2,4
-Triazol-2-yl or 1-pyrazolyl
Can be The aliphatic hydrocarbon group, aromatic group and heterocyclic group
When has a substituent, a typical substituent is
Atom, R₄₇O-group, R₄₆S-group, R₄₇CON (R₄₈)
-Group, R₄₇N (R₄₈) CO-group, R₄₆OCON (R₄₇)
-Group, R₄₆SO_Two N (R₄₇) -Group, R₄₇N (R₄₈) SO
_Two -Group, R₄₆SO_Two -Group, R₄₇OCO- group, R₄₇ N (R
₄₈) CON (R₄₉) -Group, R₄₆A group with the same meaning as

Embedded imageR₄₆COO- group, R₄₇OSO_Two Group, cyano group or d
And a toro group. Where R₄₆Is an aliphatic group, aromatic
A heterocyclic group or a heterocyclic group;₄₇, R₄₈And R₄₉ Is each
Represents an aliphatic group, an aromatic group, a heterocyclic group or a hydrogen atom
You. The meanings of aliphatic, aromatic and heterocyclic groups have been defined previously.
It has the same meaning as justified.

Next, R₅₁~ R₆₃, D and e preferred ranges
The surroundings will be described. R₅₁Is based on the general formula (Cp-1)
Is preferably an aliphatic group or an aromatic group,
For p-2), a hydrogen atom or an aliphatic group is preferred
No. R₅₂, R₅₃And R₅₅Is a heterocyclic group or an aromatic group
preferable. R₅₄Is R₄₁A CONH- group, or R₄₁-N
(R₄₃)-Groups are preferred. R₅₆And R₅₇Is an aliphatic group,
Aromatic group, R₄₁O-group, or R₄₁S-groups are preferred.
R₅₃ Is preferably an aliphatic group or an aromatic group. General formula (C
In p-6), R₅₉Is a crawl atom, an aliphatic group or
R₄₁CONH- groups are preferred. d is preferably 1 or 2
No. R₆₀Is preferably an aromatic group. In general formula (Cp-7)
Then R₅₉Is R₄₁CONH- groups are preferred. General formula (C
In p-7), d is preferably 1. R₆₁Is an aliphatic group
Or an aromatic group is preferred. General formula (Cp-8)
E is preferably 0 or 1. R₆₂As R₄₁OCO
NH- group, R₄₁CONH-group or R₄₁ SO_Two NH- group
Are preferably substituted at the 5-position of the naphthol ring.
Good. In the general formula (Cp-9), R₆₃As R₄₁
CONH- group, R₄₁SO_Two NH- group, R₄₁N (R₄₃) S
O_Two -Group, R₄₁SO_Two -Group, R₄₁N (R₄₃) A CO- group,
Nitro or cyano groups are preferred. In general formula (Cp-10), R₆₃Is R₄₃N (R₄₃) C
O-group, R₄₃OCO-group or R₄₃CO- groups are preferred
No.

The group represented by R in the formula (I) will be described in detail below. When R represents an alkyl group, it is a linear or branched and substituted alkyl group having 1 to 4, preferably 1 to 3 carbon atoms. When R represents a pyridyl group, substituted or unsubstituted 2-, 3-, or 4-
It is a pyridyl group. R is can represent a substituted alkyl group,
Location substituent is an alkoxycarbonyl group (having 2 to 6 carbon atoms, such as methoxycarbonyl, propoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, isopropoxycarbonyl, pentyloxycarbonyl, iso-pentyloxycarbonyl, 2-methoxyethoxy carbonyl) or N , N-disubstituted carbamoyl groups (0 to 0 carbon atoms)
6, for example, N, N-diethylcarbamoyl, N-methyl-N-ethylcarbamoyl, pyrrolidinocarbonyl, piperidinocarbonyl) . When R represents a pyridyl group, a pyridyl group may have a substituent, as the substituent listed as a substituent of the alkyl group Arukokishikaru
Bonyl group, carbamoyl group (C0 to C6, for example, N,
N-diethylcarbamoyl, N-methyl-N-ethylca
Rubamoyl, pyrrolidinocarbonyl, piperidinocarbo
Nil), halogen atom (for example, chloro atom, fluorine atom
Nitro group, cyano group, alkoxy group (having 1 to 1 carbon atoms)
4, for example, methoxy, ethoxy, methoxyethoxy),
A sulfamoyl group (C0 to C6, for example, N, N-die
Tylsulfamoyl, N-methyl-N-ethylsulfa
Moyl), an aryloxy group (C6-10, for example,
4-chlorophenoxy), acyl group (2 to 6 carbon atoms, examples)
For example, acetyl, benzoyl), sulfonyl group (C 1
-6, for example, methanesulfonyl, butanesulfonyl),
Heterocyclic group (C1-5, nitrogen atom as a hetero atom, acid
3- to 6-membered heterocyclic ring selected from elementary atom or sulfur atom
Cyclic groups, for example 2-pyridyl, 3-pyridyl), suphoryl
Group (2 to 5 carbon atoms, for example, 0,0-diethylphosphoryl)
) Or an aliphatic group (1-6 carbon atoms, for example, methyl, ethyl). Specific examples of R include, for example, the following. _{-CH 2 COOC 3 H 7, -CH} 2 COOC 4 H 9, -
_{CH 2 COOC 3 H 7 (i} ), - CH 2 COOC 4 H 9
_{(I), - CH 2 COOC} 5 H 11, -CH 2 COO 5
_{H 11 (i), - CH} 2 COOC 5 H 11 (t), - C
_{H 2 CH 2 COOC 3 H 7} , -CH 2 CH 2 COOC 3
_{H 7 (t), - CH} 2 CH 2 CH 2 COOCH 3,

[0016]

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The compound represented by the general formula (I) of the present invention can be synthesized by a known method. For example, Japanese Unexamined Patent Publication No.
-151944, EP336411A or EP3
The compound can be synthesized by the method described in No. 20939A. Hereinafter, specific synthesis examples will be described.

Examples of compounds (provided that (D-20), (D-32), (D-36)
(D-39) is a reference example. )

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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Synthesis Example 1 (Synthesis of Exemplified Compound (D-1)) The compound was synthesized by the following synthesis route.

[0036]

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13.5 g of compound (ii) and triethylamine in 200 ml of N, N-dimethylformamide
9 g was added and the mixture was stirred at room temperature for 15 minutes. 20 g of the compound (i) was added to this solution, and the mixture was stirred at room temperature for 3 hours.
500 ml of ethyl acetate was added to the reaction mixture, which was transferred to a separating funnel and washed with water. The oil layer was removed and washed with diluted hydrochloric acid and water. The oil layer was removed and the solvent was distilled off under reduced pressure. 100 ml of a mixed solvent of ethyl acetate and hexane was added to the residue, and the precipitated crystals were collected by filtration to obtain 15.3 g of Exemplified Compound (D-1).

Synthesis Example 2 (Synthesis of Exemplified Compound (D-6)) The compound was synthesized by the reaction shown in the following scheme.

[0039]

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The reaction was carried out in the same manner as in Synthesis Example 1. However,
Compound (iv) was used in place of compound (ii) in Synthesis Example 1, and 14.8 g of compound (iii) was used instead of compound (i). Further, 8.5 g of the desired compound (D-6) was obtained by crystallization using a mixed solvent of isopropanol and hexane.

Synthesis Example 3 (Synthesis of Exemplified Compound (D-8)) The compound was synthesized by the reaction shown in the following scheme.

[0042]

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The reaction was carried out in the same manner as in Synthesis Example 1. However, 16.5 g of the compound (v) was used instead of the compound (i) of Synthesis Example 1, and 12.3 g of the compound (vi) was used instead of the compound (ii).
Was used. In addition, 9.8 g of Exemplified Compound (D-8) as a target product was obtained by crystallization using a mixed solvent of ethyl acetate and hexane.

Synthesis Example 4 (Synthesis of Exemplified Compound (D-9)) The compound was synthesized by the reaction shown in the following scheme.

[0045]

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The reaction was carried out in the same manner as in Synthesis Example 1. However,
15.0 of compound (vii) in place of compound (i) of Synthesis Example 1
g was used. Other than that, the target compound (D
-9) 12.1 g was obtained.

Synthesis Example 5 (Synthesis of Exemplified Compound (D-17)) The compound was synthesized by the reaction shown in the following scheme.

[0048]

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5. 17.1 g of compound (ix) and triethylamine in 200 ml of N, N-dimethylacetamide
3 g was added and stirred for 15 minutes. A solution prepared by dissolving 20 g of the compound (viii) in 100 ml of chloroform was added dropwise to this solution at room temperature over 20 minutes. The reaction was carried out at room temperature for 3 hours and then at 40 ° C. for 30 minutes. Thereafter, the same processing as in Example 1 was performed. Exemplified compound (D-17) of the target substance
Was crystallized using a mixed solvent of ethyl acetate and hexane to obtain 15.3 g.

Synthesis Example 6 (Synthesis of Exemplified Compound (D-23)) The compound was synthesized by the reaction shown in the following scheme.

[0051]

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25.5 g of the compound (iv) was dissolved in 100 ml of N, N'-dimethyl-2-imidazolidinone and cooled with ice. 2. Add sodium hydride (60%) to this solution.
7 g was added and the mixture was stirred for 20 minutes. To this solution was added 20 g of the compound (x), and the mixture was reacted at room temperature for 5 hours.
Stirred for half an hour. After the reaction, the temperature is returned to room temperature, and
ml and 200 ml of water were added and transferred to a separating funnel. The oil layer was separated, washed with water, diluted with hydrochloric acid, and washed with water. The oil layer was removed and the solvent was distilled off under reduced pressure. Ethyl acetate and hexane were added to the residue, and the precipitated crystals were collected by filtration to obtain 15.5 g of the intended exemplary compound (D-23).

The coupler of the present invention represented by the general formula (I) may be used in any layer in a light-sensitive material, but is preferably added to a light-sensitive silver halide emulsion layer and / or a layer adjacent thereto. More preferably, it is added to the non-sensitive emulsion layer when the same photosensitive layer containing the emulsion grains of the present invention comprises two or more layers having different sensitivities. The total amount of these couplers added to the light-sensitive material is usually 3 × 10 ⁻⁷ to 1 × 1.
0 ⁻³ mol / m ² , preferably 3 × 10 ^{−6 to} 5 × 10 ⁻⁴
mol / m ² , more preferably 1 × 10 ⁻⁵ to 2 × 10 ⁻⁴ mol / m ²
It is. The coupler represented by the general formula (I) of the present invention is
As described later, it can be added to a light-sensitive material in the same manner as a usual coupler.

Next, the silver halide grains of the present invention will be described. In the emulsion layer of the present invention, silver iodobromide containing 7.0 to 45 mol% of silver iodide is present in a well-defined layered structure, and the silver iodobromide content in the whole grain is 4. It is necessary to contain more than 0 mol% of chemically sensitized silver halide grains. Here, the clear layered structure can be determined by the X-ray diffraction method. An example in which the X-ray diffraction method is applied to silver halide grains is described in H. H. It is described in Hirsch's Bibliographic Journal of Photographic Science, Vol. 10 (1962), p. 129 et seq. When the lattice constant is determined by the halogen composition, the black condition (2dsinθ = n
A diffraction peak occurs at a diffraction angle satisfying λ).

The method of measuring X-ray diffraction is described in detail in Basic Analytical Chemistry Course 24, “X-ray diffraction” (Kyoritsu Shuppan), “Guide to X-ray diffraction” (Rigaku Denki Co., Ltd.) and the like. The standard measurement method uses Cu as the target and C
u Kβ-ray source (tube voltage 40kv, tube current 60m
A) This is a method of obtaining a diffraction curve of the (220) plane of silver halide. To improve the resolution of the measuring instrument, select the width of the slit (divergence slit, light receiving slit, etc.), the time constant of the device, the scanning speed of the goniometer, and the recording speed, and check the measurement accuracy using a standard sample such as silicon. There is a need to.

The clear layered structure in the present invention refers to a curve of the diffraction intensity versus the diffraction angle of the (220) plane of silver halide using Cu Kβ radiation at a diffraction angle (2θ) in the range of 38 ° to 42 °. At least two diffraction peaks corresponding to a high iodine layer containing 7.0 to 45 mol% of silver iodide and a diffraction peak corresponding to a low iodine layer containing 7 mol% or less of silver iodide. , And one minimum appears therebetween, and the diffraction intensity corresponding to the high iodine layer is 1/10 to 3/1 of the diffraction intensity of the peak corresponding to the low iodine layer.
, More preferably the diffraction intensity ratio is 1/5 to 3/1, particularly 1/3 to 3/1.

As the emulsion having substantially two distinct layered structures in the present invention, the diffraction intensity of the minimum value between the two peaks is more preferably two or more diffraction maxima (peaks), and the intensity is low. It is preferably 90% or less. It is more preferably at most 80%, particularly preferably at most 60%. A technique for resolving a diffraction curve composed of two diffraction components is well known, and is described, for example, in Experimental Physics Course 11 Lattice Defects (Kyoritsu Shuppan).

It is also useful to assume a curve curve as a function such as a Gaussian function or a Lorentz function and to use a curve analyzer made by Du Pont to break the curve. Even in the case of an emulsion having two types of grains having different halogen compositions and having no distinct layered structure, two peaks appear in the X-ray diffraction. Such emulsions cannot exhibit the excellent photographic performance obtained in the present invention.

In order to determine whether a silver halide emulsion is an emulsion according to the present invention or an emulsion in which two kinds of silver halide grains coexist as described above, in addition to the X-ray diffraction method,
This can be achieved by using the PMA method (Electron-Probo Micro Analyzer method). In this method, a sample in which emulsion grains are well dispersed so as not to come into contact with each other is prepared and irradiated with an electron beam. Elemental analysis of a very small portion can be performed by X-ray analysis by electron beam excitation. By this method, the halogen composition of each grain can be determined by determining the characteristic X-ray intensity of silver and iodine emitted from each lattice. If the halogen composition of at least 50 grains is confirmed by the EPMA method, it can be determined whether or not the emulsion is the emulsion according to the present invention.

The emulsion of the present invention preferably has a more uniform iodine content between grains. When the distribution of iodine content between particles is measured by the EPMA method, the relative standard deviation is preferably 50% or less, more preferably 35% or less. Another preferred interparticle iodine distribution is where the logarithm of the particle size and iodine content show a positive correlation.
That is, the case where the iodine content of the large-sized particles is high and the iodine content of the small-sized particles is low. Emulsions having such a correlation give favorable results in terms of graininess. This correlation coefficient is preferably at least 40%, more preferably at least 50%.

In the core portion, the silver halide other than silver iodide may be either silver chlorobromide or silver bromide, but the silver bromide ratio is preferably higher. The silver iodide content is 7.0 to 45.
Mol%, but preferably 15 to 45 mol%,
More preferably, it is 25 to 45 mol%. The most preferred core portion silver halide is silver iodobromide of 30 to 45% silver iodide. The composition of the outermost layer is silver halide containing 7.0 mol% or less of silver iodide, and more preferably 5.0 mol%.
It is a silver halide containing the following silver iodide.

As the silver halide other than silver iodide in the outermost layer, any of silver chloride, silver chlorobromide and silver bromide may be used, but a higher silver bromide ratio is preferred. Particularly preferred as the outermost layer is silver iodobromide or silver bromide containing 0.5 to 5.0 mol% of silver iodide. The halogen composition of the whole grains needs to have a silver iodide content of more than 4.0 mol%, preferably 6.0 to 25 mol%, more preferably 8.0 to 20 mol%, and still more preferably. 10 to 25 mol%.

One of the reasons for the good graininess of the silver halide emulsion used in the present invention is that light absorption was increased due to high iodination without lowering the developing activity. It is considered that the latent image forming efficiency was improved because a clear layered structure including a high iodine layer in the core portion and a low iodine layer as the outermost layer was provided. The size of the silver halide grains having a distinct layered structure of the present invention is from 0.05 to 3.0 μm, preferably from 0.1 to 3.0 μm.
It is 1.5 μm, more preferably 0.2 to 1.3 μm, and still more preferably 0.3 to 1.2 μm.

The average grain size of the silver halide grains as used in the present invention is defined as THJames.
Et al., The Theory of the Photographic
Process (The Theory of the Photographic Process)
It is a geometric mean value of particle size well-known in the art as described in the third edition, page 39, published by Macmillan Company (1966). The particle size is "Introduction to particle size measurement"
Masafumi Arakawa (Journal of the Society of Powder Technology, vol. 17, pp. 299-313 (1980)), which was represented by a sphere equivalent diameter, such as a Coulter counter method, a single particle light scattering method, or a laser light scattering method. The type of silver halide grains having a well-defined layered structure according to the present invention is a regular crystal form such as hexahedron, octahedron, dodecahedron, or tetradecahedron (normal crystal grains). And irregular crystalline forms such as spheres, potatoes, and tabular shapes. Tabular twin grains having an aspect ratio of 1.2 to 8, especially 1.5 to 5, are preferred.

In the case of normal crystal grains, grains having at least 50% of the (111) plane are particularly preferred. Particles having 50% or more of the (111) plane are particularly preferable even in the case of an irregular crystal form. The area ratio of the (111) plane can be determined by the Kubelka-Munk dye adsorption method. This preferentially adsorbs to either the (111) plane or the (100) plane and (11)
1) A dye whose spectral state is different from that of the dye on the (100) plane is selected from that of the dye on the (100) plane. By adding such a dye to the emulsion and examining the spectral spectrum in detail with respect to the amount of the dye added, the (111) plane ratio can be determined.

The emulsion of the present invention may be used in any layer of a silver halide light-sensitive material, but is preferably used in a blue- or green-sensitive emulsion layer. In the present invention, the blue- or green-sensitive emulsion layer is preferably composed of two or more layers having different sensitivities, but is particularly preferably used for a layer other than the minimum sensitivity.

In the present invention, the use of the compound represented by the following general formula (A) makes it possible to improve the sensitivity, improve the granularity and the storage stability of the photosensitive material, and reduce the fluctuation in the photographic properties of the processing solution. It is particularly preferred to achieve General formula (A) Q-SM ¹

In the formula, Q represents —SO ₃ M ² , —COOM ² ,
Represents a heterocyclic residue in which at least one selected from the group consisting of -OH and -NR ¹ R ² is directly or indirectly bonded, and M ¹ and M ² independently represent a hydrogen atom, an alkali metal,
Represents quaternary ammonium or quaternary phosphonium, R ¹ ,
R ² represents a hydrogen atom or a substituted or unsubstituted alkyl group.

It is considered that the compound of the general formula (A) is given water solubility or is improved in water solubility in a pH atmosphere in the developer and flows out of the photosensitive material into the developer. In other words, if the compound of the general formula (A) is contained in the light-sensitive material, it will dissolve in the developer and contaminate the developer. Nevertheless, it is just surprising that the change in the development finish characteristics is small and the fog is low. Such an unexpected effect is represented by the general formula (A)
When the effect of the compound is included in the photosensitive material,
This is probably due to the large difference between the spill during development and the spillage during development, but the evaluation is unknown, and future studies will reveal its behavior.

Specific examples of the heterocyclic residue represented by Q in formula (A) include an oxazole ring, thiazole ring, imidazole ring, selenazole ring, triazole ring, tetrazole ring, thiadiazole ring, oxadiazole ring, and pentazole ring. Ring, pyrimidine ring, thiadia ring,
Triazine ring, thiadiazine ring or the like, or a ring bonded to another carbon ring or a hetero ring, such as a benzothiazole ring, a benzotriazole ring, a benzimidazole ring, a benzoxazole ring, a benzoselenazole ring, a naphthooxazole ring, and a triazaindolizine ring , A diazaindolizine ring, a tetraazaindolizine ring and the like.

Among the mercapto heterocyclic compounds represented by the general formula (A), particularly preferred are the compounds represented by the general formulas (B) and (C).

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In the general formula (B), Y and Z each independently represent a nitrogen atom or CR ⁴ (R ⁴ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group). R ³ represents —SO ₃ M ² , —C
OOM ² , an organic residue substituted with at least one selected from the group consisting of —OH and —NR ¹ R ² , specifically, an alkyl group having 1 to 20 carbon atoms (for example, a methyl group, an ethyl group, Propyl, hexyl, dodecyl,
Octadecyl group), an aryl group having 6 to 20 carbon atoms (e.g., phenyl group, naphthyl group, etc.), and -L ¹
- is -S -, - O -, = N -, - CO -, - SO- and -SO ₂ - shows a linking group selected from the group consisting of, n
Is 0 or 1.

In these alkyl groups and aryl groups,
Further, a halogen atom (F, Cl, Br, etc.), an alkoxy group (methoxy group, methoxyethoxy group, etc.), an aryloxy group (phenoxy group, etc.), an alkyl group (when R ² is an aryl group), an aryl group (R ² Is an alkyl group), an amide group (acetamido group, benzoylamino group, etc.), a carbamoyl group (unsubstituted carbamoyl group, phenylcarbamoyl group, methylcarbamoyl group, etc.),
Sulfonamide group (methanesulfonamide group, phenylsulfonamide group, etc.), sulfamoyl group (unsubstituted sulfamoyl group, methylsulfamoyl group, phenylsulfamoyl group, etc.), sulfonyl group (methylsulfonyl group, phenylsulfonyl group, etc.) , Substituted by another substituent such as a sulfinyl group (methylsulfinyl group, phenylsulfinyl group, etc.), cyano group, alkoxycarbonyl group (methoxycarbonyl group, etc.), aryloxycarbonyl group (phenoxycarbonyl group, etc.), and nitro group. May be. Here, R ³ substituents —SO ₃ M, —COOM ² , —OH and NR ¹ R
^When there are two or more 2, they may be the same or different.
M ² means the same as those represented by the general formula (A).

In the formula (C), X represents a sulfur atom, an oxygen atom or —NR ⁵ —, and R ⁵ represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group. Express.

L ² is -CONR ⁶ , -NR ⁶ CO-,-
^{_{SO 2 NR 6 -, - NR}} 6 SO 2 -, - OCO -, - C
^{OO -, - S-, NR 6} -, - CO -, - SO -, - O
^{COO -, - NR 6 CONR 7} -, - NR 6 COO-,
Represents —OCONR ⁶ — or —NR ⁶ SO ₂ NR ⁷ —, wherein R ⁶ and R ⁷ each represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted aryl group.

R ³ and M ² have the same meanings as those represented by formulas (A) and (B), and n represents 0 or 1. Further, as the substituents of the alkyl group and the aryl group represented by R ⁴ , R ⁵ , R ⁶ and R ⁷ , the same substituents as the substituents of R ³ can be exemplified. In the general formula, R ³ is —SO ₃ M ² and —CO
OM ² is particularly preferred. Specific examples of preferred compounds represented by formula (A) used in the present invention are shown below.

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The compound represented by formula (A) is known.
And synthesized by the method described in the following document.
Can be U.S. Pat. No. 2,585,388,
2,541,924, JP-B-42-21842,
No. 53-50169, British Patent No. 1,275,70
No. 1, D. A. Bargees et al., "Journal of He
Telocyclic Chemistry "(D.A. Berges et.al.,"
Journal of the Heterocyclic Chemistry ") Vol. 15 9
No. 81 (1978), "The Chemistry of Hete
"Cyclic Chemistry", Imidazole &
・ Derivatives Part I ("The Chemistryof Hat
erocyclic Chemistry "Imidazole and Derivatives par
tI), pages 336-9, Chemical Abstracts (Che
mical Abstract),58, 7921 (1963), 3
94, E.C. Hogarth, "Journal of Chemical
・ Society ”(E. Hoggarth" Journal of Chemical So
ciety ") 1160-7 (1949) and S.R.
Udler, W.C. Caro, "Organic Functioner
Le Group Preparation ”, Academic
Les (S.R.Saudler, W. karo "Organic Fanctional
Group Preparation "Academic Press) 312-5
(1968); M. Chamdon, et a
l.,), Burtan de la Societe Simik de Hu ク
Reims (Bulleetin de la Societe Chimique de Fran)
ce), 723 (1954); A. Shirley, D.
W. Aley, Journal of the American Chemi
Cal Society (D.A. Shirley, D.W.Alley, J.
Amer. Chem. Soc.),79, 4922 (1954),
A. Ball, W. Marchwald Bellichte (A. Wohl,
W. Marchwald, Ber.) (Journal of the German Chemical Society), Volume 22, 5
68 pages (1889), Journal of American
Chemical Society (J. Amer. Chem. Soc.),4
41502-10, U.S. Patent No. 3,017,270.
No., UK Patent No. 940,169, JP-B-49-833
No. 4, JP-A-55-59463, Advanced In
・ Heterocyclic chemistry (Advancad in Heter
ocyclic Chemistry),9, 165-209 (196
8), West German Patent 2,716,707, The Chemist
Lee of Heterocyclic Compounds Imi
Dazol & Derivatives (The Chemis-try of
 Hetercyclic Compounds Imidazole and Derivatives)
 , Vol 1, p. 384, Organic Synthesis (Org.
 Synth.) IV., 569 (1963), Berichte (Br
e.), 9, 465 (1976), Journal of a
Merican Chemical Society (J. Amer. Chem. So
c.),45, 2390 (1923), JP-A-50-89.
No. 034, No. 53-28426, No. 55-21007
No., JP-A-40-28496.

The compound represented by the formula (A) is contained in a silver halide emulsion layer and a hydrophilic colloid layer (intermediate layer, surface protective layer, yellow filter layer, antihalation layer, etc.). It is preferable that the compound is contained in the silver halide emulsion layer or a layer adjacent thereto. Also, the amount of addition
1 × 10 ^-7 to 1 × 10 ^-3 mol / m ² , preferably 5
× 10 ^-7 to 1 × 10 ^-4 mol / m ^2, more preferably 1 × 10
⁻⁶ to 1 × 10 ⁻⁵ mol / m ² .

The emulsion containing silver halide grains of the present invention is particularly preferably a monodispersed emulsion. In the present invention, a monodispersed emulsion is defined as a coefficient of variation relating to the particle size of silver halide grains.

(Equation 1) Is an emulsion having a particle size distribution of 0.25 or less. That is, the particle size of each emulsion particle is ri, and the number is ni
, The average particle size is given by the formula

(Equation 2) And its standard deviation is

(Equation 3) Is defined as

The term “individual grain size” as used in the present invention means that a silver halide emulsion is prepared by the method of “The Theory of the Photographic Process” by TH James et al. Process) Third Edition, pp. 36-43, published by Macmillan Company (1966). The equivalent projected area equivalent diameter. Here, the projected equivalent diameter of the silver halide grain is defined by the diameter of a circle equal to the projected area of the silver halide grain as described in the above-mentioned book. Therefore, even when the shape of silver halide grains is not spherical (for example, cubic, octahedral, tetradecahedral, tabular, potato-like, etc.), the average grain size and its deviation can be determined as described above.

The variation coefficient relating to the grain size of silver halide grains is 0.25 or less, preferably 0.20 or less.
It is more preferably 0.15 or less.

In the present invention, it is more preferable to use a polymer coupler obtained from a monomer represented by the following general formula (PA) in the green-sensitive layer from the viewpoint of improving sharpness.
When a photosensitive material containing a conventional hydrolyzable DIR coupler is processed by a method of processing while replenishing a developing solution,
In particular, high contrast which is considered to be caused by the polymer coupler occurs. However, in a photosensitive material using a DIR coupler represented by the general formula (I) of the present invention, since this behavior was not observed, the polymer coupler is freely used. It became possible.

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In the formula, R ₁₂₁ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or chlorine, and -D- is -COO
-, - CONR ₁₂₁ -, or a substituted or unsubstituted phenyl group, -E- represents a substituted or unsubstituted alkylene group, phenylene group or aralkylene group,
-F- is _{-CONR 122 -, - NR 122 CONR} 122
-, -NR ₁₂₂ COO-, -NR ₁₂₂ CO-, -OCO
_{NR 122 -, - NR 122 -} , - COO -, - OCO-,
-CO -, - O-, S - , - SO 2 -, - NR 122 SO
₂ -, or -SO ₂ NR ₁₂₂ - represent. R ₁₂₂ represents a hydrogen atom or a substituted or unsubstituted aliphatic or aryl group. When two or more _R122s are present in the same molecule, they may be the same or different. p, q, and r represent 0 or 1. However, p, q, and r are never 0 at the same time. T coupler residue of a magenta coupler represented by the following general formula (PB) (Ar, X, in any part of the R _123, the general formula of (PA) - (D) - (E) -
(Binding to (F)).

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In the formula, Ar is a well-known type of substituent at the 1-position of the 2-pyrazolin-5-one coupler, for example, an alkyl group, a substituted alkyl group (for example, haloalkyl such as fluoroalkyl, cyanoalkyl, benzylalkyl, etc.), substituted or An unsubstituted heterocyclic group (eg, 4-pyridyl, 2-thiazoyl), a substituted or unsubstituted aryl group (an alkyl group (eg, methyl, ethyl), an alkoxy group (eg, Methoxy, ethoxy), aryloxy group (eg, phenyloxy), alkoxycarbonyl group (eg, methoxycarbonyl), acylamino group (eg, acetylamino), carbamoyl group, alkylcarbamoyl group (eg, methylcarbamoyl, ethylcarbamoyl), dialkylcarbamoyl group ( For example, dimethylcarbamoyl), arylcarbamoyl group (eg, phenylcarbamoyl), alkylsulfonyl group (eg, methylsulfonyl), arylsulfonyl group (eg, phenylsulfonyl), alkylsulfonamide group (eg, methanesulfonamide), arylsulfonamide group (eg, phenyl) Sulfonamides), sulfamoyl groups, alkylsulfamoyl groups (eg, ethylsulfamoyl), dialkylsulfamoyl groups (eg, dimethylsulfamoyl), alkylthio groups (eg, phenylthio), cyano groups, nitro groups, halogen atoms (eg, Fluorine, chlorine, bromine, etc.). When two or more substituents are present, they may be the same or different. Particularly preferred substituents include a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group, and a cyano group. ].

R ₂₃ is an unsubstituted or substituted anilino group, an acylamino group (eg, alkylcarbonamide, phenylcarbonamide, alkoxycarbonamide, phenyloxycarbonamide), a ureido group (eg, alkylureido, phenylureido), a sulfonamide group Represents a halogen atom (eg, fluorine, chlorine, bromine, etc.), a linear or branched alkyl group (eg, methyl, t-butyl, octyl, tetradecyl), an alkoxy group (eg, methoxy, Ethoxy, 2-
Ethylhexyloxy, tetradecyloxy), acylamino group (for example, acetamido, benzamido, butanamido, octanamido, tetradecanamido, α-
(2,4-di-tert-amylphenoxy) acetamide, α- (2,4-di-tert-amylphenoxy) butyramide, α- (3 pentadecylphenoxy) hexanamide, α- (4-hydroxy-3- tert-butylphenoxy) tetradecaneamide, 2-oxo-pyrrolidin-1-yl, 2-oxo-5-tetradecylpyrrolidin-1-yl, N-methyl-tetradecanamido), a sulfonamide group (for example, methanesulfonamide, Benzenesulfonamide, ethylsulfonamide, p-toluenesulfonamide, octanesulfonamide, p-dodecylbenzenesulfonamide, N-methyl-tetradecanesulfonamide), sulfamoyl group (for example, sulfamoyl, N-methylsulfamoyl, N- Ethyl sulfamoyl, N, N-di Chill sulfamoyl, N,
N-dihexylsulfamoyl, N-hexadecylsulfamoyl, N- [3- (dodecyloxy) -propyl] sulfamoyl, N- [4- (2,4-di-tert-
Amylphenoxy) butyl] sulfamoyl, N-methyl-N-tetradecylsulfamoyl), carbamoyl group (for example, N-methylcarbamoyl, N-butylcarbamoyl, N-octadecylcarbamoyl, N- [4-
(2,4-di-tert-amylphenoxy) butyl] carbamoyl, N-methyl-N-tetradecylcarbamoyl), diacylamino group (N-succinimide, N-phthalimide, 2,5-dioxo-1-oxazolidinyl, 3 -Dodecyl-2,5-dioxo-1-hydantoinyl, 3- (N-acetyl-N-dodecylamino) succinimide), alkoxycarbonyl group (for example, methoxycarbonyl, tetradecyloxycarbonyl, benzyloxycarbonyl), alkoxysulfonyl group (Eg, methoxysulfonyl, butoxysulfonyl, octyloxysulfonyl, tetradecyloxysulfonyl), aryloxysulfonyl group (eg, phenoxysulfonyl, p-methylphenoxysulfonyl, 2,
4-di-tert-amylphenoxysulfonyl), alkanesulfonyl group (eg, methanesulfonyl, ethanesulfonyl, octanesulfonyl, 2-ethylhexylsulfonyl, hexadecanesulfonyl), arylsulfonyl group (eg, benzenesulfonyl, 4-nonylbenzenesulfonyl) An alkylthio group (eg, methylthio, ethylthio, hexylthio, benzylthio, tetradecylthio, 2- (2,4-di-tert-amylphenoxy) ethylthio), an arylthio group (eg, phenylthio, p-tolylthio), alkyloxycarbonyl An amino group (eg, methoxycarbonylamino, ethyloxycarbonylamino, benzyloxycarbonylamino, hexadecyloxycarbonylamino), an alkylureido group (eg, N- methylureido, N, N- dimethylureido, N- methyl -N- dodecyl ureido,
N-hexadecyl ureide, N, N-dioctadecyl ureide), acyl group (for example, acetyl, benzoyl,
Octadecanoyl, p-dodecaneamidobenzoyl),
Examples thereof include a nitro group, a carboxyl group, a sulfo group, a hydroxy group, and a trichloromethyl group. However, among the above substituents, those defined as alkyl groups have 1 to 36 carbon atoms, and those defined as aryl groups have 6 to 36 carbon atoms.

Z is a coupling-off group (for example, acetoxy, propanoyloxy, benzoyloxy, ethoxyoxaloyloxy, pyruvinyloxy, cinnamoyl) linked by a hydrogen atom, a halogen atom (eg, chlorine or bromine) or an oxygen atom. Oxy, phenoxy, 4-cyanophenoxyl, 4-titanium sulfonamidophenoxy, α
-Naphthoxy, 4-cyanoxyl, 4-methanesulfonamido-phenoxy, α-naphthoxy, 3-pendadecylphenoxy, benzyloxycarbonyloxy, ethoxy, 2-cyanoethoxy, benzyloxy, 2-phenethyloxy, 2-phenoxy-ethoxy , 5-phenyltetrazolyloxy, 2-benzothiazolyloxy), those described in coupling-off groups linked by a nitrogen atom (for example, JP-A-59-99437), specifically benzenesulfone Amide, N-ethyltoluenesulfonamide, heptafluorobutanamide, 2,
3,4,5,6-pentafluorobenzamide, octanesulfonamide, p-cyanophenylureido, N,
N-diethylsulfamoylamino, 1-piperidyl,
5,5-dimethyl-2,4-dioxo-3-oxazolidinyl, 1-benzyl-5-ethoxy-3-hydantoinyl, 2-oxo-1,2-dihydro-1-pyridinyl, imidazolyl, pyrazolyl, 3,5- Diethyl-
1,2,4-triazol-1-yl, 5- or 6-
Bromo-benzotriazol-1-yl, 5-methyl-
1,2,3,4-triazol-1-yl group, benzimidazolyl), a coupling-off group linked by a sulfur atom (for example, phenylthio, 2-carboxyphenylthio, 2-methoxy-5-octylphenylthio, 4- Methanesulfonylphenylthio, 4-octanesulfonamidophenylthio, benzylthio, 2-cyanoethylthio, 5-phenyl-2,3,4,5-tetrazolylthio, 2-benzothiazolyl). Preferred is a coupling-off group connected by a nitrogen atom, and particularly preferred is a pyrazolyl group.

E represents an unsubstituted or substituted alkylene group having 1 to 10 carbon atoms, an aralkylene group or a phenylene group, and the alkylene group may be linear or branched. Examples of the alkylene group include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene, aralkylene groups such as benzylidene, and phenylene groups such as p-phenylene, m-phenylene, and methyl. There is phenylene.

As the substituent for the alkylene group, aralkylene group or phenylene group represented by E, aryl group (for example, phenyl), nitro group, hydroxyl group, cyano group,
Sulfo group, alkoxy group (eg, methoxy), aryloxy group (eg, phenoxy), acyloxy group (eg, acetoxy), acylamino group (eg, acetylamino), sulfonamide group (eg, methanesulfonamide), sulfamoyl group (eg, methylsulfa Moyl), a halogen atom (eg, fluorine, chlorine, bromine), a carboxy group, a carbamoyl group (eg, methylcarbamoyl), an alkoxycarbonyl group (eg, methoxycarbonyl), a sulfonyl group (eg, methylsulfonyl), and the like. When two or more substituents are present, they may be the same or different.

Next, examples of non-color-forming ethylene-like monomers which do not couple with an oxidized aromatic primary amine developer which can be copolymerized with the coupler monomer represented by the formula (PA) include, for example, Acrylates, methacrylates, crotonic esters, vinyl esters, maleic diesters, fumaric diesters, itaconic diesters, acrylamides, methacrylamides, vinyl ethers, styrenes and the like.

Specific examples of these monomers are shown below. As the acrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate,
Isopropyl acrylate, n-butyl acrylate,
Isobutyl acrylate, tert-butyl acrylate,
Hexyl acrylate, 2-ethylhexyl acrylate, acetoxyethyl acrylate, phenyl acrylate, 2-methoxy acrylate, 2-ethoxy acrylate, 2- (2-methoxy ethoxy) ethyl acrylate, and the like. Methacrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, tert
-Butyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate, 2-ethoxyethyl methacrylate and the like. Crotonic acid esters include butyl crotonate, hexyl crotonate and the like. Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxy acetate, and vinyl benzoate. Examples of the maleic acid diester include diethyl maleate, dimethyl maleate, dibutyl maleate and the like. Examples of the fumaric acid diester include diethyl fumarate, dimethyl fumarate, dibutyl fumarate, and the like. Examples of the itaconic acid diester include diethyl itaconate, dimethyl itaconate, and dibutyl itaconate. As acrylamides, acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide, n-butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide,
2-methoxyethylacrylamide, dimethylacrylamide, diethylacrylamide, phenylacrylamide, and the like. Examples of the methacrylamides include methyl methacrylamide, ethyl methacrylamide, n-butyl methacrylamide, tert-butyl methacrylamide, 2-methoxy methacrylamide, dimethyl methacrylamide, and diethyl methacrylamide.
Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether and the like. Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, chloromethyl styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, and vinyl benzoate. Acid methyl ester, 2-methylstyrene and the like.

Examples of other monomers include allyl compounds (eg, allyl acetate), vinyl ketones (eg, methyl vinyl ketone), vinyl heterocyclic compounds (eg, vinylpyridine), glycidyl esters (eg, glycidyl acrylate), and unsaturated monomers. Nitriles (eg, acrylonitrile), acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate (eg, monomethyl itaconate), monoalkyl maleate (eg, monomethyl maleate), citraconic acid, vinyl sulfonic acid, acryloyloxy Alkyl sulfonic acids (eg,
Acryloyloxymethylsulfonic acid), acrylamidoalkylsulfonic acid (eg, 2-acrylamide-2)
-Methylethanesulfone) and the like. These acids may be salts of alkali metals (eg, Na, K) or ammonium ions.

Among these monomers, preferably used comonomers include acrylic esters, methacrylic esters, styrenes, maleic esters, acrylamides and methacrylamides. Two or more of these monomers may be used in combination. When two or more kinds are used in combination, examples thereof include n-butyl acrylate and styrene, n-butyl acrylate and butyl styrene, and t-butyl methacrylamide and n-butyl acrylate.

The proportion of the colored portion corresponding to the general formula (PB) in the magenta polymer coupler is usually 5 to 8
Although 0% by weight is desirable, 30 to 70% by weight is preferable in terms of color reproduction and stability in terms of color reproduction. In this case, the equivalent molecular weight (gram number of polymer containing 1 mole of monomer coupler) is about 250 to 4,000, but is not limited thereto.

The polymer coupler used in the present invention is added to a silver halide emulsion layer or a layer adjacent thereto. The magenta polymer coupler is based on the coupler monomer, and in the case of the same layer as silver halide, 0.005 per mol of silver.
It is good to add mol to 0.5 mol, preferably 0.03 to 0.25 mol. When the magenta polymer coupler is used for the non-photosensitive layer, the coating amount is 0.01 g / m ² or more.
1.0 g / m ² , preferably 0.1 g / m ^{2 to} 0.5 g
/ M ² .

The polymer coupler used in the present invention is prepared by dispersing a lipophilic polymer coupler obtained by polymerization of a monomer coupler as described above in an organic solvent in the form of latex in an aqueous gelatin solution. May be
Alternatively, it may be made by a direct emulsion polymerization method.

A method for emulsifying and dispersing a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution is described in US Pat. No. 3,451,820, and emulsion polymerization is described in US Pat. Nos. 4,080,211 and 3,080. 370,952
And EP 341 088 A2. The synthesis of the above magenta polymer coupler was carried out by using a polymerization initiator and a polymerization solvent as disclosed in
-5543, JP-A-57-94752, JP-A-57-94752
Compounds described in JP-A-176038, JP-A-57-204038, JP-A-58-28745, JP-A-58-10738, JP-A-58-42044, and JP-A-58-145944. Perform using

The polymerization temperature must be set in relation to the molecular weight of the polymer to be produced, the type of initiator, and the like. The polymerization temperature can be from 0 ° C. or lower to 100 ° C. or higher, but is usually from 30 ° C. to 10 ° C.
Polymerizes in the range of 0 ° C. Next, specific examples of the magenta polymer coupler that can be used in the present invention will be described, but the present invention is not limited thereto. (Subscript numbers represent molar ratios.)

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The light-sensitive material of the present invention only needs to have at least one of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support. There is no particular limitation on the number and order of the silver halide emulsion layer and the non-photosensitive layer. A typical example is a silver halide photographic light-sensitive material having at least one light-sensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities on a support. Wherein the photosensitive layer is blue light, green light,
And a unit light-sensitive layer having color sensitivity to any of red light and a multilayer silver halide color photographic light-sensitive material. In general, the arrangement of the unit light-sensitive layers is, in order from the support side, a red light-sensitive layer, The color-sensitive layer and the blue color-sensitive layer are provided 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 color-sensitive layers are sandwiched between the same color-sensitive layers. Non-light-sensitive layers such as various intermediate layers may be provided between the silver halide light-sensitive layers and as the uppermost layer and the lowermost layer.

The intermediate layer is described in JP-A-61-43748.
No. 59-113438, No. 59-113440
Couplers, DIR compounds and the like described in JP-A Nos. 61-20037 and 61-20038 may be contained, and a color mixture inhibitor may be contained as usually used.

As described in West German Patent 1,121,470 or British Patent 923,045, a plurality of silver halide emulsion layers constituting each unit light-sensitive layer may be composed of a high-sensitivity emulsion layer and a low-sensitivity emulsion layer. A two-layer structure of layers can be preferably used. Usually, it is preferable to arrange them so that the light sensitivity decreases sequentially toward the support, and a non-photosensitive layer may be provided between the respective halogen emulsion layers. Also,
JP-A-57-112751, 62-200350
As described in JP-A-62-206541 and JP-A-62-206543, a low-speed emulsion layer may be provided on the side farther from the support and a high-speed emulsion layer may be provided on the side closer to the support.

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

As described in JP-B-55-34932, the layers may be arranged in the order of blue-sensitive layer / GH / RH / GL / RL from the side farthest from the support. JP-A-56-25738 and JP-A-62-6393.
As described in the specification of JP-A No. 6, the blue light-sensitive layer / GL / RL / GH / RH may be arranged in this order from the farthest side from the support.

As described in JP-B-49-15495, the upper layer is the silver halide emulsion layer having the highest sensitivity, the middle layer is the silver halide emulsion layer having a lower sensitivity, and the lower layer is the middle layer. In addition, an arrangement is also possible in which a silver halide emulsion layer having a lower sensitivity is arranged, and an arrangement of three layers having different sensitivities in which the sensitivities are successively decreased toward the support. Even in the case of three layers having different sensitivities, as described in JP-A-59-202264, a medium-sensitivity emulsion from the side farther from the support in the same color-sensitive layer. Layers / high-speed emulsion layers / low-speed emulsion layers. 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. In addition, the arrangement may be changed as described above even in the case of four or more layers.

In order to improve color reproducibility, US Pat. Nos. 4,663,271, 4,705,744, and 4,707,436, JP-A-62-160448.
And BL and G described in JP-A-63-89580.
It is preferable that a donor layer (CL) having a multilayer effect having a spectral sensitivity distribution different from that of the main photosensitive layer such as L and RL is disposed adjacent to or close to the main photosensitive layer. As described above, various layer configurations and arrangements can be selected according to the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is about 30 mol%.
It is silver iodobromide, silver iodochloride, or silver iodochlorobromide containing the following silver iodide. Particularly preferred is about 2 mol%
Silver iodobromide or silver iodochlorobromide containing from about 1 to about 25 mol% of silver iodide.

The silver halide grains in the photographic emulsion include those having regular crystals such as cubic, octahedral and tetradecahedral, those having irregular crystalline forms such as spherical and plate-like,
It may have a crystal defect such as a twin plane or a composite form thereof. The grain size of silver halide is about 0.2 μm
The following fine particles or large-sized particles having a projected area diameter of about 10 μm may be used, and a polydisperse emulsion or a monodisperse emulsion may be used.

The silver halide photographic emulsion usable in the present invention is, for example, Research Disclosure (RD) No.
17643 (December 1978), pp. 22-23, "
I. Emulsion preparation and types ",
No. 18716 (November 1979), 648
No. 307105 (November 1989), 863
865 pages, Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P. Glafkides, Chemie et Phisique Ph.
otographique, Paul Montel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (GF Duffin,
Photographic Emulsion Chemistry (Focal Press, 196
6)), "Manufacture and coating of photographic emulsions" by Zelikman et al., Published by Focal Press (VL Zelikman et al., Making an
d Coating Photographic Emulsion, Focal Press, 196
It can be prepared using the method described in 4).

US Pat. Nos. 3,574,628;
Monodisperse emulsions described in, for example, 655,394 and British Patent 1,413,748 are also preferable. Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention. Tabular grains are described in Photographic Science and Engineering (Gutoff,
Photographic Science and Engineering), Volume 14,
248-257 (1970); U.S. Pat.
4,226, 4,414,310, 4,43
It can be easily prepared by the methods described in 3,048, 4,439,520 and British Patent 2,112,157.

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

The above emulsion may be of a surface latent image type formed on the surface by using a latent image as a seed, an internal latent image type formed inside the grains, or a type having a latent image on both the surface and the inside. It must be a negative emulsion. Of the internal latent image type, the core / core described in JP-A-63-264740 is used.
It may be a shell type internal latent image type emulsion. A method for preparing this core / shell type internal latent image type emulsion is described in JP-A-59-13.
No. 3542. The thickness of the shell of this emulsion varies depending on the development process and the like, but is preferably 3 to 40 nm, particularly preferably 5 to 20 nm.

As the silver halide emulsion, usually, those subjected to physical ripening, chemical ripening and spectral sensitization are used. The additives used in such a process are described in Research Disclosure Nos. 17643, 18716 and N
o. 307105, and the relevant portions are summarized in the table below. In the light-sensitive material of the present invention, two types of emulsions having at least one characteristic different from one another in the grain size, grain size distribution, halogen composition, grain shape and sensitivity of the photosensitive silver halide emulsion are mixed in the same layer. Can be used.

The silver halide grains having a fogged surface described in US Pat. No. 4,082,553, and the inside of the grains described in US Pat. No. 4,626,498 and JP-A-59-214852 are covered. Silver halide grains and colloidal silver can be preferably used in a photosensitive silver halide emulsion layer and / or a substantially light-insensitive hydrophilic colloid layer. A silver halide grain having a grain inside or a surface fogged is
This refers to silver halide grains that can be uniformly (non-imagewise) developed irrespective of unexposed portions and exposed portions of the photosensitive material. A method for preparing silver halide grains having the inside or the surface of the grains fogged is described in U.S. Pat. No. 4,626,498 and JP-A-59-214852.

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

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

The fine grain silver halide preferably has an average grain size (average value of the circle equivalent diameter of the projected area) of 0.01 to 0.5 μm, more preferably 0.02 to 0.2 μm. Fine grain silver halide can be prepared by the same method as that for ordinary photosensitive silver halide. In this case, the surface of the silver halide grains is
There is no need for optical sensitization, and no spectral sensitization is required. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, benzothiazolium-based, or mercapto-based compound or a zinc compound in advance. Colloidal silver can be preferably contained in the layer containing fine silver halide grains. The coated silver amount of the light-sensitive material of the present invention is preferably not more than 6.0 g / m ² , and is 4.5.
g / m ² or less is most preferred.

Known photographic additives which can be used in the present invention are also described in the above three Research Disclosures, and the relevant portions are shown in the following table. Type of additive RD17643 RD18716 RD307105 1 Chemical sensitizer page 23, page 648, right column, page 866 2 Sensitivity enhancer, page 648, right column 3 Spectral sensitizer, page 23-24, page 648, right column 866-868 Super sensitization 〜49 right column 4 Brightener 24 page 868 5 Antifoggant 24-25 page 649 right column 868-870 and stabilizer 6 light absorber, 25-26 page 649 right column-873 filter Dye 650 page left column UV absorber 7 Stain inhibitor 25 page right column 650 page left column 872 to right column 8 Dye image stabilizer 25 page 650 page left column 872 9 hardener 26 page 651 left column 874 to Page 875 10 Binder page 26 Same as above 873 to 874 11 Plasticizers and lubricants page 27 650 right side column 876 page 12 Coating aids, page 26 to 27 Same as above 875 to 876 Surfactant 13 Static prevention page 27 Same as above 876 to 876 Page 877 Stopper 14 Matting agent 878 to 879

Further, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add a compound capable of reacting with formaldehyde described in JP-A No. 87 or 4,435, 503 and immobilizing the same to the light-sensitive material. In the light-sensitive material of the present invention, U.S. Patent Nos. 4,740,454 and 4,788,132 are used.
JP-A-62-18539, JP-A-1-28355
It is preferable to include the mercapto compound described in No. 1 above. Compounds which release a fogging agent, a development accelerator, a silver halide solvent or a precursor thereof irrespective of the amount of developed silver produced by the development processing described in JP-A-1-106052. Is preferably contained. The light-sensitive material of the present invention may be added to International Publication WO88 / 04.
Nos. 794 and 317, 308A, U.S. Pat. No. 4,420,555, and JP-A-1-259358.
It is preferable to include the dye described in (1).

Various color couplers can be used in the present invention, and specific examples thereof are described in Research Disclosure (RD) Nos. 17643, VII-CG and VII-CG and Nos. 307105 and VII-C. -G are described in the patents. As the yellow coupler, for example, U.S. Pat. Nos. 3,933,501 and 4,022,6
No. 20, No. 4,326,024, No. 4,401,
No. 752, No. 4,248,961, No. 58-1
No. 0739, British Patent Nos. 1,425,020 and 1,476,760, US Pat. No. 3,973,968
No. 4,314,023, No. 4,511,64
No. 9, EP 249,473A, etc. are preferred.

As the magenta coupler, 5-pyrazolone-based and pyrazoloazole-based compounds are preferred, and US Pat. Nos. 4,310,619 and 4,351,897.
No. 3,073,636; U.S. Pat.
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (June 1984)
), JP-A-60-33552, Research Disclosure No. 24230 (June 1984), JP-A-60-43659, JP-A-61-72238, and JP-A-60-72238.
No. 35730, No. 55-118034, No. 60-18
No. 5,951, U.S. Pat. Nos. 4,500,630, 4,540,654, 4,556,630, and WO88 / 04795 are particularly preferable.

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

Typical examples of polymerized dye-forming couplers are described in US Pat. Nos. 3,451,820 and 4,082.
No. 0,211, No. 4,367,282, No. 4,4
Nos. 09,320, 4,576,910, British Patent 2,102,137, and European Patent No. 341,188A.

Examples of couplers in which a coloring dye has an appropriate diffusibility include US Pat. No. 4,366,237, British Patent No. 2,125,570, European Patent No. 96,570, and West German Patent No. 3 (published). , 234, 533 are preferred.

A colored coupler for correcting unnecessary absorption of a coloring dye is described in Research Disclosure No.
VII-G of 17643, VII-G of No. 307105
Section G, U.S. Pat. No. 4,163,670, JP-B-57-
39413, U.S. Pat. Nos. 4,004,929 and 4,138,258, British Patent 1,146,368.
Those described in the above item are preferred. Also, U.S. Pat.
A coupler for correcting unnecessary absorption of a coloring dye by a fluorescent dye released at the time of coupling described in No. 4,181,
It is also preferable to use a coupler having a dye precursor group capable of forming a dye by reacting with a developing agent described in US Pat. No. 4,777,120 as a leaving group.

Compounds which release a photographically useful residue upon coupling can also be preferably used in the present invention.
The DIR coupler releasing the development inhibitor is the RD1 described above.
No. 7643, Section VII-F and No. 307105, VII-
Patent described in section F, JP-A-57-151944,
Preferred are those described in JP-A-57-154234, JP-A-60-184248, JP-A-63-37346, JP-A-63-37350 and U.S. Pat. Nos. 4,248,962 and 4,782,012.

The bleaching accelerator releasing couplers described in RD Nos. 11449 and 24241 and JP-A-61-201247 are effective for shortening the time of the processing step having bleaching ability. The effect is great when added to a light-sensitive material using silver halide grains.

As a coupler which releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2,099
7,140,2,131,188, JP-A-59
Preferred are those described in JP-A-157638 and JP-A-59-170840. Also, JP-A-60-107029, JP-A-60-252340, JP-A-1-44940 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 an oxidation-reduction reaction with an oxidized form of a developing agent described in JP-A-45687.

Other compounds that can be used in the light-sensitive material of the present invention include US Pat. No. 4,130,427.
No. 4,283,4.
No. 72, No. 4,338,393, No. 4,310,
No. 618, etc .;
No. 5950, Japanese Patent Application Laid-Open No. 62-24252, and the like.
R redox compound releasing couplers, DIR coupler releasing couplers, DIR coupler releasing redox compounds or DIR redox releasing redox compounds, couplers capable of releasing dyes which discolor after release as described in EP 173,302A and EP 313,308A A ligand releasing coupler described in U.S. Pat. No. 4,555,477, a leuco dye releasing coupler described in JP-A-63-75747, and a fluorescent dye described in U.S. Pat. No. 4,774,181. Emitting couplers and the like.

The coupler used in the present invention can be introduced into a light-sensitive material by various known dispersion methods. Examples of high boiling solvents used in the oil-in-water dispersion method are described in US Pat.
No. 027, etc. Specific examples of the high-boiling organic solvent having a boiling point at normal pressure of 175 ° C. or higher used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis (2,4-
Di-t-amylphenyl) phthalate, bis (2,4-
Di-t-amylphenyl) isophthalate, bis (1,
Esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxy) Ethyl phosphate,
Trichloropropyl phosphate, di-2-ethylhexylphenylphosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-hydroxybenzoate, etc.), amides (N, N-diethyldodecaneamide, N , N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2,4-di-t-amylphenol etc.), aliphatic carboxylic acid esters (bis (2-ethylhexyl) ) Sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N, N-dibutyl-2-butoxy-5-t-octyl aniline, etc.) Hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene), and the like. As the auxiliary solvent, an organic solvent having a boiling point of about 30 ° C. or more, preferably 50 ° C. or more and about 160 ° C. or less can be used, and typical examples are ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 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. 4,199,36.
No. 3, 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 and JP-A-63-257747 and JP-A-62-272248 are used.
And JP-A-1-80941, 1,2-benzisothiazolin-3-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol, 2-phenoxyethanol,
It is preferable to add various preservatives or fungicides such as (4-thiazolyl) benzimidazole.

The present invention can be applied to various color light-sensitive materials. Typical examples include color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers.

Suitable supports that can be used in the present invention are described, for example, in RD. No. 17643, page 28, and No. 18
No. 716, from the right column on page 647 to the left column on page 648;
07105, page 897. In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 28 μm or less, and 23 μm or less.
Or less, more preferably 18 μm or less,
Particularly preferably, it is 16 μm or less. Also, the film swelling speed T _1/2
Is preferably 30 seconds or less, more preferably 20 seconds or less.
The film thickness means a film thickness measured under humidity control at 25 ° C. and a relative humidity of 55% (2 days), and the film swelling rate T _1/2 can be measured according to a method known in the art. For example, Photographic Science and Engineering (Phot) by A. Green et al.
ogr. Sci Eng.), 19 vol., No. 2, by using the type of Swellometer described (swelling meter) pp 124-129, can be measured, T _1/2 is 30 ° C. with a color developer, 1/3
90% of the maximum swollen film thickness reached when the treatment is performed for 5 seconds is defined as the saturated film thickness, 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 hardening agent to gelatin as a binder or by changing the aging conditions after coating. The swelling ratio is preferably from 150 to 400%. The swelling ratio is calculated from the maximum swelling film thickness under the conditions described above by the following formula:
It can be calculated according to (maximum swollen film thickness-film thickness) / film thickness. The light-sensitive material of the present invention preferably has a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. In this back layer, the above-mentioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer,
It is preferable to include a lubricant, a coating aid, a surfactant and the like. The swelling ratio of the back layer is preferably from 150 to 500%.

The color photographic light-sensitive material according to the present invention is prepared according to the RD. No. 17643, pp. 28-29, No. 18
716, pages 880 to 881 of No. 307105.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution mainly containing an aromatic primary amine-based color developing agent. Aminophenol compounds are also useful as the color developing agent, but p-phenylenediamine compounds are preferably used, and a typical example thereof is 3-methyl-4-amino-
N, N-diethylaniline, 3-methyl-4-amino-
N-ethyl-N-β-hydroxyethylaniline, 3-
Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-
N-ethyl-N-β-methoxyethylaniline and sulfates, hydrochlorides or p-toluenesulfonates thereof. Among these, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylaniline sulfate is preferred. These compounds can be used in combination of two or more depending on the purpose.

The color developing solution may be a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt,
It generally contains a development inhibitor or an antifoggant such as a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfite, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazide, triethanolamine, catecholsulfonic acid, ethylene glycol, diethylene glycol Organic solvents such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers,
Auxiliary developing agents such as 1-phenyl-3-pyrazolidone; viscosity-imparting agents; various chelating agents represented by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids; Acetic 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'-
Tetramethylene phosphonic acid, ethylenediamine-di (o
-Hydroxyphenylacetic acid) and their salts.

When the reversal process is performed, color development is usually performed after black and white development. A known black-and-white developing agent such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone or aminophenols such as N-methyl-p-aminophenol is used alone in the black-and-white developer. Alternatively, they can be used in combination. The color developing solution and the black-and-white developing solution generally have a pH of 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the photographic material, and is reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also. When the replenishment rate is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with the air.

The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below. That is, aperture ratio = [contact area between processing solution and air (cm ² )] ÷
[Capacity of treatment liquid (cm ³ )] The above opening ratio is preferably 0.1 or less, more preferably 0.001 to 0.
05. As a method of reducing the aperture ratio in this way, in addition to providing a shield 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, No. 63-216050, for example. Reducing the aperture ratio is not only a step of color development and a step of black-and-white development, but also various subsequent steps, for example, bleaching, bleach-fixing,
It is preferably applied in all steps such as fixing, washing and stabilization. Further, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for the color development processing is usually set between 2 and 5 minutes. The processing time can be further reduced by using a high temperature, a high pH, and a high concentration of the color developing agent. Can also.

The photographic emulsion layer after color development is usually subjected to bleaching. The bleaching process may be performed simultaneously with the fixing process (bleach-fixing process) or may be performed individually. In order to further speed up the processing, a processing method of performing bleach-fixing after bleaching may be used. Furthermore, processing in two continuous bleach-fixing baths, fixing before bleach-fixing, or bleaching after bleach-fixing can be arbitrarily performed according to the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds and the like are used. Representative bleaching agents include organic complex salts of iron (III) such as amino diamines such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraacetic acid. Polycarboxylic acids or complex salts of citric acid, tartaric acid, malic acid and the like can be used. Among these, iron (III) complex salts of aminopolycarboxylic acid such as iron (III) complex salt of ethylenediaminetetraacetate and 1,3-diaminopropanetetraacetate are preferred from the viewpoint of rapid treatment and prevention of environmental pollution. . Further, the iron (III) complex salt of aminopolycarboxylic acid is particularly useful in a bleaching solution and a 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 the processing can be performed at a lower pH in order to speed up the processing. .

In the bleaching solution, the bleach-fixing solution and the prebath thereof, a bleaching accelerator can be used if necessary.
Specific examples of useful bleach accelerators are described in the following specification: U.S. Pat. No. 3,893,858, West German Patent Nos. 1,290,812, 2,059,988, JP Nos. 53-32736, 53-57831, 53
No. 37418, No. 53-72623, No. 53-95
No. 630, No. 53-95731, No. 53-10423
No. 2, No. 53-124424, No. 53-141623
Compounds having a mercapto group or a disulfide group described in Research Disclosure No. 17129 (July, 1978); thiazolidine derivatives described in JP-A-50-140129; -8506, JP-A-52-20832
No. 53-32735, U.S. Pat. No. 3,706,5
No. 61; thiourea derivative; West German Patent No. 1,12
7,715; iodide salts described in JP-A-58-16235; West German Patent Nos. 966,410 and 2,748,4.
Polyoxyethylene compounds described in No. 30;
Polyamine compounds described in JP-A-5-8836; and JP-A-49-40943, JP-A-49-59644 and JP-A-53-96444
No. 94927, No. 54-35727, No. 55-265
Nos. 06 and 58-163940; bromide ions and the like. Among them, a compound having a mercapto group or a disulfide group is preferred in view of a large accelerating effect, and in particular, U.S. Pat. No. 3,893,858, West German Patent 1,290,812, and JP-A-53-95630.
Are preferred. Further, U.S. Pat.
Compounds described in 552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material. These bleaching accelerators are particularly effective when bleach-fixing a color photographic material for photography.

It is preferable that the bleaching solution and the bleach-fixing solution contain an organic acid in addition to the above compounds for the purpose of preventing bleaching stain. Particularly preferred organic acids are compounds having an acid dissociation constant (pka) of 2 to 5, specifically acetic acid,
Propionic acid and the like are preferred.

Examples of the fixing agent used in the fixing solution or the bleach-fixing solution include thiosulfates, thiocyanates, thioether compounds, thioureas, and a large amount of iodides. Is common, and in particular, ammonium thiosulfate can be used most widely. It is also preferable to use a combination of a thiosulfate with a thiocyanate, a thioether-based compound, thiourea, or the like. As a preservative of the fixing solution or the bleach-fixing solution, a sulfite, a bisulfite, an adduct of carbonyl bisulfite, or a sulfinic acid compound described in European Patent No. 294,769A is preferable. Further, it is preferable to add various aminopolycarboxylic acids or organic phosphonic acids to the fixing solution or the bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixing solution or the bleach-fixing solution contains a compound having a pKa of 6.0 to 9.0, preferably imidazole, 1-methylimidazole, 1-ethylimidazole, It is preferable to add imidazoles such as methyl imidazole in an amount of 0.1 to 10 mol / l.

It is preferable that the total time of the desilvering step is shorter as long as defective desilvering does not occur. Preferred time is 1 minute to 3
Minutes, more preferably 1 minute to 2 minutes. Further, the processing temperature is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C. In a preferred temperature range, the desilvering speed is improved,
In addition, the occurrence of stain after processing is effectively prevented.

In the desilvering step, it is preferable that stirring is strengthened as much as possible. Specific examples of the method of strengthening the stirring include a method described in JP-A-62-183460, in which a jet of a processing solution is caused to impinge on the emulsion surface of a light-sensitive material.
No. 183461, a method of increasing the stirring effect by using the rotating means, and furthermore, by moving the photosensitive material while bringing the wiper blade provided in the liquid into contact with the emulsion surface, and making the emulsion surface turbulent, the stirring effect is improved. And a method of increasing the circulating flow rate of the entire processing liquid. Such a stirring improving means is effective for 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 increases the desilvering speed. The means for improving the stirring is more effective when a bleaching accelerator is used, and can remarkably increase the accelerating effect or eliminate the fixing inhibition effect of the bleaching accelerator.

The automatic developing machine used for processing the light-sensitive material of the present invention is described in JP-A-60-191257 and JP-A-60-191257.
It is preferable to have the photosensitive material conveying means described in JP-A Nos. 1258 and 60-191259. Japanese Unexamined Patent Publication No. Sho 6
As described in Japanese Patent Application No. 0-191257, such a conveying means can significantly reduce the carry-in of the processing liquid from the pre-bath to the post-bath, and is highly effective in preventing the performance of the processing liquid from deteriorating. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

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

According to the multistage countercurrent method described in the above-mentioned document,
Although the amount of washing water can be greatly reduced, the increase in the residence time of the water in the tank causes a problem that bacteria proliferate and generated floating substances adhere to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, a method for reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Also, Japanese Patent Application Laid-Open No.
No. 8542, isothiazolone compounds, thiabendazoles, chlorinated bactericides such as chlorinated sodium isocyanurate, and other benzotriazoles. "Sterilization, Sterilization, and Mold Prevention Technology of Microorganisms" edited by the Sanitation Technology Society (1982
The fungicide described in "Encyclopedia of Bactericidal and Fungicides" (ed. 1986), edited by the Japan Society of Bacteria and Fungi.

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

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

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

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up the processing. In order to incorporate the color developing agent, it is preferable to use various precursors of a color developing agent. For example, U.S. Pat.
Nos. 342,597; 3,342,599; Schiff base compounds described in Research Disclosure Nos. 14850 and 15159; and aldol compounds described in No. 13924. And metal salt complexes described in U.S. 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 comprises:
If necessary, various 1-
Phenyl-3-pyrazolidones may be incorporated. Typical compounds are described in JP-A-56-64339 and JP-A-57-14.
No. 4547 and No. 58-115438.

Various processing solutions in the present invention may be used at a temperature of 10 ° C. to 50 ° C.
Used at ° C. Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature promotes the processing and shortens the processing time, and a lower temperature achieves an improvement in the image quality and an improvement in the stability of the processing solution. be able to.

The silver halide light-sensitive material of the present invention is disclosed in US Pat. No. 4,500,626 and JP-A-60-1334.
No. 49, 59-218443, 61-23805
No. 6, EP 210,660 A2 and the like.

[0169]

Next, the present invention will be described in more detail with reference to examples.

Example 1 (Preparation of emulsion) An aqueous solution prepared by dissolving 20 g of inert gelatin, 2.4 g of potassium bromide and 2.05 g of potassium iodide in 800 ml of distilled water was stirred at 58 ° C., and silver nitrate 5 was added thereto. 150 g of an aqueous solution in which 0.0 g was dissolved was added instantaneously, and excess potassium bromide was further added, followed by physical ripening for 20 minutes. Further, according to the method described in U.S. Pat. No. 4,242,445, 0.2 mol / liter, 0.67 mol / liter,
Mol / liter of silver nitrate and an aqueous solution of potassium halide (a mixture of 58 mol% of potassium bromide and 42 mol% of potassium iodide) were added at a flow rate of 10 cc / min to obtain 42 mol% of silver iodobromide grains. Grew. The emulsion was washed with water for desalting. The completed amount of the emulsion a was 900 g. Emulsion a has an average grain size of 0.61 μm.
According to the emulsion a, 0.59 of a silver iodide content of 42 mol%
μm, 0.56 μm, 0.52 μm and 0.46 μm silver iodobromide grains were prepared, and used as emulsions b, c, d and e.

300 g of the emulsion a was added, 850 cc of distilled water and 30 cc of 10% potassium bromide were added, the mixture was heated to 70 ° C. and stirred, and 0.02 g of the compound (18) was added, and pAg was 8.0.
300 cc of an aqueous solution of 33 g of silver nitrate dissolved in
320 cc of an aqueous solution containing 25 g of potassium bromide and 800 g of an aqueous solution containing 100 g of silver nitrate and 860 cc of an aqueous solution containing 75 g of potassium bromide were added simultaneously for 60 minutes. Mol%, 0.88 μm silver iodobromide emulsion 1 was prepared. Emulsion 1 was twin with an aspect ratio of 2.0, and its (111) plane ratio was 80%. A silver iodobromide emulsion 2 having a silver iodide content of 12 mol% was prepared by taking 300 g of the emulsion b and shelling it in the same manner as in the preparation of the emulsion 1 with a total amount of silver nitrate of 125 g. Emulsions 3 to 5 were prepared according to this.

The same conditions as in the preparation of Emulsions 1 to 4 were used except that the conditions of shelling in the method of preparing Emulsions 1 to 4 were changed to a temperature of 60 ° C. and a pAg of 9.0, and the compound (18) was removed. To prepare Emulsions 6 to 9. 133 emulsions
g and emulsion 167g, and emulsion 3 from emulsion c 300g.
In a shell according to the method for preparing Emulsion 10, to prepare Emulsion 10. Emulsion 11 was prepared by taking 50 g of each of emulsions a and d and 200 g of emulsion c and shelling them according to the method of preparing emulsion 3 from 300 g of emulsion c. Further, a method of adjusting emulsions 3 and 4 without using compound (18) was adopted.
Emulsions 12 and 13 were prepared. Table A shows the characteristic values of these emulsions.
Summarized in

The undercoated cellulose triacetate film was coated on a support with multiple layers having the following compositions to prepare Sample 101 as a multilayer color photosensitive material.

(Composition of Photosensitive Layer) The number corresponding to each component indicates the coating amount in g / m ² , and the silver halide indicates the coating amount in terms of silver. However, as for the sensitizing dye, the coating amount is shown in mol unit with respect to 1 mol of silver halide in the same layer.

(Sample 101) First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.18 Gelatin 0.80

Second layer (intermediate layer) 2,5-di-t-pentadecylhydroquinone 0.18 EX-1 0.070 EX-3 0.020 EX-12 2.0 × 10 ^-3 U-10 0.060 U-2 0.080 U-3 0.10 HBS-1 0.10 HBS-2 0.020 Gelatin 0.70

Third layer (first red-sensitive emulsion layer) Emulsion A silver 0.25 Emulsion F silver 0.25 sensitizing dye I 6.9 × 10 ^-5 sensitizing dye II 1.8 × 10 ^-5 sensitization Dye III 3.1 × 10 ^-4 EX-2 0.34 EX-10 0.020 U-1 0.070 U-2 0.050 U-3 0.070 HBS-1 0.005 Gelatin 0.70

Fourth layer (second red-sensitive emulsion layer) Emulsion G silver 1.00 sensitizing dye I 5.1 × 10 ^-5 sensitizing dye II 1.4 × 10 ^-5 sensitizing dye III 2.3 × 10 ^-4 EX-2 0.40 EX-3 0.050 EX-10 0.015 U-1 0.070 U-2 0.050 U-3 0.070 Gelatin 0.95

Fifth Layer (Third Red Sensitive Emulsion Layer) Emulsion I Silver 1.60 Sensitizing Dye I 5.4 × 10 ^-5 Sensitizing Dye II 1.4 × 10 ^-5 Sensitizing Dye III 2.4 × 10 ^-4 EX-2 0.097 EX-3 0.010 EX-4 0.080 HBS-1 0.11 HBS-2 0.05 Gelatin 1.20

Sixth layer (intermediate layer) EX-5 0.040 HBS-1 0.020 Gelatin 0.60

Seventh layer (first green-sensitive emulsion layer) Emulsion A silver 0.15 Emulsion F silver 0.15 sensitizing dye IV 3.0 × 10 ^-5 sensitizing dye V 1.0 × 10 ^-4 sensitization Dye VI 3.8 × 10 ⁻⁴ EX-1 0.021 Preferred Polymer Coupler (P-13) of the Present Invention 0.26 EX-7 0.030 EX-8 0.025 HBS-1 0.10 HBS-3 0.010 gelatin 0.63

Eighth layer (second green-sensitive emulsion layer) Emulsion C silver 0.45 sensitizing dye IV 2.1 × 10 ^-5 sensitizing dye V 7.0 × 10 ^-5 sensitizing dye VI 2.6 × ^10-4 Preferred Polymer Coupler (P-13) of the Present Invention 0.094 EX-7 0.026 EX-8 0.018 HBS-1 0.16 HBS-3 8.0 × 10 ^-3 Gelatin 0.50

Ninth layer (third green sensitive emulsion layer) Emulsion E silver 0.10 sensitizing dye IV 3.5 × 10 ^-5 sensitizing dye V 8.0 × 10 ^-5 sensitizing dye VI 3.0 × 10 ^-4 EX-1 0.025 EX-11 0.10 EX-13 0.010 EX-6 0.025 EX-8 0.010 HBS-1 0.05 HBS-2 0.05 Gelatin 1.05

Tenth layer (yellow filter layer) Yellow colloidal silver Silver 0.050 EX-5 0.080 HBS-1 0.030 Gelatin 0.75

Eleventh layer (first blue-sensitive emulsion layer) Emulsion A silver 0.080 Emulsion B silver 0.070 Emulsion F silver 0.070 Sensitizing dye VII 3.5 × 10 ^-4 EX-8 0.042 EX -9 0.72 HBS-1 0.28 gelatin 1.10

Twelfth Layer (Second Blue-Sensitive Emulsion Layer) Emulsion C Silver 0.45 Sensitizing Dye VII 2.1 × 10 ^-4 EX-9 0.15 EX-10 7.0 × 10 ^-3 HBS-1 0.050 gelatin 0.60

Thirteenth layer (third blue-sensitive emulsion layer) Emulsion H silver 0.77 Sensitizing dye VII 2.2 × 10 ^-4 EX-9 0.20 HBS-1 0.070 Gelatin 0.69

Fourteenth Layer (First Protective Layer) Emulsion I Silver 0.20 U-4 0.11 U-5 0.17 HBS-1 5.0 × 10 ^-2 Gelatin 0.70

Fifteenth layer (second protective layer) H-1 0.30 B-1 (1.7 μm in diameter) 5.0 × 10 ^-2 B-2 (1.7 μm in diameter) 0.10 B-30 .10 S-1 0.20 gelatin 0.80

Further, in order to improve the storability, processability, pressure resistance, fungicidal and antibacterial properties, antistatic properties and coatability of all layers, W-1, W-2, W-3, B- 4, B-5, F-
1, F-2, F-3, F-4, F-5, F-6, F-
7, F-8, F-9, F-10, F-11, F-12,
F-13 and iron salts, lead salts, gold salts, platinum salts, iridium salts, and rhodium salts. Sample 101 had a dry film thickness of 17.5 μm and a swollen film thickness of 24.0 μm.
These samples were prepared by simultaneously coating 15 layers.

The structural formulas of the compounds used in the samples of this example and the following examples are shown below. The emulsions are shown in Tables 1 and 2 below.

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[0214]

[Table 1]

[0215]

[Table 2]

(Samples 102 to 114) Samples 102 to 114 were prepared by replacing Emulsion 1 in the fifth layer of Sample 101 with other emulsions as shown in Tables 3 and 4.

(Samples 115 to 128) The DIR coupler EX-8 of the seventh layer, the eighth layer and the ninth layer of the sample 101 was replaced with the DIR coupler (D-6) of the present invention in an equimolar amount, whereby the samples 115 to 128 were replaced. Produced.

(Sample 129) Couplers of the seventh and eighth layers of Sample 117 (P-13)
Was 1.25 times (P-14) by weight, HBS-1 was 1.2 times, and gelatin was 1.2 times to prepare a sample 129.

(Sample 130) EX-1 was obtained by 1.5 times the weight of (P-13) of Sample 117.
Sample No. 3 was prepared by doubling HBS-1 and doubling gelatin to 1.4 times. The relative sensitivity of the green photosensitive layers of Samples 129 and 130 by color development described below was the same as that of Sample 117. The scratch strength of these samples with a sapphire needle having a diameter of 0.05 mm hardly changed, and it was confirmed that the film strength and the photographic performance were almost the same.

After the green imagewise exposure, the sample 10
Red uniform exposure was carried out so that the cyan density of the green unexposed portion in the following color development was 0.8, and development was performed. Further, the relative sensitivity was determined from the logarithm of the reciprocal of the exposure amount that gave white imagewise exposure and gave the cyan density (fog + 0.4) (sample 10).
1). Furthermore, cyan density (fog + 0.
The RMS value of 4) was determined according to a conventional method. The sharpness of these samples was also determined by a conventional MTF method. Tables 3 and 4 show the obtained results.

The developing process used here was carried out under the following conditions.
C. was performed. The composition of the processing solution used in each step is as follows.

Color developer Sodium nitrilotriacetate 1.0 g Sodium sulfite 4.0 g Sodium carbonate 30.0 g Potassium bromide 1.3 g Hydroxylamine sulfate 2.4 g 4- (N-ethyl-N-β-hydroxyethyl) Amino) -2-methyl-aniline sulfate 4.5 g

Bleaching solution Ammonium bromide 160.0 g Ammonia water (28%) 25.0 ml Ethylenediamine-tetraacetate sodium iron salt 130 g Glacial acetic acid 14 ml Add water 1.0 L

Fixer Sodium tetrapolyphosphate 2.0 g Sodium sulfite 4.0 g Ammonium thiosulfate (70%) 175.0 ml Sodium bisulfite 4.6 g Add water 1.0 liter

Stabilizing solution Formalin 2.0 ml Add water 1.0 liter

[0226]

[Table 3]

[0227]

[Table 4]

As can be seen from Tables 3 and 4, only the sample using the emulsion of the present invention and the DIR coupler had a high sensitivity, and the granularity represented by RMS, the sharpness represented by MTF value, and the color reproduction represented by color turbidity. It turns out that it is excellent. further,
Samples 101 to 105, 115 to 119, 126 and 12
7 was slit to a width of 35 mm, processed into 135 sizes, 36 shots, and packed in patronell. A gray chart having a reflectance of 18% was photographed in each frame under the ISO400 condition. Each of the samples which were separately exposed to white imagewise while the mother liquor was placed in the following automatic developing machine was developed, and the sensitivity and gamma of the magenta image were determined. Further, after the above-mentioned 36 shots were continuously developed for 40 samples per day for 10 days for each sample, the sensitivity and gamma of each sample were determined. The results are shown in Table 5. From Table 5, it can be seen that the sample of the present invention was continuously processed while replenishing the developing solution.
It can be seen that the photographic performance is not easily changed.

The color developing process was performed by an automatic developing machine.
The following treatment was performed at ℃. Color development 3 minutes 15 seconds Bleaching 1 minute Bleaching and fixing 3 minutes 15 seconds Rinse 40 seconds Rinse 1 minute Stability 40 seconds Dry (50 ° C) 1 minute 15 seconds

[0230] In the above treatment step, washing with water means
The countercurrent washing method was adopted. Next, the composition of each processing solution will be described. The replenishment amount of each processing solution was 1 m ² of color photographic material.
Color development is 1200ml per hit, and all others are 80
The volume was 0 ml. The pre-bath carry-amount to the washing step was color light-sensitive material 1 m ² per 50 ml.

(Color developing solution) Mother liquor (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.2 Sodium sulfite 4.0 4.0 4 Potassium carbonate 30.0 30.0 Potassium bromide 1.4 0.7 Potassium iodide 1.3 mg Hydroxylamine sulfate 2.4 2.6 4- (N-ethyl-N-β-hydroxyethylamino) -2-methyl aniline sulfate 4.5 5.0 1.0 liter by adding water 1.0 liter pH 10.0 10.0

(Bleaching solution) Common to mother liquor and replenisher (g) Ferric ammonium salt of ethylenediaminetetraacetic acid 120.0 Disodium salt of ethylenediaminetetraacetic acid 10.0 Ammonium nitrate 10.0 Ammonium bromide 100.0 Bleaching accelerator (CH _{3) 2 N (CH 2)} 2 -SS- (CH 2) 2 -N (CH 3) 2 5 × 10 by the addition of pH6.3 water was added to ³ mol of aqueous ammonia 1.0 l

(Bleach-fixing solution) Common to mother liquor and replenisher (g) Ferric ammonium ethylenediaminetetraacetate 50.0 Disodium ethylenediaminetetraacetate 5.0 Sodium sulfite 12.0 Ammonium thiosulfate aqueous solution (70%) 240 ml Ammonia Add water, pH 7.3 Add water, 1.0 liter

(Washing water) Calcium ion 32 mg / l, magnesium ion 7.3
tap water containing mg / l with H-type strongly acidic cation exchange resin and OH
Water was passed through a column filled with a strong basic anion exchange resin and treated with calcium ion at 1.2 mg / l and magnesium ion at 0.4 mg / l, and 20 mg / liter of sodium isocyanurate sodium dichloride was added thereto. Used.

(Stabilizing solution) Common to mother liquor and replenisher (g) Formalin (37% w / v) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.3 Ethylenediaminetetraacetic acid Sodium salt 0.005 Add water 1.0 liter pH 5.8

(Drying) The drying temperature was 50 ° C.

[0237]

[Table 5]

Example 2 Table 6 shows D-6 of the seventh, eighth, and ninth layers of Sample 116.
Samples 201 to 207 were prepared in the same manner. D
The IR amount was adjusted so that the sensitivity, gamma and the like almost matched. These samples were evaluated in the same manner as in Example 1, and the results were shown in Table 6.
Summarized in Table 6 shows that the sample of the present invention is excellent in sharpness and color reproducibility, and has little change in photographic properties due to continuous processing.

[0239]

[Table 6]

Example 3 EX-8 of Sample 212 in JP-A-1-269935 was used as the DIR coupler (D-6) of the present invention, and EX-10 was used as the DIR coupler (D-6).
By replacing each with an equimolar amount in (-30), a light-sensitive material excellent in color reproducibility and sharpness and having little change in photographic properties in continuous processing was obtained.

[0241]

The silver halide color photographic light-sensitive material of the present invention has excellent effects such as high sensitivity, excellent granularity, sharpness and color reproducibility, and good storability of the light-sensitive material. Further, the photographic material of the present invention has a very small variation in photographic performance even when it is continuously developed.

 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Naoki Saito 210 Nakanuma, Minamiashigara-shi, Kanagawa Prefecture Inside Fujisha Shin Film Co., Ltd. (72) Inventor Masashi Motoki 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Prefecture Fujisha Shin Film Co., Ltd. (56) References JP-A-1-269935 (JP, A) JP-A-64-66643 (JP, A) JP-A-1-213655 (JP, A) JP-A-62-105141 (JP, A) JP-A-62-174760 (JP, A)

Claims (4)

(57) [Claims] 1. A silver halide color photographic light-sensitive material having at least one light-sensitive emulsion layer on a support, comprising a DIR coupler represented by the following general formula (I), wherein said emulsion layer contains 7.0: Silver iodobromide containing .about.45 mol% of silver iodide is present with a distinct layered structure and furthermore chemically sensitized in which the silver iodide content in the whole grain exceeds 4.0 mol%. A silver halide color photographic light-sensitive material comprising an emulsion containing silver halide grains. General formula (I) (Wherein, A represents a coupler residue, and when A represents a phenol-type or naphthol-type coupler residue, n represents 1)
Wherein A represents another coupler residue, n represents 0, and R represents an alkoxycarbonyl group or N,
It represents an alkyl group having 1 to 4 carbon atoms or a pyridyl group, which is substituted with an N-disubstituted carbamoyl group and excluding these . ) 2. The silver halide color photographic light-sensitive material according to claim 1, comprising a compound represented by the general formula (A). General formula (A) Q-SM ¹ (wherein Q is a complex in which at least one member selected from the group consisting of —SO ₃ M ² , —COOM ² , —OH and —NR ¹ R ² is directly or indirectly bonded) Represents a ring residue, M ¹ and M ² independently represent a hydrogen atom, an alkali metal, a quaternary ammonium or a quaternary phosphonium, and R ¹ and R ² represent a hydrogen atom or an alkyl group.) 3. A silver halide color photographic light-sensitive material according to claim 1, wherein said silver halide grains are monodisperse emulsions having a coefficient of variation relating to the grain size of 0.25 or less. . 4. A red-sensitive silver halide emulsion layer containing a cyan coupler, a green-sensitive silver halide emulsion layer containing a magenta coupler, and at least one blue-sensitive silver halide emulsion layer containing a yellow coupler. 4. A silver halide color photographic light-sensitive material according to claim 1, wherein the material has a layer and a magenta polymer coupler is contained in the green light-sensitive silver halide emulsion layer.